CN110691822A - Coating film, coating composition, and article having the coating film - Google Patents
Coating film, coating composition, and article having the coating film Download PDFInfo
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- CN110691822A CN110691822A CN201780091307.9A CN201780091307A CN110691822A CN 110691822 A CN110691822 A CN 110691822A CN 201780091307 A CN201780091307 A CN 201780091307A CN 110691822 A CN110691822 A CN 110691822A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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Abstract
A coating film, comprising: the fluorine-containing oil composition comprises a fluorine oil, a fluororesin in an amount of 1 to 100 mass% inclusive relative to the content of the fluorine oil, and flaky particles in an amount of 1 to 50 mass% inclusive relative to the content of the fluorine oil, wherein the average particle diameter of the flaky particles is 1 to 100 [ mu ] m inclusive. The fluororesin and the fluorine oil are preferably selected from a combination in which a contact angle of the fluorine oil with respect to a film composed of the fluororesin becomes 40 ° or less at a measurement temperature of 20 ℃.
Description
Technical Field
The present invention relates to a coating film, a coating composition, and an article having the coating film.
Background
Oil stains such as lubricating oil in machine tools and cooking oil in range hoods are hardened with the passage of time, and removal thereof is difficult. Therefore, a technique of forming a coating film capable of suppressing the adhesion of oil stains on the surface of various articles is useful. The film for inhibiting the adhesion of the oil stain as described above needs to stably maintain excellent lubricity against the oil for a long period of time.
As a material for forming a coating film having high lubricity and stability against a deposit such as oil stain, a fluorine compound is generally used. For example, patent document 1 discloses a surface treatment composition containing a fluororesin and a fluorine oil at a specific ratio.
Patent document 1: japanese patent laid-open No. 2014-65884
Patent document 2: international publication No. 2016/125409
Disclosure of Invention
However, the film formed by the surface treatment composition disclosed in patent document 1 or patent document 2 has lubricity to oil, but has a problem that its performance gradually decreases in long-term use.
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a coating composition, a coating film, and an article, which are capable of forming a coating film having high lubricity to a deposit such as oil stain and capable of stably maintaining the performance for a long period of time.
The present invention has been made to solve the above-described problems, and as a result, it has been found that in a conventional coating film, fluorine oil in the coating film gradually evaporates and decreases with the passage of time, and that fine irregularities are generated on the surface of the film due to evaporation of the fluorine oil to degrade flatness, and that this is a cause of performance degradation. The present inventors have therefore studied various coating film components in order to suppress the evaporation of the fluorine oil, and as a result, have found that it is effective to blend the fluorine resin and the fluorine oil with the scale-like particles.
That is, the present invention is a coating film comprising: the coating film is characterized by comprising a fluorine oil, a fluororesin in an amount of 1% by mass or more and 100% by mass or less relative to the content of the fluorine oil, and scaly particles in an amount of 1% by mass or more and 50% by mass or less relative to the content of the fluorine oil, wherein the average particle diameter of the scaly particles is 1 μm or more and 100 μm or less.
In addition, the present invention is a coating composition comprising: the coating film is characterized by comprising a fluorine oil, a fluorine-based solvent, a fluororesin in an amount of 1% by mass or more and 100% by mass or less relative to the content of the fluorine oil, and scaly particles in an amount of 1% by mass or more and 50% by mass or less relative to the content of the fluorine oil, wherein the average particle diameter of the scaly particles is 1 μm or more and 100 μm or less.
The present invention is also an article, wherein the coating film is formed on a surface of a substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a coating film having excellent lubricity to a deposit such as oil stain and capable of stably maintaining the performance thereof for a long period of time, and a coating composition capable of forming the coating film.
Further, according to the present invention, an article in which adhesion of oil stains is suppressed can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing a coating film according to embodiment 1 of the present invention.
Fig. 2 is a diagram illustrating the movement of the adhering oil on the coating film according to embodiment 1 of the present invention.
Fig. 3 is a schematic cross-sectional view showing a coating film according to embodiment 2 of the present invention.
Fig. 4 is a diagram showing an example of an article on which a coating film according to embodiments 1 and 2 of the present invention is formed.
Fig. 5 is a diagram showing an example of an article on which a coating film according to embodiments 1 and 2 of the present invention is formed.
Fig. 6 is a graph showing the relationship between the amount of flaky particles contained and the oil-slipping property of the coating film with respect to the amount of fluorine oil contained.
Fig. 7 is a graph showing the relationship between the fluorine resin content relative to the fluorine oil content and the oil-slipping property of the coating film.
Detailed Description
< coating composition >
The coating composition of the present embodiment includes a fluorine oil, a fluorine-based solvent, a fluororesin, and scale-like particles.
The fluorine-containing oil contained in the coating composition of the present embodiment is a liquid that is not miscible with water, vegetable oil, and hydrocarbon oil, and if mixed with the fluorine-containing resin, it is not separated but mixed at a molecular level, and if the fluorine-containing solvent contained in the coating composition evaporates, a gel having no fluidity can be formed. The gel (gel-like) here is preferably in a state of no fluidity in which the fluororesin and the fluorine oil are homogeneously mixed at a molecular level, but may be in a state of slight phase separation. From the viewpoint of maintaining lubricity for oil for a long period of time, it is preferable to use a fluorine oil having a low evaporation rate. The evaporation rate here means a mass reduction rate in the case where the fluorine oil is applied to a flat plate to form a film thickness of several μm or so and then left at 100 ℃ for 24 hours. The fluorine oil having a low evaporation rate preferably has a mass reduction ratio of 30% or less, more preferably 3% or less. If the fluorine oil showing a mass reduction ratio of 30% or less is blended, the lubricity of the coating film against the oil can be maintained for a long period of time even in a high-temperature environment.
The kinematic viscosity of the fluorine oil is preferably 600cSt or less, more preferably 300cSt or less at a temperature at which the surface of the article forming the coating film is generally used, from the viewpoint of obtaining excellent lubricity against the deposit such as oil stain. If the fluorine oil having a kinematic viscosity of 600cSt or less is formulated, lubricity of the coating film against the oil can be sufficiently exerted. For example, in the case of a ventilation fan used at room temperature, since the surface on which a coating film is formed is at a temperature of about 20 ℃, a fluorine oil having a kinematic viscosity of 600cSt or less at 20 ℃ may be used. In general, in the case of a machine tool to which heat is applied from a motor, the temperature of the surface on which a coating film is formed is about 100 ℃, and therefore, a fluorine oil having a kinematic viscosity of 600cSt or less at 100 ℃ may be used. The kinematic viscosity of the fluorine oil herein is a viscosity obtained by arithmetically averaging 10 times of values measured by a capillary viscometer.
The fluorine oil is not limited, and examples thereof include polymer compounds composed of linear fluorinated carbons or branched fluorinated carbons such as perfluoropolyether (PFPE) and Polychlorotrifluoroethylene (PCTFE), and compounds obtained by introducing various substituent groups to these polymer compounds. Further, a carbon fluoride group may be introduced into a polymer compound of organosilicon or hydrocarbon.
The content of the fluorine oil is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, based on the coating composition. If the content of the fluorine oil is 0.1 mass% or more and 50 mass% or less, high oil-slipping property of the coating film is obtained, the fluidity of the coating composition becomes good, and the flaky particles are easily arranged in parallel with the surface of the coating film.
The fluorine-containing solvent contained in the coating composition of the present embodiment may be any solvent capable of dissolving the fluororesin such as perfluoroalkoxy resin (PFA), Polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), and examples thereof include Hydrofluoroether (HFE), fluorochlorohydrocarbon (HCFC), Hydrofluorocarbon (HFC), and a mixture thereof.
The content of the fluorine-based solvent is preferably 50% by mass or more and 99.9% by mass or less, and more preferably 90% by mass or more and 99% by mass or less, based on the coating composition. If the content of the fluorine-based solvent is not less than 50% by mass and not more than 99.9% by mass, the coating composition has good fluidity and the scale-like particles are easily arranged parallel to the surface of the coating film.
The fluororesin contained in the coating composition of the present embodiment is soluble in a fluorine-based solvent, and any fluororesin may be used as long as it can form a homogeneous coating film when coated, and examples thereof include perfluoroalkoxy resin (PFA), Polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene copolymer (ETFE), fluorinated ethylene propylene copolymer (FEP), ethylene chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene/perfluorodimethyldioxole copolymer (TFE/PDD), Polytetrafluoroethylene (PTFE), and materials obtained by introducing a functional group into these fluororesins. The introduced functional group may or may not have reactivity, but if a fluororesin having a reactive functional group introduced is used, the adhesion between the fluororesin and the scale-like particles and the adhesion between the fluororesin and the substrate are improved. Examples of the reactive functional group include a hydroxyl group, an epoxy group, a carbamate group, a carbonyl group, and an amino group. The same effect of improving the adhesion can be obtained by adding the crosslinking agent.
The content (as a solid content) of the fluororesin is not less than 1% by mass and not more than 100% by mass, preferably not less than 5% by mass and not more than 50% by mass, relative to the content of the fluorine oil. If the content of the fluororesin exceeds 100% by mass, not only the lubricity of the coating film against the oil is not obtained, but also the fluidity of the coating composition is lowered, and it becomes difficult to arrange the scale-like particles in parallel with the surface of the coating film. On the other hand, if the content of the fluororesin is less than 1% by mass, the strength of the coating film is insufficient, and the coating film is easily broken when the adhered matter such as oil stains is peeled off.
Further, the fluorine oil and the fluorine resin are preferably combined with each other so as to have high affinity and easily form a gel by mixing them. This makes it difficult to separate the fluororesin and the fluorine oil, and a more uniform coating film can be formed. The affinity between the fluororesin and the fluorinated oil can be determined by using as an index the contact angle of the fluorinated oil with respect to the film made of the fluororesin. It can be said that the smaller the contact angle, the higher the affinity between the two. Specifically, the contact angle of the fluorine oil with respect to the film composed of the fluorine resin is preferably 40 ° or less, more preferably 30 ° or less at the measurement temperature of 20 ℃.
The scale-like particles contained in the coating composition of the present embodiment function as a cap for suppressing evaporation of the fluorine oil in the formed coating film. The flaky particles may be in the form of thin plates, and examples thereof include oxides of Si, oxides of metals such as Al, Fe, Ti, and Mg, carbon materials such as metals and graphene, glass, materials obtained by coating a metal with a resin, and materials obtained by coating glass with a metal oxide. Specific examples of the oxide include silica, alumina, iron oxide, titanium oxide, and magnesium oxide. The scale-like particles are preferably in a coating composition in a non-agglomerated or weakly agglomerated state. If the scale-like particles are strongly aggregated in the coating composition, the effect of suppressing the evaporation of the fluorine oil is not easily obtained, and the flatness of the coating film surface is lowered, and the lubricity against the oil may be lowered. Further, if the coating composition contains fine particles in the form of needles or spheres, the fine particles are randomly arranged in the coating film without being oriented like scaly particles, and therefore, unevenness is formed on the surface of the coating film, and the lubricity to the oil is lowered. Further, the surface area of the coating film increases with the formation of the irregularities, and therefore, the evaporation of the fluoro oil is promoted.
The flaky particles have an average particle diameter (average major axis) of 1 μm or more and 100 μm or less, preferably 10 μm or more and 50 μm or less. If the average particle diameter of the scale-like particles is less than 1 μm, the effect of suppressing the evaporation of the fluorine oil is not obtained. On the other hand, if the average particle diameter of the scale-like particles exceeds 100 μm, the scale-like particles protrude from the mixed gel film of the fluororesin and the fluorine oil, and the flatness of the surface of the coating film is lowered, resulting in a decrease in the lubricity against the oil.
The average thickness of the flaky particles is preferably 0.1 μm or more and 1 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. If the average thickness of the scaly particles is 0.1 μm or more and 1 μm or less, the scaly particles are less likely to protrude from the film of the mixed gel of the fluorine oil and the fluorine resin, the surface of the coating film becomes flat, and the lubricity against the oil is improved. The average particle diameter of the above flaky particles is a particle diameter at which 50% of the volume accumulation of the particle size distribution is measured by a laser diffraction/scattering method. The particle diameter of the flaky particles is a value represented by the square root of the area S when the flaky particles are viewed in plan. The average thickness of the flaky particles is a value obtained by measuring the thicknesses of 50 flaky particles by a scanning electron microscope and arithmetically averaging the results.
The content of the flaky particles is not less than 1% by mass but not more than 50% by mass, preferably not less than 1% by mass but not more than 30% by mass, based on the content of the fluorine oil. If the content of the scale-like particles exceeds 50 mass%, the scale-like particles protrude from the mixed gel film of the fluororesin and the fluorine oil, and the flatness of the surface of the coating film is lowered, resulting in a decrease in the lubricity against the oil. On the other hand, if the content of the scale-like particles is less than 1 mass%, the effect of suppressing the evaporation of the fluorine oil is not obtained.
The solid content concentration in the coating composition, that is, the concentration of the fluororesin and the flaky particles, is preferably not more than 5% by mass, respectively. When the concentration of the fluororesin and the concentration of the scale-like particles are each 5% by mass or less, the coating composition has good fluidity and the scale-like particles are easily oriented on the surface of the coating film.
In the coating composition of the present embodiment, a surfactant may be added in order to more uniformly mix the fluororesin and the fluorine oil. In the coating composition of the present embodiment, an alcohol such as ethanol or isopropyl alcohol may be added in a range of 5 mass% or less. If the amount of the alcohol added is less than or equal to 5% by mass, the solubility of the fluororesin or the fluorine oil is hardly affected.
< preparation method of coating composition >
Next, a method for preparing the coating composition of the present embodiment will be described.
The method for preparing the coating composition is not particularly limited, but is preferably carried out by the following method.
Preferably, the fluorine-based solvent and the fluorine resin are mixed. The fluororesin to be mixed here may be a single resin or may be dissolved in another solvent. Thereafter, the flaky particles are added and dispersed in the liquid. The fluorine oil may be mixed at any stage. The scale-like particles can be dispersed by a known method such as stirring or ultrasonic vibration. When the scale-like particles are not easily dispersed in a liquid, it is preferable to perform a treatment by a wet type micronizing apparatus. In the wet type microparticulation apparatus, the liquid containing the scale-like particles is passed through the fine pores at a high pressure or is collided, and the scale-like particles in the liquid are forcibly dispersed by being impacted. The fluororesin present in the liquid adheres to the surfaces of the dispersed scale-like particles, and the scale-like particles are stabilized without being maintained in a dispersed state. The liquid after the dispersion treatment may have a reduced fluidity with the passage of time. In this case, the above-described dispersion treatment is performed again before the coating composition is applied, whereby the scale-like particles can be uniformly dispersed in the coating composition.
In the coating composition prepared as described above, the fluororesin and the fluorine oil are present in a dissolved state and are present in a state in which the scale-like particles are dispersed in the fluorine-based solvent.
< coating film >
Next, a coating film formed using the coating composition of the present embodiment will be described with reference to fig. 1. As shown in fig. 1, a coating film 2 using the coating composition of the present embodiment is formed on a substrate 1. The coating film 2 contains a fluorine oil, a fluororesin in an amount of 1% by mass or more and 100% by mass or less relative to the content of the fluorine oil, and scaly particles 3 in an amount of 1% by mass or more and 50% by mass or less relative to the content of the fluorine oil. The scale-like particles 3 have an average particle diameter of 1 μm or more and 100 μm or less, and are arranged in parallel to the surface of the coating film 2. Specifically, the top surface of the flaky particles 3 and the surface of the paint film 2 are arranged in parallel. The table top referred to herein is not an end surface but a largest flat portion of the flaky particles 3. The parallel state here includes not only a state in which all the scale-like particles 3 are arranged parallel to the surface of the paint film 2 but also a state in which they are slightly deviated from the parallel state (hereinafter, sometimes referred to as "substantially parallel").
Since the outermost surface of the coating film 2 is composed of a fluororesin and a fluorine oil having low surface energy, the coating film 2 has oil repellency, water repellency, surface smoothness, and stain resistance. In particular, fluorine oil is present on the outermost surface of the coating film 2, and therefore the outermost surface has a very soft property. Therefore, even if oil droplets or solid oil adheres to the paint film 2, the oil easily flows or is easily removed according to the softness of the outermost surface, as compared with a film made of only a fluororesin. For example, as shown in fig. 2, by applying a very small driving force such as gravity or wind pressure generated by an air flow to the adhering oil, the adhering oil 4 moves in the moving direction 5 on the surface of the paint film 2.
The substrate 1 on which the coating film 2 is formed is not particularly limited, and examples thereof include various instruments and daily necessities which require performance for preventing adhesion of oil stains and the like. The surface of the substrate 1 may be a flat surface or a curved surface, or may have an angle, an unevenness, or the like. When the surface of the substrate 1 has irregularities, the effect of flattening the surface of the substrate 1 by coating the surface with the paint film 2 is obtained. The arithmetic average roughness Ra of the surface of the base material 1 is preferably 2000 μm or less, more preferably 0.5 μm or more and 20 μm or less. Even if the coating film 2 is formed on the surface of the substrate 1 having Ra of more than 2000 μm, the adhered oil stains are easily accumulated in the surface depressions, and good oil lubricity may not be obtained. Examples of the material of the substrate 1 include general-purpose plastics such as polyethylene, polyurethane, polyester, Acrylonitrile Butadiene Styrene (ABS), polystyrene, polyvinyl chloride, and polyethylene terephthalate (PET), metals such as glass, stone, stainless steel, and aluminum, and materials obtained by applying an organic coating or an inorganic coating to the surface of these materials.
The coating film 2 may be formed by applying the coating composition to the surface of the substrate 1 and drying the coating composition as needed. In the coating composition of the present embodiment, the fluorine-based solvent, the fluororesin, and the fluorine oil are mixed at a molecular level, and the scaly particles 3 are dispersed in the liquid. Therefore, if the fluorine-based solvent is evaporated after the coating composition is applied, a film in which the scale-like particles 3 are arranged substantially parallel to the surface of the coating film 2 in the gel composed of the mixture of the fluororesin and the fluorine oil is obtained. Here, the coating method of the coating composition is not particularly limited, and examples thereof include dip coating, spin coating, flow coating, spray coating, roll coating, and the like. The drying method is not particularly limited as long as the fluorine-based solvent in the coating film can be evaporated, and the coating film may be dried at room temperature or dried by heating.
The flaky particles 3 contained in the coating composition are thin plate-like particles and have high orientation due to their shape. When the coating composition flows and spreads on the surface of the base material 1, the table surfaces of the scale-like particles 3 are aligned so as to be parallel to the surface of the coating film 2 by the force of the flow of the liquid, and finally, are arranged substantially parallel to the surface of the coating film 2. In addition, when the fluidity of the coating composition is small as in the case of coating by spray coating, the scale-like particles 3 are also oriented so as to be substantially parallel to the surface of the coating film 2 with a decrease in the thickness of the coating film when the fluorine-based solvent evaporates. If the top surface of the scaly particles 3 is arranged in a direction perpendicular to the surface of the base material 1, a convex portion is formed on the surface of the coating film, but in this case, a force acts in a direction in which the scaly particles 3 are flattened, that is, flattened by the surface tension of the liquid. The above-described action makes it easy to dispose the scale-like particles 3 near the surface of the paint film 2. In the present invention, since the loss of the fluorine oil from the surface of the coating film 2, which is an important role of the flaky particles 3, is suppressed, it is preferable to dispose the flaky particles 3 in the vicinity of the surface of the coating film 2.
In an environment where the fluorine oil is easily lost (for example, a high-temperature environment, a strong environment blown by wind, or the like), the flaky particles 3 are also arranged in a specific state in the coating film 2, and therefore the reduction of the fluorine oil is suppressed. Specifically, the scale-like particles 3 function as a cap in the coating film 2, and have an effect of lengthening the path until the fluorine oil contained in the coating film 2 moves to the outermost surface. The scale-like particles 3 serve to fix the shape of the gel composed of the fluororesin and the fluorine oil, and have an effect of preventing volume shrinkage caused by escape of the fluorine oil. By these effects, the decrease of the fluorine oil is suppressed. As a result, the flatness of the surface of the coating film 2 is maintained, and the high lubricity of the coating film 2 against oil can be maintained for a long period of time. The gel composed of the fluororesin and the fluorine oil is preferably in a state in which the fluororesin and the fluorine oil are homogeneously mixed and are mixed at a molecular level, but may be in a state in which they are slightly phase-separated. It is preferable that the maximum particle size of the fluorine oil single phase generated by the phase separation is not more than about 10 μm because the fluorine oil is not easily separated from the coating film 2 naturally.
The film thickness of the coating film 2 is preferably 0.3 μm or more and 50 μm or less, more preferably 0.5 μm or more and 8 μm or less as an average film thickness. If the film thickness of the coating film 2 is less than 0.3 μm, deterioration due to the decrease in the fluorine oil may be accelerated. On the other hand, if the film thickness of the paint film 2 exceeds 50 μm, the surface may be easily uneven due to volume shrinkage caused by evaporation of the fluorine-based solvent when the paint film 2 is formed.
In embodiment 2, a description will be given of a mode in which a coating film is multilayered by forming a lower layer between the coating film and the base material described in embodiment 1. As shown in fig. 3, a lower layer 6 is formed on a substrate 1, and a paint film 2 described in embodiment 1 is formed as an upper layer on the lower layer 6. The lower layer 6 is a non-flowable gel in which a fluorine oil and a fluorine resin in an amount of 1% by mass or more and 100% by mass or less relative to the content of the fluorine oil are mixed at a molecular level. In the multilayer coating film composed of the upper layer (coating film 2) and the lower layer 6, since the lower layer 6 does not contain the scale-like particles 3, the content of the fluorine oil in the lower layer 6 can be increased as compared with the upper layer, the orientation of the scale-like particles 3 can be improved by making the film thickness of the upper layer thin, or the content of the scale-like particles 3 in the upper layer can be increased, and therefore, the evaporation of the fluorine oil can be more effectively suppressed. As the fluorine oil and the fluorine resin constituting the lower layer 6, the same materials as those described in embodiment 1 can be used.
As a method for forming a multilayer coating film, first, a coating composition containing a fluorine oil, a fluorine-based solvent, and a fluorine resin in an amount of 1 mass% or more and 100 mass% or less, preferably 5 mass% or more and 50 mass% or less relative to the content of the fluorine oil and not containing the flaky particles 3 is applied to the surface of the substrate 1 and dried as necessary to form the lower layer 6, and then the coating composition described in embodiment 1 is applied to the lower layer 6 and dried as necessary to form the upper layer (coating film 2). The content of the fluorine oil and the fluorine-based solvent contained in the coating composition used for forming the lower layer 6 is the same as that in embodiment 1. The preparation method of the coating composition used for forming the lower layer 6 is the same as that of embodiment 1, except that the flaky particles 3 are not added. The coating method and the drying method of the coating composition used for forming the lower layer 6 are the same as those in embodiment 1.
In embodiment 3, an article to which the coating film described in embodiments 1 and 2 is applied will be described. Fig. 4 and 5 are views showing an example of an article in which the coating film according to embodiments 1 and 2 is formed on the surface of the base material.
Fig. 4 shows a spindle motor that is a part of a machine tool used for metal cutting or the like. The motor 7 is provided inside a cylindrical frame 8, and a plurality of air-cooling air passages 9 are provided in the frame 8. In order to cool the motor 7, the fan 10 provided at the upper portion of the frame 8 is operated, and the air is discharged from the fan cover 11 through the air-cooling duct 9.
During operation, oil mist of the cutting oil adheres to the air-cooling air passage 9, the fan 10, and the fan cover 11. Therefore, the paint films according to embodiments 1 and 2 are formed on the inner wall of the air-cooling air passage 9, the surface of the fan 10, and the surface of the fan cover 11, thereby preventing the adhesion of oil stains.
Fig. 5 is a ventilation fan for exhausting air in a kitchen or the like. The ventilation fan has a fan 10 and a fan cover 11 for protecting the fan 10. When cooking fumes or the like are exhausted, oil stains adhere to the fan 10 and the fan cover 11. Therefore, the paint films according to embodiments 1 and 2 are formed on the surface of the fan 10 and the surface of the fan cover 11, whereby adhesion of oil stains can be prevented.
[ examples ] A method for producing a compound
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these.
(example 1)
As shown in the components in table 1, perfluoropolyether (fuweilin (registered trademark) Y45, manufactured by suweisse polymer japan, kinematic viscosity 470cSt at 20 ℃), fluororesin coating liquid (Novec 1700, manufactured by 3M, solid concentration 2 mass%) as a fluororesin, and hydrofluoroether (Novec (registered trademark) 7200, manufactured by 3M) as a fluorine-based solvent were mixed, and after dissolving the fluororesin and the fluorine oil in the fluorine-based solvent, iron oxide particles (average particle size 12 μ M to 15 μ M, average thickness 0.2 μ M to 0.3 μ M, manufactured by titanium industries, ltd.) as scale-like particles were mixed, and the liquid was dispersed by a wet atomization apparatus (ナノヴェイタ (registered trademark), manufactured by yoda mechanical co) to prepare a coating composition of example 1. Further, the contact angle between the film made of fluororesin and the fluorine oil used herein was 26 °.
(examples 2, 3, 5, 7 and 8 and comparative examples 1 and 4)
Coating compositions of examples 2, 3, 5, 7 and 8 and comparative examples 1 and 4 were prepared in the same manner as in example 1 except that the components shown in Table 1 or 2 were changed.
(example 4)
A coating composition of example 4 was prepared in the same manner as in example 1 except that a fluororesin coating liquid (WOP-019 XQA, manufactured by Seika Screen printing Co., Ltd., solid content concentration 8% by mass) was used in place of the fluororesin coating liquid (Novec 1700, manufactured by 3M., solid content concentration 2% by mass) as the fluororesin, and the components shown in Table 1 were changed. Further, the contact angle between the film made of fluororesin and the fluorine oil used herein was 26 °.
(example 6)
A coating composition of example 6 was prepared in the same manner as in example 1 except that a fluororesin coating liquid (WOP-019 XQA, manufactured by Seika Screen printing Co., Ltd., solid content concentration 8% by mass) was used in place of the fluororesin coating liquid (Novec 1700, manufactured by 3M., solid content concentration 2% by mass) as the fluororesin, and the components shown in Table 1 were changed.
(example 9)
The coating composition of example 9 was prepared in the same manner as in example 1 except that graphene (product of ITEC., iGurafen (registered trademark) -alpha., average particle diameter of 10 to 100 μm, and average thickness of about 0.01 μm) was used in place of the iron oxide particles (product of titanium industries, Ltd., average particle diameter of 12 to 15 μm, and average thickness of 0.2 to 0.3 μm) as the scale-like particles.
(example 10)
The coating composition of example 10 was prepared in the same manner as in example 1, except that a low-viscosity perfluoropolyether (manufactured by suweifen polymer japan, flurbipalin (registered trademark) Y45, kinematic viscosity at 20 ℃ 470cSt) was used in place of the perfluoropolyether (manufactured by suweifen polymer japan, flurbipalin Y15, kinematic viscosity at 20 ℃ 156cSt) as the fluorine oil. Further, the contact angle between the film made of fluororesin and the fluorine oil used herein was 21 °.
(example 11)
The coating composition of example 11 was prepared in the same manner as in example 1 except that a low-viscosity perfluoropolyether (manufactured by suweifen polymer japan, flurbipalin (registered trademark) Y45, kinematic viscosity at 20 ℃ 470cSt) was used in place of the perfluoropolyether (manufactured by suweifen polymer japan, flurbipalin Y25, kinematic viscosity at 20 ℃ 250cSt) as the fluorine oil. Further, the contact angle between the film made of fluororesin and the fluorine oil used herein was 23 °.
(example 12)
A coating composition of example 12 was prepared in the same manner as in example 1, except that a crosslinkable heat-curable (reactive) type fluororesin coating liquid (3M, Novec2702, solid content 2 mass%) was used in place of the fluororesin coating liquid (3M, Novec1700, solid content 2 mass%).
Comparative example 2
A coating composition of comparative example 2 was prepared in the same manner as in example 1, except that the scaly particles were not added and the components shown in table 2 were changed.
(comparative example 3)
A coating composition of comparative example 3 was prepared in the same manner as in example 1, except that a fluororesin coating liquid (WOP-019 XQA, manufactured by Seika Screen printing Co., Ltd., solid content concentration 8% by mass) was used in place of the fluororesin coating liquid (Novec 1700, manufactured by 3M., solid content concentration 2% by mass) as the fluororesin, and the components shown in Table 2 were changed.
Comparative example 5
A coating composition of comparative example 5 was prepared in the same manner as in example 1, except that carbon black (Asahi carbon Co., Ltd., Asahi #52, average particle diameter 0.06 μm) was used in place of iron oxide particles (manufactured by titanium industries, Ltd., average particle diameter 12 μm to 15 μm, average thickness 0.2 μm to 0.3 μm) as scale-like particles.
Comparative example 6
A coating composition of comparative example 6 was prepared in the same manner as in example 1 except that a scaly glass flake (glass flake, hard material series 5150PS, average particle size 150 μm, average thickness 5 μm, manufactured by Songada industries, Ltd.) was used in place of iron oxide particles (iron oxide particles, manufactured by titanium industries, Ltd., average particle size 12 μm to 15 μm, average thickness 0.2 μm to 0.3 μm).
[ TABLE 1 ]
1 of
[ TABLE 2 ]
TABLE 2
After the coating composition of example 1 was applied to the surface of a glass plate by a bar coater, the coating composition was dried at 100 ℃ for 15 minutes to evaporate the fluorine-based solvent, thereby forming a translucent coating film. The formed paint film is such that the scale-like particles are arranged substantially parallel to the surface of the paint film as shown in fig. 1. Similarly, coating films were formed using the coating compositions of examples 2 to 12 and comparative examples 1 to 6, respectively. The components of the coating film obtained in the above manner are shown in table 3.
[ TABLE 3 ]
TABLE 3
< evaluation of oil-slipping Property of coating film >
The obtained coating films were evaluated for oil-slipping properties.
The oil-slipping property was evaluated by placing a glass plate provided with a coating film horizontally, dropping 10. mu.L of hexadecane by a micropipette, then gently tilting the glass plate, and measuring the tilt angle at which the droplets of hexadecane started to move as the roll-off angle. The roll off angle was measured immediately after the coating film was formed and after heating in an oven at 100 ℃ for 7 days. Heating in an oven at 100 ℃ for 7 days simulates the state after long-term use of the coating film.
The initial roll off angle indicates the ease of lubrication of the oil in the coating film, and the smaller the roll off angle, the higher the oil-slipping property, and the oil stain and other lubricity was judged to be excellent. The difference between the roll off angle at the initial stage and that after heating is an index of how much deterioration of the coating film is suppressed, and the smaller the value, the more deterioration of the coating film is determined to be suppressed.
Here, if the roll off angle is less than 50 °, the oil-slipping property is slightly high and the lubricity against oil is excellent, and if it is less than or equal to 30 °, the oil-slipping property is high and the lubricity against oil is judged to be particularly excellent. Further, if the difference between the roll off angle in the initial stage and that after heating is within 15 °, it is determined that the deterioration of the coating film with time is suppressed.
< case where the content of the flaky particles is changed with respect to the content of the fluorine oil >
The difference between the initial roll off angle and the initial roll off angle after heating of each coating film in the coating films of examples 1 to 3 and comparative examples 1 to 2 in which the content of the scale-like particles was changed with respect to the content of the fluorine oil is shown in tables 4 and 6.
[ TABLE 4 ]
TABLE 4
As shown in the graphs and graphs of table 4 and fig. 6, it is understood that the coating films of examples 1, 2, and 3 in which the content of the scale-like particles is 10 mass% to 40 mass% with respect to the content of the fluorine oil have a high oil-slipping property with a small roll-off angle of hexadecane of 25 ° or less. In the coating films of examples 1, 2 and 3, the difference between the roll-off angle at the initial stage and that after heating was within 15 °, the oil-slipping property was maintained, the oil-lubricating property of the coating film was maintained for a long period of time, and it was confirmed that the deterioration with time was suppressed.
On the other hand, in the coating film of comparative example 1 in which the content of the scale-like particles exceeds 50 mass% with respect to the content of the fluorine oil, since the flatness of the film surface was lowered, the roll-off angle was 50 °, and the oil-slip property was low. In the coating film of comparative example 2 containing no flaky particles, the initial roll-off angle was 15 °, whereas the roll-off angle after heating was 50 °, since evaporation of the fluorine oil was not suppressed by the flaky particles, the oil-slip property was greatly reduced. Therefore, the difference between the roll off angle at the initial stage and that after heating was 30 °, and it was found that if the coating film did not contain scale-like particles, the deterioration of the coating film with time could not be suppressed.
< case where the content of the fluororesin is changed with respect to the content of the fluorine oil >
The initial roll off angle and the difference between the initial roll off angle and the roll off angle after heating of the coating films of examples 1, 4 to 6 and comparative example 3, in which the content of the fluorine resin was changed with respect to the content of the fluorine oil, are shown in the graphs and graphs of table 5 and fig. 7.
[ TABLE 5 ]
TABLE 5
As shown in the graphs and graphs of table 5 and fig. 7, it was confirmed that in the coating films of examples 1 and 4 to 6 in which the content of the fluororesin was 5 to 90 mass% with respect to the content of the fluorine oil, the lower the content of the fluororesin with respect to the content of the fluorine oil, the higher the oil-slipping property was. In particular, it is found that the coating films of examples 1, 4 and 5 in which the content of the fluororesin is 5 to 50 mass% relative to the content of the fluorine oil exhibit high oil-slipping property and excellent oil-lubricating property. In addition, it was confirmed that the difference between the initial roll off angle and the roll off angle after heating was 10 ° in the coating films of examples 1 and 4 to 6, and the coating films were inhibited from deteriorating with time while maintaining high oil slip properties.
In contrast, the coating film of comparative example 3 in which the content of the fluororesin exceeds 100 mass% based on the content of the fluorine oil had low oil-slipping property because the flatness of the film surface was lowered
< case where the fluorine oil content in the coating film was changed >
The coating films of examples 1, 7 and 8 and comparative example 4 in which the content of the fluorine oil in the coating film was changed were shown in table 6 for the difference between the initial roll off angle and the initial roll off angle after heating.
[ TABLE 6 ]
TABLE 6
The coating films of examples 7 and 8 showed high oil-slipping properties and the effect of suppressing the deterioration of the coating film with time by suppressing the evaporation of the fluorine oil, as in example 1. Further, if the coating films of examples 7 and 8 were compared, it was confirmed that the roll off angle was small both at the initial stage and after heating in example 7 in which the content of the fluorine oil in the coating film was large, and that the oil-slipping property was high.
In contrast, the coating film of comparative example 4 suggests that the amount of the fluorine oil is small relative to the amount of the fluorine resin and the scale-like particles, and therefore the fluorine oil is less likely to bleed out to the surface of the coating film, and the oil-slipping property is reduced.
< cases where the types and sizes of the flaky particles were changed >
The difference between the initial roll-off angle and the initial and post-heating roll-off angles of the coating films obtained in the case where the types of flaky particles were changed (example 9), the case where particles other than flaky particles were used (comparative example 5), and the case where flaky particles having an excessively large average particle diameter were used (comparative example 6) are shown in table 7.
[ TABLE 7 ]
TABLE 7
As shown in table 7, in example 9, the raw material was different from that of the scale-like particles of example 1, but since the same flake-shaped graphene was used, the same oil-slipping property as in example 1 was obtained, and the effect of suppressing the deterioration of the coating film with time by suppressing the evaporation of the fluorine oil was obtained.
On the other hand, it can be confirmed that in comparative example 5, since a paint film containing particles other than scale-like particles, for example, is formed, the flatness of the surface of the paint film is lowered. Therefore, the initial roll off angle was larger than that of the coating film of example 1, and the oil-slip property was low. Further, since the effect of suppressing evaporation of the fluorine oil is small, the oil-slipping property after heating is further reduced.
In comparative example 6, since a coating film containing scale-like particles having an excessively large average particle diameter was formed, the roll-off angle was large and the oil-slip property was low because irregularities were present on the surface of the film at the initial stage, as in the coating film of comparative example 5. And it was confirmed that the effect of suppressing the deterioration of the coating film with time was small.
< case where kinematic viscosity of fluorine oil is changed >
The coating films of examples 1, 10 and 11 in which the kinematic viscosity of the fluorine oil at 20 ℃ was changed were each characterized by having a roll off angle in the initial stage and a difference between the roll off angle in the initial stage and that after heating shown in table 8.
[ TABLE 8 ]
TABLE 8
As shown in Table 8, if the kinematic viscosity of the fluorine oil at 20 ℃ is 600cSt or less, the roll off angle of the coating film is small and the oil-slipping property is improved. In the coating films of examples 10 and 11, low-viscosity fluorine oil was used. It was confirmed that the oil-slipping property of the surface of the coating film becomes higher when the fluorine oil is low in viscosity.
< case where the kind of the fluororesin is changed >
The coating films of examples 1 and 12, in which the type of the fluororesin was changed, were each provided with a difference in initial roll-off angle and initial and post-heating roll-off angles as shown in table 9.
[ TABLE 9 ]
TABLE 9
As shown in table 9, it was confirmed that the coating film of example 12 using the crosslinkable fluororesin exhibited high oil-slipping properties similar to those of example 1 and the effect of suppressing the deterioration of the coating film with time by suppressing the evaporation of the fluorine oil.
< case where the membrane is different in structure >
Comparative example 7
In comparative example 7, a coating film having a different film structure was used, and the oil-slipping property and the like were compared, the coating film being substantially the same as that of example 1. Specifically, a coating film in which scale-like particles are randomly layered and a fluororesin and a fluorine oil are separated is formed. In this coating film, scale-like particles (iron oxide particles, manufactured by titanium industries, Ltd., average particle diameter of 12 μ M to 15 μ M, average thickness of 0.2 μ M to 0.3 μ M) were coated with a fluororesin (manufactured by 3M, Novec1700, solid content concentration of 2 mass%), and a fluorine oil (manufactured by Suweiter Polymer Japan, Flurbine Y45, kinematic viscosity at 20 ℃ of 470cSt) was filled in the gaps between the scale-like particles.
As a difference in film structure, table tops of the scale-like particles were arranged parallel to the paint film surface in example 1, whereas the scale-like particles were randomly layered in comparative example 7. In contrast to example 1, which is a non-flowable gel in which a fluorine oil and a fluorine resin were mixed at a molecular level, comparative example 7 shows a gel in which the fluorine resin and the fluorine oil were in contact with each other but were not mixed.
In comparative example 7, the oil-slipping property was low at the initial stage because of the presence of irregularities on the film surface. Also, in comparative example 7, the surface area of the film was large due to the unevenness and the fluorine oil was in a monomer state, so the fluorine oil was easily evaporated. Therefore, after heating at 100 ℃ for 7 days, the fluorine oil decreased and the oil-slipping property decreased.
(example 13)
With respect to the coating composition of example 1, the oil-slipping property was evaluated by changing the base material on which the coating film was formed and the coating method. The results are shown in Table 10.
[ TABLE 10 ]
As shown in table 10, it was confirmed that the same oil-slipping property and the same effect of suppressing the deterioration of the coating film with time as in example 1 were obtained even when the coating film formation method was dip-coating and the base material was an aluminum plate. This suggests that the coating film of the present invention can maintain excellent lubricity against oil for a long period of time regardless of the substrate and the coating method.
(example 14)
The multilayer coating film described in embodiment 2 was evaluated for oil-slipping properties.
Specifically, the coating composition of comparative example 2 containing no scaly particles was applied to the surface of a glass plate by the same method as in example 1 and dried to form a lower layer, and then the coating composition of example 1 was applied to the surface of the lower layer and dried to form a coating film as an upper layer in which the scaly particles were arranged substantially parallel to the surface of the film.
The obtained multilayer coating film was evaluated for oil-slipping property, and as a result, the initial roll-off angle was 20 °, and high oil-slipping property was confirmed. The roll off angle after heating was 25 °, the difference between the initial roll off angle and the roll off angle after heating was 5 °, and it was confirmed that the coating film was inhibited from deterioration with time. It is found that the evaporation suppressing effect by the scale-like particles in the coating film formed on the lower layer is effective, and therefore higher stability over time is obtained.
(example 15)
The coating composition prepared in the same manner as in example 1 was applied to the inner wall of the air-cooling air passage 9 of the frame 8 of the machine tool component shown in fig. 4, and then dried to form a coating film. The coating composition is applied by moving a sponge containing the coating composition while being attached to the inner wall of the air-cooling air duct 9. A frame 8 was set so that the air-cooling air duct 9 was perpendicular to the floor surface, and 10 μ L of a 20-fold diluted water-soluble cutting oil (manufactured by synechooil co., ltd. "マルチクー ル" (registered trademark) CSF-9000) was dropped onto the inner wall of the air-cooling air duct 9 by a micropipette, and as a result, the cutting oil slipped off without spreading on the surface. Accordingly, it was confirmed that the machine tool component on which the coating film of the present invention was formed had excellent lubricity against oil.
(example 16)
The surface of the ventilator fan 10 shown in fig. 5 was coated with the coating composition prepared in the same manner as in example 1, and then dried, thereby forming a coating film. The coating composition is applied by immersing the fan 10 in the coating composition. When the fan was rotated by dropping 10. mu.L of edible salad oil onto the surface of the fan 10, the salad oil slipped over the surface without spreading, and was removed from the surface in a scattered form. This confirmed that the ventilation fan having the coating film of the present invention formed thereon had excellent lubricity to oil.
Description of the reference numerals
1 substrate, 2 paint film, 3 flaky particles, 4 attached oil, 5 attached oil moving direction, 6 lower layer, 7 motor, 8 frame, 9 air cooling air path, 10 fan, 11 fan cover.
Claims (9)
1. A coating film, comprising: a fluorine oil, a fluororesin in an amount of 1 mass% or more and 100 mass% or less relative to the content of the fluorine oil, and scale-like particles in an amount of 1 mass% or more and 50 mass% or less relative to the content of the fluorine oil,
the coating film is characterized in that it is,
the flaky particles have an average particle diameter of 1 μm or more and 100 μm or less.
2. The coating film according to claim 1,
in the paint film, the mixture of the fluorine oil and the fluorine resin is in a gel state.
3. The coating film according to claim 1 or 2,
the scale-like particles are arranged parallel to the surface of the coating film.
4. The coating film according to any one of claims 1 to 3,
the fluororesin and the fluorine oil are selected from a combination in which a contact angle of the fluorine oil with respect to a film composed of the fluororesin becomes 40 ° or less at a measurement temperature of 20 ℃.
5. The coating film according to any one of claims 1 to 4,
the coating film has a film thickness of 0.3 μm or more and 50 μm or less.
6. A coating composition comprising: a fluorine oil, a fluorine-based solvent, a fluorine resin in an amount of 1% by mass or more and 100% by mass or less relative to the content of the fluorine oil, and scale-like particles in an amount of 1% by mass or more and 50% by mass or less relative to the content of the fluorine oil,
the coating film is characterized in that it is,
the flaky particles have an average particle diameter of 1 μm or more and 100 μm or less.
7. The coating composition of claim 6,
the fluororesin and the fluorine oil are selected from a combination in which a contact angle of the fluorine oil with respect to a film composed of the fluororesin becomes 40 ° or less at a measurement temperature of 20 ℃.
8. An article of manufacture characterized in that it comprises, in combination,
the coating film according to any one of claims 1 to 5 is formed on the surface of a substrate.
9. The article of claim 8,
a gel-like lower layer is formed between the paint film and the base material, the lower layer being composed of a mixture of a fluorine oil and a fluorine resin in an amount of 1 mass% or more and 100 mass% or less relative to the content of the fluorine oil.
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| PCT/JP2017/042004 WO2018220883A1 (en) | 2017-06-02 | 2017-11-22 | Coating film, coating composition, and article provided with said coating film |
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