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    • 专利摘要:
    The present invention is obtained by desolvating a curable fluorine-containing resin to obtain a main resin, and then mixing paint additives such as a curing agent to prepare a powder coating composition, or dissolving or dispersing a curable fluorine-containing resin, a curing agent, and various additives in a solvent. The present invention relates to a method for preparing a raw material solution and removing the solvent from the raw material solution to prevent gelation when preparing a powder coating directly. In the solution or dispersion of the curable fluorine-containing copolymer (A), an antigelling agent (B) is added and mixed, or an antigelling agent (B), a curing agent (C), and various additives (D) are added and mixed as necessary. Then, this solution or dispersion is supplied to a thin film vacuum evaporator to remove the solvent.
    公开号:KR20040068208A
    申请号:KR10-2004-7008849
    申请日:2002-12-19
    公开日:2004-07-30
    发明作者:야마우찌마사루；이시다도루
    申请人:아사히 가라스 가부시키가이샤；
    IPC主号:
    专利说明:

    Fluorine-containing resin powder having a curable functional group and a method for producing the coating composition thereof PROCESSES FOR PRODUCTION OF POWDERED FLUORORESINS BEARING CURABLE FUNCTIONAL GROUPS AND COATING COMPOSITIONS CONTAINING THE SAME
    [2] Dispersible thermoplastic fluorine-containing resins containing polyvinylidene fluoride as a main component, or solvent-soluble thermosetting fluorine-containing resins containing copolymers of fluoroolefins and vinyl ethers or vinyl esters as the main components, are corrosion resistant and durable. In recent years, it has been widely used in coating fields such as heavy coating, construction, and industrial use for reasons such as easy removal of foreign substances (for example, Japanese Patent Publication No. 60-21667, Japanese Patent Publication No. 59-102962). Japanese Patent Laid-Open No. 61-57609, etc.).
    [3] In addition, a low pollution type general fluorine resin coating material has been proposed to reduce the amount of organic solvent (VOC) emissions due to a serious environmental pollution problem each year (for example, Japanese Patent Application Laid-Open No. Hei 1-103670, Japanese Patent Application Laid-Open No. 2). -60968, Japanese Patent Laid-Open No. Hei 6-345822, Japanese Patent Laid-Open No. Hei 7-145332 and the like).
    [4] In general, the main resin used for powder coating is often solidified by first removing the solvent from the resin solution or the dispersion by a continuous vacuum desolvent or spray drying apparatus before mixing with other additives. , Japanese Patent Application Laid-open No. Hei 8-118357 et al.). However, in such a method, when the resin stays in the apparatus for removing the solvent and is heated for a long time, some gel particles are generated, and a process such as filtration of the gel particles is required, and at the same time, the paintability and coating properties It may fall.
    [5] Next, in the case of producing the powder coating composition, the solvent is co-pulverized after desolvating the main resin in the same manner as described above, and after curing the curing agent and various additives by dry blending, melt mixing, secondary grinding, and classification are carried out. The method to be produced is generally employed. Therefore, this multi-step manufacturing process is taken, and thus there is a problem that the manufacturing cost is higher than that of the solvent type paint. In order to solve this problem, an attempt has been made to prepare a powder coating by preparing a raw material solution obtained by dissolving or dispersing a main resin, a curing agent, and various additives as a raw material in a solution, and removing the solvent.
    [6] For example, Japanese Laid-Open Patent Publication No. 2000-34426 uses a solvent having a low boiling point such as methanol to spray-dry after mixing a main resin used in ordinary powder coating such as acrylic resin and an additive thereof, such as a curing agent, or continuously A method of providing a powder coating by providing a pressure reduction desolvation apparatus to remove volatile components has been proposed.
    [7] However, according to the inventors' findings, in the case of a fluorine-containing resin having a curable functional group, a problem remains even when using a low boiling point solvent such as an acrylic resin. That is, since one of the unreacted monomers of a relatively high boiling point still remains in the solution after polymerization, in the solvent removal by spray drying at a low temperature or a continuous vacuum desolvent, a sufficient solid content concentration as a powder coating is required. There is a problem that cannot be achieved. On the other hand, if the solvent is removed at a relatively high temperature in order to increase the solid content concentration, there may be a problem that even if the curing reaction does not occur, this time, the same gel particles as the desolvation of the main resin are generated. .
    [8] First, the present invention is to prepare a powder coating composition by desolving a solution or dispersion of a fluorine-containing resin having a curable functional group as a main resin of the powder coating composition, and then dry blending a paint additive such as a curing agent. To solve the above-mentioned problem. Secondly, a raw material solution obtained by dissolving or dispersing a fluorine-containing resin, a curing agent, and various additives having a curable functional group in a solvent is prepared, and the solvent is removed by a continuous vacuum de-solvent to produce powder coating directly. The above problem is to be solved.
    [1] The present invention relates to a method for producing a fluorine-containing resin powder and its coating composition by a thin film vacuum evaporation method, and more particularly, even if the solvent is removed by a thin film vacuum evaporator under relatively high temperature conditions. The present invention relates to a fluorine-containing resin powder having a hardenable functional group which is easy to mix uniformly and has fewer defects in coating film, and a method for producing the paint composition, as compared with the case where it is difficult to occur and melt mixed with a fluorine-containing resin powder paint material.
    [9] SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems. First, an antigelling agent (B) is added and mixed in a solution or dispersion of a fluorine-containing copolymer (A) having a curable functional group, and the solution or dispersion is thin-film vacuumed. Provided to the evaporator, and provides a method for producing a fluorine-containing resin powder having a curable functional group characterized in that the solvent is removed from the solution or dispersion. Secondly, in the solution or dispersion of the fluorine-containing copolymer (A) having a curable functional group, the present invention adds and blends an antigelling agent (B), a curing agent (C) and other powder coating additives (D) as necessary. To obtain a resin composition solution or dispersion, supply the solution or dispersion to a thin film vacuum evaporator, and remove the solvent from the resin composition solution or dispersion, thereby preparing a fluorine-containing resin powder coating composition having a curable functional group. Provide a method.
    [10] Best Mode for Carrying Out the Invention
    [11] EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail.
    [12] (Fluorine-containing copolymer (A))
    [13] First, the fluorine-containing copolymer (A) which has a curable functional group in the powder coating raw material used in the manufacturing method of this invention is demonstrated.
    [14] As said fluorine-containing copolymer (A), the fluorine-containing copolymer which has a curable functional group and consists of the following polymerized units is used preferably.
    [15] (a) 35 to 99 mol% of fluoroolefins
    [16] (b) 1 to 30 mol% of monomers having curable functional groups
    [17] (c) 0 to 64 mol% of other copolymerizable monomers
    [18] And more preferably, it consists of the following polymerization units.
    [19] (a) 35 to 65 mol% of fluoroolefins
    [20] (b) 1 to 30 mol% of monomers having curable functional groups
    [21] (c) 20 to 60 mol% of other copolymerizable monomers
    [22] In the above, the fluoroolefin of (a) may be one type, or may be used in combination of 2 or more type. If there is less fluoroolefin than this, weather resistance will fall, and if more than this, the composition of a copolymer will become nonuniform and the physical property of a coating film will fall. Moreover, when the range of the monomer which has a curable functional group of (b) is smaller than this, hardening is not fully performed, When too much, the fall of weather resistance of a coating film and coating film defects increase. Moreover, when there are too many other copolymerizable monomers of (c), film quality, such as weather resistance of a coating film, will fall. On the other hand, that the lower limit of (c) is 0% indicates that this copolymerizable monomer may not be contained at all.
    [23] In the present invention, as the fluoroolefin of (a), trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, trifluoropropylene, tetrafluoropropylene, vinylidene fluoride, pentafluoropropylene, Fluoroolefins having 2 to 4 carbon atoms containing fluorine atoms such as hexafluoropropylene, tetrafluorobutylene and pentafluorobutylene are preferable, and trifluoroethylene, chlorotrifluoroethylene and tetra Fluoroethylene, vinylidene fluoride and hexafluoropropylene are preferable. On the other hand, it may contain other halogen atoms such as chlorine atoms together with fluorine atoms.
    [24] Moreover, as a monomer which has a curable functional group of (b), although it does not specifically limit, For example, the monomer which has groups, such as (i) hydroxyl group, (ii) carboxyl group, or (iii) epoxy group, as a curable functional group, etc. are mentioned.
    [25] (i) Examples of the monomer having a hydroxyl group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1-hydroxymethyl-4 -Vinyloxymethylcyclohexane, 2-hydroxyethyl crotonic acid, 2-hydroxyethyl allyl ether, allyl alcohol, 2-hydroxyethyl (meth) acrylic acid, 3-hydroxypropyl (meth) acrylic acid, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, etc. are mentioned.
    [26] (ii) Examples of the monomer having a carboxyl group include unsaturated fatty acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 10-undecylene acid (undecenoic acid), 9-octadecenoic acid (oleic acid), fumaric acid, maleic acid, and the like. The monomer which has a carboxyl group, the carboxylic acid group containing monomer represented by following formula (1), (2), etc. are illustrated.
    [27] (1) CH 2 = CHOR 1 OCOR 2 COOM
    [28] (2) CH 2 = CHCH 2 OR 3 OCOR 4 COOM
    [29] (Wherein R 1 and R 3 are divalent hydrocarbon groups of 2 to 15 carbon atoms, R 2 and R 4 are saturated or unsaturated linear or cyclic divalent hydrocarbon groups, M is a hydrogen atom, a hydrocarbon group, an alkali) Compounds containing metal or nitrogen atoms)
    [30] Especially, 10- undecylenic acid is preferable because it has good copolymerizability with a fluoroolefin.
    [31] The monomer which has these carboxyl groups can also copolymerize as it is. In addition, when copolymerizing the monomer which is hard to copolymerize in an acidic atmosphere like vinyl ether etc., what is necessary is to block a carboxyl group in the form of alkali salt etc. at the time of superposition | polymerization, perform acid wash after superposition | polymerization, and return to a carboxyl group.
    [32] Moreover, copolymerization can be obtained using the monomer which has a hydroxyl group, and polybasic acid anhydrides, such as succinic anhydride, can be made to react with this copolymerization, and it can also be modified into the copolymer which has a carboxyl group.
    [33] (iii) As an example of the monomer which has an epoxy, glycidyl vinyl ether, glycidyl allyl ether, glycidyl (meth) acrylate, etc. are mentioned.
    [34] Moreover, as another copolymerizable monomer of (c) which can be used, Vinyl ester, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl pivalate, a vinyl caproate, a vinyl caprylate, and a vinyl stearate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether; Methyl isopropenyl ether, ethyl isopropenyl ether, isopropyl isopropenyl ether, n-propyl isopropenyl ether, n-butyl isopropenyl ether, tert-butyl isopropenyl ether, isobutyl isopropenyl ether, Isopropenyl ethers such as cyclohexyl isopropenyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, N-pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, isohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters, such as lauryl; Methyl crotonate, methyl isocrotonate, ethyl crotonate, ethyl isocrotonate, n-propyl crotonate, isopropyl crotonate, isobutyl crotonate, tert-butyl crotonate, n-hexyl crotonate, hexyl crotonate Crotonic acid ester, such as these; Allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, and isobutyl allyl ether; Olefin, such as ethylene, propylene, isobutylene, 1-hexene, and cyclohexene, etc. are mentioned. By using these suitably, compatibility with a hardening | curing agent, flexibility of a coating film, etc. can be improved.
    [35] The solution or dispersion of the fluorine-containing copolymer (A) having a curable functional group in the present invention polymerizes the monomers (a) to (c) by an appropriate method such as emulsion polymerization, solution polymerization, suspension polymerization, and the like. It can obtain by making it into the dispersion liquid (aqueous acid liquid etc.) and solution of a copolymer.
    [36] For example, in the case of emulsion polymerization, an ordinary radical initiator, in particular a water-soluble initiator, is preferably employed as the polymerization initiator, and specifically, a persulfate such as ammonium persulfate, hydrogen peroxide or these with a reducing agent such as sodium hydrogen sulfite or sodium thiosulfate Redox initiators etc. which consist of a combination are used.
    [37] The amount of the polymerization initiator to be used can be appropriately changed depending on the kind, emulsion polymerization conditions and the like. Usually, about 0.005-0.5 mass part is preferable per 100 mass parts of monomers for emulsion polymerization. In addition, these polymerization initiators may be added collectively or may be added separately.
    [38] You may use a pH adjuster for the purpose of raising the pH of an emulsion. As a pH adjuster, inorganic bases, such as sodium carbonate, potassium carbonate, sodium orthophosphate, sodium thiosulfate, and organic bases, such as triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, etc. are illustrated.
    [39] The emulsion polymerization start temperature is appropriately selected depending on the type of polymerization initiator. Usually 0-100 degreeC, especially 10-90 degreeC grade is employ | adopted preferably. In addition, polymerization temperature is about 20-120 degreeC. The polymerization pressure can be appropriately selected. Usually, 0.1 to 10 MPa, in particular, about 0.2 to 5 MPa is employed.
    [40] On the other hand, the monomer is a method of injecting the whole amount of the device into the reactor, the method of continuously injecting the total amount of the device, the method of injecting the device by dividing the total amount, the part of the monomer is put into the start of the polymerization reaction, and then the remainder is divided Alternatively, various methods such as a method of continuously injecting a device can be adopted.
    [41] (Angelling Agent (B))
    [42] Next, the antigelling agent (B) will be described.
    [43] In general, the fluorine-containing copolymer (A) having a curable functional group in the present invention does not cause gelation at the time of heat concentration unless a curing agent or the like is blended. However, the inventors have found that, in the production of powder coating by the thin film vacuum evaporator, the gelation is unexpectedly performed even at a drying temperature (for example, a drying temperature of 160 ° C. or less) that such gelation does not occur. It could be seen that.
    [44] The present invention addresses these new problems, and is characterized by first adding and blending an antigelling agent (B) in a solution or dispersion of the fluorine-containing copolymer (A). Further, the present invention is characterized in that the gelling agent (B), the curing agent (C) and the additive for powder coating (D) are added and blended in the solution or dispersion of the fluorine-containing copolymer (A).
    [45] As an antigelling agent (B) used by this invention, the following compounds are mentioned as a preferable thing.
    [46] 2,6-di-tert-butyl-4-methylphenol (BHT), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert- Butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydrate Oxyphenyl) propionate], 2,4,6-tridecylphenol, 4-tert-butylphenol, 4-nonylphenol, 3,5-dinonylphenol, 4-cyclohexylphenol, 4-phenylphenol, 4 Octylphenol, phenol, cresol, 2,3-xylenol, 4-butylphenol, 4-isopentylphenol, 4-ethylphenol, 4-isopropylphenol, 4- (2-ethylhexyl) phenol, 4- (1,1-dimethylheptyl) phenol, 4-decylphenol, 4- (1,1-dimethylhexyl) phenol, 4-isohexylphenol, 4-octadecylphenol, 3,5-diisobutylphenol, 3, Phenols such as 5-dipentylphenol and 1,3-diphenylolpropane.
    [47] Epoxidized soybean oil, epoxidized linseed oil, epoxidized paulownia oil, epoxidized fish oil, epoxidized castor oil, epoxidized safflower oil, epoxy methyl stearate, triglycidyl isocyanurate, 3- (2-xenoxy) Alkyl of -1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, 3-vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexanecarboxylic acid Epoxy compounds, such as ester and bis (3, 4- epoxycyclohexyl) adipic acid ester.
    [48] Triphenyl phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl Isooctyl phosphite, diphenyldecyl phosphite, tris (nonylphenyl) phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (dinonylphenyl) Phosphate esters, such as a phosphite, a trilauryl trithio phosphite, and a trilauryl phosphite.
    [49] Antioxidants, such as a combination system of the above-mentioned compound, and metal soaps, such as zinc stearate, calcium stearate, barium stearate, calcium ricinoleate, and barium laurate.
    [50] Bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate, abbreviated as HALS, 2,2,6,6-tetramethyl-4-piperidylstearate, 1,2, 2,6,6-pentamethyl-4-piperidylstearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (1,2,2,6,6-pentamethyl -4-piperidyl) sebacate, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2, 2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine Hindered amine light stabilizers, such as these.
    [51] These gelling inhibitors (B) are used in an amount of 0.05 to 15% by mass, preferably 0.02 to 10% by mass, more preferably about 0.05 to 5% by mass, with respect to the fluorine-containing copolymer (A).
    [52] On the other hand, in addition to the above-mentioned, triazine stabilizers such as hydroxyphenyl triazine; Sulfur-based stabilizers such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, glycerin tributylthio propionate, and glycerin trioctylpropionate can also be used.
    [53] In the present invention, the gelation of the fluorine-containing copolymer (A) during drying is substantially prevented by adding such an antigelling agent (B) and drying it in a thin film vacuum evaporator. This mechanism is not fully understood at this time. Clearly, it appears to cause gelation of traces of double bonds present in the resin structure of the copolymer, unstable groups such as hydroperoxides, unstable chlorine atoms, or traces of unstable substances remaining when the resin is isolated from the polymerization system. It is assumed that the causative agent is stabilized by adding the antigelling agent (B).
    [54] (Hardener (C))
    [55] Next, as a hardening | curing agent (C) used for this invention, block isocyanate which blocked polyisocyanate compounds, such as isophorone diisocyanate and hexamethylene diisocyanate, with blocking agents, such as (epsilon) -caprolactam and methyl ethyl ketone, A hardening | curing agent, a uretodione compound, the amide hardening agent which has a (beta) -hydroxyalkylamide group, For example, Primid XL-552 by EMS Showa Denko Corporation, A triglycidyl isocyanurate (TGIC) hardening agent, etc. are mentioned. These are hardening | curing agents hardening by heating. In addition, the hardening | curing agent hardened | cured by an ultraviolet-ray etc. belongs to the scope of the present invention. The preferable ratio of the fluorine-containing copolymer (A) / hardener (C) which has a curable functional group in this invention is 40/60-98/2 (mass basis), Especially it is 50/50-97/3.
    [56] Although the powder coating composition of this invention consists essentially of a fluorine-containing copolymer (A), an antigelling agent (B), and a hardening | curing agent (C), if necessary, it is for other powder coatings in the range which does not impair the objective of this invention. Additive (D) can also be added. Examples of such powder coating additives include surface leveling agents, silane coupling agents, ultraviolet absorbers, light stabilizers, colored pigments, metallic pigments, and extender pigments. In addition to the fluorine-containing copolymer (A), resins such as known acrylic resins, polyester resins, alkyd resins, amino resins, epoxy resins, polyurethane resins, and the like used in general coating compositions can also be used. .
    [57] (Thin vacuum vacuum evaporation)
    [58] Next, the thin film vacuum evaporation drying step will be described.
    [59] In the present invention, first, the antigelling agent (B) is added to a solution or dispersion of a fluorine-containing copolymer (A) having a curable functional group, and mixed, the solution or dispersion is supplied to a thin film vacuum evaporator, and the solution Or removing the solvent from the dispersion. The thin film vacuum evaporator may be any one of a centrifugal thin film vacuum evaporator, a belt type thin film vacuum evaporator, or a screw thin film vacuum evaporator which are commonly used, and particularly when the molten fluorine-containing copolymer (A) has a high viscosity It is preferable to use a screw-type vacuum evaporator which is easy to discharge. As the screw-type thin film vacuum evaporator, for example, a high viscosity thin film vacuum evaporator "Exeva" (trade name: manufactured by Shinko Pantec Co., Ltd.) or a twin screw extruder can be used.
    [60] The manufacturing method of a solvent is not specifically limited, It can carry out by pressure reduction, heating, or a combination thereof. In particular, the combination of reduced pressure and heating is preferable because the efficiency is good and the deterioration due to heat can be suppressed.
    [61] As heating temperature, the fluorine-containing copolymer (A) which has a curable functional group may be below the limit temperature stabilized by the antigelling agent (B), and may be more than the temperature which removes a solvent efficiently. It is preferable that it is 180 degrees C or less specifically, and 50 degrees C or more. More preferably, it is 160 degrees C or less, and 80 degreeC or more.
    [62] Next, in the present invention, in the solution or dispersion of the fluorine-containing copolymer (A) having a curable functional group, a gelling inhibitor (B), a curing agent (C), and other powder coating additives (D), if necessary The mixture is added to obtain a resin composition solution or dispersion, the solution or dispersion is supplied to a thin film vacuum evaporator, and the solvent is removed from the resin composition solution or dispersion.
    [63] The above apparatus can be used for the thin film vacuum evaporator, but the heating temperature is a range in which the fluorine-containing copolymer (A) and the curing agent (C) do not substantially cause a curing reaction and are sufficiently dried. do. For example, in the case of a block isocyanate curing agent, it is 160 degrees C or less, in the case of a TGIC curing agent, 110 degrees C or less, and in the case of the amide curing agent which has a β-hydroxyl group, it is 140 degrees C or less, and is 50 degrees C or more.
    [64] (Kneading, grinding)
    [65] Next, the kneading and grinding step will be described.
    [66] In the present invention, first, each component of the fluorine-containing copolymer (A), the antigelling agent (B), the curing agent (C), and other powder coating additives (D), if necessary, is subjected to Henschel mixer or the like in a powder state. After mixing (dry blending), the mixture is melted by a single or twin screw extruder. The temperature in an extruder is made into the range in which a fluorine-containing copolymer (A) and a hardening | curing agent (C) do not produce hardening reaction substantially as mentioned above. The sufficiently kneaded and kneaded mixture is extruded into a sheet or the like, and the extrudate is cooled and pulverized at room temperature. It is preferable to make particle size distribution after grinding | pulverization into 20-50 micrometers for blowing coating, and 70-120 micrometers for fluid immersion coating.
    [67] Next, in the present invention, secondly, in the solution or dispersion of the fluorine-containing copolymer (A) having a curable functional group, an antigelling agent (B), a curing agent (C) and other powder coating additives (D), if necessary. ) Is mixed to obtain a resin composition solution or dispersion, the solution or dispersion is supplied to a thin film vacuum evaporator, and the kneaded mixture obtained by removing the solvent from the resin composition solution or dispersion is extruded into a sheet or the like, and the extrusion is performed. Cool the water and grind at room temperature. In this case, the fluorine-containing resin powder coating composition is obtained in one step, which is a very simple manufacturing step.
    [68] As described above, the curable fluorine-containing resin powder coating composition of the present invention obtained by the thin film vacuum evaporation apparatus is used to form a coating coating film by coating the target substrate, followed by heat treatment and baking curing.
    [69] The coating method is not particularly limited and conventionally known methods such as electrostatic spray coating (blowing coating), fluid immersion coating and the like can be adopted. Although coating thickness is not specifically limited, Usually, it is 30-120 micrometers in thickness of a coating film. The heat treatment temperature (curing temperature) is 140 to 220 ° C, preferably about 150 to 200 ° C, and the heat treatment time is about 10 to 60 minutes, preferably about 15 to 30 minutes.
    [70] The base material which the coating composition of this invention makes object is, for example, steel plate, stainless steel, aluminum, zinc-treated steel plate, etc., The surface thereof may be subjected to chromium phosphate treatment, zinc phosphate treatment, chromate treatment, etc. in advance. .
    [71] Although a synthesis example and an Example are given to the following and this invention is concretely demonstrated to it, this invention is not limited at all by this description. In addition, the number of copies in a following example shows a mass part, unless there is particular notice, and% represents the mass%.
    [72] Synthesis Example 1
    [73] Into a pressure-resistant container with a stainless steel stirrer (inner pressure 5.0 Mpa) having a content of 50 L, 26.2 kg of xylene, 2.7 kg of cyclohexyl vinyl ether (CHVE), 1.5 kg of isobutyl vinyl ether (iBVE), 4-hydroxybutyl vinyl ether ( 4.2 kg of HBVE), 0.17 kg of potassium carbonate and 0.01 kg of perbutylperpivalate (PBPV) were charged and dissolved oxygen was removed by solidification degassing with liquid nitrogen.
    [74] Thereafter, 8.3 kg of chlorotrifluoroethylene (CTFE) was introduced and gradually heated up. The reaction was continued under stirring while maintaining the temperature at 65 ° C. After 10 hours, the reactor was cooled with water to stop the reaction. After cooling to room temperature, the reactor was opened by purging the unreacted monomer. The obtained reaction solution was filtered through diatomaceous earth to remove solids.
    [75] Synthesis Example 2-6
    [76] The same experiment as in Synthesis Example 1 was conducted except that the monomer was changed to the composition shown in Table 1 and polymerized.
    [77] Synthesis ExampleOne23456 Monomer composition (mol%)CTFE5051 5050 TFE 4545 CHVE152545101515 EVE 12 iBVE1010 Vinyl benzoate 15105 Veova10 15105 HBVE25121015 GVE15Undecylenic acid 15 Solid content concentration (%)393840383941 Fluorine-containing copolymer solution (nominal)A-1A-2A-3A-4A-5A-6 TFE: Tetrafluoroethylene CTFE: Chlorotrifluoroethylene CHVE: Cyclohexyl vinyl ether EVE: Ethyl vinyl ether iBVE: Isobutyl vinyl ether HBVE: 4-hydroxybutyl vinyl ether GVE: Glycidyl vinyl ether
    [78] (Example 1)
    [79] As shown in Table 2, 8.4 g of tridecyl phosphite was added and mixed with respect to 30 kg of the fluorine-containing copolymer solution (A-1) obtained in Synthesis Example 1. Next, this solution was supplied from the inlet of the thin film vacuum evaporator "Exeva" (brand name: Shinko Pantec Co., Ltd.) so that a feed rate might be 30 kg / hour. In the apparatus, the vacuum degree of -0.09 MPa (gauge pressure) and the temperature of the fruit were set to 95 ° C, the stirring speed of the thin film vacuum evaporator was 400 rpm, and the stirring speed of the melt discharging screw was 300 rpm. The non-volatile content concentration of the solid fluorine-containing copolymer obtained by removing the solvent was 99.5%. This solid fluorine-containing copolymer is referred to as (A'-1).
    [80] Next, 137 g of the powder of (A'-1) was used as the solid fluorine-containing copolymer, adduct B1530 (trade name: 휼 -caprolactam block isocyanate curing agent manufactured by Hughes, Inc.), moderflow 2000 (trade name: Monsanto). 0.5 g of benzoin, 0.5 g of benzoin and 30 g of titanium oxide are mixed with a dry blender (Hensel mixer blender manufactured by Mitsui Chemicals, Inc.) for about 1 minute, and then at a temperature of 90 to 130 ° C. It melt-mixed using the extrusion kneading machine (brand name: Fusconider PR-46, the product made from Futh Corporation). The proportions of the components of the molten mixture are shown in Table 3.
    [81] After cooling this melt mixture to 20 degreeC, it was grind | pulverized with the impact hammer mill, it sieved with 180 mesh of gold nets, and the curable fluorine-containing resin powder coating composition was obtained.
    [82] The obtained powder coating composition was electrostatic coated on a zinc phosphate treated steel sheet, and cured in an oven at 180 ° C. for 20 minutes to obtain a coating film.
    [83] About the obtained coating material and coating film, physical properties were measured as follows. The results are reported in Table 4.
    [84] [Blocking Resistance]
    [85] The following references | standards evaluated the coating material after storing for 7 days at 40 degreeC.
    [86] (Circle): A lump is not seen at all.
    [87] (Triangle | delta): There exists a small amount of lump and it breaks easily into a powder.
    [88] X: There are many lumps, and it cannot turn into a powder even if force is applied.
    [89] [Film appearance (smoothness)]
    [90] (Circle): No abnormality is found at all.
    [91] (Triangle | delta): A foreign material is found a little.
    [92] X: The foreign material is found significantly.
    [93] [Gloss (60 °)]
    [94] According to JIS K5400 7.6.
    [95] (Examples 2 to 6)
    [96] The solvent was removed similarly to Example 1 in the fluorine-containing copolymer solution (A-2-A-6) shown in Table 2, and the solid fluorine-containing copolymer (A'-2-A'-6) was obtained. Subsequently, the powder coating composition of the ratio shown in Table 3 was manufactured similarly to Example 1, and the result of having coated this like Example 1 is shown in Table 4.
    [97] (Comparative Examples 1 and 2)
    [98] Solid fluorine-containing copolymer (A'-7) by removing the solvent in the same manner as in Example 1 without adding the antigelling agent to the fluorine-containing copolymer solution (A-4 to A-5) obtained in Synthesis Examples 4 to 5 A'-8) was obtained. Subsequently, the powder coating composition of the ratio shown in Table 3 was produced like Example 1, and this coating was carried out similarly to Example 1. The results are shown in Table 4.
    [99] Raw material nameExampleComparative example One23456One2 Solid fluorine-containing copolymer A'-1A'-2A'-3A'-4A'-5A'-6A'-7A'-8 Fluorine-containing copolymer solutionA-1137 A-2 138 A-3 141A-4 139 139A-5137 137 A-6 137 Gelling agentTridecyl phosphite0.10.10.1Diphenylolpropane 0.10.1 Sanol LS744 * 1 0.1 * 1: Sanol LS744 (hindered amine light stabilizer manufactured by Nihon Chiba Chemical Co., Ltd.)
    [100] Raw material nameExampleComparative example One23456One2 Solid Fluorinated CopolymerA'-153.4 A'-2 52.4 A'-3 56.4A'-4 52.8 A'-553.4 A'-6 56.2 A'-7 52.8A'-8 56.2 HardenerAdduct B-153015.015.015.0 15.015.0 Adduct BF-1540 * 215.0 Dodecan 2-mountain5.6 TGIC 18.2 additiveModer Flow 20000.50.50.50.50.50.50.50.5 Benzoin0.50.50.50.50.50.50.50.5 Titanium oxide3030303030303030 Painting conditionBaking Temperature (℃)180180180180180180140140 Baking time (minutes)2020202020202020 * 2: Adduct BF-1540 (Huretodione curing agent manufactured by Hewz Co., Ltd.)
    [101] ExampleComparative example One23456One2 Blocking resistance○○○○○○△× Coating appearance○○○○○○×× Polish137120135138129120108110
    [102] (Example 7)
    [103] The solution was mixed for 1 hour until the entire components of the composition of Example 7 shown in Table 5 were homogeneous. This resin composition solution was supplied from the inlet of the thin film vacuum evaporator "Exeva" (brand name: Shinko Pantec Co., Ltd.) so that a feed rate might be 30 kg / hour. In the apparatus, the vacuum degree of -0.09 MPa (gauge pressure) and the temperature of the fruit were set to 95 ° C, the stirring speed of the thin film vacuum evaporator was 400 rpm, and the stirring speed of the melt discharging screw was 300 rpm. The nonvolatile matter concentration of the obtained solid resin composition was 99.5%.
    [104] After cooling this solid resin composition to 20 degreeC, it was grind | pulverized with the impact hammer mill, it sieved by the 180-mesh metal mesh, and the curable fluorine-containing resin powder coating composition was obtained. The obtained powder coating composition was electrostatic coated on a zinc phosphate treated steel sheet, and cured in an oven at 180 ° C. for 20 minutes to obtain a coating film.
    [105] About the obtained coating material and coating film, physical properties were measured similarly to Example 1. The results are shown in Table 6.
    [106] (Examples 8-12, Comparative Examples 3-4)
    [107] The fluorine-containing copolymer composition (solution) shown in Table 5 was obtained with a powder coating composition under the same conditions as in Example 7, and was coated in the same manner as in Example 7. The results are shown in Table 6.
    [108] Raw material nameExampleComparative example 78910111234 Fluorine-containing copolymer solutionA-1137 A-2 138 A-3 141A-4 139 137A-5137 138 A-6 137 Gelling agentsDodecyl phosphite0.10.10.1Diphenylolpropane 0.10.1 Sanol LS744 0.1 HardenerAdduct B-153015.015.015.0 15.015.0 Adduct BF-1540 15.0 Dodecan 2-mountain5.6 TGIC 18.2 additiveModer Flow 20000.50.50.50.50.50.50.50.5 Benzoin0.50.50.50.50.50.50.50.5 Titanium oxide3030303030303030 Painting conditionBaking Temperature (℃)180180180180180180140140 Baking time (min)2020202020202020
    [109] ExampleComparative example 78910111234 Blocking resistance○○○○○○△× Coating appearance○○○○○○×× Polish136119136137129121107111
    [110] According to the present invention, even when the solvent is removed by a thin film vacuum evaporator under relatively high temperature conditions, the fluorine-containing resin having a hardenable functional group which hardly gels the resin, and easily mixes the composition uniformly and has few defects in the coating film Powder and its coating composition can be obtained.
    权利要求:
    Claims (5)
    [1" claim-type="Currently amended] In the solution or dispersion of the fluorine-containing copolymer (A) having a curable functional group, an antigelling agent (B) is added and mixed, the solution or dispersion is supplied to a thin film vacuum evaporator, and the solvent is removed from the solution or dispersion. A method for producing a fluorine-containing resin powder having a curable functional group.
    [2" claim-type="Currently amended] In the solution or dispersion of the fluorine-containing copolymer (A) having a curable functional group, an antigelling agent (B), a curing agent (C), and other powder coating additives (D) are added and mixed as necessary, and the resin composition solution or dispersion is added. A method of producing a fluorine-containing resin powder coating composition having a curable functional group, wherein the solution or dispersion is supplied to a thin film vacuum evaporator and the solvent is removed from the resin composition solution or dispersion.
    [3" claim-type="Currently amended] The manufacturing method of Claim 1 or 2 whose curable functional group of a fluorine-containing copolymer (A) is 1 or more types chosen from the group which consists of a hydroxyl group, a carboxyl group, and an epoxy group.
    [4" claim-type="Currently amended] The production method according to any one of claims 1 to 3, wherein the gelling inhibitor (B) is at least one member selected from the group consisting of phenols, epoxy compounds, phosphite esters, and hindered amine light stabilizers.
    [5" claim-type="Currently amended] The production process according to any one of claims 2 to 4, wherein the temperature at the time of removing the solvent is a temperature at which the fluorine-containing copolymer (A) and the curing agent (C) do not cause a curing reaction.
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    同族专利:
    公开号 | 公开日
    TW200301264A|2003-07-01|
    EP1460090B1|2008-09-10|
    DE60228884D1|2008-10-23|
    CN1310958C|2007-04-18|
    JPWO2003051931A1|2005-04-28|
    EP1460090A1|2004-09-22|
    JP4232633B2|2009-03-04|
    AT407954T|2008-09-15|
    AU2002357618B2|2007-11-01|
    US7144948B2|2006-12-05|
    EP1460090A4|2006-04-12|
    US20040225060A1|2004-11-11|
    WO2003051931A1|2003-06-26|
    CN1606573A|2005-04-13|
    KR100958559B1|2010-05-18|
    AU2002357618A1|2003-06-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-12-19|Priority to JP2001386061
    2001-12-19|Priority to JPJP-P-2001-00386061
    2002-12-19|Application filed by 아사히 가라스 가부시키가이샤
    2002-12-19|Priority to PCT/JP2002/013316
    2004-07-30|Publication of KR20040068208A
    2010-05-18|Application granted
    2010-05-18|Publication of KR100958559B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2001386061|2001-12-19|
    JPJP-P-2001-00386061|2001-12-19|
    PCT/JP2002/013316|WO2003051931A1|2001-12-19|2002-12-19|Processes for production of powdered fluororesins bearing curable functional groups and coating compositions containing the same|
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