WO2001036190A1 - Structure et film dont la surface presente une durete elevee et favorise le glissement de l'eau, et procede de preparation associe - Google Patents

Structure et film dont la surface presente une durete elevee et favorise le glissement de l'eau, et procede de preparation associe Download PDF

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WO2001036190A1
WO2001036190A1 PCT/JP2000/007841 JP0007841W WO0136190A1 WO 2001036190 A1 WO2001036190 A1 WO 2001036190A1 JP 0007841 W JP0007841 W JP 0007841W WO 0136190 A1 WO0136190 A1 WO 0136190A1
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water
surface roughness
hardness
high hardness
film
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PCT/JP2000/007841
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English (en)
Japanese (ja)
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Akira Nakajima
Toshiya Watanabe
Kazuhito Hashimoto
Akira Fujishima
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Center For Advanced Science And Technology Incubation, Ltd.
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Publication of WO2001036190A1 publication Critical patent/WO2001036190A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

Definitions

  • the present invention relates to a surface structure, a film, a method for producing the same, and a coating agent used for the same, which are easy to control the structure and have both excellent lubricity and hardness.
  • ⁇ y ⁇ ⁇ is the surface (interface) free energy between solid-gas, solid-liquid, and liquid-gas, and 0 is the contact angle.
  • many water-slidable surfaces are obtained by treating the surface with silicon fluoride.
  • a water-slidable surface obtained from a smooth surface by such a conventional technique has a contact angle with water of about 100 to 110 °, and the falling angle of a droplet is 50 to 200 mg. ⁇ 60 °. And this treatment has already been put to practical use for clothing, car glass, painted surfaces, etc.
  • a surface having a very high water repellency (super water repellency) having a contact angle of 150 ° or more can be obtained.
  • ⁇ and 6 ' are the contact angles of the smooth and rough surfaces, respectively, and r is the roughness factor, which is the actual surface area increased by the surface roughness divided by the apparent surface area.
  • Cassie ABS Cassie, Discuss. Farady Soc., 3, 11 (1948)] assumes that the interface with a liquid is a composite phase of solid and gas, and the contribution from each phase depends on the area fraction. In consideration of the fact that the contact angle between gas and water can be approximated to 180 °, the water repellency due to air entering the solid-liquid interface was described by the following equation.
  • the water repellency When the surface roughness is added to the smooth water repellent surface, the water repellency first increases in the Wenzel mode, and when the roughness exceeds a certain level, the air enters the solid-liquid interface and the Cassie module starts to operate. This was demonstrated by experiments on a water-repellent coating material mixed with wax.
  • the super-water-repellent surface can significantly reduce the contact area between the surface and water, thus suppressing the progress of chemical reactions, formation of local batteries, short-circuits of electric circuits, or the formation of hydrogen bonds through water. be able to. For this reason, it prevents snow and raindrops, prevents water, and has electrical insulation.
  • reducing the resistance to water compared to a water-repellent surface with a contact angle of about 100 to 110 ° obtained from a conventional smooth surface, Higher effects can be expected.
  • the applicable range is the exterior of vehicles such as automobiles and Shinkansen, bottom paint, exterior lights, kitchen and kitchen utensils, bathrooms and washrooms and their supplies, fishing nets, buoys, dental supplies, electrical equipment, and residential floors.
  • Super-water-repellent materials that combine super-water-repellency, high water-sliding properties, and hardness have traditionally been extremely difficult to design, and have not been manufactured so far. For this reason, the practical use of super water-repellent materials has been delayed, despite the fact that many applications are expected.
  • An object of the present invention is to provide a super-water-repellent surface structure and a film that are easy to control the structure and have both excellent hardness and water-slidability, a method for producing the same, and a coating agent used in the production method. It is in.
  • the following high hardness and high water sliding surface structure is provided.
  • a high-hardness and high-sliding surface structure in which at least a part of the surface of the basic structure having the first surface roughness is provided with a second surface roughness smaller than the first surface roughness.
  • a roughness smaller than that of the basic structure is introduced into the basic structure such as a porous, needle-like, column-like, or groove-like shape by coating, cutting, grinding, etching, or the like.
  • grooves or columns may be formed by cutting or the like, and at the same time, appropriate roughness may be introduced to the cut side surface.
  • the surface of the base material is formed by a first uneven surface formed with a first surface roughness and a first unevenness formed by the first surface roughness.
  • the underlayer is formed on a surface having a double surface roughness with at least a part of the second uneven surface formed on the first uneven surface with a small second surface roughness. It is characterized in that a high hardness and high water-sliding film is produced by performing a water-repellent treatment on at least a part of the film.
  • a metal alkoxide and / or a sol having a primary particle diameter of 100 nm or less are separated from these in a solvent
  • a substance or a substance that has the property of decomposing, burning, and sublimating at temperatures from room temperature to 700 ° C is prepared as a solution or emulsion added to a solvent and used at room temperature (room temperature).
  • room temperature room temperature
  • a method of keeping the temperature from room temperature to 700 ° C. for a certain period of time to remove the above substances can be mentioned.
  • a photocatalyst can be contained in the porous underlayer.
  • the present invention provides the following.
  • a high-hardness and high-slidability film having both practical hardness and high-slidability having both practical hardness and high-slidability.
  • the contact angle is 140 ° or more
  • the falling angle of a 7 mg droplet is 30 ° or less
  • the hardness is H or more in pencil hardness.
  • the falling angle is preferably 20 ° or less, and more preferably 15 ° or less.
  • the pencil hardness is preferably 2 H or more, more preferably 3 H or more. It is to be noted that both of the falling angle and the hardness can be achieved by applying the present invention.
  • At least a portion of the surface of the basic structure having the first surface roughness is provided with a second surface roughness smaller than the first surface roughness.
  • a second surface roughness smaller than the first surface roughness is provided to at least a part of the surface of the basic structure having the first surface roughness, and at least, A high hardness and high water-slidable surface structure, wherein a water-repellent layer is formed on at least a part of the surface of the structure.
  • a method for producing a high hardness and high water-sliding surface structure characterized in that at least a part of the surface of the basic structure is provided with roughness by grinding, etching or coating.
  • the first uneven surface formed with the first surface roughness and the first surface roughness is smaller than that of the second uneven surface formed on at least part of the first uneven surface on the first uneven surface. Characterized by high hardness and high water-sliding membrane.
  • the lower limit of the second surface roughness is not particularly limited, the surface is further improved by superposing the water repellency by interposing air in the concave portion due to the surface roughness, and the second phase is formed by utilizing the phase separation and the inclusion of fine particles. From the viewpoint of practically forming the surface roughness of No. 2, the lower limit of the second surface roughness is about 1 nm, and more preferably about 3 nm.
  • the first uneven surface is formed by using phase separation
  • the second uneven surface is formed by using phase separation or contained particles.
  • the first uneven surface is formed using particles having a larger particle diameter or agglomerated particles
  • the second uneven surface is formed using particles having a smaller particle diameter or primary particles.
  • the photocatalyst is characterized in that it is dispersed in the valleys of the surface roughness. (3) Or (4) a high-hardness, high-sliding surface structure.
  • the photocatalyst By disposing the photocatalyst at such a position, the direct decomposition of the water-repellent film due to the generated radicals is reduced, and the self-cleaning effect due to the addition of the photocatalyst can be more effectively emphasized.
  • a phase separation is formed between the raw material liquid of the membrane base material, a predetermined solvent, a substance to be removed after the raw material liquid of the membrane base material is solidified, and a sol having a primary particle diameter of 100 nm or less.
  • An undiluted solution of a coating agent for forming a high hardness and high water-sliding film comprising:
  • the “raw material liquid for the membrane base material” is capable of forming a phase separation with other components, and is also required to give practical hardness to the finally obtained water-slidable film. Any material can be used as long as it is possible.
  • An example is a metal alkoxide which is a raw material for the sol-gel method.
  • the “substance that is removed after the raw material liquid of the membrane base material is solidified” includes a substance having a property of being removed at a temperature from room temperature to 700 ° C. (particularly, from room temperature to 70 ° C.). A substance having the property of decomposing, burning, and sublimating at a temperature of up to 100 ° C).
  • a coating agent for forming a high-hardness and high-slippery film comprising a solution in which a solvent is added to a solvent or an emulsion.
  • the property removed at room temperature to 700 ° C.” means, for example, the property that decomposes, burns, and sublimes at such a temperature, and a group of substances having such properties (for example, a substance that can form a phase separation with other components is appropriately selected from among a group of thermosublimable substances).
  • thermosublimable substances include, for example, organic polymers (which generally decompose and burn when heated), are insoluble in metal alkoxides, and are soluble in certain solvents such as ethanol and ethyl acetate. Things can be mentioned.
  • a coating material for forming a high-hardness and highly water-slidable film comprising a solution or an emulsion obtained by adding a substance having a particle diameter of less than 100 nm to a solvent.
  • a coating agent for forming a high hardness and high water-sliding film comprising particles or aggregated particles having a particle diameter of 100 nm or more and particles or primary particles having a particle diameter of less than 100 nm.
  • the coating agent according to (22) above is applied to a substrate, and the first surface roughness is formed by particles having a particle diameter of 100 nm or more or aggregated particles.
  • An underlayer having a surface having a double surface roughness with the second uneven surface formed on the uneven surface is formed, and a water repellent is applied to at least a part of the underlayer.
  • the first uneven surface has a surface roughness of 100 ⁇ ⁇ to 2 ⁇ , and the second uneven surface has a surface roughness of less than 100 nm.
  • the final state is obtained by adjusting the state of the phase separation and adjusting the heat treatment step.
  • Water slide The method for adjusting the slipperiness strength and / or the hardness of the water-soluble membrane.
  • FIG. 1 is a diagram showing a phase diagram of a three-component system including three components of a solvent, a metal alkoxide, and a polymer according to Example 1.
  • FIG. 2 is a diagram showing a scheme for forming a phase separation according to Example 1.
  • FIG. 3 is a diagram illustrating an assumed phase separation state according to the first embodiment.
  • FIG. 4 is a diagram showing an SEM photograph of the surface of the microporous material obtained in Example 1.
  • Fig. 5 is an assumed view of the cross section of the micropore shown in Fig. 4.
  • FIG. 6 is a schematic cross-sectional view schematically showing a substrate having only the first uneven surface.
  • FIG. 7 is a schematic cross-sectional view schematically showing a substrate in which a second uneven surface is formed on a first uneven surface.
  • FIG. 8 is a diagram showing a SEM photograph of the film surface obtained in Example 2.
  • FIG. 9 is a diagram showing the relationship between the surface roughness and the contact angle in the third embodiment.
  • FIG. 10 is a diagram showing the contact angles of water droplets on the surface obtained according to Example 4.
  • the difference between the advancing contact angle (contact angle on the advancing side of the droplet) and the receding contact angle (contact angle on the retreating side of the droplet) when the droplet falls on the inclined surface In order to achieve this, it is effective to impart a certain degree of roughness to the film and make the surface water-repellent to increase the contribution of air penetration (Johnson Jr.). , RE & Dettre, RH Contact Angle Hysteresis, I. Study of an Ideal Rough Surface, Adv. Chem. Ser., 43, 112-135, (1963)). Specifically, it is most desirable to make the surface structure acicular in order to obtain good lubricity.
  • the high hardness and high water sliding surface structure according to the present invention includes at least a part of the surface of the basic structure having the first surface roughness, and the first surface of the surface of the basic structure.
  • a surface morphology combining two or more roughnesses having different sizes is formed, and at least the surface of the basic structural body is formed. At least a part thereof is formed with a water-repellent layer.
  • the material itself has a low surface energy, such as an organic material
  • a high hardness and high water-repellent surface can be formed without forming a surface water-repellent layer, as long as the above structure can be simply formed. It becomes a structure.
  • the basic structure of the water-repellent film to which the present invention can be applied is porous, needle-like, column-like, groove-like, and the like.
  • Such a basic structure includes coating, grinding, cutting, etching, and the like. Introduce smaller roughness. Even on a smooth surface that does not have a basic structure in advance, it is possible to form grooves and columns by cutting and at the same time introduce appropriate roughness to the cut surface. The effect of introducing small roughness depends on the shape of the basic structure and the location where it is introduced into the basic structure, but the transition from the peak to the valley rather than the top of the peak or the bottom of the valley, That is, when introduced into the side surface or the slope portion, the air easily gets into the valley portion and the water repellency is easily increased.
  • a first concave-convex surface which is slightly water-repellent by itself but easily obtains hardness, is formed on the surface of the substrate by a porous layer forming method, and the first concave-convex surface is formed.
  • Form a surface with double surface roughness with a finer second uneven surface formed on top To achieve.
  • a method for achieving the second surface roughness for forming the second uneven surface a method for forming by containing fine particles such as colloidal silicide force, and a method finer than the phase separation described above.
  • a photocatalyst can be dispersed in such a film. Preferably, it is about 0.5 to 10%, and more preferably, it is dispersed in the valleys of the surface irregularities.
  • water repellent it is possible to use a fluorine-silicon based water repellent or a combination thereof, but those containing fluorine are preferred because they have a large effect of lowering the surface energy. Fluoroalkylsilanes are particularly preferred.
  • surface treatment agents such as monofluoroenoalkynolecarboxylic acid type, perfluoroalkylenosolenoic acid type, perfluoroalkylphosphoric acid type, etc., perfluoroalkyl group-containing oligomers
  • PTFE polytetrafluoroethylene
  • fluoride graphite fluoride graphite
  • pitch fluoride etc.
  • the wet method is most excellent in efficiency and cost as in the case of the microporous underlayer, but depending on the raw material, it may be performed by the vapor deposition method or the sputtering method.
  • the photocatalyst material that can be added is mainly titanium oxide, and one of titanium oxide, zinc oxide, strontium titanate, tungsten oxide, iron oxide, and copper oxide. They can be used in combination of types or multiple types. Examples of these precursors include various inorganic and organic compounds generated by heating these photocatalysts.
  • titanium alkoxides such as titanium hydroxide and titanium tetrapropoxide
  • Titanium chloride Titanium sulfide, Titanium bromide, Titanium iodide
  • Biscyclopentagenenyltitanium Dicanolepoxide biscyclopentagenenyltitanium
  • Chlorobi examples thereof include cyclopentageninoletitanium, dichlorobiscyclopentageninoletitanium, dimethinole biscyclopentene, pentageninoletitanium, and tricyclone mouth, pentageninoletitanium, and tetrabenzil titanium.
  • the structure of the film may be a combination of a plurality of substances as long as the size and solubility conditions are satisfied.
  • a titanium oxide photocatalyst has a property of decomposing an organic water repellent. Therefore, when a titanium oxide photocatalyst is put into a film, its concentration is adjusted to about 2 wt%, or an oxide or hydroxide of silicon, aluminum, zirconium, or a mixture thereof.
  • the base material is composed of a titanium oxide photocatalyst in an amount in the range of 0.5 to 10 wt% of the base material.
  • the film of the present invention having both practical hardness and excellent slipperiness can be used for the exterior of vehicles such as automobiles and Shinkansen, ship bottom paints, exterior lights, kitchen and kitchen appliances, bathrooms and washrooms and their accessories, fishing nets, buoys , Dental supplies, electrical equipment, floors and exteriors of houses, entrance doors and knobs, rooftops, pools and poolsides, piers, gates, post, benches, steel towers, antennas, wires, garages, tents, umbrellas, raincoats, Lubrication of sports products and sports clothing, leather products such as helmets, shoes, etc., outdoor loudspeakers and audio equipment such as cameras, videos, paper, speakers, etc., lubrication of carpets, carpets, gasoline stands, etc.
  • a wide range of applications can be considered, such as chemical plants such as nozzles and refineries, metal tools, nails and screws, and buckets.
  • phase separation was formed according to the scheme.
  • the resulting phase separation is heterogeneous, as shown in Figure 3 with alcohol (solvent). It is probable that polymer particles were dispersed in the alkoxides dissolved in each other. It is also probable that silica fine particles (for example, colloidal silica) that had formed silica sol were dispersed.
  • finer irregularities are formed on the surface irregularities. Can be raised.
  • Such fine irregularities can also be formed by a method using phase separation, and include a phase-separation-forming substance having a finer dispersion diameter than the dispersed polymer for forming crater-like irregularities described above. It can also be formed by removing it by heat treatment.
  • the surface of the base material 20 is further finer.
  • the liquid droplets 23 can exhibit more excellent water repellency.
  • Ethanol 20 g, tetraethylorthosilicate (TEOS) 2 g and hydrochloric acid 1.2 g were mixed for 36 hours and hydrolyzed.
  • the acrylic polymer was dissolved in ethanol and the solid content was adjusted to 5.4%.
  • 4 g of this acrylic polymer-Z ethanol solution was added to the TEOS solution, and 4 g of ethanol was further added.
  • silica sol (colloidal silica) was added to the solution.
  • a coating solution was prepared by adding 2 g. This coating solution contains an acrylic polymer in a hydrolyzed TEOS ethanol solution. A dispersed phase separation was formed.
  • the phase-separated coating solution was spin-coated on Pyrex glass at 150 rotations, and the coat-dry cycle was repeated 5 times, followed by firing at 500 ° C. for 30 minutes.
  • the thus obtained film was subjected to a water-repellent treatment by coating a fluoroalkylsilane hydrolyzed with an equivalent amount of water by a thermal CVD method to produce a water-slidable film.
  • the resulting water-sliding membrane has a crater-like microporous structure with an average pore diameter of 1 ⁇ , on which finer irregularities of colloidal silica are further formed.
  • the contact angle was 152 °
  • the falling angle of a 7-mg droplet was 6.5 °
  • the film was a highly hard water-slidable film having a pencil hardness of H.
  • a sol obtained by dispersing 0.24 wt% of nitric acid-containing basemite in an ethanol solution of acetylacetylaluminum (2.37 wt%) was applied to Pyrex glass with a spin coat, and then applied.
  • the cycle of baking for 20 seconds on a hot plate at 00 ° C was repeated five times to produce a transparent film.
  • This transparent film was immersed in a 2% methanol solution of fluoroalkylsilane hydrolyzed with an equivalent amount of water for 40 minutes, and then dried at 140 ° C for 20 minutes to perform a water-repellent treatment. Thus, a water-slidable film was obtained.
  • the resulting water-slidable membrane had a microporous structure with an average pore diameter of 200 nm, and its contact angle was 155 ° C, but the falling angle of a 7 mg droplet was 3
  • the hardness was about 0 °, and the hardness was 3 B in pencil hardness.
  • a coating agent having the same composition as the coating agent according to the above-mentioned Example 1 was prepared alone except that the acrylic polymer was not added, and film formation and water repellency were performed in the same manner as in the above-mentioned Example. Processing was performed.
  • the obtained film was dense and transparent, the hardness was as high as 3 H in pencil hardness, and the contact angle was 133, but even if the film was tilted at 90 °, 7 mg droplets did not fall down. Water slip did not appear.
  • Ethanol 10 g, concentrated HC1: ⁇ . 6 g, tetraethyl orthosilicate: 1.0 g were mixed for 19 hours, and showed an affinity for methyl ethyl ketone (MEK).
  • Commercial silica sol (particle size: 15 nm) was added and spin coating was performed at 1500 rpm. This was subjected to a water repellent treatment in the same manner as in Example 1 by thermal CVD. The contact angle of water was 152 °, the falling angle of a 7 mg droplet was 30 °, and the pencil hardness was 3H, which was higher than 3H.
  • a water-repellent film was obtained. This film had a double roughness structure in which a silica sol with a primary particle size of 15 nm formed a secondary structure with a size of 600 nm.
  • Figure 8 shows the SEM photograph.
  • Example 2 an alcohol-based silicasol (particle size: 15 nm) having excellent dispersibility in ethanol was used. As a result, the contact angle was only 13 °, and the 7 mg droplet did not fall down even when tilted at 90 °.
  • the obtained roughness factor of the surface was calculated by geometrically calculating the area of the side surface of the groove, assuming that the side surface of the groove was as smooth as the silicon wafer.
  • Figure 9 shows the change in the contact angle actually obtained with respect to the calculated roughness factor.
  • the contact angle of the silicon wafer after the water-repellent treatment without grooves was 117 °.
  • the solid line in the figure shows the calculated contact angle change in Wenzel's mode when roughness is introduced by cutting a groove in this water-repellent surface.
  • the actual groove width will differ by about 5 microns.However, if a sufficiently deep groove is formed, wetting of the side surfaces of the groove will occur.
  • the neglected solid-liquid contact area fractions are 0.21, 0.26, 0.32, and 0.44, respectively, and the calculated contact angle values in Cassie mode are 153 °, 149 °, 146 °, and 139 °, respectively.
  • Fig. 1 there is a portion where the groove cut is shallow, that is, there is a portion where the contact angle is higher than the calculated value in Wenzel mode in the region with low roughness (low roughness factor). Is close to the angle expected from Cassie mode. Further observations of water droplets on this surface from the lateral direction show that they have already entrained air at the solid-liquid interface and that Cassie mode contributed. It was confirmed that.
  • the grooves introduced by the dicing machine are provided with roughness on the side surfaces to increase the water repellency, thereby making it easier for air to enter the grooves.
  • This roughness is derived from a few micron diamonds and is smaller than the size of the cut grooves. That is, by introducing fine roughness on the side surface of the groove, it becomes possible to inject air into the shallow groove, and the Ca ssie mode is activated, thereby obtaining a water-repellent state. .
  • Fig. 10 shows the obtained water droplets on the structure.
  • the roughness factor is about 1.4.
  • the contact angle is about 135 °, but in the actual measurement, the contact angle deviates to the left from that line, and is a much higher value (153 °). The air was engulfed.
  • a highly rigid and highly water-slidable film having a controlled structure can be easily produced. It can be suitably used for various industrial products and contributes to a wide range of applications.
  • a surface structure having excellent water repellency can be easily produced. This can be suitably used for various industrial products, and is important in applying the super water repellent technology to a wider range of applications.
  • the water-repellent surface structure of the present invention further provides a desired surface area. Since the present invention can easily impart excellent water repellency, the present invention can be suitably used in various fields in which high water repellency and high water repellency are desired.
  • Available fields include exteriors of vehicles such as automobiles and Shinkansen, bottom paint, exterior lights, kitchen and kitchenware, bathrooms and washrooms and supplies, fishing nets, buoys, dental supplies, electrical equipment, residential floors and exteriors, Entrance doors and knobs, roofs, pools and poolsides, piers, gates, bosses, benches, pylons, antennas, wires, garages, tents, umbrellas, raincoats, sports equipment and sporting clothing, helmets, shoes
  • Leather products such as shinto, camera, video, paper, paper It covers a wide area such as outdoor loudspeakers such as cars, sound equipment, curtains, carpets, oil nozzles such as gasoline stands, chemical plants such as refineries, metal tools, nails and screws, and buckets.

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  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

L'invention concerne une structure et un film dont la surface présente une dureté élevée et favorise le glissement de l'eau. Cette invention se caractérise en ce qu'une partie au moins de la surface d'une structure de base présentant une première rugosité possède également une seconde rugosité inférieure à ladite première rugosité. La structure ou le film comporte une surface sensiblement glissante pour les gouttes d'eau, cette surface présentant en même temps une dureté élevée.
PCT/JP2000/007841 1999-11-16 2000-11-08 Structure et film dont la surface presente une durete elevee et favorise le glissement de l'eau, et procede de preparation associe WO2001036190A1 (fr)

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JP11/326093 1999-11-16
JP32609399 1999-11-16
JP2000/268026 2000-09-05
JP2000268026A JP2001207123A (ja) 1999-11-16 2000-09-05 高硬度高滑水性膜およびその製造方法

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JP3533606B2 (ja) * 2002-02-15 2004-05-31 世明 白鳥 超撥水性膜の製造方法
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