Articles containing corrosion-inhibiting coatings and methods of making same

Abstract

To provide an article comprising a substrate comprising a corrosion-inhibiting coating having excellent adhesion to the substrate. do. The present invention relates to a substrate and a corrosion-inhibiting coating present on at least a portion of the surface of the substrate. and the corrosion-inhibiting coating comprises at least one functional group R 1 Contains Crosslinked inorganic-organic hybrid coating, R 1 is C1-C 20 Alkyl, C1-C 20 S alkyl, C1-C 10 Aryl, amide, amine, mercapto, and epoxy and further comprising at least one halogen atom. The coating contains silicon and / or titanium and has oxygen-silicon bonds or oxide bonds. The present invention further provides a method for producing a titanium-based alloy comprising the steps of: This application discloses a method for making such an article.

Description

[Technical Field]

[0001] The present invention provides an article comprising a substrate and a corrosion-inhibiting coating on at least a portion of a surface of the substrate. The present invention further relates to methods for making such articles and uses of such articles. Regarding use. [Background technology]

[0002] Corrosion is the main mechanism of deterioration of materials and articles containing metals. It can be defined as the reaction of a material with its surrounding environment. Both affect the rate of the corrosion reaction, thus slowing it down, i.e. There are various known approaches to prevent corrosion.

[0003] For example, in the corrosion process, the metal constituting the substrate is coated with a corrosion-protective component. It is known to dope the material with elements that enrich it.

[0004] Alternatively, it is known to add a corrosion inhibitor, which acts on the surface of the substrate. It strongly adsorbs the metals contained in the material, preventing them from reacting with oxidizing agents and preventing corrosion. The inhibitor protects the metal by forming a protective film of passive nature, i.e., a passivation layer. However, commonly used corrosion inhibitors are quite expensive and However, recent legislation has deemed it to be poisonous.

[0005] Also, the surface of the substrate, especially areas requiring protection against corrosion, such as areas containing metals, It is also known to deposit protective coatings. These coatings provide a protective barrier against corrosive environments. However, many traditional corrosion protection coatings are not toxic according to current legislation, e.g. Today, they are considered environmentally harmful coatings because they contain compounds that are considered to be harmful to the environment.

[0006] In recent years, coatings obtained using the sol-gel process have been attracting attention. is environmentally friendly, has high performance, is compatible with existing coating deposition techniques, and provides coating properties on demand. This is desirable from the standpoint of ease of adjustment.

[0007] In particular, the compounds known by the registered trademark "Ormocer" are obtained by the sol-gel process. Inorganic-organic hybrid coatings, such as those described in the previous paper, are attracting attention. It may be possible to combine the properties inherent in inorganic materials with those inherent in organic polymers. Inorganic-organic hybrid materials have properties that cannot be obtained with pure inorganic or organic materials. Generally, organic polymer materials have good elasticity and toughness. Inorganic materials are generally hard, rigid, and thermally stable. By changing the inorganic and organic structural units with the inorganic-organic hybrid coating, It is possible to change and optimize the properties of the inorganic-organic hybrid coating. Due to its inorganic network, the polymer has high mechanical, chemical and thermal stability even in harsh environments. It is possible to demonstrate qualitative

[0008] Inorganic-organic hybrid coatings involve direct bonding between inorganic and organic structural units. Therefore, inorganic-organic hybrids are characterized by bonding on a molecular scale. The polymer coating contains a three-dimensional inorganic network and a three-dimensional organic network interconnected by covalent bonds. - is.

[0009] The sol-gel process is a sustainable and non-toxic way to create solid materials from small molecules. This process is thought to convert the monomer into a colloidal solution (sol). The colloidal solution is then formed into a unified network of discrete particles or polymers (crosslinked polymers). It acts as a precursor to the network (or gel).

[0010] Literature, “Hybrid sol-gel coatings: smart and green materials for corrosion mitig "Hybrid Sol-Gel Coatings: Smart and Green Materials for Corrosion Mitigation" R. Figueira, I. Fontinha, et al., Coatings 2016, 6, 12, for steel, aluminum and This paper discloses a sol-gel coating for corrosion protection of titanium and its alloys. The coating is tetraethyl orthosilicate (TEOS), 3-methacryloxypropyltrimethylsilane (3-methacryloxypropyltrimethylsilane), methyltriethoxysilane (MAPTS), methyltriethoxysilane (MTES), and triiso By copolymerizing various combinations of two of the propoxy(methyl)silanes Obtained.

[0011] European patent document EP1729892 describes inorganic-organic hybrids produced by the sol-gel process. It discloses producing a coating by exposure to atmospheric pressure plasma. The prepolymer (the so-called "sol") is crosslinked by the polymerization of hydroxybenzoates, thereby forming a crosslinked inorganic-organic hybrid. A hybrid coating (a so-called "gel") is obtained.

[0012] The problem with the above inorganic-organic hybrid coating is that it has a limited adhesion to the substrate. This can cause peeling of the coating, preventing water or moisture from getting into the interface between the coating and the substrate surface. This can reach the surface and lead to corrosion.

[0013] Another challenge with the above methods, especially CVD and PVD processes, is the need to avoid contamination. In addition, working in a glove box filled with inert gas or under reduced pressure For this reason, such methods may require working in a controlled environment such as The challenge with using plating to deposit coatings is that it is complicated and expensive. Therefore, the deposition rate of the coating is very low, the process of coating deposition is long, and the chemical The environmental impact of such methods is also unclear. In order to reduce the This makes the method complicated and expensive. Summary of the Invention [Problem to be solved by the invention]

[0014] The present invention aims to overcome one or more of the above problems. The present invention provides an article comprising a substrate having a corrosion-inhibiting coating that exhibits excellent adhesion to the substrate. Another object of the present invention is to provide an article comprising a substrate and a coating, wherein the coating is applied to the substrate. These coatings may provide excellent corrosion protection and are non-toxic.

[0015] Another object of the present invention is a method for making such an article, which method comprises the steps of: The method does not require the use of compounds that can cause catalysis, is carried out at moderate temperatures, and does not require long processing times. It may also provide a method that consumes less energy than prior art methods. One of the purposes is to provide [Means for solving the problem]

[0016] In a first aspect of the present invention, there is provided a method for manufacturing a corrosion-resistant substrate, comprising: and a protective coating.

[0017] The substrate comprises a metal element and / or an alloy of metal elements. At least a portion of the surface of the material contains a metal element and / or its alloy. The metal element and / or its alloy may be present only on the surface of the substrate. Additionally, the substrate may consist essentially of metallic elements and / or alloys thereof.

[0018] Preferably, the metal element is iron or copper. Iron, for example, alloys containing iron, such as steel. Preferably, the steel is any type of Steels such as lap steels can be used for components of watches (e.g., wristwatches, pocket watches), among others. For example, the alloy of iron may be stainless steel. Alternatively or additionally, the substrate may be copper, e.g., brass, or carbon steel. Copper-containing alloys such as

[0019] In the context of the present invention, a "corrosion-inhibiting coating" means that the presence of this coating on a substrate is sufficient to inhibit corrosion. The formation of corrosion in the surface area of ​​the substrate is reduced and preferably avoided. means.

[0020] The corrosion-inhibiting coating further comprises at least one functional group R 1 Crosslinked inorganic-organic It is a hybrid coating.1 is C1-C 20 Alkyl, C1-C 20 Shik alkyl, C1-C 10 Aryl, amide, amine, ether, mercapto (i.e., and one or more functional groups selected from the group consisting of thiol and epoxy. To, R 1 contains at least one halogen atom. Preferably, said halogen atom is fluorine, chlorine, bromine, or iodine. 1 If contains two or more halogen atoms In this case, they can be the same or different, i.e., fluorine The corrosion-inhibiting substrate may be a combination of two or more of chlorine, bromine, and iodine. The coating further comprises silicon and / or titanium.

[0021] In one embodiment, R 1 is C1-C 20 Alkyl, i.e., 1 to 20 alkyl groups in the chain Preferably, R is an alkyl group containing carbon atoms. 1 is the formula -(CH2) x (CF2) y C1-C represented by CF3 20 alkyl, x is 0 to z-1, y is zx-1, z is , the total number of carbon atoms, i.e., 1 to 20. For example, R 1 When is a C8 alkyl In this case, i.e., when z is 8, R 1 is the formula -(CH2)2(CF2)5CF3 (x is 2, y can be expressed as 5).

[0022] Instead, R 1 contains an amide functional group and one or more ether functional groups. For example, R 1 is -(CH2)3NHC(O)OCH2CF(CF3)OCF2CF(CF3)O(CF2)2 It can be CF3.

[0023] The crosslinked inorganic-organic hybrid coating has at least one metal element or alloy thereof of the substrate. "At least partially covalently bound" means that the The coating is bonded to a metal element or an alloy thereof by at least one, preferably a plurality of, covalent bonds. Preferably, when the corrosion-inhibiting coating contains silicon, Preferably, the corrosion-inhibiting coating is titanium. In the case where the titanium compound contains an oxygen atom, the covalent bond comprises an oxygen-titanium bond.

[0024] Preferably, the crosslinked inorganic-organic hybrid coating further comprises a carbon-silicon Includes joins.

[0025] The corrosion-inhibiting coating is present on at least a portion of the surface of the substrate. The corrosion inhibiting coating preferably covers at least a portion of the surface of the substrate. Alternatively, the corrosion-inhibiting coating is present on portions of the substrate that are prone to corrosion. The coating is present on or covers the entire surface of the substrate.

[0026] Examples of articles of the present disclosure include those used in corrosive environments such as marine components. Components used in electronic devices such as printed circuit boards Components that are prone to corrosion during storage, and aesthetics such as color and brightness that may be affected by oxidation or corrosion. A specific example of an article of the present disclosure is a watch. and components for non-portable watches.

[0027] In a second aspect of the present invention, as claimed, a substrate and a surface of said substrate and a corrosion-inhibiting coating on at least a portion of a surface thereof.

[0028] Preferably, the article is according to the first aspect of the invention. Preferably, the substrate is provided with a surface of at least one of the substrate. Preferably, the metal element and / or alloy of the metal element are included in the part. and alloys thereof as described above.

[0029] The method includes providing a first compound represented by formula (I).

[0030] [ka]

[0031] where M is silicon or titanium, and R 1 is C1-C 20 Alkyl, C1-C 20 S Chloroalkyl, C1-C 10 Aryl, amide, amine, ether, mercapto (i.e. , thiol), and epoxy; and a group containing at least one halogen atom, R 2 , R 3 and R 4 are respectively, Independently of each other, H, C1-C 20 Alkyl, C1-C 10 Aryl, C1-C 20 alkenyl, C1-C 20 Alkylaryl, or C1-C 20 It is arylalkyl.

[0032] Preferably, the halogen atom is fluorine, chlorine, bromine, or iodine. 1 If contains two or more halogen atoms, they may be the same or different, and That is, combinations of two or more of fluorine, chlorine, bromine and iodine.

[0033] The method further comprises providing a second compound of formula (II).

[0034] [ka]

[0035] where M is silicon or titanium, and R 5 is a crosslinkable functional group, and R 6 , R 7 and R 8 are, independently of each other, H, C1-C 20 Alkyl, C1-C 10 aryl, C1-C 20 Alkenyl, C1-C 20 Alkylaryl, or C1-C 20 Aryl alkyl is.

[0036] A "crosslinkable functional group," in the context of this disclosure, is a functional group that is capable of reacting with another functional group. Upon reaction, a covalent bond is formed, thereby forming a crosslinked polymer. Crosslinked polymers can be thought of as polymers with three-dimensional structures.

[0037] Preferably, R 5 is a thermally crosslinkable group and / or a photocrosslinkable group. Wachi, R 5can be thermally crosslinkable, photocrosslinkable, or both.

[0038] "Thermally crosslinkable group" refers, in the context of this disclosure, to R 5 The crosslinking of the polymer is called thermal curing. By bridge, we mean induced and / or generated. Exposing a crosslinkable group, such as a prepolymer containing such crosslinkable groups in this disclosure, to elevated temperatures This is done by heating the prepolymer.

[0039] "Photocrosslinkable group" refers, in the context of this disclosure, to R 5 The crosslinking of Photochemical crosslinking refers to crosslinking induced and / or caused by photochemical crosslinking. The photocuring is carried out by using a prepolymer containing (photo)crosslinkable groups, in this disclosure, such crosslinkable groups. Preferably, the radiation is infrared (IR) radiation. ) radiation, ultraviolet (UV) radiation, or visible light (VIS) wavelength range The term "radiation" includes one or more of the following light radiations:

[0040] Preferably, R 5 Epoxy, (meth)acrylate, ester, mercapto, The functional group is selected from the group consisting of vinyl and (meth)acrylated urethane. In the above, "(meth)acrylate" means a compound having a functional group of acrylate or methacrylate. This means that it can be

[0041] Preferably, R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are each independently of each other, H or C1-C 20 Alkyl, preferably C1-C8 alkyl, more preferably C1-C6 alkoxy alkyl, most preferably C1-C4 alkyl. In particular, R 2 , R 3 , R 4 , R 6 , R 7 Oh BiR 8 are each independently methyl (-CH3, i.e., C1 alkyl), or ethyl It is a C2 alkyl (-C2H5, i.e., C2 alkyl).

[0042] The first compound and the second compound are hydrolyzed in the presence of water. In this case, R 2 , R 3 , R 4 , R 6 , R 7 and R 8 C1, wherein one of the C1-C8 alkyl groups is C1 The -C8 alkyl chain is converted to a hydrogen atom, thereby forming a hydroxyl group and a C x H 2x+1 Form an alcohol molecule of OH, where x is R 2 , R 3 , R 4 , R 6 , R 7 oh Yobi R 8 is the number of carbon atoms in the C1-C8 alkyl chain (i.e., x is 1 to 8). .

[0043] Next, the hydrolyzed first compound and the hydrolyzed second compound are condensed. During the condensation, water is removed. During the condensation, the hydrolyzed first compound and the hydrolyzed A prepolymer is obtained from the first compound and the second compound. The prepolymer has R as a functional group. 1 oh Yobi R 5This prepolymer can be considered a so-called "sol."

[0044] The prepolymer is deposited on at least a portion of the surface of the substrate. a porous polymer on at least a portion of the surface comprising said metal element and / or its alloy; This deposition can be accomplished by methods known in the art, such as by coating the substrate with a prepolymer. casting or dipping the prepolymer into the substrate; spraying the prepolymer onto the substrate; This can be done by roll-to-roll coating or roll-to-roll coating.

[0045] If desired, the substrate may be washed prior to depositing the prepolymer onto at least a portion thereof. Preferably, the group on which the prepolymer is deposited is At least a portion of the surface of the material is pre-cleaned. This pre-cleaning is performed by a method known in the art. This can be done by methods known in the art, such as grinding and polishing, chemical cleaning, ultra-cleaning, and the like. Sonic cleaning, sandblasting, plasma treatment at atmospheric or reduced pressure, corona treatment (air plasma Zuma) is an example.

[0046] The prepolymer deposited on at least a portion of the surface of the substrate is crosslinked. The crosslinking of the prepolymer is carried out by the addition of a crosslinkable functional group R 5 This is achieved by cross-linking.

[0047] R 5 is a thermally crosslinkable functional group, said crosslinking is preferably carried out by It is induced and / or performed by exposure to temperatures up to 250°C. The temperature is preferably 25 to 250°C, more preferably 50 to 200°C, and even more preferably 75 to 185°C, for example, 100 to 175°C, or 125 to 160°C.

[0048] R 5 is a photocrosslinkable functional group, said crosslinking is preferably carried out by photocrosslinking the prepolymer Preferably, the method is induced and / or performed by exposure to radiation. The radiation may be IR radiation or UV radiation, or a combination thereof.

[0049] Upon crosslinking, a corrosion-inhibiting coating is obtained on the surface of the substrate where the prepolymer is deposited. The coating is covalently bonded to the metal element or its alloy of the substrate by utilizing oxygen-M bonds. Here, M is silicon or titanium.

[0050] The corrosion-inhibiting coating comprises at least one functional group R 1 A crosslinked inorganic-organic hybrid comprising It is a thick coating (a so-called "gel").

[0051] In a third aspect of the present invention, there is provided a method for producing a medicament according to the first aspect, as set forth in the accompanying claims. The use of the article or article obtained by the second aspect is disclosed. The article is used in a watch.

[0052] Certain aspects of the present invention will now be described in detail with reference to the accompanying drawings, in which: The numbers indicate the same features. [Brief explanation of the drawings]

[0053] [Figure 1] 1 is a cross-sectional view showing a schematic view of an article according to the present invention; [Figure 2] 1 is a graph showing open circuit potential values ​​for substrates coated according to the present invention and substrates with a reference coating. DETAILED DESCRIPTION OF THE INVENTION

[0054] FIG. 1 shows a schematic diagram of an article 1 according to the present invention. The article 1 comprises a substrate 2 and a and a corrosion-inhibiting coating 3 covering at least a portion of the surface.

[0055] The substrate 2 comprises a metal element and / or an alloy of a metal element. At least a portion of the surface comprises a metal element and / or an alloy thereof. At least a portion, for example all, of the surface portion containing the metal element and / or its alloy is corroded. This allows for a stable and reliable handling, storage, manufacturing and operation. In addition, any corrosion-prone areas of the substrate can be effectively protected from corrosion. 1, substantially the entire surface of the substrate 2 is covered with the corrosion-inhibiting coating 1. It is overturned.

[0056] Examples of the metal elements include iron, copper, aluminum, zinc, silver, gold, tin, manganese, and and nickel. The substrate contains two or more metal elements and / or alloys thereof. Preferably, the substrate comprises iron and / or copper.

[0057] For example, the substrate may comprise or consist essentially of iron. When the substrate comprises iron, the substrate may be or comprise steel, such as carbon steel. do.

[0058] For example, the substrate may comprise or consist essentially of copper. When the substrate comprises copper, the substrate may be or comprise brass or bronze. .

[0059] In the present invention, the term "consisting essentially of" refers to impurities or other components present in the substrate. The amount of is preferably less than 1% by weight, more preferably less than 0.5% by weight, and even more preferably less than 0.1% by weight, for example, to determine the composition, such as X-ray photoelectron spectroscopy (XPS) This means that the level is below the detection limit of the analytical technique used.

[0060] If desired, the substrate may contain additional non-metallic elements and / or non-metallic compounds. Examples of such non-metallic elements are phosphorus, or metals such as silicon and arsenic. Examples of non-metallic compounds include polytetrafluoroethylene (PT FE), polyethylene, polypropylene, polyurethane, polyamide, polyimide, poly These include amide-imide, epoxy resins such as FR4, and glass.

[0061] Preferably, the corrosion inhibiting coating is an inorganic-organic hybrid coating. In particular, the corrosion-inhibiting coating is a crosslinked inorganic-organic hybrid coating. The corrosion-inhibiting coating is at least partially covalently bonded to the surface of the substrate, particularly to the metal element. Or, when the metal element exists as an alloy, the metal element contained in the alloy and at least Preferably, the corrosion-inhibiting coating is at least partially covalently bonded to the metal element. The metal element is covalently bonded to the metal by a bond containing oxygen, such as an oxygen atom of the coating that is covalently bonded to the metal element. It fits together.

[0062] Preferably, the crosslinked inorganic-organic hybrid coating is made of silicon, titanium, silica, and preferably, one or more of: ruthenium, aluminum, iron, or boron. Preferably, the crosslinked inorganic-organic hybrid comprises silicon and / or titanium. When the coating contains silicon and / or titanium, the coating may be silicon-oxygen. - A small amount of titanium is bonded to the metal element of the substrate by the metal element and / or titanium-oxygen-metal bond. At least partially covalently bonded.

[0063] Preferably, the inorganic-organic hybrid coating comprises at least one functional group R 1 Including Fortunately, R 1 is C1-C 20 Alkyl, C1-C 20 Cycloalkyl, C1-C 10 Aryl, amide, amine, ether, mercapto (i.e., thiol), and epoxy and / or comprising or consisting of one or more functional groups selected from the group consisting of:

[0064] Hopefully, "C1-C 20 "Alkyl" refers to an alkyl group containing 1 to 20 carbon atoms in the chain. Preferably, the alkyl functional group is C1-C 20 Alkyl is C1-C 12 Alkyl, preferably C1-C 10 Alkyl, for example, C1-C8 alkyl, C1-C6 alkyl, C1-C4 alkyl It's a kill.

[0065] Hopefully, "C1-C 20 Cycloalkyl is a group consisting of 1 to 20 carbon atoms in total in the chain. It contains a cycloalkyl functional group containing a cycloalkyl group.

[0066] Hopefully, "C1-C 10 "Aryl" refers to an aryl group containing 1 to 10 carbon atoms in the chain. Contains a methyl group, e.g., R 1 may contain a phenyl functionality, or C1-C20 It can be alkylphenyl.

[0067] Preferably, R 1 If R contains an amide functional group, 1 is the formula -(CH2) a (CF2) b It is represented by C(O)NH2, where a is 0 to c-2, b is ca-1, and c is a carbon atom. Preferably, c is 2 to 20, preferably 2 to 10, for example 2 to 8, 2-6, or 2-4, for example, 2, 3, or 4.

[0068] Preferably, R 1 If R contains an amine functional group, 1 is the formula -(CH2) p (CF2) q It is represented by NH2, where p is 0 to r-1, q is rp-1, and r is the total number of carbon atoms. Preferably, r is 1 to 20, preferably 1 to 10, for example, 1 to 8, 1 to 6, or 1 to 4, for example 1, 2, 3 or 4.

[0069] Preferably, R 1 If contains a mercapto (thiol) functional group, R 1 is the formula, -(C H2) u (CF2) v It is expressed as SH, where u is 0 to w-1, v is wu-1, and w is is the total number of carbon atoms. Preferably, w is 1 to 20, preferably 1 to 10, e.g. For example, 1 to 8, 1 to 6, or 1 to 4, for example, 1, 2, 3, or 4.

[0070] Preferably, the inorganic-organic hybrid coating further comprises at least one halogen. Preferably, the halogen atom is fluorine, chlorine, bromine, or iodine. It is prime. R 1 When contains two or more halogen atoms, they can be the same or and may be different, i.e., two or more of fluorine, chlorine, bromine and iodine. The corrosion-inhibiting coating may further comprise silicon and / or a combination thereof. Contains titanium.

[0071] Preferably, R 1 is represented by formula (III), -(CH2) x (CF2) y CF3(III) C1-C represented by 20 alkyl, where x is 0 to z-1; and y is z-1-x, where z is the number of carbon atoms in the chain and is 0 to 20.

[0072] For example, R 1 is -(CH2)2(CF2)5CF3, i.e., z is 8, x is 2, y is 5, For example, R 1 is -(CH2)5CF3, i.e., z is 6, x is 5, y can be 0;

[0073] R 1 is -(CF2) y C1-C, represented by CF3 20 perfluoroalkyl, i.e. , alkyl, in which all hydrogen atoms are replaced by fluorine atoms; In formula (III), x is 0, y is z-1, and z is 1 to 20. For example, R 1 is C8 Perfluoroalkyl, i.e., —(CF2)7CF3 (where z=8 and x= 0 and y=7), C6 perfluoroalkyl, i.e., —(CF2)5CF3 (formula (III) ) where z=6, x=0 and y=5), or C4 perfluoroalkyl, i.e. , -(CF2)3CF3 (where z=4, x=0 and y=3 in formula (III)). Cut.

[0074] Preferably, the coating has a thickness of 1 μm to 20 μm, preferably 1.2 μm to 10 μm, For example, the coating has a thickness of 1.5 μm to 5 μm. The optimum thickness of the protective layer will depend, inter alia, on the substrate to be protected, particularly its composition and shape, and the intended use of the article. Depends.

[0075] Preferably, when the substrate comprises iron, e.g., steel, especially carbon steel, the coating is at least at least 2 μm, for example at least 2.1 μm, preferably at least 2.2 μm, for example having a thickness of at least 2.3 μm, at least 2.4 μm, or at least 2.5 μm When the coating has such a thickness, it provides efficient corrosion protection to the substrate.

[0076] Preferably, when the substrate comprises copper, such as brass or bronze, the coating comprises at least at least 1 μm, preferably at least 1.2 μm, for example at least 1.3 μm, The coating has a thickness of at least 1.4 μm, at least 1.5 μm. When the substrate is coated with the coating, the substrate is effectively protected from corrosion.

[0077] Preferably, when the article is a component for a watch, i.e. When the article is used in a watch, the thickness is preferably 5 μm or less. As is known in the field of watch components, a higher thickness is necessary for the functionality of the watch. This may affect the system performance and require a redesign of the component. This is very expensive. The inventors have found that the thickness of the coating is at most 5 μm. products can significantly reduce corrosion while avoiding the need for design changes. I discovered it.

[0078] For example, if the substrate comprises iron, such as carbon steel, the coating is preferably 2 μm thick. The thickness is 2.2 μm to 5 μm, preferably 2.2 μm to 5 μm, and more preferably 2.4 μm to 5 μm. It has.

[0079] For example, if the substrate comprises copper, such as bronze or brass, the coating preferably comprises: 1 μm to 5 μm, preferably 1.2 μm to 5 μm, for example 1.3 μm to 5 μm, more preferably Or, it has a thickness of 1.5 μm to 5 μm.

[0080] example Two types of substrates were prepared: carbon steel plate and brass plate.

[0081] A reference article was obtained by depositing a reference corrosion-inhibiting coating on both substrates. The coating was a halogen-free coating.

[0082] Four different prepolymers according to the present invention were prepared. Table 1 lists the functional groups in detail. The two prepolymers are fluorinated alkylene compounds with the formula -(CH2)2(CF2)5CF3. The total weight of the corresponding prepolymers was 1.2g / g (B1 and B2 in Table 1). On a mass basis, B1 contains a low proportion of fluorinated alkyl functional groups and B2 contains a high proportion of Two other prepolymers contained fluorinated alkyl functional groups of the formula -(CH2)3N Represented by HC(O)OCH2CF(CF3)OCF2CF(CF3)O(CF2)2CF3 The functional groups contained amide and ether functional groups (C1 and C2 in Table 1). Based on the total weight of the prepolymer, C1 contains a low proportion of functional groups and C2 contains a high proportion. It contained functional groups with high efficiency.

[0083] [Table 1]

[0084] The substrate is immersed in the prepolymer and then thermally cured at 160°C. The bright prepolymer was deposited on carbon steel and brass substrates. The resulting coating on the carbon steel substrate was All have a thickness of 1 μm to 3 μm, and the coating on the brass substrate is 1.5 μm to 2. It had a thickness of 5 μm.

[0085] All four coatings of the present invention (B1, B2, C1, C2) are light-transmitting and Furthermore, coating C2 is more flexible than coating C1. High strength (low rigidity) and increased thickness reduces the risk of defects such as cracks occurring. It was found that coating B2 can contribute to reducing the content of fluorine-based functional groups. It was found to be easier to clean and had a slightly lower surface energy than coating B1, which has less This surface energy was determined by measuring the water contact angle according to the standard ASTM D5946. By converting contact angles to surface energy values ​​using known, publicly available conversion tables. So I measured it.

[0086] The corrosion protection properties of all five articles and the unprotected substrate were compared by 0.1 The test was carried out by measuring the open circuit potential (OCP) in a 0.5% NaCl aqueous solution. High values ​​of γ are effective against corrosion because damage such as short circuits caused by corrosion is significantly reduced. This is an indicator of high protection performance. A saturated calomel electrode (SCE) is used as the reference electrode. The OCP was measured at 24°C by the EC-pen method using the EC-pen. The results are shown in Figure 2. "Uncoated" indicates the OCP value for a substrate without corrosion protection. The value 4 indicated by a circle represents the OCP value for the carbon steel substrate, and the value 5 indicated by a circle represents the OCP value for the brass substrate. are.

[0087] From Figure 2, it can be seen that all corrosion-inhibiting or corrosion-protective coatings applied to carbon steel are superior to uncoated protective coatings. It is clear that this leads to higher OCP values ​​than the unprotected substrate. As previously mentioned, unprotected carbon steel is prone to corrosion. , indicating that all coatings protect the carbon steel substrate from corrosion. While the functional group-based coatings (C1 and C2) provided better protection than the reference coating, The alkyl functional groups (B1 and B2) represent slightly less protection, but this protection is still large compared to the bare substrate.

[0088] Coatings on brass substrates did not significantly improve corrosion protection in terms of OCP values However, as is generally known, brass itself, i.e., without any protection, Please note that untreated materials already have some resistance to corrosion. This indicates that the bare brass substrate has a significantly higher OC than the bare carbon steel substrate. Therefore, it is clear from Figure 2 that both coatings have the same P value. It can be seen that the inherent corrosion protection of the copper substrate is not diminished. The coatings showed significantly higher OCP values ​​than the substrates.

[0089] As a second test to evaluate corrosion protection, the release of ions from the substrate was measured. The release of ions contained in the material, i.e., elution, is a major cause of side reactions such as corrosion. This indicates that the damage to the substrate is significant.

[0090] The untreated substrate and the substrates with coatings B1 and C1 were tested for ion release. These substrates were left in a 0.9% NaCl solution at 37°C for 7 days. was measured by inductively coupled plasma spectroscopy (ICP-MS).

[0091] Table 2 shows the results for the carbon steel substrate, and Table 3 shows the results for the brass substrate. "< LOD" indicates that the This means that the concentration of the detected ion was below the limit of detection (LOD).

[0092] [Table 2]

[0093] From Table 2, the coated carbon steel substrate showed a significant increase in corrosion resistance compared to the substrate without corrosion protection ("uncoated"). In the case of the material, iron (Fe) ions and manganese (Mn) ions are dissolved from the substrate into the NaCl solution. It is clear that the concentration of ions is significantly lower. Furthermore, neither release nor elution of lead (Pb) ions was detected in the coated substrate. This indicates that the coating of the present invention effectively protects the carbon steel substrate. There are.

[0094] [Table 3]

[0095] From Table 3, the coated brass, as opposed to the substrate without corrosion protection ("uncoated"), In the base material, copper (Cu) ions and zinc (Zn) ions, which are the main components of brass, are released. It is clear that the brass substrate is not dissolved in the NaCl solution. This demonstrates that the coating effectively protects the brass substrate.

[0096] In addition, for uncoated brass substrates, exposure to the atmosphere (sunlight, air) I found that the color and luster changed within 3 to 5 days after application. The gold-like color turned orange. The brass components are used in watches and other outdoor applications. When viewed from the side, such changes in hue, gloss or color are aesthetically undesirable. In contrast to coated brass, the same substrate coated with the coating of the present invention was exposed to the atmosphere for several months. It has been found that it shows no signs of corrosion even when exposed to sunlight (tested for up to 6 months with no visible signs of corrosion). No changes were observed).

[0097] The adhesive strength of coatings B1 and C1 on both substrates was tested according to EN ISO 2409 (so-called "cross-cut" All test samples were scored 0. This means that This means that the edges of the grid are smooth and none of the grid squares have peeled off. [Explanation of symbols]

[0098] 1 article 2 Base material 3. Corrosion-inhibiting coating 4 OCP value of carbon steel 5 OCP value of brass

Claims

[Claim 1] An article comprising a base material and a corrosion-inhibiting coating present on at least a portion of the surface of the base material, The substrate comprises a metal element and / or an alloy of a metal element. The corrosion-inhibiting coating comprises at least one functional group R 1 A cross-linked inorganic-organic hybrid coating containing, R 1 C 1 -C 20 Alkyl, C 1 -C 20 Siloalkyl, C 1 -C 10 It comprises one or more functional groups selected from the group consisting of aryl, amide, amine, mercapto, and epoxy, R 1 is further substituted with at least one halogen atom, The crosslinked inorganic-organic hybrid coating comprises silicon and / or titanium. Each of the crosslinked inorganic-organic hybrid coatings is covalently bonded to a metal element or its alloy by oxygen-silicon bonds or oxygen-titanium bonds. An article characterized by the following:

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