JP2017094661A - Synovial membrane, method for producing the same, and article having surface coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synovial membrane which can be easily formed on a flat surface.SOLUTION: A synovial membrane has: a layer having a functional group having a pi electron, as a base film; and a layer having a pi interaction part that bonds to the pi electron functional group of the base film by pi interaction and a synovial action part that has low affinity with a fluid to be a synovial object in a molecule, as a synovial agent layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a synovial fluid film, in particular, a synovial fluid film retaining a synovial agent by π-electron interaction, a method for producing the same, and an article having a surface coated thereby.

  In many fields, such as solar cells, automobiles, medical equipment, fuel transportation, construction, and food containers, development of antifouling surfaces is desired. For example, although non-wetting surfaces based on the Lotus-leaf effect have been studied for decades, they are stable against low surface tension liquids, drop impacts, extreme temperatures or pressures It was very difficult to get something. In recent years, slippery liquid-infused porous surfaces (SLIPS) have been reported as a new type of antifouling surface, which is a low-energy microporous surface impregnated with a liquid lubricant (see Non-Patent Document 1). SLIPS is non-wetting to almost all fluids and is stable to high temperatures and pressures because the lubricant is in the pores. For this reason, SLIPS is a very attractive material.

  Although many SLIPS manufacturing methods have been reported, it has not been sufficiently versatile due to the following points. Won et al. Use a poly (tetrafluoroethylene) mesh (hereinafter referred to as PTFE mesh) and an epoxy resin array as a rough surface for applying a lubricant (see Non-Patent Document 1). PTFE mesh has very poor moldability, so it cannot be applied to surfaces with complex structures and is not transparent in the visible light region. In addition, although the epoxy resin array surface can have a complicated structure, the two-stage soft-lithography process takes a long time. These manufacturing processes are not suitable for mass production and are not versatile.

  In addition to these, complicated and time consuming and expensive processes include photolithography, deep reactive ion etching, chemical vapor deposition, and the like. On the other hand, a SLIPS manufacturing process using alumina sol-gel has been reported by Ma et al. As a simple method with a lower cost for forming a rough surface (see Non-Patent Document 2). This is a simple wet process, and a layer having high light transmittance in the visible light region can be obtained. However, it is necessary to perform annealing at a high temperature of about 400 ° C. and decrease the surface energy, which limits the selectivity of the substrate and requires additional processes and materials, which increases costs. In addition, there are similar problems in production methods such as boehmite treatment of aluminum, alkaline etching of copper, and electrolytic polymerization of polypyrrole.

  Also, among the substrates used as porous rough surfaces in conventional SLIPS, epoxy resin arrays by photolithography and porous silicon by etching, etc., have needle-like fine irregularities or discontinuous fine through-holes (lotus root) on the surface. Mold through hole). The alumina thin film formed by the sol-gel method also has only fine irregularities on the surface. For this reason, liquid lubricants impregnated on these porous rough surfaces as SLIPS exude or leak relatively easily and must be replenished frequently for actual use. .

  The porous PTFE sheet formed by the stretching method has a more complex pore structure, but it is in the form of a saddle that is stretched in a uniaxial direction or a spider web that is stretched in a biaxial direction. The liquid lubricant cannot be held in the pores for a long period of time, and it cannot be said that it is particularly satisfactory in terms of durability against vibration and pressure.

  In addition, for example, it is considered to be very useful to develop a transparent film that can be applied to a product that requires transparency, such as a window glass or an automobile windshield, to impart an antifouling effect. However, SLIPS using photolithography, etching, sol-gel method or the like directly treats the surface of an article and does not form an independent film. On the other hand, the porous PTFE sheet obtained by the stretching method can be an independent film, but is inferior in transparency because it is relatively thick. For this reason, none of the conventional SLIPS has sufficient strength while having high transparency.

Wong, T.-S .; Kang, S. H .; Tang, S. K. Y .; Smythe, E. J .; Hatton, B.D .; Grinthal, A .; Aizenberg, J. Nature 2011, 477, 443-447. Ma, W .; Higaki, Y .; Otsuka, H .; Takahara, A. Chem. Commun. 2013, 49, 597-599.

  The present invention has been made in view of the above-described prior art, and a problem to be solved is to provide a synovial membrane that can be easily formed on a flat surface and has high maintainability and repairability.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, functional groups such as phenyl groups having a high concentration of π-electrons are modified on the flat surface of the article, and the lubricant is formed by the π-interaction. The inventors have found that a synovial membrane excellent in synovial fluid properties and repairability can be formed by holding on a flat surface, and the present invention has been completed.
That is, the synovial membrane according to the present invention is
A layer having a functional group having π electrons as a base film;
As a synovial fluid layer, a layer having in the molecule a π interaction part that binds by π interaction with the π electron functional group of the base film and a synovial fluid action part having a low affinity with the fluid to be synovial fluid,
It is characterized by including.
In the present invention, the base film is preferably formed on a flat surface of an article.
In the present invention, the base film preferably has a high concentration π electron-containing functional group selected from an aromatic group and / or an alkyne group.
In the present invention, the π-interaction part of the lubricant is an ethoxy group, a methoxy group, a phenyl group, a hydroxy group, a carbonyl group, an aldehyde group, or an —XH group (X is an arbitrary atom) that interacts with π electrons. Is preferably selected from:
In the present invention, the fluid to be synovial fluid is a hydrophilic medium, and the synovial fluid action part of the synovial fluid is an alkyl group, an alkyl-modified siloxane group, an alkylphenyl-modified siloxane group, or a fluorinated alkyl group. Is preferred.
In the base film forming method according to the present invention, a base film constituent material having a π-electron-containing functional group is bonded to the surface of the article or intermolecularly interacted to form a base film.
On the base film, a synovial agent having a π interaction part bonded to the π electron functional group of the base film by π interaction and a synovial liquid action part having a low affinity with the fluid to be synovial fluid in the molecule is provided on the base film. It is characterized by being applied to.
The article according to the present invention is characterized by having a surface coated with the synovial fluid film.
Moreover, the medical device concerning this invention has the surface coat | covered with the said synovial fluid film, It is characterized by the above-mentioned.

Moreover, the container concerning this invention has the surface coat | covered with the said synovial fluid film, It is characterized by the above-mentioned.
The optical device according to the present invention is characterized in that it has a surface coated with the synovial fluid film.
The antifouling glass according to the present invention has a surface covered with the synovial fluid film.
Moreover, the solar cell concerning this invention has the surface coat | covered with the said synovial fluid film, It is characterized by the above-mentioned.
The synovial fluid film according to the present invention is also applicable to power transmission lines, building materials (roofs, windows, walls), transportation equipment (automobiles, ships, aircraft), pipe materials (heat transfer condensers, heat absorption, heat dissipation equipment), and the like. .
In addition, the synovial fluid film (hereinafter sometimes referred to as SPLASH) according to the present invention has the following characteristics as compared with conventional SLIPS.
(1) Whereas SLIPS requires a nano-micro order sponge structure underlayer for retaining the lubricant, SPLASH can hold the lubricant in a completely flat (Rrms = 0.237 nm) underlayer.
(2) Thereby, even when the lubricating liquid is reduced, exposure of the base uneven structure can be prevented and stable performance can be exhibited.
(3) Since the undercoat layer is flat, it can retain an extremely low viscosity lubricating liquid (the sponge structure soaks in and cannot form a liquid film).
(4) Since there are no irregularities in the underlayer, the flow resistance of the lubricating liquid is not impaired.
(5) From (3) and (4), it showed smoother synovial properties than SLIPS, and it was able to tumbl down micro liquids such as mist (relative to SLIPS where micro liquids could not fall). The same is true for low-density ice. The same applies to the durability of high temperature liquids and boil tests, which have hardly been reported so far.
(6) The underlying layer is flat and there is no worry about the destruction of the structure. It has high durability.
(7) Since the underlayer is flat and the scattering loss of transmittance is small, it has higher transparency than before.
(8) Has flexibility. In the case of SLIPS, the underlying concavo-convex structure is exposed due to a change in the lubricating liquid due to bending or the like, and the synovial fluid target liquid cannot fall down. However, SPLASH is stable because the underlying layer is flat and there is no exposure of the concavo-convex structure due to the change in the height of the lubricating liquid.
(9) Simple, all-wet process, and a wide range of lubricant selection (SLIPS is mostly limited to fluorine-based lubricants, at most silicon oil or fluorine-based oil).
(10) Since the lubricating liquid is adsorbed by π electrons, oil does not disappear even when rubbed with cotton. Even when shear stress is applied, the oil film thickness is maintained (about 500 nm).

  According to the present invention, a base film is formed on the surface of an article, and the base film retains the lubricant by π interaction. In addition, its durability is very good. Further, according to the present invention, a synovial fluid film having high transparency and sufficient strength can be obtained.

It is explanatory drawing of the structure of the synovial fluid film concerning one Embodiment of this invention. It is explanatory drawing of the manufacture state of the synovial fluid film concerning one Embodiment of this invention. It is explanatory drawing of the base film concerning one Embodiment of this invention. It is explanatory drawing which showed each layer thickness of the synovial fluid film concerning one Embodiment of this invention. It is explanatory drawing of the comparative example which couple | bonded DTMS with the article | item surface directly. It is explanatory drawing which shows the result of the X-ray photoelectron spectroscopy measurement of one Embodiment of this invention, and a comparative example. It is explanatory drawing of the evaluation method of synovial fluid property. It is explanatory drawing of the synovial property of the base film of this invention, and a comparative example. It is explanatory drawing of the synovial property of the synovial membrane concerning this invention. It is explanatory drawing of synovial fluid transparency of this invention and a comparative example. It is explanatory drawing of the state which applied the synovial fluid film concerning one Embodiment of this invention to the steel can inner surface coated with PET resin, and boiled and retort-treated. It is explanatory drawing of the bending tolerance test of the synovial fluid film concerning this invention. It is explanatory drawing of the scratch tolerance test of the synovial fluid film concerning this invention. It is explanatory drawing of the wiping resistance test of the synovial fluid film concerning this invention.

[Synovial membrane]
FIG. 1 shows a schematic diagram of a synovial fluid film according to an embodiment of the present invention.
In the figure, the synovial fluid film 10 according to the present invention includes a base film 16 having a π-electron functional group (phenyl group) 14 modified on the surface of an article 12, and π-electron functional groups 14 and π of the base film 16. And a synovial fluid (decyltrimethoxysilane) 22 having in its molecule a π-interacting portion (methoxy group) 18 bonded by interaction and a synovial fluid acting portion (hydrocarbon group) 20 exhibiting hydrophobicity.
Then, due to the hydrophobicity and water slidability of the decyltrimethoxysilane 22 held by the π-electron functional group 14 of the base film due to the π interaction, the water droplet 24 on the film 10 slides down by slightly tilting the article surface 12. .
Moreover, when silicone oil KF54 was used for the synovial fluid layer, it was confirmed that any of mayonnaise, soy sauce, carbonara sauce, ketchup, coffee, honey, and curry sauce slipped without remaining on the surface. Furthermore, hot water, salt water, ice and blood can be slid down as well.

[Base film]
In the present invention, the base film 16 preferably has a fixing group (for example, a silane group) on the surface of the article together with a π-electron functional group having a high concentration of π-electrons. Aromatics such as groups and alkynes are preferred.
Specific examples of the base film constituent material include phenyltriethoxysilane, phenyltrimethoxysilane, phenylchlorosilane, and phenylmethylchlorosilane. In order to increase the π-electron concentration of a π-electron functional group such as a phenyl group, the insulating part (SiO ₂ ) can move the movement of π electrons to a phenyl group, such as a phenyl group-insulating part (for example, Ph-SiO ₂ ). It is considered that it is particularly preferable to fit within the group.
In addition, as the base film constituent materials, acetylene, graphene, polyphenylene materials, hydrophobic conjugated polymers such as carbon tubes, polystyrene, phenethyl alcohol, phenol, phenanthreneol, cresol tetrahydro-phenanthrenol, etc. Aromatic alcohols such as phenylacetaldehyde, methoxybenzaldehyde, cuminaldehyde, hexylcinnamaldehyde, aromatic aldehydes such as phenanthrenecarboxaldehyde, phthalic acid and benzoic acid, aromatic isocyanates such as takenate, thio Aromatic thiols such as phenol, alcohols containing graphene 60, 61, 70, aldehydes containing graphene 60, 61, 70, carboxylic acids containing graphene 60, 61, 70, raw Examples of body-derived substances include β-carotene monolayer, hemoglobin, phenyl chlorides, and anilines.
In order to form a base film using these base film constituent materials, a casting method, a squeegee method, a dip method, a spin coating method, or the like can be used. The article surface on which the base film is formed preferably has a solvophilic property with respect to the base film constituent material, but even if it is poorly solvent, it can be formed by using alkali treatment or UV / O ₃ treatment in combination. It is.
In the case where cleaning is performed after the base film is formed, it is preferable to use an organic solvent. Organic solvents for washing include toluene, benzene, pentane, hexane, heptane, cyclohexane, methyl chloride, methyl bromide, ethyl acetate, diethyl ether, tetrahydrofuran, ethyl cellosolve, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n -Propanol, isopropanol, n-butanol, isobutanol, t-butanol, chloroform and the like.

[Synovial fluid]
In the present invention, the synovial fluid is a liquid having a synovial fluid action part that exhibits little lyophobic properties with respect to the liquid to be synovial fluid, and has a π interaction part that interacts with π electrons. It is preferable that
Preferable examples of the π interaction part include an ethoxy group, a methoxy group, a phenyl group, a hydroxy group, a carbonyl group, an aldehyde group, and an —XH group (X is an arbitrary atom).
If it is a lubricant that has the π-interaction part and has lubricity, it forms a liquid film almost independent of viscosity and surface tension, stable transparency (about 90% in the visible light region), Synovial fluid performance can be shown. When the synovial fluid is an aqueous liquid, examples of the synovial agent used in the present invention include silicone oil, fatty acid, higher alcohol, silane coupler, and other organic hydrophobic liquid substances. More specifically, decamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methylsilicone, methylphenylsilicone, methylhydroxysilicone, amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified as silicone oil Silicone oil, carbinol modified silicone oil, methacrylic modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, fatty acid ester modified silicone oil, partially fluorine modified Examples include silicone oils, and lower saturated fatty acids, higher saturated fatty acids, and lower unsaturated fats. Acids, higher unsaturated fatty acids, higher alcohols, and fatty acid compounds (sesame oil, rapeseed oil, almond oil, cottonseed oil, salad oil, etc.), fluoroalkylethoxysilane, fluoroalkylmethoxysilane, alkylethoxysilane, alkylmethoxysilane, DB2-EOS, EF -DB2, P3-EOS, and low volatility hydrocarbons (CnHx (n> 4 or more) alkane, alkene, alkyne) may also be used.
The following compounds containing a phenyl group can be used for either the base film or the lubricant.
2- (4,6-diphenyl 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol,
1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy} -2,2,6,6-tetramethylpiperidine,
4,4′-bis (α, α-dimethyl-benzyl) diphenylamine,
2,4-diamino-phenyl-1,3,5-triazine,
Tris (nonylphenyl) phosphite,
Tris (mixed, mono and dinonylphenyl) phosphite,
Tris (2,4-di-t-butylphenyl) phosphite,
4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite),
A mixture of 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-t-butyl-phenyl) butane and diphenyl phosphite;
4,4′biphenylenediphosphinic acid tetrakis (2,4 di-t-butylphenyl),
Cyclic neopentanetetraylbis (2,4-di-t-butylphenylphosphite),
Tris (cyclohexylphenyl) phosphite,
2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -P-cumenylbis (P-nonylphenyl) phosphite,
Bis- [2-methyl-4,6-bis- (1,1-dimethylethyl) phenyl] ethyl phosphite,
3,9-bis {2,4-bis (1-methyl-1-phenylethyl) phenoxy} -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane,
6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy-2,4,8,10-tetra-tert-butylbenz [d, f] [1,3,2] dioxa Phosfepin,
n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate,
4,4′-butylidenebis (6-t-butyl-m-cresol) or 1,1-bis (2′-methyl-4′-hydroxy-5′-t-butyl-phenyl) butane,
Triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
2,2′-oxamidobis (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate),
1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane),
2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate,
Tetrakis [methylene-3- (3 ′, 5) di-tert-butyl-4′-hydroxyphenyl] propionate] methane,
Bis [3,3-bis (4′-hydroxy-3′-t-butylphenyl) butanoic acid] glycol ester,
1,4-Benzenedicarboxylic acid bis [2- (1,1-dimethylethyl) -6-[[3- (1, edimethylethyl) -2-hydroxy-5-methylphenyl] methyl] -4-methylphenyl 〕ester,
N, N, -bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl} hydrazine,
3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] Undecane,
2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate,
p-t-butylphenyl salicylate,
2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate,
2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole,
Phenyl salicylate or phenyl salicylate,
2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol,
2- (2′hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole and methyl methacrylate copolymer,
2-ethylhexyl 2-cyano-3,3-diphenylacrylate,
Poly (oxy-1,2-ethanediyl), α- [4- (3-butoxy-2-cyano-3-oxo-1-propen-1-yl) -2-methoxyphenyl] -ω-hydroxy-2- (2′-hydroxy-3′5′-di) -t-amylphenyl) benzotriazole,
Polyoxyethylene (4-50 mol) alkyl (C7 or higher) phenyl ether,
Polyoxyethylene (4 to 50 mol) alkyl (C7 or higher) phenyl ether sulfate (Na, NH4),
Polyoxyethylene (5-55 mol) nonylphenyl phosphate,
a mixture of α (p-nonylphenyl) -ω-hydroxypoly (oxyethylene) dihydrogen phosphate, monohydrogen phosphate,
Methylphenyl polysiloxane,
Polyorgano (C1-C32 alkyl group and / or phenyl group) siloxane and polyalkylene (C2-C3) glycol condensate,
Benzene-1,2-dimethyl-4,5-bis (1-phenylethyl) (25-45%),
Benzene-4- (1,3 diphenylbutyl) -1,2 dimethyl (20-40%),
A mixture of benzene [1- (3,4-dimethylphenyl) ethyl] (1-phenylethyl) (25-45%),
Branched polycarbonate: The branching agent is limited to tris (parahydroxyphenyl) ethane.
Addition amount of branching agent is 2.0% or less,
Bis (4-tert-butylphenyl) sodium phosphate,
2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate zinc zinc phosphate (II),
7,8,9-trideoxy-3,5: 4,6-O-bis- (4-propylphenyl) methylene = D-glycero-L-glo-nonitol.

Table 1 below shows a synovial fluid having particularly high water slidability and its characteristics.

[Table 1]

FIG. 2 shows the production process of the synovial fluid film according to the present invention.
As shown in the figure, a functional group (OH group) is formed on the surface of the article (in this embodiment, glass) by UV / O ₃ treatment or strong alkaline solution, and a base film constituent material ( In this embodiment, phenyltriethoxysilane (hereinafter referred to as PTES) is applied by spin coating or dipping, squeegee, casting, or the like to cause a silane reaction and fix the base film on the article surface. At this time, since the phenyl group does not participate in the silane reaction, the phenyl residue is modified in a pendant form on the base film. The chemical bonding state of the surface by PTES is estimated as schematically shown in FIG.

Next, the base membrane is washed with ethanol to remove unreacted PTES and other residues that are not fixed to the surface of the article, and a lubricant (in this embodiment, decyltrimethoxysilane, hereinafter DTMS: viscosity of about 0 at 25 ° C.) .003 Pa.s, surface tension 27 mNm ⁻¹ ) is applied. Then, excess DTMS is removed, and a synovial fluid film is formed on the surface of the article.
The details of the manufacturing process are as follows.
(a) PTES: 1.8 mmol, TMOS: 9.06 mmol, EtOH: 10.0 mL are mixed and stirred for 10 minutes.
(b) Add H ₂ O: 0.042 mol, HClaq: 2 μL, and stir for 24 hours.
(c) The glass substrate is treated with UV / O ₃ .
(d) The PTES solution is spin-coated (1000 rpm, 5 sec → 2000 rpm, 10 sec).
(e) Dry for 24 hours.

FIG. 4 shows a conceptual diagram of the synovial fluid film according to the present invention. As shown in the figure, a base film is formed on the glass surface at about 144 nm, and is retained on the surface by CH-π interaction. The DTMS layer is formed to a thickness of 500 to 800 nm. At the time of DTMS application, an excess DTMS layer of 2 to 3 μm was formed, but this is removed.
Although DTMS is in a liquid state and can be almost removed from the surface of a normal article by simple wiping, in this embodiment, the methoxy group of DTMS is bonded to the phenyl group on the base film by CH-π interaction. Therefore, DTMS is firmly held by the synovial membrane while maintaining fluidity.
The fluidity of this DTMS has a great influence not only on the synovial fluid of the synovial membrane but also on the restorability. Unless the base membrane is destroyed, even if the DTMS at a specific site is removed, DTMS that has flowed in from other sites Are re-coupled by the CH-π interaction and the synovial properties are restored.

As shown in FIG. 5, when DTMS is directly modified on the surface of the article by silane reaction, there is no ability to bind other DTMS by CH-π interaction, so when DTMS is applied excessively. However, the lubricant layer as in the present invention was hardly formed.
The manufacturing method of the DTMS direct bonding film is specifically shown below.
(a) DTMS: 1.8 mmol, TEOS: 9.06 mmol, EtOH: 10.0 mL are mixed and stirred for 10 minutes.
(b) Add H ₂ O: 0.042 mol, HClaq: 2 μL, and stir for 24 hours.
(c) The glass substrate is treated with UV / O ₃ .
(d) Spin coating (1000 rpm, 5 sec → 2000 rpm, 10 sec) with the DTMS solution.
(e) Dry for 24 hours.

FIG. 6 shows the evaluation results by X-ray photoelectron spectroscopy of the DTMS coupling film (FIG. 6A) directly bonded to the article surface and the PTES base film (FIG. 6B). As is clear from FIG. 5B, a peak derived from π electrons was observed in the PTES conjugate.
From the above, it was confirmed that the base film according to the present embodiment effectively has phenyl groups having a high concentration of π electrons.

Next, the present inventors evaluated the synovial fluid of the synovial membrane according to the present invention.
That is, as shown in FIG. 7, the test liquid was dropped on a glass plate on which a synovial fluid film was formed, the glass slope was inclined, and the angle at which the sliding occurred was examined. In addition, as shown to the same figure (b), when a test liquid will get wet, this test liquid may have the characteristic as a synovial fluid.
First, the present inventors have various cases in the case of a DTMS-bonded film in which DTMS is directly silane-bonded to a glass slope, and in the case of a PTES base film in which PTES is silane-bonded to a glass slope (without applying DTMS). The sliding property of the test solution was examined. The results are shown in FIG.
As is clear from the figure, the water slipped at about 20 degrees with respect to both the DTMS binding film and the PTES base film, and a large difference was not recognized. However, polar organic solvents such as oleic acid, toluene, acetone, methanol, and ethanol all cause slipping at 10 degrees or less for DTMS-bonded membranes, but all wet for PTES-based membranes. It did not slide down. From the above points, it is considered that the PTES base membrane has a certain synovial property with respect to water and hydrocarbons, but has a binding property based on π interaction with a polar solvent. It is also understood that the DTMS binding membrane does not have a liquid lubricant retention capability.

Next, the present inventors verified the contact angle and sliding-down angle for glass, PTES base film, PTES base film + DTMS (synovial fluid). The results are shown in FIG.
First, regarding the contact angle, glass has high wettability and is less than 20 degrees. On the other hand, the PTES base film and the PTES base film + DTMS are both close to 70 degrees, and have substantially the same low wettability.
On the other hand, as for the sliding angle, the glass causes wetting, but the PTES base film is about 20 degrees as described above, and the PTES base film + DTMS is 0.5 degrees, and the contact angle simply increases (the contact area decreases). A behavior different from the improvement of rolling property or sliding property due to was observed. It is considered that this has a great influence on the fluidity of DTMS on the base film.

Furthermore, the present inventors evaluated the optical characteristics of the synovial fluid film. That is, since so-called SLIPS needs to form a porous state on the surface of an article, optical properties such as transparency tend to be inferior. On the other hand, the synovial fluid film according to the present embodiment does not need to form irregularities on the surface of the article. Rather, since the base film is flattened by forming the base film and the synovial agent layer, and the base is flat, the pure synovial surface Even if the thickness is reduced, scattering loss due to the base does not occur, and stable optical transparency can be obtained, so that an improvement in optical characteristics is expected. The evaluation results are shown in FIG.
From the figure, when DTMS is directly silane-bonded to the substrate (glass), the total transmittance (T. T) and the straight transmittance (P. T.) are almost the same, but the haze value and Diffusion transmittance (DTF) tends to decrease.

  On the other hand, when the PTES base film is formed on the glass substrate, the total transmittance and the straight transmittance are not significantly changed as compared with the substrate alone, but the haze value and the diffuse transmittance are greatly reduced. Further, when the PTES base film is formed on the glass substrate and DTMS is formed as the lubricant layer, the haze value and the diffuse transmittance tend to increase as compared with the case of only the PTES base film. Compared with the case where DTMS is directly silane-bonded, it can be kept low.

From these facts, it is understood that the synovial fluid film according to the present invention has high transparency and excellent optical characteristics, and in particular, the formation of a PTES base film or a DTMS layer ensures flatness more than the substrate, and the optical characteristics. Is understood to improve.
Further, FIG. 11 shows the result of study on the case where the present invention is applied to the inner surface of the can.
That is, a boil test and a retort test were performed on the case where a PTES base film and an oleic acid (lubricant) layer were formed on the inner surface of a steel can coated with PET resin. The results are shown in FIG.
As is clear from the figure, when oleic acid is used for the lubricant layer, even after being immersed in hot water at 90 ° C. for 30 minutes in a can with an open lid and a sealed can, it changes from before the test with respect to water droplets. Without falling, it showed a sliding angle of 5 degrees or less, and maintained excellent synovial fluid performance.
In addition, when DTMS was used for the lubricant layer, it showed excellent durability for the boil test, but the sliding angle increased (deteriorated) for the retort test. However, with respect to the retort test product as well, when the DTMS was dropped and applied again, the sliding angle was reduced, suggesting that the base film was maintained.

Furthermore, the present inventors conducted a bending resistance test of the synovial fluid film as shown in FIG.
That is, in the case of SLIPS, the convex portion of the porous portion holding the lubricant is exposed by stretching the surface, and the synovial fluid effect may be significantly reduced due to the pinning effect by the convex portion.
However, according to the synovial fluid film according to the present embodiment, the article surface, the base film, and the synovial agent layer are all flattened, and the synovial properties are not lowered by bending or the like of the article surface.
Further, as shown in FIG. 13, the present inventors conducted a scratch resistance test when the synovial fluid film was damaged by a sharp blade, but the synovial agent layer was repaired due to its high affinity for the base membrane. Is called.

Further, FIG. 14 shows a case where the synovial fluid film is rubbed, and in this case as well, as in the case where the synovial fluid film is damaged, the synovial fluid layer is repaired.
As described above, it is understood that the synovial membrane according to the present embodiment has an extremely high repairability and is an excellent synovial membrane.
Water droplets (10 μL) did not slide down on the glass surface, but slipped down at a sliding angle of 0.5 ° by forming a lubricant layer with DTMS. In general, an ultra-low viscosity liquid does not form a liquid film unless the substrate is flat, but in this embodiment, ultra-low viscosity DTMS is applied to a flat glass surface. Thus, according to the synovial membrane according to the present invention, the selectivity of the synovial fluid (pure synovial fluid) is very wide, and it can be said that the problem that the synovial fluid that can be used as in the past is limited is solved. .
In this embodiment, the synovial fluid film is formed on the glass. However, the base film formation by the silane bond used in this embodiment can be applied to any surface subjected to hydrophilic treatment. For example, when a base film was formed on a PET film, excellent performance was exhibited.
In addition, the synovial membrane of this embodiment showed excellent sliding properties against water, warm water (90 ° C.), saline (5 wt%), ice blocks, and blood. Although hot water has a lower surface tension than water and is accompanied by the deposition of a micro liquid by vapor, there are few reports of hot water sliding down, but the membrane of this case was able to slide down. This is considered to be because the fine liquid can be slid and the coalescence of the liquid particles proceeds. Further, the synovial fluid film according to the present embodiment showed blood slidability. In addition, blood showed complete non-adhesion performance for the dipping test on blood and the output image through the endoscope lens.
So far, SLIPS and super water-repellent surface (SHS) have been reported as approaches for non-adherent liquid surfaces. SLIPS slides liquids with immiscible lubricants (rolls the surface depending on conditions), while super water-repellent surfaces create an air layer at the interface between the liquid and the surface of the article, reducing the contact area. Can be rolled. According to Zuankai Wang et al. And Tak-sin wong et al., The liquid sliding speed is roughly inversely proportional to the viscosity of the lubricant layer. In addition, KK Varanasi et al. Report that the liquid sliding speed increases as the unevenness of the article surface decreases. The present inventors have also confirmed that unevenness on the surface of the article significantly reduces the liquid sliding property. And according to the present embodiment, DTMS (μ = 0.003 Pa · sec) which is significantly lower than the viscosity of the conventional lubricant can be maintained, and the unevenness of the article surface is RMS <1 nm or less. It can be said that the sliding speed was greatly increased.
There is also an example of forming the super-water-repellent SLIPS by making the uneven structure on the surface of the article into a needle-like structure, but the super-water-repellent SLIPS also depends on the lubricant viscosity. As a result, the water sliding speed of the synovial fluid film according to the present invention was dramatically improved as compared to SLIPS.
On the SHS surface, micro liquid is trapped in the concavo-convex structure, so that the pinning effect occurs and does not slide down (when <5 μL). As for SLIPS, the liquid slides very slowly (almost does not move) unless the liquid diameter becomes large to some extent. For this reason, it is difficult to remove the liquid from the surface of the article. It is very important to slide a micro liquid at a certain speed, for example, it is important to remove liquid that becomes difficult to remove due to coagulation and growth over time, such as blood and ice nuclei. . In particular, in the case of SLIPS, if the liquid enters the lubricant due to some external force such as spray pressure, the intruding liquid may not be removed. According to the synovial fluid film according to the present embodiment, the sliding speed greatly increased as the amount of the dropped liquid increased. The SLIPS, SHS, and untreated surfaces were transferred to a wet state with respect to repeated mist spraying, whereas the synovial fluid film according to this embodiment exhibited resistance to spraying. On the synovial membrane according to the present embodiment, it was confirmed that the micro liquid was efficiently removed by continuous Coalescence process and Sweep process. The Coalescence process is an aggregation phenomenon of micro liquids. On the surface of this synovial membrane, micro liquid also has a constant sliding speed. The micro liquids will gather together, including their affinity, and will gradually grow. Subsequently, the Sweep process causes a phenomenon in which the liquid grown by the Coalescence process slips at a higher speed while absorbing a minute liquid. Since the absorption capacity of the micro liquid is much smaller than the force that tries to stay on the surface of the synovial membrane, the growing liquid slides down while sucking in the micro liquid like a vacuum cleaner, and cleans the micro water droplets on the surface. . The continuation of these two processes promoted the sliding of the micro liquid on the surface of the sliding film.
This sliding membrane showed excellent sliding properties of ice blocks, but when mass is m, ρ is density, and V is volume, it is possible to slide a material having V smaller than m = ρV. It is thought that even ice-like objects can slide down.

Claims (11)

A layer having a functional group having π electrons as a base film;
As a synovial fluid layer, a layer having in the molecule a π interaction part that binds by π interaction with the π electron functional group of the base film and a synovial fluid action part having a low affinity with the fluid to be synovial fluid,
A synovial membrane characterized by containing.   2. The synovial fluid film according to claim 1, wherein the base film is formed on a flat surface of an article.   3. The synovial fluid film according to claim 1, wherein the base film has a high concentration π electron-containing functional group selected from an aromatic group and / or an alkyne group. The synovial fluid film according to any one of claims 1 to 3, wherein the π interaction part of the synovial agent is an ethoxy group, a methoxy group, a phenyl group, a hydroxy group, a carbonyl group, an aldehyde group, which interacts with π electrons, A synovial membrane characterized by being selected from -XH group (X is an arbitrary atom).   The synovial fluid film according to any one of claims 1 to 4, wherein the fluid to be synovial fluid is a hydrophilic medium, and the synovial fluid action part of the synovial agent is an alkyl group or an alkyl-modified siloxane group, an alkylphenyl-modified siloxane. A synovial membrane characterized by being a group or a fluorinated alkyl group. A base film constituent material having a π-electron-containing functional group is bonded to the surface of the article or interacted between molecules to form a base film
On the base film, a synovial agent having a π interaction part bonded to the π electron functional group of the base film by π interaction and a synovial liquid action part having a low affinity with the fluid to be synovial fluid in the molecule is provided on the base film. A base film forming method comprising applying to a base material.   A medical instrument comprising a surface covered with the synovial fluid film according to claim 1.   A container having a surface covered with the synovial fluid film according to claim 1.   An optical apparatus having a surface covered with the synovial fluid film according to claim 1.   An antifouling glass comprising a surface covered with the synovial fluid film according to any one of claims 1 to 5. A solar cell, a power transmission line, a building material (roof, window, wall), a transporting device (automobile, ship, aircraft) characterized by having a surface covered with the synovial fluid film according to any one of claims 1 to 5. , Tube material (heat transfer condenser, heat absorption, heat dissipation equipment).