JP2006102671A - Manufacturing method of coating base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a coating base material which can improve raindrop stain resistance even when a coating film on the base material is made of either an organic clear coating or an organic enamel coating. <P>SOLUTION: An organic compound containing silicic acid and/or a compound having a hydrolyzable silyl group are mixed in the organic clear coating or organic enamel coating. Then this coating is applied to the base material and dried to form a coating film. Subsequently the coating film is subjected to heating treatment. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a coated base material that can be suitably used when forming an outer wall of a building, a roof, a shutter, and other structures.

In recent years, a base material for forming an outer wall of a building, a roof, a shutter, other structures, and the like has been subjected to a treatment for imparting dripping resistance from the viewpoint of emphasizing the appearance of the city. For example, when forming a coating film with raindrop stain resistance on a substrate, a stain-resistant paint composition for a precoat metal containing a silicate-modified epoxy group-containing polyester resin and a compound having a predetermined reactive functional group The thing is used (for example, refer patent document 1). Also, as a different method, there is known a method in which a base paint containing a predetermined amount of wax is applied to a substrate, and then a clear paint containing a silicate-modified acrylic silicon resin composition is applied to the base paint. (For example, refer to Patent Document 2). Furthermore, using a coating composition containing a fluorinated olefin polymer, a predetermined copolymer, and a compound having a hydrolyzable silyl group, it is also practiced to impart raindrop resistance (for example, patents). Reference 3).
JP 2004-43559 A JP 2001-334200 A JP 10-36754 A

  However, with the method described in Patent Document 1, it is easy to improve the raindrop resistance of a coating film mainly composed of a polyester resin, but it is difficult for a coating film mainly composed of a fluororesin. is there. Moreover, although the method described in Patent Document 2 is effective for a coating film formed with an organic clear coating, it cannot be said to be effective for a coating formed with an organic enamel coating. . Furthermore, in the method described in Patent Document 3, a fluororesin is an essential component, and it is difficult to improve the raindrop resistance of a coating film mainly composed of a resin other than the fluororesin. As described above, none of the conventional methods has general versatility in terms of imparting raindrop contamination.

  The present invention has been made in view of the above points, and it is a coating substrate that can improve the dripping resistance even if the coating film on the substrate is formed of either an organic clear coating or an organic enamel coating. The object is to provide a manufacturing method.

  According to a first aspect of the present invention, there is provided a method for producing a coated substrate, comprising blending an inorganic compound containing silicic acid and / or a compound having a hydrolyzable silyl group into an organic clear paint or an organic enamel paint, and then using the paint. A coating film is formed by applying to a material and drying, and then the coating film is subjected to heat treatment.

  The invention of claim 2 is characterized in that, in claim 1, colloidal silica is used as the inorganic compound containing silicic acid.

  The invention of claim 3 is characterized in that, in claim 1 or 2, an organic clear paint or organic enamel paint mainly comprising an acrylic resin and / or a polyester resin is used.

  The invention of claim 4 is characterized in that, in claim 1 or 2, an organic clear paint or organic enamel paint containing a fluororesin as a main component is used.

  The invention of claim 5 is characterized in that, in claim 1 or 2, the organic clear paint or organic enamel paint is composed mainly of a silicate-modified acrylic resin and / or a silicate-modified polyester resin. .

  A sixth aspect of the invention is characterized in that, in the first or second aspect, the organic clear paint or the organic enamel paint is mainly composed of a fluororesin having a hydrophilic group.

  The invention of claim 7 is characterized in that in any one of claims 1 to 6, at least one kind or two kinds or more selected from flame treatment, plasma treatment and corona discharge treatment is performed as the heat treatment. To do.

The invention of claim 8 is characterized in that in any one of claims 1 to 6, a frame process exceeding 300 kJ / m ² / min is performed as the heat treatment.

  The invention of claim 9 is characterized in that, in any one of claims 1 to 8, any one of a metal material, a plastic material, wood, mortar, and stone material is used as a base material.

  According to the method for producing a coated base material according to claim 1 of the present invention, it is possible to improve the dripping resistance even if the coating film on the base material is formed of either an organic clear paint or an organic enamel paint. It is.

  According to the invention of claim 2, the rain dripping resistance can be further improved.

  According to the invention of claim 3, it is possible to further improve the rain-spill resistance. In addition, since the polyester resin, which is the main component of the paint, is generally low in price, it is possible to produce a coated base material excellent in raindrop contamination resistance at a low cost.

  According to the invention of claim 4, the rain-spill resistance can be further improved. Moreover, since the fluororesin which is the main component of the paint is excellent in corrosion resistance and weather resistance, these properties can be imparted to the coated substrate.

  According to the invention of claim 5, it is possible to further improve the resistance to raindrop contamination. Moreover, since the silicate modified polyester resin which is the main component of the paint can be produced at a low cost, a coated base material having excellent raindrop stain resistance can also be produced at a low cost.

  According to the sixth aspect of the present invention, the rain dripping resistance can be further enhanced by the hydrophilic group of the fluororesin. Moreover, since the fluororesin which is the main component of the paint is excellent in corrosion resistance and weather resistance, these properties can be imparted to the coated substrate.

  According to invention of Claim 7, hydrophilicity can be easily provided to the surface of a coating film.

  According to invention of Claim 8, hydrophilicity can be provided to the surface of a coating film still more easily.

  According to invention of Claim 9, since the kind of base material is abundant, a suitable coating base material can be obtained according to a use.

  Embodiments of the present invention will be described below.

  In the method for producing a coated substrate according to the present invention, first, an inorganic compound containing silicic acid and / or a compound having a hydrolyzable silyl group is blended in an organic clear paint or an organic enamel paint. Next, a coating film is formed by applying this paint to a substrate and drying it. Thereafter, this coating film is subjected to heat treatment. According to this method, even if the coating film on the substrate is formed of either an organic clear paint or an organic enamel paint, it is possible to improve the dripping resistance. In addition, the coating film on a base material may consist of a single layer, or may consist of a several layer. In the following, first, the paint is described, and then the heat treatment is described.

<Inorganic compounds containing silicic acid>
Examples of inorganic compounds containing silicic acid include silicon dioxide (SiO ₂ ), also known as silicic acid anhydride, silica, compounds such as orthosilicic acid, metasilicic acid, silica gel, etc., compounds composed of silicon, oxygen, hydrogen, aluminum, magnesium, iron, etc. For example, naturally occurring compounds such as feldspar and mica, and artificially produced compounds such as cement, glass and enamel can be used. Examples of the silicic acid used include silica powder and silica fiber, and generally include colloidal silica such as “Snowtex” manufactured by Nissan Chemical Industries, Ltd. The most common compound as the silicate compound is silicate glass, which can be used as a fine powder or glass fiber.

<Colloidal silica>
When colloidal silica is used as the inorganic compound containing silicic acid, it is possible to further enhance the rain-stain resistance of the coated substrate. As colloidal silica, those having a particle diameter of 2 to 100 nm are commercially available. Such colloidal silica can be used by selecting the particle diameter as required. From the viewpoint of surface coating, it is desirable to select fine colloidal silica. In addition, those having different particle diameters can be mixed and used.

<Compound having hydrolyzable silyl group>
Although it will not specifically limit if it has a hydrolyzable silyl group, As a specific example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane, dimethylcyclosilane, trimethylchlorosilane, methyltrichlorosilane, dimethylvinyltriethoxysilane and compounds obtained by fluorine modification thereof Or a condensate thereof, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptop Pills trimethoxysilane, .gamma.-aminopropyltrimethoxysilane and fluorine modified compounds of the silane coupling agent, further may be mentioned condensates thereof and the like. These may be used alone or in combination of two or more.

  The above-mentioned compound having a hydrolyzable silyl group may be used alone as an additive, or may be used by being incorporated in a skeleton resin of a paint. That is, a silicate modified resin may be used as a skeleton resin or a sub skeleton resin. For example, by polymerizing a vinyl monomer having an epoxy group with a radical polymerization initiator in the presence of a carboxyl group-containing polyester resin, the hydrolyzable silane monomer and / or its condensate, or an organic solvent. A silicate-modified epoxy group-containing polyester resin can be produced. Similarly, various resins can be silicate-modified. And when using this silicate modification resin as a coating material, in order to promote a hydrolysis reaction, you may use acidic catalysts, such as hydrochloric acid, a sulfuric acid, phosphoric acid, an acetic acid, p-toluenesulfonic acid, with water. In particular, when an organic clear paint or organic enamel paint, which will be described later, is one having a silicate-modified acrylic resin and / or a silicate-modified polyester resin as a main component (base), it can further enhance the rain-stain resistance of the coating substrate. It can be done. Moreover, since the silicate modified polyester resin which is the main component of the paint can be produced at a low cost, a coated base material having excellent raindrop stain resistance can also be produced at a low cost.

<Organic clear paint and organic enamel paint>
As the main component of organic clear paint and organic enamel paint, synthetic resin paint is generally used industrially. For example, alkyd resin paint, phenol resin paint, amino resin paint, amino alkyd resin paint, polyester resin paint, epoxy Resin paints, polyurethane resin paints, acrylic resin paints, vinyl chloride resin paints, fluororesin paints and the like can be mentioned. Further, cellulose-based paints such as lacquers obtained by chemically treating natural materials can also be mentioned. These may be used alone or in combination of two or more. In particular, it is preferable to use a low-cost polyester resin paint or a fluororesin paint excellent in corrosion resistance and weather resistance. And it can be used as an organic clear paint by not blending a pigment in the above-mentioned various organic paints, and by blending a pigment such as an inert titanium oxide pigment or a colored pigment in the above-mentioned various organic paints, It can be used as an enamel paint. When an organic clear paint or organic enamel paint containing an acrylic resin and / or a polyester resin as a main component is used, it is possible to further improve the resistance to raindrops. Moreover, when using a polyester resin, since the polyester resin used as the main component of a coating material is generally low-cost, a coated base material excellent in raindrop resistance can be produced at low cost. Further, even when an organic clear paint or organic enamel paint containing a fluororesin as a main component is used, it is possible to further improve the resistance to raindrops. Moreover, when using a fluororesin, since the fluororesin used as the main component of a coating material is excellent in corrosion resistance and weather resistance, these characteristics can also be provided to a coating base material.

<Polyester resin paint>
In general, a polyester resin is a resin in which a dicarboxylic acid and a diol are combined.

  Examples of dicarboxylic acids include fatty acid dicarboxylic acids having 2 to 22 carbon atoms such as succinic acid, adipic acid, azelaic acid, sebacic acid and decamethylene dicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and tetrahydrophthalic acid. Examples thereof include alicyclic dicarboxylic acids such as acid, hexahydrophthalic acid, methylhexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. These dicarboxylic acids may be used alone or in combination of two or more.

  Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 1,6- Examples thereof include fatty acid diols having 2 to 22 carbon atoms such as hexanediol, diethylene glycol, and pentanediol. These diols may be used alone or in combination of two or more.

  As the linear polyester resin composed of structural units of dicarboxylic acid and diol, linear polyester resin obtained by polycondensation of dicarboxylic acid and diol, linear polyester resin obtained by addition reaction of dicarboxylic acid anhydride and diol, Furthermore, the linear polyester resin etc. which are obtained by transesterification can be mentioned, and not only the linear polyester resin whose raw materials are dicarboxylic acid and diol, but the structural unit in the linear polyester resin is derived from dicarboxylic acid. And those having the same structure as a structural unit derived from a diol.

  Such a linear polyester resin has a slight amount of trifunctional groups or more as long as it does not impair the properties as a linear polyester resin for the purpose of reducing crystallinity or introducing a carboxyl group. A component derived from a compound having a carboxyl group, a compound having a hydroxyl group, or the like may be included. Specific examples thereof include a linear polyester resin in which a carboxyl group is introduced by addition reaction of trimellitic acid to a linear polyester resin having a hydroxyl group at the terminal, trimethylolpropane, 1,2,3- A linear polyester resin branched by slightly containing hexanetriol, trimellitic acid, pyromellitic acid, etc., and a trifunctional structure such as trimellitic acid or trimethylolpropane in the molecular skeleton to reduce crystallinity. For example, a compound having a slight amount of introduced compound may be used. A compound having a carboxyl group having three or more functional groups and a compound having a hydroxyl group may be used alone or in combination of two or more.

When the above-mentioned inorganic compound containing silicic acid and / or a compound having a hydrolyzable silyl group is added to a polyester resin used as a normal coating material, it is possible to ensure the rain-stain resistance, but higher rain-stain resistance. In order to secure the properties, it is necessary to further improve the hydrophilicity of the coating film by introducing a hydroxyl group or an organosilicate into some or all of the molecules of the polyester resin. For example, a resin disclosed in Japanese Patent Application Laid-Open No. 2004-43559 (Patent Document 1) can be used. That is, (A) (a) a number average molecular weight of 1,500 to 50,000 and a resin acid value of 2 to 30 mgKOH / g, a carboxyl group-containing polyester resin, and (b) a vinyl-based epoxy group A polymer as a constituent component, the mass ratio of (a) / (b) is from 1/99 to 80/20, and a part of the epoxy group of (b) and the carboxyl group of (a) are equivalent The epoxy group-containing polyester resin containing a hydroxyl group, which is reacted at a ratio of 0.1 or less, is represented by the general formula (1):
_{^{(R 1) m -Si- (OR}} 2) 4-m (1)
(Wherein R ¹ and R ² are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, and m is 0 or 1), and / or a condensate thereof. A silicate-modified epoxy group-containing polyester resin having an epoxy equivalent of 200 to 2,000 g / mol, and (B) a carboxyl blocked in one molecule with a carboxyl group, a carboxylic acid anhydride group and an alkyl vinyl ether compound What contains the compound which has at least 1 sort (s) chosen from the reactive functional group of group can be used as a polyester resin in this invention. Such a resin may be used alone or in combination with other polyester resins. In addition, in JP-A-2004-43559 (Patent Document 1), in addition to the above (A) and (B), (C) general formula (2):
_{^{(R 3) n -Si- (OR}} 4) 4-n (2)
(Wherein R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and n is 0 or 1), and / or a condensate thereof. Further, what is contained is disclosed.

  Here, a slight mention is made of silicate modification of the polyester resin.

  Since there is a difficulty in modifying a normal linear polyester resin with a silicate, it is preferable to use an epoxy group-containing vinyl polymer having a hydroxyl group. The carboxyl group of the carboxyl group-containing polyester resin and a part of the epoxy group of the epoxy group-containing vinyl polymer having a hydroxyl group react and bond. This can significantly improve the compatibility of two different polymers. Further, the hydroxyl group of the epoxy group-containing polyester resin having a hydroxyl group reacts with the organosilicate and / or the condensate thereof, whereby the organosilicate or the like is bonded to the epoxy group-containing polyester resin.

  The epoxy group-containing vinyl polymer is a polymer of a vinyl monomer having an epoxy group, or a polymer of a vinyl monomer having an epoxy group and another vinyl monomer. Specific examples of the vinyl monomer having an epoxy group include glycyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) allyl ether, 3,4-epoxycyclohexylmethyl (meth). Examples include allyl ether. Of these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate, which are (meth) acrylic acid esters, have higher reactivity between radical polymerization and epoxy group / carboxyl group, and more preferable examples are given. It is done. The vinyl monomer having an epoxy group may be used alone or in combination of two or more.

  The epoxy group-containing vinyl polymer is preferably a copolymer obtained by copolymerizing an epoxy group-containing vinyl monomer and another vinyl monomer. Examples of other vinyl monomers copolymerized with the epoxy group-containing vinyl monomer include (meth) acrylic acid esters. Examples of the organic group include saturated hydrocarbon groups, organic groups having a reactive functional group such as a hydroxyl group, acetal group, cyclocarbonate group, or blocked carboxyl group. When selecting a functional group, it is necessary to select a functional group that does not exhibit strong reactivity with the epoxy group under the copolymerization conditions with a vinyl monomer having an epoxy group.

  Specific examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2-ethylhexyl, and (meth) acrylic. Examples include lauryl acid, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate. Other preferred vinyl monomers include itaconic acid, maleic acid, fumaric acid and other esters, styrene, vinyl toluene, dimethyl styrene, ethyl styrene and other nuclear substituted styrene, acrylonitrile, vinyl acetate, vinyl chloride, etc. Can be mentioned. These may be used alone or in combination of two or more.

  Next, an example of an organic paint mainly composed of a polyester resin will be described. This paint can be produced by blending the following (A component) to (C component) and the like. An organic paint mainly composed of an acrylic resin can be similarly produced by replacing the polyester resin with an acrylic resin.

(Component A: Silicate-modified epoxy group-containing polyester resin)
When an appropriate amount of a carboxyl group-containing polyester resin, an epoxy group-containing polyester resin having a hydroxyl group, and an organosilicate are reacted, the carboxyl group of the carboxyl group-containing polyester resin reacts with the epoxy group of the epoxy group-containing polyester resin having a hydroxyl group. By doing so, an ester bond is formed while having a hydroxyl group. The organosilicate and the condensate thereof are taken into the epoxy group-containing polyester resin by reacting with the hydroxyl group of the epoxy group-containing polyester resin to obtain a silicate-modified epoxy group-containing polyester resin. The organosilicate represented by the general formula (1) described above is a substance typified by the above silanes, and the condensate thereof is one or two or more branched or linear forms of the above silanes. It refers to a condensate, preferably having a weight average molecular weight in the range of 200 to 2,000.

(B component)
The baking paint requires a component that undergoes a thermosetting reaction as (B component). This component is a compound that undergoes a thermosetting reaction with the silicate-modified epoxy group-containing polyester resin (component A) described above, and carboxyl groups blocked with a carboxyl group, a carboxylic anhydride group, and an alkyl vinyl ether compound in one molecule. A compound having at least one selected from the reactive functional groups (hereinafter also simply referred to as “curing agent”). Examples of such a curing agent having a carboxyl group in one molecule include succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dimer acid, phthalic acid, Mention may be made of maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid and the like.

(C component)
As described above, after the silicate modification of the polyester resin and further adding the organosilicate and its condensate as (C component), they float on the surface of the coating film to form a concentrated layer, thereby forming the coating film. It is effective because it can exhibit a high degree of raindrop resistance in a short time after curing. Organosilicates are represented by silanes.

(Other ingredients)
In addition to the above (A component) to (C component), the following additives can be added as necessary. That is, inorganic pigments such as inert titanium oxide, carbon black, iron oxide, chromate, calcium carbonate, organic pigments such as cyanine green and cyanine blue, metal powders such as aluminum powder, copper powder and nickel powder, antibacterial agents, Deodorant, antistatic agent, silicone oil, fluoroplastic powder, silicone powder, extender pigments such as talc, antifoaming agent, rust preventive agent, leveling agent, wax, UV absorber, coupling agent, surfactant, Additives such as plasticizers, drying accelerators, curing catalysts, and organic solvents such as xylene and siloxane. As already explained, when no pigment is used as the (other component), an organic clear paint can be produced. When a pigment is used as the (other component), an organic enamel paint is produced. can do.

<Fluorine resin paint>
Next, an example of an organic paint mainly composed of a fluororesin will be described. This paint can be manufactured by blending the following (I component) to (IV component) and the like. Among the fluororesins, those having a hydrophilic group are particularly preferable for forming a coating film excellent in raindrop stain resistance, and therefore, an example of an organic paint mainly composed of a fluororesin having a hydrophilic group will be described below. . An organic paint mainly composed of a fluororesin having a hydrophilic group and a normal fluororesin (a fluororesin having no hydrophilic group) is also preferred.

(I component)
As the fluororesin as the base resin, a fluorinated olefin polymer alone can secure weather resistance, but there is no problem, but from the viewpoint of compatibility with the fluorinated olefin polymer, adhesion to the substrate, etc. That is, it is desirable to use a polymer of a monomer having a (meth) acryloyl group as the (IV component) described later.

  The fluorinated olefin polymer refers to a polymer containing a fluorinated olefin monomer, and is dispersed or dissolved in an organic solvent. Specific examples thereof include polytetrafluoroethylene, polyvinylidene fluoride, (ethylene / tetrafluoroethylene) copolymer, (vinylidene fluoride / tetrafluoroethylene) copolymer, and (tetrafluoroethylene / hexafluoropropylene) copolymer. , Polyfluorinated vinyl ether, polychlorotrifluoroethylene, (ethylene / chlorotrifluoroethylene) copolymer, (fluorinated vinyl ether / tetrafluoroethylene) copolymer, and the like. These are paint resins such as “Lumiflon” manufactured by Asahi Glass Co., Ltd., “Fluonate” manufactured by Dainippon Ink and Chemicals, “Zaflon” manufactured by Toagosei Co., Ltd., and “Zeffle” manufactured by Daikin Industries, Ltd. It is sold as. The fluorinated olefin polymer may be a single polymer or a combination of two or more polymers, but is compatible with other acrylic components and processability such as solubility in solvents. In addition, it is desirable to contain a vinylidene fluoride polymer in that it has both rain and dripping resistance.

(II component)
This component includes the following (II-A component) fluorinated (meth) acrylate, (II-B component) hydrophilic structural unit-containing ethylenically unsaturated monomer, and (II-C component) other than the above two components It is a copolymer obtained by polymerizing an ethylenically unsaturated monomer. This copolymer is a polymer in which a hydrophobic segment and a hydrophilic segment are copolymerized in the same chain. However, if a copolymer having such a structure is lacking, there is a risk that the dripping resistance will be lowered. is there. The hydrophilic segment is one having a hydrophilic group such as polyalkylene oxide, hydroxyl group, carboxyl group, sulfonyl group, phosphate, amino group, isocyanate group, glycidyl group, ammonium salt or various metal salts in the molecule. Okay, this will improve the dripping resistance.

(II-A component)
As the fluorinated (meth) acrylate, those having an acrylic ester group and an analogous group thereof can be used. Specific examples include the following.
_{CH 2 = CHCOOCH 2 CH 2 C} 8 F 17
_{CH 2 = CHCOOCH 2 CH 2 C} 12 F 25
_{CH 2 = CHCOOCH 2 CH 2 C} 10 F 21
_{CH 2 = CHCOOCH 2 CH 2 C} 6 F 13
_{CH 2 = CHCOOCH 2 CH 2 C} 4 F 9
_{CH 2 = CFCOOCH 2 CH 2 C} 6 F 13
CH ₂ = CHCOOCH ₂ CF _{3
CH 2 = CHCOOCH 2 C 8 F} 17
_{CH 2 = CHCOOCH 2 C 20 F} 41
_{CH 2 = CFCOOCH 2 C 2 F} 5
_{CH 2 = CHCOOCH 2 (CH 2} ) 6 CF (CF 3) 2
_{CH 2 = CHCOOCH 2 (CF 2} ) 2 H
_{CH 2 = CHCOOCH 2 (CF 2} ) 4 H
CH ₂ = CHCOOCH ₂ CF _{3
CH 2 = CHCOOCH 2 CH (OH} ) CH 2 C 8 F 17
_{CH 2 = CHCOOCH 2 CH 2 N} (C 3 H 7) SO 2 C 8 F 17
_{CH 2 = CHCOOCH 2 CH 2 N} (C 2 H 5) COC 7 F 15
_{CH 2 = CHCOO (CH 2)} 8 N (CH 3) COC 12 F 25
_{CH 2 = CHCOO (CH 2)} 2 N (CF 2) 8 CF (CF 3) 2
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 8 F 17
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 12 F 25
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 10 F 21
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 6 F 13
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 20 F 41
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 4 F 9
_{CH 2 = C (CH 3)} COO (CH 2) 6 C 10 F 21
_{CH 2 = C (CH 3)} COOCH 2 CF 3
_{CH 2 = C (CH 3)} COOCH 2 C 8 F 17
_{CH 2 = C (CH 3)} COOCH 2 C 20 F 41
_{CH 2 = C (CH 3)} COOCH 2 CF (CF 3) 2
_{CH 2 = C (CH 3)} COOCH 2 CFHCF 3
_{CH 2 = C (CH 3)} COOCHCF 2 CFHCF 3
_{CH 2 = C (CH 3)} COOCH 2 (CF 2) 2 H
_{CH 2 = C (CH 3)} COO (CF 2) 4 H
_{CH 2 = C (CH 3)} COO (CF 2) 6 H
_{CH 2 = C (CH 3)} COOCH 2 CH (OH) (CH 2) 4 C 18 F 37
_{CH 2 = C (CH 3)} COOCH 2 CH 2 N (CH 3) SO 2 C 6 F 13
_{CH 2 = C (Cl) COO} (CH 2) 6 NHSO 2 C 12 F 25
In addition, these may use only 1 type or may mix and use 2 or more types.

(II-B component)
Specific examples of the hydrophilic structural unit-containing ethylenically unsaturated monomer include α, β-ethylenically unsaturated carboxylic acid, that is, monovalent to acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like. Divalent carboxylic acids and (meth) acrylic acid hydroxyl alkyl esters having 1 to 18 carbon atoms, ie, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 4-hydroxybutyl ester, etc. (meth) acrylic acid Glycidyl esters, that is, glycidyl (meth) acrylate, etc., and repeating units such as ethylene oxide and propylene oxide in the side chain, that is, monomers containing a polyalkylene oxide.

(II-C component)
The ethylenically unsaturated monomer other than the above two components is not particularly limited, but specific examples include fatty acids such as styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, vinyl acetate and the like. Vinyl, (meth) alkyl ester having 1 to 18 carbon atoms in the alkyl group, aminoalkyl ester having 1 to 18 carbon atoms in (meth) acrylic acid, ether oxygen-containing alkyl having 1 to 18 carbon atoms in (meth) acrylic acid Examples thereof include esters and alkyl vinyl ethers having 1 to 18 alkyl carbon atoms.

  In producing the copolymer (II component) by polymerizing the above-mentioned (II-A component) to (II-C component), the production method is not limited at all, and a known method, That is, based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, and an anionic polymerization method, a solution polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used. A radical polymerization method that is particularly simple is preferable. .

(III component)
Furthermore, when organosilicate and its condensate are added as (III component), they float on the surface of the coating film to form a concentrated layer. Is effective. Organosilicates are represented by silanes.

(IV component)
From the standpoint of compatibility with the fluorinated olefin polymer, compatibility with raindrop contamination and substrate adhesion, an acrylic resin, that is, a polymer of a monomer having a (meth) acryloyl group (IV It is preferable to use it together as a component. The polymer of the monomer having the (meth) acryloyl group is not particularly limited. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, octel (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, acrylonitrile, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, dibutyl fumarate, dimethyl fumarate, (meth) acrylic acid, etc. A homopolymer or a copolymer can be mentioned.

(Other ingredients)
In addition to the above (I component) to (IV component), the following additives can be added as necessary. That is, inorganic pigments such as inert titanium oxide, carbon black, iron oxide, chromate, calcium carbonate, organic pigments such as cyanine green and cyanine blue, metal powders such as aluminum powder, copper powder and nickel powder, antibacterial agents, Deodorant, antistatic agent, silicone oil, fluoroplastic powder, silicone powder, extender pigments such as talc, antifoaming agent, rust preventive agent, leveling agent, wax, UV absorber, coupling agent, surfactant, Additives such as plasticizers, drying accelerators, curing catalysts, and organic solvents such as xylene and siloxane. As already explained, when no pigment is used as the (other component), an organic clear paint can be produced. When a pigment is used as the (other component), an organic enamel paint is produced. can do.

(Other base resins)
The physical properties required for the fluorinated olefin polymer as the base resin, such as adhesion to various substrates, scratch resistance, etc., vary depending on the application, so that other properties may be added as necessary to satisfy these properties. It is also possible to use a known polymer that can be a base resin in combination. Such a polymer is not particularly limited, and examples thereof include acrylic resins, urethane resins, alkyd resins, epoxy resins, amino resins, polyester resins, phenol resins, silicone resins and modified products thereof. Can do.

<Base material on which coating film is formed>
In the present invention, various materials can be used as the substrate. For example, examples of the base material include metal materials, plastic materials, wood, mortar, and stone materials. More specifically, as the metal material, a steel plate, a plated steel plate, a coated steel plate (for example, a fluorine resin coated steel plate, a polyester coated steel plate, etc.), an aluminum plate, an aluminum coated plate, a titanium plate, a nickel plate, a cobalt plate, a copper plate, etc. Can be illustrated. Examples of the plastic material include thermoplastic resins represented by polyethylene, polystyrene, poly (meth) acrylate, polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, rubbers, and urethanes. Examples thereof include those formed of resin, alkyd resin, phenol resin, epoxy resin, silicon resin, polycarbonate resin, acrylic resin, and the like. Moreover, a veneer board etc. can be illustrated as a timber. Examples of the stone material include natural stones such as quartz, glass, silica, limestone, and marble. Thus, since the types of base materials are abundant, a suitable coated base material can be obtained according to the application. In addition, as a base material, not only a plate-shaped thing but the thing processed into various shapes can be used.

  And a coating base material can be manufactured as follows. First, an organic clear paint or organic enamel paint is applied to the surface of the substrate and cured to form a coating film. Then, a coating base material can be manufactured by performing the heat processing mentioned later on the surface of a coating film. When heat treatment is performed in this way, many OH groups are introduced to the surface of the coating film to impart hydrophilicity, and the entire surface of the coating film is always covered with a water film at the molecular level. Even if dirt adheres, the dirt does not adhere firmly and can be easily washed away, and the raindrop stain resistance of the coating film can be maintained well over a long period of time.

  The coated substrate as described above can be produced by either a continuous method or a batch method. FIG. 1 shows an example of equipment for producing a coated base material by a continuous method. When this production facility is used, for example, when a plate-like substrate 3 is used, a coated substrate can be produced as follows. A long steel plate (for example, plate thickness: 0.16 to 3.00 mm, plate width: 610 to 1219 mm) is used as the substrate 3, and this steel plate is conveyed in the longitudinal direction (for example, conveyance speed: 20 to 130 m). / Min) First, an organic clear paint or an organic enamel paint 5 is applied to the surface of the steel sheet with a coater which is a coating machine 6. Next, the organic clear paint or organic enamel paint 5 is cured by passing the steel plate coated with the organic clear paint or organic enamel paint 5 as described above through an oven serving as a dryer 7 to form a coating film. The maximum reached temperature of the steel sheet by the oven is set to 224 ° C., for example. Then, the heating means 8 heat-treats the surface of the coating film while conveying the steel sheet on which the coating film is formed in the longitudinal direction. In this way, a coated substrate can be produced in a continuous manner. In FIG. 1, 9 is a transport roll.

  In the present invention, as the heat treatment, at least one or two or more treatments selected from flame treatment (also referred to as flame treatment, F treatment), plasma treatment, and corona discharge treatment can be performed. Whichever treatment is performed, the surface of the coating film can be heated, whereby hydrophilicity can be easily imparted to the surface of the coating film. The flame treatment can be performed using a burner such as a curtain burner or a slit burner as a heating means. That is, as shown in FIG. 1, a burner is arranged on the downstream side of the oven, the opening of the burner as the heating means 8 is directed to the coating film of the base material 3, and the frame (flame) is conveyed while transporting the base material 3. The flame treatment can be performed by applying to the surface of the coating film. The plasma treatment can be performed using a plasma jet gun as the heating means 8. That is, as shown in FIG. 1, a plasma jet gun is arranged on the downstream side of the oven, and this nozzle is directed toward the coating film of the base material 3, and plasma is sprayed on the surface of the coating film while transporting the base material 3. Thus, plasma processing can be performed.

  Here, assuming that the amount of heat given to the coating film by the heating means per unit time is constant, in a continuous method, if the conveyance speed of the substrate is increased, the amount of heat given to the coating film of the substrate can be reduced, Conversely, if the transport speed of the base material is slowed, the amount of heat given to the coating film of the base material can be increased.

As the heat treatment, it is preferable to perform a frame treatment exceeding 300 kJ / m ² / min. When the strength (heating energy) of the frame treatment is set as described above, hydrophilicity can be imparted to the surface of the coating film more easily. However, if the strength of the frame processing is smaller than 300 kJ / m ² / min, the above effects may not be sufficiently obtained. If the strength of the frame treatment is too high, the coating film may be carbonized or the manufacturing cost of the coated substrate may increase due to an increase in energy cost. Therefore, the upper limit of the strength is 1200 kJ / m ^2. / Min.

  On the other hand, according to the batch method, for example, a coated substrate can be manufactured as follows. A steel plate (for example, plate thickness: 0.16 to 3.00 mm, plate width: 610 to 1219 mm) that has been cut into a predetermined shape as a base material is used. A paint or organic enamel paint is sprayed onto the surface of the steel sheet. Next, the organic clear paint or organic enamel paint applied to the steel sheet is cured in an oven as a dryer to form a coating film. At this time, the maximum temperature reached by the oven in the steel sheet is set to 224 ° C., for example. Thereafter, the surface of the coating film thus formed on the steel sheet is subjected to heat treatment by a heating means such as a hand burner. In this way, a coated substrate can be produced in a batch system.

  And since the coating base material manufactured as mentioned above has the rain-stain-resistant contamination property of a coating film over a long period of time, when forming the outer wall of a building, a roof, a shutter, other structures, etc. Can be suitably used. For example, conventional roll-up type shutters are not very good in rain-resistant contamination, so when the shutter is rolled up, water droplets containing dirt on the shutter surface are also involved. And since the water droplet etc. which were confine | sealed in the shutter in this way are hard to evaporate, corrosion of a shutter is accelerated | stimulated. However, if the shutter is manufactured with the coated base material obtained by the present invention, this shutter is excellent in raindrop contamination, so that water droplets including dirt on the shutter surface are not involved, and the shutter Corrosion can be prevented.

  Hereinafter, the present invention will be specifically described by way of examples.

<Polyester resin / acrylic resin coating system>
First, an organic paint mainly composed of polyester resin / acrylic resin will be described.

(Polyester resin)
Commercially available polyester resin “GK150” (manufactured by Toyobo Co., Ltd., carboxyl group-containing polyester resin, hydroxyl value: 6.0 mgKOH / g, acid value 6.0 mgKOH / g, number average molecular weight: 12000, hereinafter referred to as “polyester GK150” .)
(Synthesis example of component A)
In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, xylene, cyclohexanone, polyester GK150, and methyl silicate 51 (trade name, Colcoat Co., Ltd.) in the blending amounts shown in [Table 1] below. Product, low-condensate methyl silicate, weight average molecular weight: 500 to 900, hereinafter referred to as “methyl silicate 51”), and heated under stirring to maintain 120 ° C. Next, as a monomer shown in the following [Table 1] at a temperature of 120 ° C., glycidyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, and a polymerization initiation catalyst, t-Butyl peroxylaurate was added dropwise at a constant speed from a dropping funnel over 2 hours. After the completion of the dropping, the temperature of 120 ° C. was maintained for 1 hour, and then the reaction temperature was lowered to 100 ° C. Thereafter, 2,2′-azobisisobutyronitrile and cyclohexanone were added as additional catalyst solutions shown in [Table 1] below, and the temperature was further maintained at 100 ° C. for 2 hours. And the modified resin solution A which has a non volatile matter as (A component) was obtained. In this resin, the carboxyl group / epoxy group equivalent ratio was 0.013, the nonvolatile content (mass%) was 60.4%, and the epoxy equivalent was 762 g / mol.

(Synthesis example of component B)
A four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel was charged with 134 parts by mass of trimethylolpropane and 425.3 parts by mass of cyclohexanone, and heated to 120 ° C. with stirring. Next, 504 parts by mass of methylhexahydrophthalic anhydride is added dropwise over 2 hours while maintaining a temperature of 120 ° C., and the acid value of the mixture (pyridine / water = 9/1 (mass ratio) mixture is about 50 mass). By diluting the solution twice and titrating the solution heat-treated at 90 ° C. for 30 minutes with a potassium hydroxide standard solution) until it becomes 160 or less, (B component) has a non-volatile content of 60% by mass, A curing agent solution B having a carboxylic acid equivalent of 355 as a solution was obtained.

(Synthesis example of acrylic resin)
A four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel is charged with 35 parts by mass of xylene, 20 parts by mass of cyclohexanone, and 51:12 parts by mass of methyl silicate, and heated with stirring. Maintained 120 ° C. Next, at a temperature of 120 ° C., glycidyl methacrylate: 28.4 parts by mass, n-butyl methacrylate: 10.0 parts by mass, 2-ethylhexyl acrylate: 11.6 parts by mass, 2-hydroxyethyl methacrylate: 3 0.0 part by mass, t-butyl peroxylaurate: 1.0 part by mass was added dropwise at a constant speed from a dropping funnel over 2 hours. After the completion of the dropping, the temperature of 120 ° C. was maintained for 1 hour, and then the reaction temperature was lowered to 100 ° C. Thereafter, 2,2′-azobisisobutyronitrile: 0.5 part by mass and cyclohexanone: 8.5 part by mass were added, and the reaction was terminated by maintaining the temperature at 100 ° C. for 2 hours. An acrylic resin solution E having an epoxy group of 0.7% and an epoxy equivalent of 648 as a solution was obtained.

(Example of manufacturing organic enamel paint)
Synthesized as described above (component A) or acrylic resin solution E and inert titanium oxide were placed in a sand mill and dispersed until the particle size became 10 μm or less. Then, the remaining components shown in [Table 2] below were added and mixed to obtain paints 1 to 6 as organic enamel paints.

(Example of manufacturing organic clear paint)
Without adding inert titanium oxide, each component was added and mixed in the blending amounts shown in the following [Table 2] to obtain paint 7 as an organic clear paint.

  In addition, in said [Table 2], the substance of (1)-(9) shows the following.

  (1): The modified resin solution A of the above synthesis example is shown.

  (2): The curing agent solution B of the above synthesis example is shown.

(3): Silicate C: MKC silicate MS57 (trade name, manufactured by Mitsubishi Chemical Corporation, partially hydrolyzed condensate of tetramethoxysilane, weight average molecular weight: 1400)
(4): Snowtex XBA-ST (trade name, manufactured by Nissan Chemical Industries, Ltd., colloidal silica)
(5): The acrylic resin solution E having an epoxy group of the above synthesis example is shown.

(6): Zinc octylate (7): Inactive titanium oxide for paint (8): Neostan U-340 (trade name, manufactured by Nitto Kasei Co., Ltd., dibutyltin bisisononyl-3-mercaptopropionate)
(9): Modaflow (trade name, manufactured by Nippon Monsanto Co., Ltd., acrylic resin leveling agent)
(Manufacturing example of enameled plate)
As a coating substrate, a molten 55% Al-galvanized steel plate (galvalume steel plate) having a plate thickness of 0.3 mm and a plate width of 250 mm was used, and after degreasing, a coating type chromate treatment was performed. The undercoat was an epoxy paint and dried and baked at 200 ° C. for 40 seconds to obtain a film thickness of 5 μm. And the said coating materials 1-6 were apply | coated to this base material, and the coating films 1-6 and the coating films 8-13 with a film thickness of 15 micrometers were obtained by performing dry baking at 230 degreeC for 50 second (following [Table 3]). In addition, the drying baking temperature shown here is PMT (the highest temperature reached of the coated plate).

(Production example of clear coated plate)
As a coating substrate, a molten 55% Al-galvanized steel plate (galvalume steel plate) having a plate thickness of 0.3 mm and a plate width of 250 mm was used, and after degreasing, a coating type chromate treatment was performed. The undercoat was an epoxy paint and dried and baked at 200 ° C. for 40 seconds to obtain a film thickness of 5 μm. The coating material 3 was further applied thereto, followed by drying and baking at 220 ° C. for 50 seconds to obtain a 15 μm coating film. And the coating material 7 was apply | coated to this base material, and the 5-micrometer coating film 7 and the coating film 14 were obtained by performing 50 second drying baking at 230 degreeC (refer following [Table 3]). In addition, the drying baking temperature shown here is PMT (the highest temperature reached of the coated plate).

(Frame processing)
About 7 types of coated steel plates in which the coating films 1-7 were formed on the surface, the frame process was performed with the hand burner. The flame treatment was performed by burning butane gas at a rate of 200 kJ / m ² / min while moving the coated steel plate in the longitudinal direction at 30 m / min. The distance from the burner tip to the coated steel plate was 30 mm. On the other hand, no flame treatment was performed on the seven types of coated steel sheets having the coating films 8 to 14 formed on the surface.

(Characteristic measurement method)
The following tests were conducted on the 14 types of coated steel sheets obtained as described above.

<Outdoor exposure test>
An exposed specimen (width 145 mm × length 200 mm) and an exposed substrate (width 145 mm × length 100 mm) were cut out from each coated steel plate. Next, 1-1-1 Nishiura, Funabashi-shi, Chiba Pref. An exposure test piece was attached to the inclined surface of the exposure table inclined 45 ° facing south in the Nippon Steel Sheet Funabashi Factory and exposed for 3 months. On the other hand, the exposed substrate was stored in an indoor storage for the same period. Three months after the start of exposure, the exposure test specimen was removed from the exposure table, and the exposed substrate was taken out of the storage. Then, the surface of the exposed test piece is not wiped off, and the L value between the exposed substrate and the exposed test piece is measured with the SM color computer “SM-5” manufactured by Suga Test Instruments Co., Ltd. based on Japanese Industrial Standard (JIS): Z-8729. By measuring the difference (ΔL), the degree of contamination was investigated. In addition, arbitrary 5 places on the surface of the exposed test piece were selected as measurement sites, and the median value was used as a representative value. The results are shown in [Table 3] below.

<Rain dripping resistance>
The outline of the test (acceleration test) for evaluating raindrop resistance is shown below.

1. Test piece A test piece having a size of about 50 mm × 300 mm was cut out from each coated steel plate.

2. Contaminated liquid (1) Contaminated powder Kanto loam: 35 g, tar: 6.5 g, carbon black: 8.5 g were used as contaminated powder.

(2) Contaminated liquid The above contaminated powder was added to tap water at a rate of 0.5 g / l, and this was mixed and stirred to prepare a contaminated liquid.

3. Test method (1) Dripping of contaminated liquid (equivalent to rain dripping)
The test piece obtained as described above is tilted, and the above-mentioned contaminated liquid is dropped at a rate of 200 ml / Hr for 6 hours at a fixed location (place) on the top of the test piece.

(2) Washing with clean water When the dripping of the contaminated liquid is completed, clean water is showered on the test piece.

(3) Drying The test piece after the shower was dried indoors at room temperature.

4). Evaluation Method The test piece after drying as described above was compared with the substrate (without dripping the contaminated liquid) by visual observation, and the raindrop resistance was evaluated according to the following criteria. The results are shown in [Table 3] below.

  A: No rain streaks (streaks due to contaminated liquid) remain.

  ○: Rain lines are slightly recognized.

  Δ: Rain lines are clearly recognized.

  X: The blackness of the rain stripe is conspicuous.

  *: If the raindrops are not made, the traces of water drops are very black and dirty, or if rains are made, extremely black stripes are made.

<Water contact angle>
A test piece was cut out from each coated steel plate, and the test piece was immersed in water for 1 hour. And after removing the water of the surface of the test piece taken out from the water by air blow and further drying for 1 hour, using a FACE automatic contact angle measuring instrument (CA-Z type) manufactured by Kyowa Interface Science Co., Ltd. The contact angle of water was measured. The results are shown in [Table 3] below.

  From the above [Table 3], it is confirmed that when the flame treatment is performed as the heat treatment, the rain dripping resistance is improved. Moreover, it is confirmed that one or both of the inorganic compound containing silicic acid and the compound having a hydrolyzable silyl group are essential components. It is also confirmed that both enamel and clear are effective. In addition, it is confirmed that those mainly composed of a silicate-modified polyester resin or a silicate-modified acrylic resin are particularly excellent.

<Frame processing strength>
Next, it is demonstrated that the contact angle of water becomes smaller and the raindrop resistance is improved when the strength (heating energy) of the frame treatment is set higher.

A coated steel sheet coil having a sheet width of 1000 mm and a sheet thickness of 0.30 mm was manufactured using the same coated steel sheet as in Example 5 in [Table 3] (polyester-based outermost layer being clear). Next, a frame processing apparatus having a butane gas burner having a width of 1100 mm was installed in an actual line (see FIG. 1), and a coated steel sheet fed from the coil was passed through. The flow rate of butane gas is constant (11.8 Nm ³ / H), the line passing speed (Ls) is changed to 130, 90, 70, 40, and 20 m / min. Tests and water contact angles were measured. The result of the raindrop contamination test is shown in FIG. 2, and the measurement result of the water contact angle is shown in FIG. Further, as corresponding to FIG. 2, color photographs of a sample without frame processing and a sample with frame processing (Ls = 130, 90, 70, 40, 20 m / min) are shown in FIG. In FIG. 2, the raindrop scores “5”, “4”, “3”, “2”, and “1” respectively correspond to “◎”, “◯”, “Δ”, “×”, and “*” described above.

<Mechanism to improve dripping contamination resistance by frame processing>
Measurements by XPS (X-ray photoelectron spectroscopy) were performed on the outermost layer before and after the flame treatment of the coated steel sheet (polyester-based and outermost layer is clear) as in Example 5 in [Table 3]. FIG. 4 shows the result of elemental analysis in the depth direction from the outermost surface of the coating film to 15 nm. From this figure, it can be seen that C (carbon) in the outermost layer is decreased by the flame treatment, and O (oxygen) and Si (silicon) are increased. A decrease in C means a decrease in organic substances (organic substances in the paint), and an increase in O means exposure of SiO ₂ (silica) and an increase in hydroxyl groups (—OH). The same applies to the increase in Si. Therefore, these phenomena mean that the outermost layer of the coating film has been made hydrophilic by the frame treatment.

  The XPS analyzer and analysis conditions are as follows.

(XPS analyzer)
PHI 5500 type XPS analyzer (Analysis conditions)
X-ray source: MgKα (1486.6 eV)
X-ray output: 14 kV x 28.6 mA (400 W)
Measurement depth: 0 nm (outermost surface), 5 nm, 10 nm, 15 nm
Measurement area: 800μmφ
Analysis room vacuum: 1.0 × 10 ⁻⁷ Pa
<Fluoropolymer paint system>
Next, an organic paint mainly composed of a fluororesin paint will be described.

(II component: Synthesis example of copolymer obtained by polymerizing fluorinated (meth) acrylate, hydrophilic structural unit-containing ethylenically unsaturated monomer and ethylenically unsaturated monomer other than the above two components)
In a glass flask equipped with a stirrer, a condenser, and a thermometer, (II-A component) as a fluorine-based monomer: CH ₂ = CHCOOCH ₂ CH ₂ C ₆ F ₁₃ : 16 parts by mass, (II-B component) Polyethylene oxide chain-containing methacrylate M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.): 71 parts by mass, 2-hydroxylethyl methacrylate: 5 parts by mass, (III-C component) as methyl methacrylate: 8 parts by mass, and methyl Isobutylketone: 233 parts by mass, under reflux in a nitrogen gas stream, azobisisobutyronitrile: 1 part by mass as a polymerization initiator, and 2-mercaptoethanol: 7.5 parts by mass as a molecular weight regulator After the addition, polymerization was carried out by refluxing for 8 hours. The copolymer (component II) thus obtained is hereinafter referred to as “Copolymer 1”.

(Production example of enamel paint)
(Paint 1)
Hylar 5000 (trade name: manufactured by Augmont: Polyvinylidene fluoride, hereinafter referred to as “Hyler 5000”) (12.9 parts by mass) (12.9 parts by mass) in the isophorone (65 parts by mass) as the fluorinated olefin-based polymer which is (component I) As a polymer of a monomer having a (meth) acryloyl group that is (IV component), a paraloid B-44 (trade name: manufactured by Rohm and Haas Co .: acrylic resin, (Referred to as “Paraloid B-44”) (5.7 parts by mass) in xylene solution (xylene: 5 parts by mass) and ethyl silicate 40 having a hydrolyzable silyl group (component III) (trade name: Colcoat Co., Ltd.) ), Hereinafter referred to as “ethyl silicate 40”) (1.5 parts by mass), white pigment (titanium oxide for inert paint) (9.9 parts by mass) And the solid concentration: the 30% of the paint 1 was prepared.

(Paint 2)
Helarer 5000 (12.6 parts by mass) was partially dissolved and dispersed in isophorone (65 parts by mass), together with paraloid B-44 (5.4 parts by mass) in a xylene solution (xylene: 5 parts by mass). By blending polymer 1 (0.6 parts by mass), ethyl silicate 40 (1.5 parts by mass), and white pigment (titanium oxide for inert paint) (9.9 parts by mass), the solid content concentration: 30 % Paint 2 was prepared.

(Paint 3)
Helarer 5000 (12.9 parts by mass) was partially dissolved and dispersed in isophorone (65 parts by mass). A xylene solution of paraloid B-44 (5.7 parts by mass) (xylene: 5 parts by mass) and ( Snowtex XBA-ST (trade name, manufactured by Nissan Chemical Industries, Ltd .: colloidal silica, hereinafter referred to as “colloidal silica XBA-ST”) (1.5 parts by mass) ) And white pigment (titanium oxide for inert paint) (9.9 parts by mass) to prepare paint 3 having a solid content concentration of 30%.

(Paint 4)
Helarer 5000 (12.6 parts by mass) was partially dissolved and dispersed in isophorone (65 parts by mass), together with paraloid B-44 (5.4 parts by mass) in a xylene solution (xylene: 5 parts by mass). By blending polymer 1 (0.6 parts by mass), colloidal silica XBA-ST (1.5 parts by mass), white pigment (titanium oxide for inert paint) (9.9 parts by mass), the solid content concentration : 30% of paint 4 was prepared.

(Paint 5)
Helarer 5000 (14.1 parts by mass) is partially dissolved and dispersed in isophorone (65 parts by mass), paraxylene B-44 (6 parts by mass) in xylene solution (xylene: 5 parts by mass), white pigment ( A paint 5 having a solid content concentration of 30% was prepared by blending (titanium oxide for inert paint) (9.9 parts by mass).

(Paint 6)
Helarer 5000 (13.5 parts by mass) partially dissolved and dispersed in isophorone (65 parts by mass), paraxylene B-44 (6 parts by mass) in xylene solution (xylene: 5 parts by mass) and copolymer 1 (0.6 parts by mass) and white pigment (titanium oxide for inactive paint) (9.9 parts by mass) were blended to prepare paint 6 having a solid content concentration of 30%.

(Example of manufacturing clear paint)
(Paint 7)
Helarer 5000 (15 parts by mass) was partially dissolved and dispersed in isophorone (65 parts by mass), paraxylene B-44 (9 parts by mass) in xylene solution (xylene: 5 parts by mass) and copolymer 1 ( 2.1 parts by mass) and ethyl silicate 40 (3.9 parts by mass) were blended to prepare paint 7 having a solid content concentration of 30%. Pigments such as white pigment (titanium oxide for inert paint) were not added.

  The ratio (mass%) in the solid content (nonvolatile content) of the coating materials 1 to 7 is as shown in [Table 4] below.

(Manufacturing example of enameled plate)
About the coating materials 1-6, the sample of the coated steel plate was obtained with the following method. That is, the above-mentioned paints were applied on a galvanized steel sheet primer-treated with an epoxy resin (film thickness: 5 μm) with a bar coater (dry film thickness: 20 μm), and PMT (maximum material temperature) was 250 ° C. The sample was baked for 1 minute and then rapidly cooled. Coating films 1 to 6 and coating films 8 to 13 are formed on the surface of each sample (see [Table 5] below).

(Production example of clear coated plate)
For paint 7, a sample of a coated steel plate was obtained by the following method. That is, the above-mentioned paint 5 was applied with a bar coater (dried film thickness: 20 μm) on a galvanized steel sheet primer-treated with an epoxy resin (film thickness: 5 μm), and PMT (maximum material temperature) was 240 ° C. After baking for 1 minute, it was cooled rapidly. Further, the above paint 7 was applied with a bar coater (dry film thickness: 3 μm), baked at 250 ° C. for 1 minute at PMT (maximum material temperature), and then rapidly cooled to prepare a sample. A coating film 7 and a coating film 14 are formed on the surface of each sample (see [Table 5] below).

(Frame processing)
About the sample of 7 types of coated steel plates in which the coating films 1-7 were formed on the surface, the frame process was performed with the hand burner. The flame treatment was performed by burning butane gas at a rate of 250 kJ / m ² / min while moving the coated steel plate at 30 m / min. The distance from the burner tip to the coated steel plate was 30 mm.

  For the 14 types of coated steel sheets obtained as described above, the same tests as in the case of polyester resin / acrylic resin-based paint were performed. The results are shown in [Table 5] below.

  From the above [Table 5], it is confirmed that when the frame processing is carried out, the rain-stain resistance is improved. Moreover, it is confirmed that one or both of the inorganic compound containing silicic acid and the compound having a hydrolyzable silyl group are essential components. It is also confirmed that both enamel and clear are effective. Further, it is confirmed that those mainly composed of a fluororesin having a hydrophilic group are excellent.

<Corona discharge treatment and plasma discharge treatment>
(Corona discharge treatment)
On the galvanized steel sheet primer-treated with epoxy resin (film thickness: 5 μm), paint 2 in the above [Table 4] as a fluororesin paint was applied with a bar coater (dry film thickness: 20 μm), and PMT (maximum reach) The sample was baked at 250 ° C. for 1 minute at the material temperature and then rapidly cooled. Two samples were prepared and both were cut so as to have a size of 100 mm × 100 mm. One sample (1) was subjected to heat treatment by corona discharge treatment under the following conditions, and the other sample (2) was not subjected to heat treatment. In the corona discharge treatment, the distance between the electrode and the sample (1) is set to 50 mm in air reduced in pressure by a vacuum pump to 13.3 hPa (10 mmHg), and a voltage of 40000 V is applied between them for 20 seconds. This was done by applying.

  Then, the outdoor exposure test similar to the above was done about sample (1) (2). As a result, the following results were obtained.

Dirt after 3 months (ΔL)
Sample (1) Heat-treated by corona discharge treatment: -0.62
Sample (2) No heat treatment: -2.31
(Plasma discharge treatment)
On the galvanized steel sheet primer-treated with epoxy resin (film thickness: 5 μm), paint 2 in the above [Table 4] as a fluororesin paint was applied with a bar coater (dry film thickness: 20 μm) and PMT (maximum reach) The sample was baked at 250 ° C. for 1 minute at the material temperature and then rapidly cooled. Two samples were prepared and both were cut to a size of 150 mm × 200 mm. One sample (1) was subjected to heat treatment by plasma discharge treatment under the following conditions, and the other sample (2) was not subjected to heat treatment. The plasma discharge treatment is performed after the tip of the nozzle of the plasma jet gun set at nozzle diameter: 4 mm, interelectrode distance: 5 mm, argon flow rate: 40 L / min, and current: 100 A is separated from the sample (1) by 20 to 30 mm. This was performed by spraying plasma from the nozzle of the plasma jet gun. The plasma jet was about 15 mm.

  Then, the outdoor exposure test similar to the above was done about sample (1) (2). As a result, the following results were obtained.

Dirt after 3 months (ΔL)
Sample (1) Heat-treated by plasma discharge treatment: -0.55
Sample (2) No heat treatment: -2.33

It is the schematic which shows an example of the manufacturing equipment of the rain-spilling pollution coating base material by a continuous system. It is a graph which shows the relationship between heating energy and a raindrop pollution test result. It is a graph which shows the relationship between heating energy and a water contact angle. It is a graph which shows the effect of surface modification by frame processing. It is a color photograph which shows the sample without a frame process, and the sample with a frame process (Ls = 130,90,70,40,20m / min).

Explanation of symbols

3 Base material 5 Organic clear paint or organic enamel paint

Claims (9)

  After forming a coating film by blending an inorganic compound containing silicic acid and / or a compound having a hydrolyzable silyl group into an organic clear coating or organic enamel coating, and then applying the coating to a substrate and drying it, A method for producing a coated substrate, wherein the coating film is subjected to a heat treatment.   The method for producing a coated substrate according to claim 1, wherein colloidal silica is used as the inorganic compound containing silicic acid.   The method for producing a coated substrate according to claim 1 or 2, wherein an organic clear paint or an organic enamel paint is mainly composed of an acrylic resin and / or a polyester resin.   The method for producing a coated substrate according to claim 1 or 2, wherein an organic clear paint or organic enamel paint is mainly composed of a fluororesin.   The method for producing a coated base material according to claim 1 or 2, wherein the organic clear paint or organic enamel paint comprises a silicate-modified acrylic resin and / or a silicate-modified polyester resin as a main component.   The method for producing a coated base material according to claim 1 or 2, wherein the organic clear paint or organic enamel paint comprises a fluororesin having a hydrophilic group as a main component.   The process for producing a coated substrate according to any one of claims 1 to 6, wherein at least one kind selected from flame treatment, plasma treatment and corona discharge treatment is performed as the heat treatment. Method. The method for producing a coated substrate according to any one of claims 1 to 6, wherein a flame treatment exceeding 300 kJ / m ² / min is performed as the heat treatment.   The method for producing a coated substrate according to any one of claims 1 to 8, wherein any one of a metal material, a plastic material, wood, mortar, and stone is used as the substrate.