WO2008010503A1 - Polyester copolymérisé, composition de polyester copolymérisé pour agent de revêtement pulvérulent comprenant ledit polyester copolymérisé, et agent de revêtement pulvérulent - Google Patents

Polyester copolymérisé, composition de polyester copolymérisé pour agent de revêtement pulvérulent comprenant ledit polyester copolymérisé, et agent de revêtement pulvérulent Download PDF

Info

Publication number
WO2008010503A1
WO2008010503A1 PCT/JP2007/064141 JP2007064141W WO2008010503A1 WO 2008010503 A1 WO2008010503 A1 WO 2008010503A1 JP 2007064141 W JP2007064141 W JP 2007064141W WO 2008010503 A1 WO2008010503 A1 WO 2008010503A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
group
compound
ester
copolyester
Prior art date
Application number
PCT/JP2007/064141
Other languages
English (en)
Japanese (ja)
Inventor
Keiichiro Togawa
Yoshitaka Eto
Original Assignee
Toyo Boseki Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Priority to JP2008525872A priority Critical patent/JP5267795B2/ja
Publication of WO2008010503A1 publication Critical patent/WO2008010503A1/fr

Links

Classifications

    • 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
    • C09D5/03—Powdery paints
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • Copolyester, copolymer polyester composition for powder coating comprising the same, and powder coating
  • the present invention does not use a metal compound such as a tin compound, an antimony compound, a germanium compound, or a titanium compound as a main component of the catalyst, and a polycondensation catalyst mainly composed of an aluminum compound.
  • the present invention relates to a copolymerized polyester and a copolymerized polyester composition having excellent transparency and color tone, and a powder coating material having excellent long-term weather resistance and excellent coating properties.
  • Polyester resin has been used in many fields in terms of its physical properties, environmental suitability, adhesive properties, cost, and the like.
  • low molecular weight polyesters having a number average molecular weight of less than 7000 are used in powder paints, adhesives, various coating agents, binders and the like.
  • a catalyst for promoting esterification or transesterification reaction is usually used for polyester polymerization.
  • antimony, titanium, germanium, and tin compounds are often used. These catalyst compounds are selected from the viewpoint of catalytic activity.
  • the color of rosin is darkened when antimony is used, and yellow when titanium is used.
  • germanium there is another problem that it is difficult to use germanium in that it has a good hue of rosin and is very expensive. It is a problem common to germanium and titanium
  • force polymerization there is also a problem that the catalyst activity is lowered due to the generated water, and the polymerization time is prolonged or the addition of a catalyst is required.
  • tin compounds there is a problem that the color of the resin becomes yellow.
  • Polyester for white powder coatings having excellent color tone by esterification with an organotin compound and polycondensation reaction using a phosphoric acid / antioxidant and triacid / antimony A technique for producing a resin has been disclosed (for example, see Patent Document 1). However, this technique has completely solved the problem of the resin when the color of the resin is darkened.
  • polymerization catalysts such as tin compounds and antimony compounds contain heavy metals, and polyester resins for powder coatings are desired without these.
  • Patent Document 1 Japanese Patent Laid-Open No. 9-286847
  • An object of the present invention is to solve the above-mentioned problems of the prior art, and metal compounds such as these titanium compounds, antimony compounds, tin compounds, germanium compounds and the like are used. Not included as the main component of the catalyst! / Copolyester polycondensed using a soot catalyst, that is, using a catalyst that can be polycondensed at a speed that does not cause any problems in productivity compared to so-called heavy metal catalysts.
  • Copolymer polyester with excellent properties, color tone, weather resistance, and impact resistance, and weather resistance and coating film properties comprising the same, and excellent reactivity at the time of crosslinking with a curing agent, especially gel fraction, workability, water resistance
  • An object of the present invention is to provide a powder coating material that is excellent in adhesion, and adhesion after water resistance.
  • the present invention has been completed as a result of intensive studies in order to solve the above problems. That is, the present invention is as follows.
  • the a trifunctional or higher polycarboxylic acid is 1 to 10 mol%, or, the number 20 following the alkylene glycol having a carbon 90 to 99 mole 0/0, the trifunctional or higher polyhydric alcohol is 1 to: Copolyester according to (1), characterized in that it is L0 mol%.
  • the polyvalent carboxylic acid component contains at least one selected from the group power of isophthalic acid, orthophthalic acid, 2, 6 naphthalene dicarboxylic acid power, and the co-polymer according to (1) or (2) Polymerized polyester.
  • An alkylene glycol having 20 or less carbon atoms is ethylene glycol, 1,2 propanediol, 1,3 propanediol, 1,4 butanediol, 1,6 hexanediol, 1,4-cyclohexanedimethanol, 2 Any one of (1) to (3), characterized in that it contains at least one selected from the group consisting of methyl-1,3 propanediol, neopentyl darcol, 3-methyl-1,5 pentanediol Copolymer polyester.
  • the polycondensation catalyst has at least one kind selected from a group force consisting of an aluminum compound power and at least one kind selected from a phosphorus compound, (1) to (4), Copolyester as described.
  • the polycondensation catalyst is composed of at least one selected from the group force of an aluminum compound force and an alkali metal and / or an alkaline earth metal. (1) to (4) Copolyester as described.
  • the polycondensation catalyst is characterized by comprising at least one selected from a group force consisting of an aluminum compound, at least one selected from phosphorus compounds, and an alkali metal and / or an alkaline earth metal.
  • the copolymer polyester according to any one of (1) to (4).
  • the phosphorus compound includes at least one of a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, or a phosphine compound.
  • a phosphonic acid compound a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, or a phosphine compound.
  • (5), (7) and (8) ! Copolyester described in any of the above.
  • a copolymer polyester for powder coatings comprising the copolymer polyester according to any one of (1) to (10) and a curing agent capable of reacting with the copolymer polyester. Composition.
  • a powder paint comprising the copolyester composition for powder paint according to any one of (11) or (12).
  • the copolymerized polyester of the present invention has transparency using a catalyst capable of polycondensation at a speed that does not cause any problems in productivity compared with heavy metal catalysts such as tin compounds and antimony compounds. From this, it is possible to obtain a powder coating material excellent in weather resistance, color tone and coating film properties, particularly with good reactivity with a curing agent.
  • metal aluminum As the aluminum compound constituting the polycondensation catalyst used in the polyester of the present invention, metal aluminum, known aluminum compounds can be used without limitation.
  • the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum Carboxylates such as aluminum lichloroacetate, aluminum lactate, aluminum citrate, aluminum salicylate, inorganic salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum Methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum Aluminum alkoxides such as side, aluminum acetyl cetate, aluminum acetyl acetate, aluminum cetyl acetate, aluminum acetyl acetate di-iso-propoxide, etc., trimethylaluminum, triethylaluminum And organoaluminum compounds such as these and partial partial water hydrolys
  • carboxylic acid salts Inorganic acid salts, and chelate compounds are preferred.
  • the amount of the aluminum compound used in the polyester of the present invention is 0.001 based on the monolet number of all the constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. ⁇ 1.0 mono %%, more preferably 0.005 to 0.5 mol%.
  • the amount of the additive of the aluminum component is required to be wide because the catalytic activity varies greatly depending on the type and combination of polyvalent carboxylic acid and diol used, and the polycondensation method. This shows the same tendency with other polycondensation catalysts. In particular, if polycondensation is not performed under reduced pressure, the amount of polycondensation catalyst must be greatly increased.
  • the polycondensation catalyst used in the polyester of the present invention exhibits sufficient catalytic activity. As a result, the resulting polyester has excellent thermal stability, thermal acid stability, and hydrolysis resistance, and foreign substances caused by aluminum. Generation and coloring are suppressed.
  • Examples of preparation of an aqueous solution of basic aluminum acetate are as follows. That is, after adding water to basic aluminum acetate and thoroughly diffusing at room temperature, an aqueous solution is prepared by dissolving at room temperature to 100 ° C. In this case, a lower temperature is preferable and a shorter heating is preferable.
  • the concentration of the aqueous solution is preferably 10 to 30 g / l, particularly preferably 15 to 20 g / l.
  • the basic aluminum acetate aqueous solution is the same ethylene glycol solution. That is, ethylene glycol is added to the above aqueous solution.
  • the added amount of ethylene glycol is preferably 0.5 to 5.0 times the volume of the aqueous solution. More preferably 0.8 to 2.0 times the amount.
  • the water is distilled off by heating and stirring at 80 to 120 ° C. More preferably, heating is performed under reduced pressure and / or in an atmosphere of an inert gas such as nitrogen or argon, and water is distilled off to prepare a catalyst solution.
  • an inert gas such as nitrogen or argon
  • ethylene glycol is an example, and other alkylene glycols can be used in the same manner.
  • the basic aluminum acetate described above is soluble in water and other solvents such as water glycol, especially water and water soluble in Z or ethylene glycol. This is also preferable from the viewpoint of reducing foreign matter.
  • the phosphorus compound constituting the polycondensation catalyst used in the polyester of the present invention is not particularly limited, but includes phosphoric acid, trimethyl phosphoric acid, triethyl phosphoric acid, phenylphosphoric acid, triphenylphosphoric acid, and the like.
  • More preferable phosphorus compounds used in the polyester of the present invention include a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound. It is at least one Linyi compound selected from the group.
  • these phosphorus compounds an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as thermal stability of the polyester is seen.
  • the use of phosphonic acid-based compounds is preferable because of their great effects of improving physical properties and improving catalytic activity.
  • it is preferable to use a compound having an aromatic ring structure because of the large effect of improving physical properties and the improvement of catalytic activity.
  • Examples of the phosphonic acid compound used in the polyester of the present invention include dimethyl methyl phosphonate, diphenyl methyl phosphonate, dimethyl phosphophosphonate, jetyl phosphophosphonate, diphenol phosphophosphonate, benzyl phosphonic acid. Examples thereof include dimethyl and benzyl phosphonate.
  • Examples of phosphinic acid compounds used in the polyester of the present invention include diphenylphosphinic acid and diphenylphosphine. And methyl phosphinate, phenyl phosphinate, phenyl phosphinate, phenyl phosphinate, phenyl phosphinate, and phenyl phosphinate.
  • Examples of the phosphine oxide compound used in the polyester of the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, and the like.
  • the phosphorus compound used in the polyester of the present invention is represented by the following formula:
  • the compounds represented by 7) to (Chemical Formula 12) are preferred.
  • the phosphorus compound used in the polyester of the present invention is represented by the following general formula:
  • RR 4 and RR 6 are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a carbon group containing a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 and R 3 each independently represent a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl naphthyl.
  • Examples of the phosphorus compound used in the polyester of the present invention include compounds in which R 4 , R 5 and R 6 are groups having an aromatic ring structure in the above formulas (Chemical Formula 13) to (Chemical Formula 15). preferable.
  • Examples of the phosphorus compound used in the polyester of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, jetyl phenylphosphonate, diphenol phenylphosphonate, benzylphosphone.
  • dimethyl ferrphosphonate and jetyl benzylphosphonate are particularly preferred.
  • a phosphorus metal salt compound is particularly preferable as the phosphorus compound.
  • the phosphorus metal salt compound is not particularly limited as long as it is a phosphorus compound metal salt.
  • a metal salt of a phosphonic acid compound is used, the polyester which is the subject of the present invention is used.
  • the effect of improving the physical properties and improving the catalytic activity are greatly preferred.
  • metal salts of phosphorus compounds include monometal salts, dimetal salts, and trimetal salts.
  • the catalytic activity is obtained when the metal portion of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn.
  • the improvement effect is greatly preferred.
  • Li, Na, and Mg are particularly preferable.
  • R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group
  • R 3 represents hydrogen, a hydrocarbon having 1 to 50 carbon atoms Represents a hydrocarbon group having 1 to 50 carbon atoms, including a group, a hydroxyl group or an alkoxyl group or carbonyl, 1 is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less.
  • M represents a (l + m) -valent metal cation
  • n represents an integer of 1 or more
  • the hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl naphthyl.
  • R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like.
  • R 2 examples include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n butyl group, sec butyl group, tert butyl group, long chain aliphatic group, fur group, naphthyl group. A substituted full group, a naphthyl group, a group represented by CH 2 CH 3 OH, and the like.
  • Examples include hydroxide ions, alcoholate ions, acetate ions and cetylacetone ions.
  • R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a hydrocarbon group containing 1 to 50 carbon atoms, 1 is an integer of 1 or more, m is 0 Or an integer of 1 or more, l + m is 4 or less, M represents a (l + m) -valent metal cation, and the hydrocarbon group is an alicyclic structure such as cyclohexyl, a branched structure, or phenyl naphthyl. Or an aromatic ring structure such as
  • R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like.
  • R 30 examples include hydroxide ions, alcohol ions, acetate ions and acetylacetone ions.
  • Phosphorus metal salt compounds used in the polyester of the present invention include lithium [(1-naphthinole) methinorephosphonate ethinore], sodium [(1 naphthinore) methinorephosphonate ethyl], magnesium bis [ (1 naphthyl) methylphosphonate], potassium [(2-naphthyl) methylphosphonate], magnesium bis [(2-naphthyl) methylphosphonate], lithium [benzylphosphonate], sodium [benzylphosphonate] ,
  • lithium [(1-naphthyl) methylphosphonate] sodium [(1 naphthyl) methylphosphonate]
  • magnesium bis [(1 naphthyl) methylphosphonate] lithium [benzylphosphonate]
  • sodium [Benzylphosphonate] magnesium bis [benzylphosphonate]
  • sodium benzylphosphonate sodium benzylphosphonate
  • magnesium bis [benzylphosphonate] sodium benzylphosphonate
  • sodium benzylphosphonate sodium benzylphosphonate
  • magnesium bis [benzylphosphonate] sodium benzylphosphonate
  • a phosphorus compound having at least one P—OH bond is particularly preferable as the phosphorus compound.
  • these phosphorus compounds are combined with the aluminum compound used in the polyester of the present invention during the polycondensation of the polyester. The effect of improving the catalytic activity can be seen greatly when used together.
  • the phosphorus compound having at least one P—OH bond is not particularly limited as long as it is a phosphorus compound having at least one P—OH in the molecule.
  • the use of a phosphonic acid compound having at least one POH bond facilitates complex formation with an aluminum compound, thereby improving the physical properties of the polyester and improving the catalytic activity. Largely preferred.
  • the physical properties can be improved by using at least one compound selected from the compound power represented by the following general formula (Chemical Formula 18).
  • the effect and the improvement effect of catalyst activity are large and preferable.
  • R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and a hydrocarbon group having 1 to 50 carbon atoms, n represents an integer of 1 or more, (It may also contain alicyclic structures such as hexyl, branched structures, and aromatic ring structures such as phenyl naphthyl.)
  • R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like.
  • R 2 examples include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n butyl group, sec butyl group, tert butyl group, long chain aliphatic group, fur group, naphthyl group. A substituted full group, a naphthyl group, a group represented by CH 2 CH 3 OH, and the like.
  • Examples of the phosphorus compound having at least one P-OH bond used in the polyester of the present invention include (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonate, (2-naphthyl) methylphosphonate. Ethyl, benzyl phosphonate, benzyl phosphonate, (9-anthryl) methyl phosphonate, 4-hydroxybenzyl phosphonate, 2-methylbenzyl phosphonate, 4-clonal benzyl phosphonate, 4-amino benzyl phosphone And methyl 4-ethyl and 4-methoxybenzylphosphonate. Of these, (1 naphthyl) methylphosphonate, benzylphosphonate are particularly preferred.
  • Preferable phosphorus compounds used in the polyester of the present invention include phosphorus compounds represented by the chemical formula (Chemical Formula 19). [0064] [Chemical 19]
  • R 1 represents a hydrocarbon group having 1 to 49 carbon atoms, or a hydrocarbon group having 1 to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, which is an alicyclic structure or branched structure. And may contain an aromatic ring structure.
  • the phosphorus compound used in the polyester of the present invention has a large molecular weight and thus is less likely to be distilled off at the time of polycondensation.
  • the phosphorus compound used in the polyester of the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule.
  • a phosphorus compound having a phenol moiety in the same molecule in addition to enhancing the physical properties of the polyester by containing a phosphorus compound having a phenol moiety in the same molecule, the use of a phosphorus compound having a phenol moiety in the same molecule during polycondensation of the polyester The effect of increasing the catalytic activity is greater, so the polyester productivity is excellent.
  • the phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphor compound having a phenol moiety in the same molecule.
  • Sphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, phosphine compound power Physical properties of polyester when one or more compounds selected from the group consisting of The improvement effect and the improvement effect of catalyst activity are large and preferable.
  • the use of a phosphonic acid compound having one or more phenol moieties in the same molecule is particularly preferred for improving the physical properties and improving the catalytic activity of the polyester.
  • R 1 represents a substituent having a phenol moiety, such as a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 4 , R 5 and R 6 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group or an alkoxyl group, Represents a hydrocarbon group having 1 to 50 carbon atoms containing a substituent such as an amino group, etc.
  • R 2 and R 3 are each independently a substituent such as hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group having 1 to 50 carbon atoms, including a branched structure, which may include an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl naphthyl. The ends of R 2 and R 4 may be bonded to each other.)
  • a phosphorus compound having a phenol moiety used in the polyester of the present invention in the same molecule For example, p-hydroxyphenylphosphonic acid, p-hydroxyphenylphosphonic acid dimethyl, p-hydroxyphenylphosphonic acid jetyl, p-hydroxyphenylphosphonic acid diphenol, bis (p-hydroxyphenyl- ) Phosphinic acid, bis (p-hydroxyphenol) methyl phosphinate, bis (p-hydroxyphenol) phosphinate, p-hydroxyphenol phosphinic acid, p-hydroxyphenol -Methyl phosphinate, p-hydroxyphenol phosphinate, p-hydroxyphenol phosphinate, p-hydroxyphenol phosphinate, p-hydroxyphenol phosphinate phenyl, Bis (p-hydroxyphenol) phosphine oxide, Tris (p-hydroxyphenol) phosphine oxide, Bis ( and p-hydroxyphenyl) methylphosphine oxide and compounds represented
  • SANKO-220 manufactured by Sanko Co., Ltd. is available and can be used.
  • the compound is selected from a metal salt compound of a specific phosphorus represented by the following general formula (Chemical Formula 33) At least one is particularly preferred.
  • R 2 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
  • R 4 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl.
  • R 4 Examples of the o include hydroxide ions, alcohol ions, acetate ions, and acetylacetone ions.
  • 1 represents an integer of 1 or more
  • m represents 0 or an integer of 1 or more
  • l + m is 4 or less.
  • M represents a (l + m) -valent metal cation.
  • n represents an integer of 1 or more.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • At least one selected from the compound power represented by the following general formula (Formula 34) is preferable.
  • ⁇ ⁇ ⁇ ⁇ represents an n-valent metal cation.
  • N represents 1, 2, 3 or 4.
  • M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu and Zn.
  • Li, Na, and Mg are particularly preferable.
  • Specific phosphorus metal salt compounds used in the polyester of the present invention include lithium [3,5-di-tert-butyl 4-hydroxybenzylphosphonate], sodium [3,5-di-tert Butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl 4-hydroxybenzylphosphonate], potassium [3,5-ditert-butyl 4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butylenyl 4-hydroxybenzenolephosphonate ethinole] ⁇ magnesium bis [3,5-di-tert-butyl 4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-butyl 4 —Methyl hydroxybenzylphosphonate], strontium bis [3,5-ditert-butyl-4-hydroxybenzylphosphonate], normbisbis [3,5-di 1-tert-butyl 4-hydroxybenzenorephosphonic acid
  • lithium [3,5-diter tert-butyl 4-hydroxybenzylphosphonate] sodium [3,5-ditert-butyl 1-hydroxybenzylphosphonate]
  • magnesium bis [3 , 5-di-tert-butyl 4-hydroxybenzylphosphonate] is particularly preferred!
  • a specific phosphorus compound having at least one P-OH bond represented by the following general formula (Formula 35) Particularly preferred is at least one selected from U ⁇ .
  • R 2 independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
  • n represents an integer of 1 or more.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • At least one selected from compound power represented by the following general formula (Formula 36) is preferable.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
  • a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
  • R 3 examples include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenol group, and naphthyl.
  • R 3 examples include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenol group, and naphthyl.
  • Specific phosphorus compounds having at least one P—OH bond used in the polyester of the present invention include 3,5-ditertbutyl 4-hydroxybenzylphosphonate, 3,5-ditert-butyl 4- Methyl hydroxybenzyl phosphonate, 3,5-di-tert-butyl 4 Isopropyl hydroxybenzyl phosphonate, 3,5-di-tert butyl 4-hydroxybenzyl phosphonate phenol, 3,5-di-tert-butyl 4-hydroxy Examples include octadecyl benzyl phosphonate, 3,5-ditert-butyl 4-hydroxybenzyl phosphonate, and the like. Of these, ethyl 3,5-ditert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-ditert-butyl 4-hydroxybenzylphosphonate are particularly preferred.
  • phosphorus compounds having the phenol moiety used in the polyester of the present invention in the same molecule at least one phosphorus compound having a specific phosphorus compound force represented by the following general formula (Chemical Formula 37) is also selected. Compounds are preferred.
  • R ⁇ R 2 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
  • R 4 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
  • n represents an integer of 1 or more.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • the compound is selected from the compounds represented by the following General Formula (Chemical Formula 38) It is preferable to use at least one of the above, since the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are high.
  • each RR 4 independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
  • the group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • R 3 and R 4 include a short-chain aliphatic group such as hydrogen, a methyl group, and a butyl group, a long-chain aliphatic group such as octadecyl, a phenyl group, a naphthyl group, and a substituted group.
  • a short-chain aliphatic group such as hydrogen, a methyl group, and a butyl group
  • a long-chain aliphatic group such as octadecyl
  • a phenyl group a naphthyl group
  • a substituted group examples include an aromatic group such as a naphthyl group and a group represented by CH 2 CH 3 OH.
  • Specific phosphorus compounds used in the polyester of the present invention include diisopropyl 3,5-ditert-butyl 4-hydroxybenzylphosphonate, 3,5-ditert-butyl 4-hydroxybenzylphosphonic acid Examples thereof include di n-butyl, 3,5-di-tert-butyl 4-hydroxybenzylphosphonate dioctadecyl, 3,5-di-tert-butyl 4-hydroxybenzil phosphonate diphenol, and the like. Of these, dioctadecyl 3,5-ditertbutyl 4-hydroxybenzyl phosphonate and diphenyl 3,5-ditertbutyl 4-hydroxybenzylphosphonate are particularly preferred.
  • Irganoxl222 manufactured by Ciba 'Specialty' Chemicals
  • Irganoxl425 manufactured by Chinoku 'Specialty' Chemicals
  • phosphorus compounds preferably used in the present invention include the following phosphonic acid compounds having a linking group (X) represented by (Chemical Formula 41) or (Chemical Formula 42) or (Chemical Formula 43). And a phosphonic acid compound having no linking group (X) represented by:
  • R 1 represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms, and the aromatic ring structure or heterocyclic structure has a substituent.
  • X is a linking group and is an aliphatic hydrocarbon having 1 to 10 carbon atoms (a linear, branched or alicyclic structure does not matter) or a substituent containing 1 to 10 carbon atoms. Aliphatic hydrocarbon (does not matter even if it is linear, branched or alicyclic), O 1, -OCH 1, SO-, 1 CO-, -COCH 1, -CH OCO, 1 NHCO-
  • R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group.
  • the hydrocarbon group has an alicyclic structure, a branched structure, or an aromatic ring structure! /. ]
  • the aromatic ring structure and heterocyclic structure substituent of the phosphorus compound represented by the formula (Chemical Formula 41) is a hydrocarbon group having 1 to 50 carbon atoms (even if it is a straight chain, an alicyclic structure, a branched structure)
  • An aromatic ring structure which may be halogen-substituted), a hydroxyl group, a halogen group, an alkoxyl group having 1 to 10 carbon atoms or an amino group (alkyl having 1 to 10 carbon atoms).
  • it can be substituted with an alkenol, or is a tro group or a carboxyl group, is an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms!
  • Is a formyl group or an acyl group Is a sulfonic acid group, a sulfonic acid amide group (it does not matter if it is substituted with an alkyl or alkyl group having 1 to 10 carbon atoms), phosphoryl-containing group, nitrile group, cyanoalkyl group, force 1 type or 2 selected More than a seed.
  • Examples of the phosphorus compound represented by the formula (Formula 41) include the following. Specifically, benzylphosphonic acid, benzylphosphonic acid monoethyl ester, 1-naphthylmethylphosphonic acid, 1 naphthylmethylphosphonic acid monoethyl ester, 2-naphthylmethylphosphonic acid, 2 naphthylmethylphosphonic acid monoethyl ester 4-phenyl, benzylphosphonic acid, 4-phenyl, benzylphosphonic acid monoethyl ester, 2-phenyl, benzylphosphonic acid, 2-phenyl, benzylphosphonic acid monoethyl ester, 4-chloro, benzene 4-chloro, benzylphosphonic acid monoethyl ester, 4-chloro, benzylphosphonic acid monoethyl ester, 4-methoxy, benzylphosphonic acid, 4-methoxy, benzylphosphonic acid monoethyl este
  • R represents a hydroxyl group, an alkyl group of C1 -C10, COOH group or - CO OR 4 (R 4 represents an alkyl group C1 -C4), an alkylene glycol group or Monoa alkoxy Represents an alkylene glycol group (monoalkoxy represents C1-C4, alkylene glycol represents C1-C4 glycol).
  • R 1 is benzene, naphthalene, biphenyl, diphenylenoatenore, diphenenorethioatenore, diphenenolesnorephone, diphenenoremethane, diphenyldimethylmethane, diphenylketone, anthracene, phenanthrene and pyrene, etc.
  • Represents an aromatic ring structure of R 2 and R 3 each independently represent a hydrogen atom, a C1-C4 hydrocarbon group, a hydroxyl group or a C1-C4 hydrocarbon group having an alkoxyl group.
  • m represents an integer of 1 to 5, and when there are a plurality of groups, they may be the same substituent or a combination of different substituents.
  • n represents 0 or an integer of 1 to 5.
  • examples of the phosphorus compound in which the aromatic ring structure having a substituent is benzene include the following. That is, 2-hydroxybenzylphosphonic acid jetyl ester, 2-hydroxybenzylphosphonic acid monoethyl ester, 2-hydroxybenzylphosphonic acid, 4-hydroxybenzylphosphonic acid jetyl ester, 4-hydroxybenzylphosphonic acid monoethyl ester, 4-hydroxy Examples include, but are not limited to, benzylphosphonic acids in which a hydroxyl group is introduced into the benzene ring, such as benzylphosphonic acid, 6-hydroxybenzylphosphonic acid diethyl ester, 6-hydroxybenzylphosphonic acid monoethyl ester, and 6-hydroxybenzylphosphonic acid. It's not something.
  • 2 n-butylbenzylphosphonic acid jetyl ester 2 n-butylbenzylphosphonic acid monomethyl ester, 2 n-butylbenzylphosphonic acid, 3 n-butylbenzylphosphonic acid jetyl ester, 3-n-butylbenzyl Phosphonic acid monoethyl ester, 3-n-butylbenzylphosphonic acid, 4 n-butylbenzylphosphonic acid jetyl ester, 4 n-butylbenzylphosphonic acid monoethyl ester, 4 n-butylbenzylphosphonic acid, 2,5 n-dibutylbenzyl Phosphonic acid jetyl ester, 2,5 n-dibutylbenzylphosphonic acid monoethyl ester, 2,5 n-dibutylbenzylphosphonic acid, 3,5-n-dibutylbenzylphosphonic acid jetyl ester, 3,5-n-dibutylbenz
  • 2 carboxybenzylphosphonic acid jetyl ester 2 carboxybenzylphosphonic acid monoethyl ester, 2 carboxybenzylphosphonic acid, 3 carboxybenzylphosphonic acid jetyl ester, 3-carboxybenzylphosphonic acid monoethyl ester, 3 —Carboxybenzylphosphonic acid, 4 Carboxybenzylphosphonic acid jetyl ester, 4 Carboxybenzylphosphonic acid monoethyl ester, 4 Carboxybenzylphosphonic acid, 2, 5 Dicarboxybenzylphosphonic acid jetyl ester, 2, 5 Dicarboxybenzylphosphonic acid Acid monoethyl ester, 2,5 dicarboxybenzylphosphonic acid, 3,5-dicarboxybenzylphosphonic acid jetyl ester, 3,5-dicarboxybenzylphosphonic acid monoethyl ester, 3, 5- Carboxy benzylated acid, 2-methoxycarbonyl - le benzyl
  • the phosphorus compound in which the aromatic ring structure having a substituent is benzene is not limited to the above-mentioned single substituent species.
  • a hybrid of a substituted group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compound in which the aromatic ring structure having a substituent is naphthalene include the following.
  • naphthalene rings such as butyl methylphosphonic acid monoethyl ester and 2- (6-methoxyethoxy) naphthylmethyl phosphonic acid.
  • naphthalene rings such as butyl methylphosphonic acid monoethyl ester and 2- (6-methoxyethoxy) naphthylmethyl phosphonic acid.
  • examples thereof include, but are not limited to, phosphonic acids.
  • the phosphorus compound having an aromatic ring structure having a substituent is naphthalene is not limited to the above-mentioned single substituent species.
  • a mixture of the above-mentioned substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds represented by the formula (Chemical Formula 42) used in the polyester of the present invention are bifuran are as follows. . 4 (4-hydroxyphenol) benzylphosphonic acid jetyl ester, 4 -(4-hydroxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid, 4- (4 n-butylphenol) benzylphosphonic acid jetyl ester, 4- (4 — N-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenol) benzylphosphonic acid, 4- (4-carboxyphenyl) benzylphosphonic acid jetyl ester, 4- (4- Carboxyphenol) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid, 4- (4-me
  • Examples thereof include, but are not limited to, phosphonic acids in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into the ring ring.
  • the phosphorus compound in which the aromatic ring structure having a substituent is biphenyl is not limited to the above-mentioned single substituent species.
  • a mixture of the above-mentioned substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compound in which the aromatic ring structure having a substituent is diphenyl ether include the following. It is done.
  • the Linich compound in which the aromatic ring structure having a substituent is diphenyl ether is not limited to the above-mentioned single substituent species. And a hybrid of a substituted group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can be used.
  • examples of the phosphorus compound having a substituent aromatic ring structure as diphenyl ether are as follows. That is, 4- (4-hydroxyphenylthio) benzylphosphonic acid methyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid, 4- (4-n —Butylphenyl-thiothio) benzylphosphonic acid monoethyl ester, 4- (4 n-butylphenol) benzylphosphonic acid monoethyl ester, 4- (4-butylphenylthio) benzylphosphonic acid, 4- (4-carboxy (Phenylthio) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenylthio) benzylphosphonic acid monoeth
  • the phosphorus compound in which the aromatic ring structure having a substituent is a diphenyl ether is not limited to the above-mentioned single substituent species. And a hybrid of a substituted group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can be used.
  • phosphorus compounds represented by the formula (Formula 42) used in the polyester of the present invention examples include the following. It is done.
  • the phosphorus compound whose aromatic ring structure having a substituent is diphenylsulfone is not limited to the above-mentioned single substituent species.
  • a mixture of the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compound in which the aromatic ring structure having a substituent is diphenylmethane include the following. It is done.
  • the phosphorus compounds represented by the formula (Chemical Formula 42) are limited to the above-mentioned single substituent species.
  • a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • phosphorus compounds represented by the formula (Chemical Formula 42) used in the polyester of the present invention examples of the phosphorus compound in which the aromatic ring structure having a substituent is diphenyldimethylmethane are as follows. Can be mentioned.
  • the phosphorus compound in which the aromatic ring structure having a substituent is diphenyldimethylmethane is not limited to the above-mentioned single substituent species.
  • a mixture of the above-mentioned substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compound in which the aromatic ring structure having a substituent is diphenol ketone include the following. It is done.
  • the phosphorus compounds whose aromatic ring structure having a substituent is diphenylketone are not limited to the above-mentioned single substituent species.
  • a mixture of a substituent, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compound in which the aromatic ring structure having a substituent is anthracene include the following. . 9- (10-hydroxy) anthrylmethylphosphonic acid jetyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid, 9- (10 — N-Butyl) anthrylmethylphosphonic acid jetyl ester, 9- (10—n-butyl) anthrylmethylphosphonic acid monoethyl ester, 9— (10—n-butyl) anthrylylmethylphosphonic acid, 9— (10-carboxyl) C) Anthrylmethylphosphonic acid jetyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-carboxy) anthrylmethylphosphonic acid, 9- (10-carboxy
  • the phosphorus compound having an aromatic ring structure having an anthracene is not limited to the above-mentioned single substituent species.
  • a hybrid of the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds represented by the formula (Chemical Formula 42) used in the polyester of the present invention examples of the phosphorus compounds having a substituted aromatic ring structure as phenanthrene include the following.
  • the phosphorus compound having a substituent aromatic ring structure is phenanthrene is not limited to the above-mentioned single substituent species.
  • a hybrid of the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compound in which the aromatic ring structure having a substituent is pyrene include the following. That is, 1- (5-hydroxy) pyrenylmethylphosphonic acid jetyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid, 1 (5-n-butyl) pyrylmethylphosphonate monoethyl ester, 1- (5-n-butyl) pyrylmethylphosphonate monoethyl ester, l- (5-n-butyl) 1- (5-carboxy) pyrenylmethylphosphonic acid, 1- (5-carboxy) pyrenylmethylphosphonic acid diethyl ester, 1- (5-carboxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-carboxy) pyrenyl
  • alkyl group on the pyrene ring, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxy group
  • alkylene glycol group monomethoxy group
  • examples thereof include, but are not limited to, phosphonic acids into which an alkylene glycol group has been introduced.
  • the phosphorus compound in which the aromatic ring structure having a substituent is pyrene is not limited to the above-mentioned single substituent species. And a mixture of a substituted group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can be used.
  • Substituents such as hydroxyl group, alkyl group, carboxyl group, force oxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group introduced into the series of aromatic rings are the same as those in the polycondensation of polyester. Presumably involved in complex formation with aluminum atoms.
  • a carboxyl group or a hydroxyl group that is a functional group at the time of polyester formation is also included, and it is easily dissolved or taken into the polyester matrix. Therefore, it is considered to be particularly effective in reducing polymerization activity and foreign matters.
  • Examples of the substituent bonded to the aromatic ring structure include C1 to C10 alkyl groups, carboxyl and carboxy ester groups, alkylene glycols and monoalkoxyalkylene glycols. More preferred in terms of the effect of reducing foreign matter are carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxyalkylene glycols. The reason for this is unknown, but it is presumed to be due to improved compatibility with the polyester and the catalyst medium, alkylendalycol.
  • a phosphorus compound (Chemical Formula 43) having no linking group (X) that is preferably used in the present invention is as follows.
  • R 1 is an aromatic ring structure having 6 to 50 carbon atoms, represents a heterocyclic structure having 4 to 50 carbon atoms, and the aromatic ring structure or the heterocyclic structure may have a substituent!
  • R 2 and R 3 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group.
  • the structure or branched structure may have an aromatic ring structure.
  • the substituent of the aromatic ring structure and heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 43) is a hydrocarbon group having 1 to 50 carbon atoms (even if it is a straight chain, an alicyclic structure, a branched structure, an aromatic ring These may be structures which may be halogen-substituted), hydroxyl groups, halogen groups, C1-C10 alkoxyl groups or amino groups (C1-C10 alkyl or alkyl groups). ) Or -tro group or carboxy group is an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms!
  • Is a formyl group or an acyl group ⁇ is a sulfonic acid group , Sulfonic acid amide groups (which may not be substituted even if substituted with an alkyl or alkyl group having 1 to 10 carbon atoms), phosphoryl-containing groups, nitrile groups, and cyanoalkyl groups are also selected from one or more.
  • the aromatic ring structure of (Chemical Formula 43) is also selected from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, anthracene, phenanthrene, and pyrene power.
  • the heterocyclic structure is selected from furan, benzofuran, isobenzofuran, dibenzofuran, naphthalane and phthalide .
  • at least one of R 2 and R 3 in the above formula (Formula 43) is a hydrogen atom.
  • Examples of the phosphorus compound represented by the formula (Formula 43) that can be used in the present invention include the following phosphorus compounds. That is, (3--toro, 5-methyl) -phenylphosphonic acid jetyl ester, (3--toro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3--toro, 5-methyl) -Phenolphosphonic acid, (3-Tro, 5-methoxy) -Phenolphosphonic acid ethyl ester, (3-Tro, 5-methoxy) -Phenolphosphonic acid monoethyl ester, (3-Nitro, 5 —Methoxy) -phenylphosphonic acid, (4 chloro) -phenylphosphonic acid jetyl ester, (4 chloro,)-phenylphosphonic acid monoethyl ester, (4 chloro) -phenylphosphonic acid, (5-chloro) ,)-Phenolphosphonic acid jet
  • Phosphorus compound is a force known as a heat stabilizer for polyesters. Even if these compounds are used in combination with conventional metal-containing polyester polycondensation catalysts, melt polycondensation can be greatly promoted. It was an unprecedented force. Actually, when the polyester is melt polycondensed using a polycondensation catalyst such as an antimony compound, a titanium compound, a tin compound, or a germanium compound, which is a typical catalyst for polyester polycondensation, the polyester of the present invention is used. Addition of the phosphorus compound used is not observed to promote polycondensation to a substantially useful level.
  • a polycondensation catalyst such as an antimony compound, a titanium compound, a tin compound, or a germanium compound, which is a typical catalyst for polyester polycondensation
  • the amount of Rini ⁇ product to be used in the polyester of the present invention 0.1 relative to the number of moles of the entire constituent units of polycarboxylic acid components in the resulting Poriesu ether 001 to 2.0 mole 0/0 Is more preferably 0.005 to 1.0 mol%. If the addition amount of the phosphorus compound is less than 0.001 mol%, the effect of addition may not be exhibited. If the addition amount exceeds 2.0 mol%, the catalytic activity as a polyester polycondensation catalyst may be reduced. There is a tendency of the change depending on the amount of aluminum used.
  • the present invention in addition to aluminum or a compound thereof, it is preferable that a small amount of alkali metal, alkaline earth metal and at least one selected from the compound force coexist as a second metal-containing component. It is an aspect.
  • the coexistence of a strong second metal-containing component in the catalyst system is effective in improving productivity because a catalyst component having higher catalytic activity and thus higher reaction rate can be obtained.
  • alkali metal when adding alkaline earth metals and their compounds, its amount M (mol 0/0), to the number of moles of all the polycarboxylic acids units constituting the polyester, 1 X 10- 6 or 1.0 is preferably more preferably fixture less than mole% 5 X 10- 6 ⁇ 0. 5 Mo A le%, more preferably 1 X 10- 5 ⁇ 0. 3 mol%, particularly preferably 1 X 10 ⁇ 0. 1 mol%. Since the amount of alkali metal and alkaline earth metal added is small, it is possible to increase the reaction rate without causing problems such as reduced thermal stability, generation of foreign matter, coloring, and degradation of hydrolysis resistance. It is.
  • the alkali metal and alkaline earth metal constituting the second metal-containing component include Li, Na, K, Rb, Cs. Among these, at least one selected from Li, Na, Mg or its compound power is more preferable among at least one selected from Be, Mg, Ca, Sr, and Ba.
  • the alkali metal or alkaline earth metal compound include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid of these metals, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid.
  • Aromatic carboxylates such as acid salts and benzoic acid, halogen-containing carboxylates such as trichlorodiacetic acid, hydroxycarboxylates such as lactic acid, citrate, and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, carbonic acid Inorganic acid salts such as hydrogen, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid, 1-propanesulfonic acid, 1-pentanesulfonic acid, naphthalenesulfonic acid, etc.
  • Organic sulfonates organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert butoxy Alkoxides, Kiretoi ⁇ products of such Asechirua Setoneto, hydrides, oxides, and hydroxides and the like.
  • alkali metals alkaline earth metals, or compounds thereof
  • a strongly alkaline substance such as a hydroxide
  • these are dissolved in an organic solvent such as a diol such as ethylene glycol or an alcohol.
  • a diol such as ethylene glycol or an alcohol.
  • it since there is a tendency, it must be added to the polycondensation system in an aqueous solution, which may cause a problem in the polycondensation process.
  • an alkaline strong material such as a hydroxide
  • the polyester tends to be subjected to side reactions such as hydrolysis during polycondensation, and the polycondensed polyester tends to be easily colored, resulting in resistance to heat. Water decomposability also tends to decrease.
  • the Al force used in the polyester of the present invention Suitable as a lithium metal or a compound thereof or an alkaline earth metal or a compound thereof is a saturated aliphatic carboxylate, unsaturated aliphatic carboxylate, aromatic carboxylate or halogen of an alkali metal or alkaline earth metal. Containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Organic sulfonates, organic sulfates, chelate compounds, and acids.
  • a saturated aliphatic carboxylate of alkali metal or alkaline earth metal particularly acetate.
  • a cobalt compound is further added as a cobalt atom in an amount of less than lOppm with respect to the polyester.
  • Cobalt compounds are known to have a certain degree of polymerization activity per se, but as mentioned above, when added to such an extent that a sufficient catalytic effect is exerted, the brightness of the resulting polyester is reduced and the heat stability is increased. Sexual decline occurs.
  • the polyester obtained according to the present invention can be obtained by adding a power compound having good color tone and thermal stability in an addition amount such that the catalytic effect of the addition is not clear in a small amount as described above. Coloring can be more effectively eliminated without causing a decrease in the brightness of the resulting polyester.
  • the cobalt compound in the present invention is for the purpose of eliminating coloration, and the addition time does not matter at any stage of polycondensation or after completion of the polycondensation reaction.
  • the cobalt compound is not particularly limited, and specific examples include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof. Of these, cobalt acetate tetrahydrate is particularly preferred.
  • the addition amount of the cobalt compound is preferably such that the total of aluminum atoms and cobalt atoms is 50 ppm or less and the cobalt atoms are less than lOppm with respect to the finally obtained polymer.
  • the total force of the aluminum atom and the cobalt atom is Oppm or less
  • the cobalt atom is 8 ppm or less
  • more preferably the sum of the aluminum atom and the cobalt atom is 25 ppm or less
  • the cobalt atom is 5 ppm or less.
  • the total of aluminum atoms and cobalt atoms is less than 50 ppm and that the cobalt atoms are lOppm or less. Also enough touch In order to have a medium activity, the total amount of aluminum atoms and cobalt atoms is preferably more than 0.001 ppm.
  • the catalyst used in the present invention has catalytic activity not only in a polycondensation reaction but also in an esterification reaction and an ester exchange reaction.
  • polycondensation by transesterification of an alkyl ester of dicarboxylic acid such as dimethyl terephthalate with glycol such as ethylene glycol is usually performed in the presence of a transesterification catalyst such as a titanium compound or a zinc compound.
  • a transesterification catalyst such as a titanium compound or a zinc compound.
  • the catalyst used in the present invention can be used in place of these catalysts or in the presence of these catalysts.
  • the catalyst used in the present invention has catalytic activity not only in melt polycondensation but also in solid phase polymerization and solution polycondensation, and polyester can be produced by any method.
  • the polycondensation catalyst used in the present invention can be added to the reaction system at any stage of the polycondensation reaction. For example, before the start of the esterification reaction or transesterification reaction and at any stage during the reaction, is immediately before the start of the polycondensation reaction !, can be added to the reaction system at any stage during the polycondensation reaction .
  • aluminum or its compound is preferably added immediately before the start of the polycondensation reaction.
  • the polycondensation catalyst used in the present invention is composed of one or more other polycondensation catalysts such as antimony compounds, titanium compounds, germanium compounds, tin compounds, and the like.
  • the addition of ingredients in the range of additions that do not cause problems in the product, such as polyester characteristics, processability, and color tone as described above, is useful for improving productivity by shortening the polycondensation time.
  • the antimony compound can be added in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polycondensation. More preferably, it is added in an amount of 30 ppm or less. When the amount of added antimony is more than 50 ppm, metallic antimony is precipitated, and darkening and foreign matter are generated in the polyester.
  • the titanium compound can be added in a range of 10 ppm or less with respect to the polymer obtained by polycondensation. More preferably, it is added in an amount of 5 ppm or less, more preferably 2 ppm or less. If the amount of added force of titanium is more than lOppm, the thermal stability of the resulting resin will be significantly reduced.
  • the germanium compound can be added so that the amount of germanium atoms remaining in the polyester obtained by polycondensation is 30 ppm or less. A more preferred residual amount is 20 ppm or less. If the residual amount of germanium is 30 ppm or more, it is not preferable because it is costly disadvantageous.
  • an antimony compound, a titanium compound, a germanium compound, or a tin compound can be used.
  • the antimony compound, titanium compound, germanium compound and tin compound used in the present invention are not particularly limited.
  • antimony compound examples include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoxide, and the like, among which antimony trioxide is preferable.
  • titanium compounds include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, and oxalic acid titanate.
  • tetra n-butoxy titanate is preferable.
  • germanium compounds include germanium dioxide, germanium tetrachloride, and the like. Among these, germanium dioxide is preferable.
  • tin compounds include dibutyltin oxide, methylphenol tin oxide, tetraethyltin, hexaethylditin oxide, triethyltinno, id-oxide, monobutylhydroxytin oxide, triisobutyltin adetate, diphenoltin Examples include dilaurate, monobutyltin trichloride, dibutyltin sulfide, dibutylhydroxytin oxide, methylstannic acid, ethylstannic acid, and particularly preferable is use of monobutylhydroxytin oxide.
  • the addition method of the polycondensation catalyst used in the present invention may be powdered or neat added calorie, or addition of Daricols such as ethylene glycol in the form of a slurry or solution.
  • Daricols such as ethylene glycol
  • it may be added as a mixture or complex in which aluminum metal or a compound thereof and other components, preferably the phosphorus compound used in the present invention are mixed in advance, or these may be added separately.
  • Aluminum Alternatively, the metal metal or a compound thereof and other components, preferably a phosphorus compound, may be added to the polycondensation system at the same addition time, or the respective components may be added at different addition times.
  • Basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich) was dispersed in distilled water at a concentration of 2 Og / 1, and dissolved by heating at 95 ° C. for 2 hours with stirring.
  • An equal amount (volume ratio) of ethylene glycol was charged into the flask together with the aqueous solution, and water was distilled off from the system while stirring at 70 to 90 ° C under reduced pressure (133 Pa) to obtain a 20 g / l aluminum compound.
  • An ethylene glycol solution was prepared.
  • Irganox 1222 (manufactured by Chinoku 'Specialty 1' Chemicals) as a phosphorus compound was charged into the flask together with the ethanol render, and heated for 12 hours at a liquid temperature of 160 ° C with stirring under nitrogen. An ethylene glycol solution was prepared.
  • Lithium acetate manufactured by Nacalai Co., Ltd., reagent grade
  • ethylene glycol was charged into a flask together with ethylene glycol, and an ethylene glycol solution of an alkali metal compound at 30 g / l was prepared at room temperature while stirring under nitrogen substitution.
  • an alkali metal compound and / or an alkaline earth metal ethylene glycol solution is used in combination with the ethylene glycol solution / phosphorus compound ethylene glycol solution of the above aluminum compound. Needless to say, it can also be used.
  • the amount of terephthalic acid based on the total polyvalent carboxylic acid component of the copolyester of the present invention is preferably 55 mol% or more, more preferably 60 mol% or more. If it is less than 50 mol%, impact resistance tends to decrease when used as a powder coating.
  • Examples of other polyvalent carboxylic acids used in the present invention include isophthalic acid, orthophthalic acid, and 2,6 naphthalenedicarboxylic acid. When these are used, they are heat resistant and weather resistant. The improvement of property can be aimed at.
  • the polyvalent carboxylic acid component other than the polyvalent carboxylic acid used in the present invention includes 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, 2 , 7 Naphthalenedicarboxylic acid, diphenyl 4,4-dicarboxylic acid, 4,4, biphenyl ether dicarboxylic acid, 1,2 bis (phenoxy) ethane-p, p, -dicarboxylic acid, anthracene dicarboxylic acid and Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1, 3- Cyclobutanedica
  • the amount of alkylene glycol is 20 hereinafter carbon atoms, preferably 90 to 99 mole 0/0, more preferably 92-97 mol% . If it is less than 90 mol%, it is preferable since a weather-resistant copolyester excellent in chemical resistance cannot be obtained.
  • the alkylene glycol having 20 or less carbon atoms used in the present invention includes, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,2-butylene.
  • Glycol 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane diol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-sic hexane dimethanol, 1,4-cyclohexane dimethanol, 3-methyl- 1 , 5-pentanediol, 2-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, neo Nethyl glycol, 2-ethyl 2-methyl-1,3-propanediol, 2,2-jetyl 1,3-propanediol, 2-methyl-2-n-butyl-1,3-prop
  • ethylene glycol is also preferred for economic efficiency, and neopentyl glycol is preferred from the viewpoint of improving weather resistance.
  • alkylene dialys having more than 20 carbon atoms have a low soft spot and are difficult to handle because they tend to block.
  • polyhydric alcohol components can be used in the form of one or a mixture of two or more.
  • glycols used in the present invention include aliphatic glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polypropylene glycol, hydroquinone, 4,4, -dihydroxyl Cisphenol, 1,4-bis (j8-hydroxyethoxy) benzene, 1,4-bis ( ⁇ -hydroxyethoxyphenyl) sulfone, bis ( ⁇ -hydroxyphenyl) ether, bis ( ⁇ -hydroxyphenyl) sulfone, bis ( ⁇ -hydroxyphenyl) methane, 1,2-bis ( ⁇ -hydroxyphenyl) -Aromatic glycols such as ethane, bisphenol ⁇ , and alkylene oxide adducts of bisphenol ⁇ .
  • aliphatic glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polypropylene glycol, hydroquinon
  • the trifunctional or higher polyvalent carboxylic acid constituting the copolymerized polyester of the present invention includes trimellitic acid, pyromellitic acid, methylcyclohexenticarboxylic acid, oxydiphthalic acid dihydrate (ODPA), 3,3 ', 4,4'—Benzophenone tetracarboxylic dianhydride (BTDA), 3, 3, 4, 4, diphenyltetracarboxylic dianhydride (BPDA) 3, 3, 4, 4, -diphenyl sulfonetetracarboxylic dianhydride (DSDA), 4, 4, mono (hexafluoroisopropylidene) diphthalic dianhydride (6FDA) 2,2, monobis [(dicarboxyphenoxy) Phenyl] propan anhydride (BSAA) and the like.
  • trimellitic acid trimellitic acid
  • pyromellitic acid methylcyclohexenticarboxylic acid
  • ODPA oxydiphthalic acid dihydrate
  • Examples of the tri- or higher functional polyhydric alcohol constituting the copolymer polyester of the present invention include glycerin, pentaerythritol, trimethylolethane, trimethylolpentane, and trimethylolpropane. From these, one or more can be selected and used.
  • These tri- or higher functional polycarboxylic acid and polyhydric alcohol are each 0 to 10 mol%, preferably 1 to 10 mol%, based on the total acid component and total glycol component constituting the copolymer polyester. mole 0/0, more preferably 3 to 8 mol 0/0. Even if both of these trifunctional or more polyfunctional rubonic acids and polyhydric alcohols are 0 mol%, and the other composition is as described above, a fatal problem does not occur when a coating film is formed. However, when the deviation of polycarboxylic acid or polyhydric alcohol is 1 mol% or more, the reaction between the main agent (copolyester) and the curing agent occurs after baking after electrostatic coating. Tend to improve and the occurrence of sagging of the paint film tends to be reduced. On the other hand, if it exceeds 10 mol%, gelling is likely to occur, which is a problem.
  • the copolymerized polyester of the present invention may contain a known phosphorus compound as a copolymerization component.
  • a bifunctional phosphorus compound is preferable, for example, (2-carboxylethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, 9, 10 dihydro-1,10-oxa (2, 3-Carboxypropyl) 10 phosphaphenanthrene 10-oxide and the like.
  • Copolymerize these phosphorus compounds By including it as a component, it is possible to improve the flame retardancy of the copolymerized polyester obtained.
  • the copolymer polyester of the present invention is obtained by removing the catalyst from the copolymer polyester after polycondensation or by deactivating the catalyst with an additive such as a phosphorus compound.
  • the thermal stability of can be further increased.
  • the number average molecular weight measured by gel permeation chromatography is preferably 2000 to 7000, more preferably 2500 to 6500. . If the number average molecular weight is lower than 2000, the mechanical properties of the coating film may be insufficient, and if it exceeds 7000, the smoothness of the coating film may be inferior. When used for other purposes, those having a number average molecular weight of 2000 to 500000 are preferred.
  • the hydroxyl value is preferably 20 to 70 mgKOHZg, more preferably 25 to 65 mgKOHZg. If the hydroxyl value is lower than 20 mgKOHZg, sufficient mechanical properties tend to be difficult to obtain, and if it exceeds the range of 70 mg KOHZg, an appropriate amount of curing agent (for example, blocked isocyanate) should be added. In addition, the cost is increased, the strength and the performance of the coating film cannot be expected, and the hardness of the coating film is increased and the flexibility may be deteriorated.
  • curing agent for example, blocked isocyanate
  • the blending amount of the block silicate curing agent is less than the amount commensurate with the hydroxyl value, sufficient mechanical properties of the coating film can be obtained.
  • those with a hydroxyl value of less than 20 mg KOHZg are also used.
  • the copolymer polyester of the present invention has a soft spot measured by the ring and ball method (JIS K2207) of 105 to 140 ° C when used as a powder coating, more preferably 110 to 135 ° C. is there . When used for water-dispersed or solvent-soluble types, those with a soft spot of 140-220 ° C are also used.
  • the copolymer polyester of the present invention preferably has a glass transition temperature measured by differential scanning calorimetry (DSC) of 40 to 75 ° C, more preferably 40 to 70 ° C when used as a powder coating. is there.
  • soft softening point and glass transition temperature when the softening point is lower than 105 ° C and the glass transition point temperature is lower than 40 ° C, when powder coating is used, blocking is likely to occur during storage.
  • the softening point is 140 ° C.
  • the glass transition temperature higher than the above is higher than 75 ° C, the finished appearance of the coating film, in particular, smoothness may be deteriorated.
  • glass transition temperature below 40 ° C or above 75 ° C is used.
  • the solution haze of the copolymerized polyester of the present invention is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, still more preferably 2.0% or less, and most preferably. 1. It is preferably 5% or less. 10. If the content exceeds 0%, there are many problems such as poor transparency of the molded product with many foreign substances in the copolyester, poor gloss of the coating film of the powder coating, or during filtration in the molding process. Problems such as frequent filter clogging are undesirable.
  • the method for producing the copolyester of the present invention is not particularly limited, and is a direct esterification method between a polycarboxylic acid containing terephthalic acid and a polyhydric alcohol, or an alkyl ester such as terephthalic acid and a polyhydric alcohol.
  • An oligomer of terephthalic acid or the like and a polyhydric alcohol can be obtained by this transesterification method, and then subjected to melt polycondensation under normal pressure or reduced pressure to obtain the copolymer polyester of the present invention.
  • an esterified soot catalyst or the aforementioned polycondensation catalyst can be used as necessary.
  • the melt polycondensation reaction may be performed in a batch reactor or may be performed in a continuous reactor.
  • the esterification reaction or ester exchange reaction may be performed in one step or may be performed in multiple steps.
  • the melt polycondensation reaction may be performed in one stage or may be performed in multiple stages.
  • a depolymerization reaction or a modification reaction may be performed after completion of the above polymerization reaction.
  • a polyvalent carboxylic acid and Z or a polyhydric alcohol to the molten polyester to react.
  • auxiliary raw material component for example, polyhydric carboxylic acid or polyhydric alcohol capable of constituting the above-described copolymer polyester can be used. At this time, the reaction is controlled, and the reactive end groups are increased.
  • terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, ethylene glycol, neopentyl glycol, trimethylolpropan, pentaerythritol Glycerin and the like are preferably used.
  • the reaction is preferably carried out in the range of 150 to 290 ° C for 1 to 300 minutes.
  • Examples of the modification reaction include a ring-opening addition reaction of a latathone monomer to a copolyester. This makes it possible to produce a block-type copolymer polyester in which a poly-strength prolatatone is bonded to the end of the copolymer polyester.
  • ⁇ -force prolatatone is preferable.
  • the reaction is preferably carried out in the range of 150 to 290 ° C. over a period of 1 to 300 minutes.
  • grafting polyacrylicol containing double bonds to the copolymerized polyester and graft copolymerizing acrylic, acrylic silicon, etc. with the double bond as a base point by grafting, There is a tendency to improve weather resistance, rain resistance and chemical resistance. Examples thereof include methods such as JP 2000-204292, JP 2000-178473, JP 2000-204291, and JP 2003-020317.
  • the copolymer polyester of the present invention can be blended with a curing agent capable of reacting therewith to form a copolymer polyester composition for powder coatings.
  • the curing agent capable of reacting with the copolyester include alkyl etherified aminoformaldehyde resins, epoxy compounds and isocyanate compounds, alkyl ether phenol resins, and silane coupling agents.
  • alkyl etheraminoformaldehyde resins are preferred in terms of reactivity and hardness.
  • Epoxy compounds are preferred in terms of weather resistance and acid resistance.
  • blocked isocyanate is preferable in terms of solution stability and toughness.
  • Alkyl etherified aminoformaldehyde resins are, for example, formaldehyde or paraformaldehyde alkylated with 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, and n-butanol.
  • Examples thereof include benzoguanamine, methoxylated methylol melamine, butoxylated methylol melamine, methoxy Z-butoxy mixed methylol melamine, and butoxylated methylol benzoguanamine.
  • epoxy compounds diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of hydrogenated bisphenol A and its oligomer, ortho Diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, p-oxybenzoic 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 ether, propylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether and polyalkylene glycol diglycidyl Ethers, trimellitic acid triglycidinole esterol,
  • the isocyanate compounds include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds.
  • aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds.
  • the isocyanate compound may be a blocked isocyanate.
  • Isocyanate blocking agents include, for example, phenols such as phenol, thiophenol, methylthiophenol, ethinoretioenole, crezo monole, xylenenole, resonoresinole, nitrophenol, kuroenofenol, acetooxime, methyl Oximes such as ethyl ketoxime and hexanone oxime, methanol, ethanol, propanol, butane Alcohols such as diols, halogen-substituted alcohols such as ethylene chlorohydrin, 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ⁇ —force prolatatum, ⁇ — Examples include ratatams such as valerolatatam, y -butyral latatam, and
  • the blocked isocyanate is obtained by subjecting the above isocyanate compound and the isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.
  • silane coupling agents include j8— (3,4 epoxycyclohexylene) ethinotritrimethoxysilane, j8— (3,4 epoxycyclohexyl) ethyltrimethylsilane, ⁇ -glycidoxypropyl Examples include methyl ethoxysilane and ⁇ -glycidoxypropyl methyl jetoxy silane.
  • the hardener component is preferably a blocked isocyanate compound from the viewpoint of handling reactivity when used as a powder coating.
  • the mixing ratio of the curing agent is preferably such that the ratio of the reactive functional group equivalent of the curing agent to the hydroxyl equivalent of the copolymerized polyester is in the range of 0.8 to 1.2.
  • the copolyester composition for powder coatings of the present invention includes pigments such as titanium oxide, carbon black, organic color pigments, and inorganic color pigments, dyes, aluminum flakes, and silica depending on the purpose and application.
  • pigments such as titanium oxide, carbon black, organic color pigments, and inorganic color pigments, dyes, aluminum flakes, and silica depending on the purpose and application.
  • Additives such as extender pigments such as talc and barium sulfate, glass fiber, colloidal silica, and wax can be added.
  • the inorganic pigment used in the present invention is an inorganic pigment, a colored pigment, a bright material, an extender pigment, an anti-glare pigment, or the like.
  • inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, chromate, carbon black, acid silicate, zinc phosphate, iron phosphate, aluminum phosphate, zinc phosphite, aluminum tripolyphosphate, etc.
  • Phosphoric acid-based anti-pigment pigments calcium molybdate, aluminum molybdate, barium molybdate, etc., molybdate-type anti-fog pigments, vanadium-type anti-fog pigments such as vanadium oxide, chromate pigments such as strontium chromate and zinc chromate
  • silicate pigments such as calcium silicate, fine silica such as water-dispersed silica, fumed silica, and the like can be used.
  • Aluminum frame Bright materials such as copper, copper bronze flakes, mica-like iron oxides, mica flakes, mica-like iron oxides coated with metal oxides, mica flakes coated with metal oxides can also be mentioned.
  • organic pigments such as phthalocyanine blue, phthalocyanine green, carbazole dioxazine violet, anthrapyrimidine yellow, isoindolinone yellow, indanthrene bunore, quinatalidone red may be used in combination.
  • the copolymerized polyester of the present invention is preferable because its effect is maximized when it is used as a raw material for powder coatings. Of course, it can be used at all as a solvent-soluble or water-dispersed coating raw material. .
  • the copolymerized polyester of the present invention When used as a powder coating, it is usually added to the copolymerized polyester of the present invention with a pigment or other filler, a flow modifier such as an acrylate polymer, a curing catalyst, benzoin, etc. Are mixed with a known melt-kneader and then pulverized and classified into a powder coating material.
  • a pigment or other filler such as an acrylate polymer, a curing catalyst, benzoin, etc.
  • the powder coating thus obtained is applied and baked onto a metal steel plate or the like by a known electrostatic coating method or fluidized immersion coating method.
  • copolymerized polyester of the present invention can be used widely for adhesives, coating agents, toner binders, raw materials for synthesizing polyurethane resin, plasticizers, molded products, laminates, etc., only for paint applications. .
  • Example 1 the copolymerized polyester of the present invention can be used widely for adhesives, coating agents, toner binders, raw materials for synthesizing polyurethane resin, plasticizers, molded products, laminates, etc., only for paint applications. .
  • KF—802, 804, 806 were used.
  • 0.2 g of the pulverized polyester sample was dissolved in 20 cm 3 of black mouth form, and titrated with 0.1 N potassium hydroxide ethanol solution.
  • As the indicator phenolphthalein was used. Units mgKOHZg.
  • acetylating agent acetic anhydride pyridine solution 0.5 mol ZL
  • 10 ml of pure water was added and allowed to cool to room temperature.
  • the solution was titrated with ⁇ / 5-NaOH-CH OH solution using phenolphthalein as an indicator. The unit is mgKOH / g.
  • DSC differential scanning calorimeter
  • NMR analysis was carried out using a Varian nuclear magnetic resonance analyzer (NMR) diemi--200 in heavy chloroform solvent, and the integral ratio was determined.
  • NMR Varian nuclear magnetic resonance analyzer
  • the polyester was evaluated and judged as described below by visual observation while maintaining a sheet shape of almost the same thickness after polycondensation.
  • the powder paint is fused to form a lump, and it does not break even if it is held by hand.
  • the paint film is colored yellow or gray
  • the coated steel sheet was measured with Nippon Denshoku TC108 DPA by the 60 ° method according to optical conditions JIS K-5400.
  • the coated steel sheet was measured for impact resistance using a DuPont method from the back side of the painted surface using a sphere with a diameter of 1.27 mm and a weight of 500 g.
  • the height (cm) when a crack occurred in the coating film was measured. (Higher shows better properties.)
  • a 180-degree fold is provided at the bottom of the paint plate with the coating surface facing outward, and a special l-type fold-up type Dubon impact tester is used.
  • the length of the cracks in the coating film at the bent part that occurred when the weight was dropped as much as 50 cm in height was measured and evaluated according to the following criteria.
  • the coated plate was dipped in 125 ° C deionized water for 35 minutes in an autoclave and pulled up, and then the whitening state of the coated film was observed and evaluated according to the following criteria.
  • Table 1 shows the resin properties, powder coating properties, and coating properties of the resulting copolyester.
  • the copolymerized polyester had good coloration and solution haze, and also exhibited good properties such as powder coating blocking resistance, coating color tone, accelerated weather resistance, and impact resistance.
  • Copolyesters having the respective compositions shown in Table 1 were obtained by a method according to the synthesis of the copolyester of Example 1.
  • Table 1 shows the composition and characteristic values of each copolyester obtained.
  • a copolyester was obtained by polycondensation in the same manner as in Example 1 except that the raw material composition was changed as shown in Table 1.
  • Table 1 shows the composition and characteristic values of the obtained copolyester.
  • the impact resistance of the coating film is low, which is a problem.
  • a copolyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to antimony triacid-antimony (0.04 mol% in terms of antimony atom based on the total acid component).
  • Table 1 shows the composition and characteristic values of the obtained copolyester.
  • the appearance color of the resin is gray, the solution haze is 11.0%, and the color of the paint film is also gray.
  • a copolyester was obtained by polycondensation in the same manner as in Example 1 except that the polycondensation catalyst was changed to tetrabutyl titanate (0.008% in terms of titanium atom based on the total acid component).
  • Table 1 shows the composition and characteristic values of the obtained copolyester.
  • the solution haze was as low as 0.8%, but the appearance color of the resin was extremely yellow, and the color of the coating film was yellow, which is a problem with X.
  • the present invention uses a polycondensation catalyst mainly composed of an aluminum compound without using a metal compound such as a tin compound, an antimony compound, a germanium compound and a titanium compound as a main component of the catalyst.
  • a polycondensation catalyst mainly composed of an aluminum compound without using a metal compound such as a tin compound, an antimony compound, a germanium compound and a titanium compound as a main component of the catalyst.
  • a copolyester having excellent transparency and color tone, and a powder coating having excellent long-term weather resistance and excellent coating properties.

Landscapes

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

Abstract

L'invention concerne un polyester copolymérisé, que l'on produit en menant une polycondensation à l'aide d'un catalyseur de polycondensation qui comprend au moins un élément choisi parmi le groupe constitué par l'aluminium et un composé de celui-ci. Dans l'invention, un composant d'acide polycarboxylique constituant le polyester copolymérisé est composé de 50 % en moles, ou plus, d'acide téréphtalique et d'entre 0 et 10 % en moles d'un acide polycarboxylique à trois fonctions ou plus, et un composant de polyalcool constituant le polyester copolymérisé est composé de 90 à 100 % en moles d'un alkylène glycol possédant 20 atomes de carbone ou moins, et d'entre 0 et 10 % en moles d'un polyalcool à trois fonctions ou plus. Le polyester copolymérisé présente d'excellentes qualités de transparence, de teinte, de résistance aux intempéries et de résistance aux chocs. En utilisant le polyester copolymérisé, on peut produire un agent de revêtement pulvérulent qui présente une excellente résistance aux intempéries, d'excellentes propriétés de film de revêtement et une excellente réactivité avec un agent de durcissement pendant le procédé de réticulation, et qui présente par conséquent des qualités particulièrement remarquables en ce qui concerne la proportion de gel, la maniabilité, la résistance à l'eau, les propriétés d'adhésion et les propriétés d'adhésion après test de résistance à l'eau.
PCT/JP2007/064141 2006-07-19 2007-07-18 Polyester copolymérisé, composition de polyester copolymérisé pour agent de revêtement pulvérulent comprenant ledit polyester copolymérisé, et agent de revêtement pulvérulent WO2008010503A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008525872A JP5267795B2 (ja) 2006-07-19 2007-07-18 共重合ポリエステル、それからなる粉体塗料用共重合ポリエステル組成物並びに粉体塗料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-196452 2006-07-19
JP2006196452 2006-07-19

Publications (1)

Publication Number Publication Date
WO2008010503A1 true WO2008010503A1 (fr) 2008-01-24

Family

ID=38956834

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/064141 WO2008010503A1 (fr) 2006-07-19 2007-07-18 Polyester copolymérisé, composition de polyester copolymérisé pour agent de revêtement pulvérulent comprenant ledit polyester copolymérisé, et agent de revêtement pulvérulent

Country Status (2)

Country Link
JP (1) JP5267795B2 (fr)
WO (1) WO2008010503A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110088505A (ko) * 2008-09-18 2011-08-03 그루포 페트로테멕스 에스.에이. 데 씨.브이. 개선된 열산화 안정성을 갖는 폴리에스터 용융상 조성물, 및 이의 제조 방법 및 이용 방법
WO2020080051A1 (fr) * 2018-10-16 2020-04-23 東洋紡株式会社 Résine de polyester pour film thermorétractable, film thermorétractable, étiquette thermorétractable, et emballage

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04505343A (ja) * 1989-05-23 1992-09-17 ピーピージー　インダストリーズ，インコーポレイテッド 粉体塗料組成物
JPH0770475A (ja) * 1993-09-02 1995-03-14 Nippon Yupika Kk 粉体塗料および粉体塗料用ポリエステル樹脂
JP2001106775A (ja) * 1999-10-04 2001-04-17 Nippon Ester Co Ltd 粉体塗料用ポリエステル樹脂及び組成物、並びにこれを用いた粉体塗料
JP2001163963A (ja) * 1999-09-30 2001-06-19 Toyobo Co Ltd ポリエステル重合触媒およびこれを用いて製造されたポリエステルならびにポリエステルの製造方法
JP2001163964A (ja) * 1999-09-29 2001-06-19 Toyobo Co Ltd ポリエステル重合触媒およびこれを用いて製造されたポリエステルならびにポリエステルの製造方法
JP2002322254A (ja) * 2001-02-20 2002-11-08 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2002332337A (ja) * 2001-03-07 2002-11-22 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2006290907A (ja) * 2005-04-05 2006-10-26 Toyobo Co Ltd 塗料用樹脂組成物およびこれを塗布した塗装金属板
JP2006312721A (ja) * 2005-04-04 2006-11-16 Toyobo Co Ltd 共重合ポリエステル樹脂およびそれを用いた塗料
JP2007009139A (ja) * 2005-07-04 2007-01-18 Nippon Ester Co Ltd ポリエステル系粉体塗料用樹脂およびその製造方法、ならびにポリエステル系粉体塗料

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0672178B2 (ja) * 1988-03-07 1994-09-14 大日精化工業株式会社 絶縁塗料
JP2002249567A (ja) * 2001-02-23 2002-09-06 Toyobo Co Ltd 共重合ポリエステル、中空成形体、およびシート状物質
JP2006233068A (ja) * 2005-02-25 2006-09-07 Nippon Ester Co Ltd 共重合ポリエステル

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04505343A (ja) * 1989-05-23 1992-09-17 ピーピージー　インダストリーズ，インコーポレイテッド 粉体塗料組成物
JPH0770475A (ja) * 1993-09-02 1995-03-14 Nippon Yupika Kk 粉体塗料および粉体塗料用ポリエステル樹脂
JP2001163964A (ja) * 1999-09-29 2001-06-19 Toyobo Co Ltd ポリエステル重合触媒およびこれを用いて製造されたポリエステルならびにポリエステルの製造方法
JP2001163963A (ja) * 1999-09-30 2001-06-19 Toyobo Co Ltd ポリエステル重合触媒およびこれを用いて製造されたポリエステルならびにポリエステルの製造方法
JP2001106775A (ja) * 1999-10-04 2001-04-17 Nippon Ester Co Ltd 粉体塗料用ポリエステル樹脂及び組成物、並びにこれを用いた粉体塗料
JP2002322254A (ja) * 2001-02-20 2002-11-08 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2002332337A (ja) * 2001-03-07 2002-11-22 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2006312721A (ja) * 2005-04-04 2006-11-16 Toyobo Co Ltd 共重合ポリエステル樹脂およびそれを用いた塗料
JP2006290907A (ja) * 2005-04-05 2006-10-26 Toyobo Co Ltd 塗料用樹脂組成物およびこれを塗布した塗装金属板
JP2007009139A (ja) * 2005-07-04 2007-01-18 Nippon Ester Co Ltd ポリエステル系粉体塗料用樹脂およびその製造方法、ならびにポリエステル系粉体塗料

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110088505A (ko) * 2008-09-18 2011-08-03 그루포 페트로테멕스 에스.에이. 데 씨.브이. 개선된 열산화 안정성을 갖는 폴리에스터 용융상 조성물, 및 이의 제조 방법 및 이용 방법
JP2012503066A (ja) * 2008-09-18 2012-02-02 グルポ、ペトロテメックス、ソシエダッド、アノニマ、デ、カピタル、バリアブレ 熱酸化安定性が改良されたポリエステル溶融相組成物およびその製造方法、ならびにその使用方法
KR101722271B1 (ko) 2008-09-18 2017-03-31 그루포 페트로테멕스 에스.에이. 데 씨.브이. 개선된 열산화 안정성을 갖는 폴리에스터 용융상 조성물, 및 이의 제조 방법 및 이용 방법
WO2020080051A1 (fr) * 2018-10-16 2020-04-23 東洋紡株式会社 Résine de polyester pour film thermorétractable, film thermorétractable, étiquette thermorétractable, et emballage
JP6741184B1 (ja) * 2018-10-16 2020-08-19 東洋紡株式会社 熱収縮性フィルム用ポリエステル樹脂、熱収縮性フィルム、熱収縮性ラベル、及び包装体
KR20210039504A (ko) * 2018-10-16 2021-04-09 도요보 가부시키가이샤 열수축성 필름용 폴리에스테르 수지, 열수축성 필름, 열수축성 라벨 및 포장체
KR102296003B1 (ko) 2018-10-16 2021-09-01 도요보 가부시키가이샤 열수축성 필름용 폴리에스테르 수지, 열수축성 필름, 열수축성 라벨 및 포장체

Also Published As

Publication number Publication date
JP5267795B2 (ja) 2013-08-21
JPWO2008010503A1 (ja) 2009-12-17

Similar Documents

Publication Publication Date Title
PL181186B1 (pl) Sposób wytwarzania poliestrów i kopoliestrów
JP2006206860A (ja) ポリエステル樹脂の製造方法
JP6011742B1 (ja) 共重合ポリエステル樹脂、及びその製造方法
JP2015518915A (ja) ポリエステル樹脂およびその製造方法
JP6844748B2 (ja) 共重合ポリエステル樹脂、成形品、及び熱収縮性フィルム
JP2008081576A (ja) ポリエステル樹脂の製造方法及びそれにより得られたポリエステル樹脂
JP2008007718A (ja) アルキッド樹脂、水系アルキッド塗料用樹脂組成物およびそれらの製造方法
JP2008007717A (ja) ウレタン変性アルキッド樹脂、水系ウレタン変性アルキッド塗料用樹脂組成物およびそれらの製造方法
JP5267795B2 (ja) 共重合ポリエステル、それからなる粉体塗料用共重合ポリエステル組成物並びに粉体塗料
JP2008007719A (ja) ポリエステル樹脂水分散体及びこれを用いた接着剤、コーティング剤、塗料
CN113603872B (zh) 一种超延时机械性能的聚酯树脂及其制备方法和应用
JP4701516B2 (ja) 光学用被覆フィルム
JP2008001854A (ja) ポリエステルおよびその成形体
JP2007254702A (ja) 結晶性ポリエステル樹脂及びこれを用いたホットメルト接着剤、押し出しコーティング剤
JP2007077268A (ja) 缶内面用塗料樹脂組成物およびこれを塗布した缶内面用塗装金属板
JP2008007716A (ja) （メタ）アクリル変性油性アルキッド樹脂、水系アルキッド塗料用樹脂組成物およびそれらの製造方法
WO2021210488A1 (fr) Résine de copolyester, article moulé, film thermorétractable et fibre
JP2006290907A (ja) 塗料用樹脂組成物およびこれを塗布した塗装金属板
JP2008007714A (ja) 油性アルキッド樹脂、油性アルキッド塗料用樹脂組成物およびそれらの製造方法
JP2006312721A (ja) 共重合ポリエステル樹脂およびそれを用いた塗料
JP2008019330A (ja) 不飽和ポリエステル樹脂および不飽和ポリエステル樹脂組成物とそれらの製造方法
JP5911734B2 (ja) ポリエステル樹脂組成物及びその製造方法
JP2008007720A (ja) ハイブリッド樹脂水分散体、及びこれを用いた接着剤、コーティング剤、塗料
JP2006282938A (ja) 共重合ポリエステル樹脂の製造方法、共重合ポリエステル樹脂、塗料用樹脂組成物及びこれを塗布した塗装金属板
JP2008019329A (ja) 不飽和ポリエステル樹脂および不飽和ポリエステル樹脂組成物とそれらの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07790896

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008525872

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07790896

Country of ref document: EP

Kind code of ref document: A1