JP7101469B2 - Substrate protection solution, substrate protection method, and substrate - Google Patents

Description

In the present invention, a substrate protective liquid that forms a substrate protective film that exerts an antifouling function by applying a combination of positive and negative charges to the surface of various substrates, and a substrate that forms a substrate protective film with the substrate protective liquid. It relates to a protection method and a substrate on which a substrate protective film is formed by the substrate protective liquid.

Conventionally, as a technique for preventing or reducing discoloration or discoloration of the substrate over time and at the same time preventing or reducing the adhesion of contaminants, as shown in FIG. 3, the surface of the substrate a is negatively charged with a positive charge substance b. It is known that a charge holding layer d in which a charge substance c is arranged is provided, and the electrostatic repulsive force of the charge holding layer d prevents the adhesion of contaminants.

In this technique, a coating layer e having hydrophilicity, hydrophobicity, water repellency, etc. is formed on the surface of the charge holding layer d provided on the surface of the substrate a (for example, Patent Document 1). reference).

Patent No. 4926176

However, if the coating layer e is provided on the surface of the charge holding layer d provided on the surface of the substrate a as in the conventional case, the electrostatic repulsive force of the charge holding layer d may not be fully utilized. I am concerned.

Of these, for hydrophilicity, the charge holding layer d alone can be provided with hydrophilicity without providing the coating layer e, but for water repellency and oil repellency, the coating layer e must be provided. If the surface of the charge holding layer d is covered with the coating layer e, there is a concern that the antifouling function may be deteriorated due to the decrease in the electrostatic repulsive force. Therefore, there is a concern that the function of preventing the adhesion of contaminants in an environment where water repellency and oil repellency are required is not sufficiently exhibited.

The present invention has been made in view of the above circumstances, and is capable of exhibiting an excellent antifouling function due to electrostatic repulsion even in an environment where water repellency and oil repellency are required. It is an object of the present invention to provide a liquid, a method for protecting a substrate with the substrate protective liquid, and a substrate on which a protective film is formed with the substrate protective liquid.

The substrate protective liquid of the present invention for solving the above problems is a substrate protective liquid that forms a protective film on the surface of the substrate to reduce the adhesion of substances, and uses a catalyst. The first composition containing a water-repellent / oil-repellent substance as a stabilized silane compound modified into silicon by decomposing and hydrolyzing a silane compound having a water-repellent and / or oil-repellent functional group. A second composition containing at least a positively charged substance among a substance, a positively charged substance having a positive charge performance, and a negatively charged substance having a negative charge performance is provided, and these are the first composition and the second. By using it in combination with the composition, the surface of the substrate is imparted with water repellency and / or oil repellency, and the voltage band is in the range of −50 V to 50 V.

In the substrate protective liquid, the second composition may contain a positively charged substance and a negatively charged substance.

In the above-mentioned substrate protective liquid, the voltage band on the substrate surface of the protective film formed on the surface of the substrate by using the first composition and the second composition in a mixed manner is negatively charged. May be good.

In the above-mentioned substrate protective liquid, the voltage band on the substrate surface of the protective film formed on the surface of the substrate by using the first composition and the second composition in a mixed manner has a positive charge. May be good.

The method for protecting the substrate of the present invention for solving the above-mentioned problems is a state in which a silane compound having a water-repellent and / or oil-repellent functional group is modified to silicon by shrinking and hydrolyzing using a catalyst. A substrate protective solution in which a water-repellent / oil-repellent substance as a stabilized silane compound and at least a positively charged substance among a positively charged substance having a positive charge performance and a negatively charged substance having a negative charge performance are dispersed. It is applied to the surface of a substrate to form a protective film having water repellency and / or oil repellency and having a charge in the range of −50 V to 50 V on the surface of the substrate.

The method for protecting the substrate is a dispersion ratio of a water- repellent / oil-repellent substance and a positively charged substance having a positive charge performance, or a water-repellent / oil-repellent substance, a positively charged substance having a positive charge performance, and a negative charge. By adjusting the dispersion ratio of the negatively charged substance having the performance, a water-repellent and / or oil-repellent protective film may be formed on the surface of the substrate at a band voltage in the range of −50 V to 50 V. ..

The method for protecting the substrate is a dispersion ratio of a water- repellent / oil-repellent substance and a positively charged substance having a positive charge performance, or a water-repellent / oil-repellent substance, a positively charged substance having a positive charge performance, and a negative charge. By adjusting the dispersion ratio of the negatively charged substance having the performance, a water-repellent protective film may be formed on the surface of the substrate with a negatively charged voltage.

The method for protecting the substrate is a dispersion ratio of a water- repellent / oil-repellent substance and a positively charged substance having a positive charge performance, or a water-repellent / oil-repellent substance, a positively charged substance having a positive charge performance, and a negative charge. By adjusting the dispersion ratio of the negatively charged substance having the performance, a water-repellent and / or oil-repellent protective film may be formed on the surface of the substrate at a positively charged voltage.

The substrate of the present invention for solving the above-mentioned problems is a substrate formed so as to form a protective film on at least a part of the surface, and the protective film is water-repellent and / or oil-repellent by using a catalyst. A state in which a water-repellent / oil-repellent substance as a stabilized silane compound modified into silicon by hydrolyzing and hydrolyzing a silane compound having a functional group and a positively charged substance having positive charge performance are dispersed. Water / oil repellency as a stabilized silane compound modified to silicon by hydrolyzing and hydrolyzing a silane compound having a water repellent and / or oil repellent functional group using a catalyst. A substance, a positively charged substance having a positive charge performance, and a negatively charged substance having a negative charge performance are dispersed in a dispersed state, and are water repellent and / or repellent at a band voltage in the range of -50V to 50V. It is made to have oiliness.

The substrate for solving the above-mentioned problems is a substrate formed so as to form a protective film on at least a part of the surface, and the protective film is a water-repellent / oil-repellent substance and a positively charged substance having positive charge performance. Are arranged in a dispersed state, or in a state where a water- repellent / oil-repellent substance, a positively charged substance having a positive charge performance, and a negatively charged substance having a negative charge performance are dispersed, and a band of negative charges. It is made to have water repellency and / or oil repellency by electric charge.

The substrate of the present invention for solving the above problems is a substrate formed so as to form a protective film on at least a part of the surface, and the protective film has a water-repellent / oil-repellent substance and positive charge performance. It is arranged in a state in which a positively charged substance is dispersed, or a state in which a water- repellent / oil-repellent substance, a positively charged substance having a positive charge performance, and a negatively charged substance having a negative charge performance are dispersed, and is positive . It is made to have water repellency and / or oil repellency by the electric charge band voltage.

As described above, according to the present invention, a stabilized silane in a state of being modified to silicon by decomposing and hydrolyzing a silane compound having a water-repellent and / or oil-repellent functional group using a catalyst. The water-repellent / oil-repellent substance as a compound protects the positively charged substance having positive charge performance and the negatively charged substance having negative charge performance together with at least the positively charged substance without covering the charged protective layer. Since the protective layer is dispersed in the layer, the protective layer formed by the substrate protective liquid does not reduce the electrostatic repulsive force generated in the protective layer, and has excellent antifouling function, water repellent function, and / or oil repellency. It will be able to exert its function.

It is an image diagram which shows an example of the protective film of the substrate formed by the substrate protective liquid which concerns on this invention. It is an image diagram which shows another example of the protective film of the substrate formed by the substrate protective liquid which concerns on this invention. It is an image diagram which shows an example of the protective film of the conventional substrate.

Hereinafter, embodiments according to the present invention will be described with reference to the drawings.

1 and 2 show a state in which the protective film 2 is formed on the substrate 1 by the substrate protective liquid according to the present invention.

The substrate protective liquid is a substrate protective liquid that forms a protective film 2 on the surface of the substrate 1 to reduce the adhesion of substances, and is water-repellent and / or oil-repellent by using a catalyst. The first composition containing the water-repellent / oil-repellent substance 21 as a stabilized silane compound in a state of being modified to silicon by shrinking and hydrolyzing the silane compound having the functional group of the above , and positive charge performance. A second composition containing at least the positively charged substance 22 among the positively charged substance 22 having the positive charge substance 22 and the negatively charged substance 23 having the negative charge performance is provided, and these are used as the first composition and the second composition. By using the mixture in a mixed state, the water-repellent / oil-repellent substance 21 and the positively charged substance 22 are dispersed on the surface of the substrate 1 (see FIG. 2), or the water-repellent / oil-repellent substance 21 and the positive substance 21 are positively dispersed. A single protective film 2 arranged in a state in which the charged substance 22 and the negative charged substance 23 are dispersed (see FIG. 1) and has water repellency and / or oil repellency at a predetermined band voltage. It is what forms.

In addition, in FIGS. 1 and 2, the water- repellent / oil-repellent substance 21 is regularly provided in the gap between the positively charged substance 22 (FIG. 2) or the gap between the positively charged substance 22 and the negatively charged substance 23. However, it is only an image diagram, and in reality, the positively charged substance 22 and the negatively charged substance 23 are formed to have varying sizes of about 10 to 80 nm. Further, the positively charged substance 22 and the negatively charged substance 23 are in the form of a polycondensate of molecules, an aggregate of molecules, an amorphous substance, a crystal, or the like, depending on the substance. On the other hand, the water- repellent / oil-repellent substance 21 is formed to have a size of 10 nm or less, or 1 nm or less when it is small, and is a functional group on the surface of the positively charged substance 22 or the positively charged substance 22 and the negatively charged substance 23. It reacts with the functional groups on the surface and is in a state of being modified on the surface of these substances. Therefore, the protective film 2 is not limited to the case where the water / oil repellent substance 21 is regularly provided, but includes the case where the surface is modified as described above, and the size of each substance is also as described above. Including cases with variations.

The first composition is water-repellent as a stabilized silane compound modified to silicon by polypolymerization and hydrolysis of a silane compound having a water-repellent and / or oil-repellent functional group using a catalyst. / Consists of an oil-repellent substance 21.

As the water-repellent functional group used in the water- repellent / oil-repellent substance 21, the contact angle between the protective film 2 formed by the substrate protective liquid and water can be 80 degrees or more, more preferably 90 degrees or more. Things are used. For example, hydrocarbon-based functional groups can be mentioned.

The hydrocarbon-based functional groups include an alkyl group, an alkylene group, a phenyl group, a benzyl group, a phenethyl group , a naphthyl group , a thienyl group, a pyrrolyl group, a cyclohexyl group, a cyclohexenyl group, a cyclopentyl group, a cyclopentenyl group, and a methyl group . Examples thereof include a toxiethyl group , a vinyl group, an acryloxyethyl group, a methacryloxyethyl group, a glycidoxypropyl group, an acetoxy group and the like.

As the oil-repellent functional group used in the water- repellent / oil-repellent substance 21, the contact angle between the protective film 2 formed by the substrate protective liquid and the oil can be 50 degrees or more, more preferably 60 degrees or more. Things are used. For example, a fluoride-based functional group can be mentioned.

Examples of the fluoride-based functional group include a fluoroalkyl group, a fluoroalkyl group, a fluoroalkylene group, a fluorophenyl group, a fluorobenzyl group, a fluorophenethyl group, a fluoronaphthyl group, a fluorothienyl group, a fluoropyrrrolyl group, and a fluorocyclohexyl group. Fluorocyclohexenyl group, fluorocyclopentyl group, fluorocyclopentenyl group, fluoromethoxyethyl group , fluorovinyl group, or fluoroacetoxy group can be mentioned.

The functional group is, for example, a water- repellent / oil-repellent substance capable of forming a film by forming a stabilized silane compound in a state of being modified to silicon by polycondensation and hydrolysis of the silane compound having the functional group. It can be 21.

Examples of the catalyst used for the above-mentioned contraction polymerization and hydrolysis include acids (hydrogen, nitrate, sulfuric acid, acetic acid, inorganic acids, organic acids, etc.), alkalis (ammonia, amines, etc.), alcohols (ethylene glycol, amino alcohol, etc.). Etc.), β-diketones (acetylacetone, etc.), amines (alkylamines, etc.), amides (formamides, etc.) and the like can be used.

The second composition is composed of at least a positively charged substance 22 among a positively charged substance 22 having a positive charge performance and a negatively charged substance 23 having a negative charge performance.

Positively charged substances 22 having positive charge performance include cations, positively charged conductors, positively charged dielectrics, positively charged conductors and dielectric composites, positively charged conductors and semiconductors. One or more selected from the group consisting of the complex of the above can be used.

The cation is not particularly limited, but is an ion of an alkali metal such as sodium and potassium; an ion of an alkaline earth metal such as calcium; aluminum, tin, cesium, indium, cerium, selenium, chromium and cobalt. , Nickel, antimony, iron, copper, manganese, tungsten, zirconium, zinc and other metal element ions are preferable, and copper ion is particularly preferable. Further, organic molecules having a cationic group such as methyl violet, bismarck brown, methylene blue and malachite green can also be used. The valence of the ion is not particularly limited, and for example, a cation having a valence of 1 to 4 can be used.

It is also possible to use a metal salt as a source of the metal ion as the above-mentioned cation. Specifically, aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antimony chloride, 1st and 2nd iron chloride, cesium chloride, indium trichloride, 1st cerium chloride, 4 Examples thereof include various metal salts such as selenium chloride, cupric chloride, manganese chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, zirconium oxychloride, zinc chloride and barium carbonate. Further, metal hydroxides such as aluminum hydroxide, iron hydroxide, chromium hydroxide and indium hydroxide, hydroxides such as silicate tungsten acid, and oxides such as oil and fat oxides can also be used.

The conductor used in the present invention is preferably a metal from the viewpoint of durability, and is a metal such as aluminum, tin, indium, cerium, selenium, chromium, nickel, antimony, iron, silver, copper, manganese, platinum, tungsten and zinc. Can be mentioned. Oxides, complexes or alloys of these metals can also be used. The shape of the conductor is not particularly limited, and any shape such as a particle shape, a flaky shape, and a fibrous shape can be taken.

As the above-mentioned conductor, metal salts of some metals can also be used. Specifically, aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antimony chloride, 1st and 2nd iron chloride, silver nitrate, cesium chloride, indium trichloride, selenium tetrachloride. , Secondary copper chloride, manganese chloride, second platinum chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, ferric chloride, zinc chloride and various other metal salts can be exemplified. Further, hydroxides or oxides such as indium hydroxide and silica tungsten can also be used.

Further, as the above-mentioned conductors, polyaniline, polypyrrole, polythiophene, polythiophene vinylone, polyisothianaphene, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly-p-phenylene, polyphenylene sulfide, polymethoxyphenylene, polyphenylene sulfide, etc. Conductive polymers such as polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, and polyazulen can also be used.

Examples of semiconductors constituting a composite with a conductor for forming a positive charge include C, Si, Ge, Sn, GaAs, InP, GaN, ZeSe, PbSnTe, and the like, and are semiconductor oxide metals and opto-semiconductor metals. , Photo-semiconductor metal oxide can also be used. Preferably, in addition to titanium oxide (TiO ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₃ , WO ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO ₂ , etc., but when used as a semiconductor, the photocatalytic activity is inactivated with Na etc. Is preferable.

Examples of the dielectric constituting the composite with the conductor for forming a positive charge include barium titanate (PZT), which is a strong dielectric, so-called SBT, BLT, and the following PZT, PLZT- (Pb, La) (. Zr, Ti) O ₃ , SBT, SBTN-SrBi ₂ (Ta, Nb) ₂ O ₉ , BST- (Ba, Sr) TiO ₃ , LSCO- (La, Sr) CoO ₃ , BLT, BIT- (Bi, La) ) ₄ Ti ₃ O ₁₂ , BSO-Bi ₂ SiO ₅ and other composite metals can be used. Further, a silane compound and a silicone compound, which are organosilicon compounds, so-called organoknitted silica compounds can also be used.

The negatively charged substance 23 having a negative charge performance includes an anion, a conductor having a negative charge, a dielectric having a negative charge, a composite of a conductor and a dielectric having a negative charge, a conductor having a negative charge, and a semiconductor. One or more selected from the group consisting of a complex of the above, a substance having a photocatalytic function, can be used.

The anion is not particularly limited, but is a halide ion such as a fluoride ion, a chloride ion, and an iodide ion; an inorganic ion such as a hydroxide ion, a sulfate ion, a nitrate ion, and a carbonate ion. : Organic ions such as acetate ion can be mentioned. The valence of the ion is not particularly limited, and for example, 1 to 4 valent anions can be used.

Examples of the negatively charged conductor or dielectric include conductors or dielectrics in which a negative charge is generated other than the above-mentioned anions, and examples thereof include gold, silver, platinum, tin, nickel, cerium, and selenium. Metals such as; metal oxides and inorganic substances; elements such as stone ink, sulfur, selenium, tellurium; sulfides such as arsenic sulfide, antimony sulfide, mercury sulfide ; dyes such as konjo , indigo, aniline blue, eosin, naphthol yellow, etc. Colloid of. Among these, metals such as gold, silver, platinum, tin, nickel and cerium, and colloids of metal oxides are preferable, and tin colloids are more preferable. In addition to this, negative electrodes of batteries made of various conductors described later, dielectrics such as negatively charged halogens, fluororesins, vinyl chloride, polyethylene and polyester, and compounds and composites thereof can be mentioned. ..

The conductor having a negative charge used in the present invention is preferably a metal from the viewpoint of durability, and examples thereof include metals such as tin, cerium, selenium, silver, platinum, tungsten, and nickel. Also, oxides, complexes or alloys of these metals can be used. The shape of the conductor is not particularly limited, and can be any shape such as a particle shape, a flaky shape, and a fibrous shape.

As the above-mentioned conductor having a negative charge, a metal salt of some metals can also be used. Specific examples thereof include various metal salts such as 1st and 2nd tin chloride, silver nitrate, 1st cerium chloride, selenium tetrachloride, 2nd platinum chloride, 2nd gold chloride and nickel chloride, and indium hydroxide. , Hydroxides such as silicotoxy, or oxides and the like can also be used.

Further, as the above-mentioned conductor having a negative charge, a conductive polymer can also be used, for example, polyaniline, polypyrrole, polythiophene, polythiophene sulfide, polyisothianaften, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly. -P-Phenylene, polyphenylene viniron, polymethoxyphenylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, polyazulen and the like can be mentioned.

Examples of semiconductors constituting a composite with a conductor for forming a negative charge include C, Si, Ge, Sn, GaAs, InP, GaN, ZeSe, PbSnTe, and the like, and are semiconductor oxide metals and opto-semiconductor metals. , Photo-semiconductor metal oxide can also be used. Among these semiconductors, preferably, in addition to titanium oxide (TiO ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, Bathio ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₃ , WO ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO ₂ , etc., but when used as a semiconductor, photocatalytic activity is achieved with Na etc. Inactivated ones are preferred.

Examples of the dielectric constituting the composite with the conductor for forming a negative charge include barium titanate (PZT), which is a strong dielectric, so-called SBT, BLT, and the following PZT, PLZT- (Pb, La) ( Zr, Ti) O ₃ , SBT, SBTN-SrBi ₂ (Ta, Nb) ₂ O ₉ , BST- (Ba, Sr) TiO ₃ , LSCO- (La, Sr) CoO ₃ , BLT, BIT- (Bi, La) ) ₄ Ti ₃ O ₁₂ , BSO-Bi ₂ SiO ₅ and other composite metals can be used. Further, silane compounds and silicone compounds which are organic silicon compounds, so-called organic knitting silica compounds, organic polymer insulating films, allylene ether-based polymers, benzocyclobutene, fluoropolymer parylene N, F, fluorinated amorphous carbon and the like. Various low dielectric materials can also be used.

As the substance having a photocatalytic function, a substance containing a specific metal compound and having a function of oxidatively decomposing the organic and / or inorganic compound on the surface of the layer by photoexcitation can be used. The principle of photocatalyst is that a specific metal compound generates OH- and O ₂ -radical species from water or oxygen in the air by photoexcitation, and these radical species oxidatively decompose organic and / or inorganic compounds. It is generally understood that there is.

Examples of the metal compound include typical titanium oxide (TIM ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, Bathio ₃ , K ₂ NbO ₃ , and Fe ₂ O ₃ . , Ta ₂ O ₅ , WO ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO ₂ and the like are known.

The substance having a photocatalytic function may contain a metal (Ag, Pt) that improves the photocatalytic performance. Further, various substances such as metal salts can be contained within a range that does not deactivate the photocatalytic function. Examples of the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, and zinc. In addition, hydroxides or oxides can be used for some metals or non-metals. Specifically, aluminum chloride, first and second tin chloride, chromium chloride, nickel chloride, first and second antimony chloride, first and second iron chloride, silver nitrate, cesium chloride, indium trichloride, first chloride. Various metals such as cerium, selenium tetrachloride, cupric chloride, manganese chloride, calcium chloride, basal platinum chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, ferric chloride, zirconium oxychloride, zinc chloride, etc. A salt can be exemplified. Examples of the compound other than the metal salt include indium hydroxide, silicotungstic acid, silica sol, calcium hydroxide and the like.

In the excited state, the above-mentioned substance having a photocatalytic function adsorbs OH- (hydroxide radical) and O _2- (oxygenation radical) from the physically adsorbed water and oxygen on the surface of the substance, and the surface thereof is an anion. However, when a positively charged substance coexists there, the so-called photocatalytic activity decreases or is lost according to the concentration ratio. However, in the present invention, since the substance having a photocatalytic function does not need to have an oxidative decomposition action on the pollutant, it can be used as a negatively charged substance. By coexisting a positively charged substance, deterioration of the binder (typically, an inorganic polymer and an organic polymer) of the substance having a photocatalytic function due to oxidative decomposition can be avoided. Therefore, even when a substance having a photocatalytic function is fixed with a binder and used, by coexisting with the positively charged substance, the deterioration of the binder can be suppressed and the antifouling function due to both positive and negative charge characteristics can be obtained. Can be expressed.

The blending amount of the positively charged substance 22 and the negatively charged substance 23 in the second composition is adjusted in consideration of the blending amount of the water-repellent / oil-repellent substance 21 in the first composition.

For example, when it is desired to prevent both a substance having a positive charge characteristic and a substance having a negative charge characteristic from adhering to the substrate 1, the positive charge substance 22 and the negative charge substance 23 in the second composition are used. The amount of the mixture is the positive charge amount of the positive charge substance 22 in the second composition, the negative charge amount of the water / oil repellent substance 21 in the first composition, and the negative charge amount of the negative charge substance 23 in the second composition. It is preferable that the total amount of negative charges in the above is balanced, and specifically, the voltage band in the protective film 2 formed after coating on the substrate 1 is adjusted to be in the range of -50V to + 50V. Is preferable.

When it is desired to prevent a substance having a positive charge characteristic from adhering to the substrate 1, the blending amount of the positive charge substance 22 and the negative charge substance 23 in the second composition is the amount of the positive charge substance 22 in the second composition. It is preferable that the total negative charge amount of the negative charge amount of the water-repellent / oil-repellent substance 21 in the first composition and the negative charge amount of the negative charge substance 23 in the second composition is excessively larger than the positive charge amount. Specifically, it is preferable that the voltage band in the protective film 2 formed after coating on the substrate 1 is adjusted to be a negative charge band voltage.

When it is desired to prevent a substance having a negative charge characteristic from adhering to the substrate 1, the blending amount of the positive charge substance 22 and the negative charge substance 23 in the second composition is the amount of the positive charge substance 22 in the second composition. It is preferable that the total negative charge amount of the water-repellent / oil-repellent substance 21 in the first composition and the negative charge amount of the negative charge substance 23 in the second composition is excessively smaller than the positive charge amount. Specifically, it is preferable that the voltage band in the protective film 2 formed after coating on the substrate 1 is adjusted to be a positive charge band voltage.

The above-mentioned first composition and second composition may be a one-component substrate protective liquid in which both compositions are dissolved or dispersed in a solvent, or the first composition and the second composition may be used. It may be a two-component substrate protective liquid in which two solutions are prepared in a state where the composition is dissolved or dispersed in a solvent, and both solutions are mixed at the time of use. At this time, the solvent used in the first composition and the second composition is not particularly limited as long as it can form a uniform protective film as the substrate protective liquid. However, when the solution in which the first composition is dissolved or dispersed and the solution in which the second composition is dissolved or dispersed are mixed, the solvent of these two solutions may be a solvent having compatibility. For example, when one solution uses "water" or "water + alcohol" as a solvent, the other solution can use "alcohol" or "alcohol + solvent-based dispersant" as a solvent. As a specific solvent, various solvents such as a protic and aprotic polar solvent, an aprotic non-polar solvent, and an aprotic polar solvent can be used. As the protonic polar solvent, for example, water, methanol, ethanol, isopropanol, n-butanol and the like can be used. As the aprotic non-polar solvent, for example, toluene, xylene, hexane, cyclohexane, benzene, benzyl alcohol and the like can be used. As the aprotonic polar solvent, acetone, 2-butanone, 4-methyl-2-pentanone, acetonitrile, ethyl acetate, tetrahydrofuran, NN-dimethylformamide, dimethyl sulfoxide, chloroform and the like can be used.

Although both the positively charged substance 22 and the negatively charged substance 23 are contained in the second composition, the voltage band in the protective film 2 formed after coating on the substrate 1 is in a balanced state and negative as described above. As long as it can be adjusted to a charged state and a positively charged state, it may not contain the negatively charged substance 23. In this case, the blending amount of the positively charged substance 22 in the second composition is the amount of positive charge of the positively charged substance 22 of the second composition and the amount of negative charge of the water-repellent / oil-repellent substance 21 of the first composition. , Each of which is prepared to be in a balanced state, a negative charge state, and a positive charge state as described above.

The substrate protective liquid thus constructed is used by applying it to the surface of the substrate 1.

As a coating method, for example, the substrate 1 may be dipped in the substrate protective liquid to perform dip coating, or the substrate protective liquid may be spray-coated, roll-coated, or brush-coated on the substrate 1. It may be applied by sponge coating, spin coating or the like. After the coating, the protective film 2 can be formed on the surface of the substrate 1 by performing the drying step at least once.

The substrate 1 to be the subject of the present invention is not particularly limited, and various hydrophilic or hydrophobic inorganic and organic substrates, or a combination thereof can be used.

Examples of the inorganic substrate include transparent or opaque glass such as soda lime glass, metal oxides such as zirconia, and substrates made of substances such as ceramics, concrete, mortar, stone, and metal. Examples of the organic substrate include a substrate made of a substance such as an organic resin, wood, and paper. More specifically, examples of organic resins include polyethylene, polypropylene, polyvinyl carbonate, acrylic resin, PET and other polyesters, polyamides, polyurethanes, ABS resins, polyvinyl chlorides, silicones, melamine resins, urea resins, silicone resins, and fluorine. Examples thereof include resins, celluloses, and epoxy-modified resins.

The shape of the substrate 1 is not particularly limited, and any shape such as a cube, a rectangular cuboid, a sphere, a sheet shape, or a fibrous shape can be taken. The substrate may be porous.

The surface of the substrate 1 may be made hydrophilic by a corona discharge treatment, an ultraviolet irradiation treatment, or the like. As the substrate 1, a substrate or a sealing material for construction / civil engineering, equipment, a body for transporting equipment, and a display screen are suitable.

The surface of the substrate 1 may be painted, and the coating materials include alkyd resin, acrylic resin, amino resin, polyurethane resin, epoxy resin, silicone resin, fluororesin, acrylic silicon resin, unsaturated polyester resin, and ultraviolet curable resin. , A so-called paint paint containing a synthetic resin such as a phenol resin, a vinyl chloride resin, and an impregnated resin emulsion and a colorant can be preferably used.

By applying the substrate protective liquid to the surface of the substrate 1 in this way, as shown in FIG. 1, the surface of the substrate 1 has a water- repellent / oil-repellent substance 21, a positively charged substance 22, and a negatively charged substance. The protective film 2 is formed by 23 and. Further, when the substrate protective liquid containing no negatively charged substance 23 is applied to the second composition, as shown in FIG. 2, the surface of the substrate 1 has a water- repellent / oil-repellent substance 21 and a positively charged substance 22. The protective film 2 is formed by the electric charge.

When a substrate protective liquid in which a positive charge amount and a negative charge amount are balanced is applied to the substrate 1 to form a protective film 2, the protective film 2 has a water-repellent effect and / or an oil-repellent effect. , The antifouling effect can be exhibited.

When the substrate 1 is coated with a substrate protective liquid having a negative charge amount excessively larger than the positive charge amount to form the protective film 2, the protective film 2 has a water-repellent effect and / or an oil-repellent effect. It is possible to prevent a substance having a negative charge characteristic from adhering to the substrate 1.

When the substrate 1 is coated with a substrate protective liquid having a negative charge amount excessively smaller than the positive charge amount to form the protective film 2, the protective film 2 has a water-repellent effect and / or an oil-repellent effect. It is possible to prevent a substance having a positive charge characteristic from adhering to the substrate 1.

[Example 1]
-Preparation of the second composition-
As the second composition containing a positively charged substance and a negatively charged substance, one manufactured by Sustainable Technology Co., Ltd. was used. Specifically, copper-doped anatase-type titanium peroxide and potassium-doped polysilicate are mixed in the total amount at a ratio of 0.18 wt% and 0.70 wt%, respectively, and contain a positively charged substance and a negatively charged substance. (2) Used as a composition.

-Preparation of the first composition-
A first composition was prepared using a methyl group as a water-repellent group and methyltrimethoxysilane as a material for modifying the methyl group. Specifically, pure water, alcohol, and methyltrimethoxysilane were mixed at 7 wt%, 77 wt%, and 16 wt%, respectively, with the catalyst added. Acetic acid was used as the catalyst, and the pH of the solution was adjusted to be between 3-4. The mixture was allowed to stand for 12 hours until the reaction of the mixed solution was completed to obtain a first composition containing a water-repellent negatively charged substance in which the water-repellent group was modified to silicon.

-Formation of protective film with substrate protective liquid-
A substrate protective liquid composed of the first composition and the second composition was prepared.
The first composition and the second composition are mixed at a mass ratio of 5: 100, and the thickness after formation is 100 nm on the surface of a glass substrate (float glass) of 100 mm × 100 mm by the squeegee method. Applied. The coating film was formed as a protective film on the surface of the glass substrate (base) by curing at 200 ° C. for 15 minutes.

[Example 2]
-Preparation of the first composition-
A first composition was prepared using a propyl group as a water repellent group and hexyltrimethoxysilane as a material for modifying the propyl group. Specifically, pure water, alcohol, and hexyltrimethoxysilane were mixed at 7 wt%, 77 wt%, and 16 wt%, respectively, with the catalyst added. Acetic acid was used as the catalyst, and the pH of the solution was adjusted to be between 3-4. The mixture was allowed to stand for 12 hours until the reaction of the mixed solution was completed to obtain a first composition containing a water-repellent negatively charged substance in which the water-repellent group was modified to silicon.

-Preparation of the second composition-
The same second composition as in Example 1 was used.

-Formation of protective film with substrate protective liquid-
The first composition and the second composition are mixed at a mass ratio of 5: 100, and thereafter, a protective film having a thickness of 100 nm is formed on the surface of the glass substrate (base) by the same method as in Example 1 above. did.

[Example 3]
-Preparation of the first composition-
A first composition was prepared using a fluoroalkyl group as the water repellent group and 1H, 1H, 2H, 2H-nonafluorohexyltrimethoxysilane as a material for modifying the fluoroalkyl group. Specifically, pure water, alcohol, 1H, 1H, 2H, and 2H-nonafluorohexyltrimethoxysilane were mixed at 7 wt%, 77 wt%, and 16 wt%, respectively, with the catalyst added. Acetic acid was used as the catalyst, and the pH of the solution was adjusted to be between 3-4. The mixture was allowed to stand for 12 hours until the reaction of the mixed solution was completed to obtain a first composition containing a water-repellent negatively charged substance in which the water-repellent group was modified to silicon.

-Preparation of the second composition-
The same second composition as in Example 1 was used.

-Formation of protective film with substrate protective liquid-
The first composition and the second composition are mixed at a mass ratio of 5: 100, and thereafter, a protective film having a thickness of 100 nm is formed on the surface of the glass substrate (base) by the same method as in Example 1 above. did.

[Example 4]
-Preparation of the first composition-
The same first composition as in Example 1 was used.

-Preparation of the second composition-
As the second composition containing a positively charged substance without containing a negatively charged substance, a composition manufactured by Sustainable Technology Co., Ltd. was used. Specifically, a mixture of copper-doped anatase-type titanium peroxide and polysilicate in the total amount of 0.18 wt% and 0.70 wt%, respectively, was used as the second composition containing a positively charged substance. ..

-Formation of protective film with substrate protective liquid-
The first composition and the second composition are mixed at a mass ratio of 5: 100, and thereafter, a protective film having a thickness of 100 nm is formed on the surface of the glass substrate (base) by the same method as in Example 1 above. did.

[Example 5]
-Preparation of the first composition-
The same first composition as in Example 1 was used.

-Preparation of the second composition-
As the second composition containing a positively charged substance without containing a negatively charged substance, a composition manufactured by Sustainable Technology Co., Ltd. was used. Specifically, a second composition containing a positively charged substance obtained by mixing copper-doped anatase-type titanium peroxide and potassium-doped polysilicate in the total amount at a ratio of 0.18 wt% and 0.70 wt%, respectively. Using.

-Formation of protective film with substrate protective liquid-
The first composition and the second composition are mixed at a mass ratio of 5: 100, and thereafter, a protective film having a thickness of 100 nm is formed on the surface of the glass substrate (base) by the same method as in Example 1 above. did.

[Comparative Example 1]
-Preparation of substrate protective solution-
As a solution containing a positively charged substance and a negatively charged substance, a solution manufactured by Sustainable Technology Co., Ltd. was used. Specifically, copper-doped anatase-type titanium peroxide, tin-doped anatase-type titanium peroxide, Zr-doped anatase-type titanium peroxide, and potassium-doped polysilicate are 0.06 wt%, 0.06 wt%, and 0. A mixture of 06 wt% and 0.70 wt% was prepared as a substrate protective solution containing a positively charged substance and a negatively charged substance.

-Formation of protective film with substrate protective liquid-
The substrate protective liquid was applied in the same manner as in Example 1 to form a protective film having a thickness of 100 nm on the surface of the glass substrate (base).

[Comparative Example 2]
-Preparation of substrate protective solution-
The second composition of Example 1 was used as a substrate protective liquid.

-Formation of protective film by substrate protective liquid and thin film deposition-
First, the substrate protective liquid was applied in the same manner as in Example 1 to form an amphoteric charge film having a thickness of 100 nm on the surface of the glass substrate (base).

The glass plate on which the amphoteric charge film was formed and 0.5 ml of methyltrimethoxysilane were housed in a closed container, and the closed container was placed in a vacuum heating furnace. Then, by heating at 170 ° C. for 2 hours in a reduced pressure atmosphere with a furnace pressure of 0.1 kPa or less, a methyl group is adsorbed on the surface of the amphoteric charge film to form a self-assembled monolayer (SAM). The entire film formed by these two layers of film was used as a protective film.

[Comparative Example 3]
The untreated glass substrate is referred to as Comparative Example 3.

[evaluation]
The following evaluations were carried out for each of the samples of Examples 1-5 and Comparative Example 1-3.

<Visual inspection of appearance>
The appearance of the protective film is visually confirmed, and it is OK when the transparency of the uncoated glass is confirmed to the same level as the transparency, and NG when the film is opaque or has uneven distribution of components (a film having a locally cloudy part). And said.

<Measurement of water contact angle>
For each sample, the contact angle of water was measured at each of the five points of the sample, and the average value was calculated as the measured value. For the measurement, a contact angle meter DMo-501 manufactured by Kyowa Surface Chemistry Co., Ltd. was used.

<Measurement of initial transmittance>
For each sample, the visible light transmittance was measured at each of the three points of the left center, the center, and the right center of the sample, and the average value was calculated as the initial visible light transmittance. As a device for measuring the visible light transmittance, the fiber multi-channel spectroscopic system USB4E03215 manufactured by Ocean Optics was used, and the visible light transmittance was measured by the test method of JIS R3106.

<Measurement of transmittance after particle adhesion test>
For each sample, mixed particles prepared for testing (Carbon Black 1 (FW-200 "Ebonic Degusa"): 2.3 wt%, Carbon Black 2 (JIS Z 8901 test powder 12 types "Japan Corporation" Made by Powder Industry Technology Association ”): 9.3 wt%, Yellow Oaker (Natural yellow clay for pigments“ Made by Holbain Industry Co., Ltd. ”): 62.8 wt%, Baked Kanto Roam (JIS Z 8901 test dust 8 types” Japan Powder Industry Technology Association "): 20.9 wt%, silica powder (JIS Z 8901 test dust 3 types" Japan Powder Industry Technology Association "): 4.7 wt%) intermittently for 30 minutes A particle adhesion test was performed. This particle adhesion test was performed by storing each sample in a box and discharging dirty particles into the box at a discharge pressure of 0.02 MPa.

For each sample after this particle adhesion test, the visible light transmittance was measured at each of the three points of the left center, the center, and the right center of the sample, and the average value was calculated as the initial visible light transmittance. As a device for measuring the visible light transmittance, the fiber multi-channel spectroscopic system USB4E03215 manufactured by Ocean Optics was used, and the visible light transmittance was measured by the test method of JIS R3106.

The evaluation results are shown in Table 1.

From the evaluation results in Table 1, the appearance of each of Examples 1-5 was good, the initial transmittance was almost the same as that of the untreated glass plate of Comparative Example 3, and there was no problem in appearance due to the film formation of the protective film. Not seen.

The contact angle of each water of Example 1-5 is 90 degrees or more, which is the same value as that of the self-assembled monolayer of the two-time process of Comparative Example 2.

The transmittance of Example 1-5 after each particle adhesion test is higher than that of Comparative Example 3, indicating good adhesion prevention performance.

1 Hypokeimenon 2 Protective film 21 Water-repellent / oil-repellent substance
22 Positively charged substance 23 Negatively charged substance

Claims (11)

A substrate protective liquid that, when applied to the surface of a substrate, forms a protective film on the surface that reduces the adhesion of substances.
A catalyst was used to polycondensate and hydrolyze a silane compound having a water-repellent and / or oil-repellent functional group to obtain a stabilized silane compound in a silicon-modified state. The first composition containing a water / oil repellent substance and
A second composition containing at least a positively charged substance among a positively charged substance having a positive charge performance and a negatively charged substance having a negative charge performance is provided.
By using these as a mixture of the first composition and the second composition, the surface of the substrate is imparted with water repellency and / or oil repellency, and the voltage band is in the range of -50V to 50V. A substrate protective solution characterized by being made. The second composition contains a substance having a positive charge performance and a substance having a negative charge performance. The substrate protective solution according to claim 1. The voltage band on the surface of the protective film formed on the surface of the substrate by using the first composition and the second composition in a mixed manner becomes a negative charge. The substrate protective solution according to any one of claims 1 or 2. According to any one of claims 1 to 3, the voltage band on the surface of the protective film formed on the surface of the substrate by mixing and using the first composition and the second composition becomes a positive charge. The substrate protective solution described. A water / oil repellent substance which is a stabilized silane compound modified to silicon by polycondensation and hydrolysis of a silane compound having a water repellent and / or oil repellent functional group using a catalyst.
A substrate protective solution in which at least a positive charge substance among a positive charge substance having a positive charge performance and a negative charge substance having a negative charge performance is dispersed is applied to the surface of the substrate.
A method for protecting a substrate, which comprises forming a protective film having water repellency and / or oil repellency on the surface of the substrate and having a voltage band in the range of -50V to 50V. Dispersion ratio of water / oil repellent substance and positively charged substance having positive charge performance, or
By adjusting the dispersion ratio of the water-repellent / oil-repellent substance, the positively charged substance having positive charge performance, and the negatively charged substance having negative charge performance,
The fifth aspect of the present invention, wherein a water-repellent and / or oil-repellent protective film is formed on the surface of the substrate at a voltage band in the range of -50V to 50V.How to protect the substrate. Dispersion ratio of water / oil repellent substance and positively charged substance having positive charge performance, or
Dispersion ratio of water- repellent / oil-repellent substances, positively charged substances having positive charge performance, and negatively charged substances having negative charge performance,
By adjusting
The method for protecting a substrate according to claim 5 , wherein a water-repellent protective film is formed on the surface of the substrate with a negatively charged voltage . Repellent Dispersion ratio of water / oil repellent substance and positively charged substance having positive charge performance, or,
Repellent Dispersion ratio of water / oil-repellent substance, positively charged substance having positive charge performance, and negatively charged substance having negative charge performance,
By adjusting
On the surface of the substratePositiveWater repellency with charged voltageAnd or oil repellentClaim to form a protective film of5The method for protecting a substrate according to. A substrate designed to form a protective film on at least a part of the surface.
The protective film is a water-repellent / stabilized silane compound modified to silicon by polypolymerizing and hydrolyzing a silane compound having a water-repellent and / or oil-repellent functional group using a catalyst. A state in which an oil-repellent substance and a positively charged substance having positive charge performance are dispersed, or
Water- and oil-repellent substances, which are stabilized silane compounds modified to silicon by hydrolyzing and hydrolyzing a silane compound having a water-repellent and / or oil-repellent functional group using a catalyst. It is arranged in a state where a positive charge substance having a positive charge performance and a negative charge substance having a negative charge performance are dispersed, and has water repellency and / or oil repellency at a band voltage in the range of -50V to 50V. A substrate characterized by being made in this way. A substrate designed to form a protective film on at least a part of the surface.
The protective film is, RepellentA state in which a water / oil-repellent substance and a positively charged substance having positive charge performance are dispersed, or,
Repellent The water / oil-repellent substance, the positively charged substance having positive charge performance, and the negatively charged substance having negative charge performance are dispersed in a dispersed state, andThe ninth aspect of the present invention is made to have water repellency and / or oil repellency at a negative charge voltage.Hypokeimenon. A substrate designed to form a protective film on at least a part of the surface.
The protective film is, RepellentA state in which a water / oil-repellent substance and a positively charged substance having positive charge performance are dispersed, or,
Repellent The water / oil-repellent substance, the positively charged substance having positive charge performance, and the negatively charged substance having negative charge performance are dispersed in a dispersed state, andPositiveA claim made to have water repellency and / or oil repellency at a voltage band of electric charge.9The substrate according to.

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