WO2017047197A1 - Polyester copolymérisé et matériau de couche d'apprêt pour métal utilisant un tel polyester - Google Patents

Polyester copolymérisé et matériau de couche d'apprêt pour métal utilisant un tel polyester Download PDF

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Publication number
WO2017047197A1
WO2017047197A1 PCT/JP2016/069141 JP2016069141W WO2017047197A1 WO 2017047197 A1 WO2017047197 A1 WO 2017047197A1 JP 2016069141 W JP2016069141 W JP 2016069141W WO 2017047197 A1 WO2017047197 A1 WO 2017047197A1
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component
mol
acid
copolymerized polyester
acid component
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PCT/JP2016/069141
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English (en)
Japanese (ja)
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祐司 岩下
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東洋紡株式会社
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Priority to CN201680040100.4A priority Critical patent/CN107849230B/zh
Priority to KR1020177034247A priority patent/KR20180055758A/ko
Priority to JP2017539723A priority patent/JP6724921B2/ja
Publication of WO2017047197A1 publication Critical patent/WO2017047197A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C09D167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints

Definitions

  • the present invention relates to a copolyester and a metal primer paint using the same. More specifically, the present invention relates to a resin and a coating composition having excellent corrosion resistance and processability.
  • Copolyester is widely used as a raw material for resin compositions used for coating agents, inks, adhesives, and the like, and is generally composed of a polyvalent carboxylic acid and a polyhydric alcohol. Flexibility by selecting and combining polyvalent carboxylic acids and polyhydric alcohols and the molecular weight can be freely controlled, so they are widely used in various applications including coating agents and adhesives.
  • a paint using a high molecular weight copolymer polyester excellent in the flexibility of a coating film is often used (for example, patent documents). 1).
  • bisphenol A skeleton polyols that are concerned about health effects are used as essential components.
  • the solid content concentration is increased, the solution viscosity becomes very high and handling becomes difficult. .
  • the solid content concentration is lowered, it is difficult to increase the coating thickness, and it is necessary to use a large amount of solvent.
  • an object of the present invention is to provide a copolymer polyester that is effective as a binder component to be blended in a metal primer coating (metal undercoat), and also maintains a low solution viscosity that is easy to handle even at a high solid content.
  • a coating composition having a high flexibility equivalent to that of a high molecular weight polyester and capable of forming a coating film having high hardness, corrosion resistance and chemical resistance.
  • this invention consists of the following structures.
  • a copolymerized polyester comprising a polyvalent carboxylic acid component and a polyhydric alcohol component as a copolymerization component, the aromatic dicarboxylic acid component being 95 to 100 mol%, assuming that the total polyvalent carboxylic acid component is 100 mol%,
  • the glycol component represented by the general formula (1) is 1 to 30 mol%, and glass Copolyester (A) having a transition temperature in the range of 25 to 50 ° C.
  • n is an integer of 3 or more.
  • the copolymer polyester (A) preferably has a number average molecular weight in the range of 4000 to 9000. Moreover, it is preferable not to contain an aliphatic dicarboxylic acid component.
  • the general formula (1) is preferably triethylene glycol.
  • the metal primer coating using the copolymerized polyester of the present invention has a high solid content and a low solution viscosity, and further exhibits high hardness, high flexibility, high corrosion resistance and excellent chemical resistance. For this reason, it is suitable for the primer layer of the coil coating for household appliances and building materials.
  • the metal primer coating using the copolymerized polyester (A) of the present invention exhibits excellent flexibility, hardness, corrosion resistance, and chemical resistance. For this reason, it is suitable for undercoating on a metal steel sheet that requires deformation after coating, and a product produced using the copolymerized polyester (A) of the present invention has high hardness, high workability, and high corrosion resistance. A membrane is obtained.
  • the copolymerized polyester (A) of the present invention has a chemical structure that can be obtained by a polycondensate of a polyvalent carboxylic acid component and a polyhydric alcohol component, and each of the polyvalent carboxylic acid component and the polyhydric alcohol component is 1 It consists of seeds or two or more selected components.
  • the polyvalent carboxylic acid component is preferably a dicarboxylic acid, and more preferably an aromatic dicarboxylic acid.
  • the copolymerization amount of the aromatic dicarboxylic acid with respect to the total dicarboxylic acid component needs to be 95 mol% to 100 mol%. Preferably it is 98 mol% or more, More preferably, it is 100 mol%. If the dicarboxylic acid component other than the aromatic dicarboxylic acid component is contained in an amount exceeding 5 mol% as the copolymer component, the chemical resistance of the coating film may be lowered.
  • the aromatic dicarboxylic acid constituting the copolyester (A) of the present invention is not particularly limited, but terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfo Isophthalic acid or the like can be used. Of these, terephthalic acid and isophthalic acid are preferable.
  • the aliphatic dicarboxylic acid constituting the copolyester (A) of the present invention is not particularly limited, but succinic acid, adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic acid and the like can be used. . Of these, sebacic acid is preferred.
  • the copolymerization amount of the aliphatic dicarboxylic acid with respect to the total dicarboxylic acid is preferably 5 mol% or less, more preferably 2 mol% or less, and further preferably 0 mol%. If it exceeds 5 mol%, the chemical resistance of the coating film may decrease.
  • n is an integer of 3 or more. It is preferably an integer of 23 or less, more preferably an integer of 15 or less, still more preferably an integer of 5 or less, particularly preferably an integer of 4 or less, and most preferably 3.
  • n is less than 3, the flexibility of the coating film tends to decrease. On the other hand, if n becomes too large, the corrosion resistance may decrease.
  • the glycol component represented by the general formula (1) is not particularly limited, and examples thereof include triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol (number average molecular weight 650), polyethylene glycol (number average molecular weight 1000), and the like. Can be mentioned. Of these, triethylene glycol is preferred because it has a good balance between the amount of ester bonds and the amount of ether bonds that contribute to adhesion to the coated steel sheet.
  • the copolymerization amount of the glycol component represented by the general formula (1) is preferably 3 mol% or more, and more preferably 5 mol% or more when the total polyhydric alcohol component is 100 mol%. Moreover, 28 mol% or less is preferable, 25 mol% or less is more preferable, and 20 mol% or less is further more preferable. If the amount is too small, the glass transition temperature of the copolyester (A) is increased, and the flexibility (workability) may be lowered. On the other hand, if the amount is too large, the glass transition temperature of the copolyester (A) becomes too low, and the hardness and corrosion resistance may decrease.
  • the polyhydric alcohol constituting the copolymerized polyester (A) of the present invention is preferably a glycol component other than the glycol component represented by the general formula (1).
  • the glycol component other than the general formula (1) is not particularly limited.
  • Species or two or more can be used.
  • alicyclic glycol components such as 1,4-cyclohexanedimethanol and tricyclodecane dimethanol
  • polyalkylene ether glycol components such as polytetramethylene glycol and polypropylene glycol
  • the copolymerization amount of the aliphatic glycol component, the alicyclic glycol component and the polyalkylene ether glycol component other than the general formula (1) is 70 to 99 mol% when the total polyhydric alcohol component is 100 mol%. Preferably there is. If the amount is too small, the glass transition temperature of the copolyester (A) becomes too low, and the hardness and corrosion resistance may decrease. On the other hand, if the amount is too large, the glass transition temperature of the copolyester (A) is increased, and the flexibility (workability) may be lowered.
  • the copolymerization amount of the glycol component having a bisphenol skeleton is preferably 5 mol% or less, more preferably 1 mol% or less, and more preferably 0 mol% when the total polyhydric alcohol component is 100 mol%. Further preferred.
  • the glass transition temperature of the copolyester (A) of the present invention needs to be in the range of 25 to 50 ° C.
  • the temperature is preferably in the range of 30 to 48 ° C, more preferably in the range of 35 to 45 ° C.
  • the glass transition temperature is less than 25 ° C.
  • the corrosion resistance may be lowered.
  • the glass transition temperature exceeds 50 ° C., the flexibility of the coating film tends to decrease, which is not preferable.
  • the copolymerized polyester (A) of the present invention may be copolymerized with a trivalent or higher polyvalent carboxylic acid component and / or a trivalent or higher polyhydric alcohol component.
  • a trivalent or higher polyvalent carboxylic acid component include aromatic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and trimesic acid, and aliphatic such as 1,2,3,4-butanetetracarboxylic acid. Examples thereof include carboxylic acid.
  • trihydric or higher polyhydric alcohol component examples include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, ⁇ -methylglucose, mannitol, and sorbitol. One or more of these can be used. Is possible.
  • the copolymerization amount of the trivalent or higher polyvalent carboxylic acid component is preferably 5 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less, assuming that the total polyvalent carboxylic acid component is 100 mol%. Preferably, it may be 0 mol%.
  • the copolymerization amount of the trihydric or higher polyhydric alcohol component is preferably 2 mol% or less, more preferably 1 mol% or less, and 0 mol% when the total polyhydric alcohol component is 100 mol%. There is no problem. If the amount is too large, gelation may occur during the polymerization of the copolyester (A).
  • the number average molecular weight of the copolymerized polyester (A) of the present invention is preferably 2000 or more, and more preferably 4000 or more. Further, it is preferably 9000 or less, more preferably 8000 or less, and further preferably 7400 or less. A number average molecular weight of less than 2000 is not preferable because the flexibility of the coating film may be lowered. On the other hand, if it exceeds 9000, the viscosity when made into a paint is high, and handling becomes difficult, which is not preferable.
  • the reduced viscosity of the copolymerized polyester (A) of the present invention is preferably 0.15 dl / g or more, and more preferably 0.18 dl / g or more. Moreover, it is preferable that it is 0.35 dl / g or less, and it is more preferable that it is 0.32 dl / g or less. If the reduced viscosity is too small, the flexibility of the coating film may be lowered. If the reduced viscosity is too large, the viscosity when dissolved in an organic solvent becomes too high and handling may be difficult.
  • Examples of the polymerization condensation reaction for producing the copolyester (A) of the present invention include 1) heating a polyvalent carboxylic acid and a polyhydric alcohol in the presence of an arbitrary catalyst, passing through a dehydration esterification step, Method of performing polyhydric alcohol / polycondensation reaction 2) Heating an alcohol ester of polyhydric carboxylic acid and polyhydric alcohol in the presence of an arbitrary catalyst, through a transesterification reaction, depolyhydric alcohol / polycondensation reaction There are methods. In the methods 1) and 2), part or all of the acid component may be substituted with an acid anhydride.
  • a conventionally known polymerization catalyst for example, a titanium compound such as tetra-n-butyl titanate, tetraisopropyl titanate, titanium oxyacetylcetonate, antimony trioxide, Antimony compounds such as butoxyantimony, germanium compounds such as germanium oxide and tetra-n-butoxygermanium, and acetates such as magnesium, iron, zinc, manganese, cobalt, and aluminum can be used.
  • titanium compound such as tetra-n-butyl titanate, tetraisopropyl titanate, titanium oxyacetylcetonate, antimony trioxide, Antimony compounds such as butoxyantimony, germanium compounds such as germanium oxide and tetra-n-butoxygermanium, and acetates such as magnesium, iron, zinc, manganese, cobalt, and aluminum
  • These catalysts can be used alone or in combination of two or more.
  • the resin acid value of the copolymerized polyester (A) may be increased in order to enhance the substrate adhesion and crosslinkability.
  • Resin acid value is preferably at 1 eq / 10 6 g or more, more preferably 3 eq / 10 6 g or more, further preferably 5 eq / 10 6 g or more.
  • Particularly preferred is 30 eq / 10 6 g or less.
  • the copolymerized polyester (A) of the present invention can be used in a state dissolved in a known organic solvent.
  • organic solvents that can be used include aromatic hydrocarbons such as toluene, xylene, Solvesso (registered trademark), esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dibasic acid esters, methyl ethyl ketone, methyl
  • ketones such as isobutyl ketone, cyclohexanone and isophorone
  • ethers such as n-butyl cellosolve and t-butyl cellosolve, which are arbitrarily selected and blended in consideration of solubility, evaporation rate (dryability) and the like.
  • a mixed solvent of aromatic hydrocarbons and ketones is preferable, and a mixed solvent of sorbeso and cyclohexanone is preferable.
  • the polyester (A) of the present invention is preferably dissolved in the organic solvent at a concentration of 40% by mass or more at 25 ° C., more preferably dissolved at a concentration of 50% by mass or more, and a concentration of 60% by mass or more. More preferably, it dissolves.
  • the solubility is as described above, the solid content concentration as the metal primer coating can be increased, and the handling becomes easy.
  • the copolymerized polyester (A) of the present invention can be used together with a crosslinking agent (B).
  • a well-known crosslinking agent can be used for a crosslinking agent (B).
  • the cross-linking agent (B) is not particularly limited as long as it causes a cross-linking reaction to the copolyester (A).
  • Preferred examples include isocyanate compounds, epoxy resins, amino resins (general names of alkyl etherified formaldehyde resins). Phenolic resins and the like can be mentioned, and one or two or more of these can be arbitrarily selected and used.
  • the isocyanate compound is not particularly limited, and there are aromatic, alicyclic and aliphatic polyisocyanate compounds, which may be either low molecular weight type or high molecular weight type.
  • aromatic, alicyclic and aliphatic polyisocyanate compounds which may be either low molecular weight type or high molecular weight type.
  • tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or trimers of these isocyanate compounds and the aforementioned isocyanate compounds and ethylene glycol Terminal isocyanate compounds obtained by reacting with active hydrogen compounds such as trimethylolpropane, propylene glycol, glycerin, sorbitol, ethylene
  • the pot life of the metal primer paint can be extended.
  • the blocking agent of the blocked isocyanate compound include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, methanol, Active methylene such as ethanol, propanol, butanol, t-butanol, t-pentanol, etc., lactams such as ⁇ -caprolactam, other aromatic amines, imides, acetylacetone, acetoacetate ester, malonic acid ethyl ester, etc.
  • the blocked isocyanate compound is obtained by reacting the isocyanate compound with a blocking agent by a conventionally known method, and can be used alone or in combination of two or more.
  • epoxy resin examples include glycidyl ether of bisphenol-A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-hydroxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ester, propylene glycol diglycidyl ester, 1,4-butanediol diglycidyl ester, 1, 6-hexanediol diglycidyl ester, and polyalkylene glycol diglycidyl esters, trimellitic acid triglycidyl Ester, triglycidyl isocyanurate, 1,
  • the amino resin is not particularly limited, but methylol obtained by reaction of amino components such as melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, and dicyandiamide with aldehyde components such as formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.
  • aldehyde components such as formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.
  • An amino acid resin is mentioned.
  • This amino resin also includes those obtained by etherifying the methylol group of this methylolated amino resin with an alcohol having 1 to 6 carbon atoms. These can be used alone or in combination of two or more.
  • a resol type phenol resin can be used as the phenol resin.
  • the resol type phenol resin include phenol, m-cresol, m-methylphenol, 3,5-xylenol, m-methoxyphenol, o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2 , 3-xylenol, 2,5-xylenol bisphenol-A, bisphenol-F, and the like can be mentioned, and these can be used alone or in combination of two or more.
  • the crosslinking agent (B) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the copolyester (A). preferable. Moreover, it is preferable that it is 50 mass parts or less, It is more preferable that it is 40 mass parts or less, It is further more preferable that it is 30 mass parts or less. If the amount is too small, the coating film obtained from the metal primer coating is not sufficiently crosslinked, and the required hardness, fastness and adhesion strength of the coating film may not be obtained. If the amount is too large, the required flexibility of the coating film may decrease.
  • a catalyst that contributes to a crosslinking reaction between the copolymerized polyester (A) and the crosslinking agent (B) can be further used.
  • organic acid sulfonic acid compounds such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, phosphoric acid compounds, and neutralized amines thereof can be used as the acid catalyst.
  • An amine compound can be used as the base catalyst.
  • organic acid salts, halide salts, nitrates, sulfates, organic ligand compounds, and the like of various metals can be used. These catalysts can be used alone or in combination of two or more according to the curing behavior of the crosslinking agent (B).
  • the copolyester (A) of the present invention can be used together with the pigment (C).
  • the pigment (C) are not particularly limited, but titanium oxide, zinc oxide, zirconium oxide, calcium carbonate, barium sulfate, aluminum oxide, chromium oxide, chromate, kaolin clay, carbon black, iron oxide, talc, Mica, zinc phosphate, iron phosphate, aluminum phosphate, zinc phosphite, aluminum tripolyphosphate, calcium molybdate, aluminum molybdate, barium molybdate, vanadium oxide, strontium chromate, zinc chromate, calcium silicate, water-dispersed silica , Inorganic pigments such as fumed silica, and organics such as phthalocyanine blue, phthalocyanine green, carbazole dioxazine violet, anthrapyrimidine yellow, isoindolinone yellow, and induslen blue Mention may be made of the fee
  • the pigment (C) is preferably 5 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 100 parts by mass or more with respect to 100 parts by mass of the copolyester (A). . Moreover, it is preferable that it is 300 mass parts or less, It is more preferable that it is 250 mass parts or less, It is further more preferable that it is 200 mass parts or less. If the amount of the pigment (C) is too small, the intended effects such as coloring and anticorrosion may not be obtained. Moreover, when there is too much, the flexibility of a coating film may fall.
  • the additive (D) can be used as necessary.
  • Specific examples of the additive (D) are not particularly limited, but acid catalysts such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, and phosphoric acid compounds, base catalysts such as amine compounds, antifoaming agents, and leveling Agents, heat deterioration inhibitors, ultraviolet absorbers, viscosity modifiers, waxes and the like.
  • acid catalysts such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, and phosphoric acid compounds
  • base catalysts such as amine compounds, antifoaming agents, and leveling Agents, heat deterioration inhibitors, ultraviolet absorbers, viscosity modifiers, waxes and the like.
  • the additive (D) can be freely blended as long as it does not affect the physical properties of the coating film. Preferably, they are
  • the organic solvent (E) used in the present invention is not particularly limited as long as it dissolves the copolyester (A).
  • aromatic hydrocarbons such as toluene, xylene, Solvesso (registered trademark), esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dibasic acid ester, methyl ethyl ketone, methyl isobutyl ketone
  • Examples include ketones such as cyclohexanone and isophorone, and ethers such as n-butyl cellosolve and t-butyl cellosolve, which are arbitrarily selected and blended in consideration of solubility, evaporation rate (drying property) and the like.
  • a mixed solvent of aromatic hydrocarbons and ketones is preferable, and a mixed solvent of sorbeso and cyclohexanone is preferable.
  • the organic solvent (E) is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and further preferably 150 parts by mass or more with respect to 100 parts by mass of the copolyester (A). Moreover, 500 mass parts or less are preferable, More preferably, it is 400 mass parts or less, More preferably, it is 300 mass parts or less. If the amount is too small, the storage stability may be deteriorated, and if the amount is too large, the cost may be impractical.
  • the metal primer coating of the present invention is a coating containing a copolymerized polyester (A), a crosslinking agent (B), a pigment (C), an additive (D), and an organic solvent (E).
  • the metal coating plate of the present invention has the metal primer coating of the present invention as a primer layer on at least one surface of the metal plate.
  • the metal plate is not particularly limited, but for example, hot-drawn steel plate, electrogalvanized steel plate, alloy plated steel plate, aluminum zinc alloy plated steel plate, aluminum plate, tin plated steel plate, stainless steel plate, copper plate, copper plated steel plate, tin-free Metal plates such as steel, nickel-plated steel plates, ultra-thin tin-plated steel plates, and chromed steel plates are preferred.
  • KF-802, 804L and 806L manufactured by Showa Denko were used as the column.
  • Monodispersed polystyrene was used for the molecular weight standard, the number average molecular weight was a standard polystyrene equivalent value, and the part corresponding to a molecular weight of less than 1000 was omitted.
  • the glass transition temperature was measured using a differential scanning calorimeter (SII, DSC-200).
  • a sample copolymerized polyester (A)
  • a sample was placed in an aluminum-resined lid-type container, sealed, and cooled to ⁇ 50 ° C. using liquid nitrogen. Next, the temperature is increased to 150 ° C.
  • the glass transition temperature (Tg, unit: ° C.) was defined as the temperature at the intersection with the tangent toward (the tangent indicating the maximum slope between the peak rising portion and the peak apex).
  • Copolyester (a1) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 809 parts of dimethyl terephthalate, 793 parts of dimethyl isophthalate, 19 parts of trimellitic anhydride, 407 parts of ethylene glycol, 540 parts of neopentyl glycol Part, triethylene glycol 287 parts, tetrabutyl orthotitanate as a catalyst is charged in 0.03 mol% with respect to the total acid components, the temperature is increased from 160 ° C to 220 ° C over 4 hours, and transesterification is carried out through a methanol removal step. Went.
  • the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 250 ° C.
  • the pressure was reduced to 0.3 mmHg or less
  • a polycondensation reaction was performed for 60 minutes, and this was taken out.
  • the number average molecular weight was 7000, the glass transition temperature was 40 ° C., and the acid value was 20 eq / 10 6 g.
  • Table 1 The results are shown in Table 1.
  • Copolyesters (a2) to (a10) According to the production examples of the copolyester (a1), the types and blending ratios of the raw materials were changed, and the copolyesters (a2) to (a11) of the present invention were changed. Manufactured. The results are shown in Table 1.
  • Example 1 Preparation of Metal Primer Paint (A1) 80 parts of the copolyester (a1) was dissolved in a mixed solvent of 100 parts of cyclohexanone and 100 parts of Solvesso 150. To this, 50 parts of calcium silicate, 13 parts of aluminum tripolyphosphate, and 37 parts of titanium oxide were added and dispersed for 6 hours using a shaker. Furthermore, 20 parts of Cymel 303 (manufactured by Ornex Co., Ltd., melamine curing agent) was added as a crosslinking agent, and 0.2 part of dodecylbenzenesulfonic acid was added as a curing catalyst to obtain the metal primer paint (A1) of the present invention.
  • Cymel 303 manufactured by Ornex Co., Ltd., melamine curing agent
  • copolymerized polyester and coating composition of the present invention are excellent in processability, corrosion resistance, and chemical resistance, and are useful as a primer coating resin for metal plates. It is particularly useful as a component used in coil coating for home appliances.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
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  • Paints Or Removers (AREA)

Abstract

La présente invention vise à fournir un polyester copolymérisé qui est efficace en tant que composant de liant pour un matériau de couche d'apprêt pour métal pour couchage sur bande. L'invention vise également à fournir un matériau de couche d'apprêt pour métal qui comporte une composition de matériau de revêtement utilisant le polyester copolymérisé, et qui possède d'excellentes propriétés de dureté superficielle,d'aptitude au pliage, de résistance à la corrosion et de résistance chimique. À cet effet, l'invention concerne un polyester copolymérisé (A) qui comporte, comme composants de copolymérisation, un composant d'acide carboxylique polyvalent et un composant d'alcool polyhydrique, et si la quantité totale de composant d'acide carboxylique polyvalent est pris comme 100 % en pourcentage molaire; un composant acide dicarboxylique aromatique est contenu en une quantité de 95 à 100 % en pourcentage molaire et un composant d'acide dicarboxylique aliphatique est contenu en une quantité de 0 à 5 % en pourcentage molaire; et si le composant d'alcool polyhydrique total est pris comme étant de 100 % en pourcentage molaire, un composant glycol ayant une structure spécifique est contenu en une quantité de 1 à 30 % en pourcentage molaire. Ce polyester copolymérisé (A) a une température de transition vitreuse comprise entre 25 et 50° C
PCT/JP2016/069141 2015-09-16 2016-06-28 Polyester copolymérisé et matériau de couche d'apprêt pour métal utilisant un tel polyester WO2017047197A1 (fr)

Priority Applications (3)

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CN201680040100.4A CN107849230B (zh) 2015-09-16 2016-06-28 共聚聚酯及利使用该共聚聚酯的金属底漆涂料
KR1020177034247A KR20180055758A (ko) 2015-09-16 2016-06-28 공중합 폴리에스테르 및 이것을 이용한 금속 프라이머 도료
JP2017539723A JP6724921B2 (ja) 2015-09-16 2016-06-28 共重合ポリエステルおよびこれを用いた金属プライマー塗料

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JP2015-182806 2015-09-16

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WO2018084064A1 (fr) * 2016-11-04 2018-05-11 Dic株式会社 Résine de polyester polyol, et revêtement
WO2018084065A1 (fr) * 2016-11-04 2018-05-11 Dic株式会社 Résine de polyester polyol, et revêtement

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KR20210114396A (ko) * 2019-01-17 2021-09-23 도요보 가부시키가이샤 공중합 폴리에스테르 및 수분산체
TW202138424A (zh) * 2020-02-17 2021-10-16 日商東洋紡股份有限公司 芳香族聚酯及其製造方法

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JP2010235647A (ja) * 2009-03-30 2010-10-21 Unitika Ltd ポリエーテルエステルブロック共重合体、およびそれよりなる接着剤、及び積層体
JP2011184642A (ja) * 2010-03-11 2011-09-22 Unitika Ltd ポリエステル樹脂水性分散体、およびその製造方法、ならびにそれから得られる樹脂被膜
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018084064A1 (fr) * 2016-11-04 2018-05-11 Dic株式会社 Résine de polyester polyol, et revêtement
WO2018084065A1 (fr) * 2016-11-04 2018-05-11 Dic株式会社 Résine de polyester polyol, et revêtement

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JP6724921B2 (ja) 2020-07-15
JPWO2017047197A1 (ja) 2018-07-05
KR20180055758A (ko) 2018-05-25
CN107849230B (zh) 2021-02-05
TW201712051A (zh) 2017-04-01
CN107849230A (zh) 2018-03-27

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