JP5991665B2 - Transparent hybrid film and manufacturing method thereof - Google Patents

Description

  The present invention relates to a transparent hybrid film and a method for producing the same. More specifically, an organic silane having a hydrophobic functional group and a metal alkoxide are mixed with an organic solvent, water, an additive (rust inhibitor, ultraviolet absorber / For example, metals, metal oxide films, metal oxides, alloys, semiconductors, precursor solutions co-hydrolyzed and polycondensed in solutions containing light stabilizers, fungicides / antibacterial agents, bioadhesive agents, etc.) Apply to a solid surface such as polymer, ceramics, glass, resin, wood, paper, fiber, etc. to form a transparent hybrid film with excellent adhesion at the same time as volatilization of the solvent. Controlling the mobility of the functional group and immobilizing various additives between the 1 to 10 nm layers of the transparent film, while maintaining the characteristics of the base material, Water / oil repellency, Transparent hybrid film and its production that can stably provide properties such as droplet removal ability, fingerprint resistance, antifouling, corrosion resistance, weather resistance, mold resistance, antibacterial properties, and anti-biological adhesion for a long period of time It is about the method.

  The present invention provides adhesion to a substrate, water repellency / oil repellency, droplet removal ability, fingerprint resistance, antifouling properties, corrosion resistance, weather resistance, antifungal properties, antibacterial properties, biological adhesion prevention, etc. By forming a transparent hybrid film with excellent properties on the surface of the base material, for example, corrosion prevention of metal / wood materials, prevention of fingerprint adhesion to touch panel displays, etc., and addition of antibacterial properties to daily living products and food packaging materials New surface modification technology that is particularly effective in applications such as weather resistance to polymer films, paper / fiber deterioration / yellowing prevention and waterproofing, and anti-mold treatment around tiles and water. It provides new technologies and products.

  When a droplet adheres to the solid surface, the corrosion, deterioration, or contamination of the solid surface proceeds from that point. In the case of a transparent material such as glass, the adhered droplets cause poor visibility and dirt. In solar power generation, dirt on the condensing mirror has a large effect on power generation efficiency. Therefore, in many engineering fields, materials with high droplet removal performance (water-repellent / oil-repellent) / surface treatment Development is being attempted.

  As a prior art, for example, application of an organic silane monomolecular film terminated with an inert (hydrophobic) functional group having a low surface energy, such as an alkyl group or a perfluoroalkyl group, to an anticorrosive film has been studied ( Non-patent documents 1 to 3). These are techniques aimed at improving the anticorrosion property by imparting water repellency to the surface to suppress the adhesion of droplets.

  However, since these surfaces have large hysteresis, it is known that water droplets remain on the solid surface even if the solid surface is tilted by 90 ° or more in the case of minute water droplets. However, it has been found that the water droplet removal performance is not always improved (Non-Patent Document 4).

Hysteresis is indicated by the difference (θ _A −θ _R ) between the advancing contact angle (θ _A ) and the receding contact angle (θ _R ). The smaller the value, the more the droplet slides down the solid surface with a slight inclination. To do. In addition, the monomolecular film has a problem in long-term stability due to its extremely thin film thickness (<3 nm), and at the same time has a defect microscopically, so that the substrate surface is completely covered. I can not say. For this reason, the anticorrosion properties are naturally limited.

  As another prior art, for example, by utilizing self-integration of organic phosphonic acid and zirconium, a phosphonate-zirconium laminated film (film thickness of about 9 nm) is formed on a pure aluminum substrate (JIS1100P), and its anticorrosion performance is evaluated. (Non-Patent Documents 5 to 6). The evaluation result of the corrosion resistance by the salt spray test showed a high corrosion resistance of 3 times that of a ZrP chemical conversion coating (white rust generated in about 24 hours) that has been put to practical use as an anticorrosion coating for aluminum beverage cans, but after about 72 hours , White rust has occurred.

  As other prior arts, for example, galvanization and chromate treatment are well known as anticorrosion treatment for metal materials. However, the former has a problem that its durability and the shape to be processed are limited (Non-patent Document 7). On the other hand, although the latter is excellent in corrosion resistance, it has been pointed out that the effect of hexavalent chromium used on the environment and the human body has been pointed out, making it difficult to carry out chromate treatment. It is desired.

  As another prior art, Andreweva et al., For example, has developed a technique for preventing corrosion and self-healing even when damaged by a coating film composed of alternating nanolayers of a polymer electrolyte (Non-patent Document 8). When a coating film having an 8-hydroxyquinoline layer (corrosion inhibitor) is formed on the aluminum alloy surface using a plurality of polymer electrolyte layers having opposite charges, the coated surface is scratched. No corrosion was observed after 16 hours even after soaking in salt water.

  On the other hand, the untreated aluminum surface was significantly corroded only by being immersed in salt water for 6 hours. This coating film has excellent self-healing ability, but the polymer electrolyte layer is easily dissociated under high salt concentration environment such as seawater or the increase of salt concentration accompanying evaporation of aqueous solution, and it can be used in real environment. Has the problem of being unbearable.

  As another prior art, for example, in order to improve the weather resistance of a polymer material, an ultraviolet absorber is added to the polymer itself or a coating film to suppress deterioration / yellowing of the material (patent) Literatures 1-2). However, simply adding an ultraviolet absorber does not fix the ultraviolet absorber in the material matrix, so sublimation or bleedout occurs over time, and the ultraviolet-cutting ability decreases. In addition, there are many problems in developing a polymer material that realizes stable weather resistance for a long period of time due to the problem of solubility of an ultraviolet absorber in a solvent and the problem of deterioration of physical properties of the material due to addition of a high concentration.

  Moreover, in the surface modification method described above, in 1) monomolecular film treatment, the types of base materials that can be treated are limited by the difference in reactivity between the raw material molecules and the base material surface. Since the film thickness of molecular films and laminated films is several nanometers, they must be peeled and damaged by some chemical / physical factors, making it difficult to maintain long-term surface functions. 3) However, since the additive is not immobilized in the matrix, sublimation and bleed-out occur, and the ultraviolet cut ability is reduced.

  Therefore, in this technical field, stable water repellency / oil repellency, droplet removal ability, fingerprint resistance, antifouling properties, corrosion resistance, weather resistance, antifungal properties, antibacterial properties, and prevention of bioadhesion for a long time. Development of a surface modification technique that can realize the above on the surface of a practical substrate has been strongly desired.

JP 2002-20140 A JP 2003-243687 A

G. K. Jennings and P.M. E. Laibinis, Colloids Surf. A, 116, 105 (1996) G. Grumdmeier, C.I. Reinartz, M.M. Rohwerder, and M.M. Stratmann, Electrochim. Acta, 43, 165 (1998) M.M. Itoh, H .; Nishihara, and K.K. Aramaki, J. et al. Electrochem. Soc. , 142, 3969 (1995). 151 Akamatsu Yoshinori, Surface Technology, 60, 32 (2009) Azusa Shida, Masanobu Sugawara, Hiroyuki Sugimura, Osamu Takai, Surface Technology, 53, 897 (2002) A. Shida, H .; Sugmura, M .; Futsuhara, and O.R. Takai, Surf. Coat. Technol. 169-170,686 (2003) Teruaki Izaki, Surface Technology, 50, 545 (1999) Daria V. Andrewva, D.A. Fix, H .; Mohwald, and D.M. G. Shchukin, Adv. Mater. , 20, 2789 (2008)

  Under such circumstances, the present inventor, in view of the above-mentioned prior art, stably fixes various additives in the film at a high concentration and enables formation of a transparent film having excellent corrosion resistance / weather resistance. As a result of diligent research aimed at developing new surface treatment technology for practical substrates, organic silanes and metal alkoxides with hydrophobic functional groups were combined with organic solvents, water, additives (rust inhibitors, UV absorbers). / Precursor solution co-hydrolyzed and polycondensed in a solution containing a light stabilizer, fungicide / antibacterial agent, bioadhesive agent, etc.) on the substrate surface, and then for a predetermined time at room temperature and atmospheric pressure It was found that the intended purpose can be achieved by leaving it at rest.

  That is, the present inventor has 1) that a transparent film excellent in adhesion is formed simultaneously with the volatilization of the solvent, and 2) an additive (rust preventive agent) between the transparent films of 1) above. UV absorbers / light stabilizers, fungicides / antibacterial agents, bioadhesive agents, etc.) can be immobilized at a high concentration, and 3) the surface of the transparent film of 1) is composed of the same organosilane molecule. Compared with the surface of the substrate coated with a monomolecular film, the hysteresis is extremely small, and the droplet removal performance and antifouling properties are improved. 4) The effects of 2) and 3) above are combined and applied. We have found new knowledge that the water repellency / oil repellency, antifouling property, corrosion resistance, weather resistance, antifungal property, antibacterial property, prevention of biofouling, etc. of the base material are improved, The present invention has been completed.

In the present invention, an organic silane having a hydrophobic functional group is mixed with a metal alkoxide and an additive as compared with a case where the substrate is coated with an inorganic thin film such as silica or an inorganic thin film such as silica doped with an additive. Then, a transparent hybrid film is formed only by coating, the additive is fixed between the layers at a high concentration, and sublimation and bleed-out can be suppressed, and the surface has a surface tension of 18 to Very small contact angle hysteresis <dynamic contact angle [advanced contact angle (θ _A ) and receding contact angle (θ _R )] for a liquid of 73 dyn / cm (θ _A −θ _An object of the present invention is to provide a new surface modification technique capable of realizing a solid surface exhibiting _{R 1} )>.

  Furthermore, since the present invention can fix the additive at a high concentration between the layers of the coating, it can realize stable weather resistance, antifungal properties, and antibacterial properties for a long period of time, and also allows the interaction between the droplet and the solid surface. Since it can also be suppressed, water repellency / oil repellency, droplet removing ability, fingerprint resistance, and antifouling properties can be simultaneously imparted to the surface of the coating. Therefore, the present invention, for example, prevents corrosion of metal / woody materials, prevents fingerprint adhesion to touch panel displays, imparts antibacterial properties to daily life goods and food packaging materials, imparts weather resistance to polymer films, paper and fibers, etc. The purpose is to provide new technologies and new products related to new surface modification technologies that are particularly effective in industrial fields such as preventing deterioration / yellowing and imparting water resistance, and preventing mold / antibacterial treatment around tiles and water. It is.

The present invention for solving the above-described problems comprises the following technical means.
(1) A transparent hybrid film formed on the solid surface of a substrate, which is obtained by co-hydrolyzing / condensing a raw material organic silane and a metal alkoxide in a solution containing an organic solvent, water, additives, and optionally a catalyst. The film is obtained by applying a precursor solution in which the distance between the organosilanes is controlled, and the dynamic wettability of the substrate surface, that is, the dynamic contact angle [advanced contact angle (θ _A ) and receding contact angle (Θ _R )] has a characteristic that the contact angle hysteresis (θ _A −θ _R ) is smaller than that of the surface treated with organosilane alone. .
(2) The transparent hybrid film according to (1), wherein the organic silane and the metal alkoxide are mixed at an arbitrary molar ratio of 1: 0.1 or more.
(3) The transparent hybrid film according to (1) or (2), wherein the obtained transparent hybrid film has a layered structure with a repetition period of 1 to 10 nm.
(4) Any of the above (1) to (3), wherein the film contains at least one additive selected from a rust inhibitor, an ultraviolet absorber, an antifungal agent, and a biological adhesion inhibitor The transparent hybrid film described in 1.
(5) The transparent hybrid film according to any one of (1) to (4), wherein the additive is contained at a maximum of 50 wt% with respect to the total weight of the film.
(6) The transparent material according to any one of (1) to (3), wherein the additive according to (4) or (5) is immobilized in a layered structure having a repetition period of 1 to 10 nm. Hybrid film.
(7) The transparent hybrid film according to any one of (1) to (6), wherein the distance between the organic silane molecules is changed depending on the molar ratio between the organic silane and the metal alkoxide.
(8) Any of (1) to (7) above, wherein the film exhibits adhesion to adhere to a substrate selected from metals, alloys, metal oxide films, semiconductors, polymers / resins, wood, fibers, and paper The surface of the transparent hybrid film described in 1.
(9) The above-described (1) to (8), wherein the film exhibits adhesion to adhere to a mixed surface composed of at least one surface selected from a flat surface, a curved surface, an uneven surface, and a porous surface. The transparent hybrid film according to any one of the above.
(10) The transparent hybrid film according to any one of (1) to (9), wherein when a film is formed on the metal surface, the film self-repairs even if scratches are generated on the surface.
(11) From the above (1), the hysteresis as a difference between the advancing contact angle and the receding contact angle with respect to a liquid having a surface tension of 18 to 73 dyn / cm is smaller than the surface treated with organosilane alone. (9) The transparent hybrid film according to any one of (9).
(12) The hysteresis as the difference between the advancing contact angle and the receding contact angle with respect to the mixed liquid in which the liquid according to (11) and at least one kind of compound are mixed is more than the surface treated with organosilane alone. The transparent hybrid film according to any one of (1) to (9), which has a small value.
(13) The transparent hybrid film according to any one of (1) to (9), wherein the film is difficult to adhere to a fingerprint and exhibits easy wiping property to easily wipe off the attached fingerprint.
(14) The organic silane that is a raw material of the transparent hybrid film is R ¹ —Si—R ² _n-3 R ³ _{n of} the formula (A) (where n = 1, 2, or 3, R ¹ is the number of carbon atoms. A 1-30 alkyl chain or a C 1-20 perfluoro group, R ² is a C 1-6 alkyl group, R ³ is a C 1-15 alkoxy group, a chloro group, an isocyanato group, or (1) to (9) having an inactive functional group represented by an acetoxy group) and bonded with a Si—C bond, and a functional group that generates one or more Si—OH groups after hydrolysis. The transparent hybrid film according to any one of the above.
(15) R ¹ R ² —Si—R ³ _n R ⁴ _{n-3 of} the formula (B) is used as the raw material of the transparent hybrid film (where n = 1, 2, or 3, R ¹ is Hydroxyl group, vinyl group, alkyl chloride group, amino group, imino group, nitro group, mercapto group, epoxy group, carbonyl group, methacryloxy group, azide group, diazo group, benzophenyl group or their derivatives, R ² is carbon An alkyl group having 1 to 15 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, R ⁴ is an alkoxy group having 1 to 15 carbon atoms, a chloro group, an isocyanato group, or an acetoxy group), and Si The transparent hybrid film according to any one of (1) to (9), which has an active functional group bonded by a -C bond and a functional group that generates one or more Si-OH groups after hydrolysis.
(16) From (1) to (1) above, wherein the organic silane used as a raw material for the transparent hybrid film is made from at least two kinds selected from the organic silanes described in (14) and (15) above. The transparent hybrid film according to any one of 9).
(17) The metal alkoxide that is a raw material of the transparent hybrid film is M (R ¹ ) n (where n = 1, 2, 3, or 4, where M is Al, Ca, Fe, Ge, The transparent hybrid according to any one of (1) to (9), represented by a metal element of Hf, In, Si, Ta, Ti, Sn, or Zr, wherein R is an alkoxy group having 1 to 15 carbon atoms) Film.
(18) Any of (1) to (9) above, wherein the metal alkoxide used as a raw material of the transparent hybrid film is made from at least two kinds selected from the metal alkoxide described in (17) above. The transparent hybrid film according to crab.
(19) From the above (1), the additive to be immobilized between the layers of the transparent hybrid film is a rust inhibitor, an ultraviolet absorber / light stabilizer, a fungicide / antibacterial agent, and / or a bioadhesive agent. (9) The transparent hybrid film according to any one of (9).
(20) Any of the above (1) to (9), wherein the additive to be fixed between the layers of the transparent hybrid film uses at least two or more selected from the additives described in (19) as raw materials The transparent hybrid film according to crab.
(21) Co-hydrolysis / condensation of organic silane and metal alkoxide in a solution containing an organic solvent, water, rust preventive agent as additive, UV absorber, fungicide, or bioadhesive agent, and optionally a catalyst. The polymerized precursor solution is dropped on a solid surface selected from metal, metal oxide film, alloy, semiconductor, polymer, ceramics, glass, resin, wood, paper, and fiber, and then for a predetermined time at room temperature and atmospheric pressure. A method for producing a transparent hybrid film, characterized by evaporating a solvent and crosslinking the film.
(22) Use an organic solvent that is miscible with water used for hydrolysis, dissolves the organic silane, metal alkoxide, and additives after hydrolysis and degeneracy, and has a vapor pressure larger than that of water. The manufacturing method of the transparent hybrid membrane | film | coat as described in said (21).
(23) From the above (21), the catalyst used for hydrolysis has an action of promoting the hydrolysis of R ³ of formula (A), R ⁴ of formula (B), and R ^{1 of} formula (C). (22) The manufacturing method of the transparent hybrid membrane | film | coat in any one of.
(24) Volatilization of the solvent is promoted by any method selected from a spin coating method, a dip coating method, a roller coating method, a bar coating method, an ink jet coating method, a gravure coating method, and a spray method. ) To (23). The method for producing a transparent hybrid film according to any one of (23).
(25) The film thickness is controlled from 10 to 10000 nm depending on the concentration of the organic silane, metal alkoxide and additive in the precursor solution, and the molar concentration of the organic solvent. The manufacturing method of the organic-inorganic transparent hybrid film | membrane of description.
(26) The transparent hybrid according to any one of (21) to (25), wherein the precursor solution prepared by the method described in (21) to (25) can be used even after storage for at least 20 days. A method for producing a film.
(27) A solid surface coated with the transparent hybrid film according to any one of (1) to (9), wherein the surface is water repellency / oil repellency, droplet removal ability, and fingerprint resistance. Solid surface characterized by exhibiting properties, antifouling properties, corrosion resistance, weather resistance, antifungal properties, antibacterial properties, and / or biofouling prevention ability.

Next, the present invention will be described in more detail.
The present invention is a transparent hybrid film for forming on a solid surface, comprising an organic silane and a metal alkoxide, an organic solvent, water, an additive (rust inhibitor, ultraviolet absorber / light stabilizer, fungicide / antibacterial agent). A film obtained by cohydrolysis / condensation polymerization in a solution containing an agent, a bioadhesion inhibitor, and the like).

  The present invention also relates to a method for producing a transparent hybrid film, comprising co-hydrolyzing / condensing an organic silane and a metal alkoxide on a solid surface in a solution containing an organic solvent, water, and an additive. After applying the precursor solution in which the distance between them is controlled, the precursor solution is allowed to stand at room temperature and atmospheric pressure for a predetermined time. Furthermore, the present invention is a solid surface coated with the above-described transparent hybrid film, and the surface has excellent water repellency / oil repellency, droplet removal ability, fingerprint resistance, antifouling, and corrosion resistance. It is characterized by exhibiting weather resistance, antifungal property, antibacterial property, and ability to prevent biological adhesion.

  In the present invention, with the above-described configuration, various droplets (surface tension of 18 to 73 dyn / cm) are formed by forming an organic-inorganic transparent hybrid film having excellent adhesion and mobility of functional groups derived from organosilane on the film surface. And the difference (hysteresis) between the advancing contact angle and the receding contact angle of a mixed liquid in which at least two of these liquids are mixed is smaller than that of the surface treated with organosilane alone. Is realized.

  In the present invention, the organic silane and the metal alkoxide are mixed at an arbitrary molar ratio of 1: 0.1 or more, and the obtained organic-inorganic transparent hybrid film is a metal, metal oxide film, alloy, semiconductor, polymer. It is a preferred embodiment that it exhibits good adhesion that easily adheres to a substrate selected from ceramics, glass, resin, wood, fiber, and paper.

  In the present invention, the distance between the organosilane molecules is changed depending on the molar ratio of the organosilane to the metal alkoxide, and various droplets (surface tension of 18 to 73 dyn / cm) and the difference (hysteresis) between the advancing contact angle and the receding contact angle of the mixed liquid in which at least two of these liquids are mixed is smaller than that of the surface treated with organosilane alone, Or it is set as the preferable embodiment that it is hard to adhere to a fingerprint and it is difficult to adhere.

In the present invention, an organic silane as a raw material for the transparent hybrid coatings, the formula _{^{R 1 -Si-R 2 n-}} 3 R 3 n in (A) (where, n = 1, 2 or 3,, ^{R 1} Is an alkyl chain having 1 to 30 carbon atoms or a perfluoro group having 1 to 20 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is an alkoxy group having 1 to 15 carbon atoms, a chloro group, It is preferable to have an inert functional group represented by an isocyanato group or an acetoxy group) and bonded with a Si—C bond and a functional group that generates one or more Si—OH groups after hydrolysis.

Moreover, in this invention, the organosilane used as the raw material of the transparent hybrid film is R ¹ R ² —Si—R ³ _n R ⁴ _n-3 (where n = 1, 2, or 3, R ¹ is a hydroxyl group, vinyl group, alkyl chloride group, amino group, imino group, nitro group, mercapto group, epoxy group, carbonyl group, methacryloxy group, azide group, diazo group, or benzophenyl group and derivatives thereof, R ² is an alkyl group having 1 to 15 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, R ⁴ is an alkoxy group having 1 to 15 carbon atoms, a chloro group, an isocyanato group, or an acetoxy group) And having an active functional group bonded by a Si—C bond and a functional group that generates one or more Si—OH groups after hydrolysis.

In the present invention, the metal alkoxide used as a raw material for the transparent hybrid film is M (R ¹ ) n (where n = 1, 2, 3, or 4 in the above formula (C), where M is Al, Ca, It is preferably represented by a metal element of Fe, Ge, Hf, In, Si, Ta, Ti, Sn, or Zr, and R is an alkoxy group having 1 to 15 carbon atoms.

  As the additive that can be used in the present invention, conventionally known additives can be used, for example, rust preventives, ultraviolet absorbers / light stabilizers, fungicides / antibacterial agents, bioadhesive agents and the like. Although it can use suitably, if it is an additive with the same or similar effect as these, it can be used similarly. It is also possible to use a mixture of two or more additives. Specific examples of these additives include the following compounds.

That is, as an additive, the compound shown below is illustrated, for example.
[Rust preventive]
Alkanolamines, quaternary ammonium salts, alkanethiols, imidazolines, sodium metavanadate, bismuth citrate, phenol derivatives, polyalkenylamines, alkylimidazoline derivatives, dianoalkylamines, carboxylic acid amides, alkylenediamines, pyrimidines and their carboxylic acids , Naphthenic acid, sulfonic acid complex, calcium nitrite, alkylamine and ester, polyalcohol, polyphenol, alkanolamine, sodium molybdate, sodium tungstate, sodium nitrite, sodium phosphonate, sodium chromate, sodium silicate, Gelatin, polymers of carboxylic acids, aliphatic and aromatic amines and diamines, ethoxylated amines, imidazoles, benzimidazoles, nitro compounds Formaldehyde, acetylene alcohol, aliphatic and aromatic thiols and sulfides, sulfoxide, thiourea, acetylene alcohol, 2-mercaptobenzimidazole, amine or quaternary ammonium salt + halogen ion, acetylene thiol and sulfide, dibenzyl sulfoxide, alkylamine + Potassium iodide, dicyclohexylamine nitrite, cyclohexylamine benzoate, benzotriazole, tannin + sodium phosphate, triethanolamine + lauryl sarcosine, + benzotriazole, alkylamine + benzotriazole + sodium nitrite + sodium phosphate.

[Ultraviolet absorber / light stabilizer]
2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t- Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, methyl-3- [3-t-butyl-5- Condensate with (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (4,6-diphenyl-1,3,5 -Triazin-2-yl) -5 [(hexyl) oxy] -phenol, 2-ethoxy-2'-ethyl-oxalyl Bisanilide succinate.

[Anti-mold / antibacterial agent]
2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzisothiazoline-3-one, (2-pyridylthio-1-oxide) sodium, dehydroacetic acid, 2-methyl-5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazolecarbamate, methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate, mono- or dibromocyanoacetamides, 1,2-dibromo-2 , 4-dicyanobutane, 1,1-dibromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-acetoxypropane.

[Bioadhesion inhibitor]
Tetramethylthiuram disulfide, bis (N, N-dimethyldithiocarbamate) zinc, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, dichloro-N-((dimethylamino) sulfonyl) fluoro-N- (P-tolyl) methanesulfenamide, pyridine-triphenylborane, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide, cuprous thiocyanate (1), cuprous oxide , Tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylenebisdithiocarbamate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, N- ( 2,4,6-trichlorophenyl) maleimide, bis (2-pyridinethiol-1-oxy) D) Zinc salt, bis (2-pyridinethiol-1-oxide) copper salt, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-n- Octyl-4-isothiazolin-3-one, furanones, alkylpyridine compounds, gramine compounds, isotonyl compounds.

  Further, in the present invention, a precursor solution obtained by co-hydrolyzing / condensation of an organic silane and a metal alkoxide in a solution containing an organic solvent, water, an additive, and optionally a catalyst, a metal, a metal oxide film, an alloy, a semiconductor, After dripping onto a solid surface selected from polymer, ceramics, glass, resin, wood, paper, and fiber, the solvent is volatilized at room temperature and atmospheric pressure for a predetermined time.

  In the present invention, an organic compound that is miscible with a small amount of water used for hydrolysis, dissolves the organic silane, metal alkoxide, and additives after hydrolysis and degeneracy, and has a vapor pressure higher than that of water. It is preferable to use a solvent and that the molar fraction of water used for hydrolysis is larger than the molar fraction of alkoxy groups in the precursor solution composition.

Furthermore, in the present invention, a catalyst having an action of promoting hydrolysis can be used. For example, as the catalyst used for the hydrolysis, those having the action of promoting the hydrolysis of R ^{3 of} the above formula (A), R ^{4 of} the above formula (B), and R ¹ of the above formula (C) are used. Is done. In the present invention, the volatilization of the solvent is promoted by any method selected from a spin coating method, a dip coating method, a roller coating method, a bar coating method, an ink jet coating method, a gravure coating method, and a spray method. It is preferable to control the film thickness from 10 to 10,000 nm depending on the concentration of the organic silane, metal alkoxide and additive in the precursor solution.

  As the organic silane that can be used in the present invention, for example, alkyl (having 3 to 18 carbon atoms) alkoxysilane and the like can be preferably used, but any organic silane that exhibits the same or similar effect as these can be used similarly. It is possible. Specific examples of these organosilanes include the following compounds.

  That is, as the organic silane, for example, alkyl (C1-30) trimethoxysilane, alkyl (C1-30) triethoxysilane, alkyl (C1-30) methyldimethoxysilane, alkyl (C1) 30) methyldiethoxysilane, alkyl (1 to 30 carbon atoms) dimethylmethoxysilane, alkyl (1 to 30 carbon atoms) dimethylethoxysilane, alkyl (1 to 30 carbon atoms) trichlorosilane, alkyl (1 to 30 carbon atoms) Methyldichlorosilane, alkyl (1-30 carbon atoms) dimethylchlorosilane, alkyl (1-30 carbon atoms) triacetoxysilane, alkyl (1-30 carbon atoms) methyldiacetoxysilane, alkyl (1-30 carbon atoms) dimethylacetoxy Silane, alkyl (from 1 carbon atoms 0) Triisocyanacylsilane, alkyl (1 to 30 carbon atoms) methyl dicyanatosilane, alkyl (1 to 30 carbon atoms) dimethyl cyanatosilane, perfluoro (3 to 18 carbon atoms) trimethoxysilane, perfluoro (carbon) 3 to 18) triethoxysilane, perfluoro (3 to 18 carbon atoms) methyldimethoxysilane, perfluoro (3 to 18 carbon atoms) methyldiethoxysilane, perfluoro (3 to 18 carbon atoms) dimethylmethoxysilane, perfluorocarbon Fluoro (3 to 18 carbon atoms) dimethylethoxysilane, perfluoro (3 to 18 carbon atoms) trichlorosilane, perfluoro (3 to 18 carbon atoms) methyldichlorosilane, perfluoro (3 to 18 carbon atoms) dimethylchlorosilane, Fluoro (3 to 18 carbon atoms) triacetoxy Lan, perfluoro (3 to 18 carbon atoms) methyldiacetoxysilane, perfluoro (3 to 18 carbon atoms) dimethylacetoxysilane, perfluoro (3 to 18 carbon atoms) triisocyanacylsilane, perfluoro (from 3 carbon atoms) 18) Methyl dicyanatosilane and perfluoro (C3-18) dimethylcyanatosilane are exemplified.

  Moreover, as a metal alkoxide which can be used by this invention, a conventionally well-known thing can be used. For example, a metal alkoxide which is a molecule other than the above [0028] having two or more alkoxy groups centered on a metal element, or a compound shown below which exhibits the same or similar effect is exemplified.

  That is, as the metal alkoxide, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, triethoxyaluminum, tri- n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, tri-t-butoxyaluminum, dimethoxycalcium, diethoxycalcium, di-i-propoxycalcium, di-n-butoxycalcium, triethoxyiron, Tetramethoxygermanium, tetraethoxygermanium, tetra-i-propoxygermanium, tetra-n-butoxygermanium, tetra-t-butoxygermanium, tetramethoxyhafnium, te Laethoxy hafnium, tetra-i-propoxy hafnium, tetra-n-butoxy hafnium, tetra-t-butoxy hafnium, trimethoxy indium, triethoxy indium, tri-i-propoxy indium, tri-n-butoxy indium, tri-t -Butoxy indium, pentamethoxy tantalum, pentaethoxy tantalum, penta-i-propoxy tantalum, penta-t-butoxy tantalum, penta-n-butoxy tantalum, tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra- Examples thereof include n-butoxy titanium, tetra-t-butoxy titanium, tetramethoxy tin, tetraethoxy tin, tetra-i-propoxy tin, tetra-n-butoxy tin, and tetra-t-butoxy tin.

  In the present invention, in order to form a transparent and uniform film, the organic solvent is miscible with a small amount of water, and the polycondensation material of the organic silane, the metal alkoxide and the additive can be dissolved, and the precursor solution It is desirable that it is volatilized quickly when it is applied onto the substrate. That is, in the present invention, it is preferable to prepare the precursor solution using an organic solvent having a vapor pressure higher than that of water, for example, methanol, ethanol, tetrahydrofuran or the like.

  In addition, the film thickness can be controlled in the range of 10 to 10000 nm by adjusting the concentration of the organic silane, metal alkoxide, and additive. This is because when a certain amount of the precursor solution is dropped on the surface of the base material and the concentration of the organic silane, metal alkoxide and additive, which are solid components contained in the precursor solution, is higher when the film is formed due to volatilization of the solvent, the more This is because the solids are deposited on the substrate surface.

  In the present invention, it is desirable to use a catalyst in order to promote hydrolysis of reactive functional groups of organosilane and metal alkoxide, that is, generation of M-OH group (where M is a metal element), Since it is desirable to stabilize the polycondensation material of the organic silane, metal alkoxide, and additive by controlling the pH in the precursor solution with the catalyst, for example, when using an alkoxysilyl group, pH 1 It is preferable to use an acid such as hydrochloric acid which can be controlled to 3.

  Further, the amount of water to be added is such that all the reactive functional groups contained in the precursor solution are hydrolyzed to form M-OH groups (where M is a metal element), so that the number of water is equal to or greater than the number of functional groups. Is desirable. Even if the amount of water is less than the number of functional groups described above, a film can be formed, but because hydrolysis becomes insufficient, unhydrolyzed organic silane and metal alkoxide are volatilized during the treatment, and the yield increases. Since there is a problem that it falls, it is not preferable.

  In the precursor solution during the hydrolysis / condensation polymerization in the present invention, the hydrolyzed organosilane and a part of the metal alkoxide are randomly condensed. This is because the metal alkoxide after hydrolysis and the organic silane after hydrolysis are alternately polycondensed so that the distance between the organic groups derived from the organosilane is increased. That is, the metal alkoxide serves as a “binder” to separate the organic groups of the organosilane. For this reason, the mobility of the organosilane-derived substance on the film surface is improved, and a solid surface with small hysteresis can be obtained.

  Therefore, in the present invention, the distance between the organic silanes can be arbitrarily controlled by changing the amount of the metal alkoxide added to the organosilane, and the mobility of the functional group derived from the organosilane on the film surface can be adjusted. As a result, the contact angle hysteresis is reduced, so that the droplet removing ability is improved.

  In the present invention, the film formation method is not particularly limited as long as it promotes the volatilization of the solvent. For example, the spin coating method, the dip coating method, the roller coating method, the bar coating method, the ink jet coating method, the gravure coating method, A spray method is a suitable example.

  Moreover, as a base material which can be used in the present invention, for example, an appropriate material such as a metal, a metal oxide film, an alloy, a semiconductor, a polymer, ceramics, glass, a resin, wood, paper, and fiber can be arbitrarily used. it can. Specific examples of the substrate include, for example, copper, brass, silicon, various polymers (polycarbonate, acrylic, PET, polyethylene, polypropylene), glass, silicone, hinoki, ribbon and the like.

  As the shape of these base materials, a base material having an arbitrary shape such as a plate shape, an uneven shape, a powder shape, a tube shape, a porous shape, or a fiber shape can be used. In particular, no pretreatment of the substrate is required. Furthermore, in order to obtain strong adhesion, it is also effective to activate the surface by irradiating the substrate with plasma, ultraviolet rays, electron beams or the like.

  In the present invention, depending on the type of organosilane, a layered structure having an interlayer of 1 to 10 nm may be formed. This is because silanol produced after hydrolysis of organosilane shows hydrophilicity, while organic groups show hydrophobicity, and therefore, a polycondensation product of organosilane and inorganic alkoxide shakes in an amphiphilic manner during film formation. This is to self-assemble using the hydrophobic interaction of the organic part as a driving force. For example, a C4-C18 alkyl alkoxysilane is illustrated as a suitable organosilane that forms a layered structure. In addition, the hydrophobic functional groups of organic silanes and hydrophobic additives (such as rust preventives, UV absorbers / light stabilizers, fungicides / antibacterial agents, and bioadhesive agents) are hydrophobic during this self-assembly process. Aggregates due to sexual interaction and is fixed in the interlayer.

  As described above, as the organic silane, in addition to the alkylalkoxysilane, an organic silane having an inactive (hydrophobic) functional group can be used. In the present invention, as the organic silane, for example, an organic silane having an inactive (hydrophobic) functional group such as a perfluoroalkyl group or a phenyl group can also be used.

The present invention is a transparent hybrid film formed on a solid surface of a substrate, and the raw organic silane and metal alkoxide are cohydrolyzed / condensed in a solution containing an organic solvent, water, additives, and optionally a catalyst. The film is obtained by applying a precursor solution in which the distance between the organosilanes is controlled, and the dynamic wettability of the substrate surface, that is, the dynamic contact angle [advanced contact angle (θ _A ) and receding contact The transparent hybrid characterized in that the contact angle hysteresis (θ _A −θ _R ) when measuring the angle (θ _R )] is smaller than that of the surface treated with organosilane alone. Various liquid droplets (surface tension of 18 to 73 dyn / cm) by forming an organic-inorganic transparent hybrid film that is excellent in adhesion and mobility of functional groups derived from organosilane on the film surface. And this The difference (hysteresis) between the advancing contact angle and receding contact angle of a mixed liquid in which at least two of these liquids are mixed is smaller than that of the surface treated with organosilane alone. The present invention provides a novel transparent hybrid film that can be realized.

The present invention has the following effects.
(1) It is possible to introduce high concentration (up to about 50 wt.%) Additives such as rust preventives, UV absorbers / light stabilizers, fungicides / antibacterial agents, biological adhesion prevention, etc. between the layers of the film. To provide a new surface modification technology that can achieve long-lasting effects such as water repellency / oil repellency, antifouling properties, corrosion resistance, weather resistance, antifungal properties, and anti-bioadhesion properties. Can do.
(2) Since the additive is fixed between the layers, it is a new surface modification that can prevent sublimation and bleed-out, unlike conventional coatings and polymer materials that are simply mixed or kneaded. Can provide quality technology.
(3) When the additive is an organic compound, crystallization and aggregation are suppressed by completely dispersing the additive inside the hybrid film. Therefore, suppression of concentration quenching, suppression of maximum absorption wavelength shift, solubility It is possible to provide a new surface modification technology that can realize improvement.
(4) Since the additive has the ability to collect at the crack site even if a crack occurs in the coating, it is possible to provide a new surface modification technique that can suppress the progress of corrosion.
(5) Since organic silanes having an inert functional group, such as long-chain alkyltriethoxysilane, perfluoroalkyltriethoxysilane, etc. are used, the corrosion / deterioration inhibitor is hydrophobic when forming a layered structure. Providing new surface modification technology that can immobilize between layers by interaction and at the same time provide water repellency / oil repellency, droplet removal ability, fingerprint resistance, antifouling, etc. to the surface of the transparent hybrid film can do.
(6) Since an organic silane having an active functional group, for example, vinyltriethoxysilane, 2-hydroxy-4- (3-triethoxysilylpropoxy) -diphenylketone, or the like is used, when forming a layered structure, It is possible to provide a new surface modification technique that can immobilize the additive by hydrogen bonding or covalent bonding and at the same time impart biocompatibility and chemical reactivity to the surface of the transparent hybrid film.
(7) Dynamic wettability of the substrate surface, that is, contact angle hysteresis (θ _A −θ _R ) when dynamic contact angles [advanced contact angle (θ _A ) and receding contact angle (θ _R )] are measured. However, it is possible to provide a surface modification technique that makes it possible to obtain a surface with extremely small hysteresis, which is smaller than the surface treated with organosilane alone.
(8) A transparent hybrid film having extremely small hysteresis with respect to a liquid having a surface tension of 18 to 73 dyn / cm, in particular, closely contacting the base material without selecting the base material and without subjecting the base material to pretreatment. It is possible to provide a surface treatment technique that can be formed with good properties.
(9) The film thickness can be arbitrarily controlled (10-10000 nm) by the concentration of the organic silane and the metal alkoxide with respect to the organic solvent.
(10) Since the hybrid film has high transparency, the surface treatment can be performed without impairing the design properties while maintaining the appearance of the surface of the substrate to be treated.
(11) Since the prepared precursor solution is stable, it can be stored for a long time (about one month) after preparation.
(12) Since it can be cured at room temperature without any heat treatment, it can be formed on a polymer, paper, fiber, wood, or the like having a low heat-resistant temperature.
(13) By adjusting the organosilane content, the hardness, heat resistance, and flexibility of the film can be adjusted arbitrarily, so that even if bent into a sheet-like polymer, metal film, paper, Film formation that does not cause peeling is possible.
(14) Excellent water repellency / oil repellency, droplet removal ability, antifouling property, antifouling property, corrosion resistance, weather resistance, antifungal property, and anti-bioadhesion property of the transparent hybrid film, for example, metal / Prevention of corrosion of wood materials, prevention of fingerprint adhesion such as touch panel display, provision of antibacterial properties to daily life goods and food packaging materials, provision of weather resistance to polymer films, prevention of deterioration / yellowing of paper and fibers, and waterproofing, In applications such as anti-fungal / anti-bacterial treatment around tiles and water, it is possible to provide new surface modification technology that can sustain these functions over a long period of time.

FIG. 1 shows the appearance of each sample after [Corrosion Test 3] according to Example 1 and Comparative Examples 2-3.

  Next, the present invention will be specifically described based on examples. However, the following examples show preferred examples of the present invention, and the present invention is not limited to the examples. Absent.

The details of the corrosion test performed are shown below.
[Corrosion test 1]
The test piece was immersed in 0.05 M NaCl aqueous solution at room temperature for 24 hours.
[Corrosion test 2]
The test piece was immersed in a sealed container containing pure water at 100 ° C. for 240 hours.
[Corrosion test 3]
Specimens were exposed to 5 wt% salt spray.
[Corrosion test 4]
A mesh-shaped cut (10 pieces each in length and width) was put into the test piece, and immersed in a 0.05 M NaCl aqueous solution at room temperature for 12 hours.

Tetramethoxysilane (TMOS) and decyltriethoxysilane (DTES) were mixed at a ratio of TMOS / DTES (molar ratio) = 4, mixed with ethanol and hydrochloric acid, and then stirred at room temperature for a predetermined time. Then, 3.1, 6.3, 12.5, 25, 50 wt.% With respect to the total weight of the solid components of TMOS and DTES (TMOS: SiO ₂ , DTES: C ₁₀ H ₂₃ SiO _1.5 ). % Tolyltriazole (TTA) was added, and the mixture was further stirred at room temperature for a predetermined time. The obtained precursor solution was spin-coated on a copper plate and a glass plate and allowed to stand at room temperature for one day.

In Table 1, 3.1, 6.3, 12.5, 25, 50 wt. % TTA of sample containing% TTA, transparency, advancing contact angle (θ _A ), receding contact angle (θ _R ), hysteresis (θ _A −θ _R ) for water and n-hexadecane ) Value.

  Table 1 shows 3.1, 6.3, 12.5, 25, 50 wt. The result of the [corrosion test 1] of the sample (copper plate) containing% TTA is shown.

  Table 1 shows 3.1, 6.3 wt. The result of the [corrosion test 2] of the sample (copper plate) containing% TTA is shown.

  Table 1 shows that 12.5 wt. The result of [corrosion test 3] of the sample (copper plate) containing% TTA is shown.

  FIG. 1A shows a 12.5 wt. The result of [corrosion test 3] of the sample (copper plate) containing% TTA is shown.

Tetramethoxysilane (TMOS) and octadecyltrimethoxysilane (ODMS) were mixed at a ratio of TMOS / ODMS (molar ratio) = 4, mixed with ethanol and hydrochloric acid, and then stirred at room temperature for a predetermined time. Thereafter, the total weight of TMOS and ODMS solid components (TMOS: SiO ₂ , DTES: C ₁₈ H ₃₇ SiO _1.5 ) was 12.5 wt. % Tolyltriazole (TTA), or 12.5 wt. % Benzotriazole (BTA) was added to the precursor solution and further stirred at room temperature for a predetermined time. The obtained precursor solution was dip-coated on a copper plate and a glass plate and allowed to stand at room temperature for one day.

Table 1 shows the interplanar spacing obtained from the XRD pattern, transparency, water, and n of a sample containing 12.5 wt% TTA or 12.5 wt% BTA formed on a glass plate according to Example 2. -Advancing contact angle (θ _A ), receding contact angle (θ _R ), and hysteresis (θ _A -θ _R ) values for hexadecane are shown.

  Table 1 shows the results of [Corrosion Test 1] of the sample (copper plate) according to Example 2.

  Table 1 shows the results of [Corrosion Test 4] of the sample (copper plate) according to Example 2.

[Comparative Example 1]
Various corrosion tests were performed using untreated copper plates.

  Table 2 shows the results of [Corrosion Test 1] related to Comparative Example 1.

  Table 2 shows the results of [Corrosion Test 2] related to Comparative Example 1.

  Table 2 shows the results of [Corrosion Test 3] related to Comparative Example 1.

  Table 2 shows the results of [Corrosion Test 4] related to Comparative Example 1.

[Comparative Example 2]
Tetramethoxysilane (TMOS) was mixed with ethanol and hydrochloric acid and then stirred at room temperature for a predetermined time. Thereafter, 0, 3.1, 6.3, 12.5, 25, 50 wt.% With respect to the total weight of the solid component (SiO ₂ ) of TMOS. % Tolyltriazole (TTA), or 12.5 wt. % Benzotriazole (BTA) was added and further added for a predetermined time. The obtained precursor solution was spin-coated on a copper plate and a glass plate and allowed to stand at room temperature for one day.

Table 2 shows 0, 3.1, 6.3, 12.5, 25, 50 wt. % TTA of sample containing% TTA, transparency, advancing contact angle (θ _A ), receding contact angle (θ _R ), hysteresis (θ _A −θ _R ) for water and n-hexadecane ) Value.

  Table 2 shows 0, 3.1, 6.3, 12.5, 25, 50 wt. The result of the [corrosion test 1] of the sample (copper plate) containing% TTA is shown.

  Table 2 shows 3.1, 6.3 wt. The result of the [corrosion test 2] of the sample (copper plate) containing% TTA is shown.

  Table 2 shows that 12.5 wt. The result of [corrosion test 3] of the sample (copper plate) containing% TTA is shown.

  In FIG. 1B, 12.5 wt. The result of [corrosion test 3] of the sample (copper plate) containing% TTA is shown.

  Table 2 shows 0, 12.5 wt. % TTA and 12.5 wt. The result of the [corrosion test 4] of the sample (copper plate) containing% BTA is shown.

[Comparative Example 3]
Tetramethoxysilane (TMOS) and decyltriethoxysilane (DTES) were mixed at a ratio of TMOS / DTES (molar ratio) = 4, mixed with ethanol and hydrochloric acid, and stirred at room temperature for a predetermined time. The obtained precursor solution was spin-coated on a copper plate and a glass plate and allowed to stand at room temperature for one day.

Table 2 shows the surface contact distance, transparency, water, and advancing contact angle (θ _A ) and receding contact angle obtained from the XRD pattern of the sample formed on the glass plate according to Comparative Example 3. The values of (θ _R ) and hysteresis (θ _A −θ _R ) are shown.

  Table 2 shows the results of [Corrosion Test 1] of the sample (copper plate) according to Comparative Example 3.

  Table 2 shows the result of [Corrosion Test 2] of the sample (copper plate) according to Comparative Example 3.

  Table 2 shows the result of [Corrosion Test 3] of the sample (copper plate) according to Comparative Example 3.

  In FIG. 1C, 12.5 wt. The result of [corrosion test 3] of the sample (copper plate) containing% TTA is shown.

[Comparative Example 4]
Tetramethoxysilane (TMOS) and octadecyltrimethoxysilane (ODMS) were mixed at a ratio of TMOS / ODMS (molar ratio) = 4, mixed with ethanol and hydrochloric acid, and then stirred at room temperature for a predetermined time. Was dip coated on a copper plate and a glass plate and allowed to stand at room temperature for one day.

In FIG. 1, the advancing contact angle (θ _A ), receding contact angle (θ _R ), hysteresis (θ _A −) for the interplanar spacing, transparency, water and n-hexadecane obtained from the XRD pattern according to Comparative Example 4 The value of θ _R ) is shown.

  Table 2 shows the result of [Corrosion Test 1] of the sample (copper plate) according to Comparative Example 4.

  Table 2 shows the results of [Corrosion Test 4] of the sample (copper plate) according to Comparative Example 4.

  When the surface of the substrate sample produced in the above two examples and four comparative examples is relatively evaluated, even when an additive is added, it has a layered structure with excellent transparency. It became clear that a film was obtained. Further, it was found that an additive having a high concentration (up to 50 wt.%) Can be contained between the layers.

  From the results of Comparative Example 2, even in the case of a silica film, when the concentration of the additive is low, the additive can be contained in the film. However, as the concentration increases (12.5 wt.% Or more), the transparency of the film is increased. As a result, the additive was agglomerated and the additives were agglomerated and dispersed unevenly inside the film. In addition, from the results of Examples 1 and 2 and Comparative Examples 3 and 4, it is clear that any of the hybrid films exhibits excellent water repellency / oil repellency. It turns out that it does not affect sex.

  From the results of Examples 1 and 2, it was found that the hybrid film containing the additive exhibits excellent anticorrosive ability. From [Corrosion Tests 1 to 3] in Comparative Example 1, it can be seen that copper alone corrodes easily under the experimental conditions. Further, from [Corrosion Tests 1 to 3] of Comparative Examples 3 to 4, it was confirmed that the progress of corrosion could be suppressed to some extent when the hybrid film containing no additive was coated, but the effect was insufficient. . In particular, in the neutral salt spray test ([corrosion test 3]), considering the result of the decrease in the ability to inhibit corrosion, corrosion progressed because chlorine ions reached the copper surface by sewing a slight gap on the film surface. it is conceivable that.

  Even when the silica film containing the additive (Comparative Example 2) was coated, it was found that the corrosion of copper could be suppressed to some extent, but the inhibitory effect was remarkably lower than the hybrid single film (Comparative Examples 3 to 4) described above. This is because the aggregates of the additives are dispersed non-uniformly inside the silica, and as the additive dissolves, a space like a “hole” is formed where the additive originally existed. It is thought that this is because water and chlorine ions can easily access the copper surface.

  In addition, since the silica film surface is hydrophilic, it is considered that one of the factors that promoted corrosion is that water droplets are easily attached. On the other hand, the hybrid film containing the additive is considered to have realized an excellent anticorrosive ability due to the excellent droplet removing effect on the surface and the dispersing / confining effect of the additive due to the layered structure.

  When [Corrosion test 4] of Example 2 and Comparative Example 2 were compared, it was found that only the hybrid film exhibited excellent self-healing ability even though the additive concentration was the same. In the case of a hybrid film, the encapsulated additive is uniformly dispersed at the molecular level and is fixed between the layers, so that with the occurrence of cracks, the additive is quickly released and reaches the copper surface. It is considered that the progress of corrosion was remarkably suppressed. On the other hand, in the case of a silica film, since the additive is present in a non-uniformly aggregated state in the silica film, the movement of the additive to the copper surface after the occurrence of cracks is less It is thought that corrosion progressed because it was later than that of chloride ion.

  As described above in detail, the present invention relates to a transparent hybrid film and a method for producing the same. According to the present invention, an organic silane and a metal alkoxide are mixed with an organic solvent, water, an additive (rust inhibitor, ultraviolet absorber / Light stabilizers, fungicides / antibacterial agents, biofouling inhibitors, etc.), and precursor solutions co-hydrolyzed and polycondensed in a solution containing a catalyst if necessary, such as metals, metal oxide films, alloys, semiconductors, By applying to a solid surface such as polymer, wood, paper, fiber, etc., a transparent film with good adhesion is formed at the same time as the volatilization of the solvent. 1) Immobilization of a high concentration of additive between layers 2 ) By controlling the mobility of the functional group derived from organosilane on the film surface, excellent water repellency / oil repellency, droplet removal ability, and fingerprint resistance are maintained on the substrate surface while maintaining the characteristics of the substrate. Adhesion, antifouling, corrosion resistance, weather resistance, antifungal, antibacterial It is possible to provide a transparent hybrid film and a manufacturing method thereof which allows to long lasting biofouling prevention. The present invention, for example, prevents corrosion of metal / wood materials, prevents fingerprint adhesion to touch panel displays, imparts antibacterial properties to daily life products and food packaging materials, imparts weather resistance to polymer films, and degrades paper and fibers. / New technologies and products related to new surface modification technologies that are particularly effective in sustaining these functions over a long period of time in applications such as prevention of yellowing, waterproofing, and anti-fungal / antibacterial treatment around tiles and water. It is useful as a thing to provide.

Claims (9)

A transparent hybrid film made of an organic silane and a metal alkoxide formed on the surface of a substrate,
Addition of at least one kind selected from a rust inhibitor, an ultraviolet absorber / light stabilizer, an antifungal agent / antibacterial agent, and a bioadhesive agent, having a layered structure with a repetition period of 1 to 10 nm The agent is immobilized,
The contact angle hysteresis (θ _A −θ _R ) when measuring the dynamic contact angle [advanced contact angle (θ _A ) and receding contact angle (θ _R )] of the substrate surface on which the film is formed is organosilane alone. A transparent hybrid film characterized by having a characteristic that is smaller than the surface of the substrate formed of Said additive, based on the total weight of the film, the transparent hybrid film of placing serial to claim 1 containing. 3 to 50 wt%. The transparent hybrid film according to claim 1 or 2, wherein the organic silane is an alkylalkoxysilane having 4 to 18 carbon atoms. Organic silane and metal alkoxide, at least one selected from organic solvents, rust preventives as additives, UV absorbers / light stabilizers , fungicides / antibacterial agents, and bioadhesive agents , and optionally the precursor solution was cohydrolytic polycondensation in a solution containing a catalyst, was added dropwise to the surface of the substrate, Atsushi Muro, solvent is evaporated under atmospheric pressure, transparency hybrid film you characterized in that cross-linking the film Manufacturing method. The organosilane is represented by the formula (A)
R ¹ -Si- (OR ² ) ₃ ... (A)
(However, in the formula, R ¹ Is an alkyl group having 4 to 18 carbon atoms, R ² Is represented by an alkoxy group having 1 or 2 carbon atoms). The metal alkoxide has the formula (C)
Si (R ¹ ) ₄ .... (C)
(However, in the formula, R ¹ Is an alkoxy group having 1 or 2 carbon atoms)
The method for producing a transparent hybrid film according to claim 4 or 5, wherein As the organic solvent, an organic solvent that is miscible with water used for hydrolysis, dissolves the organic silane, metal alkoxide, and additives after hydrolysis and degeneracy, and has a vapor pressure larger than that of water is used. The manufacturing method of the transparent hybrid membrane | film | coat of any one of Claims 4-6 characterized by the above-mentioned. Said catalyst, according to claim 4-7, characterized in that it has an effect of promoting the hydrolysis of the group represented by R ¹ in the formula group and the formula represented by R ² in (A) (C) The manufacturing method of the transparent hybrid membrane | film | coat of any one . A solid surface coated with the transparent hybrid film according to any one of claims 1 to 3 , wherein the surface is water-repellent / oil-repellent, droplet removing ability, fingerprint resistance, and antifouling. A solid surface characterized by exhibiting properties, corrosion resistance, weather resistance, antifungal properties, antibacterial properties, and / or biofouling prevention ability.