Silicone Coating Composition and Article

Abstract

(assignment) The present invention provides a silicone coating composition that does not contain organic solvents, has excellent storage stability, cures rapidly at room temperature after coating on a substrate, and provides a cured film with excellent transparency and adhesion, which can provide excellent conformability to the curvature of the substrate, and also provides corrosion resistance of the substrate, particularly capable of reducing sulfidation caused by hydrogen sulfide, a sulfur gas. (Means of solution) (A) A hydrolyzable group-containing organotrisiloxane compound represented by the following formula (1): 100 parts by mass, (R1 and R3 are unsubstituted or halogen-substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, R2 is an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group, X is a hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, and keto-oxime groups, and a is 0 or 1.) (B) Hardening catalyst: 0.01 to 10 parts by mass A silicone coating composition containing

Description

Technology Field

[0001] The present invention relates to a moisture-curing type room-temperature curable silicone coating composition that crosslinks and cures through hydrolysis and condensation reactions with moisture (water) in the atmosphere at room temperature (23℃±15℃), and in particular, to a silicone coating composition used for electrical and electronic components, structural components, etc. The silicone coating composition of the present invention has excellent storage stability and, after coating on various substrates, cures rapidly at room temperature, and can obtain a cured film with excellent transparency, flexibility (following of the curvature of the substrate), adhesion (adhesion to the substrate), and low gas permeability, thereby making it a silicone coating composition capable of imparting various functionalities such as surface protection, water repellency, rust prevention, water resistance, weather resistance, chemical resistance, and stain resistance to various substrates. Background Technology

[0002] Unlike other hydrocarbon-based organic resins, silicone resins (organopolysiloxane resins) exhibit excellent heat resistance, weather resistance, water resistance, and flame retardancy, and can form a cured film with a high-hardness surface. Consequently, curable silicone rubber compositions (silicone elastomer compositions) and silicone resin-based resins (such as polyorganosilsesquioxane resins having a three-dimensional network structure) that have crosslinking groups, such as alkoxy groups or silanol groups bonded to silicon atoms within the molecule, are widely used in various applications and fields, including surface protective materials for various substrates, heat-resistant coatings, weather-resistant coatings, water-repellent agents, and various binders. Among these, silicone resins are used as conformal coatings for electronic substrates in home appliances and electronic components due to their excellent heat resistance and electrical insulation properties. Furthermore, research on resin compositions has made it possible to produce coating compositions that do not require diluting organic solvents, and coating agents with excellent safety and VOC (volatile organic compound) issues are commercially available. However, general silicone rubber-based or silicone resin-based coating compositions have a low protective effect on electrode metals (especially silver electrodes) against corrosive gases such as hydrogen sulfide, and a solution was desired.

[0003] Conventionally, to reduce metal corrosion caused by corrosive gases such as hydrogen sulfide, it has been necessary to use acrylic resin-based or urethane resin-based coating agents; however, these organic resin coating materials are generally used in a diluted state with organic solvents, which presents issues regarding VOCs and safety. Furthermore, due to problems with heat resistance and electrical properties, the range of application for acrylic and urethane-based coating agents is limited.

[0004] In light of the above, there was a demand for a solvent-free silicone-based coating agent that, in addition to heat resistance and electrical properties, has excellent ability to prevent metal corrosion caused by corrosive gases such as hydrogen sulfide.

[0005] The present invention relates to a type of material that forms a hard film after curing, among silicone-based coating agents. As such a silicone coating agent composition, a so-called silicone varnish solution has been widely used in the past, in which a curable silicone resin having terminal silanol groups and an average molecular weight of about 3,000 to 2,000,000 is dissolved in an organic solvent such as toluene or xylene. When using this, a film with excellent surface hardness, adhesion, heat resistance, weather resistance, and water resistance can be obtained. However, because organic solvents are essential components and a dehydration condensation crosslinking reaction between silanol groups is utilized, heat curing at 150°C or higher for a long time is generally required to form the film.

[0006] In response to this, there is a demand for a one-component, solvent-free, room-temperature curing silicone coating composition that does not contain organic solvents, is capable of room-temperature curing, and has excellent storage stability. Consequently, the use of a relatively low molecular weight silicone alkoxyoligomer obtained by partially (co)hydrolyzing and condensing an organoalkoxysilane is being considered. At the same time, research on curing catalysts that effectively promote the moisture-induced hydrolysis and dealolysis condensation reactions of the silicone alkoxyoligomer to form a cross-linked film through siloxane bonds is also being actively conducted, and the cited technology has been proposed (Patent Documents 1 and 2: Japanese Patent Publication No. 60-233164, Japanese Patent No. 4110402).

[0007] However, since the hardened film obtained from any technology is rigid and has poor flexibility, it has poor conformability to the curvature of the substrate, and it was not possible to prevent metal corrosion caused by hydrogen sulfide.

[0008] Meanwhile, regarding solvent-free silicone compositions, examples of technologies aimed at preventing corrosion of a base metal by sulfurous corrosive gases include a technology that reduces corrosion of the base metal by adding metal powder, such as silver or copper, to the composition and causing sacrificial corrosion of the metal powder (Patent Documents 3 and 4: Japanese Patent No. 4114037, Japanese Patent No. 4530137), or a technology that reduces corrosion of the base metal by using organic additives (Patent Document 5: Japanese Patent No. 6418115). Although both are excellent technologies, they are means of neutralizing corrosive gas species penetrating the silicone film through reactions within the film, and their effectiveness was insufficient depending on the type of corrosive gas. Prior art literature

[0009] Japanese Patent Publication No. 60-233164, Japanese Patent No. 4110402, Japanese Patent No. 4114037, Japanese Patent No. 4530137, Japanese Patent No. 6418115 The problem to be solved

[0010] The present invention is made to solve the above-mentioned defects and aims to provide a silicone coating composition that does not contain organic solvents, does not impair the inherent properties of the curable organosilicon compound, has excellent storage stability as a coating composition, cures rapidly at room temperature after coating on a substrate, has excellent transparency and adhesion, and can provide a cured film with excellent conformability (flexibility) to the curvature of the substrate, and also has low gas permeability, which enables corrosion prevention of the substrate, particularly reducing sulfidation caused by hydrogen sulfide, a sulfur gas. means of solving the problem

[0011] The inventors, having conducted a thorough examination to achieve the above objective, discovered that by using a condensation reaction curable silicone coating composition containing a curing catalyst, the composition is based on an organotrisiloxane compound having a specific molecular structure that has at least one unsubstituted or substituted phenyl group in the molecule represented by the following general formula (1) and also contains at least four, preferably four to six, hydrolyzable groups in the molecule, thereby exhibiting excellent preservation in a sealed state, rapidly curing by a hydrolysis condensation reaction with moisture in the air under an open atmosphere, and providing a cured film with excellent transparency, adhesion, etc., and excellent conformability (flexibility) to the curvature of the substrate, and also, because of its low gas permeability, it is possible to reduce sulfidation caused by hydrogen sulfide in the cured film, and thus completed the present invention.

[0012] That is, the present invention provides articles sealed, coated, fixed, or bonded by the following silicone coating composition and a cured product of the composition.

[0013] [1]

[0014] (A) A hydrolyzable group-containing organotrisiloxane compound represented by the following general formula (1): 100 parts by mass,

[0015]

[0016] (during food, R 1 , R 3 Each is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 is an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group, X is each independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, and keto-oxime groups, and a is independently 0 or 1 for each bonded silicon atom.)

[0017] (B) Curing catalyst: 0.01 to 10 parts by mass

[0018] A silicone coating composition containing

[0019] [2]

[0020] In the above general formula (1), R 3 The silicone coating composition described in [1], which is an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group.

[0021] [3]

[0022] A silicone coating composition described in [1] or [2], wherein X is a methoxy group, an ethoxy group, an isopropenoxy group, or a keto-oxime group in the above general formula (1).

[0023] [4]

[0024] A silicone coating composition described in any one of [1] to [3], wherein, for every 100 parts by mass of component (A), 0.1 to 100 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) other than component (A) and / or a partially hydrolyzed condensate (C) thereof.

[0025]

[0026] (during food, R 1 , X, and a are each the same as above.)

[0027] [5]

[0028] A silicone coating composition described in any one of [1] to [4] that does not contain an organic solvent.

[0029] [6]

[0030] (A) The following general formula (2)

[0031]

[0032] (during food, R 1 , X, and a are each the same as above.)

[0033] A hydrolyzable organosilane compound represented by, and the following general formula (3)

[0034]

[0035] (during food, R 2 , R 3 Each is identical to the above.)

[0036] A silicone coating composition described in any one of [1] to [5], which is a hydrolysis and condensation reaction product with diorganosilanediol represented by.

[0037] [7]

[0038] Articles sealed, coated, fixed, or bonded with a cured silicone coating composition as described in any one of [1] to [6]. Effects of the invention

[0039] According to the present invention, a silicone coating composition is obtained that has excellent storage stability, can be coated on a substrate without containing organic solvents, rapidly forms a cured film at room temperature after coating, and provides a cured film with excellent transparency and adhesion, and excellent conformability (flexibility) to the curvature of the substrate, and also has low gas permeability, which enables corrosion prevention of the substrate, particularly reducing sulfidation caused by hydrogen sulfide, a sulfur gas. Specific details for implementing the invention

[0040] The present invention will be described in detail below.

[0041] [(A) component]

[0042] (A) The component is the main component of the silicone coating composition of the present invention and is an organotrisiloxane compound of a specific molecular structure represented by the following general formula (1), having at least one unsubstituted or substituted phenyl group in the molecule and also containing at least 4, preferably 4 to 6, hydrolyzable groups in the molecule.

[0043] The hydrolyzable group-containing organotrisiloxane compound of component (A) rapidly crosslinks and cures by hydrolysis and condensation reaction with moisture (water) in the atmosphere at room temperature (23℃±15℃, hereinafter the same) in the presence of the curing catalyst of component (B) described below, and can provide a cured film with excellent transparency and adhesion, excellent conformability (flexibility) to the curvature of the substrate, and suppressed gas permeability.

[0044]

[0045] (during food, R 1 , R 3 Each is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 is an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group, X is each independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, and keto-oxime groups, and a is independently 0 or 1 for each bonded silicon atom.)

[0046] In the above formula (1), R 1 , R 3Each is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, etc.; a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclohexenyl group, etc.; a straight-chain, branched, or cyclic alkenyl group having 2 to 10 carbon atoms such as a phenyl group, tolyl group, xylyl group, naphthyl group, etc.; an aryl group having 6 to 10 carbon atoms such as a mesethyl group. Examples include alkyl aryl groups having 7 to 10 carbon atoms, benzyl groups, phenylethyl groups, and aralkyl groups having 7 to 10 carbon atoms, or halogen-substituted monovalent hydrocarbon groups in which some of the hydrogen atoms of these groups are substituted with halogen atoms, such as chloromethyl groups, 2-bromoethyl groups, 3,3,3-trifluoropropyl groups, 3,3,4,4,5,5,5-heptafluoropentyl groups, 2,3,3-trifluoro-2-chlorocyclobutyl groups, 3,4-dibromo-1-chlorohexyl groups, difluoromonochlorovinyl groups, 2-iodoccyclohexanyl groups, chlorophenyl groups, perchlorophenyl groups, fluorophenyl groups, perfluorophenyl groups, 2,2,2-trifluorotolyl groups, and 2,4-dibromobenzyl groups.

[0047] Among these, R 1 As such, methyl, ethyl, propyl, vinyl, and phenyl groups are preferred, and also R described below 2 As explained in the paragraph, when the low gas permeability of the resulting cured film is important, it is preferable that the phenyl group be unsubstituted, halogen-substituted, or alkyl-substituted; however, various other monovalent organic groups may be selected for reasons of designing the curing rate by hydrolysis and condensation reactions of the composition of the present invention.

[0048] R 3In terms of reducing the gas permeability of the resulting cured film, it is preferable that the phenyl group be an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group, such as a phenyl group, tolyl group, xylyl group, chlorophenyl group, perchlorophenyl group, fluorophenyl group, perfluorophenyl group, or 2,2,2-trifluorotolyl group.

[0049] Also R 3 As such, by using a monovalent hydrocarbon group other than the aforementioned unsubstituted, halogen-substituted, or alkyl-substituted phenyl group, the Tg of the cured film can be controlled, and R can be adjusted to the desired low gas permeability and Tg. 3 Various designs are possible. Among these, alkyl groups, allyl groups, and fluoroalkyl groups are preferred in that the resulting cured film has good release properties and water repellency.

[0050] In the above formula (1), R 2 is an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group, and the organotrisiloxane compound represented by formula (1) of component (A) needs to have at least one unsubstituted, halogen-substituted, or alkyl-substituted phenyl group (e.g., the phenyl group, tolyl group, xylyl group, chlorophenyl group, perchlorophenyl group, fluorophenyl group, perfluorophenyl group, 2,2,2-trifluorotolyl group, etc. exemplified above) in one molecule. When low gas permeability is important, preferably two (i.e., R) in the molecule. 2 and R 3 It is preferable that both sides of the phenyl group have unsubstituted, halogen-substituted, or alkyl-substituted phenyl groups.

[0051] The gas permeability of the cured film is reduced by these unsubstituted or substituted phenyl groups, and in the case of an organotrisiloxane compound that does not have unsubstituted or substituted phenyl groups in the molecule, the gas permeability of the cured film is increased, and it is not possible to reduce corrosion of the base metal by corrosive gases.

[0052] In the above formula (1), X is at least one hydrolytic group independently selected from an unsubstituted or alkoxy-substituted alkoxy group, an aryloxy group, an alkenyloxy group, an acyloxy group, and a ketooxyme group. Specifically as X, preferably, at least one hydrolytic group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, and ketooxy groups having 1 to 7 carbon atoms may be included, for example, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, isobutoxy groups, sec-butoxy groups, tert-butoxy groups having 1 to 6 carbon atoms, preferably alkoxy groups having 1 to 4 carbon atoms, alkoxy-substituted alkoxy groups having 2 to 4 carbon atoms, such as methoxy-substituted methoxy groups, methoxy-substituted ethoxy groups, ethoxy-substituted methoxy groups, ethoxy-substituted ethoxy groups, etc., alkenyloxy groups having 2 to 4 carbon atoms, such as vinyloxy groups, allyloxy groups, propenyloxy groups, isopropenyloxy groups, butenyloxy groups, etc., aryloxy groups having 6 to 10 carbon atoms, such as phenyloxy groups, acetoxy groups, etc. Examples include acyloxy groups having 2 to 4 carbon atoms, such as propionoxy groups, and ketooxy groups having 3 to 6 carbon atoms, such as dimethyl ketooxy groups, methyl ethyl ketooxy groups, and diethyl ketooxy groups. Preferably, they are methoxy groups, ethoxy groups, isopropenoxy groups, methyl ethyl ketooxy groups, etc.

[0053] a is independently 0 or 1 for each silicon atom bonded, preferably 1.

[0054] (A) The hydrolyzable group-containing organotrisiloxane compound of the above formula (1) has at least 4 hydrolyzable groups X in one molecule, preferably 4 to 6, more preferably 4, and a suitable degreasing agent can be selected to achieve the desired curing speed and preservation characteristics.

[0055] As a hydrolyzable group-containing organotrisiloxane compound represented by formula (1), specifically, the following compounds may be exemplified.

[0056]

[0057]

[0058] In addition, the hydrolyzable group-containing organotrisiloxane compound represented by the above general formula (1) of component (A) is a monovalent hydrocarbon group bonded to a silicon atom represented by the following general formula (2), and is the above R 1 A hydrolyzable organosilane compound having a hydrolyzable group X, and the above-mentioned R as a monovalent hydrocarbon group bonded to a silicon atom represented by the following general formula (3). 2 and R 3 A diorganosilanediol (diorganodihydroxysilane) having at least one, preferably two, unsubstituted, halogen-substituted, or alkyl-substituted phenyl group among molecules having one of each can be easily prepared by hydrolyzing and condensing it under conventionally known conditions in the presence of a condensation reaction catalyst.

[0059]

[0060]

[0061] (among each formula, R 1 , R 2 , R 3 , X, and a are each the same as above.)

[0062] Examples of hydrolyzable organosilane compounds represented by the above formula (2) include, specifically, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, methyltriisopropenoxysilane, etc.

[0063] As a diorganosilanediol represented by the above formula (3), specifically examples include diphenylsilanediol, methylphenylsilanediol, ethylphenylsilanediol, etc.

[0064] The reaction ratio of the hydrolyzable organosilane compound represented by formula (2) and the diorganosilanediol represented by formula (3) is preferably such that there is at least 1 mole of the hydrolyzable organosilane compound represented by formula (2) per 1 mole of silanol groups in the diorganosilanediol represented by formula (3), but it is more preferable that there are at least 2 moles of the hydrolyzable organosilane compound per 1 mole of silanol groups in order to reduce the residual silanol groups in the reaction product. The upper limit of the reaction molar ratio of the hydrolyzable organosilane compound represented by formula (2) should be about 5 moles or less. If there are many residual silanol groups in the reaction product, it may reduce the curing reaction rate of the subsequent composition.

[0065] Examples of condensation reaction catalysts used in the above reaction include titanium chelate compounds, guanidyl group-containing silane compounds such as tetramethylguanidylpropyltrimethoxysilane, aluminum chelate compounds, and organic zirconium compounds.

[0066] The amount of condensation reaction catalyst added is sufficient to allow the condensation reaction of the diorganosilanediol represented by the formula (3) and the hydrolyzable organosilane compound represented by the formula (2) to proceed at room temperature to under heating, and typically, 0.01 to 10 parts by mass, particularly 0.1 to 5 parts by mass, is preferred for a total of 100 parts by mass of the diorganosilanediol and the hydrolyzable organosilane compound.

[0067] As reaction conditions, the reaction product (component (A)) can be obtained by reacting at a temperature of 0 to 150°C, particularly 25 to 100°C, for 5 to 120 minutes, particularly 10 to 60 minutes, preferably while removing alcohols, etc., that are by-products of the condensation reaction.

[0068] In the silicone coating composition of the present invention, the hydrolyzable group-containing organotrisiloxane compound of component (A) may be used alone or in combination of two or more types.

[0069] [(B) component]

[0070] The curing catalyst of component (B) is a condensation reaction catalyst necessary for the composition of the present invention to rapidly reach a cured film by hydrolyzing and condensing the hydrolyzable group-containing organotrisiloxane compound of component (A) represented by the above general formula (1) with moisture (water) in the atmosphere during the curing process, and is selected from organic tin compounds, organic aluminum compounds, organic titanium compounds, organic zirconium compounds, and organic base compounds, and a suitable catalyst is selected according to the reactivity of the hydrolyzable group X selected in the above general formula (1) of component (A).

[0071] Examples of such condensation reaction catalysts include hydroxides, oxides, or basic metal salts of alkali metals or alkaline earth metals. Specifically, examples include hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, chlorides of alkaline earth metals such as calcium chloride and magnesium chloride, oxides of alkaline earth metals such as calcium oxide and magnesium oxide, and basic metal salts such as basic zinc carbonate and basic magnesium carbonate.

[0072] In addition, aluminum chelate compounds, organic titanium compounds, organic tin compounds, aminoalkylalkoxysilanes, ammonium salts, etc., may also be used as catalysts for other condensation reactions. Examples of aluminum chelate compounds include aluminum ethylacetoacetate diisopropylate, aluminum tris(ethyl acetate), aluminum tris(ethyl acetonate), and aluminum bisethylacetoacetate monoacetylacetonate. Examples of organic titanium compounds include tetraisopropoxytitanine, tetra-n-butoxytitanine, and tetrakis(2-ethylhexoxy)titanine. Examples of organotin compounds include tin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoeate, stannous octoate, stannous naphthenate, stannous oleate, stannous isobutyrate, stannous linoleate, stannous stearate, stannous benzolate, stannous naphthoate, stannous lauricate, o-tinous acid, β-benzoylpropionate, stannous crotonicate, stannous tropate, p-stannous bromobenzoate, stannous palmitoleate, stannous cinnamate, and stannous phenylacetate. Examples of aminoalkylalkoxysilanes include γ-aminopropyltrimethylmethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(dimethylamino)propyltrimethoxysilane, etc. Examples of ammonium salts include salts of acids and amines, and examples of acids include acetic acid, formic acid, etc., and examples of amines include allylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3-diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, tri-n-octylamine, tert-butylamine, sec-butylamine, propylamine, 3-methoxypropylamine, etc.

[0073] The amount of curing catalyst of component (B) is 0.01 to 10 parts by mass, and particularly 0.02 to 5 parts by mass, with respect to 100 parts by mass of the hydrolyzable group-containing organotrisiloxane compound of component (A), so that the reaction proceeds well and the curability of the obtained silicone coating composition is good.

[0074] [(C) component]

[0075] The silicone coating composition of the present invention may additionally contain, in addition to the above components (A) and (B), a hydrolyzable organosilane compound (C) represented by the above formula (2), which is the same as that used in the preparation of the above component (A). By incorporating this component (C), the preservation properties of the composition can be improved, and the curing time (pot life) of the composition can be controlled.

[0076] In addition, when obtaining component (A) by reacting the hydrolyzable organosilane compound represented by the above formula (2) with the diorganosilanediol represented by the above formula (3), the hydrolyzable organosilane compound represented by the above formula (2) may be reacted in excess, and the excess hydrolyzable organosilane compound represented by the above formula (2) after the reaction may be used as is.

[0077] The content of the hydrolyzable organosilane compound represented by the above formula (2) should be 100 parts by mass or less (0 to 100 parts by mass) per 100 parts by mass of component (A), and preferably about 0.1 to 50 parts by mass.

[0078] [Other ingredients]

[0079] In addition to the silicone coating composition of the present invention, a small amount of various additives, such as plasticizers, release agents, flame retardants, antioxidants, UV absorbers, or pigments or dyes such as titanium dioxide, carbon black, or iron oxide, may be incorporated as needed within a range that does not impair the purpose of the present invention. Likewise, aerosolized silica, silica aerogel, silica gel, and reinforcing silica fillers treated with organic silanes, organic siloxanes, or organic silases thereof, as well as fillers such as asbestos, crushed fused quartz, aluminum oxide, aluminum silicate, zirconium silicate, magnesium oxide, zinc oxide, talc, diatomaceous earth, mica, calcium carbonate, clay, zirconia, glass, sand, graphite, barium sulfate, zinc sulfate, aluminum powder, sawdust, cork, polymer powder of fluorocarbons, silicone rubber powder, silicone resin powder, etc., may be incorporated within a range that does not impair the purpose of the present invention.

[0080] Additionally, while it is acceptable to incorporate organic solvents as needed, for the sake of VOCs and safety, it is preferable not to include organic solvents or to use them in small amounts, as long as the composition has a process-safe viscosity.

[0081] In preparing the silicone coating composition of the present invention, a predetermined amount of the above-mentioned components (A) and (B) is simply mixed. In this case, the temperature during mixing is not limited, but there is no need to perform operations such as heating. The composition can be easily obtained by simply stirring and mixing at room temperature for at least 10 minutes, preferably 10 to 60 minutes. Furthermore, during this mixing, it is preferable to perform the mixing under a nitrogen atmosphere to prevent hydrolyzable groups, such as alkoxy groups, from being hydrolyzed due to the incorporation of moisture.

[0082] In this way, the silicone coating composition of the present invention can provide an article sealed, coated, fixed, or bonded with a cured product of the composition.

[0083] The silicone coating composition of the present invention can be applied and cured to various metal substrates, wood, stone, mortar boards, slate boards, roof tiles, concrete, glass, ceramics, plastic products, organic resin coating products, etc., by a conventionally known method to form a coating film. In this case, specific application methods include brushing, spraying, dipping, flow coater, knife coater, spin coater, etc., and on-site painting is also possible. In addition, the amount of application varies depending on the type of substrate or the purpose of the coating, but generally, the thickness of the film after curing should be in the range of 0.1 to 200 μm, and preferably in the range of 1 to 100 μm.

[0084] Although the curing conditions of the silicone coating composition of the present invention are not particularly limited, since the film is formed by curing with moisture in the air, it can be dried by leaving it for about 1 minute to 2 hours in a temperature range of room temperature to 80°C (tack-free state), and the curing reaction can be completed by leaving it for several hours to several days.

[0085] In this way, the silicone coating composition of the present invention can provide an article sealed, coated, fixed, or bonded with a cured product of the composition.

[0086] (Example)

[0087] The present invention will be specifically described below by presenting preparation examples, embodiments, and comparative examples, but the present invention is not limited to the following embodiments. In addition, in each example, room temperature is 25°C, and viscosity is the value measured by a rotational viscometer at 25°C.

[0088] [Jo Je-ye]

[0089] (A) component

[0090] (A-1)

[0091] Diphenylsilanediol (16.2g), vinyltrimethoxysilane (25g), and titanium chelate catalyst (0.2g, Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) were added to a 100ml flask and reacted at 100°C for 60 minutes, after which the methanol and excess vinyltrimethoxysilane generated were removed by a nitrogen gas flow, thereby obtaining an organotrisiloxane compound (A-1) represented by the following formula.

[0092]

[0093] (A-2)

[0094] Diphenylsilanediol (16.2g), phenyltrimethoxysilane (25g), and titanium chelate catalyst (0.2g, Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) were added to a 100ml flask and reacted at 100°C for 60 minutes, after which the methanol generated was removed by a nitrogen gas flow, and then the excess phenyltrimethoxysilane was removed by heating under reduced pressure, thereby obtaining an organotrisiloxane compound (A-2) represented by the following formula.

[0095]

[0096] (A-3)

[0097] Diphenylsilanediol (16.2g), methyltrimethoxysilane (25g), and titanium chelate catalyst (0.2g, Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) were added to a 100ml flask and reacted at 100°C for 60 minutes, after which the methanol generated and excess methyltrimethoxysilane were removed by a nitrogen gas flow, thereby obtaining an organotrisiloxane compound (A-3) represented by the following formula.

[0098]

[0099] (A-4)

[0100] Diphenylsilanediol (16.2g), vinyltriisopropenoxysilane (25g), and tetramethylguanidylpropyltrimethoxysilane (0.2g) were added to a 100ml flask and reacted at 100°C for 60 minutes, after which the acetone generated was removed by a nitrogen gas flow, and then the excess vinyltriisopropenoxysilane was removed by heating under reduced pressure, thereby obtaining an organotrisiloxane compound (A-4) represented by the following formula.

[0101]

[0102] (A-5)

[0103] Methylphenylsilanediol (16.2g, some of which is dimerized), vinyltrimethoxysilane (25g), and titanium chelate catalyst (0.2g, Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) were added to a 100ml flask and reacted at 100°C for 60 minutes, after which the methanol and excess vinyltrimethoxysilane generated were removed by a nitrogen gas flow, thereby obtaining an organotrisiloxane compound (A-5) represented by the following formula.

[0104]

[0105] (A) Ingredient (for comparison)

[0106] (a-1)

[0107] Dimethylsilanediol (12.3g, some of which is dimerized), methyltrimethoxysilane (20g), and titanium chelate catalyst (0.2g, Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) were added to a 100ml flask and reacted at 100°C for 60 minutes, after which the methanol generated and excess methyltrimethoxysilane were removed by a nitrogen gas flow, thereby obtaining an organotrisiloxane compound (a-1) represented by the following formula.

[0108]

[0109] (a-2)

[0110] A terminal hydroxyl group type dimethylsilicon polymer (700 mPa.s, 300 g), methyltrimethoxysilane (25 g), and titanium chelate catalyst (0.2 g, manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) were added to a 100 ml flask and reacted at 100°C for 60 minutes, after which the methanol generated was removed by a nitrogen gas flow, and then the excess methyltrimethoxysilane was removed by heating under reduced pressure, thereby obtaining an organopolysiloxane compound (a-2) represented by the following formula.

[0111]

[0112] (In the equation, n is 250.)

[0113] [Examples 1–5, Comparative Examples 1–3]

[0114] Each component shown in Tables 1 and 2 was mixed in the respective amounts in a 10 ml glass cup and stirred with water at room temperature for 10 minutes to obtain a silicone coating composition. In addition, (A-1) to (A-5), (a-1), and (a-2) do not contain solvent components. The appearance and characteristics of the obtained silicone coating composition were visually inspected and listed in Tables 1 and 2.

[0115] In addition, the silicone coating composition obtained above was cured under curing conditions of 23℃ / 50% Rh × 7 days. The appearance and characteristics of the obtained cured product were visually inspected and listed in Tables 1 and 2.

[0116] In addition to component (A) obtained in the above preparation example, the raw materials used are shown below.

[0117] (B) component

[0118] (B-1)

[0119] Tin Catalyst: U-830 (Manufactured by Nitto Kasei Co., Ltd., Dioctyl Tin)

[0120] (B-2)

[0121] Amine catalyst: Tetramethylguanidylpropyltrimethoxysilane

[0122] (C) component

[0123] (C-1)

[0124] vinyltrimethoxysilane

[0125] (A) Ingredient (for comparison)

[0126] (a-3)

[0127] A solvent-type coating agent based on acrylic resin components: Humiseal (registered trademark)-1B66NS was prepared. It has a solid content of 35 mass% (solvent component 65 mass%), and in order to apply a thin film, it was diluted by 1 / 2 with an additional solvent (diluent Humiseal (registered trademark) thinner 901).

[0128]

[0129]

[0130] Next, the appearance of the cured product, tack-free time, corrosion resistance test, and flexibility were evaluated using the silicone coating compositions of the above examples and comparative examples, and Comparative Example 3 using the above (a-3) component. These results are shown in Table 3.

[0131] (Curing material appearance)

[0132] In the evaluation of the following tack free time, the cured film on the aluminum petri dish was evaluated for transparency and degree of coloration by visual inspection.

[0133] (Take-free time)

[0134] 0.20g of each composition (liquid) was placed on an aluminum petri dish, and a 2cm × 2cm (4cm) plate was placed on it. 2 The composition was spread in a square shape, and the time until the adhesiveness of the surface of each composition was lost due to tack was evaluated as the curing time (tack-free time).

[0135] (Corrosion resistance test)

[0136] 0.08g of each material (silicone coating composition) (liquid) is applied to a 2cm × 2cm (4cm) surface of a silver-plated aluminum plate so that a hardened film of approximately 200μm is formed.2 It was spread in a square shape and cured under the conditions of 23℃ / 50% Rh × 7 days, and the corrosion state of the silver-plated surface was observed over time (initial, after 1 day, after 3 days, after 7 days, after 14 days) using a hydrogen sulfide gas corrosion tester. The corrosion conditions are as follows.

[0137] Hydrogen sulfide concentration: 2 ppm

[0138] Temperature: 23℃

[0139] Humidity: 50% Rh

[0140] The silver-plated surface was observed before and after the corrosion test, and it was determined that corrosion occurred at the point when the initial silver luster changed (blackening, graying).

[0141] (Song quality)

[0142] After the above corrosion prevention test was completed, when the silver-plated aluminum plate (having a cured film of the silicone coating composition) was bent, it was evaluated whether the coating layer could follow the substrate without breaking.

[0143]

[0144] (result)

[0145] From the above results, it was confirmed that the silicone coating composition of the present invention has excellent curability and transparency at room temperature, as well as excellent effect in preventing corrosion of the metal substrate from corrosive gases and excellent substrate-following ability (flexibility).

Claims

Claim 1 (A) A hydrolyzable group-containing organotrisiloxane compound represented by the following general formula (1): 100 parts by mass, (during food, R 1 is independently an unsubstituted or halogen-substituted straight-chain, branched, or cyclic alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, unsubstituted or halogen-substituted, and R 2 (B) A silicone coating composition containing 0.01 to 10 parts by mass of a curing catalyst. Claim 2 In claim 1, in the above general formula (1), R 3 A silicone coating composition characterized by being an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group. Claim 3 A silicone coating composition according to claim 1, characterized in that, in the general formula (1), X is a methoxy group, an ethoxy group, an isopropenoxy group, or a keto-oxime group. Claim 4 In claim 1, in the above general formula (1), R 1 A silicone coating composition characterized by being an unsubstituted, halogen-substituted, or alkyl-substituted phenyl group. Claim 5 A silicone coating composition according to claim 1, characterized in that, for every 100 parts by mass of component (A), it additionally contains 0.1 to 100 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) other than component (A) and / or a partially hydrolyzed condensate (C) thereof. (during food, R 1 , X, and a are each the same as above.) Claim 6 A silicone coating composition according to claim 1, characterized in that it does not contain an organic solvent. Claim 7 In claim 1, component (A) is the following general formula (2) (during food, R 1 A hydrolyzable organosilane compound represented by , X, and a, respectively, as above, and the following general formula (3) (during food, R 2 , R 3 A silicone coating composition characterized by being a hydrolysis and condensation reaction product with a diorganosilanediol, indicated as (each identical to the above). Claim 8 An article sealed, coated, fixed, or bonded with a cured product of a silicone coating composition described in any one of claims 1 to 7.

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