Silicone coating agent composition and article

Abstract

An organosiloxane mixture containing hydrolyzable groups, which is based on a specific molecular structure of an organotrisiloxane compound having at least one unsubstituted, halogen-substituted or alkyl-substituted phenyl group in the molecule and at least 4 hydrolyzable groups at both ends of the molecular chain, and an organodisiloxane compound having at least 2 unsubstituted, halogen-substituted or alkyl-substituted phenyl groups on the same silicon atom in the molecule and at least 2 hydrolyzable groups on the other same silicon atom in the molecule, and used in a specific compounding ratio, is used as the main component. The condensation reaction curable organosilicon coating agent composition containing a curing catalyst has excellent storage stability even without an organic solvent, cures rapidly at room temperature after being coated on a substrate, and can form a cured film with excellent transparency, adhesion, etc., excellent followability to bending of the substrate, and having substrate corrosion prevention properties.

Description

Technical Field

[0001] The present invention relates to a moisture-curing type room-temperature curable silicone coating agent composition which crosslinks and cures by hydrolysis and condensation reactions using moisture (water) in the atmosphere at room temperature (23°C ± 10°C), and particularly relates to a silicone coating agent composition used for protection, sealing, etc. of electrical and electronic components, structural components, etc. The silicone coating agent composition of the present invention has excellent storage stability, rapidly cures at room temperature after being coated on various substrates, and can obtain a cured film with excellent transparency, flexibility (followability to substrate bending), adhesion (adhesion to the substrate), low gas permeability, etc. Therefore, a silicone coating agent composition (so-called silicone conformal coating agent composition) capable of imparting various functions such as surface protection, water repellency, rust prevention, water resistance, weather resistance, chemical resistance, stain resistance, etc. to various substrates can be prepared. Background Art

[0002] Silicone resins (organopolysiloxane resins) are different from other general organic resins of hydrocarbon series, and are excellent in heat resistance, weather resistance, water resistance, flame retardancy, etc., and can form a cured film having a surface with high hardness. Therefore, curable silicone rubber compositions (organosilicon elastomer compositions) and silicone resin-based resins (such as polyorganosilsesquioxane resins having a three-dimensional network structure) having crosslinkable groups such as alkoxy groups and silanol groups bonded to silicon atoms in the molecule have been widely used in various applications and fields such as surface protection materials for various substrates, heat-resistant coatings, weather-resistant coatings, water repellents, various adhesives, etc. Among them, silicone resins have good heat resistance and electrical insulation properties, and are therefore used in conformal coatings of electronic substrates such as home appliances and electronic components. In addition, through efforts on the resin composition, a coating composition that does not require a diluting organic solvent can also be realized, and a coating agent excellent in terms of VOC (volatile organic compound) problems and safety has been put on the market. However, general silicone rubber-based and silicone resin-based coating agent compositions have a low protective effect on electrode metals (especially silver electrodes) against corrosive gases such as hydrogen sulfide, and a solution to this problem is desired.

[0003] In the past, in order to reduce metal corrosion caused by corrosive gases such as hydrogen sulfide, it has been necessary to use coating agents based on acrylic resin systems and polyurethane resin systems. However, such organic resin coating materials are generally used in a state diluted with organic solvents, and have problems of VOC and safety. In addition, due to problems of heat resistance and electrical properties, there are limitations in the range of use (use temperature, insulation) for acrylic-based and polyurethane-based coating agents.

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

[0005] The present invention relates to a material of a type that forms a hard cured film after curing in a silicone-based coating agent. As such a silicone coating agent composition, a so-called silicone varnish solution in which a curable silicone resin having a terminal silanol group and an average molecular weight of about 3,000 to 2,000,000 is dissolved in an organic solvent such as toluene or xylene has been widely used so far. If this silicone varnish solution is used, a film with excellent surface hardness, adhesion, heat resistance, weather resistance, water resistance, etc. can be obtained. However, since it uses an organic solvent with a large environmental load as an essential component and utilizes the dehydration condensation crosslinking reaction between silanol groups, generally, for film formation, heating and curing at 150°C or higher for a long time are required.

[0006] In contrast, a one-component solvent-free room-temperature curable silicone coating agent composition that does not contain an organic solvent, can be cured at room temperature, and has excellent storage stability has been long awaited. The use of a lower molecular weight organosiloxane oligomer formed by partial (co)hydrolysis and condensation of an organoalkoxysilane has been studied. At the same time, research on a curing catalyst that effectively promotes the hydrolysis reaction and de-alcohol condensation reaction of the organosiloxane oligomer with moisture to form a crosslinked film based on siloxane bonds has been actively carried out, and the cited technologies have been proposed (Patent Documents 1 and 2: Japanese Patent Laid-Open No. 60-233164, Japanese Patent No. 4110402).

[0007] However, all of these technologies have a problem that the obtained cured film is rigid and has poor flexibility, so the followability to the bending of the substrate is poor. In addition, they cannot prevent the metal corrosion caused by hydrogen sulfide.

[0008] On the other hand, in a solvent-free silicone composition, as an example of a technology for preventing the corrosion of the substrate metal caused by sulfuric corrosive gases, there are technologies such as adding metal powders such as silver and copper to the composition and reducing the corrosion of the substrate metal by the sacrificial corrosion of the metal powder (Patent Documents 3 and 4: Japanese Patent No. 4114037, Japanese Patent No. 4530137); technologies for reducing the corrosion of the substrate metal by using organic additives (Patent Document 5: Japanese Patent No. 6418115). These are all excellent technologies, but as a means of rendering harmless the corrosive gas source that has invaded the silicone film by internal reactions of the film, the effects are insufficient depending on the type of corrosive gas.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Laid-Open No. 60-233164

[0012] Patent Document 2: Japanese Patent No. 4110402

[0013] Patent Document 3: Japanese Patent Publication No. 4114037

[0014] Patent Document 4: Japanese Patent Publication No. 4530137

[0015] Patent Document 5: Japanese Patent Publication No. 6418115 Summary of the Invention

[0016] Problems to be Solved by the Invention

[0017] The present invention has been completed to solve the above-mentioned drawbacks, and an object thereof is to provide a silicone coating agent composition which, even without containing an organic solvent, does not impair the inherent properties of the curable silicone compound, has excellent storage stability as a coating agent composition, rapidly cures at room temperature (23°C ± 10°C, the same hereinafter) after being coated on a substrate, can form a cured film, the cured film has excellent transparency, adhesion, etc., excellent followability (flexibility) to bending of the substrate, and since it has low gas permeability, it can reduce the corrosion resistance of the substrate, particularly sulfidation caused by hydrogen sulfide as a sulfurous gas. An object is to provide a silicone coating agent composition (silicone conformal coating agent composition) and an article sealed, coated, fixed or bonded with a cured product of the silicone coating agent composition, particularly in the protection, sealing, etc. of target electrical and electronic components, structural components, etc., by expanding the usable temperature range of the sealing member, and by further lowering the glass transition temperature (Tg) of the cured film while maintaining the corrosion resistance of the coating agent, it can be used particularly in a wider temperature range on the low temperature side.

[0018] Means for Solving the Problems

[0019] The inventors of the present invention conducted in-depth research to achieve the above object, and as a result, found that: by using an organotrisiloxane compound having a specific molecular structure in which the molecule has at least one unsubstituted, halogen-substituted or alkyl-substituted phenyl group and contains at least 4, preferably 4 to 6 hydrolyzable groups at both ends of the molecular chain, and an organodisiloxane compound having a specific molecular structure in which at least 2 unsubstituted, halogen-substituted or alkyl-substituted phenyl groups are present on the same silicon atom in the molecule and at least 2, preferably 2 or 3 hydrolyzable groups are contained on the other same silicon atom in the molecule, and using a hydrolyzable group-containing organosiloxane mixture mainly composed of these two compounds in a specific blending ratio, a condensation reaction curable organosilicon coating agent composition containing a curing catalyst can be obtained. The organosilicon coating agent composition exhibits excellent storage stability under closed conditions (in an air barrier environment), and rapidly cures by a hydrolysis-condensation reaction caused by moisture in the atmosphere in an open atmosphere, and can form a cured film having excellent transparency, adhesion, etc., and excellent followability (flexibility) to bending of the substrate. Moreover, due to its low gas permeability, sulfidation caused by hydrogen sulfide in the cured film can be reduced, and further, the glass transition temperature (Tg) of the cured product can be lowered. Therefore, it can be used particularly in a wider temperature range on the low temperature side, and the present invention was completed.

[0020] That is, the present invention provides the following organosilicon coating agent composition and an article sealed, coated, fixed or bonded with a cured product of the composition.

[0021] [1] An organosilicon coating agent composition, comprising:

[0022] (A) 100 parts by mass of a hydrolyzable group-containing organosiloxane mixture containing 20 to 95 parts by mass of (A-1) an organotrisiloxane compound having a hydrolyzable group represented by the following general formula (1-1) and 80 to 5 parts by mass of (A-2) an organodisiloxane compound having a hydrolyzable group represented by the following general formula (1-2) (wherein the total of the (A-1) component and the (A-2) component is 100 parts by mass):

[0023] [Chemical formula 1]

[0024]

[0025] [Chemical formula 2]

[0026]

[0027] (In each formula, R 1 、R 3 、R 4 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 2is 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 ketoxime groups, and a is independently 0 or 1 for each bonded silicon atom.)

[0028] (B) Curing catalyst: 0.01 to 10 parts by mass.)

[0029] [2] The organosilicon coating agent composition according to [1], wherein, in the general formula (1-1), R 3 is an unsubstituted, halogen-substituted or alkyl-substituted phenyl group.)

[0030] [3] The organosilicon coating agent composition according to [1] or [2], wherein, in the general formulas (1-1) and (1-2), X is each a methoxy group, an ethoxy group, an isopropenyloxy group or a ketoxime group.)

[0031] [4] The organosilicon coating agent composition according to any one of [1] to [3], further containing 0.1 to 100 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and / or its partial hydrolysis condensate (C) other than the components (A-1) and (A-2) with respect to 100 parts by mass of the component (A),

[0032] (R 1 ) a Si(X) (4-a) (2)

[0033] (In the formula, R 1 , X and a are the same as above respectively.)

[0034] [5] The organosilicon coating agent composition according to any one of [1] to [4], which does not contain an organic solvent.)

[0035] [6] The organosilicon coating agent composition according to any one of [1] to [5], wherein the component (A-1) is a hydrolysis and condensation reaction product of a hydrolyzable organosilane compound represented by the following general formula (2) and a diorganosilane diol represented by the following general formula (3),

[0036] (R 1 ) a Si(X) (4-a) (2)

[0037] (In the formula, R 1 , X and a are the same as above respectively.)

[0038] [Chemical formula 3]

[0039]

[0040] (In the formula, R 2 , R 3 are the same as those described above respectively.)

[0041] The component (A-2) is a hydrolyzed and condensed reaction product of a hydrolyzable organosilane compound represented by the above general formula (2) and a triorganohydroxysilane represented by the following general formula (4),

[0042] [Chemical formula 4]

[0043]

[0044] (In the formula, R 2 , R 4 are the same as those described above respectively.)

[0045] [7] An article sealed, coated, fixed or adhered with a cured product of the organosilicon coating agent composition according to any one of [1] to [6].

[0046] Effects of the Invention

[0047] According to the present invention, an organosilicon coating agent composition, particularly an organosilicon conformal coating agent composition, can be provided, which has excellent storage stability, can be coated on a substrate even without an organic solvent, can rapidly form a cured film at room temperature after coating, the cured film has excellent transparency, adhesion, etc., excellent followability (flexibility) to substrate bending, and low gas permeability, so that the corrosion resistance of the substrate, particularly sulfidation caused by hydrogen sulfide, can be reduced, and furthermore, the glass transition temperature (Tg) of the cured product can be lowered, so that it can be particularly used in a wider temperature range on the low temperature side. Detailed Description of the Invention

[0048] The present invention will be described in detail below.

[0049] [Component (A)]

[0050] The component (A) is a hydrolyzable organosiloxane mixture containing a hydrolyzable group-containing organotrisiloxane compound represented by the following general formula (1-1) (A-1) and a hydrolyzable group-containing organodisiloxane compound represented by the following general formula (1-2) (A-2) in a specific ratio.

[0051] The hydrolyzable organosiloxane mixture containing the component (A-1) and the component (A-2) rapidly crosslinks and cures by hydrolysis and condensation reaction using moisture (water) in the air in the presence of a curing catalyst of the following component (B) at room temperature (23°C ± 10°C, the same below), and can form a cured film with excellent transparency, adhesion, etc., excellent followability (flexibility) to substrate bending, and at the same time, gas permeability is suppressed.

[0052] [Component (A-1)]

[0053] (Component (A-1) serves as the main component of the silicone coating agent composition of the present invention and is an organotrisiloxane compound having a specific molecular structure represented by the following general formula (1-1), having at least 1, preferably 1 to 4 unsubstituted, halogen-substituted or alkyl-substituted phenyl groups in the molecule, and containing at least 4, preferably 4 to 6 hydrolyzable groups in the molecule (on the silicon atoms at both ends of the molecular chain).)

[0054] [Chemical Formula 5]

[0055]

[0056] (In the formula, R 1 , R 3 are each 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 ketoxime groups. a is independently 0 or 1 for each bonded silicon atom.)

[0057] In the above formula (1-1), R 1 , R 3 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl; alkenyl groups having 2 to 10 carbon atoms such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, and cyclohexenyl; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, xylyl, mesityl, and naphthyl; aralkyl groups having 7 to 10 carbon atoms such as benzyl and phenylethyl; and halogen-substituted monovalent hydrocarbon groups in which a part of the hydrogen atoms of these groups are substituted with halogen atoms such as chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,3,3-trifluoro-2-chlorocyclobutyl, 3,4-dibromo-1-chlorohexyl, difluoromonochloroethenyl, 2-iodocyclohexenyl, chlorophenyl, perchlorophenyl, fluorophenyl, perfluorophenyl, 2,2,2-trifluorotolyl, and 2,4-dibromobenzyl.

[0058] Among these, as R 1 , methyl, ethyl, propyl, vinyl, and phenyl are preferred. In addition, as will be described later, R 2As described in the items above, in the case where the low gas permeability of the obtained cured film becomes important, it is preferably an unsubstituted, halogen-substituted or alkyl-substituted phenyl group. Due to the design reasons of the curing rate caused by the hydrolysis and condensation reactions of the composition of the present invention, various other monovalent organic groups can be selected.

[0059] As R 3 , from the viewpoint of reducing the gas permeability of the obtained cured film, it is preferably an unsubstituted, halogen-substituted or alkyl-substituted phenyl group such as phenyl, tolyl, xylyl, chlorophenyl, perchlorophenyl, fluorophenyl, perfluorophenyl, 2,2,2-trifluorotolyl, etc.

[0060] In addition, as R 3 , by making it a monovalent hydrocarbon group other than the above unsubstituted, halogen-substituted or alkyl-substituted phenyl group, the Tg of the cured film can be controlled, and various Rs can be designed according to the target low gas permeability and Tg. 3 . Among these, from the viewpoint of good releasability and water repellency of the obtained cured film, an alkyl group, an allyl group, or a fluoroalkyl group is preferred.

[0061] In the above formula (1-1), R 2 is an unsubstituted, halogen-substituted or alkyl-substituted phenyl group, and examples thereof include phenyl, tolyl, xylyl, chlorophenyl, perchlorophenyl, fluorophenyl, perfluorophenyl, 2,2,2-trifluorotolyl, etc. Phenyl is preferred.

[0062] The organotrisiloxane compound having a hydrolyzable group represented by the formula (1-1) of the component (A-1) must have at least one unsubstituted, halogen-substituted or alkyl-substituted phenyl group in one molecule (on the silicon atom other than the terminal of the molecular chain). In the case where low gas permeability is emphasized, it is preferably to have 2 (i.e., both R 2 and R 3 ) unsubstituted, halogen-substituted or alkyl-substituted phenyl groups in the molecule of the formula (1-1) of the component (A-1).

[0063] By using this unsubstituted, halogen-substituted or alkyl-substituted phenyl group, the gas permeability of the cured film is reduced. For an organotrisiloxane compound having a hydrolyzable group that does not have an unsubstituted, halogen-substituted or alkyl-substituted phenyl group in the molecule, the gas permeability of the obtained cured film increases, and the corrosion of the substrate metal caused by the corrosive gas can no longer be alleviated.

[0064] In the above formula (1-1), each X is independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, and ketoxime groups. Specifically, as X, there can be mentioned alkoxy groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc., alkoxy-substituted alkoxy groups having 2 to 4 carbon atoms, such as methoxy-substituted methoxy, methoxy-substituted ethoxy, ethoxy-substituted methoxy, ethoxy-substituted ethoxy, etc., alkenyloxy groups having 2 to 4 carbon atoms, such as vinyloxy, allyloxy, propenyloxy, isopropenyloxy, butenyloxy, etc., aryloxy groups having 6 to 10 carbon atoms, such as phenoxy, acyloxy groups having 2 to 4 carbon atoms, such as acetyloxy, propionyloxy, etc., ketoxime groups having 3 to 6 carbon atoms, such as dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, etc. Preferred are methoxy, ethoxy, isopropenyloxy, methyl ethyl ketoxime group, etc.

[0065] In the above formula (1-1), a is independently 0 or 1 for each silicon atom to which it is bonded, and preferably 1.

[0066] (A-1) The hydrolyzable group-containing organotrisiloxane compound has at least 4, preferably 4 to 6, more preferably 4 hydrolyzable groups X in one molecule (on the silicon atoms at both ends of the molecular chain) in the above formula (1-1).

[0067] Specifically, as the hydrolyzable group-containing organotrisiloxane compound represented by the formula (1-1), the following compounds can be exemplified.

[0068] [Chemical formula 6]

[0069]

[0070] [Chemical formula 7]

[0071]

[0072] Furthermore, the hydrolyzable group-containing organotrisiloxane compound represented by the above general formula (1-1) of the component (A-1) can be easily prepared by subjecting a hydrolyzable organosilane compound having the above hydrolyzable group X or R 1 and the hydrolyzable group X as a monovalent hydrocarbon group bonded to a silicon atom and a diorganosilane diol having at least 1, preferably 2 unsubstituted, halogen-substituted or alkyl-substituted phenyl groups as a monovalent hydrocarbon group bonded to a silicon atom represented by the following general formula (3) to a de-HX and condensation reaction in the presence of a condensation reaction catalyst under known conditions. 2 and one of the above R 3 as a monovalent hydrocarbon group bonded to a silicon atom in the molecule to carry out a de-HX and condensation reaction in the presence of a condensation reaction catalyst under known conditions.

[0073] (R 1 ) a Si(X) (4-a) (2)

[0074] [Chemical Formula 8]

[0075]

[0076] (In each formula, R 1 , R 2 , R 3 , X, and a are the same as those described above.)

[0077] As the hydrolyzable organosilane compound represented by the above formula (2), specifically, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, vinyltriisopropenyloxysilane, phenyltriisopropenyloxysilane, methyltriisopropenyloxysilane, etc. can be exemplified.

[0078] As the diorganosilane diol (diorganodihydroxysilane) represented by the above formula (3), specifically, diphenylsilane diol, methylphenylsilane diol, etc. can be exemplified.

[0079] Regarding the reaction ratio of the hydrolyzable organosilane compound represented by formula (2) and the diorganosilane diol represented by formula (3), it is preferably that the molar ratio of the silanol group of the diorganosilane diol represented by formula (3) to the hydrolyzable organosilane compound represented by formula (2) is 2 or less. In order to reduce the residual silanol groups in the reaction product, it is more preferably that the above molar ratio is 0.5 or more and 1.5 or less. When there are many residual silanol groups of the diorganosilane diol represented by formula (3) from the raw materials in the reaction product, the curing reaction rate of the subsequent composition may sometimes be reduced.

[0080] As the condensation reaction catalyst used in the above reaction, organotitanate compounds, titanium chelate compounds, aluminum chelate compounds, organozirconium compounds and other organometallic catalysts, guanidine compounds such as tetramethylguanidinopropyltrimethoxysilane and other non-metallic catalysts can be exemplified.

[0081] Regarding the addition amount of the condensation reaction catalyst, as long as it is an amount sufficient for the condensation reaction of the hydrolyzable organosilane compound represented by formula (2) and the diorganosilane diol represented by formula (3) to proceed at room temperature to heating, it is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, relative to a total of 100 parts by mass of the hydrolyzable organosilane compound represented by formula (2) and the diorganosilane diol represented by formula (3).

[0082] As reaction conditions, at a temperature of 0 to 150 °C, particularly around 25 to 100 °C, it is preferably 30 seconds to 5 hours, particularly 1 to 120 minutes, and further around 10 - 60 minutes. Additionally, it is preferred to carry out the reaction while removing the compound HX (such as alcohol, acetone, etc.) that is eliminated and by-produced through the condensation reaction, and humidification can also be carried out as needed.

[0083] In the organosilicon coating agent composition of the present invention, the organotrisiloxane compound (A-1) containing a hydrolyzable group that constitutes the component (A) can be used alone or in combination of two or more.

[0084] [Component (A-2)]

[0085] (Component (A-2) and component (A-1) together form the main agent of the organosilicon coating agent composition of the present invention. It is an organodisiloxane compound having a specific molecular structure represented by the following general formula (1-2), having at least 2, preferably 2 or 3 unsubstituted, halogen-substituted or alkyl-substituted phenyl groups on the same silicon atom in the molecule, and containing at least 2, preferably 2 or 3 hydrolyzable groups on the other same silicon atom in the molecule. By blending component (A-2) at a specific blending ratio with respect to the above-mentioned component (A-1), the glass transition temperature (Tg) of the target cured product can be reduced. By reducing the Tg of the cured film, the flexibility of the material can be maintained in a wider temperature range, particularly on the low-temperature side, which is a very important characteristic from the viewpoint of widening the use temperature range of the target sealing member.

[0086] [Chemical formula 9]

[0087]

[0088] (In the formula, R 1 , R 2 , X, and a are the same as above. R 4 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms.)

[0089] In the above formula (1-2), R 1 , R 2 , X, and a can exemplify the same definitions as those exemplified for R 1 , R 2 , X, and a in the above formula (1-1). Additionally, these R 1 , R 2 , X, and a can be the same as or different from R 1 , R 2 , X, and a in formula (1-1).

[0090] In the above formula (1-2), R 4is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include the same groups as those exemplified for R in formula (1-1). 1 and R 3 in the formula. It is preferably an alkyl group or an alkenyl group, more preferably a methyl group, an ethyl group, a propyl group, a trifluoropropyl group or a vinyl group.

[0091] (A-2) The organodisiloxane compound having a hydrolyzable group represented by formula (1-2) must have at least 2, preferably 2 or 3, more preferably 2 unsubstituted, halogen-substituted or alkyl-substituted phenyl groups on the same silicon atom in the molecule (on the silicon atom not having a hydrolyzable group). By using the unsubstituted, halogen-substituted or alkyl-substituted phenyl group, the gas permeability of the cured film is reduced. In the case of an organodisiloxane compound having a hydrolyzable group that does not have an unsubstituted, halogen-substituted or alkyl-substituted phenyl group in the molecule, the gas permeability of the obtained cured film is increased, and the corrosion caused by the corrosive gas of the base metal can no longer be reduced.

[0092] (A-2) The organodisiloxane compound having a hydrolyzable group represented by formula (1-2) is used together with the (A-1) component, so that in a state of maintaining low air permeability, compared with the film obtained by curing the composition of the (A-1) component alone, a cured film having a low glass transition temperature (Tg) and flexibility in a wider temperature range on the low temperature side can be formed.

[0093] (A-2) The organodisiloxane compound having a hydrolyzable group in the above formula (1-2) has at least 2, preferably 2 or 3, more preferably 2 hydrolyzable groups X on the same silicon atom in one molecule (single terminal of the molecular chain). As the hydrolyzable group X, a group suitable for achieving the required curing rate and storage properties can be selected.

[0094] Specific examples of the organodisiloxane compound having a hydrolyzable group represented by formula (1-2) include the compounds shown below.

[0095] [Chemical formula 10]

[0096]

[0097] [Chemical formula 11]

[0098]

[0099] Furthermore, the organodisiloxane compound having a hydrolyzable group represented by the above general formula (1-2) of the (A-2) component is obtained by using a compound having the above hydrolyzable group X or R represented by the following general formula (2). 1The hydrolyzable organic silane compound having a hydrolyzable group X as a monovalent hydrocarbon group bonded to a silicon atom and the R having two of the above-mentioned R represented by the following general formula (4) 2 and one R 4 The triorganohydroxysilane having at least two unsubstituted, halogen-substituted or alkyl-substituted phenyl groups as monovalent hydrocarbon groups bonded to silicon atoms in the molecule is subjected to a de-HX condensation reaction in the presence of a condensation reaction catalyst under known conditions, and thus can be easily produced.

[0100] (R 1 ) a Si(X) (4-a) (2)

[0101] [Chemical Formula 12]

[0102]

[0103] (In each formula, R 1 , R 2 , R 4 , X, and a are the same as those described above.)

[0104] As the hydrolyzable organic silane compound represented by the above formula (2), the same hydrolyzable organic silane compound as the hydrolyzable organic silane compound used in the production of the hydrolyzable group-containing organotrisiloxane compound represented by the above formula (1-1) can be exemplified.

[0105] As the triorganohydroxysilane (triorganosilanol) represented by the above formula (4), specifically, methyldiphenylsilanol and the like can be exemplified.

[0106] Regarding the reaction ratio of the hydrolyzable organic silane compound represented by the formula (2) to the triorganohydroxysilane represented by the formula (4), it is preferable that the molar ratio of the triorganohydroxysilane represented by the formula (4) to the hydrolyzable organic silane compound represented by the formula (2) is 2 or less. In order to reduce the amount of the triorganohydroxysilane represented by the formula (4) remaining in the reaction product, the above molar ratio is more preferably 0.5 or more and 1.5 or less. When the residual amount of the triorganohydroxysilane represented by the formula (4) as a raw material in the reaction product (i.e., the residual silanol group) is large, the curing reaction rate of the subsequent composition may sometimes be reduced.

[0107] As the condensation reaction catalyst used in the above reaction, organotitanate compounds, titanium chelate compounds, aluminum chelate compounds, organozirconium compounds and other organometallic catalysts, guanidine compounds such as tetramethylguanidinopropyltrimethoxysilane and other non-metallic catalysts can be exemplified.

[0108] Regarding the addition amount of the condensation reaction catalyst, as long as it is an amount sufficient for the condensation reaction of the hydrolyzable organosilane compound represented by the formula (2) and the triorganohydroxysilane represented by the formula (4) to proceed at room temperature to heating temperature, it is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass in total of the hydrolyzable organosilane compound represented by the formula (2) and the triorganohydroxysilane represented by the formula (4).

[0109] As reaction conditions, at a temperature of 0 to 150 °C, particularly around 25 to 100 °C, it is preferably 30 seconds to 5 hours, particularly 1 to 120 minutes, and further preferably around 10 to 60 minutes. In addition, it is preferable to carry out the reaction while removing the compounds HX (alcohol, acetone, etc.) that are separated and by-produced through the condensation reaction, and humidification can also be carried out as needed.

[0110] In the organosilicon coating agent composition of the present invention, the organodisiloxane compound (A-2) containing a hydrolyzable group that constitutes the component (A) can be used alone or in combination of two or more.

[0111] In the organosiloxane mixture containing a hydrolyzable group of the component (A), regarding the usage ratio of the component (A-1) and the component (A-2), the component (A-1): the component (A-2) is expressed by a mass ratio and is 20:80 to 95:5, preferably 40:60 to 95:5, and more preferably 30:70 to 80:20. If the component (A-1) is more than the above range (the component (A-2) is less than the above range), the hardness of the cured film is too high, and sometimes it becomes the main cause of cracks in the coated film. If the component (A-1) is less than the above range (the component (A-2) is more than the above range), sometimes the curing of the film becomes insufficient.

[0112] Furthermore, in the organosilicon coating agent composition of the present invention, there is no limitation on the mixing order of the component (A-1) and the component (A-2) in the organosiloxane mixture containing a hydrolyzable group that constitutes the component (A). After pre-mixing the component (A-1) and the component (A-2) to prepare a mixture of the component (A), the mixture of the component (A) can be mixed with the component (B) to prepare the composition of the present invention. In addition, after mixing either the component (A-1) or the component (A-2) with the component (B), the remaining component (A-1) or the remaining component (A-2) can be mixed in this mixture to prepare the composition of the present invention.

[0113] [Component (B)]

[0114] (B) The curing catalyst of the component contains, in a specific ratio, an organosiloxane mixture containing hydrolyzable groups, which is a component (A) composed of (A-1) an organotrisiloxane compound containing hydrolyzable groups represented by the above general formula (1-1) and (A-2) an organodisiloxane compound containing hydrolyzable groups represented by the above general formula (1-2). It becomes a condensation reaction catalyst required for quickly forming a cured film through hydrolysis and condensation reactions with moisture (water) in the atmosphere. A suitable catalyst is selected according to the reactivity of the hydrolyzable group X selected from the above general formula (1-1) of the component (A-1) and the above general formula (1-2) of the component (A-2).

[0115] Examples of such condensation reaction catalysts include hydroxides, chlorides, oxides, or basic metal salts of alkali metals or alkaline earth metals. Specifically, 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 can be exemplified.

[0116] In addition, as other condensation reaction catalysts, aluminum chelate compounds, organic titanium compounds, organic zirconium compounds, organic tin compounds, aminoalkylalkoxysilanes, ammonium salts, etc. can also be used.

[0117] Examples of aluminum chelate compounds include diisopropoxyaluminum (ethyl acetoacetate), isopropoxyaluminum bis(ethyl acetoacetate), aluminum tris(ethyl acetoacetate), diisopropoxyaluminum (acetylacetone), isopropoxyaluminum bis(acetylacetone), aluminum tris(acetylacetone), bis(ethyl acetoacetate)mono(acetylacetone)aluminum, bis(acetylacetone)mono(ethyl acetoacetate)aluminum, etc.

[0118] Examples of organic titanium compounds include titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra(2-ethylhexoxy), etc.

[0119] Examples of organic zirconium compounds include zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra(2-ethylhexoxy), etc.

[0120] Examples of organic tin compounds include tin salts of carboxylic acids such as dioctyltin, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, stannous octoate, stannous naphthenate, stannous oleate, stannous isobutyrate, stannous linoleate, stannous stearate, stannous benzoate, stannous naphthoate, stannous laurate, stannous orthothymate, stannous β-benzoylpropionate, stannous crotonate, stannous tropate, stannous p-bromobenzoate, stannous palmitoleate, stannous cinnamate, and stannous phenylacetate.

[0121] Examples of the aminoalkylalkoxysilane include tetramethylguanidinopropyltrimethoxysilane, γ-aminopropyltrimethylmethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(dimethylamino)propyltrimethoxysilane, and the like.

[0122] Examples of the ammonium salt include salts of acids and amines. Examples of the acid include acetic acid, formic acid, etc. In addition, examples of the amine include allylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3-diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, tri-n-octylamine, tert-butylamine, sec-butylamine, propylamine, 3-methoxypropylamine, and the like.

[0123] From the viewpoint that the reaction proceeds well and the curability of the obtained silicone coating agent composition becomes good, the compounding amount of the curing catalyst of component (B) is 0.01 to 10 parts by mass, particularly preferably 0.02 to 5 parts by mass, based on 100 parts by mass of the hydrolyzable group-containing silicone oxygen compound mixture of component (A) (that is, the total of component (A-1) and component (A-2)).

[0124] [Component (C)]

[0125] In addition to the above components (A-1), (A-2), and (B), the silicone coating agent composition of the present invention may further contain, as an optional component, a hydrolyzable organosilane compound represented by the above formula (2) and / or its partial hydrolysis condensate (C) which is the same as the components used as raw materials in the production of the above components (A-1) and (A-2). If the component (C) is compounded, the effects of improving the storage stability of the composition and controlling the curing time can be obtained.

[0126] Furthermore, when reacting the hydrolyzable organosilane compound represented by the above formula (2) with the diorganosilane diol represented by the above formula (3) or the triorganohydroxysilane represented by the above formula (4) to obtain component (A-1) or component (A-2), the hydrolyzable organosilane compound represented by the above formula (2) can be reacted in excess, and the remaining hydrolyzable organosilane compound represented by the above formula (2) and / or its partial hydrolysis condensate after the reaction can be directly used.

[0127] The content of component (C) may be 100 parts by mass or less (0 to 100 parts by mass) based on 100 parts by mass of component (A). When compounded, it is preferably 0.1 to 100 parts by mass, and more preferably about 0.1 to 50 parts by mass. If the amount of component (C) is too large, it may cause thermal deterioration and discoloration of the cured film.

[0128] [Other components]

[0129] In the silicone coating agent composition of the present invention, if necessary, a small amount of various additives can be blended within the scope not detrimental to the object of the present invention, such as plasticizers, release agents, flame retardants, antioxidants, ultraviolet absorbers, pigments such as titanium dioxide, carbon black or iron oxide, and dyes. Similarly, within the scope not detrimental to the object of the present invention, fumed silica, silica aerosol, silica gel, and reinforcing silica fillers treated with silanes, siloxanes or silazanes, as well as asbestos, crushed fused quartz, alumina, aluminum silicate, zirconium silicate, zinc oxide, talc, diatomaceous earth, mica, calcium carbonate, clay, zirconia, glass, sand, graphite, barium sulfate, zinc sulfate, aluminum powder, sawdust, cork, fluorocarbon polymer powder, silicone rubber powder, silicone resin powder and other fillers can be blended.

[0130] If necessary, an organic solvent can also be blended. From the considerations of VOC and safety, as long as the viscosity of the composition is suitable for use in the process, it is preferably free of or contains a small amount of organic solvent.

[0131] When manufacturing the silicone coating agent composition of the present invention, it is only necessary to simply mix the specified amounts of the above components (A-1), (A-2) and (B). In this case, there is no limitation on the temperature during mixing. In particular, no operations such as heating are required. By simply stirring and mixing at room temperature for 10 minutes or more, preferably 10 to 60 minutes, it can be easily obtained. Further, during this mixing, in order to prevent hydrolysis of hydrolyzable groups such as alkoxy groups due to the incorporation of moisture, it is preferably carried out under a nitrogen atmosphere.

[0132] Furthermore, the component (A-1) and the component (A-2) can be separately prepared and then mixed. Alternatively, a mixture of the diorganosilane diol represented by the above formula (3) and the triorganohydroxysilane represented by the above formula (4) can be simultaneously subjected to a condensation reaction with the hydrolyzable organosilane compound represented by the above formula (2) to prepare a mixture containing the component (A-1) and the component (A-2).

[0133] In this way, the silicone coating agent composition of the present invention can provide an article sealed, coated, fixed or adhered with a cured product of the composition.

[0134] The silicone coating agent composition of the present invention can be coated and cured on various metal substrates, wood, stone, plasterboard, slate, tile, concrete, glass, ceramics, plastic products, organic resin film products, etc. by using known methods to form a coating film. In this case, as the coating method, specifically, methods such as brush coating, spraying, dipping, flow coater, knife coater, spin coater, etc. can be cited, and on-site painting can also be carried out. In addition, the coating amount varies depending on the type of substrate and the purpose of coating. Generally, it is sufficient that the thickness of the cured film is in the range of 0.1 to 300 μm, and preferably in the range of 1 to 200 μm.

[0135] As the curing conditions of the silicone coating agent composition of the present invention, there are no particular limitations. Since the film is formed by curing with moisture in the air, it can be dried (tacky-free state) by being placed in the temperature range of room temperature to 80°C for about 1 minute to 2 hours, and then the curing reaction can be completed by being placed for several hours to several days.

[0136] In this way, the silicone coating agent composition of the present invention can provide articles sealed, coated, fixed or bonded with the cured product of this composition.

[0137] Examples

[0138] Preparation examples, examples and comparative examples are shown below to specifically illustrate the present invention, but the present invention is not limited by the following examples. Further, room temperature means 23°C. In addition, % in the table is mass %.

[0139] [Preparation Example]

[0140] (Component (A-1))

[0141] (A-1-1)

[0142] Diphenylsilanediol (16.2 g), vinyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatix TC-401) were added to a 100 ml flask. While reacting at 100°C for 60 minutes, the generated methanol was removed by nitrogen flow, and then the remaining vinyltrimethoxysilane was removed by nitrogen flow to obtain an organotrisiloxane compound (A-1-1) represented by the following formula.

[0143] [Chemical Formula 13]

[0144]

[0145] (A-1-2)

[0146] In a 100 ml flask, diphenylsilanediol (16.2 g), phenyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Organatix TC-401) were added. While reacting at 100 °C for 60 minutes, the methanol produced was removed by nitrogen flow. Then, the remaining phenyltrimethoxysilane was removed by heating under reduced pressure, thereby obtaining an organotrisiloxane compound (A-1-2) represented by the following formula.

[0147] [Chemical formula 14]

[0148]

[0149] (A-1-3)

[0150] In a 100 ml flask, diphenylsilanediol (16.2 g), vinyltriisopropenyloxysilane (25 g), and tetramethylguanidinopropyltrimethoxysilane (0.2 g) were added. While reacting at 100 °C for 60 minutes, the acetone produced was removed by nitrogen flow. Then, by removing the remaining vinyltriisopropenyloxysilane by heating under reduced pressure, an organotrisiloxane compound (A-1-3) represented by the following formula was obtained.

[0151] [Chemical formula 15]

[0152]

[0153] (Component (A-2))

[0154] (A-2-1)

[0155] In a 100 ml flask, methyldiphenylsilanol (29 g), vinyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Organatix TC-401) were added. While reacting at 100 °C for 60 minutes, the methanol produced was removed by nitrogen flow, and then, the remaining vinyltrimethoxysilane was removed by nitrogen flow, thereby obtaining an organodisiloxane compound (A-2-1) represented by the following formula.

[0156] [Chemical formula 16]

[0157]

[0158] (A-2-2)

[0159] In a 100 ml flask, methyl diphenylsilanol (29 g), phenyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Organatix TC-401) were added. While reacting at 100 °C for 60 minutes, the methanol produced was removed by nitrogen flow. Then, the remaining phenyltrimethoxysilane was removed by heating under reduced pressure, thereby obtaining an organodisiloxane compound (A-2-2) represented by the following formula.

[0160] [Chemical Formula 17]

[0161]

[0162] (A-2-3)

[0163] In a 100 ml flask, methyl diphenylsilanol (29 g), vinyltriisopropenyloxysilane (25 g), and tetramethylguanidinopropyltrimethoxysilane (0.2 g) were added. While reacting at 100 °C for 60 minutes, the acetone produced was removed by nitrogen flow. Then, by removing the remaining vinyltriisopropenyloxysilane by heating under reduced pressure, an organodisiloxane compound (A-2-3) represented by the following formula was obtained.

[0164] [Chemical Formula 18]

[0165]

[0166] (Component (A-1) (for comparison))

[0167] (a-1)

[0168] In a 100 ml flask, dimethylsilanediol (12.3 g, partially dimerized), methyltrimethoxysilane (20 g), and a titanium chelate catalyst (0.2 g, Organatix TC-401) were added. While reacting at 100 °C for 60 minutes, the methanol produced was removed by nitrogen flow, and then, the remaining methyltrimethoxysilane was removed by nitrogen flow, thereby obtaining an organotrisiloxane compound (a-1) represented by the following formula.

[0169] [Chemical Formula 19]

[0170]

[0171] (Component (A-2) (for comparison))

[0172] (a-2)

[0173] Trimethylsilanol (13.5 g), methyltrimethoxysilane (20 g), and a titanium chelate catalyst (0.2 g, Organatix TC-401) were added to a 100 ml flask. While reacting at 100 °C for 60 minutes, the methanol generated was removed by nitrogen flow, and then the remaining methyltrimethoxysilane was removed by nitrogen flow, thereby obtaining an organodisiloxane compound (a-2) represented by the following formula.

[0174] [Chemical formula 20]

[0175]

[0176] [Examples 1-6, Comparative Examples 1-9]

[0177] In a 10 ml glass, the respective components shown in Tables 1-3 were compounded in the respective compounding amounts, stirred at room temperature for 10 minutes, and uniformly mixed to obtain a silicone coating agent composition. Furthermore, Examples 1-6 and Comparative Examples 1-8 did not contain a solvent component. The appearance and properties of the obtained silicone coating agent composition were visually confirmed and are collectively shown in Tables 1-3.

[0178] In addition, the obtained silicone coating agent composition was cured into a film shape with a thickness of about 2 mm under the curing conditions of 23 °C / 50% Rh × 7 days. The appearance and properties of the obtained cured product (cured film) were visually and tactilely confirmed and are collectively shown in Tables 1-3. Furthermore, as the properties of the cured product, the case where no change was found in the surface shape of the cured film after pressing the cured film with a finger at 23 °C was determined as a "hard film", and the case where a depression caused by the finger was generated on the surface of the film was determined as a "soft film".

[0179] The raw materials used other than the component (A) obtained in the above preparation example are shown below.

[0180] (Component B)

[0181] (B-1)

[0182] Tin catalyst: U-830 (manufactured by Nitto Kasei Co., Ltd., dioctyltin)

[0183] (B-2)

[0184] Amine catalyst: tetramethylguanidylpropyltrimethoxysilane

[0185] (Component A) (for comparison)

[0186] (a-3)

[0187] Prepare a solvent-based coating agent with an acrylic resin component as the main body: Humiseal (registered trademark)-1B66NS. The solid content is 35% by mass (solvent component 65% by mass). For thin film coating, it is diluted twice with an additional solvent (thinner: Humiseal (registered trademark) Thinner901).

[0188] [Table 1]

[0189]

[0190] [Table 2]

[0191]

[0192] [Table 3]

[0193]

[0194] Next, using the silicone coating agent compositions of Examples 1 to 6 and Comparative Examples 1 to 9 above, the appearance of the cured product, the tack-free time, the glass transition temperature, the corrosion resistance test, and the flexibility were evaluated. These results are shown in Tables 4 and 5.

[0195] (Appearance of the cured product)

[0196] For the film cured on an aluminum dish prepared in the evaluation of the tack-free time below, the transparency and the degree of coloring were evaluated visually.

[0197] (Tack-free time)

[0198] Take about 0.20 g of the above silicone coating agent composition on an aluminum dish, coat and spread it into a square shape of about 2 cm × 2 cm, and evaluate the adhesion / curing time of the surface of the composition by finger touch.

[0199] (Glass transition temperature (Tg))

[0200] Using DSC manufactured by Mettler, the glass transition temperature (Tg) was measured from the endothermic characteristics.

[0201] Inject about 0.03 g of the above silicone coating agent composition into an aluminum dish, cure it under the curing conditions of 23°C / 50% Rh × 7 days, and use the product as a sample. The temperature increase conditions are set to -60°C to 150°C, and the heating rate is set to 10°C / minute.

[0202] (Corrosion resistance test)

[0203] For each material (silicone coating agent composition), about 0.08 g of the above silicone coating agent composition was coated and spread into a square shape of about 2 cm × 2 cm on the surface of the silver-plated aluminum plate so that the cured film became about 200 μm, and cured under the curing conditions of 23°C / 50% Rh × 7 days. Using a hydrogen sulfide gas corrosion test machine, the corrosion state of the silver-plated surface was observed after a certain elapsed time (initial stage, 1 day later, 3 days later, 7 days later, 14 days later). The corrosion conditions are as described below.

[0204] Hydrogen sulfide concentration: 2 ppm

[0205] Temperature: 23°C

[0206] Humidity: 50% RH

[0207] The silver-plated surface before and after the corrosion test was observed, and corrosion was judged at the moment of change in the silver luster (blackening, graying) from the initial stage.

[0208] (Flexibility)

[0209] For the silver-plated plate after the above anticorrosion test was completed (with a cured film of silicone coating agent composition), when the cured film was bent at an angle of 90° with the outside as the reference at 23°C, it was evaluated whether the coating did not crack and could follow the substrate.

[0210] [Table 4]

[0211]

[0212] [Table 5]

[0213]

[0214] (Results)

[0215] From the above results, it was confirmed that the solvent-free silicone coating agent composition of the present invention has excellent curability and transparency at room temperature, the cured film obtained by curing this composition has excellent transparency, and at the same time has excellent effects of preventing the corrosion of corrosive gases on the metal substrate and following the substrate (flexibility), and has a lower glass transition temperature, enabling a wider temperature range to be used.

Claims

1. An organosilicon coating agent composition, comprising: 100 parts by mass of an organosiloxane mixture having a hydrolyzable group, which contains 20 to 95 parts by mass of (A-1) an organotrisiloxane compound having a hydrolyzable group represented by the following general formula (1-1) and 80 to 5 parts by mass of (A-2) an organodisiloxane compound having a hydrolyzable group represented by the following general formula (1-2), wherein, (A-1) component and (A-2) component in a total of 100 parts by mass, [Chemical formula 1] [Chemical formula 2] In each formula, R 1 , R 3 , R 4 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 2 is an unsubstituted, halogen-substituted or alkyl-substituted phenyl group, X are each independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups and ketoxime groups, and a is independently 0 or 1 for each silicon atom to which it is bonded, 0.01 to 10 parts by mass of (B) curing catalyst.

2. The silicone coating agent composition according to claim 1, wherein, In the general formula (1-1), R 3 is an unsubstituted, halogen-substituted or alkyl-substituted phenyl group.

3. The silicone coating agent composition according to claim 1 or 2, wherein In the general formulas (1-1) and (1-2), each X is a methoxy group, an ethoxy group, an isopropenyloxy group or a ketoxime group.

4. The silicone coating agent composition according to any one of claims 1 to 3, wherein, Relative to 100 parts by mass of the (A) component, it further contains 0.1 to 100 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and / or its partial hydrolysis condensate (C) other than the (A-1) and (A-2) components, (R 1 ) a Si(X) (4-a) (2) In the formula, R 1 、X, and a are the same as those above respectively.

5. The silicone coating agent composition according to any one of claims 1 to 4, wherein, Does not contain organic solvents.

6. The silicone coating agent composition according to any one of claims 1 to 5, wherein, (A-1) component is a hydrolysis and condensation reaction product of a hydrolyzable organosilane compound represented by the following general formula (2) and a diorganosilane diol represented by the following general formula (3), (R 1 ) a Si(X) (4-a) (2) wherein, R 1 , X, and a are the same as those described above, [Chemical formula 3] wherein, R 2 and R 3 are the same as those described above, respectively (A-2) component is a hydrolysis and condensation reaction product of a hydrolyzable organosilane compound represented by the above general formula (2) and a triorganohydroxysilane represented by the following general formula (4), [Chemical formula 4] In the formula, R2 and R4 are the same as above respectively.

7. An article sealed, coated, fixed or bonded with a cured product of the organosilicon coating agent composition according to any one of claims 1 to 6.

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