JPH10310740A - Planing coating composition and member having planing surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that can readily flow down liquid particles stuck thereto without leaving trace water and can readily form transparent coating layer by using an acrylic polymer, a silicone and a fluorine polymer. SOLUTION: The objective composition comprises (A) an acrylic polymer and/or its precursor as methyl acrylate, ethyl acrylate, (B) a silicone or silica or silanol and/or their precursors as methyl-trimethoxysilane, (C) a fluorine polymer and/or its precursor as polytetrafluoroethylene or polyvinyl f'luoride. In a preferred embodiment this composition contains a curing agent, preferably at least one from isocyanate curing agents and carbonyl curing agents. The content of the component B is 1-30 pts.wt. per 100 pts.wt. of the component A and the component C is 3-10 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for forming a coating film on a surface of an article or a member, the method comprising:
The present invention relates to a coating composition having a surface that has a property of sliding down without leaving a trace of water due to a slight inclination (this property is referred to as “sliding property” in the present invention). More specifically, the present invention relates to a member having a surface having excellent drip-proof property. Further, the present invention relates to a member having a surface having excellent drainage properties. Further, the present invention relates to a member having a surface to which water-based dirt does not easily adhere. In addition, the present invention relates to a member having a surface having excellent running water washability. In addition, the present invention relates to a member having a surface having excellent snow prevention properties.

[0002]

2. Description of the Related Art It is often experienced that windshields, side glasses, door mirrors, fender mirrors, and road mirrors of automobiles lose visibility due to rainfall and splashes of rain and a large number of discrete water droplets adhering thereto. It is. Further, when water droplets adhere to the transmission line, the shape of the water droplets becomes a downward conical shape, so that the discharge becomes easy and leads to a power transmission loss. Also, in the winter, water drops droop like icicles,
The tip is sharp and the discharge amount is further increased. In addition, the creepage insulation of the insulator is significantly reduced due to the adhesion of water droplets. Also,
In the heat exchanger, the moisture adhering to the fins grows in the form of water droplets and is retained between the fins by capillary action, so that the water droplets become the resistance of the air flowing between the fins, thereby lowering the heat exchange efficiency. In addition, the roof in a snowfall area may be deformed due to the weight of the roof due to the large amount of snow, so that it is necessary to frequently perform heavy snow removal.
Also, in the case of an antenna in a snowfall area, icing snow sometimes causes a communication failure such as a decrease in electric field strength. Further, in the bathtub, water stains easily adhere to the apron portion, which may impair the aesthetic appearance of the bathtub used.

[0003]

The above-mentioned problems caused by the adhesion of water droplets can be solved by forming a flowable surface. According to conventional wisdom, in order to express the above-mentioned dripping properties on the surface,
It has been proposed to coat a substrate surface with a water-repellent paint such as polytetrafluoroethylene (PTFE).
However, when a water droplet is attached to the surface coated with the water-repellent paint and the substrate is tilted, the water droplet does not easily move unless tilted by 60 ° or more, and when moved, the top of the water droplet has priority. In this case, the water droplets move in such a manner as to draw a thread, and water marks remain on the moved part after the water droplets fall, so that they do not have sufficient dripping properties and drip-proof properties.

Recently, it has been proposed to coat a substrate with a water-slidable paint such as a graft polymer of a fluoropolymer having a hydroxyl group and a silicone having an epoxy group at one end (Asahi Shimbun, 1997). (February 8, morning edition). With this coating, water droplets adhering to the surface move with a slight inclination of about 20 ° without slipping and leaving no trace of water. It is thought to have. However, in the above coating,
The following problems were considered due to the fact that the fluoropolymer was the main component. (1) Since the fluorine-based polymer has a low surface energy and is hardly fixed to other substances, the coating film is inferior in abrasion resistance and film forming property. (2) Since fluorinated polymers have the property of easily aggregating, cloudiness tends to occur during film formation.

[0005] Therefore, an object of the present invention is to provide a coating composition which has a property that adhered water droplets easily flow and does not leave traces of water, and can easily form a transparent coating film. .

[0006]

According to the present invention, in order to solve the above-mentioned problems, (A) an acrylic polymer and / or a precursor thereof, and (B) silicone or silica or silanol and / or a precursor thereof The present invention provides a water-slidable coating composition comprising a body and (C) a fluorine-based polymer and / or a precursor thereof. In a preferred embodiment of the present invention, from the viewpoint of film-forming properties, (B) silicone or silica or silanol, based on 100 parts by weight of the acrylic polymer and / or its precursor,
And / or 1 to 30 parts by weight of a precursor thereof, (C) a fluoropolymer, and / or 3 to 10 parts by weight of a precursor thereof,
Is contained. In a preferred embodiment of the present invention, a hardener is further added to improve abrasion resistance. In a preferred embodiment of the present invention, the curing agent is at least one of an isocyanate-based curing agent and a carbonyl-based curing agent.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Acrylic polymers and precursors thereof usable in the present invention include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, and the like. Octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, stearyl acrylate, oleyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, β-hydroxyethyl acrylate, diethylene glycol acrylate,
Polyethylene glycol acrylate, β-hydroxypropyl acrylate, glycidyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, diethylaminoethyl acrylate, 7-amino-3,7-dimethyloctyl acrylate, β -Ethoxyethyl acrylate (cellosolve acrylate), 2-cyanoethyl acrylate, aryl acrylate, alkoxycarbonyl acrylate, benzyl acrylate, vinyl-substituted benzyl acrylate, 3-acryloxy-2-hydroxypropyltrimethylammonium chloride,
Sulfoacrylate, pentachlorophenyl acrylate, isocyanate-added acrylate, phosphorus-containing acrylate, trisacryloxyethyl phosphate, carboalkoxyvinylmethylphosphonic acid, methyl 2-oxymethylacrylate, dialkylphosphate alkyl acrylate, 2-di (2- Chloroethyl)
Phosphate propyl acrylate, dibromopropyl acrylate, mono (2-hydroxyethyl-α-chloroacrylate) acid phosphate, 2-chloroethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, fluoroalkyl acrylate,
Benzoyloxyalkyl acrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,4-butanediol diacrylate, 1.6
Hexanediol diacrylate, sulfopropyl acrylate, and oligomers, polymers, copolymers and the like containing at least one of them can be suitably used.

[0008] Silicone, silica, and the like which can be used in the present invention.
Silanol and its precursors include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane,
Methyltrichlorosilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltrit
-Butoxysilane, n-hexyltrimethoxysilane,
n-hexyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, phenyltrichlorosilane, phenyltribromosilane, dimethyldimethoxysilane, dimethyldi Ethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxy Silane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldipropoxysilane, phenylmethyldibutoxy , Diphenyldimethoxysilane, diphenyldiethoxysilane, trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, vinyltrimethoxysilane, vinyltriethoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltrimethoxysilane, trifluoropropyl Fluoropropyltriethoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ-glycoxydoxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane,
γ-acryloxypropylmethyldimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane, alkyl silicates, their (partial) hydrolysates, polymers, mixtures, etc. It can be suitably used.

Examples of the fluorine-based polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyhexafluoropropylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, and ethylene-chlorotrifluoroethylene. Copolymers, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, perfluorocyclopolymers, vinyl ether-fluoroolefin copolymers, vinylester-fluoroolefin copolymers, and the like can be suitably used.

As the curing agent, for example, an isocyanate-based curing agent, a carbonyl-based curing agent, an epoxy-based curing agent, a siloxane-based curing agent, a vulcanized-based curing agent, and the like can be used.

[0011] Coating compositions include solvents such as water, ethanol, propanol and toluene, leveling agents such as diacetone alcohol and cellosolve, propellants such as dimethyl ether, silver, copper, zinc and zeolite, apatite, and the like. An antibacterial agent such as an inorganic antibacterial agent supported on titania, alumina, silica, or the like, or an ultraviolet absorber may be added.

In order to form a coating film on the surface of a substrate using the coating composition of the present invention, the coating composition is applied to the surface of the substrate and cured. As a method for applying the coating composition, methods such as spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, sponge coating, and gravure printing can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.

The base material applicable to the present invention is preferably made of metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth, a combination thereof, or a laminate thereof. Available. The substrate to which the present invention can be applied can be applied to any substrate which is required to have a drip-proof property on a surface, a water-repellent property, an antifouling property for water-based dirt, a washing property for running water, an anti-icing snow property and the like.

[0014] As a base material which is required to have a drip-proof surface,
Vehicle windshields such as vehicle side glass, window glass for railway vehicles, etc., vehicle windshields such as automotive windshields, motorcycle windshields, vehicle mirrors such as vehicle door mirrors, motorcycle rearview mirrors, etc., in front of the vehicle Vehicle lighting covers such as headlight covers, motorcycle headlight covers, instrument panel covers such as motorcycle instrument panel covers, architectural window glasses, road mirrors, outdoor lighting covers, eyeglass lenses, goggles, motorcycle helmets Transparent substrates such as shields, camera lenses, camera lens covers, and mirror substrates (or films attached to them) that lose visibility due to the attachment of raindrops, etc .; insulators (or films attached to them) The adhesion of water droplets reduces electrical insulation, such as fins for heat exchangers (or a film attached on them) As in, which reduces efficiency by connecting the water droplets in the air passage; and can be suitably used. When applied to the above transparent substrate, the coating is preferably substantially transparent.

[0015] The base material which is required to have a drainable surface is a tableware, a bathtub, a toilet, a sink, a kitchen sink, a sink, a cooking range, a dishwasher, a dish dryer, a cupboard, a drain basket, a bathroom floor. Good surface drainage, such as wood, bathroom wall materials, bathroom ceiling materials, vehicle exteriors and coatings (or films attached to them), so that they dry quickly and prevent the growth of microorganisms due to water adhesion. It can be suitably used for a substrate that can be expected.

The base material which is required to prevent water-based soil from adhering thereto includes tableware, bathtubs, toilet bowls, sinks, kitchen sinks, sinks, cooking ranges, dishwashers, dish dryers, cupboards, drainboards, Like bathroom floor materials, bathroom wall materials, bathroom ceiling materials, aircraft, seaside buildings (or films attached to them), scales, calcium salts and magnesium salts adhere to the surface, In addition, those which show a stain on the appearance due to the following; those which adhere to an alkali salt and diffuse in the interior for a long period of time to attack the core material, such as concrete building materials, can be suitably used.

The base material which is required to have surface flushing properties includes building materials, building exteriors, window frames, architectural windows, vehicle windows, vehicle exteriors and paints, signboards, traffic signs, road noise barriers, Sound insulation walls for railways, guardrail exteriors and coatings,
Outdoor lighting cover, bridge, insulator, solar battery cover, solar water heater heat collecting cover, greenhouse, vehicle lighting cover, gaze guide, road reflector, road decorative board, railing, vehicle mirror, outdoor Outdoor components, such as surveillance cameras (or films affixed thereon), that are exposed to rainfall and can be cleaned thereby; tunnel interiors and coatings, building materials, building interiors, window frames, windowpanes, housing equipment, toilets, bathtubs , Washbasins, lighting fixtures, lighting covers, kitchen utensils, dishes, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods,
A member that can be washed with running water, such as a ventilation fan, a bathroom floor material, a bathroom wall material, a bathroom ceiling material, a kitchen sink (or a film stuck thereon), and the like can be preferably used.

As the base material which is required to have a surface with anti-icing and snow-preventing properties, a roofing material, an antenna, a power transmission line, an ice and snow glider, etc. can be suitably used.

In addition, the present invention can be used for a substrate, such as an inner wall of a vacuum vessel (or a film to be stuck thereon), which requires rapid removal of water adhering to the surface of the substrate, and a biocompatible material. There is.

[0020]

【Example】

Embodiment 1 FIG. (Inclination) (1) Preparation of Coating Agent First, samples # 1 and # 2 were prepared as working samples, and samples # 3 to # 5 were prepared as comparative samples by the following method. Acrylic prepolymer (Mitsui Toatsu Chemical, Q164) 3g
And diol type silicone (Shin-Etsu Chemical, KF600
1) 50 mg and a fluorine-based polymer (Asahi Glass, LF-6
(00) 70 mg was dissolved in 10 ml of a solvent in which toluene and methyl isobutyl ketone were mixed at a weight ratio of 7: 3, and the mixture was stirred for 15 minutes. Further, as a curing agent, an isocyanate-based curing agent (Mitsui Toatsu Chemicals, P53-70) 0.55
After adding g, the mixture was stirred for 15 minutes to obtain a coating agent # 1 sample. Acrylic prepolymer (Mitsui Toatsu Chemical, Q1
64) 3 g with a diol type silicone (Shin-Etsu Chemical Co., Ltd.)
90 mg of KF6001) and 90 mg of a fluorinated polymer (Asahi Glass, LF-600) in a 10 ml solvent prepared by mixing toluene and methyl isobutyl ketone at a weight ratio of 7: 3.
And stirred for 15 minutes. Furthermore, after adding 75 μl of succinic chloride as a curing agent, the mixture was stirred for 15 minutes to obtain a coating agent # 2 sample. 3 g of an acrylic prepolymer (Mitsui Toatsu Chemical, Q164) was dissolved in 10 ml of a mixed solvent of toluene and methyl isobutyl ketone at a weight ratio of 7: 3, and the mixture was stirred for 15 minutes. further,
Isocyanate-based curing agents (Mitsui Toatsu Chemical,
After adding 0.53 g of P53-70), the mixture was stirred for 15 minutes to obtain a coating agent # 3 sample. 3 g of acrylic prepolymer (Mitsui Toatsu Chemical, Q164) and 50 mg of diol type silicone (Shin-Etsu Chemical, KF6001)
After being dissolved in 10 ml of a solvent in which toluene and methyl isobutyl ketone were mixed at a weight ratio of 7: 3, the mixture was stirred for 15 minutes. Further, after adding 0.54 g of isocyanate-based curing agent (Mitsui Toatsu Chemicals, P53-70) as a curing agent,
After stirring for 15 minutes, a coating agent # 4 sample was obtained. 3 g of acrylic prepolymer (Mitsui Toatsu Chemical, Q164) and 70 mg of fluoropolymer (Asahi Glass, LF-600)
After being dissolved in 10 ml of a solvent in which toluene and methyl isobutyl ketone were mixed at a weight ratio of 7: 3, the mixture was stirred for 15 minutes. Further, after adding 0.54 g of isocyanate-based curing agent (Mitsui Toatsu Chemicals, P53-70) as a curing agent,
After stirring for 15 minutes, a coating agent # 5 sample was obtained. Table 1 summarizes the above preparation conditions.

[0021]

[Table 1]

(2) Preparation of Coating Film Samples of coating agents # 1 to # 5 were applied on a polymethyl methacrylate plate, allowed to cure at room temperature (about 20 ° C.) for one week, and then #A to #E A sample was obtained.

(3) Experiment With respect to the samples #A to #E, the contact angle with water and the angle at which water droplets start sliding down were examined. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) as a value about 15 seconds after dropping 10 μl of a water droplet from a micro syringe. Since the angle at which a water drop starts to slide depends on the size of the water drop, a 20 μm
The values obtained when 1, 30, and 50 μl of water droplets were dropped were determined.

(4) Results and Discussion Table 2 shows the results.

[0025]

[Table 2]

Table 2 shows the following. 1. The #A and #B samples containing three components of acrylic polymer, silicone, and fluorine-based polymer have a smaller starting angle of water droplet sliding than the #C to #E samples containing only one or two of the three components. Low, showing good lubricity. 2. In the case of #A and #B samples containing three components of acrylic polymer, silicone, and fluoropolymer, when 50 μl of water droplets are dropped, the sliding start angle of the water droplets is very low at 10 ° or less, which is very good. Shows slipperiness. 3. In the samples #A and #B containing three components of acrylic polymer, silicone and fluorine polymer, the drop start angle of the water drop when dropping 30 μl of water was very low at 10 ° or less, which was very good. Shows slipperiness. 4. For #A and #B samples containing three components of acrylic polymer, silicone and fluorine polymer, the drop start angle of the water drop when dropping 20 μl of water was very low at 20 ° or less, and good water slippage Is shown. 5. The good water-sliding properties of the #A and #B samples are properties irrelevant to the water-repellent properties of the sample surface as judged from the data of the contact angle with water.

From the above, it has been found that when a coating film is formed with a coating agent containing three components of an acrylic polymer, silicone and a fluorine-based polymer, good water slip is exhibited.

Embodiment 2 FIG. (Glass Bottle) A coating film of the coating agent # 1 sample of Example 1 was formed inside the glass bottle in the same manner as in Example 1. After the glass bottle was half filled with water, the bottle was tilted to remove water from the bottle. When the inner wall of the glass bottle was observed thereafter, no water droplet remained. From the above, it was confirmed that when a coating film was formed with a coating agent containing three components of an acrylic polymer, silicone and a fluorine-based polymer, attached water droplets easily flowed and did not leave water marks.

Comparative example. (Film-forming property) Acrylic prepolymer (Mitsui Toatsu Chemical, Q164) 3g
And diol type silicone (Shin-Etsu Chemical, KF600
1) 900 mg and a fluoropolymer (Asahi Glass, LF-
600) was dissolved in 10 ml of a solvent in which toluene and methyl isobutyl ketone were mixed at a weight ratio of 7: 3, and the mixture was stirred for 15 minutes. Further, an isocyanate-based curing agent (Mitsui Toatsu Chemicals, P53-70) is used as a curing agent.
After adding 55 g, the mixture was stirred for 15 minutes, and the coating agent #
Six samples were obtained. An attempt was made to apply the coating agent # 6 sample on a polymethyl methacrylate plate, but the film could not be formed successfully. Thus, it was confirmed that when silicone was added in an amount of 30 parts by weight or more or a fluorine-based polymer in an amount of 30 parts by weight or more with respect to the acrylic polymer, there was a problem in film-forming properties.

[0030]

According to the coating composition of the present invention,
It has the property that attached water droplets easily flow and does not leave water marks, and it is possible to easily form a transparent coating film.

Claims (9)

[Claims] 1. An acrylic polymer and / or a precursor thereof, (B) a silicone or silica or a silanol, and / or a precursor thereof, and (C) a fluoropolymer and / or a precursor thereof. And a body, comprising a water-slidable coating composition. 2. 1 to 30 parts by weight of component (B) and 1 to 30 parts by weight of component (C) based on 100 parts by weight of component (A).
A water-slidable coating composition comprising parts by weight. 3. The water-slidable coating composition according to claim 1, further comprising a curing agent. 4. The water-slidable coating composition according to claim 3, wherein the curing agent is at least one of an isocyanate-based curing agent and a carbonyl-based curing agent. 5. A member having a water-slidable surface, on which a coating film of the water-slidable coating composition according to claim 1 is formed. 6. The member having a water-slidable surface according to claim 5, wherein the coating film is transparent. 7. The water-sliding surface according to claim 5, wherein the surface of the coating film has a property that water slides down at least 10 degrees when 50 μl of water is dropped. Member to have. 8. The water-sliding surface according to claim 5, wherein the surface of the coating film has a property that water slides down when tilted by at least 10 degrees when 30 μl of water is dropped. Member to have. 9. The water-sliding surface according to claim 5, wherein the surface of the coating film has a property that water slides down at least 20 degrees when 20 μl of water is dropped. Member to have.