WO2017047197A1 - Copolymerized polyester and metal primer coating material using same - Google Patents

Copolymerized polyester and metal primer coating material using same 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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Prior art keywords
component
mol
acid
copolymerized polyester
acid component
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PCT/JP2016/069141
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French (fr)
Japanese (ja)
Inventor
祐司 岩下
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020177034247A priority Critical patent/KR20180055758A/en
Priority to CN201680040100.4A priority patent/CN107849230B/en
Priority to JP2017539723A priority patent/JP6724921B2/en
Publication of WO2017047197A1 publication Critical patent/WO2017047197A1/en

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Classifications

    • 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.

Abstract

To provide a copolymerized polyester which is effective as a binder component for a metal primer coating material for coil coating. Additionally, to provide a metal primer coating material which has a coating material composition using the copolymerized polyester, and which has excellent surface hardness, bendability, corrosion resistance and chemical resistance. A copolymerized polyester (A) which has, as copolymerization components, a polyvalent carboxylic acid component and a polyhydric alcohol component, and wherein: if the total polyvalent carboxylic acid component is taken as 100% by mole, an aromatic dicarboxylic acid component is contained in an amount of 95-100% by mole and an aliphatic dicarboxylic acid component is contained in an amount of 0-5% by mole; and if the total polyhydric alcohol component is taken as 100% by mole, a glycol component having a specific structure is contained in an amount of 1-30% by mole. This copolymerized polyester (A) has a glass transition temperature within the range of 25-50°C.

Description

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Copolyester and metal primer coating using the same
　本発明は、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に関する。更に詳しくは、耐食性と加工性に優れる樹脂および塗料組成物に関するものである。 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.
　共重合ポリエステルはコーティング剤、インキおよび接着剤等に用いられる樹脂組成物の原料として広く使用されており、一般に多価カルボン酸と多価アルコールから構成される。多価カルボン酸と多価アルコールの選択と組合せによる柔軟性や、分子量の高低を自由にコントロールできるため、コーティング剤用途や接着剤用途をはじめ、様々な用途で広く使用されている。 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.
　その中でも金属薄板上に樹脂成分を含む塗料をコーティングしてなるプレコーテッドメタルにおいては、塗膜の屈曲性に優れる高分子量の共重合ポリエステルを用いた塗料が多く使用されている（例えば、特許文献１）。しかし、健康影響に懸念を有するビスフェノールＡ骨格のポリオールを必須成分として用いており、さらに高分子量のポリエステルは塗料化する際に固形分濃度を高くすると溶液粘度が非常に高くなり、取扱いが難しくなる。一方、固形分濃度を下げると、塗膜厚を上げることが難しく、溶剤を多量使用する必用もあるため、経済上、環境上において問題がある。 Among them, in a pre-coated metal obtained by coating a paint containing a resin component on a metal thin plate, 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). However, bisphenol A skeleton polyols that are concerned about health effects are used as essential components. Furthermore, when a high molecular weight polyester is made into a paint, if the solid content concentration is increased, the solution viscosity becomes very high and handling becomes difficult. . On the other hand, if 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.
特開平５－２９５２３９号公報JP-A-5-295239
　本発明は、かかる従来技術の課題を背景になされたものである。すなわち、本発明の目的は、金属プライマー塗料（金属下塗り塗料）に配合するバインダー成分として有効な共重合ポリエステルを提供することであり、更には高固形分でも取り扱いの容易な低溶液粘度を維持しつつ、高分子量ポリエステルと同等の高屈曲性を有し、さらに高硬度、耐食性、耐薬品性に優れる塗膜を形成可能な塗料組成物を提供することである。 The present invention has been made against the background of the problems of the prior art. That is, 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. On the other hand, it is to provide 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.
　本発明者らは鋭意検討した結果、以下に示す手段により、上記課題を解決できることを見出し、本発明に到達した。
　すなわち、本発明は、以下の構成からなる。 As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention.
That is, this invention consists of the following structures.
　多価カルボン酸成分と多価アルコール成分を共重合成分とする共重合ポリエステルであって、全多価カルボン酸成分を１００モル％としたときに、芳香族ジカルボン酸成分が９５～１００モル％、脂肪族ジカルボン酸成分が０～５モル％であり、かつ全多価アルコール成分を１００モル％としたときに、一般式（１）で表されるグリコール成分が１～３０モル％であり、ガラス転移温度が２５～５０℃の範囲である共重合ポリエステル（Ａ）。
Figure JPOXMLDOC01-appb-C000002
 　一般式（１）中、ｎは３以上の整数である。 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%, When the aliphatic dicarboxylic acid component is 0 to 5 mol% and the total polyhydric alcohol 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.
Figure JPOXMLDOC01-appb-C000002
 In general formula (1), n is an integer of 3 or more.
　前記共重合ポリエステル（Ａ）は、数平均分子量が４０００～９０００の範囲であることが好ましい。また、脂肪族ジカルボン酸成分を含まないことが好ましい。 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.
　前記一般式（１）は、トリエチレングリコールであることが好ましい。 The general formula (1) is preferably triethylene glycol.
　前記いずれかに記載の共重合ポリエステル（Ａ）、架橋剤（Ｂ）、顔料（Ｃ）、添加剤（Ｄ）、および有機溶剤（Ｅ）を含有する金属プライマー塗料。 Metal primer paint containing copolymer polyester (A), crosslinker (B), pigment (C), additive (D), and organic solvent (E) as described above.
　前記の金属プライマー塗料をプライマー層として有する金属塗装板。 ¡Metal paint plate with the above metal primer paint as a primer layer.
　本発明の共重合ポリエステルを用いた金属プライマー塗料は、高固形分且つ、低溶液粘度であり、さらに高硬度、高屈曲性、高耐食性および優れた耐薬品性を発揮する。このため、家電や建材用のコイルコーティングのプライマー層に好適である。 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.
　以下、本発明を詳述する。 Hereinafter, the present invention will be described in detail.
＜共重合ポリエステル（Ａ）＞
　本発明の共重合ポリエステル（Ａ）を用いた金属プライマー塗料は優れた屈曲性、硬度、耐食性、および耐薬品性を発揮する。このため、コーティング後に変形加工が必要な金属鋼板への下塗りに好適であり、本発明の共重合ポリエステル（Ａ）を用いて製造された製品は高硬度且つ、高加工性、高耐食性を有する塗膜が得られる。 <Copolymerized polyester (A)>
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.
　本発明の共重合ポリエステル（Ａ）は、多価カルボン酸成分と多価アルコール成分との重縮合物によって得ることのできる化学構造からなり、多価カルボン酸成分と多価アルコール成分とはそれぞれ１種または２種以上の選択された成分からなるものである。 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.
　本発明の共重合ポリエステル（Ａ）において、多価カルボン酸成分としてはジカルボン酸であることが好ましく、芳香族ジカルボン酸であることがより好ましい。全ジカルボン酸成分に対する、芳香族ジカルボン酸の共重合量は９５モル％～１００モル％であることが必要である。好ましくは９８モル％以上であり、さらに好ましくは１００モル％である。共重合成分として芳香族ジカルボン酸成分以外のジカルボン酸成分が５モル％を超えて含まれると塗膜の耐薬品性が低下することがある。 In the copolymerized polyester (A) of the present invention, 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.
　本発明の共重合ポリエステル（Ａ）を構成する芳香族ジカルボン酸としては、特に限定されないが、テレフタル酸、イソフタル酸、オルトフタル酸、ナフタレンジカルボン酸、４，４’－ジカルボキシビフェニル、５－ナトリウムスルホイソフタル酸などを使用することができる。なかでもテレフタル酸、イソフタル酸が好ましい。 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.
　本発明の共重合ポリエステル（Ａ）を構成する脂肪族ジカルボン酸としては、特に限定されないが、コハク酸、アジピン酸、アゼライン酸、セバシン酸、シクロヘキサンジカルボン酸、テトラヒドロフタル酸などを使用することができる。なかでもセバシン酸が好ましい。全ジカルボン酸に対する、脂肪族ジカルボン酸の共重合量は５モル％以下であることが好ましく、２モル％以下であることがより好ましく、０モル％であることがさらに好ましい。５モル％を超えると塗膜の耐薬品性が低下することがある。 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.
　本発明の共重合ポリエステル（Ａ）において、全多価アルコール成分に対して、一般式（１）で表されるグリコール成分が１～３０モル％共重合されていることが必要である。
Figure JPOXMLDOC01-appb-C000003
 　一般式（１）中、ｎは３以上の整数である。好ましくは２３以下の整数であり、より好ましくは１５以下の整数であり、さらに好ましくは５以下の整数であり、特に好ましくは４以下の整数であり、最も好ましくは３である。ｎが３未満であると塗膜の屈曲性が低下する傾向にある。一方、ｎが大きくなりすぎると、耐食性が低下することがある。 In the copolymerized polyester (A) of the present invention, it is necessary that the glycol component represented by the general formula (1) is copolymerized in an amount of 1 to 30 mol% with respect to all the polyhydric alcohol components.
Figure JPOXMLDOC01-appb-C000003
 In general formula (1), 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. When 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.
　一般式（１）で表されるグリコール成分としては、特に限定されないが、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ポリエチレングリコール（数平均分子量６５０）、ポリエチレングリコール（数平均分子量１０００）等が挙げられる。なかでも塗装鋼板との密着性に寄与するエステル結合量とエーテル結合量のバランスが良好であることからトリエチレングリコールが好ましい。 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.
　一般式（１）で表されるグリコール成分の共重合量は、全多価アルコール成分を１００モル％としたときに、３モル％以上が好ましく、５モル％以上がより好ましい。また、２８モル％以下が好ましく、２５モル％以下がより好ましく、２０モル％以下がさらに好ましい。少なすぎると共重合ポリエステル（Ａ）のガラス転移温度が高くなり、屈曲性（加工性）が低下することがある。一方、多すぎると共重合ポリエステル（Ａ）のガラス転移温度が低くなりすぎ、硬度や耐食性が低下することがある。 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.
　本発明の共重合ポリエステル（Ａ）を構成する多価アルコールとしては、一般式（１）で表されるグリコール成分以外のグリコール成分であることが好ましい。一般式（１）以外のグリコール成分としては特に限定されないが、例えば、エチレングリコール、１，２－プロパンジオール、１、３－プロパンジオール、１，３－ブタンジオール、１，２－ブタンジオール、１、４－ブタンジオール、２－メチル－１，３－プロパンジオール、ネオペンチルグリコール、１、５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、１－メチル－１，８－オクタンジオール、２，２－ジエチル－１，３－プロパンジオール、２－エチル－２－ブチル－１，３－プロパンジオール等の脂肪族グリコール成分が使用でき、これらの内から、１種、または２種以上を使用できる。また、１，４－シクロヘキサンジメタノール、トリシクロデカンジメタノール等の脂環族グリコール成分、ポリテトラメチレングリコール、ポリプロピレングリコールなどのポリアルキレンエーテルグリコール成分も使用できる。好ましくはエチレングリコール、１，２－プロパンジオール、２－メチル－１，３－プロパンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、２－エチル－２－ブチル－１，３－プロパンジオール、１，４－シクロヘキサンジメタノールである。 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. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,2-butanediol, 4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1-methyl- Aliphatic glycol components such as 1,8-octanediol, 2,2-diethyl-1,3-propanediol and 2-ethyl-2-butyl-1,3-propanediol can be used. Species, or two or more can be used. In addition, alicyclic glycol components such as 1,4-cyclohexanedimethanol and tricyclodecane dimethanol, and polyalkylene ether glycol components such as polytetramethylene glycol and polypropylene glycol can also be used. Preferably, ethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2 -Butyl-1,3-propanediol, 1,4-cyclohexanedimethanol.
　前記一般式（１）以外の脂肪族グリコール成分、脂環族グリコール成分およびポリアルキレンエーテルグリコール成分の共重合量は、全多価アルコール成分を１００モル％としたときに、７０～９９モル％であることが好ましい。少なすぎると共重合ポリエステル（Ａ）のガラス転移温度が低くなりすぎ、硬度や耐食性が低下することがある。一方、多すぎると共重合ポリエステル（Ａ）のガラス転移温度が高くなり、屈曲性（加工性）が低下することがある。 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.
　また、ビスフェノールＡ、ビスフェノールＦ等のビスフェノール骨格を有するグリコール成分は、内分泌撹乱物質としての懸念があることから少なくすることが好ましい。ビスフェノール骨格を有するグリコール成分の共重合量は、全多価アルコール成分１００モル％としたときに、５モル％以下であることが好ましく、１モル％以下であることがより好ましく、０モル％がさらに好ましい。 Also, it is preferable to reduce the glycol component having a bisphenol skeleton such as bisphenol A and bisphenol F because there is a concern as an endocrine disrupting substance. 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.
　本発明の共重合ポリエステル（Ａ）のガラス転移温度は２５～５０℃の範囲であることが必要である。ガラス転移温度を２５～５０℃の範囲にすることで、耐食性と屈曲性を両立することができる。好ましくは３０～４８℃の範囲であり、さらに好ましくは３５～４５℃の範囲である。ガラス転移温度が２５℃未満になると、耐食性が低下することがある。また、ガラス転移温度が５０℃を超えると塗膜の屈曲性が低下する傾向にあり、好ましくない。 The glass transition temperature of the copolyester (A) of the present invention needs to be in the range of 25 to 50 ° C. By setting the glass transition temperature in the range of 25 to 50 ° C., both corrosion resistance and flexibility can be achieved. The temperature is preferably in the range of 30 to 48 ° C, more preferably in the range of 35 to 45 ° C. When the glass transition temperature is less than 25 ° C., the corrosion resistance may be lowered. Moreover, when the glass transition temperature exceeds 50 ° C., the flexibility of the coating film tends to decrease, which is not preferable.
　本発明の共重合ポリエステル（Ａ）には、３価以上の多価カルボン酸成分および／または３価以上の多価アルコール成分を共重合しても良い。３価以上の多価カルボン酸成分としては、例えばトリメリット酸、ピロメリト酸、ベンゾフェノンテトラカルボン酸、トリメシン酸などの芳香族カルボン酸、１，２，３，４－ブタンテトラカルボン酸などの脂肪族カルボン酸などが挙げられる。３価以上の多価アルコール成分としては、例えば、グリセリン、トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトール、α－メチルグルコース、マンニトール、ソルビトールが挙げられ、これらより１種、又は２種以上の使用が可能である。３価以上の多価カルボン酸成分の共重合量は、全多価カルボン酸成分を１００モル％としたとき、５モル％以下が好ましく、２モル％以下がより好ましく、１モル％以下がさらに好ましく、０モル％であっても差し支えない。また、３価以上の多価アルコール成分の共重合量は、全多価アルコール成分を１００モル％としたとき、２モル％以下が好ましく、１モル％以下がより好ましく、０モル％であっても差し支えない。多すぎると共重合ポリエステル（Ａ）の重合中にゲル化することがある。 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. Examples of the 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. Examples of the trihydric or higher polyhydric alcohol component include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, α-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).
　本発明の共重合ポリエステル（Ａ）の数平均分子量は２０００以上であることが好ましく、４０００以上であることがより好ましい。また、９０００以下であることが好ましく、８０００以下であることがより好ましく、７４００以下であることがさらに好ましい。数平均分子量が２０００未満だと、塗膜の屈曲性が低下することがあるため、好ましくない。一方、９０００を超えると塗料にした際の粘度が高く、取り扱いが難しくなり、好ましくない。 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.
　本発明の共重合ポリエステル（Ａ）の還元粘度は０．１５ｄｌ／ｇ以上であることが好ましく、０．１８ｄｌ／ｇ以上であることがより好ましい。また、０．３５ｄｌ／ｇ以下であることが好ましく、０．３２ｄｌ／ｇ以下であることがより好ましい。還元粘度が小さすぎると塗膜の屈曲性が低下することがあり、大きすぎると有機溶剤に溶解した際の粘度が高くなりすぎて、取り扱いが難しくなることがある。 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.
　本発明の共重合ポリエステル（Ａ）を製造する重合縮合反応の方法としては、例えば、１）多価カルボン酸と多価アルコールを任意の触媒存在下で加熱し、脱水エステル化工程を経て、脱多価アルコール・重縮合反応を行う方法、２）多価カルボン酸のアルコールエステル体と多価アルコールを任意の触媒存在下で加熱、エステル交換反応を経て、脱多価アルコール・重縮合反応を行う方法、などがある。前記１）２）の方法において、酸成分の一部またはすべてを酸無水物に置換しても良い。 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.
　本発明の共重合ポリエステル（Ａ）を製造する際には、従来公知の重合触媒、例えば、テトラ－ｎ－ブチルチタネート、テトライソプロピルチタネート、チタンオキシアセチルセトネートなどのチタン化合物、三酸化アンチモン、トリブトキシアンチモンなどのアンチモン化合物、酸化ゲルマニウム、テトラ－ｎ－ブトキシゲルマニウムなどのゲルマニウム化合物、その他、マグネシウム、鉄、亜鉛、マンガン、コバルト、アルミニウムなどの酢酸塩などを使用することが出来る。これらの触媒は１種、または２種以上を併用することができる。 In producing the copolymerized polyester (A) of the present invention, 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. These catalysts can be used alone or in combination of two or more.
　本発明の共重合ポリエステル（Ａ）を製造する際に、基材密着性、架橋性を高めるため、共重合ポリエステル（Ａ）の樹脂酸価を上げても良い。樹脂酸価は、１ｅｑ／１０６ｇ以上であることが好ましく、３ｅｑ／１０６ｇ以上であることがより好ましく、５ｅｑ／１０６ｇ以上であることがさらに好ましい。また、２００ｅｑ／１０６ｇ以下であることが好ましく、１００ｅｑ／１０６ｇ以下であることがより好ましく、５０ｅｑ／１０６ｇ以下であることがさらに好ましく、４０ｅｑ／１０６ｇ以下であることが特に好ましく、３０ｅｑ／１０６ｇ以下であることが最も好ましい。樹脂酸価を上記範囲内とすることによってこれらの効果が期待できる。樹脂酸価が小さすぎると基材密着性や架橋性の向上は得られにくいことがあり、大きすぎると基材密着性や架橋性は向上されるが、耐薬品性が低下してしまうことがあるため、耐久性を要求される用途には適さない。 When the copolymerized polyester (A) of the present invention is produced, 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. Also, preferably not more than 200 eq / 10 6 g, more preferably at most 100 eq / 10 6 g, and still more preferably at most 50 eq / 10 6 g, or less 40 eq / 10 6 g Particularly preferred is 30 eq / 10 6 g or less. These effects can be expected by setting the resin acid value within the above range. If the resin acid value is too small, it may be difficult to improve substrate adhesion and crosslinkability. If it is too large, substrate adhesion and crosslinkability will be improved, but chemical resistance may be reduced. Therefore, it is not suitable for uses that require durability.
　本発明の共重合ポリエステル（Ａ）の酸価を上げる方法としては、例えば、（１）重縮合反応終了後に、多価カルボン酸および／または無水多価カルボン酸を添加し、反応させる、（２）重縮合反応時に、熱、酸素、水などを作用させ、意図的に樹脂変質を行う、などの方法があり、これらを任意で行うことが出来る。 As a method for increasing the acid value of the copolymerized polyester (A) of the present invention, for example, (1) after completion of the polycondensation reaction, polyhydric carboxylic acid and / or polyhydric anhydride is added and reacted. ) During the polycondensation reaction, heat, oxygen, water or the like is allowed to act to intentionally alter the resin, and these can be optionally performed.
　本発明の共重合ポリエステル（Ａ）は公知の有機溶剤に溶解した状態で使用することができる。使用できる公知の有機溶剤としてはトルエン、キシレン、ソルベッソ（登録商標）などの芳香族系炭化水素類、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、二塩基酸エステルなどのエステル類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロンなどのケトン類、ｎ－ブチルセロソルブ、ｔ－ブチルセロソルブなどのエーテル類等が挙げられ、溶解性、蒸発速度（乾燥性）などを考慮して任意に選択、配合される。なかでも芳香族系炭化水素類とケトン類との混合溶媒であることが好ましく、ソルベッソとシクロヘキサノンの混合溶媒であることが好ましい。 The copolymerized polyester (A) of the present invention can be used in a state dissolved in a known organic solvent. Known 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 Examples thereof include ketones such as isobutyl ketone, 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 (dryability) and the like. Among these, a mixed solvent of aromatic hydrocarbons and ketones is preferable, and a mixed solvent of sorbeso and cyclohexanone is preferable.
　本発明のポリエステル（Ａ）は、前記有機溶剤に２５℃で４０質量％以上の濃度で溶解することが好ましく、５０質量％以上の濃度で溶解することがより好ましく、６０質量％以上の濃度で溶解することがさらに好ましい。前記の溶解度であることで、金属プライマー塗料としての固形分濃度を上げることができ、取り扱いが容易となる。 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. When the solubility is as described above, the solid content concentration as the metal primer coating can be increased, and the handling becomes easy.
＜架橋剤（Ｂ）＞
　本発明の共重合ポリエステル（Ａ）は架橋剤（Ｂ）とともに使用することができる。架橋剤（Ｂ）は公知の架橋剤を使用することが出来る。架橋剤（Ｂ）は、共重合ポリエステル（Ａ）に対して架橋反応を生じるものであれば特に限定されないが、好ましい例としてイソシアネート化合物、エポキシ樹脂、アミノ樹脂（アルキルエーテル化ホルムアルデヒド樹脂の一般名称）、フェノール樹脂などを挙げることができ、これらより１種、または２種以上を任意に選択して使用できる。 <Crosslinking agent (B)>
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.
　イソシアネート化合物としては、特に限定されないが、芳香族、脂環族、脂肪族のポリイソシアネート化合物があり、低分子量タイプ、高分子量タイプのいずれでもよい。例えばテトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、水素化ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネート、或いはこれらイソシアネート化合物の３量体、および前記したイソシアネート化合物とエチレングリコール、トリメチロールプロパン、プロピレングリコール、グリセリン、ソルビトール、エチレンジアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ポリエステルポリオール類、ポリエーテルポリオール類、ポリアミド類などの活性水素化合物と反応させて得られる末端イソシアネート化合物が挙げられる。これらは１種、または２種以上の併用ができる。 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. For example, 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, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, polyester polyols, polyether polyols, polyamides, etc. Can be mentioned. These can be used alone or in combination of two or more.
　また、イソシアネート化合物としてブロック化イソシアネート化合物を使用すると、金属プライマー塗料のポットライフを長くすることができる。ブロック化イソシアネート化合物のブロック剤としては例えば、フェノール、チオフェノール、メチルチオフェノール、クレゾール、キシレノール、レゾルシノール、ニトロフェノール、クロロフェノール等のフェノール類、アセトオキシム、メチルエチルケトオキシム、シクロヘキサノンオキシム等のオキシム類、メタノール、エタノール、プロパノール、ブタノール、ｔ－ブタノール、ｔ－ペンタノール等のアルコール類、ε－カプロラクタム等のラクタム類、その他芳香族アミン類、イミド類、アセチルアセトン、アセト酢酸エステル、マロン酸エチルエステルなどの活性メチレン化合物、メルカプタン類、イミン類、尿素類、等を挙げることができる。ブロック化イソシアネート化合物は前記イソシアネート化合物とブロック化剤とを従来公知の方法により反応させて得られ、１種、又は２種以上を併用して使用できる。 Also, when a blocked isocyanate compound is used as the isocyanate compound, the pot life of the metal primer paint can be extended. Examples of 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 ε-caprolactam, other aromatic amines, imides, acetylacetone, acetoacetate ester, malonic acid ethyl ester, etc. Examples thereof include compounds, mercaptans, imines, ureas and the like. 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.
　エポキシ樹脂としては、例えばビスフェノール－Ａのグリシジルエーテル及びそのオリゴマー、オルトフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、ｐ－ヒドロキシ安息香酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、エチレングリコールジグリシジルエステル、プロピレングリコールジグリシジルエステル、１，４－ブタンジオールジグリシジルエステル、１，６－ヘキサンジオールジグリシジルエステル、およびポリアルキレングリコールジグリシジルエステル類、トリメリット酸トリグリシジルエステル、トリグリシジルイソシアヌレート、１，４－グリシジルオキシベンゼン、ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールエタングリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、グリセロールアルキレンオキシド付加物のトリグリシジルエーテルなどを挙げることが出来る。これらは１種、または２種以上を併用して使用することができる。 Examples of the epoxy resin 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, 1,4-glycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane glycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol alkylene oxide adduct A triglycidyl ether etc. can be mentioned. These can be used alone or in combination of two or more.
　アミノ樹脂としては、特に限定されないが、メラミン、尿素、ベンゾグアナミン、アセトグアナミン、ステログアナミン、スピログアナミン、ジシアンジアミドなどのアミノ成分とホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒドなどのアルデヒド成分との反応によって得られるメチロール化アミノ樹脂が挙げられる。このメチロール化アミノ樹脂のメチロール基を炭素原子１～６のアルコールによってエーテル化したものもこのアミノ樹脂に含まれる。これらを単独で、または２種以上併用して使用することができる。 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. 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.
　フェノール樹脂としては、レゾール型フェノール樹脂を使用することができる。レゾール型フェノール樹脂としては、例えばフェノール、ｍ－クレゾール、ｍ－メチルフェノール、３，５－キシレノール、ｍ－メトキシフェノール、ｏ－クレゾール、ｐ－クレゾール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－エチルフェノール、２，３－キシレノール、２，５－キシレノールビスフェノール－Ａ、ビスフェノール－Ｆ等を原料とするフェノール樹脂を挙げることができ、これらを単独でまたは２種以上を併用して使用することができる。 As the phenol resin, a resol type phenol resin can be used. Examples of 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.
　架橋剤（Ｂ）は、共重合ポリエステル（Ａ）１００質量部に対して、１質量部以上であることが好ましく、５質量部以上であることがより好ましく、１０質量部以上であることがさらに好ましい。また、５０質量部以下であることが好ましく、４０質量部以下であることがより好ましく、３０質量部以下であることがさらに好ましい。少なすぎると、金属プライマー塗料から得られる塗膜の架橋が不十分となり、必要とする塗膜の堅さ、堅牢さや密着強度が得られない場合がある。多すぎると、必要とする塗膜の屈曲性が低下する場合がある。 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.
　本発明では、共重合ポリエステル（Ａ）と架橋剤（Ｂ）との架橋反応に寄与する触媒をさらに使用することができる。例えば酸触媒として、ｐ－トルエンスルホン酸、ドデシルベンゼンスルホン酸、カンファースルホン酸等の有機スルホン酸化合物、リン酸化合物、およびこれらのアミン中和体を使用することが出来る。塩基触媒としてはアミン化合物を使用することが出来る。金属触媒としては、各種金属の有機酸塩、ハロゲン化塩、硝酸塩、硫酸塩、有機配位子化合物などが使用できる。これら触媒は架橋剤（Ｂ）の硬化挙動に合わせて１種、または２種以上を併用できる。 In the present invention, a catalyst that contributes to a crosslinking reaction between the copolymerized polyester (A) and the crosslinking agent (B) can be further used. For example, 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. As the metal 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).
＜顔料（Ｃ）＞
　本発明の共重合ポリエステル（Ａ）は、顔料（Ｃ）とともに使用することができる。顔料（Ｃ）の具体例としては特に限定されないが、酸化チタン、酸化亜鉛、酸化ジルコニウム、炭酸カルシウム、硫酸バリウム、酸化アルミニウム、酸化クロム、クロム酸塩、カオリングレー、カーボンブラック、酸化鉄、タルク、マイカ、リン酸亜鉛、リン酸鉄、リン酸アルミニウム、亜リン酸亜鉛、トリポリリン酸アルミニウム、モリブデン酸カルシウム、モリブデン酸アルミニウム、モリブデン酸バリウム、酸化バナジウム、ストロンチウムクロメート、ジンククロメート、カルシウムシリケート、水分散シリカ、ヒュームドシリカなどの無機顔料やフタロシアニンブルー、フタロシアニングリーン、カルバゾールジオキサジンバイオレット、アントラピリミジンイエロー、イソインドリノンイエロー、インダスレンブルーなどの有機顔料を挙げることができる。これらを１種または２種以上添加することで、着色、防食、耐久性の向上、といった効果が期待できる。 <Pigment (C)>
The copolyester (A) of the present invention can be used together with the pigment (C). Specific examples of 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. By adding one or more of these, effects such as coloring, corrosion prevention, and improvement in durability can be expected.
　顔料（Ｃ）は、共重合ポリエステル（Ａ）１００質量部に対して、５質量部以上であることが好ましく、５０質量部以上であることがより好ましく、１００質量部以上であることがさらに好ましい。また、３００質量部以下であることが好ましく、２５０質量部以下であることがより好ましく、２００質量部以下であることがさらに好ましい。顔料（Ｃ）が少なすぎると、目的としている着色や防食等の効果が得られない場合がある。また、多すぎると塗膜の屈曲性が低下する場合がある。 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.
＜添加剤（Ｄ）＞
　本発明の共重合ポリエステル（Ａ）は添加剤（Ｄ）を必要に応じて使用することができる。添加剤（Ｄ）の具体例としては特に限定されないが、ｐ－トルエンスルホン酸、ドデシルベンゼンスルホン酸、カンファースルホン酸、リン酸化合物などの酸触媒、アミン化合物などの塩基触媒、消泡剤、レベリング剤、熱劣化防止剤、紫外線吸収剤、粘度調整剤、ワックスなどが挙げられる。これらを１種または２種以上使用することができる。添加剤（Ｄ）は塗膜物性に影響を与えない程度であれば、自由に配合することが出来る。好ましくは、共重合ポリエステル（Ａ）１００質量部に対して、０．１質量部以上５質量部以下である。 <Additive (D)>
In the copolymerized polyester (A) of the present invention, 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. One or more of these can be used. The additive (D) can be freely blended as long as it does not affect the physical properties of the coating film. Preferably, they are 0.1 mass part or more and 5 mass parts or less with respect to 100 mass parts of copolyester (A).
＜有機溶剤（Ｅ）＞
　本発明で用いる有機溶剤（Ｅ）は、共重合ポリエステル（Ａ）を溶解するものであれば特に限定されない。具体的には、トルエン、キシレン、ソルベッソ（登録商標）などの芳香族系炭化水素類、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、二塩基酸エステルなどのエステル類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロンなどのケトン類、ｎ－ブチルセロソルブ、ｔ－ブチルセロソルブなどのエーテル類等が挙げられ、溶解性、蒸発速度（乾燥性）などを考慮して任意に選択、配合される。なかでも芳香族系炭化水素類とケトン類との混合溶媒であることが好ましく、ソルベッソとシクロヘキサノンの混合溶媒であることが好ましい。 <Organic solvent (E)>
The organic solvent (E) used in the present invention is not particularly limited as long as it dissolves the copolyester (A). Specifically, 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. Among these, a mixed solvent of aromatic hydrocarbons and ketones is preferable, and a mixed solvent of sorbeso and cyclohexanone is preferable.
　有機溶剤（Ｅ）は、共重合ポリエステル（Ａ）１００質量部に対して、５０質量部以上であることが好ましく、より好ましくは１００質量部以上であり、さらに好ましくは１５０質量部以上である。また、５００質量部以下が好ましく、より好ましくは４００質量部以下であり、さらに好ましくは３００質量部以下である。少なすぎると保存安定性が低下することがあり、多すぎるとコストがかかるなど実用的でなくなることがある。 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.
＜金属プライマー塗料＞
　本発明の金属プライマー塗料は、共重合ポリエステル（Ａ）、架橋剤（Ｂ）、顔料（Ｃ）、添加剤（Ｄ）および有機溶剤（Ｅ）を含有する塗料である。 <Metal primer paint>
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).
＜金属塗装板＞
　本発明の金属塗装板は、金属板の少なくとも片面に、本発明の金属プライマー塗料をプライマー層として有するものである。塗装方法について、特に限定はされないが、ロールコーター塗装、カーテンフローコーター塗装、エアースプレー塗装、静電スプレー塗装、スクリーン印刷等を取ることができる。
　また、金属板としては、特に限定されないが、例えば熱延伸鋼板、電気亜鉛メッキ鋼板、合金メッキ鋼板、アルミニウム亜鉛合金メッキ鋼板、アルミニウム板、錫メッキ鋼板、ステンレス鋼板、銅板、銅メッキ鋼板、ティンフリースチール、ニッケルメッキ鋼板、極薄錫メッキ鋼板、クロム処理鋼板などの金属板が好ましい。 <Metal painted plate>
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. Although it does not specifically limit about the coating method, Roll coater coating, curtain flow coater coating, air spray coating, electrostatic spray coating, screen printing, etc. can be taken.
Further, 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.
　以下、実施例を挙げて本発明を具体的に説明する。なお、本実施例および比較例において、部は質量部を示すこととする。 Hereinafter, the present invention will be specifically described with reference to examples. In addition, in a present Example and a comparative example, suppose that a part shows a mass part.
（１）共重合ポリエステル（Ａ）の組成の測定
　４００ＭＨｚの１Ｈ－核磁気共鳴スペクトル装置（以下、ＮＭＲと略記することがある）を用い、共重合ポリエステル（Ａ）を構成する多価カルボン酸成分、多価アルコール成分のモル比定量を行った。溶媒には重クロロホルムを使用した。なお、酸後付加により共重合ポリエステルの酸価を上げた場合には、酸後付加に用いた酸成分以外の酸成分の合計を１００モル％として、各成分のモル比を算出した。 (1) Measurement of composition of copolymerized polyester (A) Polyhydric carboxylic acid constituting copolymerized polyester (A) using 400 MHz 1 H-nuclear magnetic resonance spectrometer (hereinafter sometimes abbreviated as NMR) The molar ratio of the component and the polyhydric alcohol component was determined. Deuterated chloroform was used as the solvent. In addition, when the acid value of the copolyester was increased by post acid addition, the molar ratio of each component was calculated with the total of the acid components other than the acid component used for the post acid addition being 100 mol%.
（２）共重合ポリエステル（Ａ）の数平均分子量の測定
　試料（共重合ポリエステル（Ａ））４ｍｇを、４ｍＬのテトラヒドロフランに溶解した後、孔径０．２μｍのポリ四フッ化エチレン製メンブランフィルターでろ過した。これを試料溶液とし、ゲル浸透クロマトグラフィー（ＧＰＣ）で分析を行った。装置はTOSOH　HLC－８２２０、検出器は示差屈折率検出器、移動相はテトラヒドロフランを用い、流速１ｍＬ／分、カラム温度４０℃で測定した。カラムは昭和電工製ＫＦ－８０２、８０４Ｌ、８０６Ｌを用いた。分子量標準には単分散ポリスチレンを使用し、数平均分子量は標準ポリスチレン換算値とし、分子量１０００未満に相当する部分を省いて算出した。 (2) Measurement of number average molecular weight of copolymerized polyester (A) 4 mg of sample (copolymerized polyester (A)) was dissolved in 4 mL of tetrahydrofuran, and then filtered through a membrane filter made of polytetrafluoroethylene having a pore size of 0.2 μm. did. This was used as a sample solution and analyzed by gel permeation chromatography (GPC). The measurement was performed using a TOSOH HLC-8220 apparatus, a differential refractive index detector as a detector, tetrahydrofuran as a mobile phase, a flow rate of 1 mL / min, and a column temperature of 40 ° C. As the column, KF-802, 804L and 806L manufactured by Showa Denko were used. 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.
（３）ガラス転移温度の測定
　示差走査型熱量計（ＳＩＩ社、ＤＳＣ－２００）を用いて測定した。試料（共重合ポリエステル（Ａ））５ｍｇをアルミニウム抑え蓋型容器に入れ密封し、液体窒素を用いて－５０℃まで冷却した。次いで１５０℃まで２０℃／分の昇温速度にて昇温させ、昇温過程にて得られる吸熱曲線において、吸熱ピークが出る前（ガラス転移温度以下）のベースラインの延長線と、吸熱ピークに向かう接線（ピークの立ち上がり部分からピークの頂点までの間での最大傾斜を示す接線）との交点の温度をもって、ガラス転移温度（Ｔｇ、単位：℃）とした。 (3) Measurement of glass transition temperature The glass transition temperature was measured using a differential scanning calorimeter (SII, DSC-200). A sample (copolymerized polyester (A)) (5 mg) 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. at a rate of temperature increase of 20 ° C./min, and in the endothermic curve obtained in the temperature increasing process, an extension line of the baseline before the endothermic peak appears (below the glass transition temperature) and the endothermic peak 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).
（４）酸価の測定
　試料（共重合ポリエステル（Ａ））０．２ｇを精秤しクロロホルム４０ｍｌに溶解した。次いで、０．０１Ｎの水酸化カリウムのエタノール溶液で滴定を行った。指示薬にはフェノールフタレインを用いた。試料に対して、水酸化カリウム当量を求め、測定値を試料１０６ｇあたりの当量に換算し、単位は当量／１０６ｇとした。 (4) Measurement of acid value 0.2 g of a sample (copolymerized polyester (A)) was precisely weighed and dissolved in 40 ml of chloroform. Next, titration was performed with an ethanol solution of 0.01 N potassium hydroxide. Phenolphthalein was used as an indicator. The sample, determine the potassium hydroxide equivalent, converts the measured values into equivalent per sample 10 6 g, the unit was equivalent / 10 6 g.
（５）還元粘度ηｓｐ／ｃ（ｄｌ／ｇ）の測定
　試料（共重合ポリエステル（Ａ））０．１０ｇをフェノール／テトラクロロエタン（重量比６／４）の混合溶媒２５ｃｃに溶かし、ウベローデ粘度管を用いて３０℃で測定した。 (5) Measurement of reduced viscosity ηsp / c (dl / g) 0.10 g of a sample (copolyester (A)) was dissolved in 25 cc of a mixed solvent of phenol / tetrachloroethane (weight ratio 6/4), and an Ubbelohde viscosity tube was used. And measured at 30 ° C.
　以下、本発明の共重合ポリエステル（Ａ）、および比較例となる共重合ポリエステルの製造例を示す。 Hereinafter, production examples of the copolyester (A) of the present invention and a copolyester as a comparative example will be shown.
　共重合ポリエステル（a１）の製造例
　攪拌機、コンデンサー、温度計を具備した反応容器にテレフタル酸ジメチル８０９部、イソフタル酸ジメチル７９３部、トリメリット酸無水物１９部、エチレングリコール４０７部、ネオペンチルグリコール５４０部、トリエチレングリコール２８７部、触媒としてオルトチタン酸テトラブチルを全酸成分に対して０．０３モル％仕込み、１６０℃から２２０℃まで４時間かけて昇温、脱メタノール工程を経ながらエステル交換反応を行った。次に重縮合反応工程は、系内を２０分かけて５ｍｍＨｇまで減圧し、さらに２５０℃まで昇温を進めた。次いで、０．３ｍｍＨｇ以下まで減圧し、６０分間の重縮合反応を行い、これを取り出した。得られた共重合ポリエステル（a１）はＮＭＲによる組成分析の結果、モル比でテレフタル酸／イソフタル酸／トリメリット酸／エチレングリコール／ネオペンチルグリコール/トリエチレングリコール＝５０／４９／１／４０／４０／２０［モル比］であった。また、数平均分子量は７０００、ガラス転移温度は４０℃、酸価は２０ｅｑ／１０６ｇ、であった。結果を表１に記した。 Production Example of 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. Next, in the polycondensation reaction step, the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 250 ° C. Next, the pressure was reduced to 0.3 mmHg or less, a polycondensation reaction was performed for 60 minutes, and this was taken out. As a result of compositional analysis by NMR, the obtained copolymer polyester (a1) was terephthalic acid / isophthalic acid / trimellitic acid / ethylene glycol / neopentyl glycol / triethylene glycol = 50/49/1/40/40 in terms of molar ratio. / 20 [molar ratio]. The number average molecular weight was 7000, the glass transition temperature was 40 ° C., and the acid value was 20 eq / 10 6 g. The results are shown in Table 1.
　共重合ポリエステル（a２）～（a１０）の製造例
　共重合ポリエステル（a１）の製造例に準じ、原料の種類と配合比率を変更して、本発明の共重合ポリエステル（a２）～（a１１）を製造した。結果を表１に記した。 Production Examples of 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.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
実施例１
　金属プライマー塗料（Ａ１）の調製
　共重合ポリエステル（a１）８０部をシクロヘキサノン１００部、ソルベッソ１５０　１００部の混合溶剤で溶解した。これにカルシウムシリケート５０部、トリポリリン酸アルミニウム１３部、酸化チタン３７部をいれ、振とう機を用い６時間分散した。さらに、架橋剤としてサイメル３０３（オルネクス社製、メラミン硬化剤）２０部、硬化触媒としてドデシルベンゼンスルホン酸０．２部入れ、本発明の金属プライマー塗料（Ａ１）とした。 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.
実施例２～１０、比較例１～３
　金属プライマー塗料（Ａ２）～（Ｋ１）の調製
　金属プライマー塗料（Ａ１）と同様の方法にて、本発明の実施例または比較例である金属プライマー塗料（Ａ２）～（Ｋ１）を得た。配合比率は表２に示した。 Examples 2 to 10, Comparative Examples 1 to 3
Preparation of Metal Primer Paints (A2) to (K1) Metal primer paints (A2) to (K1) as Examples or Comparative Examples of the present invention were obtained in the same manner as the metal primer paint (A1). The blending ratio is shown in Table 2.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　金属塗装板の評価
　試験片の作成
　０．５ｍｍ厚の溶融亜鉛めっき鋼板を用意し、これに前記実施例に記載の金属プライマー塗料を乾燥後の膜厚が５μmとなる様に塗装し、２１０℃で４５秒乾燥した。さらにこの上に乾燥後の膜厚が１５μmとなるように数平均分子量が１５０００でガラス転移温度が３８℃の共重合ポリエステル樹脂１６質量部、メラミン樹脂４質量部、酸化チタン２０質量部とシクロヘキサノン６０質量部より作製した上塗り塗料を塗装し、２５０℃で６０秒乾燥し、金属塗装板の試験片を得た。 Evaluation of metal coated plate Preparation of test piece A 0.5 mm thick hot dip galvanized steel sheet was prepared, and this was coated with the metal primer coating described in the above examples so that the film thickness after drying was 5 μm, and 210 ° C. For 45 seconds. Further, 16 parts by mass of a copolyester resin having a number average molecular weight of 15000 and a glass transition temperature of 38 ° C., 4 parts by mass of melamine resin, 20 parts by mass of titanium oxide and 60 parts of cyclohexanone so that the film thickness after drying is 15 μm. The top coating material produced from the part by mass was applied and dried at 250 ° C. for 60 seconds to obtain a test piece of metal coated plate.
（塗膜硬度）
　前記金属塗装板試験片の塗装面に対し鉛筆の芯を４５度の角度で当て、１ｋｇの荷重で前方向に滑らせた。鉛筆の芯の堅さは硬い方から、Ｈ、Ｆ、ＨＢ、Ｂ、２Ｂを用い、傷がつかない最高硬度を評価した。硬度が高いほど塗膜の硬度は高く、傷がつきにくい。
評価基準
　○：Ｈ以上
　△：Ｆ～Ｂ
　×：２Ｂ以下 (Coating hardness)
A pencil core was applied to the painted surface of the metal coated plate test piece at an angle of 45 degrees and slid forward with a load of 1 kg. The hardness of the pencil lead was evaluated from the hardest, using H, F, HB, B, and 2B, and the highest hardness without scratches was evaluated. The higher the hardness is, the higher the hardness of the coating film is, and the harder it is to scratch.
Evaluation criteria ○: H or higher △: F to B
×: 2B or less
（屈曲性）
　前記金属塗装板試験片を２５℃下で１８０°折り曲げ試験を行い。目視にて、塗膜の割れを確認した。２Ｔとは、試験金属板と同じ厚さの金属板を２枚挟んで折り曲げた際に塗膜の割れが発生しないことである。数字が小さいほど屈曲性が良好である。
　○：０～２Ｔ
　△：３～４Ｔ
　×：５Ｔ以上 (Flexibility)
The metal-coated plate test piece was subjected to a 180 ° bending test at 25 ° C. The crack of the coating film was confirmed visually. 2T means that the coating film does not crack when two metal plates having the same thickness as the test metal plate are sandwiched and bent. The smaller the number, the better the flexibility.
○: 0 to 2T
Δ: 3-4T
×: 5T or more
（耐食性）
　前記金属塗装板試験片の端部をテープで保護し、カッターナイフで表面に素地まで達するクロスカットを施した後に、ＪＩＳ　Ｚ２３７１－２０１５記載の方法で５００時間の中性塩水噴霧試験を実施した。試験後の塗装板のクロスカット部からの膨れの大きさを測定した。膨れの大きさが小さいほど、耐食性が良好である。
評価基準
　○：直径３ｍｍ以下
　△：直径３ｍｍを超えて７ｍｍ未満
　×：直径７ｍｍ以上 (Corrosion resistance)
After the end of the metal-coated plate test piece was protected with tape and a cross-cut reaching the substrate surface with a cutter knife was performed, a neutral salt spray test was conducted for 500 hours by the method described in JIS Z2371-2015. The magnitude | size of the swelling from the crosscut part of the coating board after a test was measured. The smaller the blister size, the better the corrosion resistance.
Evaluation criteria ○: Diameter 3 mm or less △: Diameter exceeding 3 mm and less than 7 mm ×: Diameter 7 mm or more
（ハイソリッド適性（溶液粘度））
　得られた共重合ポリエステル（Ａ）をシクロヘキサノンとソルベッソ150の同重量比率の混合溶液に固形分濃度６０重量％で溶解し、Ｂ型回転粘度計（東京計器（株）製，EM型、ローターＮｏ．４、１２ｒｐｍ）を用いて、２５℃条件下で溶液粘度を測定した。溶液粘度が２００ポイズを超えると塗料製造時の取り扱いが難しくなる。
評価基準
　○：１３０ポイズ未満
　△：１３０ポイズ以上２００ポイズ以下
　×：２００ポイズを超える (High solid suitability (solution viscosity))
The obtained copolyester (A) was dissolved in a mixed solution of cyclohexanone and Solvesso 150 in the same weight ratio at a solid concentration of 60% by weight, and a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd., EM type, rotor No. 4 and 12 rpm), the solution viscosity was measured under the condition of 25 ° C. When the solution viscosity exceeds 200 poise, handling during coating production becomes difficult.
Evaluation criteria ○: Less than 130 poises △: 130 poises or more and 200 poises or less ×: Over 200 poises
（耐薬品性）
　前記金属塗装板試験片の端部をテープで保護し、２５℃雰囲気下、５重量％の水酸化ナトリウム水溶液に４８時間浸漬後、外観を目視し、評価した。膨れ等が少ないほど耐薬品性が良好である。
　○：膨れなし～直径１ｍｍ未満の微小な膨れ
　△：直径１ｍｍ以上の大きな膨れがある
　×：塗膜が剥がれる (chemical resistance)
The edge part of the said metal-coated board test piece was protected with the tape, and after visual immersion for 48 hours in 25 weightC sodium hydroxide aqueous solution in 25 degreeC atmosphere, the external appearance was visually observed and evaluated. The less blistering, the better the chemical resistance.
○: No swelling to minute swelling with a diameter of less than 1 mm Δ: Large swelling with a diameter of 1 mm or more ×: The coating film peels off
　本発明の共重合ポリエステル、および塗料組成物は、加工性、耐食性、耐薬品性に優れ、金属板のプライマー塗料用樹脂として有用である。特に家電用のコイルコーティングに用いる成分として有用である。 The 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.

Claims (6)

  1. 　多価カルボン酸成分と多価アルコール成分を共重合成分とする共重合ポリエステルであって、全多価カルボン酸成分を１００モル％としたときに、芳香族ジカルボン酸成分が９５～１００モル％、脂肪族ジカルボン酸成分が０～５モル％であり、かつ全多価アルコール成分を１００モル％としたときに、一般式（１）で表されるグリコール成分が１～３０モル％であり、ガラス転移温度が２５～５０℃の範囲である共重合ポリエステル（Ａ）。
    Figure JPOXMLDOC01-appb-C000001
     　一般式（１）中、ｎは３以上の整数である。     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%, When the aliphatic dicarboxylic acid component is 0 to 5 mol% and the total polyhydric alcohol 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.
    Figure JPOXMLDOC01-appb-C000001
     In general formula (1), n is an integer of 3 or more.
  2. 　数平均分子量が４０００～９０００の範囲である請求項１に記載の共重合ポリエステル（Ａ）。 The copolymer polyester (A) according to claim 1, wherein the number average molecular weight is in the range of 4000 to 9000.
  3. 　脂肪族ジカルボン酸成分を含まない請求項１～２に記載の共重合ポリエステル（Ａ）。 The copolymer polyester (A) according to claim 1 or 2, which does not contain an aliphatic dicarboxylic acid component.
  4. 　前記一般式（１）がトリエチレングリコールである請求項１～３のいずれかに記載の共重合ポリエステル（Ａ）。 The copolymer polyester (A) according to any one of claims 1 to 3, wherein the general formula (1) is triethylene glycol.
  5. 　請求項１～４のいずれかに記載の共重合ポリエステル（Ａ）、架橋剤（Ｂ）、顔料（Ｃ）、添加剤（Ｄ）、および有機溶剤（Ｅ）を含有する金属プライマー塗料。 A metal primer paint containing the copolyester (A) according to any one of claims 1 to 4, a crosslinking agent (B), a pigment (C), an additive (D), and an organic solvent (E).
  6. 　請求項５に記載の金属プライマー塗料をプライマー層として有する金属塗装板。
     
     
          A metal-coated plate having the metal primer paint according to claim 5 as a primer layer.


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