JP6983121B2 - A coating composition containing a hydrolyzable group-containing silicone resin, a coating film, and an article having the film. - Google Patents

Description

The present invention relates to a coating composition containing a hydrolyzable group-containing silicone resin, a coating film formed by curing the composition, and an article having the film.

Conventionally, a coating agent composition containing a silicone resin has been applied and applied to a building material, a painted steel sheet, or the like for the purpose of imparting water repellency, improving the appearance, and protecting the surface.

Patent Documents 1, 2, 3, and 4 disclose a composition obtained by diluting a reactive silicone resin having an alkoxysilyl group at the end of a molecular chain with a large amount of an organic solvent. Patent Document 5 describes a composition obtained by diluting a reactive silicone resin having an alkoxysilyl group at the end of a molecular chain with an isoparaffin-based solvent having a high boiling point (distillation temperature range of 185 ° C. or higher) as the first layer, and an organopoly having an amino group. A two-layer coating using a composition containing siloxane as a second layer is disclosed. In Patent Document 6, the reactive silicone resin is diluted with a naphthenic hydrocarbon solvent having a boiling point or a distillation range of 140 to 220 ° C. in an amount of 600 to 1700 parts by mass with respect to 100 parts by mass of the silicone resin. The composition is disclosed.

Japanese Unexamined Patent Publication No. 2009-13863 Japanese Unexamined Patent Publication No. 2009-13862 Japanese Unexamined Patent Publication No. 2013-166957 Japanese Unexamined Patent Publication No. 2010-202717 Japanese Unexamined Patent Publication No. 2012-241093 WO2017 / 187874

However, there is a trade-off between curability, workability, and wear resistance of the coating film, and it is difficult to achieve all of them. For example, when a high boiling point solvent is used to improve the workability of the coating agent composition, the curability of the coating film deteriorates. When the amount of the active ingredient of silicone is reduced by using a large amount of solvent, the wear resistance of the coating film deteriorates. Further, if the amount of the curing catalyst is increased in order to improve the curability or if a highly active curing catalyst is used, there arises a problem that the workability deteriorates. As described above, it is difficult for the coating agent compositions described in Patent Documents 1 to 6 to satisfy all of workability, curability and abrasion resistance at the same time. Further, when the construction is carried out for the purpose of protecting the surface of the base material, in addition to the above-mentioned properties, it is also required to form a film having excellent water repellency.

The present invention has been made in view of the above circumstances, and is excellent in workability when the uncured composition is applied by wiping operation to form a uniform film, and the film is cured after the application. It is an object of the present invention to provide a coating composition having excellent properties, water repellency, and abrasion resistance.

As a result of diligent studies to achieve the above object, the present inventors have conducted a partial hydrolysis condensate of tetraalkoxytitanium in which the catalytic activity is appropriately suppressed in a coating composition containing a hydrolyzable group-containing silicone resin. By using the above as a curing catalyst and using it in combination with a diluting solvent having a specific boiling point or distillation range, it is possible to wipe evenly with a cloth at the time of construction without using a large amount of diluting solvent, and the coating film after construction. Has found that it is possible to provide an extremely excellent coating agent which can have good curability and achieves excellent workability, curability, and abrasion resistance of a cured film, and has achieved the present invention.

That is, the present invention
(A) Hydrolyzable group-containing silicone resin having a kinematic viscosity of 90 to ^{200 mm 2 / s at 25 ° C .: 100 parts by mass,}
(B) Partial Hydrolyzed Condensate of Tetraalkoxytitanium However, the weight ratio of _{TiO 2} obtained when it is assumed that the partially hydrolyzed condensate is completely hydrolyzed to 100 parts by weight of the partially hydrolyzed condensate is 31.0 to 35.1 wt%: 1 to 10 parts by mass and (C) a distillation range (dry from the initial distillate point ) when the boiling point is in the range of 150 to 180 ° C. or when the boiling point is not a single temperature. temperature range up to the point) is in the range of 150 to 180 ° C., saturated hydrocarbon solvents: providing a coating composition comprising 75 to 200 parts by weight.

The coating composition of the present invention can impart a thin film coating layer having excellent water repellency, water slipperiness, and abrasion resistance to a metal surface, a painted surface, a resin surface, or the like, and also has good workability and curing during wiping. Has sex. Therefore, it can be suitably used for coating vehicles such as automobiles and trains, building materials, and molded bodies.

Hereinafter, each component will be described in detail.
(A) Hydrolytic group-containing silicone resin (A) The component is a silicone resin having a hydrolyzable group. The silicone resin is hydrolyzed and condensed in the presence of the component (B) described later and cured. In particular, it hydrolyzes and condenses in the presence of moisture in the air. The silicone resin has a kinematic viscosity of 90 to ²⁰⁰ mm 2 / s at 25 ° C., preferably 95 to 180 mm ² / s.

In the cured film obtained from the coating composition of the present invention, the component (A) plays a major role in exhibiting water repellency, water slipperiness and abrasion resistance. The component (A) may be a silicone resin having a hydrolyzable group, but is preferably a molecular chain terminal and / or a side chain obtained by partially hydrolyzing and dealcoholizing a polyfunctional alkoxysilane. It is preferable to use a silicone resin having a hydrolyzable group. The silicone resin has a linear or three-dimensional network structure. The silicone resin preferably has a weight average molecular weight of 1,600 to 18,000, preferably 2,000 to 15,000. By setting the weight average molecular weight in this range, the viscosity of the silicone can easily be in the above-mentioned preferable range. In the present invention, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

Examples of the silicone resin include a partially hydrolyzed condensate of alkoxysilane represented by the following structural formula (1).

R ¹ _x −Si (OR ² ) _4-x (1)

In the formula (1), R ¹ is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and more preferably 1 to 1 carbon atoms which may have a substituent. 4, more preferably, an aliphatic hydrocarbon group having 1 or 2 carbon atoms. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a trill group, an aralkyl group such as a benzyl group, or a carbon atom of these groups. A monovalent hydrocarbon group in which a part or all of the hydrogen atoms bonded to is substituted with a hydroxy group, a cyano group, a halogen atom other than fluorine, an alkoxysilyl group, a polyoxyalkylene group, an epoxy group, a carboxyl group, etc. is mentioned. Be done. Of these, a methyl group or an ethyl group is preferable. x is an integer of 0 to 3, more preferably 1 or 2.

R ² is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms which may have a hydrogen atom or a substituent, and is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Examples thereof include the groups exemplified in ^1. A hydrogen atom, a methyl group, an ethyl group, and a propyl group are more preferable, and a hydrogen atom, a methyl group, or an ethyl group is particularly preferable from the viewpoint of curability.

The silicone resin is obtained by stirring the compound represented by the above formula (1) in the presence of a hydrolysis catalyst and water while heating to partially cause a hydrolysis condensation reaction.

In the production of the silicone resin, the alkoxysilane represented by the above formula (1) may be used alone or in combination of two or more. However, the obtained partial (co) hydrolysis condensate (that is, the silicone resin which is the component (A)) has two or more groups represented by the ^{OR 2 in one molecule.}

The catalyst used for the hydrolysis condensation may be any conventionally known catalyst. For example, acids such as hydrochloric acid, nitrate, sulfuric acid, hydrogen halide, carboxylic acid and sulfonic acid, acidic or weakly acidic inorganic salts, solid acids such as ion exchange resin, inorganic bases such as ammonia and sodium hydroxide, and tributylamine. , 1,5-diazabicyclo [4.3.0] nonen-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and other organic bases, organic tin compounds, organic titanium Examples thereof include compounds, organic zirconium compounds, organic metal compounds such as organic aluminum compounds, and these may be used alone or in combination of two or more.

Component (A), kinematic viscosity 90~200mm ² / s, preferably 95~180mm ² / s, more preferably 100~180mm ² / s, particularly preferably from 110~170mm ² / s. In the present invention, the kinematic viscosity is measured at 25 ° C. by a Canon-Fenceke viscometer according to JIS-Z-8803. When the kinematic viscosity of the component (A) is within the above range, the coating composition can have excellent workability, curability, water repellency of the cured film, water slipperiness, and wear durability.

As the component (A), a commercially available product can be used. For example, X-40-9250 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., 160 mm ² / s, represented by the above formula (1), where R ¹ and R ² are both methyl groups, and x = 1 or 2. Partial hydrolysis condensate of alkoxysilane mixture), X-40-9225 (manufactured by Shinetsu Chemical Industry Co., Ltd., 100 mm ² / s, represented by the above formula (1), where R ¹ and R ² are both methyl groups. Yes, a partial hydrolysis condensate of alkoxysilane with x = 1), SH550 (Toray Dow Corning Co., Ltd. product, 135 mm ² / s, represented by the above formula (1), R ¹ is a methyl group and a phenyl group, R ² is a methyl group, and a partially hydrolyzed condensate), and the alkoxysilane is x = 2. These may be used alone or in combination of two or more.

(B) Partial hydrolyzed condensate of tetraalkoxytitanium The component (B) is a partially hydrolyzed condensate of tetraalkoxytitanium, and the hydrolyzable group (Si-OR ₂ ) possessed by the component (A) is in the air. It is a catalyst for reacting with the moisture of the above to cause a condensation reaction. Although tetraalkoxytitanium has high catalytic activity, it suppresses catalytic activity by increasing steric hindrance by partially hydrolyzing and condensing it into a polymer. The partially hydrolyzed condensate of the tetraalkoxytitanium can be produced, for example, by the methods described in US Pat. No. 2,689,858 and US Pat. No. 4,346,131.

In the partially hydrolyzed condensate of tetraalkoxytitanium, _{a part or all of the alkoxy groups of tetraalkoxytitanium (Ti (OR) 4} ) are hydrolyzed, and the Ti—OH groups are condensed to form a Ti—O—Ti bond. It was formed. However, in the present invention, the partially hydrolyzed condensate has at least one Ti-OR group and / or Ti-OH group. In the above formula, -OR is an alkoxy group having 1 to 8 carbon atoms, for example, n-butoxy, sec-butoxy, tert-butoxy, n-propoxy, i-propoxy, ethoxy, methoxy, and 2-ethylhexyloxy. It is preferable, more preferably n-butoxy, i-propoxy, and even more preferably n-butoxy.

As described above, the component (B) is obtained by hydrolyzing a part or all of the alkoxy groups of tetraalkoxytitanium and condensing the Ti—OH groups to form a Ti—O—Ti bond. The degree of polymerization is such that the weight ratio (%) of _{TiO 2} obtained when it is assumed that the partially hydrolyzed condensate is completely hydrolyzed to 100 parts by weight of the partially hydrolyzed condensate is 31.0 to 35.1 wt. It is characterized by being%, preferably 32.0 to 35.0 wt%, and more preferably 33.0 to 34.5 wt%. _{The weight of TiO 2} obtained assuming that the partially hydrolyzed condensate is completely hydrolyzed is, in other words, all -ORs bonded to the titanium atom in the partially hydrolyzed condensate are hydrolyzed and condensed. It is the weight of _{TiO 2} obtained when a condensate consisting of _4/2 units of TiO is formed. Hereinafter, it is referred to as a TiO ₂ equivalent weight ratio (%).

The TiO ₂ equivalent weight ratio can also be expressed by the following formula.
TiO _{2 equivalent weight ratio (%) = (weight of TiO 2} obtained assuming that the partially hydrolyzed condensate is completely hydrolyzed) / (weight of the partially hydrolyzed condensate) × 100
For example, in the case of a dimer formed by partial hydrolysis condensation of tetra-n-butoxytitanium, it is assumed that 2 mol (79.87 × 2 g) of _{TiO 2 is generated from 1 mol of the condensate (79.87 × 2).} It can be calculated as /550.42 × 100 = 29.0 (%).
_{Further, the TiO 2} equivalent weight assumed to be generated from the partially hydrolyzed condensate is completely obtained by heating the partially hydrolyzed condensate in air using a differential scanning calorimeter (DSC), solid content measurement, or the like. It can be calculated by hydrolysis and condensation. _{Therefore, the weight of TiO 2} obtained when it is assumed that the partially hydrolyzed condensate is completely hydrolyzed may be the weight of _{TiO 2} obtained by actually completely hydrolyzing the partially hydrolyzed condensate. ..

By adjusting the degree of polymerization so that the TiO ₂ equivalent weight ratio is at least the above lower limit value, the coating composition of the present invention can have moderately suppressed curability, and preferable workability can be obtained. .. Further, when the TiO ₂ equivalent weight ratio is not more than the above upper limit value, the component (B) can have an appropriate catalytic activity, and the coating composition of the present invention can have a preferable curability. The component (B) may be a partially hydrolyzed condensate of one or more tetraalkoxytitanium compounds.

式中、ｍ、ｎ、ｐ、及びｑは０又は正の数であり、但しｍ≠ｎ≠ｐ≠０であり、ＴｉＯ_２換算重量割合が３１．０〜３５．１ｗｔ％となる数であり、−OＲは上記の通りである。ＴｉＯ_２換算重量割合は好ましくは３２．０〜３５．０ｗｔ％、より好ましくは３３．０〜３４．５ｗｔ％となるのがよい。Ｒは互いに独立に、メチル、エチル、ｎ−プロピル、ｉ―プロピル、ｎ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、及び２−エチルヘキシルであり、特に好ましくはｎ−ブチルである。該部分加水分解縮合物としては市販品を使用することができ、例えば、日本曹達（株）製のＢ−４、Ｂ−７等が挙げられる。 The partially hydrolyzed condensate can be expressed by the following formula.

In the formula, m, n, p, and q are 0 or positive numbers, but m ≠ n ≠ p ≠ 0, and the TiO ₂ conversion weight ratio is 31.0 to 35.1 wt%. , -OR is as described above. The TiO ₂ equivalent weight ratio is preferably 32.0 to 35.0 wt%, more preferably 33.0 to 34.5 wt%. R are independent of each other, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, and 2-ethylhexyl, with particular preference being n-butyl. Commercially available products can be used as the partially hydrolyzed condensate, and examples thereof include B-4 and B-7 manufactured by Nippon Soda Co., Ltd.

The blending amount of the component (B) in the coating composition of the present invention is in the range of 1 to 10 parts by mass, preferably 2 to 8 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of the component (B) is at least the above lower limit value, the coating composition of the present invention can have appropriate curability, and when the blending amount of the component (B) is at least the above upper limit value. , Preferred workability can be obtained.

(C) Aliphatic Saturated Hydrocarbon Solvent (C) component has an aliphatic boiling point and a distillation range (temperature range from the initial distillate point to the dry point) of 150 to 180 ° C., preferably 166 to 177 ° C. It is an organic solvent of saturated hydrocarbon solvent. It is a component necessary for uniformly dissolving and diluting the component (A) and the component (B) to form a thin film. The number of carbon atoms of the aliphatic saturated hydrocarbon is not particularly limited as long as the boiling point of the solvent or the distillation range satisfies the above range. For example, examples of the aliphatic saturated hydrocarbon solvent having the above boiling point or distillation range include a solvent containing an aliphatic saturated hydrocarbon having 9 to 12 carbon atoms as a main component. The aliphatic saturated hydrocarbon is, for example, isoparaffin, normal paraffin, naphthene, and particularly preferably an isoparaffin solvent. A compound having the structure may have one or more functional groups such as a halogen group or various organic groups in the structure.

When the boiling point or the distillation range of the component (C) is at least the above lower limit value, the coating composition of the present invention can stay in a liquid state on the substrate for a time required for forming a coating film. Further, when the boiling point or the distillation range is not more than the above upper limit value, the coating composition of the present invention can have appropriate volatility and preferable curability can be obtained. Here, when the boiling point is not a single temperature because the component is a mixture or the like, the distillation range (temperature range from the initial distillate point to the dry point) is preferably 150 to 180 ° C. instead of the boiling point. May be in the range of 166 to 177 ° C. In this case, it is particularly preferable that the temperature difference (temperature distribution) between the initial distilling point and the dry point is in the range of 20 ° C. from the viewpoint of workability.

The aliphatic saturated hydrocarbon solvent may be any one having the above boiling point or distillation range, and a commercially available product can be used. Examples of the commercially available products include Marcazole R (boiling point 177 ° C.) manufactured by Maruzen Petrochemical Co., Ltd., Cactus Normal Paraffin N-10 (initial distilling point 169 ° C., dry point 173 ° C.) manufactured by JXTG Energy Co., Ltd., ExxonMobil. Isoper G (initial distilling point 166 ° C., dry point 177 ° C.) of a product of Co., Ltd. can be mentioned. These aliphatic saturated hydrocarbon compounds may be used alone or as a mixture of a plurality of types. In the case of a mixture, if the distillation range is included in the above temperature range, an aliphatic saturated hydrocarbon compound whose boiling point of the compound alone is not in the range of 150 to 180 ° C. may be contained.

The blending amount of the component (C) in the coating composition of the present invention is 75 to 200 parts by mass, preferably 80 to 150 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of the component (C) is at least the above lower limit value, the coating composition of the present invention has appropriate workability and can realize the formation of a uniform cured film. Further, when the blending amount of the component (C) is not more than the above upper limit value, the coating composition of the present invention can obtain preferable curability and wear resistance after curing.

The coating composition of the present invention may appropriately contain any additive as long as the effect of the present invention is not impaired. Examples of such additives include non-reactive silicone oils, reactive silicone oils, adhesion-imparting agents such as silane coupling agents, antistatic agents, rust preventives, colorants, surfactants, rheology adjusters, and the like. UV absorbers, infrared absorbers, fluorescent agents, abrasives, fragrances, fillers, dyes, leveling agents, reactive diluents such as alkoxysilanes, non-reactive polymer resins, antioxidants, UV absorbers, light Examples thereof include stabilizers, antifoaming agents, dispersants, antistatic agents, and thixotropy-imparting agents.

The coating composition of the present invention can be applied to a base material such as various metals, glass, ceramics, and resin, and is preferably applied to a metal steel sheet, a painted metal steel sheet, or a glass surface. In particular, it is preferably applied to a painted steel sheet used for the exterior of a vehicle such as an automobile.

The means for forming a film of the coating composition of the present invention is not particularly limited. For example, any application means can be appropriately selected, such as hand coating using fibers impregnated with the composition, brush coating, and machine coating using an automatic machine. Particularly preferred methods in the present invention are as follows.
That is, the coating composition of the present invention is impregnated into a dry sponge or a fiber such as a waste cloth in an appropriate amount, spread thinly on the surface of the substrate by hand, and wiped evenly with a cloth before the coating composition is cured. By raising the coating film, an extremely thin coating film is formed, and the volatile components are volatilized by natural drying or using a dryer or the like.

In this step, the component (A) comes into contact with the moisture in the air, the hydrolysis reaction proceeds by the action of the component (B), and the resin is cross-linked and cured on the substrate in parallel with the volatilization of the volatile component. Form a cured product. The volatile component includes the organic solvent which is the component (C), and alcohol and water generated by the condensation reaction.

Titanium-based catalysts and aluminum-based catalysts have been used in conventionally known coating compositions. However, the aluminum-based catalyst has low activity and is inferior in curability after construction. Further, since the titanium-based catalyst has a high reaction activity and the curing reaction proceeds quickly when it is spread thinly on the surface of the base material, it is difficult to wipe it uniformly with a cloth. In order to supplement the workability when the titanium-based catalyst is applied, the construction time can be extended by using a large amount of diluting solvent. However, in this case, the film thickness of the coating film after construction becomes thin, and it becomes difficult to exhibit good wear resistance. Further, when the workability is supplemented by using a high boiling point solvent, the curability deteriorates. On the other hand, the coating composition of the present invention uses a partially hydrolyzed condensate of tetraalkoxytitanium having an appropriately suppressed catalytic activity as a curing catalyst, and is used in combination with a diluting solvent having a specific boiling point or distillation range to obtain a large amount. It can be wiped evenly with a cloth at the time of construction without using a diluting solvent, and the coating film after construction can have good curability, and has excellent workability, curability, and a cured film. Provided is an extremely excellent coating agent that has achieved abrasion resistance.

The film thickness of the coating film obtained by curing the coating composition of the present invention is preferably 0.01 to 20 μm, more preferably 0.02 to 10 μm, and even more preferably 0.05 to 2 μm. When the film thickness of the cured film is within the range, good water repellency, water slipperiness, abrasion resistance and aesthetics can be achieved at the same time. The above-mentioned natural drying is carried out by allowing the mixture to stand at room temperature (25 ° C.) for, for example, 2 hours, more preferably 5 hours. When using a dryer or the like, for example, by drying at 40 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C., more preferably 60 ° C. to 120 ° C., for example, for 1 hour, more preferably 3 hours. Will be done. The coating composition of the present invention can be cured by the above-mentioned natural drying or drying step in a dryer.

Further, in the coating composition of the present invention, the surface of the coating film exhibits antifouling, water-repellent, and aesthetically-enhancing properties. Due to these characteristics, it becomes difficult to be soiled by fingerprints, sebum, human oil such as sweat, cosmetics, etc., and even if stains are attached, a cured product surface having excellent wiping property is provided. Therefore, the coating composition of the present invention is an antifouling composition used for forming a coating film or a protective film on the surface of an article that may be contaminated by human fat, cosmetics, etc. when the human body touches it. It is also useful as.

Examples of such antifouling-treated articles include optical recording media such as optical magnetic discs, optical discs such as CDs, LDs, DVDs, and Blu-ray discs, and optical recording media such as hologram recording; glasses lenses, prisms, lens sheets, and pellicle. Optical components and optical devices such as membranes, polarizing plates, optical filters, wrenchular lenses, frennel lenses, antireflection films, optical fibers and optical couplers; CRTs, liquid crystal displays, plasma displays, electroluminescence displays, rear projection displays, fluorescent display tubes Various screen display devices such as (VFD), field emission projection displays, toner-based displays; especially PCs, mobile phones, mobile information terminals, game machines, electronic book readers, digital cameras, digital video cameras, automatic cash withdrawal deposit devices, cash Automatic payment machines, vending machines, navigation devices for automobiles, image display devices such as security system terminals, and touch panel (touch sensor, touch screen) type image display input devices that also operate them; mobile phones, mobile information terminals, Input devices such as electronic book readers, portable music players, portable game machines, remote controllers, controllers, keyboards, panel switches for in-vehicle devices; housings for mobile phones, mobile information terminals, cameras, portable music players, portable game machines, etc. Surfaces; Automotive exteriors, pianos, luxury furniture, marble and other surfaces; Art display protective glass, show windows, showcases, advertising covers, photostand covers, watches, automotive front glass, trains, aircraft, etc. Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as window glasses, automobile headlights, and tail lamps; various mirror members and the like can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 9 and Comparative Examples 1 to 14]
Each of the following components was mixed at the mass ratio shown in Table 1 or Table 2 to prepare a coating composition.
[(A) component]
(A-1): A methoxy group-containing silicone resin (X-40-9250, manufactured by Shin-Etsu Chemical Co., Ltd.) having a weight average molecular weight of about 10,000 and a kinematic viscosity of 160 mm ^{2 / s at 25 ° C.}
(A-2): A methoxy group-containing silicone resin compound (X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd.) having a weight average molecular weight of about 3,500 and a kinematic viscosity of 100 mm ^{2 / s at 25 ° C.}

[Ingredients for comparative examples]
(A-3): A compound having a weight average molecular weight of about 5,000 and a kinematic viscosity of 80 mm ² / s at 25 ° C. (X-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd.).
(A-4): Methyl silicone resin compound (KR-500, manufactured by Shin-Etsu Chemical Co., Ltd.) having a weight average molecular weight of about 1,500 and a kinematic viscosity of 25 mm ^{2 / s at 25 ° C.}
(A-5): Methylphenyl-based silicone resin compound having a weight average molecular weight of about 20,000 and a kinematic viscosity of 220 mm ² / s at 25 ° C. (XR-31-B2733, manufactured by Toray Dow Corning Co., Ltd.)

[(B) component]
In terms of TiO ₂ weight ratio in the following A (wt%), partially hydrolyzed condensates partially hydrolyzed condensate completely hydrolyzed assuming the weight ratio of TiO ₂ obtained when the that for 100 parts by weight (wt%) Is.
(B-1): Partial hydrolysis condensate of tetra-n- _{butoxytitanium (TIO 2} equivalent weight ratio 34.1 wt%, B-7, manufactured by Nippon Soda Co., Ltd.)
(B-2): Partial hydrolysis condensate of tetra-n- _{butoxytitanium (TIO 2} equivalent weight ratio 32.1 wt%, B-4, manufactured by Nippon Soda Co., Ltd.)

[Ingredients for comparative examples]
(B-3): Partial hydrolysis condensate of tetra-n- _{butoxytitanium (TIO 2} equivalent weight ratio 35.2 wt%, B-10, manufactured by Nippon Soda Co., Ltd.)
(B-4): Tetra-n- _{butoxytitanium dimer (TIO 2} equivalent weight ratio 29.0 wt%, Organtics TA-23, manufactured by Matsumoto Fine Chemical Co., Ltd.)
(B-5): Tetra-n- _{butoxytitanium (TIO 2} equivalent weight ratio 23.5 wt%, B-1, manufactured by Nippon Soda Co., Ltd.)
(B-6): Aluminum alkoxide compound (DX9740, manufactured by Shin-Etsu Chemical Co., Ltd.)

[(C) component]
(C-1): Organic solvent composed of a mixture of isoparaffin (initial distillation point 166 ° C., dry point 177 ° C., Isopar G, manufactured by ExxonMobil).

[Ingredients for comparative examples]
(C-2): Organic solvent composed of a mixture of isoparaffin (initial distillation point 180 ° C., dry point 188 ° C., Isopar H, manufactured by ExxonMobil).
(C-3): Organic solvent composed of a mixture of isoparaffin (initial distillation point 114 ° C., dry point 139 ° C., Isopar E, manufactured by ExxonMobil).

Each of the coating compositions of Examples and Comparative Examples was evaluated by the following method. The results are shown in Tables 1 and 2.

Workability evaluation method 2 ml of each coating composition is applied to a black coated plate (material: SPCC-SD, standard: JIS-G-3141, dimensions: 0.8 mm x 70 mm x 150 mm, aminoalkyd on one side after chemical electrodeposition. It was dropped on a black-painted product (Asahi Bee Techno Co., Ltd. product), thinly applied by hand using tissue paper, and allowed to stand at 25 ° C. for 5 minutes. Then, the excess was wiped off with a dry microfiber cloth. At this time, those that can be wiped lightly and evenly are ○, those that are slightly uneven or have a slightly heavy wiping resistance are △, and those that are markedly uneven or difficult to wipe are ×. As shown in Table 1 or 2.

Curability evaluation method A test piece to which the coating composition was applied was prepared by the same method as the workability evaluation. This was further allowed to stand at 25 ° C. for 2 hours to be cured and cured to obtain a test piece having a film made of the cured product. When the coated surface of the test piece was touched with a finger, the one with no tack remaining and showing slipperiness was 〇, the one with no tack remaining but not showing slipperiness was △, and the tack remained. It is shown in Table 1 or 2 as x.

Water repellency / slipperiness evaluation method A test piece to which the coating composition was applied was prepared by the same method as the workability evaluation. This was further allowed to stand at 25 ° C. for 12 hours to be cured and cured to obtain a test piece having a film made of the cured product. One drop (about 2 μl) of purified water is dropped on the test piece, and the contact angle of water is measured using a contact angle meter (device name: Drop Master DM-701, Kyowa Interface Science Co., Ltd. product) to determine the water repellency. evaluated. The desirable contact angle for water repellency is a value of about 100 ° or more. In addition, one drop (about 20 μl) of purified water was dropped on the same test piece and gradually inclined from a horizontal state, and the angle at which the water drop began to flow was used as the water sliding angle to evaluate the water slipperiness (water sliding property). did. The evaluation criteria are shown in Table 1 or 2 as those having a water sliding angle of less than 35 ° as ◯, those having a water sliding angle in the range of 35 to 45 ° as Δ, and those having a water sliding angle of more than 45 ° as x.

Abrasion resistance evaluation method A test piece to which the coating composition was applied was prepared by the same method as the workability evaluation. This was further allowed to stand at 25 ° C. for 12 hours to be cured and cured to obtain a test piece having a film made of the cured product. A wear resistance test was carried out on the surface of the test piece to which the composition was applied using a simple friction tester (product of Imoto Seisakusho). In the test, the moving plate to which the test piece is fixed moves 100 mm per reciprocating motion at a speed of 30 times per minute, and a friction object loaded with a load of 500 g by a weight is placed at the center thereof and reciprocated 400 times. This caused wear. The water contact angle of the surface after wear was measured by the same method as described above, and the wear resistance was evaluated. The evaluation of wear resistance is as follows: ○ for those whose water contact angle after 400 reciprocating motions is more than 90% of the water contact angle before wear, Δ for those in the range of 75 to 90%, and less than 75%. Those are marked with x and are listed in Table 1 or 2. Here, the friction material used in the test is a dry and clean cloth having a width of 40 mm (water-absorbing cloth made of cellulose / cotton composite fiber, ThreeBond Co., Ltd. product "ThreeBond 6644E") containing distilled water in diameter. It was wound around a 20 mm stainless steel cylinder, and installed so that the axis of the cylinder faces in a direction orthogonal to the moving direction of the moving plate.

Among the above test items, it is particularly preferable that there is no item of determination × and the number of determination Δ is 3 or less.

As shown in Table 2 above, the coating agents of Comparative Examples 1 and 2 using an isoparaffin organic solvent whose distillation range does not meet the range of the present invention instead of the component (C) of the present invention have excellent workability and curability. It was inadequate. Further, the coating compositions of Comparative Examples 3, 4, and 5 in which the silicone oil whose kinematic viscosity does not meet the range of the present invention is used in place of the silicone oil of the present invention are poor in curability and water repellency.
Further, _{the coating compositions of Comparative Examples 6 and 7 in which a partially hydrolyzed condensate having a content of 4/2} units of TiO which does not meet the scope of the present invention was used instead of the component (B) had good workability and curability. Either is inferior. The coating composition of Comparative Example 8 using tetra-n-butoxytitanium is inferior in workability, and the coating composition of Comparative Example 9 using an aluminum alkoxide compound is inferior in curability.
In the coating agent of Comparative Example 10 in which the blending amount of the component (C) is less than the lower limit of the present invention, the component (A) has a high concentration and sufficient workability cannot be obtained. In the coating composition of Comparative Example 11 in which the blending amount of the component (C) exceeds the upper limit of the present invention, the composition became thin, a sufficient film thickness could not be formed, and the wear resistance was poor. The coating composition of Comparative Example 12 also secured workability, but could not form a sufficient film thickness, resulting in poor wear resistance. Further, the coating composition of Comparative Example 13 in which the blending amount of the component (B) is less than the range of the present invention is inferior in curability, water repellency, water slipperiness, and abrasion resistance, and the blending amount of the component (B) is the present. The coating composition of Comparative Example 14, which is beyond the scope of the invention, was inferior in workability.
On the other hand, as shown in Examples 1 to 9 of Table 1, the coating compositions of the present invention all have good workability and provide a coating film having good water repellency, water slipperiness and abrasion resistance. rice field.

The coating composition of the present invention is excellent in workability and curability, and the film after curing can have excellent water repellency, water slippage and abrasion resistance. Therefore, it is useful for forming a thin film coating layer for imparting protective performance such as water repellency, water slippage, and durability to a vehicle such as an automobile or a train, a building material, a metal surface such as a molded body, a painted surface, or a resin surface. Is.

Claims (10)

(A) Hydrolyzable group-containing silicone resin having a kinematic viscosity of 90 to ^{200 mm 2 / s at 25 ° C .: 100 parts by mass,}
(B) Partial Hydrolyzed Condensate of Tetraalkoxytitanium However, the weight ratio of _{TiO 2} obtained when it is assumed that the partially hydrolyzed condensate is completely hydrolyzed to 100 parts by mass of the partially hydrolyzed condensate is 31.0 to 35.1 wt%: 1 to 10 parts by mass and (C) a distillation range (dry from the initial distillate point ) when the boiling point is in the range of 150 to 180 ° C. or when the boiling point is not a single temperature. temperature range up to the point) is in the range of 150 to 180 ° C., saturated hydrocarbon solvents: 75-200 parts by weight coating composition comprising. The coating composition according to claim 1, wherein the component (A) has a kinematic viscosity of 100 to 180 mm ^{2 / s at 25 ° C.} The coating composition according to claim 1 or 2, wherein the content of the component (B) is 2 to 8 parts by mass. The coating composition according to any one of claims 1 to 3, wherein the content of the component (C) is 80 to 150 parts by mass. _{In the component (B), the weight ratio of TiO 2} obtained when it is assumed that the partially hydrolyzed condensate is completely hydrolyzed to 100 parts by weight of the partially hydrolyzed condensate is 33.0 to 35.1 wt%. The coating composition according to any one of claims 1 to 4. The one according to any one of claims 1 to 5, wherein the component (C) contains one or more of an aliphatic saturated hydrocarbon having 9 to 12 carbon atoms, which may have one or more halogen groups or functional groups. Coating composition. The coating composition according to any one of claims 1 to 5, wherein the component (C) contains one or more selected from isoparaffin, normal paraffin and naphthen, which may have one or more halogen groups or functional groups. thing. A coating formed by curing the coating composition according to any one of claims 1 to 7. The coating film according to claim 8, which has a film thickness of 0.01 to 20 μm. The article having the coating film according to claim 8 or 9.