CN1239128A - Water repelling tunicle, its mfg. process and water repelling paint compsn. - Google Patents
Water repelling tunicle, its mfg. process and water repelling paint compsn. Download PDFInfo
- Publication number
- CN1239128A CN1239128A CN 99107680 CN99107680A CN1239128A CN 1239128 A CN1239128 A CN 1239128A CN 99107680 CN99107680 CN 99107680 CN 99107680 A CN99107680 A CN 99107680A CN 1239128 A CN1239128 A CN 1239128A
- Authority
- CN
- China
- Prior art keywords
- tunicle
- drainage
- described drainage
- water
- base
- 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.)
- Pending
Links
Images
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
To enable easy removing of a dew condensate from air-conditioning equipment, for example and thereby prevent the freezing of the fins of a heat exchanger by forming a water-repellent coating film which has a fluoroalkyl group and also an uneven surface and further contains water-repellent microparticles or titanium oxide microparticles or both of them on the surface of a base material. The solution according to the present invention is: a coating film 12 of phosphoric acid chromate is formed on the surface of a base material 11 such as an aluminum plate, and a coating film forming solution of a mixture of 3 wt.% water-repellent microparticles 3 and 25 wt.% CF3 (CF2 )7 -(CH2 )2 -SiCl3 with a cyclic dimenthyl silicone oil, is applied. Further, the cyclic dimethyl silicone oil is vaporized in an atmosphere having 45% relative humidity at a room temperature, and the moisture of an air and the -SiCl3 group are subjected to a dehydrochlorination reaction to form an uneven coating film 13 on fins 11. Thus it is possible to form the coating film 13 with about 171 deg. contact angle with water on account of 1-40 mu m surface roughness (unevenness).
Description
The present invention relates to drainage tunicle and manufacture method thereof and drainage coating composition.In more detail, relate to have fluoro-alkyl, the surface for concavo-convex and contain drainage micropartical or titanium oxide microparticle or they the two drainage tunicle and manufacture method thereof and be used for its drainage coating composition.
Always, the heat exchanger fin of heat exchangers such as air conditioning machinery, because the surface is hydrophilic, so on the heat exchanger of the indoor when cold-room turns round, perhaps on the outdoor heat exchanger when greenhouse turns round, moisture content condenses becomes dew, and it hinders passing through of air, and therefore the reduction of heat exchanger effectiveness easily takes place.Particularly at cold zone, when greenhouse turned round in the winter time, the dew of outdoor heat exchanger freezed (frost), and this freezes water and breaks away from difficulty, and running efficiency is reduced, and also will freeze aqueous fusion eliminates (defrosting) therefore must to stop operation of air conditioner sometimes.
For addressing this problem, attempt heat exchanger fin surface with heat exchanger and make drainage, so that dew is difficult to adhere to.For example, open in the flat 5-126482 communique, proposed to make the fluorocarbon particle to disperse the compound plating of eutectoid the spy.It is that the fluorocarbon particle is dispersed in the coating on heat exchanger fin surface, owing to the drainage of fluorocarbon particle makes dew be difficult to adhere to.
But, because above-mentioned compound plating must make the fluorocarbon particle disperse eutectoid, so while be to stir the plating bath plating, but, realize equably that drainingization is difficult in the occasion of the such baroque object of heat exchanger being carried out coating.And also has the problem of cost up for plating on the big base material of the such surface-area of heat exchanger.
And, when the drainage deterioration of heat exchanger is necessary to carry out the processing of draining once more, heat exchanger must be dipped in the plating bath by taking out in the air-conditioning plant, it is difficult in fact will carrying out the draining processing once more.
Purpose of the present invention is exactly in order to solve the above-mentioned problem that exists in the past, expeditiously for high a kind of tunicle with good drainage.Purpose of the present invention particularly will provide a kind of and remove the air conditioning machinery dew easily, can prevent the drainage tunicle that freezes, can make the air conditioning machinery continuous operation and the manufacture method and the drainage coating composition of heat-exchanging fin for heat-exchanger.
Another object of the present invention is to provide a kind of and heat exchanger just can not carried out drainage tunicle and manufacture method and the drainage coating composition that draining is handled by taking out in the air conditioning machinery.
For achieving the above object, the 1st kind of drainage tunicle of the present invention is characterised in that, be to contain fluoro-alkyl bonded Siliciumatom at least mutually by siloxanes (Si-O-Si) key bonded polymkeric substance and the atomic tunicle of drainage, above-mentioned tunicle surface is concavo-convex.Take this, can provide relative water droplet that the high contact angle and the tunicle of good drainage are arranged.
In above-mentioned tunicle, the silicon-dioxide that the drainage micropartical is preferably handled through draining, granular of polyorganosiloxane, particulate fluorocarbon resin any or their mixture.If according to such example, just can keep good drainage for a long time.
The 2nd kind of drainage tunicle of the present invention is characterised in that, is to contain fluoro-alkyl bonded Siliciumatom at least mutually by the tunicle of siloxanes (Si-O-Si) key bonded polymkeric substance and titanium oxide microparticle, and above-mentioned tunicle surface is concavo-convex.Take this, though drainage itself is poorer slightly than the 1st kind of drainage tunicle of the present invention, but because the photocatalyst effect of titanium oxide microparticle can make pollutent carry out photolysis, so even can provide the good tunicle of stain resistance that drainage is continued adhering to.
Self-evident, also can make the formation of the formation of above-mentioned the 1st kind of drainage tunicle and the 2nd kind of drainage tunicle combined, that is, contain at least fluoro-alkyl bonded Siliciumatom mutually by siloxanes (Si-O-Si) key bonded polymkeric substance, drainage micropartical and titanium oxide microparticle, the surface is concavo-convex tunicle.The result can provide the tunicle with good drainage and good stain resistance.
The above-mentioned the 1st and the formation of the 2nd kind of drainage tunicle in, the concave-convex surface of drainage tunicle is preferably the concavo-convex of 0.1-100 mu m range.If, can present high contact angle by this example.
In addition, in above-mentioned tunicle, fluoro-alkyl bonded Siliciumatom is with represented preferable of following general formula (change 2).If according to this example, then can provide weather resistance good drainage tunicle.[changing 2]
(wherein, n is the integer of 0-9, and R is the substituting group that contains alkylidene group, vinylidene, ethynylene, arylidene (arylen), silicon or Sauerstoffatom, and m is 0 or 1)
In addition, in above-mentioned tunicle, tunicle contains polysiloxane oil or the soluble poly siloxanes is preferable.By this example, can provide weather resistance good drainage tunicle.
And in above-mentioned tunicle, base material is metal, applies anti-corrosion processing on its surface, and it is good forming the drainage tunicle more thereon.Take this, the base material of the drainage with excellent durability can be provided.
In the above-described configuration, metal is preferably aluminum or aluminum alloy.If, can provide heat conductivity good base material by this example.And in the above-described configuration, the processing of anti-corrosion processing preferably phosphoric acid, chromate treating, oxide treatment, anodic oxidation treatment, coated with silica, glass cover any of processing, resin-coated processing or their Combined Processing.Example can provide weather resistance good base material like this.
In addition, in the above-described configuration, it is good that the metal asperities is turned to.Example like this, the base material that can provide the draining tunicle to be difficult to peel off.And in the above-described configuration, the asperitiesization of metal is preferably scope concavo-convex of 0.1-50 μ m.Example can provide the draining tunicle the extremely difficult base material of peeling off like this.
In addition in the above-described configuration, preferable alloy is as the heat exchanger fin of heat exchanger.By this example, the dew of heat exchanger is removed easily, prevent freezing of heat exchanger fin, make the continuous operation of air conditioning machinery become possibility.In addition in the above-described configuration, the heat exchange department that heat exchanger fin is entered air conditioning machinery is good.By this example, but can provide continuous operation and comfortableness also good province's energy type air conditioning machinery.
The 1st kind of drainage coating composition of the present invention comprises the organic solvent of material, drainage micropartical and the non-water system of the water-disintegrable base that contains Si and fluoro-alkyl at least.Use this coating can make the 1st kind of drainage tunicle of the invention described above expeditiously.
In above-mentioned drainage coating composition, the drainage micropartical is preferably any of the silicon-dioxide handled through draining, granular of polyorganosiloxane, particulate fluorocarbon resin or their mixture.By this example, can keep good drainage for a long time.
The 2nd kind of drainage coating composition of the present invention is the organic solvent that comprises material, titanium oxide microparticle and the non-water system of the water-disintegrable base that contains Si and fluoro-alkyl at least.By this example, can make the 2nd kind of drainage tunicle of the invention described above expeditiously.
Certainly, also can take the formation of above-mentioned the 1st kind of drainage coating composition and the 2nd kind of drainage coating composition combinedly, promptly comprise the drainage coating composition of organic solvent of material, drainage micropartical, titanium oxide microparticle and the non-water system of the water-disintegrable base that contains Si and fluoro-alkyl at least.
The above-mentioned the 1st and the 2nd kind of drainage coating composition in, the organic solvent of non-water system preferably by dimethylbenzene, toluene, normal alkane, and silicone in select at least a kind.When using such solvent, can make drainage tunicle concavo-convexization during fabrication.
In addition, in above-mentioned drainage coating composition, contain the water-disintegrable base of Si and the material of fluoro-alkyl and preferably use the material of representing with following formula: CF
3-(CF
2) n-(R) m-SiX
pCl
3-p(wherein, n is the integer of 0-9, and R is that the substituting group that contains alkylidene group, vinylidene, ethynylene, arylidene, silicon or Sauerstoffatom (is specially-CH
2CH
2-,-C
6H
4-(phenylene) ,-C
2H
4Si (CH
3)
2C
10H
20-), m is 0 or 1, X is H, alkyl, alkoxyl group, isocyanate group, contains the substituting group of fluoroalkyl or fluoroalkoxy that P is 0,1,2 or 3).Owing to use such material, can improve the drainage and the weather resistance of drainage tunicle more.
In this external above-mentioned drainage coating composition, the use level that contains the material of the water-disintegrable base of Si and fluoro-alkyl is preferably the scope of 1-50% (weight), atomic use level is preferably the scope of 1-30% (weight), and the use level of non-water system organic solvent is preferably the scope of 20-98% (weight).In this external above-mentioned drainage coating composition, contain polysiloxane oil or the soluble poly siloxanes is preferable.By this example, can make the good drainage tunicle of weather resistance.
The manufacture method of the 1st kind of drainage tunicle of the present invention, it is characterized in that, to contain has the water-disintegrable base that contains Si and the material and the atomic solution of drainage of fluoro-alkyl to be coated with, and makes the hydrolysis of said hydrolyzed base and the polymerization materialization in containing the atmosphere of moisture again, forms the tunicle of concave-convex surface.Constitute by this, the 1st kind of tunicle of the invention described above can be provided effectively and rationally.
In above-mentioned manufacture method, the drainage micropartical is preferably any of the silicon-dioxide handled through draining, granular of polyorganosiloxane, particulate fluorocarbon resin or their mixture.By this example, can keep good drainage for a long time.
The manufacture method of the 2nd kind of drainage tunicle of the present invention, it is characterized in that, to contain has the water-disintegrable base that contains Si and the material of fluoro-alkyl and the solution of titanium oxide microparticle to be coated with, and makes the hydrolysis of said hydrolyzed base and the polymerization materialization in containing the atmosphere of moisture again, forms the tunicle of concave-convex surface.Constitute by this, the 2nd kind of tunicle of the invention described above can be provided effectively and rationally.
Certainly, also the manufacture method of above-mentioned the 1st kind of drainage tunicle and the manufacture method of the 2nd kind of drainage tunicle can be made up, promptly, the solution that will contain material, drainage micropartical and the titanium oxide microparticle of water-disintegrable base that Si is arranged and fluoro-alkyl is coated with, in containing the atmosphere of moisture, make the hydrolysis of said hydrolyzed base and the polymerization materialization again, form the tunicle of concave-convex surface.
The above-mentioned the 1st and the 2nd kind of drainage by film manufacturing method in, solution preferably contains polysiloxane oil or soluble poly siloxanes.Here said " solubility " refers to the solvability for above-mentioned non-water system organic solvent.By this example, can make the good drainage tunicle of weather resistance.In addition above-mentioned drainage by film manufacturing method in, water-disintegrable base is preferably the mixture of any or they of halo silyl, alkoxysilyl, silylation, isocynate silane base.By this example, can make the good drainage tunicle of weather resistance.
The manufacture method of first kind of drainage base material of the present invention, it is characterized in that, the metallic surface is applied anti-corrosion processing, to contain has the material that contains water-disintegrable base of Si and fluoro-alkyl and the solution of drainage particle to be coated with, in containing the atmosphere of moisture, make the hydrolysis of said hydrolyzed base and the polymerization materialization again, form the tunicle of concave-convex surface.Constitute by this, the base material of the drainage with good drainage can be provided.
The manufacture method of the 2nd kind of drainage base material of the present invention, it is characterized in that, the metallic surface is applied anti-corrosion processing, to contain has the material that contains water-disintegrable base of Si and fluoro-alkyl and the solution of titanium oxide microparticle to be coated with, in containing the atmosphere of moisture, make the hydrolysis of said hydrolyzed base and the polymerization materialization again, form the tunicle of concave-convex surface.Constitute by this, the base material of the drainage with good stain resistance can be provided.Certainly, also can be coated with containing the two solution of drainage micropartical and titanium oxide microparticle.
In the manufacture method of above-mentioned drainage base material, metal is preferably aluminum or aluminum alloy.By this example, can provide heat conductivity good base material.In addition in the manufacture method of above-mentioned drainage base material, anti-corrosion processing is preferably that phosphoric acid processing, chromate treating, oxide treatment, anodic oxidation treatment, coating silicon-dioxide, glass cover and handle, resin-coated processing any or their Combined Processing.By this example, can provide weather resistance good base material.
In the manufacture method of above-mentioned drainage base material, it is good that the metal asperities is turned in addition.By this example, can provide to be difficult to base material that the draining tunicle is peeled off.And in the manufacture method of above-mentioned drainage base material, the asperitiesization of metal is preferably the concavo-convex of 0.1-50 mu m range.By this example, can provide the extremely difficult base material that the draining tunicle is peeled off.
In the manufacture method of this external above-mentioned drainage base material, metal is preferably the heat exchanger fin of heat exchanger for air conditioner.According to this example, the dew of heat exchanger can be removed easily, prevent the freezing of heat exchanger fin, air conditioning machinery can continuous operation.
Below, use Fig. 1 that embodiments of the present invention are described.
Figure 1A-C represents the manufacturing process of draining base material of the present invention, Figure 1A is the base material sectional view that applies before draining is handled, Figure 1B is the constructed profile that the surface was applied the base material of anti-corrosion processing, Fig. 1 C is the constructed profile that the surface forms concavo-convex tunicle, and Fig. 1 D is the constructed profile that the tunicle surface X of C is partly expanded to molecular level.Heat exchanger fin 11 is that air conditioning machinery and extraneous gas carry out heat exchange action, is made of good aluminium sheet of pyro-conductivity etc.Anti-corrosion epithelium 12 has been to prevent the corrosive effect, is that epithelium, oxide scale film, silicon-dioxide epithelium, glass tectum etc. constitute by phosphoric acid-chromic salt epithelium, zinc phosphate.Concavo-convex tunicle 13 has been the effects that prevent dewfall and preventing frost, is made of the polymkeric substance of fluoro-alkyl bonded Siliciumatom polymerization materialization by siloxane bond and drainage micropartical 14 or titanium oxide microparticle, and the surface is concavo-convex tunicle.
As the drainage micropartical, through silicon-dioxide, granular of polyorganosiloxane, the sub-easy handling of particulate fluorocarbon resin that draining is handled, the weight mean diameter of primary particle is 5nm-100 μ m, is more preferred from 7nm-50 μ m.The weight mean diameter of offspring (agglutination particle) is different because of the kind of particle, and granular of polyorganosiloxane is 2-20 μ m, and particulate fluorocarbon resin is the degree of 3-10 μ m.In the occasion of above-mentioned silicon-dioxide, be the agglomeration of absent-mindedness, be easy to disperse, therefore roughly can use with primary particle.
Tunicle surface concavo-convex if be chosen to the concavo-convex of 0.1-100 μ m, better 0.5-50 μ m, can obtain high drainage, and particularly when making 0.5-50 μ m concavo-convex, the contact angle that can obtain water is more than 160 degree.
In the manufacture method of such tunicle, the operation that is coated with by the coating that will contain the material that has the water-disintegrable base that contains Si and fluoro-alkyl at least and drainage micropartical or titanium oxide microparticle and make the reaction that in containing the atmosphere of moisture, is hydrolyzed of said hydrolyzed base form siloxane bond.Take this to make the tunicle of concave-convex surface.At this moment, if when containing the water-disintegrable base halo silyl, alkoxysilyl, silylation of Si or isocynate silane base, can make the as easy as rolling off a log generation of hydrolysis reaction, this is well suited in manufacturing process.
As the material that contains fluoro-alkyl and water-disintegrable base, for example can use the such compound of following formula (changing 3).
(changing 3)
CF
3-(CF
2)
n-(R)
m-SiX
pC
3-p(wherein, n is the integer of 0-9, and R is that the substituting group that contains alkylidene group, vinylidene, ethynylene, arylidene, silicon or Sauerstoffatom (is specially-CH
2CH
2-,-C
6H
4-(phenylene) ,-C
2H
4Si (CH
3)
2C
10H
20-), m is 0 or 1, X is H, alkyl, alkoxyl group, isocyanate group, contains the substituting group of fluoroalkyl or fluoroalkoxy that P is 0,1,2 or 3)
Except that mentioned reagent,, then can use the such compound of following formula (changing 4) if will enumerate material more specifically.
[changing 4]
(1)CF
3CH
2O(CH
2)
15SiHCl
2
(2)CF
3(CH
2)
2Si(CH
3)
2(CH
2)
15SiCl
3
(3)CF
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OCH
3)Cl
2
(4)CF
3(CH
2)
7(CH
2)
2Si(CH
3)
2(CH
2)
10SiCl
3
(5)CF
3COO(CH
2)
15Si(NCO)Cl
2
(6)CF
3(CF
2)
7(CH
2)
2SiCl
3
(7)CF
3(CF
2)
7(CH
2)
2Si(NCO)
3
(8)CF
3(CF
2)
5(CH
2)
2SiCl
3
(9)CF
3(CF
2)
5(CH
2)
2Si(NCO)
3
(10)CF
3(CF
2)
5(CH
2)
2SiCH
3Cl
2
(11)CF
3(CF
2)
7C
6H
4SiCl
3
Here example has gone out to comprise the molecule of straight chain base, but so long as contain the hydrolyzable group of Si and the material of fluoro-alkyl at least, even the molecule that contains side chain radical is also without any obstruction.
In addition, also can and use the method that makes the substrate surface asperitiesization, at this moment, can utilize with metallic brush and grind or sandblasting, or chemical etching method etc.But,, just be not defined as these methods so long as can make it the method for asperitiesization with micron order.At this moment, substrate surface concavo-convex be if become 0.1-50 μ m at least, during better 0.3-10 μ m concavo-convex, just can obtain high drainage, obtains the good tunicle of drainage.Special if 0.3-10 μ m's is concavo-convex, and the contact angle that can easily obtain water is more than 160 degree.
In addition, with the method that the material that contains the water-disintegrable base of Si and fluoro-alkyl at least is coated with, applicable pickling process, spraying method, bristle coating method etc. are any.And above-mentioned substance both can directly be coated with, also can be diluted in the non-water solvents such as normal alkane or dimethylbenzene and be coated with.In the occasion of dilution, water-free non-water solvent then can improve volatility if use fully, can shorten time of drying, and protection is water-disintegrable before coating suits aspect basic.
At least the use level that contains the material of the water-disintegrable base of Si and fluoro-alkyl is preferably 1-50% (weight).Use level than this numerical value also after a little while, it is thin that tunicle became, and makes the drainage variation.In addition, use level than this numerical value for a long time, it is big that the viscosity of solution becomes, and makes the coating difficulty.
In addition, the use level of drainage micropartical or titanium oxide microparticle is preferably 1-30% (weight).Atomic use level than this numerical value also after a little while, drainage is insufficient, several tunicle becomes fragile also for a long time if use level is than this, makes the weather resistance reduction.
In above-mentioned solution, except the water-disintegrable base and the material of fluoro-alkyl and the part the micropartical that contain Si at least, the organic solvent that is non-water system is good.Thereby the use level of non-water system organic solvent is that the scope of 20-98% (weight) is good.In addition, owing to formed the tunicle of such concave-convex surface on the heat exchanger fin surface of air conditioner heat exchanger,, can provide efficient air conditioning machinery high, that comfortableness is also good so well heater is used in unnecessary other thawing.
Embodiment
Below, use embodiment to be described more specifically the present invention.In following embodiment, be wettability test machine (Wetability measuring apparatus with レ ス カ society system to the contact angle of water droplet.MODELWET-6000, RHESCA CO.LTD) measure with the close method of William.That is, the base material that forms tunicle is vertically inserted facing to the water surface.This moment is according to the stress determination contact angle by the water surface, and advancing contact angle is calculated in the stress determination when inserting base material, and receding contact angle is calculated in the stress determination when putting on base material.Wherein, contact angle is the angle of water droplet when static, the contact angle when dynamic contact angle is water drops flows down, and the contact angle of water droplet the place ahead part is an advancing contact angle, the contact angle of rear part is a receding contact angle.
In the following embodiments, % only is shown and then represents a certain weight %.
Embodiment 1
Wipe aluminium (Al) plate with wire brush in advance, form the concavo-convex of 8-10 μ m on the surface, be prepared to the heat exchanger fin base material 11 (Figure 1A) of the good Al system of cleaning.Then, heat exchanger fin base material 11 was immersed down in phosphoric acid-chromate chemistry coating agent (the Japanese パ-system ボ of カ ラ イ ジ Application グ Co., Ltd. Application デ ラ イ ト 701) 2 minutes at 50 ℃, form the Plessy's green anti-corrosion tunicle 12 of hydrochlorate (Figure 1B).
To carry out silicon dioxide particles (the Japanese ア エ ロ ジ Le system RX200 of Co., Ltd.) 3% (weight) of the median size 12nm that draining handles and as 17 fluoro decyltrichlorosilane (CF of the material of water-disintegrable base that contains Si and fluoro-alkyl as the atomic surface of drainage
3(CF
2)
7-(CH
2)
2-SiCl
3) 25% (weight) is blended in the silicone oil of being made by the ring-type dimethyl siloxane (the system KF994 of Shin-Etsu Chemial Co., Ltd) as non-water solvent, is modulated into tunicle and forms solution, is coated with into the thickness of 1-10 μ m with hairbrush.Then, at room temperature make the evaporation of ring-type dimethylsilicone oil in the atmosphere of relative humidity 45% (obtaining good result when above), because the moisture in the atmosphere remains in 17 fluoro decyltrichlorosilane hydrolysis rapidly on the heat exchanger fin 35%.At this moment, airborne moisture and-SiCl
3Base carries out the desalination acid-respons, and the reaction of following formula (changing 5) takes place, and ends with reaction in about 10 minutes, forms concavo-convex tunicle 13 (Fig. 1 C) on heat exchanger fin 11.
[changing 5]
(Rf represents to contain fluoroalkyl, and n represents integer)
This tunicle is made of polymkeric substance and the drainage micropartical 14 by the crosslinked fluoro-alkyl of siloxane bond (Si-O-Si) that contain through shown in Fig. 1 D (expanded view of the X part of Fig. 1 C), almost can not peel off, and weathering resistance is high.In addition, the surfaceness that determines is the scope of 1-40 μ m, is 171 ° to the contact angle of water.Also measured dynamic contact angle as prerequisite with application to air conditioning machinery.Be shown in table 1 after will the results are summarized in.
As anti-corrosion processing, be to flood 1 minute in the chemical coating agent (the system グ ラ ノ ジ of Japanese ペ イ Application ト Co., Ltd. Application 38) in zinc phosphate under 60 ℃, forming zinc phosphate is anti-corrosion tunicle, or be to flood 2 minutes in the chemical coating agent (the system ボ of Japanese パ カ ラ イ ジ Application グ Co., Ltd. Application デ ラ イ ト 713) in chromic salts under 50 ℃, form the anti-corrosion tunicle of chromic salt, also can obtain effect same.In addition,, in boiling water, soak 30 minutes formation oxide film thereon (boehmite), perhaps in 5% oxalic acid solution, carry out anodic oxidation and form oxide film thereon, also can obtain same effect as anti-corrosion processing.
And the water-disintegrable base that no matter contains Si is halo silyl, alkoxysilyl, silylation or carbimide silylation, though the speed of response difference can both obtain same effect.And, use the compound shown in above-mentioned (changing 5) also can obtain roughly same result as the material that contains fluoro-alkyl and water-disintegrable base.
Distinguished that in above-mentioned experimentation the apparent speed of response of desalination acid-respons (hydrolysis reaction among the embodiment) that is to say that the humidity in the reaction atmosphere is epochmaking.Studies show that in more detail, the concavo-convex confidential relation that exists on the speed of hydrolysis reaction and tunicle surface, speed of response is fast more, tunicle surface concavo-convex just big more.Additional disclosure be, in experiment similarly to Example 1, humidity is taken as 35% when above, the difference of the COS θ of the contact angle that water droplet moves forward and backward can confirm in practicality it is preferred value below 0.1.
Embodiment 2
Give and prepare good aluminium (Al) the system heat exchanger fin of cleaning earlier.Coating thereon contains the ethanolic soln of tetraethoxysilane 10%, acetate 1%, water 5%, heats 1 hour down at 200 ℃, forms the silicon-dioxide anticorrosion film.
Then, with granular of polyorganosiloxane of median size 2 μ m (the eastern レ ダ ウ コ-ニ Application グ シ リ コ-system ト レ of Application Co., Ltd. Off イ Le E-605) 5% (weight), soluble poly siloxanes (the eastern レ ダ ウ コ-ニ Application グ シ リ コ-system ト レ of Application Co., Ltd. Off イ Le R910) 5% (weight), as the 17 fluoro decyltrichlorosilanes (10% weight concentration) of the material of water-disintegrable base that contains Si and fluoro-alkyl, in non-water solvent normal alkane (150 ℃ of boiling points), dilute and modulate.Use hairbrush that this tunicle is formed with coating and be coated on the above-mentioned Al system heat exchanger fin, form the thickness of 1-10 μ m.Then, at room temperature in the atmosphere of relative humidity 45% (can obtain good result more than 35%), make the normal alkane evaporation,, make the said hydrolyzed base hydrolysis rapidly that remains on the heat exchanger fin because of the moisture in the atmosphere in relative humidity, at this moment, airborne moisture and-SiCl
3Base carries out the desalination acid-respons, forms the tunicle shown in the following formula (changing 5).
This reaction ended with 10 minutes approximately.On heat exchanger fin, form tunicle polymkeric substance, concave-convex surface that contains the fluoro-alkyl crosslinked by siloxane bond.This tunicle almost can not peel off and weathering resistance high.In addition, the surfaceness of mensuration is average 1-40 μ m, is 172 ° to the contact angle of water.And measured dynamic contact angle as prerequisite with the application in the air conditioning machinery, show the result in table 1.
Embodiment 3
In advance aluminium (Al) plate is carried out chemical etching in the bath of phosphoric acid 60%-nitric acid 20%-water 20%, form the concavo-convex of 8-10 μ m on the surface, and clean, be prepared to the heat exchanger fin base material of Al system through good.As anti-corrosion processing, in boiling water, soak 30 minutes formation oxide film thereon (boehmite) then.Modulate again by as particulate fluorocarbon resin of the atomic median size 0.3 μ m of drainage (the system Le Block ロ of ダ イ キ Application Industrial Co., Ltd Application L-2) 2% (weight), as the CF of the material of water-disintegrable base that contains Si and fluoro-alkyl
3(CF
2)
7(CH
2)
2Si (CH
3)
2(CH
2)
10-SiCl
320% (weight), polysiloxane oil (the system KF96-1000 of Shin-Etsu Chemial Co., Ltd) 2% (weight) and the solution that constitutes as the toluene 78% of non-aqueous solvent.This tunicle is formed solution be coated with, form the thickness of 1-10 μ m with hairbrush.Then, at room temperature in the atmosphere of relative humidity 40% (relative humidity 30-60% can obtain good result), make toluene evaporates,, remain in the water-disintegrable base hydrolysis rapidly on the base material because of the moisture in the atmosphere.At this moment, airborne moisture and-SiCl
3Base carries out the desalination acid-respons, forms the tunicle shown in the following formula (changing 5).
Reaction roughly ended with about 10 minutes, formed tunicle polymkeric substance, concave-convex surface that contains by the crosslinked fluoro-alkyl of above-mentioned siloxane bond on heat exchanger fin.This tunicle almost can not peel off and weathering resistance high.In addition, measuring surfaceness is 1-12 μ m, is 174 ° to the contact angle of water.And measured dynamic contact angle as prerequisite with the mensuration of air conditioning machinery.Show the result in table 1.
The surfaceness of base material is suitable at 0.1-50 μ m.As long as can realize this surfaceness, the method for surperficial asperitiesization uses methods such as sandblasting method or electrolytic etching method all can obtain same effect.
Tunicle is formed the humidity that makes the atmosphere of toluene evaporates after solution is coated with hairbrush, depend on surfaceness, for example surfaceness is the occasion of 0.1 μ m-8 mu m range, hope is not carried out in relative humidity 60% (relative humidity 40-80% can obtain good result), surfaceness is in the occasion of 8 μ m-50 μ m, wishes to carry out under relative humidity 40% (relative humidity result that 30-60% can obtain).When the above-mentioned scope of psychromatic ratio was also low, the concavo-convex of tunicle surface diminished, and drainage has the tendency of reduction.And the higher occasion of the above-mentioned scope of psychromatic ratio, film is bad easily, has the tendency of weather resistance variation.
Embodiment 4
Cover at the good enterprising oozy glass of cleaning of aluminium (Al) system heat exchanger fin in advance and handle, form the anti-corrosion tunicle of glass of the about 0.5 μ m of thickness.
Follow titanium oxide microparticle (the Japanese ア エ ロ ジ Le system P25 of Co., Ltd.) 5% (weight) with median size 21nm, with 17 fluoro decyltrichlorosilanes (10% weight concentration) as the material that contains the water-disintegrable base of Si and fluoro-alkyl, dilution modulation in non-aqueous solvent dimethylbenzene, with hairbrush this tunicle formation is coated on the heat exchanger fin of above-mentioned Al system with coating, makes it to become the thickness of 1-10 μ m.Then, at room temperature make the dimethylbenzene evaporation in the atmosphere of relative humidity 45% (relative humidity can obtain good result more than 35%), make the said hydrolyzed base hydrolysis rapidly that remains on the heat exchanger fin because of the moisture in the atmosphere.At this moment, airborne moisture and-SiCl
3Base carries out the desalination acid-respons, forms tunicle.
This reaction ended with 10 minutes approximately, formed tunicle polymkeric substance, concave-convex surface that contains by the crosslinked fluoro-alkyl of siloxane bond on heat exchanger fin.This tunicle almost can not peel off and weathering resistance high.In addition, surfaceness is average 1-40 μ m after measured, is 172 ° to the contact angle of water.And measured dynamic contact angle as prerequisite with the application in the air conditioning machinery.Show the result in table 1.
Embodiment 5
Similarly to Example 1, wipe aluminium (Al) plate, form concavo-convexly on the surface, form the anti-corrosion tunicle of Plessy's green hydrochlorate with phosphoric acid-chromate chemistry coating agent with wire brush.
Again will be as silicon dioxide particles (the Japanese ア エ ロ ジ Le system RX200 of Co., Ltd.) 3% (weight) of the atomic surface of drainage through the median size 12nm of draining processing, the titanium oxide microparticle of median size 21nm (the Japanese ア エ ロ ジ Le system P25 of Co., Ltd.) 3% (weight), with 17 fluoro decyltrichlorosilanes 10% (weight) as the material that contains the water-disintegrable base of Si and fluoro-alkyl, in ring-type dimethylsilicone oil (the system KF994 of Shin-Etsu Chemial Co., Ltd), mix, the tunicle that obtains is formed solution be coated with into 1-10 μ m thickness with hairbrush as non-water solvent.Then, at room temperature make the evaporation of ring-type dimethylsilicone oil in the atmosphere of relative humidity 45% (can obtain good result more than 35%), because of the moisture in the atmosphere, make the 17 fluoro decyltrichlorosilane hydrolysis rapidly that remain on the heat exchanger fin, form the tunicle that contains by the crosslinked fluoro-alkyl of siloxane bond.
This tunicle almost can not be peeled off, and weathering resistance is high.Having measured surfaceness in addition is average 1-40 μ m, is 172 ° to the contact angle of water.And measured dynamic contact angle as prerequisite with the application in the air conditioning machinery.Show the result in table 1.
Embodiment 6
The coating epoxy is a coating on stainless steel plate, makes the road markings plate.Coating fluid similarly to Example 1 is coated on the marking plate, is hydrolyzed, be covered with at the Resins, epoxy of marking plate and form the draining tunicle.This tunicle almost can not peel off and weathering resistance high.In addition, measuring surfaceness is average 1-5 μ m, is 172 ° to the contact angle of water.And exposure place does not almost have adhering to of snow and ice when wind and snow, and the visibility of marking plate is good.
Embodiment 7
The heat exchanger fin of making is similarly to Example 1 entered the outdoor heat exchanger of air conditioning machinery, and when carrying out the greenhouse running, the initial stage does not almost have water droplet or frost to adhere on heat exchanger fin, demonstrates high drainage.After carrying out running in 1 year, find the part that many places have water droplet to adhere on the heat exchanger fin, when outside air temperature hanged down, water droplet freezed and produces frost.By taking out in the heat exchanger, the usefulness spray gun sprays coating fluid similarly to Example 1 on heat exchanger fin, form the draining tunicle once more with the heat exchanger fin in 1 year of this operation.Humidity during the spraying coating fluid is 45%.On heat exchanger fin, form new draining tunicle thus, present the drainage same once more with the initial stage.
Comparative example 1
Except that reaction atmosphere, adopt same condition among the embodiment 1, change reaction atmosphere, the desalination acid-respons at room temperature takes place in the air of relative humidity 20%.After ending with reaction in about 14-15 minute, form tunicle polymkeric substance, concave-convex surface that contains fluoro-alkyl this moment too on heat exchanger fin.And this tunicle also almost can not peel off, and weathering resistance is high.But, when measuring surfaceness,, be below the 0.1 μ m though big ripple is arranged, be 149 ° to the contact angle of water.The measurement result of dynamic contact angle is shown in table 1 with embodiment 1.
Comparative example 2
In embodiment 1, except not having the drainage micropartical, adopt same condition to form tunicle.After ending with reaction in about 14-15 minute, form tunicle polymkeric substance, concave-convex surface that contains fluoro-alkyl this moment too on heat exchanger fin.And this tunicle also almost can not peel off, and weathering resistance is high.But the difference of dynamic contact angle becomes big.The measurement result of dynamic contact angle is shown in table 1 with embodiment 1.
| The base material asperitiesization | Anti-corrosion tunicle | Add micropartical | Contact angle to water | COS θ's is poor | ||
| Advancing contact angle | Receding contact angle | |||||
| Embodiment 1 | Wire brush | The Plessy's green hydrochlorate | Draining silicon-dioxide | 175° | 169° | 0.015 |
| Embodiment 2 | Do not have | The silicon-dioxide tunicle | Polysiloxane | 175° | 162° | 0.045 |
| Embodiment 3 | Chemical corrosion | Oxide film thereon | Fluoro-resin | 177° | 172° | 0.008 |
| Embodiment 4 | Do not have | Glass covers | Titanium oxide | 174° | 161° | ?0.049 |
| Embodiment 5 | Wire brush | The Plessy's green hydrochlorate | Draining silicon-dioxide/titanium oxide | 175° | 163° | 0.040 |
| Comparative example 1 | Wire brush | The Plessy's green hydrochlorate | Draining silicon-dioxide | 153° | 84° | 0.996 |
| Comparative example 2 | Wire brush | The Plessy's green hydrochlorate | Do not have | 175° | 155° | 0.090 |
In the table 1, the difference of COS θ be advancing contact angle (θ a) and receding contact angle (θ r) COS separately poor (COS θ r-COS θ a).The commentaries on classics angle of fall of the difference of this COS and water droplet (angle that water droplet begins to slide) α has the relation that following formula is represented.
(cos θ r-cos θ a) for [several 1] mg sin α=2R γ
M: the quality of water droplet
G: universal gravity constant
R: the radius of the face on water droplet contact substrate surface
R: the surface tension of water
That is to say, demonstrated easy more the falling of the more little then water droplet of difference of COS.
As being seen by table 1, in the middle of handling with method of the present invention, dynamic contact angle is high, and the difference of the COS of advancing contact angle and receding contact angle also can be below 0.05.Can reach the surface property of adhering to the such level of water droplet hardly.
As discussed above, as long as according to the present invention, just can provide the tunicle that has high contact angle of water droplet and good drainage.And can improve the dried up property of substrate surface.In addition by containing titanium oxide microparticle, because the photocatalyst effect can make the pollutent photolysis as micropartical.Thereby can often keep peace and quiet surface, can improve the dried up property of substrate surface more.
In addition, according to the present invention, on the heat exchanger fin surface of air conditioner heat exchanger, formation contains the polymkeric substance and tunicle drainage micropartical and/or titanium oxide microparticle, concave-convex surface of fluoro-alkyl, therefore have following effect: in the winter time and unnecessary other the thawing of cold zone use well heater, the air conditioning machinery that efficient is high, comfortableness is also good can be provided.
Secondly, drainage of the present invention by the feature of film manufacturing method is, is coated on the operation that same intramolecularly comprises the solution of the material of the water-disintegrable base that contains Si and fluoro-alkyl and drainage micropartical and/or titanium oxide microparticle at substrate surface.And make above-mentioned substance hydrolysis reaction in containing the atmosphere of moisture, form the tunicle that contains polymkeric substance fluoro-alkyl, and polymerization materialization crosslinked by siloxane bond.According to this formation, just can provide weather resistance, drainage, all good tunicle of dried up property effectively and rationally.
Secondly, the occasion that the present invention is used in the manufacture method of base materials such as drainage heat-exchanging fin for heat-exchanger, it is characterized in that, comprise following operation: in advance to substrate surface carry out anti-corrosion processing, then will comprise the material of the water-disintegrable base that contains Si and fluoro-alkyl and drainage micropartical and or the solution of titanium oxide microparticle in the operation that above-mentioned substrate surface is coated with, make the tunicle that constitutes by above-mentioned substance in containing the atmosphere of moisture hydrolysis so that form the operation of the tunicle of the polymkeric substance of polymerization materialization that contains fluoro-alkyl at above-mentioned substrate surface by siloxane bond.Adopt aforesaid method, can make good, that have good drainage and the good heat-exchanging fin for heat-exchanger of dried up property of weather resistance effectively and rationally.
Figure 1A-C represents the manufacturing process of the embodiment of the invention 1, Figure 1A is the sectional view of base material, Figure 1B is the constructed profile after the surface of base material forms anti-corrosion processing film, Fig. 1 C is the constructed profile that forms behind the drainage tunicle, and Fig. 1 D is the constructed profile after the X with the substrate surface of C partly enlarges.
The explanation of symbol
11 aluminium (Al) heat exchanger fin
12 anticorrosion films
13 concavo-convex tunicles
14 drainage microparticals
Claims (32)
1. drainage tunicle, it is the drainage tunicle that forms on the surface of base material, it is characterized in that, above-mentioned drainage tunicle contains fluoro-alkyl bonded Siliciumatom by siloxanes (Si-O-Si) key bonded polymkeric substance, with by at least a kind of micropartical selecting in drainage micropartical and the titanium oxide microparticle, and the surface of above-mentioned tunicle is concavo-convex.
2. the described drainage tunicle of claim 1 is characterized in that, the drainage micropartical is by the silicon-dioxide of handling through draining, granular of polyorganosiloxane, reaches at least a kind that selects in particulate fluorocarbon resin.
3. the described drainage tunicle of claim 1 is characterized in that, tunicle contain drainage micropartical and titanium oxide microparticle the two.
4. the described drainage tunicle of claim 1 is characterized in that, the concavo-convex of surface is the concavo-convex of 0.1-100 mu m range.
5. the described drainage tunicle of claim 1 is characterized in that, fluoro-alkyl bonded Siliciumatom is by following general formula (changing 1) expression, [changing 1]
(in the formula, n is 0 or integer, and R is the substituting group that contains alkylidene group, vinylidene, ethynylene, arylidene, silicon or Sauerstoffatom, and m is 0 or 1).
6. the described drainage tunicle of claim 1 is characterized in that, tunicle contains at least a kind of polysiloxane compound selecting by in polysiloxane oil and the soluble poly siloxanes.
7. the described drainage tunicle of claim 1 is characterized in that base material is a metal, applies anti-corrosion processing on its surface.
8. the described drainage tunicle of claim 7 is characterized in that, metal is by at least a kind of metal selecting in aluminium and the aluminium alloy.
9. the described drainage tunicle of claim 7, it is characterized in that anti-corrosion processing is to cover at least a kind of processing selecting in processing and the resin-coated processing by phosphoric acid processing, chromate treating, oxide treatment, anodic oxidation treatment, coated with silica, glass.
10. the described drainage tunicle of claim 7 is characterized in that, makes the metal asperitiesization.
11. the described drainage tunicle of claim 10 is characterized in that the asperitiesization of metal is the concavo-convex of 0.1-50 mu m range.
12. the described drainage tunicle of claim 7 is characterized in that metal is the heat exchanger fin of heat exchanger.
13. the described drainage tunicle of claim 12 is characterized in that heat exchanger fin enters the heat exchange department of air conditioning machinery.
14. the drainage coating composition is characterized in that, contains at least: contain the compound of water-disintegrable base of Si and fluoro-alkyl, by at least a micropartical of selecting in drainage micropartical and the titanium oxide microparticle and the organic solvent of non-water system.
15. the described drainage coating composition of claim 14 is characterized in that, the drainage micropartical is by the silicon-dioxide of handling through draining, granular of polyorganosiloxane, reaches at least a kind that selects in particulate fluorocarbon resin.
16. the described drainage coating composition of claim 14 is characterized in that, coating composition contain drainage micropartical and titanium oxide microparticle the two.
17. the described drainage coating composition of claim 14 is characterized in that, the organic solvent of non-water system is by dimethylbenzene, toluene, normal alkane, reaches at least a kind of solvent selecting in the silicone.
18. the described drainage coating composition of claim 14 is characterized in that, water-disintegrable base is by halo silyl, alkoxysilyl, silylation, reaches at least a kind of base selecting in the isocynate silane base.
19. the described drainage coating composition of claim 14 is characterized in that, contains the water-disintegrable base of Si and the material of fluoro-alkyl, is the material that is expressed from the next,
CF
3-(CF
2) n-(R) m-SiX
pCl
3-p(wherein, n is the integer below 0 or 9, and R is that the substituting group that contains alkylidene group, vinylidene, ethynylene, arylidene, silicon or Sauerstoffatom (is specially-CH
2CH
2-,-C
6H
4-(phenylene) ,-C
2H
4Si (CH
3)
2C
10H
20-), m is 0 or 1, X is H, alkyl, alkoxyl group, isocyanate group, contains the substituting group of fluoroalkyl or fluoroalkoxy that P is 0,1,2 or 3).
20. the described drainage coating composition of claim 14, it is characterized in that, the use level that contains the material of the water-disintegrable base of Si and fluoro-alkyl is 1-50% (weight), atomic use level is 1-30% (weight), and the use level of the organic solvent of non-water system is the scope of 20-98% (weight).
21. the described drainage coating composition of claim 14 is characterized in that the drainage coating composition contains at least a kind of polysiloxane compound selecting by in polysiloxane oil and the soluble poly siloxanes.
22. the manufacture method of drainage tunicle, it is characterized in that, to contain material that the water-disintegrable base that contains Si and fluoro-alkyl are arranged and by the surface of at least a kind that selects in drainage micropartical and the titanium oxide microparticle atomic solution coat at base material, in containing the atmosphere of moisture, make the hydrolysis of said hydrolyzed base and the polymerization materialization again, form the tunicle of concave-convex surface on the surface of base material.
23. the manufacture method of the described drainage tunicle of claim 22 is characterized in that, the drainage micropartical is by the silicon-dioxide of handling through draining, granular of polyorganosiloxane, reaches at least a kind that selects in particulate fluorocarbon resin.
24. the manufacture method of the described drainage tunicle of claim 22 is characterized in that, solution contain at least drainage micropartical and titanium oxide microparticle the two.
25. the manufacture method of the described drainage tunicle of claim 22 is characterized in that, solution is the solution that contains by at least a kind of polysiloxane compound selecting in polysiloxane oil and the soluble poly siloxanes.
26. the manufacture method of the described drainage tunicle of claim 22 is characterized in that, water-disintegrable base is by halo silyl, alkoxysilyl, silylation, reaches at least a kind of base selecting in the isocynate silane base.
27. the manufacture method of the described drainage tunicle of claim 22 is characterized in that base material is a metal, applies anti-corrosion processing on its surface.
28. the manufacture method of the described drainage tunicle of claim 27 is characterized in that, metal is by at least a kind of metal selecting in aluminium and the aluminium alloy.
29. the manufacture method of the described drainage tunicle of claim 27, it is characterized in that anti-corrosion processing is to be covered by phosphoric acid processing, chromate treating, oxide treatment, anodic oxidation treatment, silica-coating, glass to handle, reach at least a kind of processing selecting in the resin-coated processing.
30. the manufacture method of the described drainage tunicle of claim 27 is characterized in that, makes the metal asperitiesization.
31. the manufacture method of the described drainage tunicle of claim 30 is characterized in that the asperities of metal turns to the concavo-convex of 0.1-50 mu m range.
32. the manufacture method of the described drainage tunicle of claim 27 is characterized in that, metal is the heat exchanger fin of heat exchanger.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP117519/98 | 1998-04-27 | ||
| JP11751998A JPH11300270A (en) | 1998-04-27 | 1998-04-27 | Water-repellent coating film, manufacture thereof and water-repellent coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1239128A true CN1239128A (en) | 1999-12-22 |
Family
ID=14713787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99107680 Pending CN1239128A (en) | 1998-04-27 | 1999-04-27 | Water repelling tunicle, its mfg. process and water repelling paint compsn. |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH11300270A (en) |
| CN (1) | CN1239128A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098945B (en) * | 2004-08-27 | 2014-07-16 | 中央硝子株式会社 | Treatment for forming waterdrop slidable films and process for forming waterdrop slidable films |
| CN107922785A (en) * | 2015-08-07 | 2018-04-17 | 大金工业株式会社 | coating and laminate |
| CN109590190A (en) * | 2018-11-19 | 2019-04-09 | 中国水利水电科学研究院 | A method of prevent pipeline from condensing |
| CN111849225A (en) * | 2020-08-03 | 2020-10-30 | 中铝瑞闽股份有限公司 | Graphene/alkane composite coating for aluminum alloy plate strip and preparation method thereof |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001207123A (en) * | 1999-11-16 | 2001-07-31 | Sentan Kagaku Gijutsu Incubation Center:Kk | Film having high hardness and high droplet slidability and method for producing the same |
| JP2001303296A (en) * | 2000-04-25 | 2001-10-31 | Chukin:Kk | Metallic material having photocatalytic function and producing method thereof |
| EP1323805A1 (en) * | 2000-09-14 | 2003-07-02 | Sekisui Jushi Kabushiki Kaisha | Snow sliding icy coating |
| JP4812945B2 (en) * | 2001-01-19 | 2011-11-09 | 日本曹達株式会社 | Water repellent layer carrying structure and manufacturing method thereof |
| TW569195B (en) | 2001-01-24 | 2004-01-01 | Matsushita Electric Ind Co Ltd | Micro-particle arranged body, its manufacturing method, and device using the same |
| EP1398362A1 (en) | 2001-03-30 | 2004-03-17 | Central Glass Company, Limited | Hydrophobic article |
| JP3867548B2 (en) * | 2001-10-26 | 2007-01-10 | 日本曹達株式会社 | Water-repellent film and method for producing the same |
| JP4014853B2 (en) * | 2001-11-08 | 2007-11-28 | 松下電器産業株式会社 | Article having antifouling coating and method for producing the same |
| JP3533606B2 (en) * | 2002-02-15 | 2004-05-31 | 世明 白鳥 | Manufacturing method of super water repellent film |
| JP4635217B2 (en) * | 2003-09-17 | 2011-02-23 | 学校法人慶應義塾 | Surface treatment agent and material, and surface treatment method |
| JP2008038630A (en) * | 2006-08-01 | 2008-02-21 | Aisan Ind Co Ltd | Flow passage arranging member of internal combustion engine |
| JP2008246968A (en) * | 2007-03-30 | 2008-10-16 | Kagawa Univ | Water-repellent and oil-repellent anti-staining reflecting plate, its manufacturing method and tunnel, road sign, display plate, signboard, vehicle and building using water-repellent and oil-repellent anti-staining reflecting plate |
| JP4973335B2 (en) * | 2007-06-27 | 2012-07-11 | パナソニック株式会社 | Dust collector filter and dust collector |
| JP4969341B2 (en) * | 2007-07-03 | 2012-07-04 | 古河スカイ株式会社 | Metal coating material and manufacturing method thereof |
| JP2010251745A (en) * | 2009-04-10 | 2010-11-04 | Asml Netherlands Bv | Immersion lithography device and device manufacturing method |
| JP6298513B2 (en) * | 2015-10-19 | 2018-03-20 | イビデン株式会社 | Toilet booth decorative board and toilet booth |
| JP6200477B2 (en) * | 2015-11-09 | 2017-09-20 | イビデン株式会社 | Antiviral decorative board, method for restoring function of antiviral decorative board, and antiviral imparting composition |
| EP4245427A4 (en) * | 2020-11-11 | 2024-01-10 | Mitsubishi Electric Corporation | Water-repellent structure, method for producing water-repellent structure, and method for recovering water repellency |
| CN117355718A (en) * | 2021-05-21 | 2024-01-05 | 大金工业株式会社 | Heat exchanger |
| WO2023182400A1 (en) * | 2022-03-25 | 2023-09-28 | 日東電工株式会社 | Heat exchanger |
-
1998
- 1998-04-27 JP JP11751998A patent/JPH11300270A/en active Pending
-
1999
- 1999-04-27 CN CN 99107680 patent/CN1239128A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098945B (en) * | 2004-08-27 | 2014-07-16 | 中央硝子株式会社 | Treatment for forming waterdrop slidable films and process for forming waterdrop slidable films |
| CN107922785A (en) * | 2015-08-07 | 2018-04-17 | 大金工业株式会社 | coating and laminate |
| CN107922785B (en) * | 2015-08-07 | 2020-05-12 | 大金工业株式会社 | Coating material and laminate |
| CN109590190A (en) * | 2018-11-19 | 2019-04-09 | 中国水利水电科学研究院 | A method of prevent pipeline from condensing |
| CN111849225A (en) * | 2020-08-03 | 2020-10-30 | 中铝瑞闽股份有限公司 | Graphene/alkane composite coating for aluminum alloy plate strip and preparation method thereof |
| CN111849225B (en) * | 2020-08-03 | 2021-11-05 | 中铝瑞闽股份有限公司 | Graphene/alkane composite coating for aluminum alloy plate strip and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11300270A (en) | 1999-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1239128A (en) | Water repelling tunicle, its mfg. process and water repelling paint compsn. | |
| CN1086726C (en) | Water-repeellent covered film and mfg. method and device and water-repellent paint composition | |
| JP5591363B2 (en) | Method for producing coating composition, heat exchanger and air conditioner | |
| CN110248800B (en) | Water-repellent coating film and product having the same | |
| US6068911A (en) | Super water-repellent coating material, and super water-repellent coating film using the same | |
| CN1203152C (en) | Hydrophobic material | |
| KR940007204B1 (en) | Heat exchanger | |
| CN1386805A (en) | Metal surface treating agent | |
| CN100345921C (en) | Coating material and mirror coated therewith | |
| CN1771351A (en) | Composition for coating metals to protect against corrosion | |
| JP2023506022A (en) | Selectively applied gradient film-forming composition | |
| US20070114011A1 (en) | Heat exchanger | |
| JPH08323285A (en) | Member with excellent water repellency and anti-frosting property and its preparation | |
| JPH10132483A (en) | Heat exchanger fins having function to prevent adhesion of water droplet and heat exchanger provided with fins | |
| CN1458971A (en) | Snow sliding icy coating | |
| CN1251059A (en) | Hydrophobic film | |
| JP2001201289A (en) | Aluminum fin material for heat exchanger | |
| CN1103904C (en) | Outdoor heat exchanger unit and air-conditioner using the unit | |
| JP3247313B2 (en) | Water-repellent coating, method for producing the same, device therefor, and water-repellent coating composition | |
| JP2000256579A (en) | Hydrophilic coating material composition and hydrophilic coating film formed from the same composition | |
| JPH10130540A (en) | Powdered paint and coated layer and coating method | |
| JP5436481B2 (en) | Heat exchanger and manufacturing method thereof | |
| JP2584109B2 (en) | Paint for water-repellent coating and heat exchanger coated with the paint | |
| JPH1143777A (en) | Aluminum or aluminum alloy material excellent in water repellency and frosting preventability and its production | |
| JP3963230B2 (en) | Pre-coated metal plate and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |