TW202120631A - Powder coating composition and liquid coating composition comprising fluororesin useful in baking, coating and coated body comprising the powder coating composition or the liquid coating composition comprising fluororesin useful in baking - Google Patents

Abstract

The problems to be solved by the present invention are to obtain a powder coating composition useful in baking that has excellent corrosion resistance and processability, and simultaneously has the property of high durability and chemical resistance, as well as to form a good lining film without causing defects such as cracks, and a liquid coating composition useful in baking; and to obtain a coating containing the powder coating composition useful in baking or the liquid coating composition useful in baking, and a coated body. A powder coating composition useful in baking comprises a fluororesin. In the fluororesin, least one kind of porous coordination polymer (PCP) / metal organic structure (MOF) formed by coordinating an organic ligand and a central metal, is dispersed.

Description

Powder coating composition and liquid coating composition for firing containing fluororesin, film and film body containing the powder coating composition or liquid coating composition for firing

The present invention relates to a powder coating composition and liquid coating composition for sintering containing fluororesin, a coating film containing the powder coating composition or liquid coating composition for sintering, and a coating body. In more detail, the present invention relates to a fluororesin containing a porous coordination polymer (PCP)/metal organic structure (MOF) in which organic ligands are dispersed and coordinately bonded to a central metal. The powder coating composition and the liquid coating composition, the coating film containing the powder coating composition or the liquid coating composition for burning, and the coating body.

Fluororesin-based resins are excellent in heat resistance, corrosion resistance, water repellency, antifouling properties, lubricity, friction resistance, etc., and can be used as a lining film for a substrate made of metal or the like.

For example, Patent Document 1 discloses a machine for forming a lining film made of a fluororesin that has improved corrosion resistance to hydrofluoric acid. Patent Document 1 discloses that a fluororesin powder coating material is mixed with a filler in order to improve the corrosion resistance to hydrofluoric acid to obtain a lining film that alleviates the shrinkage force and has high durability.

[Patent Document 1] Japanese Patent Laid-Open No. 11-241045

[Problems to be solved by the invention]

However, as shown in Patent Document 1, the use of fillers improves the permeability of the lining film to chemical liquids and the like. Since the permeability of the lining film is improved, there is a problem that the lining film becomes easily corroded. That is, the corrosion resistance of the lining film becomes low. In addition, due to the use of fillers, the processability of the lining film is also reduced.

The present invention was completed in view of the above-mentioned problems. The problem to be solved is to obtain excellent corrosion resistance and workability, and at the same time have high durability and chemical resistance properties; the formation does not cause cracks, etc. The powder coating composition and liquid coating composition for burning of the good lining film, the film containing the powder coating composition or liquid coating composition for burning, and the film body. 〔Means to solve the problem〕

The powder coating composition for sintering containing fluororesin of the present invention relates to a powder coating composition for sintering containing fluororesin, and the fluororesin is dispersed with organic ligands to coordinately bond with the central metal The resulting porous coordination polymer (PCP)/metal organic structure (MOF).

Powder coatings use thermoplastic resins, so solvent-insoluble resins can be used, and a coating film with high solvent resistance can be obtained.

The aforementioned porous coordination polymer (PCP)/metal organic structure (MOF) is in powder form, measured by thermogravimetric differential thermal analysis (TG-DTA) under air conditions from 200°C to 5% decomposition temperature. The melting point of the aforementioned fluororesin is even higher; and it is blended at 0.02% by weight to 20.00% by weight relative to the entire powder coating composition for baking.

The aforementioned fluororesin-based thermoplastic is insoluble in either of polar solvents and non-polar solvents, and is blended at 70.00% to 99.98% by weight relative to the entire powder coating composition for baking. .

According to the powder coating composition for sintering of the present invention, it is possible to provide an unsuitable and good lining film that has excellent durability, chemical resistance, penetration resistance, and corrosion resistance, and can be formed without cracks. The powder coating composition used for burning.

Compared with the entire powder coating composition for sintering, if the blending amount of the porous coordination polymer (PCP)/metal organic structure (MOF) is insufficient, the desired result cannot be obtained. Sufficient durability, chemical resistance, corrosion resistance, etc. In addition, when the blending amount is excessive, it will not be possible to form a good film on the substrate.

The blending amount of the porous coordination polymer (PCP)/metal organic structure (MOF) is preferably 0.10% by weight to 5.50% by weight relative to the entire powder coating composition for sintering.

The aforementioned central metal system is selected from Al ^{3 +} , Co ^{3 +} , Co ^{2 +} , Ni ^{2 +} , Ni ⁺ , Cu ^{2 +} , Cu ⁺ , Zn ^{2 +} , Fe ^{3 +} , Fe ^{2 +} , Ti ^{3 +} , and One or more metal ions selected from the Zr ^{4 +} constituent group are present; the aforementioned metal ions are preferably coordinately bonded to the aforementioned organic ligands and are present in the aforementioned porous coordination polymer (PCP)/metal organic structure Body (MOF).

According to the configuration of the present invention, it is possible to obtain changes in the pore structure with different valences of metal ions, and it is possible to prepare durability, chemical resistance, corrosion resistance, heat resistance, etc. as required.

At least one of the aforementioned central metal supports more than one anion; the aforementioned central metal is preferably coordinately bonded to the aforementioned organic ligand and exists in the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF).

According to the structure of the present invention, since the polymer structure having a pore structure is assembled, the permeation of components that reduce the durability of the film can be prevented and extended, and therefore, it is possible to obtain a sintered film that can provide a lining film with excellent durability. Powder coating composition used.

Preferably, the anionic containing from OH ^-, CO ₃ ^{2 -,} and O ^{2 -} group constituting the selected one or more types of anions.

The configuration of the present invention, due to _{^{OH -, CO 3 2 -,}} O 2 - and drug interactions, can be obtained provides excellent corrosion resistance to the comparative film, with chemical resistance of the baked powder coating compositions.

At least one of the aforementioned central metals preferably forms an oxo structure together with the aforementioned anion.

According to the structure of the present invention, due to the interaction between the oxo structure and the chemical, it is possible to obtain a powder coating composition for sintering that can provide excellent corrosion resistance and chemical resistance to the film.

The aforementioned organic ligands preferably contain 1,4-phthalic acid, 1,3,5-benzenetricarboxylic acid, 4,4'-bipyridine, imidazole, 1,3,5-tris(4-carboxylic acid) Phenyl) benzene, fumaric acid, terephthalic acid, and maleic acid constitute more than one organic ligand selected from the group.

According to the constitution of the present invention, by assembling a polymer structure having a pore structure, the permeation of components that reduce the durability of the film can be prevented and spread, and a lining film having excellent durability can be obtained. In addition, by adjusting the blending amount of organic ligands, porous coordination polymers (PCP)/metal organic structures (MOF) with various polymer structures can be obtained.

In one embodiment of the present invention, by the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF), the powder coating composition for burning is a characteristic that can impart adsorbed gas Things.

The aforementioned gas may be a corrosive gas containing at least hydrogen chloride.

Since fluororesin has gas permeability, it cannot have sufficient corrosion resistance when the base material of the fluororesin lining film is reactive with gas. Porous coordination polymer (PCP)/metal organic structure (MOF) absorbs gas, so it can reduce the gas permeability of the fluororesin lining film and improve the corrosion resistance.

Although fluororesin is permeable to corrosive gas, the adhesion of the film may be inappropriate. However, because the porous coordination polymer (PCP)/metal organic structure (MOF) adsorbs the gas, it can provide A powder coating composition that can form a lining film with excellent durability, chemical resistance, penetration resistance, and corrosion resistance.

The porous coordination polymer (PCP)/metal organic structure (MOF) preferably has a pore area of 0.15 nm ² to 7.00 ^{nm 2} .

When the open area of the pores is less than 0.15 nm ² , gas molecules with a large molecular weight cannot be adsorbed. When the pore area of the pore is larger than 7.00nm ² , the effect of capillary condensation will be attenuated and the gas adsorption characteristics will be reduced.

The aforementioned porous coordination polymer (PCP)/metal organic structure (MOF) preferably has a specific surface area (BET specific surface area) ^{greater than 900.00 m 3 /g.}

Since the specific surface area (BET specific surface area) is greater than 900.00 m ³ /g, the amount of gas adsorption increases, and more excellent durability, chemical resistance, penetration resistance, and corrosion resistance can be obtained.

In one embodiment of the present invention, a powder coating composition for sintering containing fluororesin, which contains at least one porous coordination polymer (PCP)/metal organic structure ( MOF), one or more porous coordination polymers (PCP)/metal organic structures (MOF) with hydrophilic properties.

Porous coordination polymers (PCP)/metal organic structures (MOF) are different based on the properties that can be adsorbed. As it contains both hydrophobic porous coordination polymer (PCP)/metal organic structure (MOF) and hydrophilic porous coordination polymer (PCP)/metal organic structure (MOF), it can adsorb There are more types of substances, and therefore, more excellent durability, chemical resistance, penetration resistance, and corrosion resistance can be obtained.

The blending amount of the aforementioned fluororesin is preferably 75.00% by weight to 90.00% by weight with respect to the entire powder coating composition for baking.

By setting the blending amount of the fluororesin to 75.00% by weight to 90.00% by weight, it is possible to provide a porous coordination polymer (PCP)/metal organic structure (MOF) with high adhesion and sufficient content, which can be formed A powder coating composition for the burning of lining films with excellent durability, chemical resistance, penetration resistance, and corrosion resistance.

The aforementioned fluororesin is preferably one or more fluororesins selected from the group consisting of PFA, FEP, ETFE, PCTFE, and ECTFE.

According to the constitution of the present invention, it is possible to obtain a powder coating composition for sintering which can provide a lining film having excellent durability.

It may further contain one or more additives selected from the group consisting of PPS, PEEK, and PES.

According to the structure of the present invention, a lining film having excellent durability can be obtained.

In one embodiment of the present invention, a liquid paint composition for burning in which the above-mentioned powder paint composition for burning is dispersed in a solvent.

According to the structure of the present invention, since the powder coating composition for burning is dispersed in the solvent, the powder coating composition can be coated on a substrate that is difficult to coat.

The coating film of the present invention is a coating film containing a powder coating composition for firing or a liquid coating composition for firing a fluororesin as described above.

According to the structure of the present invention, since the fluororesin as described above is contained, it is possible to obtain a lining film having excellent durability, chemical resistance, penetration resistance, and corrosion resistance.

In one embodiment of the present invention, the film system has a film thickness of 40 μm to 5000 μm.

When the film thickness of the film is insufficient, durability, chemical resistance, penetration resistance, and corrosion resistance cannot be obtained. If the film thickness is too large, there is a risk of loss of smoothness due to foaming in the film, cracks, irregularities, etc. on the surface of the film.

The coating system according to one embodiment of the present invention includes a substrate, a base layer formed on the surface of the substrate, and a coating body of one or more fluororesin coating layers formed on the base layer, wherein The fluororesin coating layer is a coating film as described above.

According to the structure of the present invention, since the fluororesin as described above is contained, it is possible to obtain a coated body having excellent durability, chemical resistance, penetration resistance, and corrosion resistance. [Effects of the invention]

According to the powder coating composition and liquid coating composition for baking containing fluororesin of the present invention, the coating film containing the powder coating composition or liquid coating composition for baking, and the coating body can be To provide a powder coating composition and a liquid coating composition that have excellent durability, chemical resistance, penetration resistance, and corrosion resistance, and form an inappropriate and good lining film without cracks. The coating film and the coating body containing the powder coating composition or the liquid coating composition for burning.

Porous Coordination Polymer (PCP) is a material based on complex chemistry with a porous structure formed by coordinated bonding of a central metal with an organic ligand. The porous coordination polymer (PCP) is a crystalline three-dimensional polymer structure that has a central metal and an organic ligand that are continuously coordinated and bonded, and has spaces (pores) inside.

In addition, the porous coordination polymer (PCP) is also called a metal organic structure (Metal "Organic" Framework; MOF). Although these compound groups are individual names having, for example, porous metal complexes, etc., however, they are collectively referred to as "Porous Coordination Polymer (PCP)/Metal Organic Structure (MOF)" in this specification. Therefore, the present invention should not be understood as: it is not intended to include these compound groups represented by other names such as porous metal complexes.

In addition, in this specification, when it is simply described as "paint composition", it refers to the fluororesin-containing powder paint composition for burning and the liquid paint for burning according to the present invention Things that make up a thing.

In this specification, "film" refers to a single-layer or multi-layer fluororesin lining film containing at least one layer of the coating composition of the present invention that has been coated. That is, the "film" in this specification includes a fluororesin lining film that has at least one layer of the coating composition of the present invention that is coated, and the coating layer of a general coating composition that is coated. .

In this specification, "coated body" refers to a substrate, a base layer on the substrate, and a film on the base layer to form a layered structure.

In addition, the effects and characteristics of the film of the present invention and the film body of the present invention are also interpreted as having them in the same way.

Hereinafter, embodiments of the coating composition, its coating film, and its coating body related to the present invention will be described.

＜Paint composition＞ The fluororesin-containing coating composition according to this embodiment contains a fluororesin in which a porous coordination polymer (PCP)/metal organic structure (MOF) formed by a coordination bond between an organic ligand and a central metal is dispersed The coating composition. Here, the coating composition system includes more than one porous coordination polymer (PCP)/metal organic structure (MOF).

Porous coordination polymer (PCP)/metal organic structure (MOF) is a polymer structure with a pore structure. Because it is used to prevent and spread the penetration of components that reduce the durability of the film, it can be regarded as A film with excellent durability can be realized.

The component that causes the decrease in the durability of the film is liquid and/or gas (gas). That is, the coating composition system can be endowed with the characteristic of adsorbing liquid and/or gas (gas) due to the porous coordination polymer (PCP)/metal organic structure (MOF).

Although the adsorbed gas is not limited, for example, it can be organic acids such as hydrogen sulfide, sulfurous acid, nitrous acid, chlorine, hydrogen bromide, hydrogen chloride, acetic acid, acrylic acid, etc., and alkalis such as amines and ammonia. Sexual gas and so on.

Because fluororesin has gas permeability, the base material of the film may be reactive with gas and corrode. Porous coordination polymer (PCP)/metal organic structure (MOF) absorbs gas, so it can reduce the gas permeability of the film, and inhibit the adhesion of the film and the corrosion of the substrate.

In order to uniformly disperse the porous coordination polymer (PCP)/metal organic structure (MOF) in the fluororesin, the porous coordination polymer (PCP)/metal organic structure (MOF) is in powder form. In order to form such a form, it is preferable to use a ball mill or the like to mix the fluororesin and the porous coordination polymer (PCP)/metal organic structure (MOF).

The blending amount of the porous coordination polymer (PCP)/metal organic structure (MOF) of the coating composition according to this embodiment is 0.02% by weight to 20.00% by weight relative to the entire coating composition. More preferably, the blending amount of the porous coordination polymer (PCP)/metal organic structure (MOF) is 0.04% by weight or more with respect to the entire coating composition. Furthermore, it is more desirable that the blending amount of the porous coordination polymer (PCP)/metal organic structure (MOF) is 19.00% by weight or less with respect to the entire coating composition. When the blending amount of the porous coordination polymer (PCP)/metal organic structure (MOF) is insufficient, the desired and sufficient durability, chemical resistance, and corrosion resistance cannot be obtained. Moreover, when the blending amount is too large, the substrate cannot be formed into a film satisfactorily.

The porous coordination polymer (PCP)/metal organic structure (MOF) blended in the coating composition of this embodiment is measured by thermal gravimetric differential thermal analysis (TG-DTA) under air conditions. The temperature from ℃ to 5% decomposition is higher than the melting point of the main agent fluororesin.

By making the porous coordination polymer (PCP)/metal organic structure (MOF) have this property, when the coating composition is fired to form a film, the porous coordination polymer (PCP)/metal organic The structure (MOF) is not decomposed, so the film can have excellent durability, chemical resistance, penetration resistance, and corrosion resistance. In addition, there is no risk of impairing durability, chemical resistance, penetration resistance, and corrosion resistance of the coating film when exposed to high temperature use conditions.

The core metal of porous coordination polymer (PCP)/metal organic structure (MOF) can contain Li, Be, Mg, Al, Ca, Sc, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sr , Y, Zr, Mo, Ru, Rh, Pd, Pb, In, W, Re, Pt, or metal ions such as cationic elements. Moreover, these metal ions may contain only 1 type, and may contain 2 or more types of multiple types.

In this way, the type of metal and/or the valence of the metal ion are different. Therefore, the structure of the porous coordination polymer (PCP)/metal organic structure (MOF) can be changed; the durability and chemical resistance can also be changed Chemical properties such as resistance, corrosion resistance, and heat resistance. Therefore, durability, chemical resistance, corrosion resistance, heat resistance, etc. can be adjusted according to the application.

In addition, from the viewpoint of obtaining more excellent durability, chemical resistance, corrosion resistance, and heat resistance, it is preferable to contain Al ^{3 +} , Co ^{3 +} , Co ^{2 +} , Ni ^{2 +} , Ni ⁺ , Cu ^{2 ＋} , Cu ^＋ , Zn ^{2 ＋} , Fe ^{3 ＋} , Fe ^{2 ＋} , Ti ^{3 ＋} , and Zr ^{4 ＋} constitute one or more metal ions selected from the group.

At least one of the central metal is an anion that supports more than one, and the central metal can be coordinately bonded to the aforementioned organic ligand and exist in the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF) .

For example, when a carboxylic acid is used as a ligand, _{it is coordinated to the metal in the form of -CO 2} ^- due to deprotonation. Therefore, only the metal ion of the central metal and the ligand become neutral and form internally. Pores. On the other hand, such as 4,4'-bipyridine in the neutral state of the ligand coordinated to the metal cation, due to the formation of porous coordination polymer (PCP) / metal organic structure (MOF) after the electrical Neutral, therefore, the framework of the porous coordination polymer (PCP)/metal organic structure (MOF) is positively charged, and the anions used to compensate for it enter the interior.

The anion can include F ^－ , Cl ^－ , Br ^－ , I ^－ , H ^－ , O ^{2 －} , O ₂ ^{2 －} , S ^{2 －} , N ₃ ^－ , CN ^－ , OH ^－ , HCO ₃ ^－ , CH ₃ COO ^－ , H(COO) ₂ ^－ , (COO) ₂ ^{2 －} , CO ₃ ^{2 －} , HS ^－ , HSO ₄ ^－ , SO ₄ ^{2 －} , SO ₃ ^{2 －} , S ₂ O ₃ ^{2 －} , SCN ^－ , NCS ^－ , NO ₃ ^－ , NO ₂ ^－ , ONO ^－ , ClO ^－ , ClO ₂ ^－ , ClO ₃ ^－ , ClO ₄ ^－ , H ₂ PO ₄ ^－ , HPO ₄ ^{2 －} and other anions. In addition, these anions may contain only one type, or may contain two or more types of multiple types.

From the viewpoint of obtaining more excellent durability, chemical resistance, corrosion resistance, and heat resistance, it is preferable that the anion contains one selected from the group consisting of OH ^－ , CO ₃ ^{2 －} , and O ^{2 －} The above anions.

In addition, at least one of the central metals preferably forms an oxo structure together with the aforementioned anion. The oxo structure interacts with chemicals, and a coating composition that can provide a coating film with excellent corrosion resistance and chemical resistance can be obtained.

Organic ligands can include: 1,4-phthalic acid, 1,3,5-benzenetricarboxylic acid, 4,4'-bipyridine, imidazole, 1,3,5-ginseng (4-carboxyphenyl) Benzene, fumaric acid, maleic acid, 5-cyano-1,3-phthalic acid, 9,10-anthracene dicarboxylic acid, 2,2'-diamino-4,4'-styrene dicarboxylic acid Acid, 2,5-diaminoterephthalic acid, 2,2'-dinitro-4,4'-styrene dicarboxylic acid, 2,5-dihydroxyterephthalic acid, 3,3', 5,5'-tetracarboxydiphenylmethane, 1,2,4,5-tetrakis (4-carboxyphenyl)benzene, terephthalic acid, 4,4',4'-s-triacridine-2 ,4,6-tolyl-tribenzoic acid, 1,3,5-ginseng (4'-carboxy[1,1'-biphenyl]-4-yl)benzene, tricarboxylic acid, 2,6-naphthalene Carboxylic acid, 2-hydroxyterephthalic acid, biphenyl-3,3',5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, 5-bromoisophthalic acid , Malonic acid, 2-Methylimidazole, 5-cyano-1,3-phthalic acid, 2-aminoterephthalic acid, 1,2-bis(4-pyridine)ethylene, 4,4'- Ethylene dipyridine, 2,3-pyrazine dicarboxylic acid, 1,4-diazepine ring [2.2.2] octane, 3,5-pyridine dicarboxylic acid, trans, trans-muconic acid, 5- Nitroisophthalic acid, 5-methylisophthalic acid, 2-hydroxyterephthalic acid, 4,4'-biphenyldicarboxylic acid, tricarboxylic acid and other organic ligands. In addition, these organic ligands may contain only one species, or they may contain two or more species.

In addition, from the viewpoint of obtaining more excellent durability, chemical resistance, corrosion resistance, and heat resistance, the organic ligand preferably contains 1,4-phthalic acid, 1,3,5-benzene Tricarboxylic acid, 4,4'-bipyridine, imidazole, 1,3,5-ginseng (4-carboxyphenyl)benzene, fumaric acid, terephthalic acid, and maleic acid are selected from the group 1 More than species of organic ligands.

The porous coordination polymer (PCP)/metal organic structure (MOF) preferably has an opening area of 0.15 nm ² to 7.00 ^{nm 2} .

When the open area of the pores is less than 0.15 nm ² , gas molecules with a large molecular weight cannot be adsorbed. When the pore area of the pore is larger than 7.00nm ² , the effect based on capillary condensation will be attenuated and the gas adsorption characteristics will be reduced.

Preferably, the porous coordination polymer (PCP)/metal organic structure (MOF) has a specific surface area (BET specific surface area) ^{greater than 900.00 m 3 /g.}

By making the specific surface area (BET specific surface area) greater than 900.00 m ³ /g, it is possible to obtain an increase in the amount of gas adsorption, better durability, chemical resistance, penetration resistance, and corrosion resistance.

Porous coordination polymers (PCP)/metal organic structures (MOF) have properties derived from the central metal and organic ligands of the composition. For example, thermal conductivity and dielectric properties are derived from the central metal and change accordingly. Hydrophobicity/hydrophilicity etc. are derived from organic ligands and change accordingly. Therefore, the central metal and organic ligands can be selected according to the environmental conditions of the applicable film or the film body.

The coating composition may be a porous coordination polymer (PCP)/metal organic structure (MOF) blended with multiple types. As mentioned above, the properties of the porous coordination polymer (PCP)/metal organic structure (MOF) are different depending on the central metal and organic ligand. By blending multiple types of porous coordination polymers (PCP)/metal organic structures (MOF) with different properties, various properties of the coating composition and film can be imparted.

An example of blending multiple types of porous coordination polymers (PCP)/metal organic structures (MOF), for example, for example, the coating composition may contain: more than one type of porous Coordination polymer (PCP)/metal organic structure (MOF), and one or more hydrophilic porous coordination polymer (PCP)/metal organic structure (MOF).

By containing both hydrophobic porous coordination polymer (PCP)/metal organic structure (MOF) and hydrophilic porous coordination polymer (PCP)/metal organic structure (MOF), it can An increase in the types of adsorbable substances, better durability, chemical resistance, penetration resistance, and corrosion resistance are obtained.

The fluororesin-based thermoplastic contained in the coating composition according to this embodiment is insoluble in either a polar solvent or a non-polar solvent.

One example of the polar solvent, for example, it may be water, formic acid, acetic acid, methanol, ethanol, propanol, isopropanol, n-butanol, acetone, ethyl acetate, etc. One example of the non-polar solvent, for example, it may be benzene, toluene, hexane, diethyl ether, dichloromethane and the like.

The fluororesin that is the subject of the present invention is insoluble in either polar solvents or non-polar solvents. Therefore, it is possible to provide a coating composition capable of forming a coating film with excellent chemical resistance and solvent resistance.

The blending amount of the fluororesin with respect to the entire coating composition is 70.00% by weight to 99.98% by weight. Preferably, it is 73.00% by weight to 96.00% by weight. More preferably, it is 75.00% by weight to 90.00% by weight.

When the blending amount of the fluororesin is less than 70.00% by weight, inadequacy such as cracks may occur when the film is formed. In addition, by making such a fluororesin the upper limit value, it is possible to make it contain a sufficient amount of porous coordination polymer (PCP)/metal organic structure (MOF).

The fluororesin preferably contains PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), ETFE (tetrafluoroethylene-ethylene copolymer), PCTFE ( Polychlorotrifluoroethylene copolymer) and ECTFE (chlorotrifluoroethylene-ethylene copolymer) constitute more than one fluororesin selected in the group.

These fluororesins are thermoplastic and are insoluble in either polar solvents or non-polar solvents. Therefore, by using one or more types of powder coatings containing these fluororesins, it is possible to obtain a lining film having excellent durability.

It may further contain one or more additives selected from the group consisting of PPS (polyphenylene sulfide), PEEK (polyether ether ketone), and PES (polyether sulfide).

By using one or more powder coatings containing these additives, a lining film with excellent durability can be obtained.

The coating composition is a coating composition for forming a film through firing (firing process).

The paint composition can be provided in the form of powder paint. The paint composition system provided in the form of powder paint does not contain solvents. Since it is formed in the form of a powder coating, the film thickness of the film becomes easy to adjust.

In addition, the coating composition system does not have to be limited to the form of the powder coating composition. Depending on the situation, as for the solvent, the powder coating composition may be a liquid coating composition for baking dispersed with a surfactant or the like.

As the solvent, either a polar solvent or a non-polar solvent can be used. As a solvent, although it is not limited, water, alcohols (methanol, ethanol, propanol, isopropanol, or n-butanol, etc.), ketones (acetone, etc.), aromatic compounds (benzene, etc.) can be used. Or, toluene, etc.) and so on.

In the case of the form of the liquid coating composition, compared with the form of the powder coating composition, particles of fluororesin, porous coordination polymer (PCP)/metal organic structure (MOF) and other additives The diameter system has a relatively small particle size. Although the particle size is not limited, for example, it may be a particle size of about 0.01 μm to 50 μm. For the fluororesin, a dispersion prepared by pre-dispersing particles of about 0.2 μm in a liquid mainly composed of water can be used, which is also called a dispersion.

＜The film, and the film body＞ Next, the method of forming the film according to this embodiment will be described, and the film body having the film will also be described.

The lining film system according to this embodiment is formed on the substrate via the base layer using a coating composition containing a fluororesin as described above.

Fig. 1 is a cross-sectional view of a film body (10) in which a film (liner film) (3) is formed on a substrate (1) with a base layer (2) interposed therebetween.

Although the base material (1) is not particularly limited, when the base layer (2) and the coating film (3) are formed on the base material (1), it is better to use after the sintering process Metal, glass, ceramics, etc. that can withstand the heat of burning. Among these, metals are preferred because they can obtain high corrosion resistance.

In addition, the base material (1) may be one that has been subjected to surface treatment (sandblasting, plating, silane coupling treatment, etc.) in advance in order to improve adhesion to the base layer (2).

A base layer (2) is formed on the substrate (1). By forming the base layer (2) on the substrate (1), the adhesion between the substrate (1) and the film (3) can be improved. Specifically, the base layer (2) is formed by coating the raw material of the base layer (2) on the base material (1), and drying or firing as necessary.

Although the base layer (2) is not particularly limited, it is preferably one containing fluororesin and chromic acid, or one containing resin and organic titanate

After the base layer (2) is formed, the coating composition of this embodiment is used to form a film (3) on the base layer (2).

The coating composition of this embodiment may be used all over, or the coating composition of this embodiment may be used for some layers, and a general coating composition may be used for the other parts. Although the ratio of the film thickness comprised by the coating composition of this embodiment is not specifically limited, it is 5%-100% with respect to the whole film thickness suitably.

The coating composition of this embodiment or a general coating composition is applied to the base layer (2) by electrostatic powder coating, and a coating film (3) of one layer or multiple layers can be formed by repeated firing operations.

The thickness of the formed film (3) is preferably 40 μm to 5000 μm. When the film thickness of the coating (3) is insufficient, durability, chemical resistance, penetration resistance, and corrosion resistance cannot be obtained. If the film thickness is too large, there is a risk of loss of smoothness due to foaming in the film (3), cracks, unevenness on the surface of the film, etc.

In addition, although the mixing of the coating composition differs depending on the mixing conditions, in order to prevent the uneven existence of the porous coordination polymer (PCP)/metal organic structure (MOF) or the residual consolidation, it is preferable to Ball mill, etc. and mix thoroughly. The more suitable one is to make a high-concentration dispersed masterbatch, and mix it with a Henschel mixer to obtain an appropriate concentration.

In addition, the firing conditions of the base layer (2) and the coating (3) may be, for example, conditions of firing at a temperature of 300°C to 450°C for 5 to 180 minutes, but are not particularly limited. Burning can be performed using, for example, an electric furnace.

After such a process, a substrate (1), a base layer (2) formed on the surface of the base material (1), and a film (1 or more layers) formed on the base layer (2) can be obtained. 3) The coating body (10) of the fluororesin coating layer formed. [Example]

Hereinafter, examples for evaluating the coating composition, film, and film body of the present invention are illustrated to make the effect of the present invention more clear.

However, it should be understood that the present invention is not limited to the aspects exemplified in the following Examples.

In the following examples, the porous coordination polymer (PCP)/metal organic structure (MOF) used AP004 (manufactured by Atomis Co., Ltd.), which has the same structure as MIL-100 (Fe), and has the same structure as Al ( OH) (fumarate) AP006 (manufactured by Atomis Co., Ltd.) and MOF801 (Zr) (manufactured by GS Alliance Co., Ltd.) with the same structure _{as Zr 6} O ₄ (OH) _{4 (fumarate).} In addition, the ligand of AP004 is 1,3,5-benzenetricarboxylic acid; the ligand of AP006 is fumaric acid; the ligand of MOF801 (Zr) is fumaric acid.

Figure 2 illustrates the X-ray diffraction patterns of AP004, AP006, and MOF801 (Zr).

<Example 1> Thermogravimetric differential thermal analysis of porous coordination polymer (PCP)/metal organic structure (MOF) and fluororesin

The porous coordination polymer (PCP)/metal organic structure (MOF) and fluororesin used in the examples were subjected to thermogravimetric differential thermal analysis (TG-DTA).

The porous coordination polymer (PCP)/metal organic structure (MOF) and fluororesin that were subjected to thermogravimetric differential thermal analysis (TG-DTA) are as follows.

・Porous coordination polymer (PCP)/metal organic structure (MOF) (a-i) AP004 (PCP/MOF MIL-100 (Fe) Fe ₃ (O) (OH) (C ₉ H) manufactured by Atomis Co., Ltd. ₃ O ₆ ) ₂ ; pore diameter: 2.4～2.9nm; pore area: 4.52nm ² ～6.60nm ² ; BET specific surface area: 1700～2000m ³ /g) (a-ii) AP006 (Atomis Co., Ltd. PCP/MOF Al(OH)(fumarate)=Al(OH)(C ₄ H ₂ O ₄ ); The pores are rhombus 0.57nm×0.60nm; the open area of the pores: 0.17nm ² BET specific surface area : 900～2000m ³ /g) (a-iii) MOF801 (Zr) (PCP/MOF manufactured by GS Alliance Co., Ltd.) Zr ₆ O ₄ (OH) ₄ (fumarate) = Zr ₆ O ₄ (OH) ₄ (C ₄ H ₂ O ₄ ) ₆

・Fluorine resin (B-i) MJ-501 (PFA powder coating made by Mitsui DuPont Fluorochemicals Co., Ltd.; contains 85% PFA, 10% glass fragments, and 5% PPS) (B-ii) MJ-624 (PFA powder coating made by Mitsui Kemers Fluorine Products Co., Ltd.; "Contains 85% PFA and 15% SiC filler)

The thermogravimetric differential thermal analysis (TG-DTA) results of AP004, AP006, and MOF801 (Zr) are shown in Figure 3. In addition, the results of thermogravimetric differential thermal analysis (TG-DTA) of MJ-501 and MJ-624 are shown in FIG. 4.

As shown in Fig. 3, the air temperature of AP004, AP006, and MOF801 (Zr) from about 200°C to 5% decomposition is 326.44°C, 367.83°C and 242.66°C, respectively.

Also, as shown in Figure 4, MJ-501 is 308.45°C; MJ-624 is 307.26°C; the melting temperature peak can be seen.

Therefore, the temperature from 200°C to 5% of AP004 and AP006 is higher than that of MJ-501 and MJ-624. On the other hand, the temperature of MOF801 (Zr) from 200°C to 5% decomposition is lower than that of MJ-501 and MJ-624. <Example 2> Blending of paint composition

The powder coating composition was blended in accordance with the blending examples and comparative blending examples of Table 1, Table 2, and Table 3. In addition, (a-i), (a-ii), (a-iii), (b-i), and (b-ii) of Table 1, Table 2, and Table 3 are the same as those implemented in Example 1. Thermogravimetric differential thermal analysis (TG-DTA) has the same porous coordination polymer (PCP)/metal organic structure (MOF) and fluororesin. In addition, either of (b-i) MJ-501 and (b-ii) MJ-624 is thermoplastic, and is insoluble in either a polar solvent or a non-polar solvent.

(Example of blending) According to Table 1 and Table 2, the coating composition related to the blending example was blended.

Blending was performed according to the blending amount shown in Table 1, and blending example 1 was obtained. The (a-i) and (b-i) in Table 1 were blended and mixed in a ball mill for 2 days to obtain Blending Example 1 that can pass through a 300 μm mesh sieve.

Blending Example 2 and Blending Example 3 were obtained by mixing Blending Example 1 and MJ-501 with a mixer for 2 minutes according to the blending amounts in Table 1.

Blending was performed in accordance with the blending amount shown in Table 2, and blending example 4 was obtained. The (a-ii), (b-ii) and (c-i) in Table 1 were blended and mixed in a ball mill for 2 days to obtain Blending Example 4 that can pass through a sieve of 300 μm mesh.

Blending Example 5 is obtained by mixing Blending Example 4 with (b-ii) MJ-624 and (c-i) in a mixer for 2 minutes according to the blending amount in Table 2.

Blending was performed according to the blending amount shown in Table 2 to obtain Blending Example 6. (A-iii) and (b-i) in Table 1 were blended and mixed with a ball mill for 2 days to obtain Blending Example 6 that can pass through a sieve of 300 μm mesh.

Blending Example 7 is obtained by mixing Blending Example 6 and MJ-501 with a mixer for 2 minutes according to the blending amount in Table 2.

(C-i) in Table 1 and Table 2 represents Ryton 　 V-1 (Chevron Philips Chemical Co., Ltd.) of PPS (polyphenylene sulfide).

(A) in Table 1 and Table 2 represents the blending amount of porous coordination polymer (PCP)/metal organic structure (MOF) in the coating composition; (B) represents the fluorine in the coating composition The blending amount of the resin.

(Comparative blending example) The coating composition related to the comparative blending example was obtained by blending according to Table 3.

As shown in Table 3, (b-i) was used as it is as Comparative Blending Example 1.

The blending was performed according to the blending amount shown in Table 3 to obtain Comparative Blending Example 2. Blending (b-ii) and (c-i) in Table 3 was mixed with a mixer for 2 minutes to obtain Comparative Blending Example 2.

The blending was performed according to the blending amount shown in Table 3 to obtain Comparative Blending Example 3. Blending (a-i) and (b-i) in Table 3 were mixed with a ball mill for 2 days to obtain a comparative blending example 3 that can pass through a sieve of 300 μm mesh.

(C-i) in Table 3 represents Ryton 　V-1 (Chevron Philips Chemical Co., Ltd.) of PPS (polyphenylene sulfide).

(A) in Table 3 represents the blending amount of the porous coordination polymer (PCP)/metal organic structure (MOF) in the coating composition related to the comparative blending example; (B) represents the comparative blending Example of the blending amount of fluororesin in the coating composition.

〔Table 1〕 Blending amount (wt%) Blending example 1 Blending example 2 Blending example 3 (ai) AP004 5.00 ― ― (a-ii) AP006 ― ― ― (a-iii) MOF801(Zr) ― ― ― (bi) MJ-501 95.00 80.00 98.00 (b-ii) MJ-624 ― ― ― (ci) Ryton V-1 ― ― ― (di) Blending example 1 ― 20.00 2.00 (d-ii) Blending example 4 ― ― ― (d-iii) Blending example 6 ― ― ― (A) PCP/MOF content 5.00 1.00 0.10 (B) Fluorine resin 80.75 84.15 84.92

〔Table 2〕 Blending amount (wt%) Blending example 4 Blending example 5 Blending example 6 Blending example 7 (ai) AP004 ― ― ― ― (a-ii) AP006 5.00 ― ― ― (a-iii) MOF801(Zr) ― ― 5.00 ― (bi) MJ-501 ― ― 95.00 98.00 (b-ii) MJ-624 90.25 76.00 ― ― (ci) Ryton V-1 4.75 4.00 ― ― (di) Blending example 1 ― ― ― ― (d-ii) Blending example 4 ― 20.00 ― ― (d-iii) Blending example 6 ― ― ― 2.00 (A) PCP/MOF content 5.00 1.00 5.00 0.10 (B) Fluorine resin 76.71 79.94 80.75 84.92

〔table 3〕 Blending amount (wt%) Comparative blending example 1 Comparative blending example 2 Comparative blending example 3 (ai) AP004 ― ― 20.00 (bi) MJ-501 100.00 ― 80.00 (b-ii) MJ-624 ― 95.00 ― (ci) Ryton V-1 ― 5.00 ― (A) PCP/MOF content 0.00 0.00 20.00 (B) Fluorine resin 85.00 80.75 68.00

<Example 3> Envelope formation

In order to form a coating body having a coating film using the blending example of Example 1 and the comparative blending example. First, sandblasting is performed on the substrate to form a base layer. The base material is SUS304 (thickness: 6mm, side length: 200mm).

The base layer is formed by mixing the following (1) and (2) at a weight ratio of 3:1, and performing a sintering treatment at 400°C for 60 minutes. (1) 850-G314 (made by Chemos Co., Ltd., PTFE-containing base fluid) (2) 850-G7799 (made by Chemos Co., Ltd., chromic acid-containing base liquid)

Hereinafter, the film (lining film layer) related to Example 3 will be described in further detail.

Using Blending Examples 1 to 3, 5, or 7, as shown in Table 4 below, a coating body having the coatings of Test Examples 1 to 5 on the base layer was formed, respectively. In addition, using Comparative Blending Examples 1 to 3, as shown in Table 5, coating bodies having the coating films of Comparative Examples 1 to 3 were formed, respectively. In addition, any of the coating bodies of Test Examples 1 to 5 and Comparative Examples 1 to 3 were repeated: the coating composition related to the blending example or the comparative blending example was coated by electrostatic powder coating method at 350°C A process of sintering for 60 minutes to form an overall film thickness of 400μm.

〔Table 4〕 Test example 1 Test example 2 Test example 3 Test example 4 Test Example 5 Lower level Comparative blending example 1 65μm Comparative blending example 1 90μm Blending example 3 400μm Comparative blending example 2 65μm Blending example 7 400μm middle layer Blending example 1 40μm Blending example 2 50μm ― Blending example 5 100μm ― upper layer Comparative blending example 1 295μm Comparative blending example 1 260μm ― Comparative blending example 2 235μm ― Overall film thickness 400μm 400μm 400μm 400μm 400μm The base material is SUS304; the base layer is a 3:1 mixture of 850-G314 and 850-G7799.

〔table 5〕 Comparative example 1 Comparative example 2 Comparative example 3 Lower level Comparative blending example 1 400μm Comparative blending example 2 400μm Comparative blending example 3 400μm middle layer ― ― ― upper layer ― ― ― Overall film thickness 400μm 400μm 400μm Preparation Cracks occurred on the surface of the film, and a good film could not be formed. The base material is SUS304; the base layer is a 3:1 mixture of 850-G314 and 850-G7799.

Fig. 28 shows Comparative Example 3 in which cracks occurred on the surface. Fig. 29 shows the surface of Comparative Example 3 in which a part of Fig. 28 is enlarged. In the coating body of Comparative Example 3, the blending amount of the fluororesin blended relative to the entire coating composition is as small as 68.00% by weight; as shown in Figures 28 and 29, many cracks occur on the surface of the coating. It cannot form a good film.

<Example 4> Corrosion resistance test

The coating bodies related to the prepared Test Examples 1 to 5 and Comparative Examples 1 to 2 were subjected to a corrosion resistance test using a lining tester LA-15 type (manufactured by Yamazaki Seiki Laboratory Co., Ltd.). In addition, in Comparative Example 3, as shown in the above-mentioned Example 2, since cracks occurred on the surface of the film, the corrosion resistance test could not be carried out.

The corrosion resistance test system is shown in Figure 5. In the Yamazaki-type lining tester LA-15, the lower half of the above test examples 1 to 5 and comparative examples 1 to 2 are immersed in hydrochloric acid and sealed to expose the upper half In volatile hydrochloric acid.

The test conditions were condition 1: set at 99.8°C for 4 weeks in 5% hydrochloric acid, and condition 2: set at 80°C for 4 weeks in 35% hydrochloric acid. For Test Examples 1 to 3 and Comparative Example 1, the corrosion resistance tests of Condition 1 and Condition 2 were carried out together. In Test Examples 4, 5, and Comparative Example 2, only the corrosion resistance test of Condition 1 was performed.

(Pilot projects) Specifically, condition 1 and condition 2 were evaluated in the following five items (1) to (5).

(1) Initial adhesion For the lining film before exposure to hydrochloric acid, the initial adhesion with the substrate was evaluated by conducting a peel strength test specified in JIS "K" 5400 within a width of 5 mm. Then, the same value as in Comparative Example 1 or 2 is expressed as ○; when it exceeds, it is expressed as ◎; when it is lower than, it is expressed as △; when the value is less than half, it is expressed as x. However, when the film is broken, since it is related to the thickness of the film and has nothing to do with the value, it is expressed as ○. In addition, the specific adhesion strength is described in Tables 6 to 8, and when it is confirmed that the lining film is broken, it is described as "film breakage". In addition, as shown in E of FIG. 5, the initial adhesion strength with the base material was evaluated by performing a peel strength test on the part not immersed in hydrochloric acid.

(2) Time until blisters (expansion) occur Measure the time until blisters occur. This test system stops the test every 1 week, decomposes to confirm the film, and counts the occurrence of blisters on a weekly basis. The same value as in Comparative Example 1 or 2 is expressed as ○; when it exceeds, it is expressed as ◎; when it is lower than, it is expressed as △; when the value is less than half, it is expressed as ×.

(3) The maximum diameter of blisters (expanded) after 4 weeks Measure the maximum diameter of the blisters after 4 weeks. The same value as in Comparative Example 1 or 2 is expressed as ○; when it is less than, it is expressed as ◎; when it is greater than, it is expressed as △; when the value is more than one time, it is expressed as ×. The 35% hydrochloric acid condition is not included in the calculation because it is raised in a flat shape on the envelope.

(4) Area ratio of blisters (expansion) after 4 weeks Measure the area of blisters after 4 weeks, and calculate the proportion of the area of blisters in the test area. The same value as in Comparative Example 1 or 2 is expressed as ○; when it is less than, it is expressed as ◎; when it is greater than, it is expressed as △; when the value is more than one time, it is expressed as ×. The blister or the area where the surface-like swelling occurs on the film is not calculated by the total amount of each swelling area, but is calculated by setting the range as the area of the blister.

(5) Close force after 4 weeks The peel strength test specified in JIS K 5400 is used to evaluate the adhesion to the substrate after 4 weeks. In addition, if the lowest value is almost the same as that of Comparative Example 1 or 2, it is indicated as ○; when it exceeds, it is indicated as ◎; when it is significantly lower, it is indicated as △; when the value is less than half, it is indicated as × . In addition, since the film is divided into a gas phase part and a liquid phase part, the adhesion force is measured separately; in the column of the adhesion force after 4 weeks in Tables 6 to 8, the upper half is the description of the gas phase density. Resultant force; the lower half is a record about the adhesive force of the liquid phase. In addition, in Tables 6 to 8, the measured value (N/5mm) of the peel strength test is described; when it is confirmed that the film is broken, it is described as "film breaking". In addition, when the position where the adhesion force is 0 is at the gas-liquid interface, the length in the measurement direction is described on the liquid phase side, which is used as a comparison target. In addition, as shown in FIG. 5, the measurement was performed twice on the left and right, and A and B were gas phase parts, and C and D were liquid phase parts. The numerical values of the 2 measurements are summarized in Tables 6-8.

(test results) As shown in the description of Examples 2 and 3 above, Test Examples 1 to 3, 5 and Comparative Example 1 were blended with MJ-501 as a fluororesin. On the other hand, Test Example 4 and Comparative Example 2 were blended with MJ-624 as a fluororesin. Therefore, the results of Test Examples 1 to 3, 5 and Comparative Example 1 and Test Example 4 and Comparative Example 2 are described in separate tables, respectively.

The evaluation results of the corrosion resistance test: Test Examples 1 to 3, 5 and Comparative Example 1 under 5% hydrochloric acid conditions are described in Table 6; Test Example 4 and Comparative Example 2 under 5% hydrochloric acid conditions are described in Table 7; 35 Test Examples 1 to 3 and Comparative Example 1 under the condition of% hydrochloric acid are shown in Table 8.

[Table 6] Condition 1: 99.8℃, 5% hydrochloric acid conditions; fluororesin MJ-501 blending Test example 1 Test example 2 Test example 3 Test Example 5 Comparative example 1 Initial adhesion force (N/5mm) ＞25.0 (Broken film) ○ ＞28.9 (Broken film) ○ ＞28.6 (Broken film) ○ ＞27.4 (Broken film) ○ ＞24.3 (Broken film) Time to blisters (weeks) 2 ◎ 1 ○ 1 ○ 1 ○ 1 Maximum blister diameter after 4 weeks (mm) 5 ◎ 6 ◎ 4 ◎ 8 ○～△ 7 Area of blisters occurring after 4 weeks (%) 67.48 ◎ 46.95 ◎ 31.71 ◎ 60.98 ◎ 72.36 Adhesion force (gas phase) after 4 weeks (N/5mm) 12.3～28.2 (The film is broken) ◎ 6.8～23.6 (The film is broken) ◎ 11.9～28.7 (The film is broken) ◎ 6.3～17.7 ◎ 3.0～17.2 Adhesion after 4 weeks (liquid phase) (N/5mm) 7.5～27.8 ◎ 3.3～28.3 (The film is broken) ◎ 9.8～28.3 (The film is broken) ◎ 3.9～24.9 ◎ 3.1～23.3

[Table 7] Condition 1: 99.8℃, 5% hydrochloric acid conditions; fluororesin MJ-624 blending Test example 4 Comparative example 2 Initial adhesion force (N/5mm) ＞17.8 ○ ＞17.5 Time to blisters (weeks) 1 ○ 1 ○ Maximum blister diameter after 4 weeks (mm) 3 ◎ 5 Area of blisters occurring after 4 weeks (%) 42.28 ◎ 46.95 Adhesion force (gas phase) after 4 weeks (N/5mm) ＞21.6 ○ ＞24.6 Adhesion after 4 weeks (liquid phase) (N/5mm) 9.2～21.7 (The film is broken) ◎ 5.2～21.8 (Broken film)

[Table 8] Condition 2: 80℃, 35% hydrochloric acid condition Fluorine resin MJ-501 blending Test example 1 Test example 2 Test example 3 Comparative example 1 Initial adhesion force (N/5mm) ＞24.8 (Broken film) ○ ＞28.3 (The membrane is broken) ○ ＞27.4 (Broken film) ○ ＞22.8 (capsule broken) Time to blisters (weeks) 2 ○ 2 ○ 3 ◎ 2 Maximum blister diameter after 4 weeks (mm) 3 ○ 2 ◎ 1 ◎ 3 Area of blisters occurring after 4 weeks (%) 63.41 ◎ 21.06 ◎ 14.63 ◎ 68.29 Adhesion force (gas phase) after 4 weeks (N/5mm) 0～19.2 ◎ 0.1～9.6 ○～△ 0.1～13.3 ○ 0～13.6 Adhesion after 4 weeks (liquid phase) (N/5mm) 0～23.5 (The gas-liquid interface is 17mm, the adhesion force is 0) ◎ 0～8.4 (The gas-liquid interface adhesion force is 0 none) ○ 0.1～6.0 (zero adhesion of gas-liquid interface) ○ 0～10.6 (The gas-liquid interface is 25mm, the adhesion force is 0)

As shown in Tables 6 and 8, and Figures 6 to 11, 16, 17, and 20 to 27, compared with Comparative Example 1 where the porous coordination polymer (PCP)/metal organic structure (MOF) is not blended Below, it can be confirmed that Test Examples 1 to 3 in which AP004 was blended had fewer blisters after the corrosion resistance test, and the result was that the residual adhesive force was also higher.

As shown in Table 7 and Figures 12, 13, 18 and 19, compared with Comparative Example 2 where the porous coordination polymer (PCP)/metal organic structure (MOF) is not blended, it can be confirmed that: In Test Example 4 mixed with AP006, less blisters occurred after the corrosion resistance test, and the residual adhesion force was also higher.

As shown in Table 6 and FIGS. 14 to 17, compared with Comparative Example 1, it was confirmed that Test Example 5 in which MOF801 (Zr) was blended also showed sufficient residual adhesion.

In addition, from the results of Test Example 5 and Test Examples 1 to 4, the temperature from 200°C to 5% decomposing in air is higher than the melting point of the fluororesin due to the blending of fluororesin. The porous coordination polymer (PCP)/metal organic structure (MOF), so it can be understood that a film with remarkably excellent durability, chemical resistance, penetration resistance, and corrosion resistance can be obtained.

In addition, in the test example in the gas phase, the residual adhesion force is high, and it can be judged that the porous coordination polymer (PCP)/metal organic structure (MOF) has adsorbed the volatilized hydrogen chloride gas. Therefore, it can be understood that the porous coordination polymer (PCP)/metal organic structure (MOF) adsorbs gas and can suppress the corrosion of the substrate.

These effects can be judged to be due to the porous coordination polymer (PCP)/metal organic structure (MOF) layer mixed with the porous coordination polymer (PCP)/metal organic structure (MOF) above the base layer, so it can impart improved corrosion resistance.

Therefore, the coating composition, the coating film, and the coating system related to the present invention can be formed into a film without causing cracks and other improperities, and exhibit excellent durability, chemical resistance, penetration resistance, and corrosion resistance. It can be said that It is something that has utility. 〔Possibility of industrial use〕

The fluororesin-containing powder coating composition and liquid coating composition for burning of the present invention, the coating film containing the powder coating composition or liquid coating composition for burning, and the coating system do not produce cracks It is not suitable to form a film and can be very suitable for use in equipment that must have excellent durability, chemical resistance, penetration resistance, and corrosion resistance (for example, although not limited, such as chemical plant equipment, semiconductor Manufacturing equipment, conditioning machines, etc.).

1: Substrate 2: basal layer 3: Film (lining film) 10: Encapsular body

Fig. 1 is a cross-sectional view of the structure of the coating body according to the embodiment of the present invention. Figure 2 shows the X-ray diffraction patterns of AP004, AP006, and MOF801 (Zr). Figure 3 shows the measurement results of thermogravimetric differential thermal analysis (TG-DTA) of AP004, AP006, and MOF801 (Zr). Figure 4 shows the measurement results of thermogravimetric differential thermal analysis (TG-DTA) of MJ-501 and MJ-624. Fig. 5 shows the state of the coating body during the corrosion resistance test according to the embodiment of the present invention. Figure 6 shows Test Example 1 after being immersed in 5% hydrochloric acid for 4 weeks at a temperature of 99.8°C. Fig. 7 shows the results of the adhesion measurement of Test Example 1 after being immersed in 5% hydrochloric acid for 4 weeks under the temperature condition of 99.8°C. Figure 8 shows Test Example 2 after being immersed in 5% hydrochloric acid for 4 weeks at a temperature of 99.8°C. Fig. 9 shows the results of the adhesion measurement of Test Example 2 after immersion in 5% hydrochloric acid for 4 weeks under the temperature condition of 99.8°C. Figure 10 shows Test Example 3 after being immersed in 5% hydrochloric acid for 4 weeks at a temperature of 99.8°C. Fig. 11 shows the results of the adhesion measurement of Test Example 3 after immersing in 5% hydrochloric acid for 4 weeks under the temperature condition of 99.8°C. Figure 12 shows Test Example 4 after being immersed in 5% hydrochloric acid for 4 weeks at a temperature of 99.8°C. Fig. 13 shows the results of the adhesion measurement of Test Example 4 after immersing in 5% hydrochloric acid for 4 weeks under the temperature condition of 99.8°C. Figure 14 shows Test Example 5 after being immersed in 5% hydrochloric acid for 4 weeks at a temperature of 99.8°C. Fig. 15 shows the results of the adhesion measurement of Test Example 5 after being immersed in 5% hydrochloric acid for 4 weeks under the temperature condition of 99.8°C. Figure 16 shows Comparative Example 1 after being immersed in 5% hydrochloric acid for 4 weeks at a temperature of 99.8°C. Fig. 17 shows the results of the adhesion measurement of Comparative Example 1 after being immersed in 5% hydrochloric acid for 4 weeks under the temperature condition of 99.8°C. Figure 18 shows Comparative Example 2 after being immersed in 5% hydrochloric acid for 4 weeks at a temperature of 99.8°C. Figure 19 shows the results of the adhesion measurement of Comparative Example 2 after being immersed in 5% hydrochloric acid for 4 weeks under the temperature condition of 99.8°C. Fig. 20 shows Test Example 1 after immersing in 35% hydrochloric acid for 4 weeks at a temperature of 80°C. Fig. 21 shows the results of the adhesion measurement of Test Example 1 after immersing in 35% hydrochloric acid for 4 weeks under the temperature condition of 80°C. Fig. 22 shows Test Example 2 after immersing in 35% hydrochloric acid for 4 weeks at a temperature of 80°C. Fig. 23 shows the results of the adhesion measurement of Test Example 2 after immersing in 35% hydrochloric acid for 4 weeks under the temperature condition of 80°C. Fig. 24 shows Test Example 3 after 4 weeks of immersion in 35% hydrochloric acid at a temperature of 80°C. Figure 25 shows the results of the adhesion measurement of Test Example 3 after immersing in 35% hydrochloric acid for 4 weeks under the temperature condition of 80°C. Fig. 26 shows Comparative Example 1 after immersing in 35% hydrochloric acid for 4 weeks at a temperature of 80°C. Fig. 27 shows the results of the adhesion measurement of Comparative Example 1 after immersing in 35% hydrochloric acid for 4 weeks under the temperature condition of 80°C. Fig. 28 shows Comparative Example 3 where cracks occurred on the surface. Fig. 29 shows a part of the surface of Comparative Example 3 of Fig. 28 enlarged.

1: Substrate

2: basal layer

3: Film (lining film)

10: Encapsular body

Claims (22)

A powder coating composition for sintering, which contains fluororesin dispersed with more than one type of porous coordination polymer (PCP)/metal formed by coordination bonding between organic ligands and central metal Organic structure (MOF). The powder coating composition for burning as described in claim 1, wherein the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF) is in powder form; The decomposition temperature from 200°C to 5% under air conditions measured by thermogravimetric differential thermal analysis (TG-DTA) is higher than the melting point of the aforementioned fluororesin; and With respect to the entire coating composition described above, 0.02% by weight to 20.00% by weight are blended. The powder coating composition for burning as described in claim 1, wherein the aforementioned fluororesin is thermoplastic; It is insoluble with respect to any one of a polar solvent and a non-polar solvent; and It is blended in 70.00% by weight to 99.98% by weight with respect to the entire coating composition. The powder coating composition for burning as described in claim 1, wherein the blending amount of the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF) relative to the entire coating composition is 0.10% by weight to 5.50% by weight. The powder coating composition for burning as described in claim 1, wherein the aforementioned central metal is selected from Al ^{3 +} , Co ^{3 +} , Co ^{2 +} , Ni ^{2 +} , Ni ⁺ , Cu ^{2 +} , Cu ⁺ , One or more metal ions selected from the group consisting of Zn ^{2 +} , Fe ^{3 +} , Fe ^{2 +} , Ti ^{3 +} , and Zr ^{4 +} exist; the aforementioned metal ions are coordinately bonded to the aforementioned organic ligands And it exists in the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF). The powder coating composition for burning as described in claim 1, wherein at least one of the aforementioned central metals supports more than one anion; The aforementioned central metal system is coordinately bonded to the aforementioned organic ligand and is present in the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF). As described in the requested item 6 burning powder coating compositions with the attachment, wherein the anionic comprises from OH ^-, CO ₃ ^{2 -,} and O ^{2 -} anions least one of the group selected. The powder coating composition for burning as described in claim 6, wherein at least one of the aforementioned central metal forms the aforementioned anion and oxo structure. The powder coating composition for burning as described in claim 1, wherein the aforementioned organic ligands include 1,4-phthalic acid, 1,3,5-benzenetricarboxylic acid, 4,4'- Bipyridine, imidazole, 1,3,5-ginseng (4-carboxyphenyl)benzene, fumaric acid, terephthalic acid, and maleic acid constitute more than one organic ligand selected from the group. The powder coating composition for burning as described in claim 1, wherein the porous coordination polymer (PCP)/metal organic structure (MOF) can be given the characteristic of adsorbing gas. The powder coating composition for burning as described in claim 10, wherein the gas system contains at least a corrosive gas of hydrogen chloride. The powder coating composition for burning as described in claim 1, wherein the open area of the pores of the porous coordination polymer (PCP)/metal organic structure (MOF) is 0.15nm ² ～7.00nm ² . The powder coating composition for burning as described in claim 1, wherein the aforementioned porous coordination polymer (PCP)/metal organic structure (MOF) has a specific surface area (BET ratio ^{) greater than 900.00m 3 /g} Surface area). The powder coating composition for burning as described in claim 1, which includes one or more porous coordination polymers (PCP)/metal organic structures (MOF) with hydrophobic properties, and One or more porous coordination polymers (PCP)/metal organic structures (MOF) with hydrophilic properties. The powder coating composition for baking as described in claim 1, wherein the blending amount of the fluororesin is 75.00% by weight to 90.00% by weight relative to the entire coating composition. The powder coating composition for baking as described in claim 1, wherein the fluororesin includes at least one fluororesin selected from the group consisting of PFA, FEP, ETFE, PCTFE, and ECTFE. The powder coating composition for burning as described in claim 1, which further includes one or more additives selected from the group consisting of PPS, PEEK, and PES. A liquid coating composition for burning, which is formed by dispersing the powder coating composition for burning as described in claim 1 in a solvent. A coating film comprising the powder coating composition for burning or the liquid coating composition for burning as described in any one of claims 1 to 18. The film described in claim 19 has a film thickness of 40 μm to 5000 μm. A coated body having a substrate, a base layer formed on the surface of the aforementioned substrate, and one or more fluororesin coating layers formed on the aforementioned base layer; wherein The aforementioned fluororesin coating layer is the coating described in claim 19. A coating body comprising a substrate, a base layer formed on the surface of the substrate, and one or more fluororesin coating layers formed on the base layer, The aforementioned fluororesin coating layer is the coating described in claim 20.

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