阅读说明：本技术 有机硅涂布剂组合物和物品 (Silicone coating agent composition and article ) 是由 原宽保 藤原晃嗣 于 2021-03-16 设计创作，主要内容包括：本发明提供有机硅涂布剂组合物,其不含有机溶剂,保存稳定性优异,在涂布于基材后常温下迅速地固化,能够形成透明性、密合性等优异、对于基材弯曲的追随性优异的固化被膜,并且可提高基材的防腐蚀性,特别是可减少作为含硫气体的硫化氢引起的硫化物形成。有机硅涂布剂组合物,其含有：(A)由下式(1)表示的含有水解性基团的有机三硅氧烷化合物：100质量份,(R～1、R～3为碳原子数1～10的未取代或卤素取代的一价烃基,R～2为未取代、卤素取代或烷基取代的苯基,X为选自未取代或烷氧基取代的烷氧基、芳氧基、烯氧基、酰氧基和酮肟基中的水解性基团,a为0或1。)(B)固化催化剂：0.01～10质量份。(The invention provides an organosilicon coating agent composition which does not contain organic solvent, has excellent storage stability, can be quickly cured at normal temperature after being coated on a substrate, can form a cured coating film with excellent transparency, adhesiveness and the like and excellent following performance to the bending of the substrate, and can provideThe corrosion resistance of the substrate is high, and particularly, the formation of sulfides by hydrogen sulfide as a sulfur-containing gas can be reduced. An organosilicon coating composition comprising: (A) an organotrisiloxane compound containing a hydrolyzable group represented by the following formula (1): 100 parts by mass of a water-soluble polymer, (R 1 、R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 2 Is unsubstituted, halogen-substituted or alkyl-substituted phenyl, X is a hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy, aryloxy, alkenyloxy, acyloxy and ketoxime groups, and a is 0 or 1. ) (B) curing catalyst: 0.01 to 10 parts by mass.)

1. An organosilicon coating composition comprising:

(A) an organotrisiloxane compound containing a hydrolyzable group represented by the following general formula (1): 100 parts by mass of a water-soluble polymer,

[ CHEM 1]

In the formula, R¹、R³Each independently is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R²Is unsubstituted, halogen-substituted or alkyl-substituted phenyl, X is independently selected from unsubstituted or alkoxy-substituted alkoxy, aryloxy, alkenyloxy,A is 0 or 1 independently for each bonded silicon atom,

(B) curing catalyst: 0.01 to 10 parts by mass.

2. The silicone coating agent composition according to claim 1, wherein, in the general formula (1), R³Is unsubstituted, halogen substituted or alkyl substituted phenyl.

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

4. The silicone coating agent composition according to claim 1 or 2, further comprising 0.1 to 100 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and/or a partial hydrolysis condensate thereof (C) excluding component (A) with respect to 100 parts by mass of component (A),

(R¹)_aSi(X)_(4-a) (2)

in the formula, R¹X, a are each as described above.

5. The silicone coating agent composition according to claim 1 or 2, which is free of an organic solvent.

6. The silicone coating agent composition according to claim 1 or 2, wherein component (a) is a hydrolysis-condensation reactant of a hydrolyzable organosilane compound represented by the following general formula (2) and a diorganosilanediol represented by the following general formula (3):

(R¹)_aSi(X)_(4-a) (2)

in the formula, R¹X, a are each the same as described above,

[ CHEM 2]

In the formula, R²、R³Respectively, as described above.

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

Technical Field

The present invention relates to a moisture-curable room-temperature-curable silicone coating agent composition and the like that is crosslinked and cured at room temperature (23 ℃ ± 15 ℃) by hydrolysis-condensation reaction using moisture (moisture) in the atmosphere, and particularly relates to a silicone coating agent composition and the like used for electric and electronic components, structural material components and the like. The silicone coating agent composition of the present invention has excellent storage stability, can be cured quickly at room temperature after being applied to various substrates, and can provide a cured coating film having excellent transparency, flexibility (following properties to substrate bending), adhesion (adhesiveness to substrate), low gas permeability, and the like, and therefore can provide various functional characteristics such as surface protection, water repellency, rust prevention, water resistance, weather resistance, chemical resistance, stain resistance, and the like to various substrates.

Background

Silicone resins (organopolysiloxane resins) are different from other hydrocarbon-based organic resins in that they are excellent in heat resistance, weather resistance, water resistance, flame retardancy, and the like, and can form cured films having a surface with high hardness, and therefore curable silicone rubber compositions (silicone elastomer compositions) and silicone resin-based resins (polyorganosilsesquioxane resins having a three-dimensional network structure, and the like) having crosslinkable groups such as alkoxy groups and silanol groups bonded to silicon atoms in the molecule have been widely used in applications and fields such as surface protective materials for various substrates, heat-resistant coatings, weather-resistant coatings, water repellents, and various adhesives. Among them, silicone resins are used for conformal coatings of electronic substrates such as home electric appliances and electronic components because they are excellent in heat resistance and electrical insulation. Further, by designing the resin composition, a coating composition which does not require dilution of an organic solvent is also possible, and a coating agent which is excellent in VOC (volatile organic compound) problem and safety has been on the market. However, general silicone rubber-based or silicone resin-based coating agent compositions are expected to have a low protective effect against corrosive gases such as hydrogen sulfide and electrode metals (particularly silver electrodes), and thus are desired to be solved.

Heretofore, in order to reduce metal corrosion caused by corrosive gas such as hydrogen sulfide, acrylic resin-based or urethane resin-based coating agents have to be used, but such organic resin coating materials are generally used in a state diluted with an organic solvent, and have problems of VOC and safety. In addition, the range of use of acrylic and urethane coating agents is limited due to problems of heat resistance and electrical characteristics.

From the above, a solvent-free silicone-based coating agent having excellent ability to prevent metal corrosion by a corrosive gas such as hydrogen sulfide in addition to heat resistance and electrical characteristics has been desired.

The present invention is a material of a type which forms a hard coating after curing in a silicone coating agent, but as such a silicone coating agent composition, a so-called silicone varnish solution obtained by dissolving a curable silicone resin having a terminal silanol group and an average molecular weight of about 3000 to 2000000 in an organic solvent such as toluene or xylene has been used in many cases. When used, a coating film having excellent surface hardness, adhesion, heat resistance, weather resistance, water resistance and the like can be obtained, but since an organic solvent is used as an essential component and a dehydration condensation crosslinking reaction between silanol groups is utilized, generally, heat curing at 150 ℃ or higher for a long time is required for the formation of a coating film.

On the other hand, a one-pack type (one-pack type) solventless normal temperature curable silicone coating composition which does not contain an organic solvent, can be cured at normal temperature and has excellent storage stability is required, and studies on the use of a low molecular weight organosilane oxy oligomer obtained by partial (co) hydrolytic condensation of an organoalkoxysilane and on a curing catalyst which effectively promotes a hydrolysis reaction and a dealcoholization condensation reaction by moisture of the organosilane oxy oligomer to form a crosslinked coating film having a siloxane bond have been actively conducted, and techniques of cited documents have been proposed (patent documents 1 and 2: Japanese patent application laid-open No. 60-233164 and Japanese patent application laid-open No. 4110402).

However, in all of the techniques, the cured film obtained is poor in stiffness and flexibility, so that it has poor conformability to bending of the base material, and it is impossible to prevent metal corrosion due to hydrogen sulfide.

On the other hand, in the solvent-free silicone composition, as an example of a technique for preventing corrosion of a base metal by a sulfur-containing corrosive gas, there is a technique of adding a metal powder of silver, copper or the like to the composition to reduce corrosion of the base metal by sacrificial corrosion of the metal powder (patent documents 3 and 4: Japanese patent No. 4114037 and Japanese patent No. 4530137); a technique for reducing corrosion of a base metal by using an organic additive (patent document 5: Japanese patent No. 6418115). These techniques are excellent, but the effect is not sufficient depending on the type of corrosive gas as a means for detoxifying the corrosive gas species penetrating into the silicone coating film by the reaction inside the coating film.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 60-233164

Patent document 2: japanese patent No. 4110402

Patent document 3: japanese patent No. 4114037

Patent document 4: japanese patent No. 4530137

Patent document 5: japanese patent No. 6418115

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made to solve the above-mentioned drawbacks, and an object of the present invention is to provide an organosilicon coating agent composition which does not contain an organic solvent, does not impair the original characteristics of a curable organosilicon compound, has excellent storage stability as a coating agent composition, is rapidly cured at room temperature after being applied to a substrate, can form a cured coating film having excellent transparency, adhesion, and the like, and excellent conformability (flexibility) to bending of the substrate, and has low gas permeability, so that the corrosion resistance of the substrate can be improved, and particularly the formation of sulfides due to hydrogen sulfide as a sulfur-containing gas (a sulfur-containing gas) can be reduced.

Means for solving the problems

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: the present inventors have found that a cured coating film having excellent transparency, adhesion, and the like, and excellent conformability (flexibility) to bending of a substrate can be provided by using a condensation reaction-curable silicone coating agent composition containing a curing catalyst and an organotrisiloxane compound represented by the following general formula (1) and having a specific molecular structure in which at least 1 unsubstituted or substituted phenyl group is contained in the molecule and at least 4, preferably 4 to 6 hydrolyzable groups are contained in the molecule as a main component, and that the cured coating film composition exhibits excellent storage stability under sealed conditions, is rapidly cured by a hydrolysis condensation reaction caused by moisture in the atmosphere in an open atmosphere, and has low gas permeability, so that the cured coating film can reduce the formation of sulfides due to hydrogen sulfide, and have completed the present invention.

Namely, the present invention provides the following silicone coating agent composition and an article sealed, coated, fixed or adhered with a cured product of the composition.

[1] An organosilicon coating composition comprising:

(A) an organotrisiloxane compound containing a hydrolyzable group represented by the following general formula (1): 100 parts by mass of a water-soluble polymer,

[ CHEM 1]

(in the formula, R¹、R³Each independently is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R²Is unsubstituted, halogen-substituted or alkyl-substituted phenyl, each X is independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy, aryloxy, alkenyloxy, acyloxy and ketoximino groups, and a is independently 0 or 1 for each bonded silicon atom. )

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

[2][1]The silicone coating agent composition, wherein, in the general formula (1), R³Is unsubstituted, halogen substituted or alkyl substituted phenyl.

[3] [1] the silicone coating agent composition according to [1] or [2], wherein, in the general formula (1), 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 [1] to [3], further comprising 0.1 to 100 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and/or a partial hydrolysis condensate thereof (C) excluding the component (A) per 100 parts by mass of the component (A).

(R¹)_aSi(X)_(4-a) (2)

(in the formula, R¹X, a are each as described above. )

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

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

(R¹)_aSi(X)_(4-a) (2)

(in the formula, R¹X, a are each as described above. )

[ CHEM 2]

(in the formula, R²、R³Respectively, as described above. )

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

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there is obtained an organosilicon coating agent composition which is excellent in storage stability, can be applied to a substrate even without containing an organic solvent, can form a cured coating rapidly at room temperature after application, is excellent in transparency, adhesion and the like, can obtain a cured coating excellent in followability (flexibility) to substrate bending, and is low in gas permeability, thereby improving corrosion resistance of the substrate and particularly reducing sulfide formation (sulfiting) by hydrogen sulfide which is a sulfur-containing gas.

Detailed Description

The present invention will be described in detail below.

[ (A) component ]

(A) Component (b) is a main component of the silicone coating agent composition of the present invention, and is an organotrisiloxane compound represented by the following general formula (1) having a specific molecular structure in which at least 1 unsubstituted or substituted phenyl group is present in the molecule and at least 4, preferably 4 to 6 hydrolyzable groups are present in the molecule.

(A) The hydrolyzable group-containing organotrisiloxane compound of component (a) is rapidly crosslinked and cured by hydrolysis-condensation reaction due to moisture (moisture) in the atmosphere at room temperature (23 ℃ ± 15 ℃, the same applies) in the presence of a curing catalyst of component (B) described later, and a cured coating film having excellent transparency, adhesion, and the like, excellent conformability (flexibility) to bending of a substrate, and suppressed gas permeability can be formed.

[ CHEM 3]

(in the formula, R¹、R³Each independently is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R²Is unsubstituted, halogen-substituted or alkyl-substituted phenyl, each X is independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy, aryloxy, alkenyloxy, acyloxy and ketoximino groups, and a is independently 0 or 1 for each bonded silicon atom. )

In the above formula (1), R¹、R³Each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decylLinear, branched or cyclic alkyl group having 1 to 10 carbon atoms, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclohexenyl group and the like, linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, phenyl group, tolyl group, xylyl group, naphthyl group and the like, aryl group having 6 to 10 carbon atoms, mesityl group and the like, aralkyl group having 7 to 10 carbon atoms, benzyl group, phenylethyl group and the like, chloromethyl group, 2-bromoethyl group, 3, 3, 3-trifluoropropyl group, 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl group, 2, 3, 3-trifluoro-2-chlorocyclobutyl group, 3, 4-dibromo-1-chlorohexyl group, 3, 3, 3, 4, 4, 5, 5-chlorohexyl group and the like, which are substituted with a halogen atom or the like, A halogen-substituted monovalent hydrocarbon group such as difluoromonochloroethylene, 2-iodocyclohexenyl, chlorophenyl, perchlorophenyl, fluorophenyl, perfluorophenyl, 2, 2, 2-trifluoromethylphenyl, 2, 4-dibromobenzyl.

Among these, as R¹Methyl, ethyl, propyl, vinyl, phenyl and, as in the case of R described later, R is preferred²As described in the section (a) above, when low gas permeability of the cured film to be obtained is important, it is preferable that the cured film be an unsubstituted, halogen-substituted or alkyl-substituted phenyl group, and various other monovalent organic groups can be selected for the design of the curing rate by the hydrolysis-condensation reaction of the composition of the present invention.

As R³From the viewpoint of reducing the gas permeability of the cured film obtained, an unsubstituted, halogen-substituted or alkyl-substituted phenyl group such as a phenyl group, tolyl group, xylyl group, chlorophenyl group, all-chlorophenyl group, fluorophenyl group, perfluorophenyl group, 2, 2, 2-trifluoromethylphenyl group, or the like is preferable.

In addition, as R³By using a monovalent hydrocarbon group other than the above unsubstituted, halogen-substituted or alkyl-substituted phenyl group, the Tg of the cured coating film can be controlled, and the cured coating film can have a low gas permeability and a low Tg to R³Various designs were made. Among these, alkyl groups, allyl groups, and fluoroalkyl groups are particularly preferable because the cured film obtained has good releasability and water repellency.

In the above formula (1), R²The organotrisiloxane compound represented by formula (1) of component (a) must have at least 1 unsubstituted, halogen-substituted or alkyl-substituted phenyl group in 1 molecule (for example, the above-exemplified phenyl group, tolyl group, xylyl group, chlorophenyl group, all-chlorophenyl group, fluorophenyl group, perfluorophenyl group, 2, 2, 2-trifluoromethylphenyl group, etc.). When importance is attached to low gas permeability, it is preferable to have 2 (i.e., R) in the molecule²And R³Both) unsubstituted, halogen-substituted or alkyl-substituted phenyl.

The gas permeability of the cured coating is reduced by the unsubstituted or substituted phenyl group, and the gas permeability of the cured coating is increased for the organotrisiloxane compound having no unsubstituted or substituted phenyl group in the molecule, and corrosion of the base metal by the corrosive gas can no longer be reduced.

In the formula (1), each X is independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy, aryloxy, alkenyloxy, acyloxy and ketoxime groups. Specific examples of X include a hydrolyzable group of at least one member selected from the group consisting of C1-7 unsubstituted or alkoxy-substituted alkoxy, aryloxy, alkenyloxy, acyloxy and ketoximino groups, and examples thereof include C1-6 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy groups, C2-4 alkoxy groups such as C1-4 alkoxy, methoxy-substituted methoxy, methoxy-substituted ethoxy, ethoxy-substituted methoxy and ethoxy-substituted ethoxy groups, C2-4 alkenyloxy groups such as vinyloxy, allyloxy, propenyloxy, isopropenyloxy and butenyloxy groups, C6-10 aryloxy groups such as phenoxy groups, C6-10 aryloxy groups such as acetoxy and propionyloxy groups, C2-4 acyloxy groups such as acetoxy and propionyloxy groups, and the like, And ketoxime groups having 3 to 6 carbon atoms such as a dimethyl ketoxime group, a methyl ethyl ketoxime group, and a diethyl ketoxime group. Preferred are methoxy, ethoxy, isopropenyloxy, methylethylketoximino and the like.

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

(A) The hydrolyzable group-containing organotrisiloxane compound of component (1) has at least 4, preferably 4 to 6, and more preferably 4 hydrolyzable groups X in 1 molecule, and an appropriate leaving group can be selected in order to achieve desired curing speed and storage property characteristics.

As the hydrolyzable group-containing organotrisiloxane compound represented by formula (1), the following compounds can be specifically exemplified.

[ CHEM 4]

[ CHEM 5]

Further, the above-mentioned R having a 1-valent hydrocarbon group bonded to a silicon atom represented by the following general formula (2) is reacted in the presence of a condensation reaction catalyst under conventionally known conditions¹And a hydrolyzable group X, and a hydrolyzable organosilane compound represented by the following general formula (3) each having 1 of the above-mentioned R²And R³The hydrolyzable group-containing organotrisiloxane compound represented by the above general formula (1) of component (a) can be easily produced by subjecting a diorganosilanediol (diorganodihydroxysilane) having at least 1, preferably 2 unsubstituted, halogen-substituted or alkyl-substituted phenyl groups in the molecule, which is a 1-valent hydrocarbon group bonded to a silicon atom, to a hydrolysis-condensation reaction.

(R¹)_aSi(X)_(4-a) (2)

[ CHEM 6]

(in the formulae, R¹、R²、R³X, a are each as described above. )

Specific examples of the hydrolyzable organosilane compound represented by the formula (2) include vinyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, and methyltriisopropenylsilane.

Specific examples of the diorganosilanediol represented by the formula (3) include diphenylsilanediol, methylphenylsilanediol, and ethylphenylsilanediol.

The reaction ratio of the hydrolyzable organosilane compound represented by the formula (2) to the diorganosilanediol represented by the formula (3) is preferably 1 mole or more of the hydrolyzable organosilane compound represented by the formula (2) relative to 1 mole of silanol groups in the diorganosilanediol represented by the formula (3), and more preferably 2 moles or more of the hydrolyzable organosilane compound relative to 1 mole of the silanol groups in order to reduce the number of remaining silanol groups in the reaction product. The upper limit of the reaction molar ratio of the hydrolyzable organosilane compound represented by the formula (2) may be about 5 mol or less. When many silanol groups remain in the reaction product, the curing reaction rate of the subsequent composition may be lowered.

Examples of the condensation reaction catalyst used in the above reaction include a silane compound containing a guanidine group such as a titanium chelate compound and tetramethylguanidinopropyltrimethoxysilane, an aluminum chelate compound, and an organozirconium compound.

The amount of the condensation reaction catalyst to be added may be an amount sufficient to allow the condensation reaction between 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 is usually preferably 0.01 to 10 parts by mass, particularly preferably about 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the diorganosilanediol and the hydrolyzable organosilane compound.

The reaction conditions are preferably about 0 to 150 ℃, particularly about 25 to 100 ℃, and about 5 to 120 minutes, particularly about 10 to 60 minutes, and the reaction product (component (A)) can be obtained by reacting the alcohol and the like by-produced by the condensation reaction while removing it.

In the silicone coating agent composition of the present invention, the hydrolyzable group-containing organotrisiloxane compound of component (a) can be used alone in 1 kind, or in combination of 2 or more kinds.

[ (B) component ]

(B) The curing catalyst of component (a) is a condensation reaction catalyst required for the composition of the present invention to rapidly form a cured coating film by hydrolysis-condensation reaction of the hydrolyzable group-containing organotrisiloxane compound of component (a) represented by general formula (1) with moisture (moisture) in the atmosphere in the curing step, and is selected from the group consisting of an organotin compound, an organoaluminum compound, an organotitanium compound, an organozirconium compound, and an organic base compound, and an appropriate catalyst is selected depending on the reactivity of the hydrolyzable group X selected in general formula (1) of component (a).

Examples of such a condensation reaction catalyst include hydroxides, oxides, or basic metal salts of alkali metals or alkaline earth metals, and 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, basic metal salts such as basic zinc carbonate and basic magnesium carbonate can be exemplified.

In addition, as other condensation reaction catalysts, aluminum chelate compounds, organic titanium compounds, organic tin compounds, aminoalkylalkoxysilanes, ammonium salts, and the like can also be used. Examples of the aluminum chelate compound include ethyl acetoacetate diisopropoxyaluminum, tris (ethyl acetate) aluminum, tris (acetylacetonato (アルミニウムトリス (エチルアセテート)) aluminum, bis (ethyl acetoacetate) monoacetylacetonato aluminum, and examples of the organic titanium compound include tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and examples of the organic tin compound include 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 o-thymite, stannous β -benzoylpropionate, stannous crotonate, stannous tropic acid, stannous p-bromobenzoate, stannous palmitoleate, stannous palmitate, and the like, Tin salts of carboxylic acids such as stannous cinnamate and stannous phenylacetate. Examples of aminoalkylalkoxysilanes include γ -aminopropyltrimethylmethoxysilane, γ -aminopropyltriethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropyltrimethoxysilane, γ -aminopropylmethyldimethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropylmethyldimethoxysilane and γ - (dimethylamino) propyltrimethoxysilane. Examples of the ammonium salt include salts of acids and amines, examples of the acids include acetic acid and formic acid, and examples of the amines include allylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3-diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, tri-n-octylamine, tert-butylamine, sec-butylamine, propylamine, and 3-methoxypropylamine.

The 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 organotrisiloxane compound of component (a), from the viewpoint that the reaction proceeds well and the curability of the obtained silicone coating agent composition becomes good.

[ (C) ingredient ]

The silicone coating agent composition of the present invention may further contain a hydrolyzable organosilane compound (C) represented by the above formula (2) which is the same as the component used for producing the above component (a), in addition to the above component (a) and component (B). When the component (C) is blended, the effect of improving the storage stability of the composition and controlling the curing time (pot life) of the composition can be obtained.

When the hydrolyzable silane compound represented by the above formula (2) is reacted with the diorganosilane diol represented by the above formula (3) to obtain the component (a), the hydrolyzable silane compound represented by the above formula (2) is reacted in excess, and the remaining hydrolyzable silane compound represented by the above formula (2) after the reaction can be used as it is.

The content of the hydrolyzable organosilane compound represented by the above formula (2) may be 100 parts by mass or less (0 to 100 parts by mass), preferably about 0.1 to 50 parts by mass, relative to 100 parts by mass of the component (a).

[ other ingredients ]

The silicone coating agent composition of the present invention may further contain, if necessary, a small amount of various additives, for example, a plasticizer, a release agent, a flame retardant, an antioxidant, an ultraviolet absorber, a pigment such as titanium dioxide, carbon black, or iron oxide, and a dye, in a range not to impair the object of the present invention. Similarly, fillers such as fumed silica, silica aerosol, silica gel, reinforcing silica fillers treated with organosilanes, organosiloxanes, or organosilazanes, asbestos, ground fused silica, alumina, 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 fluorocarbon, silicone rubber powder, silicone resin powder, and the like may be blended as long as the object of the present invention is not impaired.

Further, an organic solvent may be added as needed, and it is preferable that the composition contains no organic solvent or contains a small amount of organic solvent from the viewpoint of VOC and safety as long as the composition has a viscosity usable in the process.

In the production of the silicone coating agent composition of the present invention, the prescribed amounts of the above-mentioned components (a) and (B) may be simply mixed, and in this case, the temperature at the time of mixing is not limited, and in particular, the mixing can be easily achieved by stirring and mixing at room temperature for 10 minutes or more, preferably 10 to 60 minutes, without performing an operation such as heating. In addition, in the mixing, it is preferable to carry out the mixing under a nitrogen atmosphere in order to prevent hydrolysis of a hydrolyzable group such as an alkoxy group due to mixing of moisture.

Thus, the silicone coating agent composition of the present invention can provide an article sealed, coated, fixed or bonded with a cured product of the composition.

The silicone coating agent composition of the present invention can be applied and cured to various metal substrates, wood, stone, plasterboard, slate, tile, concrete, glass, ceramics, plastic products, organic resin coated products, and the like by a conventionally known method to form a coating film. In this case, as a coating method, specifically, methods such as brush coating, spray coating, dipping, flow coater, blade coater, spin coater, and the like can be cited, and further, on-site coating can be performed. The coating amount varies depending on the type of the substrate and the purpose of coating, and may be generally in the range of 0.1 to 200 μm, preferably 1 to 100 μm, in thickness of the coating after curing.

The curing conditions of the silicone coating agent composition of the present invention are not particularly limited, and since the coating film is formed by curing with moisture in the air, the coating film can be dried (tack-free state) by leaving the coating film at a temperature ranging from room temperature to 80 ℃ for about 1 minute to 2 hours, and the curing reaction can be completed by leaving the coating film for several hours to several days.

Thus, the silicone coating agent composition of the present invention can provide an article sealed, coated, fixed or bonded with a cured product of the composition.

Examples

The present invention will be described in more detail below by way of examples, which are not intended to limit the scope of the present invention. In each example, room temperature means 25 ℃ and viscosity means a measurement value obtained by a rotational viscometer at 25 ℃.

[ preparation examples ]

(A) Composition (I)

(A-1)

Diphenylsilanediol (16.2g), vinyltrimethoxysilane (25g) and a titanium chelate catalyst (0.2g, produced by Matsumoto Fine Chemical Co. Ltd., ORGATIX TC-401) were added to a 100ml flask, and after a reaction at 100 ℃ for 60 minutes, the produced methanol and the remaining vinyltrimethoxysilane were removed by flowing nitrogen gas, thereby obtaining an organotrisiloxane compound (A-1) represented by the following formula.

[ CHEM 7]

(A-2)

Diphenylsilanediol (16.2g), phenyltrimethoxysilane (25g) and a titanium chelate catalyst (0.2g, produced by Matsumoto Fine Chemical Co. Ltd., ORGATIX TC-401) were added to a 100ml flask, and after a reaction at 100 ℃ for 60 minutes, the generated methanol was removed by flowing nitrogen gas, and then the remaining phenyltrimethoxysilane was removed by heating under reduced pressure, thereby obtaining an organotrisiloxane compound (A-2) represented by the following formula.

[ CHEM 8 ]

(A-3)

Diphenylsilanediol (16.2g), methyltrimethoxysilane (25g), and a titanium chelate catalyst (0.2g, produced by Matsumoto Fine Chemical Co. Ltd., ORGATIX TC-401) were added to a 100ml flask, and after allowing to react at 100 ℃ for 60 minutes, the produced methanol and the remaining methyltrimethoxysilane were removed by flowing nitrogen gas, thereby obtaining an organotrisiloxane compound (A-3) represented by the following formula.

[ CHEM 9 ]

(A-4)

Diphenylsilanediol (16.2g), vinyltriisopropenoxysilane (25g), and tetramethylguanidinopropyltrimethoxysilane (0.2g) were added to a 100ml flask, and after 60 minutes of reaction at 100 ℃, the acetone produced was removed by flowing nitrogen gas, and then the remaining vinyltriisopropenoxysilane was removed by heating under reduced pressure to obtain an organotrisiloxane compound (a-4) represented by the following formula.

[ CHEM 10 ]

(A-5)

Methylphenylsilane diol (16.2g, partially dimerized), vinyltrimethoxysilane (25g), and a titanium chelate catalyst (0.2g, manufactured by Matsumoto Fine Chemical Co. Ltd., ORGATIX TC-401) were added to a 100ml flask, and after 60 minutes of reaction at 100 ℃, the generated methanol and the remaining vinyltrimethoxysilane were removed by flowing nitrogen gas, thereby obtaining an organotrisiloxane compound (A-5) represented by the following formula.

[ CHEM 11 ]

(A) Ingredients (for comparison)

(a-1)

Dimethylsilanediol (12.3g, partially dimerized), methyltrimethoxysilane (20g), and a titanium chelate catalyst (0.2g, produced by Matsumoto Fine Chemical Co. Ltd., ORGATIX TC-401) were added to a 100ml flask, and after 60 minutes of reaction at 100 ℃, the produced methanol and the remaining methyltrimethoxysilane were removed by flowing nitrogen gas, thereby obtaining an organotrisiloxane compound (a-1) represented by the following formula.

[ CHEM 12 ]

(a-2)

In a 100ml flask, a hydroxyl-terminated dimethyl silicone polymer (700mpa.s, 300g), methyltrimethoxysilane (25g), and a titanium chelate catalyst (0.2g, produced by Matsumoto Fine Chemical co.ltd., ORGATIX TC-401) were added, and after 60 minutes of reaction at 100 ℃, the generated methanol was removed by flowing nitrogen gas, and then the remaining methyltrimethoxysilane was removed by heating under reduced pressure, thereby obtaining an organopolysiloxane compound (a-2) represented by the following formula.

[ CHEM 13 ]

(wherein n is 250.)

Examples 1 to 5 and comparative examples 1 to 3

The components shown in tables 1 and 2 were mixed in a 10ml glass cup in respective amounts, and manually mixed, and stirred at room temperature for 10 minutes to obtain an organosilicon coating agent composition. The components (A-1) to (A-5), (a-1) and (a-2) are solvent-free. The appearance and properties of the obtained silicone coating agent composition were visually confirmed and are also shown in tables 1 and 2.

The silicone coating composition obtained above was cured under curing conditions of 23 ℃/50% Rh × 7 days. The appearance and properties of the resulting cured product were visually confirmed and are shown in tables 1 and 2.

The raw materials used in addition to the component (a) obtained in the above preparation examples are shown below.

(B) Composition (I)

(B-1)

Tin catalyst: u-830 (manufactured by Ridonghua Kabushiki Kaisha, dioctyltin)

(B-2)

Amine catalyst: tetramethyl guanidinopropyltrimethoxysilane

(C) Composition (I)

(C-1)

Vinyl trimethoxy silane

(A) Composition (I)(for comparison)

(a-3)

A solvent-based coating agent mainly containing an acrylic resin component was prepared: humiseal (registered trademark) -1B66 NS. The solid content was 35% by mass (solvent content 65% by mass), and the film was coated by diluting the film twice with an additional solvent (dilution material Humiseal (registered trademark) シンナー 901).

[ TABLE 1]

[ TABLE 2]

Next, the silicone coating agent compositions of the examples and comparative example 3 using the component (a-3) were used to evaluate the appearance, tack-free time, corrosion resistance test and flexibility of the cured product. The results are shown in Table 3.

(appearance of cured product)

The coating cured on the aluminum dish, which was produced in the evaluation of the tack-free time described below, was evaluated for transparency and degree of coloration by visual observation.

(tack free time)

0.20g of each composition (liquid) was collected on an aluminum dish and applied to a thickness of 2 cm. times.2 cm (4 cm)²) The square of (2) was evaluated by setting the time until the adhesive property of the surface of each composition was lost by touching with a finger as the curing time (tack free time).

(test for Corrosion resistance)

Each material (silicone coating agent composition) was coated on the surface of a silver-plated aluminum plate at 0.08g of each composition (liquid) to 2 cm. times.2 cm (4 cm) so that the cured coating film became about 200. mu.m²) The square of (2) was cured under curing conditions of 23 ℃/50% Rh X7 days, and a hydrogen sulfide gas corrosion tester was used for the curing over time (initial phase, time, and time,1 day later, 3 days later, 7 days later, 14 days later) of the silver plating surface. The etching conditions are as follows.

Concentration of hydrogen sulfide: 2ppm of

Temperature: 23 deg.C

Humidity: 50% Rh

The silver-plated surfaces before and after the corrosion test were observed, and it was judged that the corrosion had occurred at the time of the initial change in silver gloss (blackening, graying).

(flexibility)

When the silver-plated aluminum plate coated (having the cured coating film of the silicone coating agent composition) after the completion of the corrosion resistance test was bent, it was evaluated whether the coating layer could follow the substrate without cracking.

[ TABLE 3]

(results)

From the above results, it was confirmed that: the silicone coating agent composition of the present invention is excellent in curability and transparency at room temperature, and is excellent in the effect of preventing corrosion of a metal base material by a corrosive gas and in the ability to follow the base material (flexibility).