WO2003006565A1 - Fluororesin coating composition, coating film, and coated object - Google Patents

Abstract

A fluororesin coating composition from which any desired fluororesin can be deposited on a surface by the single-coating method in a thickness comparable to those in the double-coating method, and which not only is applicable in a range wider than the conventional range of combinations of two layers which has been limited by surface tension but gives a coating film combining high adhesion to the adherend, corrosion resistance, wearing resistance, heat resistance, nontackiness, and transparency; and various coated objects. The coating composition is characterized by being obtained by incorporating a fusible fluororesin having an average particle diameter of 1 to 1,000 µm and a fluoropolymer having an average particle diameter of 0.005 to 0.5 µm.

Description

 Specification

 Fluorine-containing paint compositions, coatings and painted products

 The present invention relates to a fluorine-containing gradient paint composition capable of forming a fluorine-containing polymer layer and a fluororesin layer thicker than before by a single coat, regardless of whether the coating is up or down. The present invention is also directed to forming a coating film having a sufficient thickness and transparency in one coat by firmly adhering to an object to be coated such as a metal, a polymer compound molded article, glass, and ceramics. The present invention relates to a fluorine-containing gradient coating composition which can be obtained, and to a coated product obtained by applying these coating compositions. Background art

 Fluororesin has excellent properties such as corrosion resistance, heat resistance, abrasion resistance, and non-adhesion, so it should be prepared as a paint, for example, for chemical equipment that requires corrosion resistance and heat resistance. It is used for various purposes such as light bulbs, cookware or rolls for OA equipment that require abrasion resistance and non-adhesiveness, and sliding members such as belts for OA equipment.

 A coating made of fluororesin is applied to various objects to be coated, such as a metal, a polymer compound molded article, glass, and pottery, to obtain a coating film, dried if necessary, and baked. It forms a coating film made of a fluororesin.

 Generally, the excellent properties of fluororesin are easily exhibited when the coating film made of fluororesin is thicker, and it is easy to maintain because it has durability. For the purpose of increasing the thickness of the coating film, the pamphlet of International Publication No. 94/057 229 contains a specific amount of a fluorine-containing molten resin having an average particle diameter of 10 to 100 μm. An aqueous dispersion composition is disclosed. Coatings made of fluororesin tend to have poor adhesion to the object to be coated because the fluororesin has excellent non-adhesiveness, and particularly weak adhesion to painted surfaces made of glass, pottery, and the like. Therefore, various measures have been taken with the aim of increasing the adhesion between the coating film and the object to be coated.

Hydroxyl groups, carboxyl groups, etc. to enhance the adhesion between the coating film and the work A paint using a fluororesin made of a copolymer containing a hydrocarbon monomer having a functional group and having no fluorine as a comonomer has been studied. However, since this paint has poor heat resistance, it may be decomposed during baking at the time of painting or use as a heated light bulb or the like, and there is a problem that the abrasion resistance and non-adhesion are insufficient. . In order to enhance the adhesive force between the coating film and the object to be coated, JP-A-9-15757578 discloses a functional group-containing fluorinated ethylenic monomer and a functional group-free fluorinated ethylenic monomer. There has been proposed a coating composition comprising a fluororesin obtained by copolymerizing a resin and a copolymer. However, this coating composition has a problem that the thickness of the formed coating film is about 5 / X m, and the corrosion resistance and the abrasion resistance are not sufficient.

 Conventionally, a primer is applied to the object in advance, and then a coating made of fluororesin is applied to obtain a coating film that has not only adhesiveness to the object but also corrosion resistance and abrasion resistance. The law was taking place. However, the two-coat method requires a process of applying a primer to the object to be coated and forming a primer film by drying, heating, etc., so a coating method that can simplify the process and save energy is required. It was desired.

 There is a one-coat method in which one paint composed of a fluororesin and a binder resin is applied once, for the purpose of simplifying the process and saving energy. In this method, a primer coating and a coating made of fluororesin, which have been obtained by a conventional two-coat method, are formed by applying one paint.

 The coating film obtained by the one-coat method is formed such that the binder resin is mainly disposed on the object to be coated and the fluororesin is mainly disposed on the surface of the coating film far from the object to be coated. The film has a concentration gradient from the object side to the surface side of the film. A paint capable of obtaining a coating film having such a concentration gradient is sometimes referred to as a gradient paint.

 The inclined paint composed of a fluororesin can form a coating film in which the binder resin and the fluororesin are arranged in an inclined manner in this manner, so that the binder resin imparts adhesiveness to an object to be coated. It has been used in a wide range of fields, taking advantage of the non-adhesiveness of fluororesins.

Polyamide as binder resin for adhesion to the object to be coated Paints using heat-resistant resins such as imides, polyimides, polyethersulfones, etc., and paints using inorganic acids such as chromic acid may damage the surface of the object to be coated or color the coating film. However, there is a problem that it is not suitable for applications that require the texture and design of the object to be coated.

 Regarding a paint made of a fluororesin used for a glass substrate, etc., Japanese Patent Publication No. 3-80741, Japanese Patent Application Laid-Open No. 5-177768, etc. add a silicone resin to this paint. Methods and methods for treating the surface of the object to be coated with a silane coupling agent have been proposed. However, the resulting coating film has poor adhesiveness to the object to be coated, and has a problem that it is not suitable for uses such as light bulbs, for example, because heat resistance and translucency are reduced. As described above, when the conventional one-coat method is not suitable for applications that require not only adhesion to the base material and heat resistance, but also design properties such as texture and colorless transparency of the object to be coated. There was. The problem of poor design cannot be solved even by increasing the thickness of the fluororesin coating using the conventional two-coat method.

 It is also desirable to take measures to prevent glass substrates from scattering at the time of impact. For the purpose of preventing scattering, International Publication No. WO 98/52874 describes a specific molar ratio of a fluorine-containing monomer having a functional group to a fluorine-containing monomer having no functional group. Discloses a heat-resistant polymer obtained by copolymerization.

 The conventional one-coat method applies a gradient paint in which fluorocarbon resin particles having an average particle diameter of about 0.5 μΐη or less are dispersed in a dispersion medium containing Pinda resin, and the resulting coating film is heated. By using the fact that the critical surface tension of the fluororesin is lower than that of the dispersion medium, the fluororesin floats on the surface by buoyancy.

 However, in the conventional one-coat method, a layer on the surface of a coating film made of a fluororesin is not used, due to the fact that a surfactant is used to disperse the binder resin and the fluororesin in the dispersion medium. Even if the layers were repeatedly coated, if they were not thin, cracks occurred, and a sufficient film thickness could not be obtained. For this reason, there has been a problem that not only excellent characteristics such as corrosion resistance and non-adhesion inherent to the fluororesin are not sufficiently exhibited, but also the durability is poor.

The conventional one-coat method also uses the difference in surface tension to cause a concentration gradient of the contained resin, and the component with the lower surface tension floats on the surface side of the coating film Therefore, a material having a higher critical surface tension could not be formed on a material having a lower critical surface tension, and there was a problem that the applicable range was limited.

 Japanese Patent No. 28141491 discloses that a fluororesin coating composition containing fluororesin particles, a surfactant and a liquid medium contains tetrafluoroethylene / perfluoro (alkyl) having an average particle diameter of 5 to 50 μm. (Vinyl ether) copolymer [PFA] The use of PFA particles comprising 20 to 80% by weight of particles and 80 to 20% by weight of PFA particles having an average particle diameter of 0.1 to 0.1: L xm is disclosed. It states that the redispersibility of PFA particles is improved. However, in this publication, there is no description or suggestion that the types of fluororesin particles used are the same and that a gradient coating film can be obtained due to the difference in particle diameter. Summary of the Invention

 In view of the above situation, an object of the present invention is to produce an arbitrary fluororesin by a one-coat method.

To provide a coating composition that can be formed on the surface with a thickness comparable to the two-coat method, and that can be widely applied by expanding the range of combination of two layers, which was limited by conventional surface tension. It is in. An object of the present invention is to provide a coating composition having such high adhesiveness, corrosion resistance, abrasion resistance, heat resistance, non-tackiness and transparency to an object to be coated, which is such a coating composition. It is an object of the present invention to provide a product that can be used for various purposes, and to provide various kinds of coated articles obtained by painting.

 The present invention is obtained by blending a fusible fluororesin having an average particle diameter of 1 to 100 μm and a fluoropolymer having an average particle diameter of 0.05 to 0.5 μππι. It is a fluorine-containing coating composition characterized by being coated.

 The present invention relates to a fluorine-containing coating obtained by blending a fusible fluororesin having an average particle diameter of 1 to 30 μm and a fluoropolymer having an average particle diameter of 0.05 to 0.5. Wherein the volume of the fusible fluororesin is 35 to 95% of the sum of the volume of the fusible fluororesin and the volume of the fluoropolymer. An elementary coating composition.

The present invention is melt processible fluororesin and an average particle child size average particle size of 1 ~ 1 0 0 0 _mu m is 0. 0 0 5-0. Disperse fluorine-containing polymer is a 3 / zm in the liquid medium Become A fluorinated coating composition, wherein the fluorinated polymer copolymerizes a functional group-containing fluorinated ethylenic monomer (a) and a functional group-free fluorinated ethylenic monomer (b). The functional group-containing fluorinated ethylenic monomer (a) has a functional group, and the functional group forms a hydroxyl group, a carboxyl group, and a salt. Wherein the fluorine-containing ethylenic monomer having no functional group (b) is a carboxyl group, an alkoxy group, or an epoxy group, and the functional group-free fluorine-containing ethylenic monomer (b) does not have the functional group. A composition.

 The present invention is a coating film obtained by applying the above-mentioned fluorine-containing coating composition.

 The present invention is a coated article having the above-mentioned coating film.

 Hereinafter, the present invention will be described in detail. Detailed Disclosure of the Invention

 The fluorine-containing coating composition of the present invention is obtained by blending a fluorine-containing polymer and a meltable fluorine resin. The fluoropolymer is conceptually different from the meltable fluororesin in that it has a different average particle diameter as described later.

 The fluorine-containing coating composition of the present invention is capable of forming a coating film by applying to an object to be coated such as a substrate, heating and drying the obtained coating film as required, and then firing. It is.

 When the fluorine-containing coating composition of the present invention is applied to an object to be coated, in the obtained coating film, the average particle diameter of the two components consisting of the fluoropolymer and the meltable fluororesin is used. Are laminated so that particles of a component having a relatively large value constitute an upper layer portion in the coating film. Particles of a component having a relatively small average particle diameter among the two components penetrate between the particles to be laminated, and are further arranged as a lower layer below the upper layer. The particles of the two components form a filled or nearly filled structure in the coating film.

In the present specification, in a coating film obtained by applying a coating composition or a coating material to an object to be coated, one located on the side of the object to be coated is referred to as a lower layer, and a side far from the object to be coated, that is, What is located on the surface side of the coating film may be referred to as an upper layer portion. As a component having a relatively small average particle diameter, any component can be used as long as the particles can enter between the particles to be laminated. Therefore, assuming that these particles are spherical, the average particle diameter of the component having a relatively small average particle diameter is 15% or less of the average particle diameter of the component having a relatively large average particle diameter. It is necessary to have something.

 The average particle diameter of the component having a relatively small average particle diameter is relatively large because the space between the particles of the component having the relatively large average particle diameter can be sufficiently secured. It is preferably 0.05 to 1% of the components. If it is less than 0.05%, it will be difficult to fill the contact surface with the object to be coated, which is the lower layer in the coating film, and the adhesive strength with the object to be coated will be insufficient. There is. If the temperature exceeds ι ° 超 え る ο, depending on the shape of the particles and how the shapes are arranged, the particles having the relatively large average particle diameter enter into the gaps between the particles to sufficiently fill the contact surface with the object to be coated. In some cases, the adhesion to the object to be coated may be insufficient.

 The average particle diameter of the component having a relatively small average particle diameter is 0.5 μπι or less in consideration of the arrangement of particles in the packing structure. If it exceeds 0.5 μπι, a fluorine-containing polymer, which is a component having a relatively small average particle size, is usually synthesized by emulsion polymerization as described later, and a product having such an average particle size is obtained. It is difficult. Preferably, it is 0.3 μπι or less. The average particle diameter of the component having a relatively small average particle diameter is preferably 0.055 μπι or more in consideration of film forming properties and the like. A more preferred lower limit is 0.11 / zm, and a more preferred upper limit is 0.15 // m.

 The average particle diameter of the component having a relatively large average particle diameter is, for example, the average particle diameter of the component having a relatively small average particle diameter, the ratio to the average particle diameter, the dispersion stability of the coating composition, and the coating. The average particle diameter is preferably 1 to 1000 tm in consideration of the uniformity of the film, the film forming property, the thickness of the obtained coating film, and the like.

The fluorine-containing coating composition of the present invention is formed using the fusible fluororesin as the component having a relatively large average particle diameter in the upper layer portion of the coating film, and the component having a relatively small average particle diameter. And forming the fluoropolymer in a lower layer portion of the coating film using the fluoropolymer. Therefore, the fluorine-containing coating composition of the present invention has a meltable fluororesin having an average particle diameter of 1 to 100 μm, and an average particle diameter of 0.05 to 0.5 / im. It is characterized by being obtained by blending a certain fluorine-containing polymer. By blending the fusible fluororesin and the fluorinated polymer each having an average particle diameter within the above range, the filling structure can be appropriately formed as described above, and Film forming properties can be obtained.

 The fluorinated coating composition of the present invention has an average particle size of 1 to 30111 as the fusible fluororesin, and an average particle size of 0.05 to 0.5 as the fluorinated polymer. / zm may be obtained.

 The fluorine-containing coating composition of the present invention has the following characteristics: It may be a mixture of a fusible fluororesin having a particle size of 1 to 100 μm and a fluoropolymer having an average particle size of 0.05 to 0.3 μπι. preferable.

 The arrangement of the particles in the coating film is based on the difference in the average particle size between the two components forming the coating film. That is, in the upper layer portion, the particles of the component having the relatively large average particle diameter are densely packed and laminated so that the volume of the gap portion is reduced, thereby forming a densely packed structure. Then, the particles of the component having a relatively small average particle diameter enter, and the gap portion is filled or almost filled.

 In the densely packed structure, the porosity expressed as a ratio of the volume occupied by the particles of the component having a relatively large average particle diameter and the total volume of the gap portion to the total volume of the gap portion is It depends on the sphericity and degree of uniformity of the particles of the component having the relatively large average particle diameter.

 In addition, when the particles of the component having a relatively large average particle diameter are spherical having the same diameter, and the particles are densely packed so that the volume of the gap portion is minimized, A dense structure is formed, and the porosity at this time is calculated to be 25.95% for close packing and 47.64% for cubic packing.

In the fluorine-containing coating composition of the present invention, the particles of the two components are practically Not a perfect sphere. As a practical particle, for example, if it is a nearly spherical powder, the porosity is said to be 33 to 66%. (Powder Engineering / Basic Edition, Bookstore, 1974, First Edition, 91) P.)

 Therefore, in the fluorine-containing coating composition of the present invention, the meltable fluororesin is used as a component having a relatively large average particle diameter, and the fluoropolymer is used as a component having a relatively small average particle diameter. In order to form the fusible fluororesin on the surface layer, the capacity of the fusible fluororesin relative to the sum of the capacity of the fusible fluororesin and the capacity of the fluorinated polymer is 35% or more. It is necessary.

 In the present specification, the above “capacity of the fusible fluororesin” means the volume occupied by the particles of the fusible fluororesin. In the present specification, the “capacity of the fluoropolymer” means the volume occupied by the fluoropolymer particles. When the volume of the fusible fluororesin or the volume of the fluorinated polymer is respectively dispersed in a liquid medium, the volume occupied by the particles of the fusible fluororesin in the volume of the liquid medium, or The volume occupied by the fluoropolymer particles.

 In order for the particles of the component having a relatively small average particle diameter to be disposed as a lower layer below the upper layer, the capacity of the gap portion in the upper layer as the component having a relatively small average particle diameter is required. It is preferable to mix them so as to occupy a capacity corresponding to the capacity of the lower layer portion.

 The volume ratio between the fusible fluororesin and the fluorinated polymer is determined by using the specific gravity of the fusible fluororesin used and the specific gravity of the fluorinated polymer. It can be expressed as a weight ratio of the solid content to the polymer. The specific gravity of a general fluorine-containing polymer that can be used in the fluorine-containing coating composition of the present invention is from 1.6 to 2.2.

In the present specification, the “solid content weight ratio J of the fusible fluororesin to the fluoropolymer” refers to the weight of the solid content of the fusible fluoropolymer and the weight of the solid content of the fluoropolymer. In the present specification, the weight of the solid content, when dispersed in a liquid medium, refers to the weight of the particles of the fusible fluororesin dispersed in the liquid medium and the fluorine-containing height. The weight of a particle of a molecule. As described above, the fluorine-containing coating composition of the present invention has a meltable fluororesin having an average particle diameter of 1 to 100 / Zm and an average particle diameter of 0.05 to 0.5 im. It is characterized by being obtained by blending a certain fluorine-containing polymer, and in this case, the solid content weight of the soluble fluororesin is based on the solid content weight of the meltable fluororesin and the fluorine-containing weight. It is preferably 35 to 99.9% of the total weight of the solid content of the polymer. When the weight ratio of the solid content is within this range, the lower layer portion of the coating film is sufficiently filled with the fluoropolymer to improve the adhesion between the obtained coating film and the object to be coated. can do.

 The fluorinated coating composition of the present invention comprises a fusible fluororesin having an average particle diameter of 1 to 30 / Zm and a fluorinated polymer having an average particle diameter of 0.05 to 0.5 m. In the case of being obtained by blending, when the fusible fluororesin is mainly contained in the upper layer portion, the capacity of the fusible fluororesin is equal to the capacity of the fusible fluororesin and the fluorinated height. It may be 35-95% of the total volume of the molecule. When the capacity of the fusible fluororesin is less than 35% of the total of the capacity of the fusible fluororesin and the capacity of the fluorinated polymer, the fluororesin layer is appropriately formed as the upper layer. If the content exceeds 95%, the amount of the fluorine-containing polymer becomes too small, and the adhesiveness of the fluorine-containing polymer required for the lower layer portion, etc. Properties may not be sufficiently exhibited. Preferably, it is 50 to 95%, more preferably 70 to 95% of the sum of the capacity of the above-mentioned fusible fluororesin and the capacity of the above-mentioned fluoropolymer.

The fluorinated coating composition of the present invention comprises a fusible fluororesin having an average particle diameter of 1 to 100 μm and a fluorinated polymer having an average particle diameter of 0.05 to 0. When obtained in combination, the solid content weight of the meltable fluororesin is 70 to 99, which is the sum of the solid weight of the meltable fluororesin and the solid content weight of the fluoropolymer. Preferably it is 9%. When the average particle diameter and the solid content weight ratio are within these ranges, the lower layer portion in the coating film can be sufficiently filled with the fluoropolymer to improve the adhesiveness with the object to be coated. A more preferred lower limit is 80% of the total of the solid content weight of the fusible fluorine resin and the solid content weight of the fluoropolymer, and a further preferred upper limit is 98%. As described above, the fact that the two components forming the coating film form the filling structure as described above is based on the difference between the average particle diameters of the two components and the appropriate mixing ratio of the two components. Things.

 The coating film having the above-described filling structure is then dried by heating, if necessary, and then fired. As a result of the baking, the components of the upper layer are melted, and accordingly, the particles of the components having the relatively large average particle diameter constituting the upper layer are gathered by their own surface tension to form a film (film formation). .

 By the baking, the lower layer portion is crosslinked to form a cured film or cooled after being melted without being crosslinked, depending on the type and chemical structure of the components constituting the lower layer portion. I do. It is preferable that the lower layer portion is crosslinked to form a cured film from the viewpoint of easily floating the components of the upper layer portion.

 As a result of the calcination, the component having the relatively large average particle size is mainly contained on the surface side of the coating film, and the component having the relatively small average particle size is mainly contained on the object side of the coating film. As such, a coating is formed. When particles of the component having a relatively large average particle diameter remain in the lower layer, a film is formed with the remaining particles being taken in the main component constituting the lower layer.

 In the present specification, among the coating films obtained through coating and baking, a layer mainly containing the fusible fluororesin is called a fluororesin layer, and a layer mainly containing the above fluoropolymer is included. It is called a fluoropolymer layer. The fluororesin layer may contain a small amount of the fluorine-containing polymer and, if necessary, other components contained in the fluorine-containing coating composition of the present invention. The fluorine-containing polymer layer may contain a small amount of the meltable fluororesin and the other components.

 Usually, the fusible fluororesin and the fluorinated polymer in both of the fluororesin layer and the fluorinated polymer layer each have a concentration gradient. Such a coating film having a concentration gradient is sometimes referred to as a gradient coating film. The boundary between these two layers can be confirmed, for example, by preparing a filter of a thinly cut section using a deflection microscope.

Since the fluorine-containing coating composition of the present invention forms a coating film by the above mechanism, the fluororesin layer is usually formed by a conventional inclined coating composition utilizing a surface tension difference of about 1 μπΐ. Compared to only those having a thickness of around, a significantly thicker one, preferably one having a thickness of 3 to 15 / im, can be obtained.

 Since the fluorine-containing coating composition of the present invention forms a coating film by the above mechanism, by adjusting the average particle diameter of the fusible fluororesin and the fluoropolymer within the above range, the fluororesin The thickness of the layer can be adjusted.

 As described above, the formation of the relatively thick fluororesin layer has not been conventionally realized by using the one-coat method, but the fluorine-containing paint composition of the present invention is formed by the one-coat method. It can be realized.

 As described above, the above-mentioned fusible fluororesin to be blended in the fluorinated coating composition of the present invention has an average particle diameter of usually 1 to 100 μm. Within the above range, a film having excellent film-forming properties and a sufficient film thickness can be uniformly obtained.

 If it is less than Ιμπι, cracks tend to occur in the coating film during firing, and a coating film having a sufficient film thickness may not be obtained. If it exceeds l OOO ^ m, the fluorine-containing paint of the present invention may be used. In the dispersion of the composition, the powder comprising the fusible fluororesin and the fluorinated polymer tends to settle, so that the dispersion state is not stable and uniform coating may be difficult. It is preferably from 1 to 300 μηι, more preferably from 1 to 500 μm, and still more preferably from 1 to 30 / xm.

 The above-mentioned fusible fluororesin to be blended in the fluorinated coating composition of the present invention may have an average particle diameter of 1 to 30 / xm as described above. If it is less than l jum, the thickness of the fluororesin layer is not sufficient, and if it exceeds 30 Aim, the resulting coating film surface may have poor smoothness. The surface layer of the coating film obtained by the conventional inclined coating method has a thickness of about 1 m, and a fluororesin layer with a thickness of about 30 μΐη has been obtained for applications such as tubes. However, there has been no fluororesin layer having a thickness of 3 to 15 μπι on the surface side of the coating film. However, those having a fluororesin layer having a thickness of 3 to 15 on the surface side of the coating film have market needs, and such a film thickness can be easily obtained. The lower limit is 2 μπι, and a more preferred upper limit is 20 μπι.

The above-mentioned melting fluorine content may be, for example, a chlorofluorobutyl monomer such as chlorofluoroethylene or trifluoroethylene as a monomer component; Examples thereof include those obtained by polymerizing one or more perfluoro monomers such as fluoroethylene, hexafenoleoethylene, and perfluoro (alkylbininole ether). The above-mentioned monomer component may further contain one or more kinds of a bubble monomer having no fluorine atom, such as ethylene and pyrene. The perfluoro monomer has a main chain composed of a carbon atom and a fluorine atom and optionally an oxygen atom and has no CH or 〇 ^ _2, and has a perfluorovinyl monomer and a perfluoro ( (Alkyl butyl ether) monomer. The oxygen atom is usually ether oxygen.

 As the above-mentioned fusible fluororesin, a monomer having a functional group such as a hydroxyl group or a carbonyl group may be used as a comonomer for copolymerizing a small amount with the above-mentioned monomer component, and a monomer having a cyclic structure may be used. A monomer may be used. Examples of the cyclic structure include those having a cyclic ether structure such as a cyclic acetal structure. Preferably, at least two carbon atoms constituting the cyclic ether structure have a main chain of the meltable fluororesin. It is a part of.

 Examples of the meltable fluororesin include: ethylene / tetrafluoroethylene copolymer [ETFE], ethylene / chlorotrifluoroethylene copolymer [EC TFE], propylene / tetrafluoroethylene copolymer Alkylene Z fluoroalkylene copolymers such as; tetrafluoroethylene z hexafluoropropylene copolymer [FEP], tetrafluoroethylene / perfluoro (alkylbutyl ether) copolymer [PFA], And perfluoropolymers such as tetrafluoroethylene / perfluoro (alkyl ether) / hexafluoropropylene copolymer [EPA]. The perfluoropolymer has the above-described perfluoromonomer as a monomer component.

Examples of the meltable fluororesin include tetrafluoroethylene copolymers such as ETFE, FEP, PFA, EPA, and propylene Z tetrafluoroethylene copolymer; ECTFE, polychlorotrifluoro It may also be a trifluoroethylene-based copolymer such as polyethylene [PCTFE] or the like; a vinylidene fluoride-based copolymer such as polyvinylidene fluoride [PV d F]. In the present specification, the above-mentioned “tetrafluoroethylene-based copolymer”, the above-mentioned “chloro-trifluoroethylene-based copolymer”, and the above-mentioned “vinylidene fluoride-based copolymer” are each tetrafluorophenol. It means a copolymer obtained by using ethylene, ethylene with ethylene and triphenylene and vinylidene fluoride as comonomer.

 As the fusible fluororesin, one kind or a combination of two or more kinds can be used.

 As the above-mentioned fusible fluororesin, the above-mentioned perfluoropolymer is preferable although it varies depending on the use. The above-mentioned perfluoropolymer has excellent non-adhesiveness and corrosion resistance, and has been used in many fields using conventional methods.However, as a conventional gradient paint, it can form a thick coating film surface layer. There were no applications, so their uses were limited. However, by using the fluorine-containing coating composition of the present invention, the above-mentioned fluororesin layer mainly containing the above-mentioned perfluoropolymer can be formed thicker by one-coat method than before.

 As the above-mentioned perfluoropolymer, a copolymer obtained by using tetrafluoroethylene as a comonomer is more preferable, and the above-mentioned perfluoromonomer as another comonomer is not particularly limited. As such a tetrafluoroethylene-based copolymer, FEP, PFA, and EPA are preferable, and FEP and PFA are more preferable, since they are particularly excellent in corrosion resistance, heat resistance, abrasion resistance, non-adhesion, and the like. As the above-mentioned fusible fluororesin, those having a melting point of 150 to 350 ° C are preferable. When the melting point is within the above range, in the baking after applying the fluorine-containing coating composition of the present invention, the layer separation between the fusible fluororesin and the fluoropolymer is promoted, and the Adhesion can be improved, and a coating film excellent in coating film properties such as mechanical strength can be easily obtained.

 The melting point of the fusible fluorine preferably has a melting point of 200 ° C. or more. It has been difficult to form a thick fluororesin having a melting point of 200 ° C. or more on the coating film surface side with the conventional inclined paint, but by using the fluorine-containing paint composition of the present invention, Even a fusible fluororesin can be suitably used.

More preferably, the melting fluorine resin has a melting point of 200 to 350 ° C. The melting point of the fusible fluororesin is within the above range, and is 50 ° C lower than the melting point. Those having a melt viscosity at a high temperature of 10 ⁶ Pa · s or less are preferred. With such a composition, the composition has sufficient flowability at the time of baking after the application of the fluorine-containing coating composition of the present invention, and sufficiently separates the meltable fluororesin and the fluorine-containing polymer into layers. The adhesiveness with the object to be coated can be improved. Melt viscosity at the temperature is within the above range, it may be for example 10 a ■ s or more, more preferred correct lower limit is 1 0 ² P a ■ s, and a more preferred upper limit 10 ⁴ P a · S. The fusible fluororesin can be prepared as a powder, and the apparent density of the powder is usually preferably 0.3 to 1.5 gZm1. When the amount is less than 0.3 g / ml, the dispersibility of the powder is reduced, and bubbles are likely to be trapped during foaming after application of the fluorine-containing coating composition of the present invention. If it exceeds 0.5 gZm1, the powder tends to settle, and the dispersion stability in the fluorine-containing coating composition of the present invention tends to decrease. A more preferred lower limit is 0.5 g / ml, and a more preferred upper limit is 1 gZm1.

 The fluorine-containing coating composition of the present invention is obtained by blending the above-mentioned fluorine-containing polymer with the above-mentioned meltable fluorine resin. The above-mentioned fluorine-containing polymer is particularly suitable when the fluorine-containing coating composition of the present invention is used in applications where heat resistance and corrosion resistance are emphasized.

 As the above-mentioned fluorine-containing polymer, as monomer components, for example, vinyl fluoride, vinylidene fluoride, trifluoromethyl ethylene, trif / leo ethylene, tetraphenylene ethylene, hexenepropylene, One or more fluoropolymer monomers such as perfluoro (anolequinolevinyl ether) and, if necessary, one or more fluoropolymer monomers such as ethylene and propylene And those obtained by polymerization.

Examples of the above-mentioned fluorine-containing polymer include bifluor tetrafluoroethylene copolymer, bifluor fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene Ethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, tetrafluoroethylene polymer [PTFE], ethylene / tetrafluoroethylene copolymer, ethylenenochlorotrifluoroethylene copolymer Coalesce, propylene / tetrafluoroethylene copolymer, Examples include trafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene z-perfluoro (alkyl vinyl ether) copolymer, and the like. The concept of the present invention is that a polymer in which all the monomers are the same kind is not used for both the above-mentioned fusible fluororesin and the above-mentioned fluoropolymer.

 When the fluorinated polymer is PTFE, by using the fluorinated paint yarn composition of the present invention, the desired fluororesin can be formed on PTFE thickly. In particular, it is possible to make the most of the effects.

 PTFE is often used because it is inexpensive and has excellent heat resistance. However, improvements in non-adhesiveness, chemical permeability, water vapor permeability, etc. are desired. A coating film having a resin disposed on the surface has been required. What has hitherto been used as a material capable of forming such a coating film is a blend between the disposable materials, and thus the meltable fluororesin cannot be selectively floated on the surface in a sufficient amount. However, the above properties were not sufficiently improved. Since the fluorine-containing paint la composition of the present invention can form an inclined coating film having a thickness of 3 to 15 μιη on the surface side by using two kinds of fluorine resins. It satisfies the above requirements sufficiently.

 The PTF E may be a conventional tetrafluoroethylene homopolymer. 1 From the viewpoint of excellent adhesion to the above-mentioned meltable fluororesin, it is preferable to use a modified PTF E. As the modified PTFE, as a monomer component, at least one selected from the group consisting of perfluoro (alkylbutyl ether), ethylene oxide and hexafluoropropylene, together with tetrafluoroethylene, It is obtained by copolymerization using a total amount of 0.5% by mass or less.

 The fluoropolymer may be a fluororubber. When a fluororubber is used as the fluorine-containing polymer, flexibility can be imparted by the fluororubber, and non-adhesion and chemical resistance can be imparted by the meltable fluororesin on the surface of the coating film. it can. In the present specification, the above-mentioned fluororubber means the above-mentioned fluorine-containing polymer having no melting point and having a glass transition point of 5 ° C or less.

The fluororubber is not particularly limited. For example, as a comonomer, vinyl fluoride o

When the above-mentioned fluorine-containing polymer having a group is used, a coating film adhered to an object to be coated can be formed only by using a fluororesin without using a primer. The functional group is preferably a hydroxyl group, a hydroxyl group, a carboxyl group forming a salt, an alkoxy group, and / or an epoxy group, since the functional group is particularly excellent in adhesion to an object to be coated. .

In the present specification, the above-mentioned "carboxyl group forming a salt" means a group in which an atom or an atomic group capable of forming a monovalent or divalent cation is bonded instead of hydrogen of a carboxyl group. I do. The carboxyl group forming the salt may be ionized in a liquid medium described below, particularly in a liquid medium containing water or a water-soluble solvent. The atom or atomic group capable of forming the cation is not particularly limited, and includes, for example, K, Na, Ca, Fe, NH _{4 and the} like. In the molecule and / or between the plurality of molecules of the above-mentioned fluoropolymer, they may be the same or different.

 The above-mentioned epoxy group is generally formed by linking two atoms of carbon bonded by a carbon chain to one atom of oxygen, and in the carbon chain between the two atoms of carbon bonded to the oxygen. The number of carbon atoms is not particularly limited. In this effort, 1,2-epoxy groups and 1,3-epoxy groups are preferred, and 1,2-epoxy groups are preferred because they are highly reactive and easily contribute to chemical bonding with the object to be coated. More preferred. The functional group capable of chemically bonding to the object to be coated may be the same type of group as the terminal group of the fluorine-containing polymer as a functional group derived from the polymerization initiator. It is preferable that the above-mentioned fluorine-containing polymer is contained in the molecule, separately from the one having the functional group derived from the polymerization initiator.

 As the fluoropolymer, a monomer having a functional group such as a hydroxyl group or a carbonyl group may be used as a comonomer for copolymerizing a small amount with the monomer component, and has a cyclic structure. A monomer may be used. Examples of the monomer having a cyclic structure include those similar to those described as the monomer component of the fusible fluororesin.

The fluorine-containing polymer is obtained by copolymerizing a functional group-containing fluorine-containing ethylenic monomer ^: (a) and a functional group-free fluorine-containing ethylenic monomer (b). Wherein the functional group-containing fluorine-containing ethylenic monomer (a) has a functional group, and the functional group includes a hydroxyl group, a carboxyl group, a carboxyl group forming a salt, and an alkoxycarbonyl group. And the functional group-free fluorine-containing ethylenic monomer (b) does not have the functional group. The fluorine-containing polymer can introduce a functional group into the fluorine-containing polymer by copolymerizing the functional group-containing fluorine-containing ethylenic monomer (a) as a monomer component. Moreover, it can be introduced into the polymer chain of the above-mentioned fluoropolymer. Due to the above-mentioned functional groups, a coating film having excellent adhesiveness not only to an object to be coated which has been conventionally adhered, but also to various objects to be coated which has been impossible or insufficient in the past. Obtainable.

 Among the functional groups contained in the functional group-containing fluorinated ethylenic monomer (a), types and combinations of a hydroxyl group, a carboxyl group, a carboxyl group forming a salt, an alkoxycarbonyl group or an epoxy group The material can be appropriately selected depending on the type and use of the material such as metal and glass on the surface of the object to be coated, but a hydroxyl group is preferred from the viewpoint of heat resistance.

 The functional group-containing fluorinated ethylenic monomer (a) has a functional group, and the functional group includes a hydroxyl group, a carboxyl group, a carboxyl group forming a salt, and an alkoxycarbol group. Or a butyl group-containing monomer having a fluorine atom directly bonded to a carbon atom, which is an epoxy group, is not particularly limited, but has the following general formula (1)

CX ¹ ₂ = CX ² — R f ^x — Y (1)

(In the formula, X ¹ and X ² are the same or different and each is a hydrogen atom or a fluorine atom, and R f ¹ is a divalent alkylene group having 1 to 40 carbon atoms or an ether bond having 1 to 40 carbon atoms. Wherein Y is a methylol group, a carboxy group, a salt-forming propyloxyl group, an alkoxycarbonyl group or an epoxy group, and the methylol group is a hydrogen atom bonded to a carbon atom. One or two of the atoms may be substituted by —CF ₃ ).

Such functional group-containing fluorine-containing ethylenic monomer (a) is not particularly limited. For example, the following formula

CF ₂ = CFOCF2CF2COOCH3, CP ₂ = CFOCF2CFOCF2CF2CH2OH,

 CFa

CF ₂ = CFCF ₂ OCF ₂ CF2CF ₂ COOH, CFa = CFCF2OCF2CFCOOCH3

CF ₃

CH ₂ = CFCF2OCFCF2OCFCH2OH,

 CFs CPs

And the like.

As the functional group-containing fluorine-containing ethylenic monomer (a), the functional group stability and か ら From the viewpoint of adhesiveness to various objects to be coated, it is more preferable that Y in the above general formula (1) is a methylol group.

 As the functional group-containing fluorine-containing ethylenic monomer (a), one or more kinds can be used, and the functional group-containing fluorine-containing ethylenic monomer (a) having the same functional group is used. May be used alone or in combination of two or more. The functional groups contained in the two or more kinds of the functional group-containing fluorine-containing ethylenic monomers (a) used may be different from each other.

The fluorine-containing ethylenic monomer containing no functional group (b) does not have the above-mentioned functional group contained in the fluorine-containing ethylenic monomer containing functional group ( _a ), and is directly attached to the carbon atom. It is a butyl group-containing monomer having a bonding fluorine atom.

 The functional group-free fluorine-containing ethylenic monomer (b) is not particularly limited as long as it is such a substance. For example, tetrafluoroethylene, the following general formula (2)

CF ₂ = CF— R f ² (2)

(In the formula, R ² is one CF ₃ or one OR f ^3. R f ³ is a perfluoroalkyl group having 1 to 5 carbon atoms.) Perfluoro (anolequinolebininoleether); perhalolefin having a halogen other than fluorine and fluorine such as chlorotrifluoroethylene;

 Vinylidene fluoride, biel fluoride, hexafluoroisobutene, the following general formula

CH ₂ = CF (CF ₂ ) _n X ³

(Wherein, X ³ is a hydrogen atom, a fluorine atom, or a chlorine atom, and n is an integer of 1 to 5.) A compound represented by the following general formula:

CH ₂ = CH (CF ₂ ) _m X ³

(In the formula, X ³ is a hydrogen atom, a fluorine atom or a chlorine atom, and m is an integer of 1 to 5.), and a halogenated olefin having hydrogen, such as a compound represented by the following formula:

As the fluorine-containing ethylenic monomer containing no functional group (b), one type or two or more types can be used. As the above-mentioned functional group-free fluorine-containing ethylenic monomer (b), tetrafluoroethylene is represented by the above general formula (2) because of excellent adhesion between the obtained coating film and the object to be coated. Perfluoro (alkyl butyl ether) represented by the above general formula (2), such as perfluoroolefin and perfluoro (propyl vinyl ether), is preferred.

 As the functional group-free fluorine-containing ethylenic monomer (b), tetrafluoroethylene and the above-mentioned general formula (2) can be used because the adhesiveness between the obtained coating film and the object to be coated is particularly excellent. It is more preferable to combine perfluoroolefin represented by the above formula or perfluoro (alkylbutyl ether) represented by the above general formula (2). In this case, the number of moles of the above tetrafluoroethylene is the same as the number of moles of the above tetrafluoroethylene, and the amount of perfluoroolefin or perfluoro (alkylbi-noreether) represented by the general formula (2). Is preferably 85 to 99.7% of the total number of moles of

 The number of moles of the functional group-containing fluorinated ethylenic monomer (a) is determined by the number of moles of the functional group-containing fluorinated ethylenic monomer (a) and the number of moles of the functional group-containing fluorinated ethylenic monomer. It is preferably 0.05 to 30% of the total number of monoles in (b). When the number of moles of the functional group-containing fluorine-containing ethylenic monomer (a) is less than 0.05%, the adhesion between the obtained coating film and the object to be coated is apt to decrease, and 30% If the amount exceeds the above range, foaming becomes severe at the time of baking after application of the fluorine-containing coating composition of the present invention, so that coating film defects are likely to occur. A more preferred upper limit is 10%, and a still more preferred upper limit is 5%. The fluorinated polymer is in addition to the functional group-containing fluorinated ethylenic monomer (a) and the functional group-free fluorinated ethylenic monomer (b), and a range that does not decrease heat resistance. In the above, an ethylenic monomer having no fluorine atom may be copolymerized. In this case, the ethylenic monomer having no fluorine atom is preferably selected from ethylenic monomers having 5 or less carbon atoms so as not to lower heat resistance. Specifically, ethylene, propylene, 1-butene, 2-butene and the like.

The fluoropolymer particles may have a core / shell structure. As the core Z-shell structure, the core part is composed of a polymer chain obtained by polymerizing the above-mentioned functional group-free fluorine-containing ethylenic monomer (b), Particles comprising a polymer chain obtained by copolymerizing the functional group-containing fluorine-containing ethylenic monomer (a) and the functional group-free fluorine-containing ethylenic monomer ( _b ). You may. It is preferable that the monomer component of the core portion does not contain the functional group-containing fluorine-containing ethylenic monomer (a). By introducing the functional group only into the shell portion in this manner, the amount of the functional group-containing fluorine-containing ethylenic monomer (a) used can be reduced, which is economical. Such a core Z-shell structure can be obtained by a known method described in, for example, JP-A-4-154842, JP-A-5-27959, and the like. And by subjecting it to seed polymerization.

 The fluoropolymer may be a functional group-containing fluororesin. The functional group-containing fluororesin does not have, as monomer components, one or more of the above-mentioned fluorinated vinyl monomers and a functional group such as a hydroxyl group or a carbonyl group at a side chain terminal. And obtained by copolymerization. When the above-mentioned fluorine-containing polymer is the above-mentioned functional group-containing fluororesin, the above-mentioned functional group at the terminal of the side chain reacts, so that it is cured by cross-linking and has an adhesive property by generating a chemical bond with an object to be coated. Can be improved.

 It is preferable that the fluoropolymer has heat resistance at least at 200 ° C. If the composition does not have heat resistance at a temperature lower than 200 ° C., it is difficult to suitably use the fluorine-containing coating composition of the present invention for applications requiring heat resistance, flexibility and durability at high temperatures. Becomes The above-mentioned fluorine-containing polymer usually has heat resistance at 200 to 350 ° C. in view of the sintering temperature after application of the fluorine-containing paint and the base material of the present invention and the use temperature after coating film formation. Anything should do.

 Since the above-mentioned fluoropolymer has excellent heat resistance, unlike the copolymer obtained by copolymerizing a non-fluorine-containing functional group-containing monomer, as described above, However, even when it is baked at a high temperature of, for example, 200 to 350 ° C. after application of the fluorine-containing coating composition of the present invention, the thermal decomposition property is low.

Since the fluorine-containing coating composition of the present invention has such low thermal decomposability, the heat-resistant fluorine-containing polymer having the above functional group has a high adhesive strength to an object to be coated, and can be colored, foamed, and pin-shaped. ^^, A coating film free from poor leveling can be obtained. Also get Even when the coated object is used at a high temperature, the coated film maintains the adhesiveness to the object to be coated, and is unlikely to cause coating defects such as coloring, whitening, foaming and pinholes.

 As the fluorine-containing polymer, a wide range of materials can be used as described above, so that the fluorine-containing coating composition of the present invention has a wide range of applications.

As described above, the fluoropolymer has an average particle diameter of 0.05 to 0.5 // 111. The fluoropolymer has an average particle diameter of 0.005 to 0.3 from the viewpoint that the filling property of the lower layer of the coating film can be enhanced and the adhesion to the object to be coated can be improved. It is preferable to use μπι and have a functional group capable of chemically bonding to the object to be coated. In this case, the functional group is preferably a hydroxyl group, a carboxyl group, a salt-forming propyloxyl group, an alkoxyl-forming liponyl group and / or an epoxy group, and these functional groups are those having these functional groups. More preferably, it is introduced by copolymerizing the functional group-containing fluorine-containing ethylenic monomer ( _a ) as a monomer component.

 When the average particle diameter of the fluoropolymer is 0.05 to 0.3 μm, the fluoropolymer is chemically bonded to the object to be coated in the fluorine-containing coating composition of the present invention. It is preferable that the fusible fluororesin has an average particle diameter of 1 to 100 μππι. In this case, a more preferred lower limit of the average particle diameter of the fluoropolymer is 0.1 μμηη, and a more preferred upper limit is 0.15 μπη.

 It is preferable that the meltable fluororesin and the fluoropolymer are dispersed in a liquid medium. As the above-mentioned liquid medium, the one usually used as a solvent is used. In the fluorine-containing coating composition of the present invention, the solvent usually contains water or a water-soluble solvent, and is preferably used because of environmental problems. The water-soluble solvent is a water-soluble organic solvent. As the solvent, a mixture of water and a water-soluble solvent, and water are more preferable.

The water-soluble solvent has a function of wetting the meltable fluororesin. When the water-soluble solvent has a high boiling point, in addition to wetting the fusible fluororesin, when the fluorinated paint composition of the present invention is applied and then dried, the fusible fluororesin mutual, Between the fluoropolymers and / or the fusible fluororesin and the It acts as a drying retarder to connect with fluoropolymers and prevent cracks. Even if the above-mentioned water-soluble solvent has a high boiling point, if the compounding amount is appropriate, it is sufficiently volatilized at the firing temperature after application of the fluorine-containing coating composition of the present invention. It does not degrade properties such as non-adhesion. The water-soluble solvent is not particularly limited, and examples thereof include low-boiling organic solvents having a boiling point of less than 100 ° C., such as methanol, ethanol, isopropanol, sec-butanol, t-butanol, acetone, and methylethylketone. A medium boiling organic solvent having a boiling point of 100 to 150 ° C., such as toluene, xylene, methyl sorb, methyl ethyl sorb, methyl isobutyl ketone, n-butanol, etc .; N-methyl-12-pyrrolidone, N, N-dimethinoleasoleamide, N, N-dimethinolefosolemamide, ketocin, ethylene glycol, propylene glycol, glycerin, dimethyl carbitol, butinoregical bitonol, Petinoleserosonoleb, Hexanoxylose, Disoptinoleketone, 1, 41 Butanediole, triethylene glycol / le, tetraethylene dalicol and the like. As the high-boiling organic solvent, an alcohol-based solvent is preferable because it has good wettability with the fusible fluororesin and is easy to handle.

 One or more of these water-soluble solvents can be used. The water-soluble solvent enhances the filling property of the lower layer of the coating film and can promote the layer separation between the lower layer and the upper layer. It is preferable to use a mixture with a boiling organic solvent.

The compounding amount of the water-soluble solvent is preferably from 0.5 to 50% of the liquid medium in the fusin-containing coating composition of the present invention. In the case of a low-boiling organic solvent, if the amount is too small, bubbles tend to be entrapped, and if the amount is too large, the fluorine-containing coating composition of the present invention becomes flammable as a whole and has the advantage of an aqueous dispersion composition. May be impaired. In the case of a medium-boiling organic solvent, if the amount is too small, the meltable fluororesin returns to powder when the fluorine-containing coating composition of the present invention is dried after application, and the film forming property may be lost. If the amount is too large, it may remain in the coated film after firing and deteriorate the physical properties of the coated film. In the case of a high boiling point organic solvent, if the amount is too large, it may remain in the fired coating film and deteriorate the coating film properties. A more preferred lower limit is 1%, which is more preferred. The upper limit is 45%.

 With respect to the blending amount of the water-soluble solvent, the amount of the liquid medium in the fluorine-containing coating composition of the present invention includes, for example, a dispersion medium when the above-mentioned fluorine-containing polymer is prepared as an aqueous dispersion.

 The fluorine-containing coating composition of the present invention has an average particle diameter of 1 to 10 since it can sufficiently fill the lower layer of the coating film and can enhance the adhesion to the object to be coated. A fluorine-containing paint yarn and a fluorine-containing coating material obtained by dispersing a meltable fluororesin having an average particle diameter of 0.005 m and a fluorine-containing polymer having an average particle diameter of 0.05 to 0.3 μπι in a liquid medium, The fluorinated polymer is obtained by copolymerizing a functional group-containing fluorinated ethylenic monomer (a) and a functional group-free fluorinated ethylenic monomer (b). The group-containing fluorine-containing ethylenic monomer (a) has a functional group, and the functional group is a hydroxyl group, a carbonyl group, an alkoxycarbonyl group or an epoxy group which forms a salt. Yes, the above functional group-free fluorine-containing ethylene The functional monomer (b) preferably does not contain the above functional group.

 In addition, the fluorine-containing coating composition of the present invention can sufficiently fill the lower layer of the above-mentioned coating film to promote layer separation between the lower layer and the upper layer, and enhance the adhesiveness with the object to be coated. From the point that it can be adjusted, a fusible fluorine resin having an average particle diameter of 1 to 100 Xm and a fluoropolymer having an average particle diameter of 0.05 to 0.3 / im are used. The fluorine-containing polymer has a functional group capable of chemically bonding to the object to be coated. It is preferably 70 to 99.9% of the total of the solid content weight of the fluorinated resin and the solid content weight of the fluoropolymer. In this case, the functional group is preferably a hydroxyl group, a carboxyl group, a salt-forming propyloxyl group, an alkoxycarbonyl group, or a Z or epoxy group, and these functional groups include these functional groups. It is more preferable that the above-mentioned functional group-containing fluorine-containing ethylenic monomer (a) is introduced by copolymerization as a monomer component.

In the case of the above average particle diameter, when the compounding amount of the fusible fluororesin exceeds 99.9% by weight, the compounding amount of the fluorinated polymer is too small and contributes to the adhesion to the object to be coated. Since the number of functional groups is reduced as a whole, adhesiveness becomes insufficient. If the amount of the fusible fluororesin is less than 70% by weight, the amount of the fluorinated polymer becomes excessive, and the fluorinated polymer becomes excessive. The polymer particles fill the contact surface with the object to be coated and are further laminated, so that the functional groups of the particles on the surface of the object to be reacted react with the functional groups of the laminated particles to form a contact with the object to be coated. Since it does not contribute to adhesion, the adhesion to the object to be coated is rather insufficient. A more preferred lower limit is 80% by weight, and a more preferred upper limit is 98% by weight.

 The fluorinated paint ffiL composition of the present invention is used in combination with the above-mentioned fusible fluororesin and the above-mentioned fluorinated polymer, and depending on the application and necessity, a pigment, a filler, a viscosity modifier, a thickener, and a film forming material. Various additives such as a stabilizer, a decomposition accelerator, an antioxidant, and an antifoaming agent can be blended. From the viewpoint of obtaining a highly transparent coating film, it is preferable to limit the amount of these additives to the minimum necessary.

 The method for preparing the fluorine-containing coating composition of the present invention is not particularly limited. For example, a conventionally known method can be used. For example, the above-mentioned fusible fluororesin, the above-mentioned pigment, the above-mentioned fluoropolymer and the like are required. According to the above, a pretreatment is performed as follows, and the meltable fluororesin and the fluoropolymer are mixed and prepared at an appropriate ratio so as to have the above-mentioned volume ratio or solid content weight ratio.

 The fluorine-containing paint and composition of the present invention can be prepared by uniformly dispersing a meltable fluororesin and a fluoropolymer in water in the presence of a water-soluble solvent and a surfactant.

 As the meltable fluororesin, a powder is produced, for example, by the method described in JP-A-63-270740, and usually dispersed in a solvent using an appropriate dispersant. The dispersant may be used, for example, after wetting the meltable fluororesin with a solvent such as a lower alcohol, a ketone, or an aromatic hydrocarbon, and then adding a non-one surfactant, a fan surfactant, or the like. And the like can be used.

The amount of the meltable fluororesin is 15 to 80% of the total weight of the fluorine-containing coating composition of the present invention. If it is less than 15%, the viscosity of the fluorine-containing coating composition of the present invention is so low that sagging is likely to occur even when applied to an object to be coated, and the film thickness of the coating film may be insufficient, If it exceeds 80%, the fluorine-containing coating composition of the present invention becomes difficult to flow, and coating may not be possible. A preferred lower limit is 20%, which is preferred. The upper limit is 75%. The amount of the above-mentioned meltable fluororesin may be appropriately selected within the above range in consideration of the coating method and the adjustment of the film thickness.In the case of spray coating or dip coating, the concentration is set to a relatively low concentration, and the press coating is performed. In such a case, it is preferable to set the paste to 50% or more.

 The pigment is usually used after pulverizing and dispersing the solvent, the fluoropolymer, the surfactant and the like by a pulverizer / disperser such as a packet mill, a dynamo mill and a ball mill.

 Since the above-mentioned fluoropolymer has a small average particle diameter of 0.05 to 0.5, it can be dispersed as it is, and is usually synthesized by emulsion polymerization or the like and concentrated using a surfactant. Can be

 As the surfactant that can be used in the fluorine-containing coating composition of the present invention, 15 to 80% by weight of the total weight of the fluorine-containing coating composition of the present invention in the above-mentioned fluorine-containing coating composition is fusible fluorine. There is no particular limitation as long as the resin powder can be uniformly dispersed, and any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. it can.

Examples of the surfactant include sodium alkyl sulfate, sodium alkyl ether sulfate, triethanolamine olenoquinolesanolate, and triethanolamine alkyl ether sulfate. Surfactants, such as ammonium sulfate, ammonium alkyl ether sulfate, sodium alkyl ether oleate, sodium fluoroalkyl carboxylate, etc .; alkyl ammonium salt, alkyl Cationic surfactants such as benzylammonium salt; polyoxyethylene alkyl ether, polyoxyethylene phenolenoether, polymethylethyleneanolequinoleesteneol, propylene glycol loop-opened pyrenoxide copolymer, perflu Oroalkyl ethylene Nonionic surfactants such as oxide adducts and 21-ethylhexano-leethylenoxide adducts; and amphoteric surfactants such as alkyla, betaine aminoacetate, betaine alkylamide acetate, and imidazolium betaine. . Among them, anionic surfactants and nonionic surfactants are preferred, and nonionic surfactants having an oxyethylene chain with a small residual amount of thermal decomposition are more preferred. The amount of the surfactant is usually 0.01 to 50% of the meltable fluororesin. If the content is less than 0.01%, the meltable fluororesin powder may not be uniformly dispersed and may partly float.If the content is more than 50%, the surfactant may be decomposed into an obtained coating film. A large amount of residue may remain and cause coloration, or the properties of the coating film such as heat resistance and non-adhesiveness may decrease. A preferred lower limit is 0.1%, a more preferred lower limit is 0.2%, a preferred upper limit is 30%, and a more preferred upper limit is 20%.

 The fluorine-containing coating composition of the present invention may be appropriately diluted with a solvent, if necessary, adjusted to a paint-thin viscosity using a viscosity modifier or the like, formed into a coating, and applied.

 The above-mentioned fluorine-containing coating composition is used for coating on an object to be coated, and the object to be coated is preferably made of a metal, a polymer compound molded article, glass or pottery.

 In the present specification, the “polymer compound molded article” means a product obtained by molding a polymer compound. The polymer compound is not particularly limited, and examples thereof include a resin and a rubber. However, the polymer compound can withstand the sintering temperature after application of the fluorine-containing coating composition of the present invention and the operating temperature of the obtained coating film. Thus, heat-resistant resins such as polyimide resins and heat-resistant rubbers such as silicone rubber are preferred.

 The fluorine-containing coating composition of the present invention was subjected to surface treatment such as degreasing and surface roughening as necessary on the object to be coated such as aluminum, stainless steel (SUS), iron, heat-resistant resin, and heat-resistant rubber. Thereafter, the composition is applied by a method such as spraying, and the obtained coating film is dried and then baked at a temperature equal to or higher than the melting point of the above-mentioned fusible fluororesin, whereby a gradient coating film can be formed.

 As the gradient coating film obtained from the fluorine-containing coating composition of the present invention, a coating film having a thickness of 3 to 15; zm can be obtained as a surface layer, depending on the amount of the meltable fluororesin. . Such a gradient coating has a thickness comparable to a coating obtained by using the conventional two-coat method. Therefore, the fluorine-containing coating composition of the present invention can be suitably used by the one-coat method, even in the field currently processed by the two-coat method.

The gradient coating film obtained from the fluorine-containing coating composition of the present invention can have a thickness of, for example, about 100 μm. The above-mentioned inclined coating film obtained from the fluorine-containing coating composition of the present invention may be provided with a top coat such as a top coat, if necessary.

 As described above, the fluorine-containing coating composition of the present invention has a different average particle diameter, that is, a fusible fluororesin having an average particle diameter of 1 to 100 wm and an average particle diameter of 0.1 to 100 wm. It is obtained by blending the two components of the fluoropolymer of 0.5 to 0.5 / ini at a volume ratio or a solid content weight ratio within the above-mentioned specific range. By coating, the above-mentioned fluororesin layer can be formed by the one-coat method with a thickness comparable to that of the two-coat method without generating cracks.

 Although the mechanism by which the fluorine-containing coating composition of the present invention enables the thickening of the film is not clear, the fusible fluorine resin to be arranged in the upper layer portion of the obtained inclined coating film is within the above range. This is probably due to the relatively large average particle size. The average particle size of fluorocarbon resin in conventional general paints was relatively small, so cracks occurred when the film thickness was more than a certain level, and the cracks could not be suppressed even by repeated coating. It is considered that the film could not be formed.

 Since the fluorine-containing coating composition of the present invention can form the above-mentioned fluororesin layer thicker than before, the heat-resistant, durable, abrasion-resistant, corrosion-resistant, and non-adhesive properties of the meltable fluororesin Excellent properties such as properties can be sufficiently exhibited.

The fluorine-containing polymer of the present invention is also characterized in that the average particle diameter of the above-mentioned fluorine-containing polymer and the average particle diameter of the above-mentioned soluble fluororesin are adjusted so that the above-mentioned fluorine-containing polymer becomes critical Even if it has a critical surface tension higher than the surface tension, it is possible to obtain a coating film formed by forming the fluorine-containing polymer layer below and above the fluororesin layer. Therefore, according to the fluorine-containing coating composition of the present invention, it is possible to arbitrarily select the type of the component constituting the upper layer and the type of the component constituting the lower layer of the obtained coating film, and to design the coating film. The room for selection of width and material can be expanded. As described above, the fluorine-containing paint and composition of the present invention can be suitably used by the one-coat method even in applications where conventionally two or more coats were required. Further, the fluorine-containing coating composition of the present invention can be appropriately selected from a wide range of substance groups as the above-mentioned fluorine-containing polymer, and by appropriately selecting these, the composition is applied so as to be suitable for use. And can be used. The fluorine-containing coating composition of the present invention can improve the adhesiveness to an object to be coated by the one-coat method, so that it is not necessary to apply a primer. Even if the object to be coated is glass, pottery, etc., the adhesiveness can be improved, so it is different from the conventional method.For example, the surface of the glass substrate is treated with a silane coupling agent or the like. There is no need to add it to the coating composition.

 The fluorine-containing coating composition of the present invention is obtained by further blending a fusible fluororesin and a fluoropolymer as described above, and comprises an inorganic acid such as chromic acid, or a polyamide imide, polyimide, or poly Since it is not necessary to incorporate a heat-resistant resin such as ether sulfone, a highly transparent coating film can be obtained.For example, it is suitably used in applications where the texture and design of the object to be coated are emphasized. be able to.

 The fluorine-containing coating composition of the present invention can further effectively prevent scattering at the time of impact when glass, pottery or the like is to be coated.

 Therefore, the fluorine-containing coating composition of the present invention can be applied to articles made of various substrates such as metal, polymer compound molded articles, glass, and ceramics to provide corrosion resistance, abrasion resistance, heat resistance, and non-adhesion. It can be used for applications where transparency and the like of the coating film, texture of the substrate itself, design property, etc. are required.

 Examples of a material to which the fluorine-containing coating composition of the present invention can be suitably applied include, for example, electrical components and the like, taking advantage of the fact that the obtained inclined coating film has different properties on the front and back.

 The fluorine-containing coating composition of the present invention can also be used for rice cookers, pots, jar pots, hot plates, irons, frying pans, home bakeries, etc. for home appliances and kitchens. ] Widely used for mold release such as rolls for equipment, belts for OA equipment, paper rolls, calender rolls for film production, injection dies; stirrers, tank inner surfaces, vessels, towers, centrifuges, etc. Is done.

The fluorine-containing coating composition of the present invention is used for preventing glass from scattering, for example, lighting equipment such as light bulbs; display devices such as CRTs and liquid crystal display devices; building materials such as glass windows; glass tableware, and other glass containers. Tableware, etc .; laboratory utensils such as glass laboratory utensils; various glass products such as fire prevention glass and functional glass such as safety glass; It can be used as a material for glass products, and in these cases, the transparency of the glass can be maintained.

 The fluorinated coating composition of the present invention provides non-adhesiveness, sliding properties, and the like by the fusible fluororesin, and has excellent durability because the fluorinated resin layer is thick. By using a fluorine-containing polymer as the elastic body, the flexibility can be improved so as not to be too hard, so that it can be suitably used particularly for OA equipment rolls or OA equipment belts. .

 In particular, when the above-mentioned fluoropolymer is the above-mentioned fluororubber, durability and flexibility can be particularly improved. For example, for OA equipment, the durability and flexibility were not sufficiently exhibited by the conventional method. When used for rolls, belts for OA equipment, etc., durability can be dramatically improved and flexibility superior to that of conventional products can be exhibited. Conventionally, rolls for OA equipment, belts for OA equipment, etc. are usually coated with silicone rubber rolls and coated with PFA, and good abrasion resistance is required. Can be suitably used.

 In addition, when the fluorine-containing coating composition of the present invention uses a functional group-containing fluororesin as the above-mentioned fluoropolymer, it exhibits high adhesion to substrates such as metal, silicone rubber, and polyimide. By coating, it can be suitably used as a roll for OA equipment or a belt for OA equipment.

 In recent years, OA equipment has been required to be more and more energy-saving, but as one of the methods for heating OA equipment belts with high thermal efficiency, an IH (induction heating) method using a metal belt as the base material has been proposed. Have been. The IH method utilizes the fact that eddy currents flow through a magnetic metal placed in an alternating magnetic field due to electromagnetic induction and generate heat. In this method, when a magnetic metal belt is used as a base material, the belt generates heat, and then the surface layer of the belt is heated by heat conduction to melt the toner. The surface layer of this belt is generally a fluororesin layer. Here, a silicone rubber layer may be provided as an intermediate layer between the base material and a surface layer such as a fluororesin layer in order to sufficiently melt the toner to obtain a high-quality image.

On the other hand, the startup time of OA equipment is expected to be shortened, and it is required that the surface layer of the belt generate heat in a shorter time. Here, silicone as the intermediate layer In the configuration in which the rubber layer is provided, there is a problem that some time lag occurs between heat generation of the belt base material and heating of the belt surface layer. In addition, the metal belt was inferior in flexibility and was insufficient in durability.

 These problems can be solved by providing a silicone rubber layer containing a magnetic material in at least a part of the intermediate layer, and providing a film made of the fluorine-containing coating composition of the present invention as a surface layer. In other words, since the intermediate layer generates heat instead of the base material, it is possible to suppress a time lag due to heat conduction.

 When a magnetic material is blended in the intermediate layer, it is desirable to use a belt made of polyimide or the like having low thermal conductivity as a base material in order to prevent heat conduction from the intermediate layer to the base material side. Polyimide also has excellent properties in terms of rigidity, has improved durability compared to metal belts, and can respond to higher speeds.

 A coating film obtained by applying the above-mentioned fluorine-containing coating composition is also one of the present invention.

 A coated article characterized by having the above-mentioned coating film is also one of the present invention.

 It is preferable that the coated object is one in which the coating film is formed on an object to be coated, and the object to be coated is made of a metal, a polymer compound molded body, glass or pottery.

 The painted object is preferably a material for a light bulb.

 The painted object is preferably a fire-resistant glass material or a safety glass material. It is preferable that the painted object is a glass tableware material or a glass laboratory tool material.

 It is preferable that the coated article is a OA device mouthpiece or an OA device belt. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. Example 1

70 g of PFA powder with an average particle size of 12 # m obtained by milling, Perfluoro Otata 5 g of an ammonium salt of oxalic acid and 100 g of ion-exchanged water were placed in a SUS container, and the surface of the PFA powder was well dispersed using a stirrer to obtain a PFA dispersion. 50 g of a 60 mass% dispersion of PTFE emulsion polymerization having an average particle diameter of 0.35 / im, 50 g of nonionic HS 210 (manufactured by NOF Corporation) as a surfactant, a thickener and 0.5 g of a thickener were added to this dispersion. g was added and dispersed well to obtain a paint.

 This paint is spray-coated on an anore mini plate (150 mm x 200 mm x 2 mm), dried at 80 for 30 minutes, and baked at 380 ° C for 20 minutes, resulting in a coating thickness of 30 μπι I got something. The coating film was peeled off, the cross section was cut thinly using a microtome (manufactured by Leica AG), and a filter was prepared using a polarizing microscope. The thickness of the layer (PFA layer) was measured. Table 1 shows the results. Example 2

 Average particle size obtained by emulsion polymerization of 99.95 parts by mass of tetrafluoroethylene and 0.05 parts by mass of perfluoro mouth (propyl butyl ether) instead of PTFE

A coating material was prepared in the same manner as in Example 1 except that a 0.25 μm thick [¾ΡTFE 60% by mass concentrate was used, to obtain a coating film, and the thicknesses of the coating film and the surface layer were measured. Table of results

Shown in 1. Examples 3 to 6

 A coating was prepared by preparing a coating in the same manner as in Example 2 except that the type of the fusible fluororesin, the average particle diameter, the particle diameter of the modified PTF II, and the compounding ratio were as shown in Table 1, and a coating was obtained. And the thickness of the surface layer. Table 1 shows the results. Example 7

As the above fluorine-containing polymer, a fluorinated bilidene-based rubber having an average particle diameter of 0.2 to 0.3 μπι (Dailatex GL 252 CR——, manufactured by Daikin Industries, Ltd.) and an acid-accepting agent-containing paint (concentration 50 Mass%, manufactured by Daikin Industries, Ltd.) 120 g of the PFA dispersion (PFA: fluororubber compounding ratio 70:30) used in the above was dispersed to obtain a PFA-containing fluororubber paint. To 100 parts by weight of this coating material, 3 parts by weight of a hardener (Daily Latex GL 200-B solution, manufactured by Daikin Industries, Ltd.) are mixed and dispersed, and the mixture is dispersed on an aluminum foil (thickness Ι Ο Ο μπι). After coating and drying at room temperature for 30 minutes, baking was performed at 80 ° C for 30 minutes and at 320 ° C for 60 minutes to obtain a coating film. Using a microtome (manufactured by Leica AG), the cross-section of this coating film with aluminum foil is thinly cut, a filter is prepared with a polarizing microscope, and the filter is enlarged 1000 times while adjusting so that the boundary can be confirmed. The thickness of the surface layer (PFA layer) was measured. Table 1 shows the results. Example 8

 Except for using the FEP dispersion used in Example 4 in place of the PFA dispersion, a paint was prepared in the same manner as in Example 7 to obtain a coating, and the thickness of the coating and the surface layer was measured. Table 1 shows the results. Example 9

 As the above-mentioned fluoropolymer, the mass ratio of flexible PFA (tetrafluoroethylene: perfluoro (propylbutyl ether)) having an average particle diameter of 0.06 / zm is 53:

A coating material was prepared in the same manner as in Example 1 except that the emulsion polymer of (47) was used, coated, dried, and baked at 320 ° C for 60 minutes to obtain a coating film. Was measured for thickness. Table 1 shows the results. Example 10

The average particle diameter obtained by emulsion polymerization using the above-mentioned fluoropolymer as a monomer component having a monomer having an OH group in a side chain at 2% by mass of the total amount of the monomer component is 0.07 / 1111. of? ? Except for using (functional group-containing PFA), a paint was prepared in the same manner as in Example 1, applied, dried, and baked at 330 ° C for 60 minutes to obtain a coating film in the same manner as in Example 1. Was. The resulting coating was firmly adhered to aluminum, so the substrate was changed to aluminum foil with a thickness of 100 ιη, and a coating was prepared in the same way. The thickness of the coating film and the surface layer was measured in the same manner as in Example 7. Table 1 shows the results. Comparative Example 1 to Comparative Example 4

A coating material was prepared in the same manner as in Example 1 except that the type and the average particle size of the fusible fluororesin, the type and the average particle size of the fluorinated polymer, and the compounding ratio were as shown in Table 1. To obtain a coating film, and the thickness of the coating film and the surface layer was prepared. Table 1 shows the results.

8 h- ¹ mix ratio

 Average particle size Particle size Surface

 Meltable fluororesin (a) Fluoropolymer (b) Average particle a / b Coating thickness / layer thickness, thickness

 (m) (μ πι)

 (Capacity ratio)

Example 1 PFA 12 PTFE 0.35 70/30 25 8

Example 2 PFA 12 modified PTFE 0.25 70/30 30 10

Example 3 PFA 5 modified PTFE 0.25 50/50 25 6

Example 4 FEP 15 Modified PTFE 0.15 70/30 25 11

Example 5 FEP 15 Modified PTFE 0.25 90/10 30 15

Example 6 FEP 15 modified PTFE 0.25 40/60 25 2

Example 7 PFA 12 Fluororubber 0.15 70/30 35 10

Example 8 FEP 15 Fluororubber 0.15 70/30 35 12

Example 9 PFA 12 Flexibility PFA 0.06 50/50 30 5

Example 10 PFA 12 functional group-containing PFA 0.07 50/50 35 6

Comparative Example 1 PFA 0.15 modified PTFE 0.25 50/50 25 Surface layer could not be confirmed Comparative Example 2 FEP 0.12 Modified PTFE 0.25 50/50 25 Surface layer could not be confirmed Comparative Example 3 FEP 0, 12 Fluororubber 0.15 50/50 30 1 ~ Two

Comparative Example 4 PFA 0.15 Fluororubber 0.15 50/50 25 1

The specific gravity of each of the components used was PTFE,? The price was 2.2 and the fluoro rubber was 1.75. From Table 1, PFA or FEP having an average particle size in the range of 1 to 30 μπι, and the above-mentioned fluoropolymer having an average particle size in the range of 0.005 to 0.5 / xm, A paint was prepared by blending such that the amount ratio was 35:65 to 95: 5, and the obtained coating films of Examples 1 to 10 had a surface layer thickness of 2 to 15 μπι, ? Or? In Comparative Examples 1 to 4 in which the average particle size of the powder was less than 1 μm, it was found that the formation of the surface layer was not confirmed or the thickness was 1 to 2 μm. Production Example 1 Production of fluorinated polymer having functional groups

で表されるパーフルオロー (1， 1, 9, 9ーテトラハイドロー 2, 5―ビスト リフノレオロメチノレー 3， 6—ジォキサ一 8—ノネノ一ノレ) 3. 8 g、 パーフルォ 口 （プロピルビエルエーテル） 〔PPVE〕 18 gを窒素ガスを用いて圧入し、 系内の温度を 70 °Cに保つた。 In a 3 liter glass-lined autoclave equipped with a stirrer, valve, pressure gauge, and thermometer, put 1,500 ml of pure water and 9.10 g of ammonium perfluorooctanoate, and sufficiently purge with nitrogen gas. 20 ml was charged. Then, the following equation (3)

Perfluoro- (1,1,9,9-tetrahydro-2,5-bis-refinoleolomethinolate 3,6-dioxa-1-nonone-nore) 3.8 g, perfluorinated Ether) [PPVE] 18 g was injected using nitrogen gas, and the temperature in the system was maintained at 70 ° C.

 While stirring, tetrafluoroethylene [TFE] gas was injected so that the internal pressure became 8.5 kg fZcm2G.

 Next, a solution in which 0.15 g of ammonium persulfate was dissolved in 5.0 g of water was injected under pressure using nitrogen to start the reaction.

Since the pressure decreases with the progress of the polymerization reaction, when the pressure drops to 7.5 kgi cm ² G, the pressure is re-pressurized to 8.5 kg cm ² with tetrafluoroethylene gas, and the pressure is reduced and raised repeatedly. Was. While continuing to supply tetrafluoroethylene, every time about 40 g of tetrafluoroethylene gas is consumed from the start of the polymerization, 1.9 of the fluorine-containing ethylenic monomer having a hydroxyl group represented by the above formula (3) is obtained. g of the polymer 3 times in total (5.7 g in total) to continue the polymerization.When about 160 g of tetrafluoroethylene was consumed from the start of the polymerization, the supply was stopped and the autoclave was cooled to remove unreacted monomers. This gives 1702 g of a translucent bluish translucent aqueous dispersion.

 The concentration of the polymer in the obtained aqueous dispersion was 10.9%, and the particle diameter measured by a dynamic light scattering method was 70.7 nm.

 A part of the obtained aqueous dispersion was subjected to freeze coagulation, and the precipitated polymer was washed and dried to isolate a white solid. The molar ratio composition of the obtained copolymer was determined by 19 F-NMR analysis and IR analysis to be TFE / PP VE / (a fluorine-containing ethylenic monomer having a hydroxyl group represented by the formula (3)) = 97 7: 1.2: 1.1 mol%.

In the infrared spectrum, characteristic absorption of 1 OH was observed at 3620 to 3400 cm- ¹ .

DSC analysis showed Tm = 310 ° C., and DTGA analysis showed 1% thermal decomposition temperature T d = 368 ° C. 2 mni using Koka type flow tester, using Nozzle length 8 mm, 372 ° C in the preheating for 5 minutes, a load 7 kgf / cm ² was measured melt Furore one preparative 1 2. 0 g / 10 minutes. Preparation Example 1 Preparation of Fluorinated Paint Composition A

Isopropyl alcohol 4 parts by weight, nonionic surfactant (trade name: DS-401, manufactured by Daikin Industries, Ltd.) 8 parts by weight, triethylene glycol 6 parts by weight, ethylene glycol 4 parts by weight, pure water 20 parts by weight, Mix and disperse 12 parts by weight of a fluoropolymer having a functional group and 26 parts by weight of PFA resin powder (average particle diameter 25, apparent density 0.8 g / ml) to obtain a uniform dispersed yarn Prepared. This was designated as fluorinated coating composition A. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 95: 5. Preparation Example 2 Preparation of Fluorine-Containing Paint Composition B

4 parts by weight of isopropyl alcohol, 8 parts by weight of nonionic surfactant (trade name: DS-401, manufactured by Daikin Industries, Ltd.), 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, 20 parts by weight of pure water , 42 parts by weight of a fluorine-containing polymer having a functional group, PFA resin powder (average particle size: 25 μΐϊΐ _Ν apparent density: 0.8 g / m 1) 26 parts by weight are mixed and dispersed to obtain a uniform dispersion composition Was prepared. This was designated as fluorinated coating composition B. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 85:15. Preparation Example 3 Preparation of Fluorinated Paint Composition C

 Isopropyl alcohol 4 parts by weight, nonionic surfactant (trade name: DS-401, manufactured by Daikin Industries, Ltd.) 8 parts by weight, triethylene glycol 6 parts by weight, ethylene glycol 4 parts by weight, pure water 20 parts by weight Parts, a fluoropolymer having a functional group: 0.2 parts by weight, 26 parts by weight of PFA resin powder (average particle size: 25 μτη, apparent density: 0.8 gZm l) were mixed and dispersed to obtain a uniform dispersion composition. Was prepared. This was designated as fluorinated coating composition C. The weight ratio of the fluorinated molten resin to the fluorinated polymer having a functional group was 99.2: 0.08. Preparation Example 4 Preparation of Fluorine-Containing Paint Composition D

 4 parts by weight of isopropyl alcohol, 8 parts by weight of non-ionic surfactant (trade name: DS-401, manufactured by Daikin Industries, Ltd.), 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, containing a functional group Mix and disperse 110 parts by weight of fluoropolymer and 26 parts by weight of PFA resin powder (average particle size 25/1 m, apparent density 0.8 g / ml) to obtain a uniform dispersion composition. Prepared. This was designated as fluorinated coating composition D. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 68:32. Preparation Example 5 Preparation of Fluorinated Paint Composition E

4 parts by weight of isopropyl alcohol, nonionic surfactant (Product name: DS-4 01, manufactured by Daikin Industries, Ltd.) 8 parts by weight, 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, 20 parts by weight of pure water, 12 parts by weight of a fluoropolymer having a functional group, FEP resin powder (average A particle diameter of 25 μΐη and an apparent density of 0.8 g / m 1) 26 parts by weight were mixed and dispersed to prepare a uniform dispersion composition. This was designated as fluorinated coating composition E. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 95: 5. Preparation Example 6 Preparation of Fluorine-Containing Paint Composition F

 Isopropyl alcohol 4 parts by weight, nonionic surfactant (trade name: DS-401, manufactured by Daikin Industries, Ltd.) 8 parts by weight, triethylene glycol 6 parts by weight, ethylene glycol 4 parts by weight, pure water 20 parts by weight, Mix and disperse 42 parts by weight of fluoropolymer having functional groups and 26 parts by weight of FEP resin powder (average particle size 25 μΐη, apparent density 0.8 g / ml) to prepare a uniform dispersion composition did. This was designated as fluorinated coating composition F. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 85:15. Preparation Example 7 Preparation of Fluorinated Paint Composition G

 Isopropyl alcohol 4 parts by weight, nonionic surfactant (trade name: DS-401, manufactured by Daikin Industries, Ltd.) 8 parts by weight, triethylene glycol 6 parts by weight, ethylene glycol 4 parts by weight, pure water 20 parts by weight, A uniform dispersion composition is prepared by mixing and dispersing 0.2 part by weight of a fluoropolymer having a functional group and 26 parts by weight of FEP resin powder (average particle size 25 μηι, apparent density 0.8 g Zm 1). did. This was designated as fluorinated coating composition G. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 99.92: 0.08. Preparation Example 8 Preparation of Fluorinated Paint Composition H

4 parts by weight of isopropyl alcohol, 8 parts by weight of nonionic surfactant (trade name: DS-401, manufactured by Daikin Industries, Ltd.), 6 parts by weight of triethylene glycol, 4 parts by weight of ethylene glycol, fluorine-containing functional group Polymer 1 10 parts by weight, FEP tree 26 parts by weight of a fat powder (average particle diameter 25 Mm, apparent density 0.8 g / m 1) was mixed and dispersed to prepare a uniform dispersion composition. This was designated as fluorinated coating composition H. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 68:32. Preparation Example 9 Preparation of Fluorine-containing Paint Composition I

 PFA dispersion (average particle diameter 0.3 m, solid content concentration 50% by weight, trade name: AD-2CR, manufactured by Daikin Industries, Ltd.) 50 parts by weight, functional group-containing fluorine-containing polymer 12 parts by weight The parts were mixed and dispersed to prepare a uniform dispersion composition. This was designated as a fluorine-containing coating composition I. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 95: 5. Preparation Example 10 Preparation of Fluorine-Containing Paint Composition J

 FEP dispersion (average particle size 0.2 μm, solid content concentration 50% by weight, trade name: ND-1, manufactured by Daikin Industries, Ltd.) 50 parts by weight, functional group-containing fluorinated polymer 12 weight The parts were mixed and dispersed to prepare a uniform dispersed yarn composition. This was designated as fluorinated coating composition J. The weight ratio of the fluorine-containing molten resin to the fluorine-containing polymer having a functional group was 95: 5. Example 1 1

 Fluorine-containing coating composition A is spray-coated on an aluminum plate (A-150), dried at 80-100 for 30 minutes, and then baked at 34 ° C for 30 minutes. A fluororesin-coated plate having a coating of 70 μm was obtained.

Regarding the adhesiveness of the coating film to the aluminum plate, strips were cut into the obtained coating film at 1 cm intervals, one end of the strip was peeled off from the aluminum plate, and then the coating was cured so that the coating surface was directly above. Fix the fluororesin-coated plate to a Tensilon Universal Testing Machine (trade name, manufactured by Orientec Co., Ltd.) using a tool and attach one end of the strip peeled from the aluminum plate to the chuck located above the coating film. Moving the strip upwards at a crosshead speed of 5 Omm / min. The film was peeled in the direction of about 90 ° from, but the peel strength at this time was measured to evaluate. Table 2 shows the results. Example 1 2

 The procedure of Example 11 was repeated except that the fluorine-containing coating composition B was used instead of the fluorine-containing coating composition A. Example 13

 The procedure of Example 11 was repeated except that the fluorine-containing coating composition C was used instead of the fluorine-containing coating composition A. Example 14

 The procedure of Example 11 was repeated, except that the fluorine-containing coating composition D was used instead of the fluorine-containing coating composition A. Example 15

 The procedure of Example 11 was repeated, except that the fluorine-containing coating composition E was used instead of the fluorine-containing coating composition A. Example 16

 Example 11 was repeated except that the fluorine-containing coating composition F was used instead of the fluorine-containing coating composition A. Example 17

 The procedure of Example 11 was repeated, except that the fluorine-containing coating composition G was used instead of the fluorine-containing coating composition A. Example 18

Conducted except that fluorine-containing coating composition H was used instead of fluorine-containing coating composition A Example 11 Comparative Example 5

 Fluorine-containing coating composition I is spray-coated on the surface of an aluminum plate (A-150), dried at 80 to 100 ° C for 30 minutes, and then baked at 340 ° C for 30 minutes. However, it was not possible to obtain a film of 30 μπι or more due to cracks. Comparative Example 6

 Fluorine-containing paint composition J is spray-coated on the surface of an aluminum plate (Α-150), dried at 80 to 100 ° C for 30 minutes, and then baked at 340 ° C for 30 minutes. However, a film of 30 / xm or more could not be obtained due to cracks. Table 2

* 1: The force that could not produce a film of 30 μm or more due to the occurrence of cracks. From Table 2, the average particle size of the fusible fluororesin is not within the range of 1 to 100 μm. Comparative Examples 5 to 6 In Examples 11 to 18 in which the average particle size of the fusible fluorine was within the range of 1 to 100 μm, cracking occurred and a thick film could not be obtained. The solid content ratio of the meltable fluororesin to the fluoropolymer is 70%. : 30 to 99.9: Examples 11 to 12 and Examples 15 to 1 in the range of 0.1

In No. 6, the peel strength was found to be higher. Example 19

 Spray-coat the silicone rubber roll with the fluorine-containing coating composition A, dry at 80 to 100 for 30 minutes, and bake at 340 ° C for 30 minutes to obtain a fluororesin-coated roll having a coating of about 30 Atm. Was.

Regarding the abrasion resistance of the obtained coating film, copy paper (trade name: recycled PPC paper, manufactured by Fuji Xerox Co., Ltd.) was pressed against the surface of the fluororesin-coated roll heated to 200 ° C with a load of 1 kg, and the rotation speed was 300 r. abrading at Ronore table surface by rotating the rolls in pm, then wettability index standard solution _{(3 1 dyn e Zc; m} ) time to contact angles by Gonio meter is 20 ° or less dropwise, or, The time required for the coating film to peel off from the silicone rubber roll substrate was evaluated as a measure of durability. Table 3 shows the results. Example 20

 The procedure of Example 19 was repeated except that the fluorine-containing coating composition B was used instead of the fluorine-containing coating composition A. Example 21

 The procedure of Example 19 was repeated except that the fluorine-containing coating composition C was used instead of the fluorine-containing coating composition A. Example 22

The procedure of Example 19 was repeated, except that the fluorine-containing coating composition D was used instead of the fluorine-containing coating composition A. Table 3

表 3より、 実施例 19〜 22では、 耐摩耗性が比較的良好であり、 溶融性フッ 素樹脂と含フッ素高分子との固形分重量比が 70 ： 30〜99. 9 : 0. 1の範 囲内にある実施例 1 9〜20では、 耐摩耗性がより良好であることがわかった。 実施例 23

As can be seen from Table 3, in Examples 19 to 22, the abrasion resistance was relatively good, and the solid content ratio of the fusible fluororesin to the fluoropolymer was 70:30 to 99.9: 0.1. In Examples 19 to 20 within the range, it was found that the abrasion resistance was better. Example 23

 Spray the fluorinated paint composition A onto a 1.5 mm thick glass plate, dry it at 80-100 ° C for 30 minutes, and bake it at 340 for 30 minutes to obtain a fluorine film with a coating thickness of about 70 μm. A resin-coated glass plate was obtained.

 The impact resistance of the obtained fluororesin-coated glass sheet was measured using a Dupont-type impact deformation tester described in JISK 5600 -5-3. Then, place a fluororesin-coated glass plate between the shooting die and the cradle, drop a 300 g weight onto the shooting die from a height of 10 Omm, and observe the destruction of the fluororesin-coated glass plate. And the weight loss due to the scattering of glass is

 Weight loss (%) = weight of scattered matter (g) / weight before test (g) Evaluated by obtaining from XI00. Table 4 shows the results.

The visible light transmittance of the fluororesin-coated glass plate was measured using a U-3310 type spectrophotometer (trade name, manufactured by Hitachi, Ltd.) in the typical visible range of 400 to 700 nm. It was evaluated by measuring. Table 5 shows the results. Example 2 4

 The procedure of Example 23 was repeated except that the fluorine-containing coating composition B was used instead of the fluorine-containing coating composition A. Example 2 5

 The procedure of Example 23 was repeated except that the fluorine-containing coating composition C was used instead of the fluorine-containing coating composition A. Example 26

 The procedure of Example 23 was repeated except that the fluorine-containing coating composition D was used instead of the fluorine-containing coating composition A. Example 2 7

 The procedure of Example 23 was repeated except that the fluorine-containing coating composition E was used instead of the fluorine-containing coating composition A. Example 2 8

 The procedure of Example 23 was repeated, except that the fluorine-containing coating composition F was used instead of the fluorine-containing coating composition A. Example 2 9

 The procedure of Example 23 was repeated except that the fluorine-containing coating composition G was used instead of the fluorine-containing coating composition A. Example 30

Example 23 was repeated except that the fluorine-containing coating composition H was used instead of the fluorine-containing coating composition A. Comparative Example 7

 Γ-Aminopropyltriethoxysilane (trade name: A_l100, manufactured by Nippon Tunica) is spray-painted on a 1.5-mm-thick glass plate as a primer, dried at 80-100 ° C for 30 minutes, and then treated with PFA powder. Body paint (average particle size 20 μm, apparent density 0.88 g / m1, trade name: MP-103, Mitsui, manufactured by Dupont Fluorochemicals Co.) is electrostatically coated and baked at 340 ° C for 30 minutes Thus, a fluororesin-coated glass plate having a coating film of about 70 m was obtained. The impact resistance of the coating was evaluated according to the procedure described in Example 23. Comparative Example 8

 The impact resistance of a solid glass plate having a thickness of 1.5 mm was evaluated according to the procedure described in Example 23. Table 4

* 2: Multiple fragments due to destruction From Table 4, it can be seen that Examples 23 to 30 can suppress the weight loss at the time of impact to the same or almost comparable to Comparative Example 7 in which primer was applied. The weight ratio of the solid content of the meltable fluororesin to the fluoropolymer is in the range of 70:30 to 99.9: 0.1. That Example 2 3-2 4 and Example 2 7-2 In 8 weight loss less it'll force ² ivy. Table 5

表 5から、 実施例 2 3〜 3 0は、 プライマーを塗装した比較例 7よりも可視線 領域の光線透過率を高くすることができ、 溶融性フッ素樹脂が P F Aである場合、 溶融性フッ素樹脂の固形分重量が、 溶融性フッ素樹脂の固形分重量及ぴ含フッ素 高分子の固形分重量の合計の 7 0 %以上である実施例 2 3〜 2 5で光線透過率が より高く、 溶融性フッ素樹脂が F E Pである場合、 5 0 0 n m以上では上記溶融 性フッ素樹脂が 7 0重量％である実施例 2 7〜 2 9で光線透過率がより高いこと がわかった。 産業上の利用可能性

From Table 5, it can be seen that Examples 23 to 30 have higher light transmittance in the visible region than Comparative Example 7 in which the primer is coated, and that the meltable fluororesin is PFA when the meltable fluororesin is PFA. In Example 23 to 25, the solid content weight of the polymer was 70% or more of the total weight of the solid content of the fusible fluororesin and the weight of the solid content of the fluorinated polymer. When the fluororesin was FEP, it was found that the light transmittance was higher in Examples 27 to 29 where the meltable fluororesin was 70% by weight above 500 nm. Industrial applicability

Since the fluorine-containing coating composition of the present invention has the above-described configuration, a layer mainly containing a fusible fluororesin can be formed in a thickness equivalent to that of the two-coat method by the one-coat method, and the corrosion resistance and the Abrasion resistance, heat resistance, non-adhesiveness, etc. are good, and critical surface It is possible to form a layer mainly containing a material having a higher tension, and to form both layers upside down. The fluorine-containing coating composition of the present invention can further obtain a coating film having high adhesiveness to an object to be coated including glass and the like and transparency.

Claims

The scope of the claims 1. It can be obtained by blending a fusible fluororesin having an average particle diameter of 1 to 100 μm and a fluoropolymer having an average particle diameter of 0.05 to 0.5 / zm. A fluorine-containing coating composition characterized by the following: 2. The fluorine-containing composition according to claim 1, wherein the solid content weight of the meltable fluororesin is 35 to 99.9% of the total of the solid content weight of the meltable fluororesin and the solid content weight of the fluoropolymer. Paint composition. 3. A fluorine-containing coating composition obtained by mixing a fusible fluororesin having an average particle diameter of 1 to 30 μm and a fluoropolymer having an average particle diameter of 0.05 to 0.5 μππι. Thing, The capacity of the meltable fluororesin is 35 to 95% of the total of the capacity of the meltable fluororesin and the capacity of the fluorine-containing polymer.  A fluorine-containing coating composition, characterized in that: 4. The fluorine-containing coating composition according to claim 1, 2 or 3, wherein the meltable fluororesin and the fluoropolymer are dispersed in a liquid medium. 5. The fluorine-containing coating composition according to claim 1, 2, 3, or 4, wherein the fluorine-containing polymer has a functional group. 6. The fluorine-containing coating composition according to claim 5, wherein the functional group is a hydroxyl group, a carboxyl group, a carboxyl group forming a salt, an alkoxycarbol group and / or an epoxy group. 7. The fluorinated polymer is obtained by copolymerizing a functional group-containing fluorinated ethylenic monomer (a) and a functional group-free fluorinated ethylenic monomer (b). So, The functional group-containing fluorine-containing ethylenic monomer (a) has a functional group, and the functional group is a hydroxyl group, a carboxyl group, a carboxy group forming a salt, an alkoxycarbonyl group or an epoxy group. Group, 7. The fluorine-containing coating composition according to claim 5, wherein the functional group-free fluorine-containing ethylenic monomer (b) does not have the functional group. 8. The fluorinated coating composition according to claim 5, wherein the fluorinated polymer has an average particle diameter of 0.005 to 0.3 μπι. 9. Including a meltable fluororesin having an average particle diameter of 1 to 100 / Xm and a fluoropolymer having an average particle diameter of 0.005 to 0.3 / m dispersed in a liquid medium. A fluorine coating composition, The fluorinated polymer is obtained by copolymerizing a functional group-containing fluorinated ethylenic monomer (a) and a functional group-free fluorinated ethylenic monomer (b), The functional group-containing fluorine-containing ethylenic monomer (a) has a functional group, and the functional group includes a hydroxyl group, a carboxyl group, a carboxy group forming a salt, and an alkoxy canoleponyl group. Or an epoxy group, The functional group-free fluorine-containing ethylenic monomer (b) does not have the functional group.  A fluorine-containing coating composition, characterized in that: 10. The method according to claim 9, wherein the solid content weight of the fusible fluororesin is 70 to 9.9% of the total of the solid content weight of the fusible fluororesin and the solid content weight of the fluoropolymer. Fluorine paint composition. 1 1. The number of moles of the functional group-containing fluorinated ethylenic monomer (a) depends on the number of moles of the functional group-containing fluorinated ethylenic monomer (a) and the number of moles of the functional group-containing fluorinated ethylenic monomer. 11. The fluorine-containing coating composition according to claim 7, which is 0.05 to 30% of the total number of moles of the monomer (b). 12. The fluorine-containing coating composition according to claim 5, 6, 7, 8, 9, 10, or 11, wherein the fluoropolymer is a functional group-containing fluororesin. 13. The fluorine-containing coating composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the fluoropolymer is a fluororubber. 14. The fusible fluororesin has a melting point of 200 ° C or higher. 4. The fluorine-containing coating composition according to 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13. 15. The meltable fluororesin is a perfluoropolymer, claims 1, 2, 3, 4, 5. The fluorine-containing coating composition according to 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14. 16. Claim 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 which is used for a roll for OA equipment or a belt for OA equipment The fluorinated coating composition according to claim 1. 17. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 11, 12, 13, 14. A coating film obtained by applying the fluorine-containing coating composition according to 15 or 16 above. 18. A coated article having the coating film according to claim 17. 1 9. The coating film is formed on the workpiece, 19. The coated object according to claim 18, wherein the object to be coated is made of a metal, a polymer compound molded body, glass or pottery. 20. The coated article according to claim 19, which is a material for a light bulb.  21. The coated article according to claim 19, which is a material for fireproof glass or a material for safety glass. 22. The material according to claim 19, which is a material for glass tableware or a material for glass laboratory equipment. 23. The coated article according to claim 19, which is a roll for OA equipment or a belt for OA equipment.