WO2022054607A1 - Coating composition, coating film, and laminate - Google Patents

Abstract

The purpose of the present disclosure is to provide a coating composition that makes it possible to form a coating film that has high-level long-term abrasion and adhesion resistance. The purpose of the present disclosure is also to provide a coating film that is obtained from the coating composition and has high-level long-term abrasion and adhesion resistance. A coating composition that includes a fluorine resin and inorganic particles. The inorganic particles have a new Mohs hardness of at least 10, an average circularity of 0.90–1.00, an average particle diameter of 1–40 μm, and a particle size distribution that has a half-width of at least 21 μm or is multi-peak.

Description

Paint composition, coating film and laminate

The present disclosure relates to coating compositions, coatings and laminates.

In cooking utensils such as frying pans, hot plates, pots, and inner pots of rice cookers, it is common practice to provide a coating film formed of fluororesin on a metal base material.

Patent Document 1 discloses that the coating film contains an inorganic powder.
Patent Document 2 discloses that particles having a true spherical shape are used as an inorganic filler.

Japanese Unexamined Patent Publication No. 2000-238205 International Publication 2016/133010

It is an object of the present disclosure to provide a coating composition capable of forming a coating film having both wear resistance and non-adhesiveness at a high level for a long period of time.
Further, it is an object of the present invention to provide a coating film having both wear resistance and non-adhesiveness obtained by the coating composition at a high level for a long period of time.

This disclosure is
A coating composition containing a fluororesin and inorganic particles.
The inorganic particles are
The new Mohs hardness is 10 or more,
The average circularity is 0.90 to 1.00,
The average particle size is 1-40 μm.
It is a coating composition characterized in that the half width of the particle size distribution is 21 μm or more or multi-peak.

The fluororesin is composed of only polytetrafluoroethylene or a fluororesin other than polytetrafluoroethylene and polytetrafluoroethylene, and is polytetrafluoro relative to the total of polytetrafluoroethylene and fluororesin other than polytetrafluoroethylene. It is preferable that the amount of ethylene is 20% by mass or more and the fluororesin is contained in an amount of 30.0 to 99.0% by mass based on the total amount of solid matter in the coating composition.

The coating composition preferably contains 1 to 50% by mass of inorganic particles with respect to the fluororesin.
The inorganic particles are preferably at least one selected from the group consisting of alumina particles and silicon carbide particles.

The present disclosure is also a coating film, characterized in that it is obtained from the coating composition described above.
The present disclosure is a coating film formed on a substrate and composed of three layers of a primer coating film (1), a middle coat coating film (2) and a top coat coating film (3).
The middle coat coating film (2) is also a coating film characterized by being a layer formed by any of the coating compositions according to claims 1 to 4.
The present disclosure is also a laminate characterized by comprising a base material and the above-mentioned coating film.

According to the present disclosure, it is possible to provide a coating film having both wear resistance and non-adhesiveness at a high level for a long period of time.

It is a figure which shows the particle size distribution of the inorganic particle used in an Example.

Hereinafter, the present disclosure will be described in detail.
The coating composition of the present disclosure is used as inorganic particles.
(A) New Mohs hardness is 10 or more (b) Average circularity is 0.90 to 1.00
(C) Average particle size is 1-40 μm
(D) The one having a feature that the half width of the particle size distribution is 21 μm or more or multi-peak is used.

The coating film containing the fluororesin and the inorganic particles obtains non-adhesiveness and abrasion resistance by exhibiting non-adhesiveness due to the fluororesin and abrasion resistance due to the inorganic particles, respectively. That is, since the fluororesin does not have sufficient wear resistance when used alone, wear resistance is obtained by blending an inorganic powder. In this case, inorganic particles having a new Mohs hardness of 10 or more are used.

However, the fluororesin gradually peels off after long-term use. Then, as the fluororesin is peeled off, the inorganic particles also fall off from the coating film. When the inorganic particles fall off, this greatly reduces the wear resistance, and then the coating film performance sharply deteriorates. As a result, the function during long-term use will deteriorate.

When spherical particles are used as such particles, a preferable effect can be obtained in terms of improving wear resistance.
In this case, in order to improve the wear resistance, it is preferable to add inorganic particles having a large particle size in a high proportion. However, when the wear resistance is improved in this way, the non-adhesiveness is deteriorated, so that it is very difficult to achieve both the wear resistance and the non-adhesiveness.
Furthermore, when spherical particles are used, if the particle size is within a narrow range and the particles have almost the same particle size and shape, many particles will be exfoliated at the same time when the exfoliation progresses to a specific thickness. At that stage, the physical properties of the coating film deteriorate sharply. Further, the particles are exposed on the surface due to the wear of the resin, so that the non-adhesiveness is lowered. Such a property tends to be more remarkable when an inorganic powder having a large particle size and a sharp particle size distribution is blended.

In the present disclosure, from this point of view, by setting the particle size distribution of the inorganic powder to be wide and the particle size to be low, both wear resistance and non-adhesiveness can be achieved for a long period of time. It was found to be a thing. That is, the presence of the inorganic powders having various particle sizes shifts the timing of the peeling of the inorganic particles. As a result, the timing at which the wear resistance performance suddenly drops significantly does not occur, and the function can be maintained for a long period of time.

Hereinafter, each performance of (a) to (b) possessed by the inorganic particles will be described in detail.
(A) New Mohs hardness The Mohs hardness is an evaluation of the relative hardness of a substance in the range of 1 to 10, but the new Mohs hardness further evaluates the hardness in 15 stages with respect to the 10 stages of the Mohs hardness. It is a fine classification.
The inorganic particles having a new Mohs hardness of 10 or more are not particularly limited, and for example, diamond, fluorinated diamond, boron carbide, silicon carbide, aluminum oxide (including ruby and sapphire), chrysoberyl, garnet, molten zirconia and the like. Particles are mentioned. Since the coating composition of the present disclosure is required to obtain abrasion resistance, these highly hard inorganic particles are blended.

(B) Average circularity The average circularity is 0.90 to 1.00.
Those having such a value are powders having a shape close to a true sphere. When the coating composition contains inorganic particles that are substantially spherical, a coating film having excellent wear resistance can be obtained. The inorganic particles do not include the inorganic particles as they are crushed, but include the inorganic particles spheroidized after being crushed.
From the viewpoint of wear resistance, the inorganic particles are preferably particles having substantially no corners. The shape of the inorganic particles is preferably a true sphere, an elliptical sphere, a polyhedron with rounded corners, or a polyhedron having a circularity close to 1.

The average circularity can be measured by an image processing program using, for example, a flow type particle image analyzer.
The inorganic particles have an average circularity of 0.90 or more when viewed from an arbitrary angle. The average circularity is more preferably 0.91 or more, further preferably 0.93 or more, particularly preferably 0.95 or more, and preferably 1.00 or less.

(C) Average particle size The inorganic particles preferably have an average particle size of 1 to 40 μm. It is more preferably 10 μm or more, and when used for a coating film of 20 μm or less, it is more preferably 30 μm or less from the viewpoint of surface smoothness.
The average particle size can be measured by, for example, a laser diffraction / scattering type particle size distribution measuring device manufactured by Nikkiso Co., Ltd. The average particle size in the present disclosure means the mode diameter, that is, the particle size of the peak top in the particle size distribution. Since the particle size distribution obtained by this method is based on the volume standard, it is also measured from the measurement result of the particle size distribution in the present disclosure.
The parameters are based on volume-based distribution. In the case of multi-peak, the average particle size of a plurality of existing peak tops is taken as the average particle size.

(D) The half-value width of the particle size distribution is 21 μm or more or the half-value width of the multi-peak particle size distribution is 21 μm or more or multi-peak. The particle size distribution is a value measured by the laser diffraction / scattering type particle size distribution measuring device manufactured by Nikkiso Co., Ltd.

The half width is more preferably 23 μm or more, and further preferably 27 μm or more.
Further, multi-peak means having two or more peaks in the particle size distribution. The positions of these plurality of peaks are not particularly limited, but it is more preferable that the difference in particle size between the peaks is 5 μm or more. In the case of multi-peak, the full width at half maximum is the sum of the full width at half maximum of each peak. Based on such a definition, in the case of multi-peak, it is preferable that the full width at half maximum is 21 μm or more at the same time. Further, when the difference between the particle sizes of the two peaks is less than 5 μm, these are regarded as a single peak and the half width is calculated, and it is preferable that the half width is 21 μm or more.

Inorganic particles having a particle size distribution that satisfies such (c) and (d) are not particularly limited in their production method.
Commercially available inorganic powder having the above particle size distribution may be used, or inorganic particles having such a particle size distribution may be produced by a known production method and used. Further, various inorganic particles obtained by commercially available or known production methods may be mixed and used having different particle sizes. Further, an inorganic powder having a specific particle size may be produced by sieving and appropriately mixed to obtain an inorganic powder satisfying the above-mentioned (c) and (d).

From the viewpoint of wear resistance, the inorganic particles are preferably at least one selected from the group consisting of alumina particles and silicon carbide particles. The inorganic particles are more preferably silicon carbide particles because the resulting coating film has higher wear resistance.
Examples of the alumina include those having an amorphous form and those having a crystalline form, for example, γ-alumina having a main crystal phase of γ phase, crystalline alumina such as α-alumina having a main crystal phase of α phase, and the like. May be.

The above-mentioned substantially spherical alumina particles can be produced by, for example, a known method such as a thermal spraying spheroidizing method.

It can also be manufactured by the following method or the like.
By simultaneously adding the aqueous solution and the aqueous solution of the neutralizing agent to the aqueous solution in which the carboxylic acid compound is dispersed or dissolved, fine particles of the hydroxide or hydrate of the above metal are formed, and the obtained fine particles are fired. (For example, Japanese Patent Application Laid-Open No. 5-139704), aluminum alkoxide is brought into contact with water in the presence of alcohol and a bipolar aproton solvent, and hydrolyzed without forming an emulsion to obtain aluminum hydroxide. (For example, Japanese Patent Application Laid-Open No. 8-198622), a flammable liquid containing an aluminum-containing compound is sprayed into droplets and burned to convert the aluminum-containing compound into alumina, and the aluminum-containing compound is converted into alumina. A method for spheroidizing (for example, JP-A-11-147711), aluminum hydroxide having a dehydration temperature of 450 ° C. or higher and a purity of 99.9% by mass or higher is placed in a chlorine atmosphere in a temperature range of 800 ° C. or higher and 1200 ° C. or lower. A method for obtaining α-alumina particles by firing in (for example, Japanese Patent Application Laid-Open No. 2001-302236), a known agent conventionally known as an alumina mineralizing agent or a crystal growth agent, such as a halogen compound and a boron compound. A method of adding a small amount to a pulverized product of fused alumina or sintered alumina and heat-treating at a temperature of 1000 ° C to 1550 ° C (for example, Japanese Patent Application Laid-Open No. 5-294613), a slurry of aluminum hydroxide powder or aluminum hydroxide powder is prepared. A method of spraying into a flame and collecting the obtained fine powder at a high temperature of 500 ° C. or higher (for example, JP-A-2001-19425, JP-A-2001-226117), alumina or aluminum hydroxide powder. A method of forming molten droplets by passing a region having a high temperature of 2000 ° C. or higher over a distance of 10 cm or more, and cooling and solidifying the molten droplets during the fall using a free-fall method to form a spherical shape (for example, JP-A-2005-). No. 179109).
The above-mentioned substantially spherical silicon carbide particles can be produced by, for example, a known method such as a sprayed spherulite method.

Further, a step of spray-drying a slurry of raw material silicon carbide having an average particle size of 1 μm or less and which is an α-type crystal to obtain porous and spherical particles, and a step of sintering the obtained porous and spherical particles. (For example, Japanese Patent Application Laid-Open No. 2013-095637) can also be produced.

From the viewpoint of abrasion resistance, the coating composition preferably contains 1 to 40% by mass of the inorganic particles with respect to the fluororesin. The content of the inorganic particles is more preferably 3% by mass or more, and more preferably 30% by mass or less.

The coating composition of the present disclosure contains a fluororesin.
Examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene (TFE) / perfluoro (alkyl vinyl ether) (PAVE) copolymer (PFA), and TFE / hexafluoropropylene (HFP) copolymer (FEP). ), Ethethylene (Et) / TFE copolymer (ETFE), Et / TFE / HFP copolymer, polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene (CTFE) / TFE copolymer, Et / CTFE At least one selected from the group consisting of the polymer and polyvinylidene fluoride (PVDF) is preferable, and at least one selected from the group consisting of PTFE, PFA and FEP is more preferable.

As the fluororesin, PTFE is particularly preferable because it can form a coating film having excellent wear resistance.

The PTFE is preferably non-melt processable. The non-melt processability means a property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.

The standard specific density [SSG] of the PTFE is preferably 2.13 to 2.23, and more preferably 2.13 to 2.19, because it is more excellent in wear resistance. The SSG is an SSG defined in ASTM D4895-89 as an index of the molecular weight of polytetrafluoroethylene having no melt molding processability.

The melting point of the PTFE is preferably 325 to 347 ° C. The melting point is a value measured by setting the temperature rise rate of differential scanning calorimetry (DSC) at 10 ° C./min.

The above-mentioned PTFE may be a TFE homopolymer consisting only of tetrafluoroethylene [TFE], or may be a modified PTFE composed of TFE and a modified monomer. The modified monomer is not particularly limited as long as it can be copolymerized with TFE, and is, for example, a perfluoroolefin such as hexafluoropropylene [HFP]; a chlorofluoroolefin such as chlorotrifluoroethylene [CTFE]; Hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perfluorovinyl ether; perfluoroalkylethylene: ethylene and the like can be mentioned. Further, the modified monomer used may be one kind or a plurality of kinds.

The perfluorovinyl ether is not particularly limited, and for example, the following general formula (1)
CF ₂ = CF-ORf (1)
(In the formula, Rf represents a perfluoroorganic group.) Examples thereof include perfluorounsaturated compounds represented by. In the present specification, the above-mentioned "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoroorganic group may have ether oxygen.

Examples of the perfluorovinyl ether include perfluoro (alkyl vinyl ether) [PAVE] in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms in the above general formula (1). The number of carbon atoms of the perfluoroalkyl group is preferably 1 to 5.

Examples of the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, and the like. Purple olo (propyl vinyl ether) [PPVE], the group of which is a perfluoropropyl group, is preferable.

Further, as the perfluorovinyl ether, in the above general formula (1), Rf is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is the following formula:

(In the formula, m represents 0 or an integer of 1 to 4), and Rf is the following formula:

(In the formula, n represents an integer of 1 to 4), and the like is a group represented by.

The perfluoroalkylethylene is not particularly limited, and examples thereof include (perfluorobutyl) ethylene (PFBE) and (perfluorohexyl) ethylene.

The modified monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PPVE, PFBE and ethylene. More preferably, it is at least one selected from the group consisting of HFP and CTFE.

In the modified PTFE, the modified monomer unit is preferably 1% by mass or less, more preferably 0.001 to 1% by mass, based on the total monomer units. In the present specification, the modified monomer unit means a part of the molecular structure of the modified PTFE and derived from the modified monomer, and the total monomer unit means all the single amounts in the molecular structure of the modified PTFE. It means the part derived from the body.

From the viewpoint of non-adhesiveness, the coating composition preferably contains 30.0 to 99.0% by mass of the fluororesin. The content of the fluororesin is more preferably 40.0% by mass or more, and more preferably 97.0% by mass or less.

The coating composition may further contain a fluororesin other than the PTFE in addition to the PTFE. The fluororesin other than the above-mentioned PTFE is not particularly limited, and for example, TFE / PAVE copolymer (PFA), TFE / HFP copolymer (FEP), ethylene (Et) / TFE copolymer (ETFE), Et / Examples thereof include TFE / HFP copolymers, polychlorotrifluoroethylene (PCTFE), CTFE / TFE copolymers, Et / CTFE copolymers, polyvinylidene fluoride (PVDF) and the like.

Fluororesin other than PTFE is preferably melt processable. Melt processability means that it is possible to melt and process a polymer using conventional processing equipment such as an extruder and an injection molding machine. Therefore, the fluororesin usually has a melt flow rate (MFR) of 0.01 to 100 g / 10 minutes.

The above MFR is measured according to ASTM D1238 using a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) at a measurement temperature determined by the type of fluororesin (for example, 372 ° C in the case of PFA or FEP, and 372 ° C in the case of ETFE). 297 ° C.), a value obtained as the mass (g / 10 minutes) of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes under a load (for example, 5 kg in the case of PFA, FEP and ETFE).

The fluororesin other than PTFE preferably has a melting point of less than 150 to 322 ° C, more preferably 200 to 320 ° C, and even more preferably 240 to 320 ° C. The melting point is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].

The coating composition preferably contains only the above-mentioned PTFE as the fluororesin, or contains the above-mentioned PTFE and a fluororesin other than the above-mentioned PTFE.

In the coating composition, the amount of the PTFE is preferably 1% by mass or more, more preferably 20% by mass or more, and more preferably 40% by mass or more, based on the total of the PTFE and the fluororesins other than the PTFE. More preferably, 70% or more is particularly preferable, and the upper limit may be 100% by mass.

When the coating composition contains the above-mentioned PTFE and a fluororesin other than the above-mentioned PTFE, the mass ratio of the above-mentioned PTFE to the above-mentioned fluororesin other than the above-mentioned PTFE is preferably 1/99 to 99/1, and 10/90 to It is more preferably 99/1, and even more preferably 20/80 to 99/1. If the amount of PTFE is too small, the wear resistance of the coating film may not be sufficient.

The mass of the PTFE contained in the coating composition can be calculated by a known analytical method such as infrared spectroscopy or thermal weight-differential thermal analysis (TG-DTA).
The coating composition may contain a heat-resistant resin. The heat-resistant resin may be any resin that is generally recognized as having heat resistance, and a resin having a continuous usable temperature of 150 ° C. or higher is preferable. However, the above-mentioned fluororesin is excluded from the above-mentioned heat-resistant resin.

The heat-resistant resin is not particularly limited, but is at least one selected from the group consisting of, for example, polyamideimide resin, polyimide resin, polyallyl ether sulfone resin, polyetherimide resin, aromatic polyester resin and polyallylensulfide resin. It is preferably a seed resin.

The above-mentioned polyamide-imide resin [PAI] is a resin composed of a polymer having an amide bond and an imide bond in its molecular structure. The PAI is not particularly limited, and for example, a reaction between an aromatic diamine having an amide bond in the molecule and an aromatic tetravalent carboxylic acid such as pyromellitic acid; and an aromatic trivalent carboxylic acid such as trimellitic anhydride. Reaction with diisocyanate such as 4,4-diaminophenyl ether or the like or diisocyanate such as diphenylmethane diisocyanate; Examples include resin. The PAI is preferably a polymer having an aromatic ring in the main chain because of its excellent heat resistance.

The polyimide resin [PI] is a resin made of a polymer having an imide bond in its molecular structure. The PI is not particularly limited, and examples thereof include a resin made of a high molecular weight polymer obtained by a reaction of an aromatic tetravalent carboxylic acid anhydride such as pyromellitic anhydride. The PI is preferably a polymer having an aromatic ring in the main chain because of its excellent heat resistance.

The above-mentioned polyether sulfone resin [PES] has the following general formula.

It is a resin made of a polymer having a repeating unit represented by. The PES is not particularly limited, and examples thereof include a resin made of a polymer obtained by polycondensation of dichlorodiphenyl sulfone and bisphenol.

The heat-resistant resin has excellent adhesion to a base material, has sufficient heat resistance even under the temperature at the time of baking when forming a cooking utensil, and the obtained cooking utensil has excellent corrosion resistance. It is preferably at least one resin selected from the group consisting of PI and PES. Each of PAI, PI and PES may be composed of one kind or two or more kinds.

The heat-resistant resin is more preferably at least one resin selected from the group consisting of PAI and PI from the viewpoint of excellent adhesion to the substrate and heat resistance.

The heat-resistant resin is preferably composed of PES and at least one resin selected from the group consisting of PAI and PI from the viewpoint of excellent corrosion resistance. That is, the heat-resistant resin may be a mixture of PES and PAI, a mixture of PES and PI, or a mixture of PES, PAI and PI. The heat-resistant resin is particularly preferably a mixture of PES and PAI.
The coating composition can be prepared by a usual mixing method such as mixing the fluororesin, the inorganic particles and the like with a mixer and a roll mill.

The coating composition contains the inorganic particles having a new Mohs hardness of 10 or more and substantially spherical, but may further contain inorganic particles having a new Mohs hardness of less than 10. .. Inorganic particles having a new Mohs hardness of less than 10 do not affect the wear resistance, and may be substantially spherical or not substantially spherical.

Inorganic particles with a new Mohs hardness of less than 10 include glass, mica, carbon black, clay, talc, tourmaline, jade, germanium, barium sulfate, calcium carbonate, silica stone, topaz, beryl, quartz, titanium oxide, iron oxide, etc. Coloring agents, potassium titanate and the like can be mentioned.

The coating composition may be liquid or powder, but is preferably liquid. When the coating composition is liquid, a smooth coating film can be obtained, and the inorganic particles are uniformly distributed on the surface of the coating film, so that the expected wear resistance effect can be obtained. ..

The coating composition may contain a liquid medium such as water and / or an organic liquid, and preferably contains water. In that case, the coating composition may have a solid content concentration of 10 to 80% by mass. The above-mentioned "organic liquid" means an organic compound which is a liquid at a room temperature of about 20 ° C.

The coating composition preferably contains a surfactant in order to form a smoother coating film. As the surfactant, conventionally known ones can be used.

The coating composition may further contain additives. The additive is not particularly limited, and is not particularly limited, for example, a leveling agent, a solid lubricant, an antistatic agent, a water absorber, a surface conditioner, a thixotropy-imparting agent, a viscosity modifier, an antigelling agent, an ultraviolet absorber, and light. Stabilizers, plasticizers, anti-coloring agents, anti-skinning agents, anti-scratch agents, anti-mold agents, anti-bacterial agents, antioxidants, anti-static agents, silane coupling agents, carbon black, clay, talc, tolmarin, Colorants such as jade, germanium, extender pigments, silica stones, topaz, beryl, quartz, scaly pigments, glass, mica, titanium oxide, iron oxide, acrylic resins, urethane resins, polyethylene glycols, polypropylene glycols and other film-forming agents. , Various reinforcing materials, various bulking materials, conductive fillers, metal powders such as gold, silver, copper, platinum, and stainless steel.

The coating composition is applied onto a substrate to form a coating film.
In the surface coating of a cooking utensil using the coating composition of the present disclosure, it is common to form a multi-layer coating film composed of three layers of a primer coating film, a middle coat coating film, and a top coat coating film. The coating composition of the present disclosure may be applied to any layer of the multi-layer coating film. Further, it may be applied to two or more layers.
The formed coating film has excellent wear resistance. A coating film obtained from the above coating composition is also one of the present disclosures.

The coating film based on the coating composition of the present disclosure is most preferably a middle-coated coating film. It is preferable to use the coating composition of the present disclosure in the middle-coated coating film, particularly in that the function can be maintained for a long period of time.

The method of applying the coating composition onto the substrate is not particularly limited, and when the coating composition is liquid, for example, spray coating, roll coating, coating with a doctor blade, dip coating, impregnation coating. , Spin flow coating, curtain flow coating and the like, and among them, spray coating is preferable. When the coating composition is a powder, electrostatic coating, a flow dipping method, a lotining method and the like can be mentioned, and electrostatic coating is preferable.

After painting the above coating composition, the coating film is fired, but it is preferable to fire after drying. The drying is preferably performed at a temperature of 80 to 200 ° C. for 5 to 30 minutes. Further, the firing is preferably performed at a temperature of 300 to 400 ° C. for 10 to 90 minutes.

One of the present disclosure is a coating film containing the fluororesin and the inorganic particles, wherein the inorganic particles have a new Mohs hardness of 10 or more and are substantially spherical. The coating film may be a top coat coating film or a primer coating film. Further, it may be a coating film constituting the middle coat coating film. The coating film of the present disclosure can be produced from the coating composition of the present disclosure.

In the coating film, the content of the fluororesin is preferably 60 to 99% by mass with respect to the total mass of the coating film. It is more preferably 70% by mass or more, and more preferably 97% by mass or less.
Examples of the fluororesin and the inorganic particles include those described as components of the coating composition of the present disclosure. Moreover, these suitable contents are also the same.

In the coating film, the content of the inorganic particles is preferably 1 to 40% by mass, more preferably 3% by mass or more, and more preferably 30% by mass or less with respect to the fluororesin. preferable.
Regardless of whether the coating film is a primer coating film, a middle coat coating film, or a top coat coating film, the film thickness of the single layer is preferably 1 to 100 μm. The film thickness is more preferably 10 μm or more, and more preferably 50 μm or less.

The coating film may contain inorganic particles having a new Mohs hardness of less than 10, a heat-resistant resin, a surfactant, and an additive, which are exemplified as optional components of the coating composition of the present disclosure.

The new moth hardness of the inorganic particles contained in the coating film is such that the coating film is heated to a temperature higher than the temperature at which organic components such as fluororesin are burned down, and the inorganic residue is subjected to scanning electron microscope / energy dispersion type X-ray spectroscopy. By specifying the material by known analytical methods such as (SEM-EDX), X-ray photoelectron spectroscopy (XPS), and flight time type secondary ion mass spectrometry (TOF-SIMS), the new moth hardness is 10 or more. It can be determined whether or not it corresponds to the above-mentioned inorganic particles.

For the average circularity of the inorganic particles having a new Mohs hardness of 10 or more contained in the coating film, heat the coating film to a temperature higher than the temperature at which organic components such as fluororesin are burned, and use SEM-EDX for the inorganic residue. By performing element mapping, a portion corresponding to a particle having a new Mohs hardness of 10 or more is identified, and the particle in this image can be measured by using an image analysis program such as Mac-View manufactured by Mountech Co., Ltd.

The mass of the PTFE contained in the coating film with respect to the total mass of the PTFE and the fluororesin other than the PTFE can be calculated by a known method such as an infrared spectroscopic spectrum or TG-DTA.

The content of the inorganic particles having a new Mohs hardness of 10 or more contained in the coating film with respect to the fluororesin can be calculated by combining known methods such as TG-DTA, elemental analysis, and image analysis by elemental mapping.

The average particle size and particle size distribution of the inorganic particles contained in the coating film can be adjusted to the average particle size and half width by heating the coating film to a temperature at which organic components such as fluororesin disappear and measuring the particle size of the inorganic residue. Measure.

Further, a laminate characterized by having the above-mentioned coating film is also one of the present disclosure.
Characters, drawings, etc. may be printed on the coating film. The printing method is not particularly limited, and examples thereof include pad transfer printing. The printing ink used for the above printing is not particularly limited, and examples thereof include a composition composed of PES, TFE homopolymer, and titanium oxide.

It is preferable that the laminate further includes a base material. The coating film may be provided directly on the substrate or may be provided on the substrate via another layer. Further, another layer may be provided on the coating film.
It is also preferable that the laminate includes two or more layers of the coating film. By providing two or more layers of the coating film, it is possible to obtain not only further improvement in wear resistance but also effects such as improvement in surface smoothness, improvement in design, and improvement in corrosion resistance.

The laminate includes a primer coating film, a middle coat coating film, and a top coat coating film as the coating film, and it is preferable that at least one of them is formed by the coating composition of the present disclosure. Of these, it is particularly preferable that the middle coat coating film is formed by the coating composition of the present disclosure.

When the primer coating film is formed by the coating composition of the present disclosure, the thickness of the primer coating film is preferably 1 to 40 μm, more preferably 5 to 35 μm.
If the thickness is too thin, the anchor effect on the surface of the primer cannot be expected, pinholes are likely to occur, and the corrosion resistance of the laminate may decrease. If the thickness is too thick, coating film defects such as cracks or swelling are likely to occur, and the wear resistance of the laminate may be lowered, the hardness may be lowered, and the corrosion resistance may be lowered. A more preferable upper limit of the thickness of the primer coating film is 30 μm, and a particularly preferable upper limit is 25 μm.

When the middle-coated coating film is formed by the coating composition of the present disclosure, the thickness of the middle-coated coating film is preferably 1 to 40 μm, more preferably 5 to 35 μm. If the thickness is too thick, coating film defects such as cracks or swelling are likely to occur, and the wear resistance of the laminate may be lowered, the hardness may be lowered, and the corrosion resistance may be lowered. A more preferable upper limit of the thickness of the middle coat coating film is 30 μm, and a particularly preferable upper limit is 25 μm.

When the topcoat coating film is formed by the coating composition of the present disclosure, the thickness of the topcoat coating film is preferably 1 to 40 μm, more preferably 5 to 35 μm. If the thickness is too thick, coating film defects such as cracks or swelling are likely to occur, and the wear resistance of the laminate may be lowered, the hardness may be lowered, and the corrosion resistance may be lowered. A more preferable upper limit of the thickness of the top coat coating film is 30 μm, and a particularly preferable upper limit is 25 μm.

In the present disclosure, it is preferable to use the inorganic particles satisfying the above-mentioned (a) to (d) in that the physical properties of the coating film can be maintained and the appropriate surface roughness can be maintained.

The material of the base material is not particularly limited, and examples thereof include simple metals such as iron, aluminum, stainless steel, and copper, metals such as alloys thereof, and non-metal inorganic materials such as hollow, glass, and ceramic. Examples of the alloys include stainless steel and the like.

The base material may be subjected to surface treatment such as degreasing treatment and roughening treatment, if necessary. The roughening treatment method is not particularly limited, and examples thereof include chemical etching with an acid or an alkali, anodizing (anodizing), and sandblasting. In the surface treatment, the primer composition for forming the primer coating film can be uniformly applied without causing cissing, and the adhesion between the substrate and the primer coating film is improved. It may be appropriately selected depending on the type of the substrate, the composition for the primer and the like, but for example, sandblasting is preferable.

The base material may be subjected to a degreasing treatment by pyrolyzing at 380 ° C. to remove impurities such as oil by thermal decomposition. In order to improve the adhesion between the base material and the coating film, it is preferable to use an aluminum base material that has been roughened with an alumina polishing material after the surface treatment.

When the laminate of the present disclosure forms a coating film including a primer coating film, a middle coat coating film, and a top coat coating film, at least one coating film is formed by the coating composition of the present disclosure. The case where these coating films are formed without using the coating composition of the present disclosure will be described below.

When the primer coating film is formed by a composition other than the coating composition of the present disclosure, it preferably contains a heat-resistant resin. The preferred heat-resistant resin is the same as the heat-resistant resin contained in the above coating composition.

The content of the heat-resistant resin is preferably 10 to 50% by mass, more preferably 15% by mass or more, more preferably 40% by mass or less, and more preferably 30% by mass of the primer coating film. % Or less is more preferable.

The primer coating film may further contain a fluororesin, but may not be contained. Examples of the fluororesin include PTFE, polychlorotrifluoroethylene [PCTFE], polyvinylidene fluoride [PVdF], polyvinyl fluoride [PVF], TFE / PAVE copolymer [PFA], and TFE / HFP copolymer [FEP]. ], TFE / CTFE copolymer, TFE / VdF copolymer, TFE / 3FH copolymer, Et / TFE copolymer [ETFE], TFE / Pr copolymer, VdF / HFP copolymer, Et / CTFE. Examples thereof include a copolymer [ECTFE] and an Et / HFP copolymer. The primer coating film preferably contains at least one selected from the group consisting of PTFE, PFA and FEP.

The content of the fluororesin is preferably 90 to 0% by mass, more preferably 85% by mass or less of the primer coating film.

The primer coating film can further contain inorganic particles. The inorganic particles are not particularly limited, and are inorganic nitrides, carbides, borides and oxides of zirconium, tantalum, titanium, tungsten, silicon, aluminum or beryllium, as well as diamond, silicon carbide and aluminum oxide. Etc. can be exemplified. Examples of the shape of the inorganic particles include, but are not limited to, particle-like, flake-like, and the like.

The primer coating film may contain additives in addition to the fluororesin, the heat-resistant resin, and the inorganic particles. The additive is not particularly limited, and for example, the additive exemplified in the coating composition can be used.

The thickness of the primer coating film is preferably 1 to 40 μm, more preferably 5 to 35 μm. If the thickness is too thin, the anchor effect on the surface of the primer cannot be expected, pinholes are likely to occur, and the corrosion resistance of the laminate may decrease. If the thickness is too thick, coating film defects such as cracks or swelling are likely to occur, and the wear resistance of the laminate may be lowered, the hardness may be lowered, and the corrosion resistance may be lowered. A more preferable upper limit of the thickness of the primer coating film is 30 μm, and a particularly preferable upper limit is 25 μm.

When the middle-coated coating film is formed by a composition other than the coating composition of the present disclosure, it is preferable that the middle-coated coating film contains a fluororesin. The preferred fluororesin is the same as the fluororesin contained in the primer coating film.

The content of the fluororesin is preferably 60 to 100% by mass with respect to the total mass of the middle-coated coating film. It is more preferably 65 to 100% by mass, still more preferably 70 to 100% by mass. By using the fluororesin in the above range, the adhesion between the middle-coated coating film and the coating film adjacent to the middle-coated coating film can be improved.

When the middle-coated coating film is composed of the fluororesin and the heat-resistant resin, the heat-resistant resin has an affinity with the heat-resistant resin in the primer coating film, and therefore has excellent adhesion to the primer coating film. There is.

The middle-coated coating film can further contain inorganic particles. The inorganic particles are at least one selected from the group consisting of inorganic nitrides of zirconium, tantalum, titanium, tungsten, silicon, aluminum or beryllium, carbides, borides and oxides, and diamonds. It is more preferable, and silicon carbide or aluminum oxide is more preferable in terms of availability and cost. Examples of the shape of the inorganic particles include, but are not limited to, particle-like, flake-like, and the like.
The content of the inorganic particles is preferably 0.1 to 30% by mass, more preferably 20% by mass or less, and even more preferably 1% by mass or more of the middle-coated coating film.
The middle-coated coating film may contain additives in addition to the fluororesin, the heat-resistant resin, and the inorganic particles. The additive is not particularly limited, and for example, the additive exemplified in the coating composition can be used.

The thickness of the middle-coated coating film is preferably 5 to 30 μm, more preferably 10 to 25 μm.

The top coat preferably contains the fluororesin. Further, it may be made of the above-mentioned fluororesin and the above-mentioned heat-resistant resin. The resin, additives, etc. used in the top coat can be the same as those of the above-mentioned middle coat coating film.

The method for forming a coating film comprising the primer coating film, the middle coat coating film, and the top coat coating film is not particularly limited, and each coating film is applied by the above method, the coating film is dried, and then the next coating film is applied. It is preferable to obtain a sintered multi-layer coating film by coating the film to form a three-layer multi-layer coating film and then firing the film.

Hereinafter, the present disclosure will be specifically described based on examples. The present disclosure is not limited to the examples.
In the following examples, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.
Each numerical value of the example was measured by the following method.

(Measurement of average circularity)
The value measured using FPIA-2100 manufactured by Sysmex Corporation was taken as the average circularity of the particles.
A sample solution prepared by mixing 1.5 g of particles with 30 ml of an appropriate solvent such as sodium hexametaphosphate was used as a sample solution, and a flow-type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation was used.
Circularity = (4πS) 1/2 / L
(However, π = pi, S = area of projection drawing, L = perimeter of projection drawing) The numerical values measured for about 10,000 particles with effective analysis were obtained from the raw material manufacturer, and the particles were obtained. The average circularity of.

In addition, for 50 arbitrary particles in the electron micrograph of the particles (magnification 100 times), circularity = (4πS) 1/2 / L using the image analysis program Mac-View manufactured by Mountech Co., Ltd.
(However, π = pi, S = area of projection drawing, L = perimeter of projection drawing)
The average circularity measured based on the above formula was almost the same as the value measured using FPIA-2100.

(Measurement of film thickness)
A dummy aluminum plate (A-1050P) was also coated at the same time as the laminated coating film described later, and the film thickness of the coating film formed on the dummy aluminum plate was measured with an eddy current film thickness meter manufactured by Sanko Electronics. , The film thickness of each coating film.

(Abrasion resistance)
3M's industrial pad (trade name: Scotch-Brite 7447C) is cut into 3 cm squares, 2 cc of 5% neutral detergent is dropped, and it slides back and forth with a load of 4.5 kg, and the number of round trips until the base material is exposed. Evaluated by.

(Non-adhesive)
Add 130 to 150 ml of water to 150 g of the pancake mix, pour 15 to 20 ml of the stirred test solution into a cylindrical shape, and heat at 180 ± 5 ° C. for 7 minutes. Immediately after heating, the cylindrical mold is pulled vertically with a load meter to measure the adhesion force, and the value divided by the bottom area of the cylindrical mold is taken as the peeling force. Non-adhesiveness was scored on a scale of 10 from the peeling force.

(Surface roughness)
The surface roughness Ra of the coating film was measured using a surface roughness measuring instrument Certronic Duo II manufactured by Taylor Hobson.

(Preparation of the paint of the present disclosure)
A predetermined amount of inorganic particles shown in Table 1 was added to an aqueous coating composition containing a fluororesin as a main component, and the mixture was stirred and mixed to obtain a coating composition. The inorganic particles have each half-value width shown in Table 1 or have a multi-peak by performing operations such as sieving and mixing powders having different particle sizes with respect to commercially available spherical inorganic particles. It was adjusted to have a certain particle distribution.
The measurement results of the particle size distribution of the inorganic particles used in Examples 1, 7, 24 and Comparative Example 4 are shown in FIG.

Examples 1 to 26, Comparative Examples 1 to 6
After mixing each component shown in the following "Preparation of primer paint", "Preparation of paint for middle coat" and "Preparation of paint for top coat", in the paint shown in Table 1, the predetermined type and amount shown in Table 1 Inorganic particles were added, stirred and mixed to obtain the coating composition of the present disclosure.

The coating composition of the present disclosure was used for forming the coating film shown in Table 1. In the layers not using the coating composition of the present disclosure, a coating film was formed using the coating composition prepared according to the following method.

(Preparation of primer paint)
Fluororesin aqueous dispersion (solid content 62%) 32.0 parts Carbon black mill base (solid content 20%) 8.4 parts PES aqueous dispersion (solid content 20%) 24.3 parts Surfactant 2.0 parts increase Thickener 14.2 parts Water 19.1 parts

(Preparation of paint for middle coat)
Fluororesin aqueous dispersion (solid content 62%) 65.7 parts Membrane-forming agent 11.4 parts Carbon black mill base (solid content 20%) 2.5 parts Surfactant 5.6 parts Water 14.8 parts

(Preparation of paint for top coat)
Fluororesin aqueous dispersion (solid content 62%) 66.7 parts Membrane-forming agent 12.4 parts Carbon black mill base (solid content 20%) 0.5 parts Glitter filler 0.8 parts Surfactant 5.6 parts 14.0 parts of water

(Preparation of test plate)
After degreasing the surface of the aluminum plate (A-1050P) with acetone, sandblasting is performed so that the surface roughness Ra value measured in accordance with JIS B 0601-2001 is 2.0 to 3.0 μm, and the surface is ground. Roughened. After removing the dust on the surface by air blowing, the paint shown in Table 1 was spray-coated as a primer at a spray pressure of 0.2 MPa using a gravity spray gun so that the dry film thickness was 10 to 15 μm. The coating film on the obtained aluminum plate was dried at 80 to 100 ° C. for 15 minutes and cooled to room temperature. Next, as the paint of the middle coat coating film 1, the paint shown in Table 1 was painted so as to have a dry film thickness in the range of 10 to 20 μm. The coating film on the obtained aluminum plate was dried at 80 to 100 ° C. for 15 minutes and cooled to room temperature. The top coat paints shown in Table 1 were spray-coated on the obtained coating film so that the film thickness after firing would be the values shown in Table 1 and overcoated.
The obtained coated plate was dried at 80 to 100 ° C. for 15 minutes and then fired at 380 ° C. for 20 minutes to obtain a test coated plate. The obtained test coating plate was a laminate in which the primer coating film, the middle coat coating film 1 and the top coat coating film shown in Table 1 were formed on an aluminum plate. The results are shown in Tables 1 to 3.

The measurement results of the particle size distribution of the inorganic particles used in Examples 1, 7, 24 and Comparative Example 4 were as shown in FIG.

Here, when the coating film of Example 1 was cut into 3 cm × 3 cm, heated to 600 ° C. or higher at which the fluororesin was burnt down, and elemental mapping was performed on the residue using SEM-EDX, the portion corresponding to silicon carbide could be identified. For 50 arbitrary silicon carbide particles in this image, the image analysis program Mac-View manufactured by Mountech Co., Ltd. was used.
Circularity = (4πS) 1/2 / L
(However, π = pi, S = area of projection drawing, L = perimeter of projection drawing)
The average circularity measured based on the above formula was 0.98, which was almost the same as the value measured before the addition of the paint.

From the results in Table 1, it is clear that the coating composition of the present disclosure was able to form a coating film having both non-adhesiveness and abrasion resistance.

The coating composition of the present disclosure can be suitably used as an industrial part such as a cooking utensil, a machine or an automobile. The above cookware is, for example, a frying pan, a pressure cooker, a pan, a grill pan, a rice cooker, an oven, a hot plate, a pan baking mold, a kitchen knife, a gas table, a home bakery, an inner surface of a microwave oven, a jar pot, an electric kettle, a snapper, and a waffle. It may be a maker, a hot sand maker, or the like. Further, the industrial parts such as machines and automobiles may be, for example, automobile engine pistons, stabilizers, reed valve seats, wires, bearings and the like.

Claims (7)

1. A coating composition containing a fluororesin and inorganic particles.
   The inorganic particles are
   The new Mohs hardness is 10 or more,
   The average circularity is 0.90 to 1.00,
   The average particle size is 1-40 μm.
   A coating composition characterized in that the half width of the particle size distribution is 21 μm or more or multi-peak.
2. The fluororesin consists of polytetrafluoroethylene only or fluororesin other than polytetrafluoroethylene and polytetrafluoroethylene, and polytetrafluoroethylene is compared with the total of polytetrafluoroethylene and fluororesin other than polytetrafluoroethylene. The coating composition according to claim 1, wherein the amount is 20% by mass or more, and the fluororesin is contained in an amount of 30.0 to 99.0% by mass based on the total amount of the solid matter of the coating composition.
3. The coating composition according to claim 1 or 2, which contains 1 to 50% by mass of inorganic particles with respect to the fluororesin.
4. The coating composition according to any one of claims 1 to 3, wherein the inorganic particles are at least one selected from the group consisting of alumina particles and silicon carbide particles.
5. A coating film obtained from any of the coating compositions according to claims 1 to 4.
6. A coating film formed on a substrate and composed of three layers of a primer coating film (1), a middle coat coating film (2), and a top coat coating film (3).
   The middle coat coating film (2) is a coating film formed by any of the coating compositions according to any one of claims 1 to 4.
7. A laminate comprising a base material and the coating film according to claim 5 or 6.

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