WO2008001795A1 - Dispersion aqueuse de résine polyester, dispersion aqueuse de résine hybride, et adhésif, matière de revêtement et matière de peinture les utilisant - Google Patents

Dispersion aqueuse de résine polyester, dispersion aqueuse de résine hybride, et adhésif, matière de revêtement et matière de peinture les utilisant Download PDF

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Publication number
WO2008001795A1
WO2008001795A1 PCT/JP2007/062854 JP2007062854W WO2008001795A1 WO 2008001795 A1 WO2008001795 A1 WO 2008001795A1 JP 2007062854 W JP2007062854 W JP 2007062854W WO 2008001795 A1 WO2008001795 A1 WO 2008001795A1
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Prior art keywords
acid
resin
group
compound
polyester
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PCT/JP2007/062854
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English (en)
Japanese (ja)
Inventor
Hideki Tanaka
Takahiro Nakajima
Naoki Watanabe
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Toyo Boseki Kabushiki Kaisha
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Priority claimed from JP2006182169A external-priority patent/JP2008007719A/ja
Priority claimed from JP2006182170A external-priority patent/JP2008007720A/ja
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Publication of WO2008001795A1 publication Critical patent/WO2008001795A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • 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
    • 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
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters

Definitions

  • Polyester resin water dispersion hybrid resin water dispersion, and adhesives, coating agents and paints using these
  • the present invention relates to a polyester resin aqueous dispersion using a polymerization catalyst mainly composed of an aluminum compound without using a metal polymerization catalyst such as tin compounds, antimony compounds, germanium compounds, and titanium compounds, TECHNICAL FIELD
  • the present invention relates to a water dispersion of polyester acrylic hybrid resin and a film, cloth and metal water-based adhesive, water-based coating agent, water-based paint and production method using the same.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2005-126619
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-292665
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-239869
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-143326
  • Patent Document 7 In order to suppress gelation, it is necessary to add a large amount of a polymerization stabilizer, and there is a problem that they greatly reduce the hue of the resin (Patent Document 7).
  • As a means of suppressing gelation attempts have been made to introduce unsaturated groups by depolymerization with unsaturated carboxylic acids such as fumaric acid after once polymerizing a high molecular weight polyester. The distribution is difficult to control and the inherent flexibility of the polyester is impaired (Patent Document 5). Attempts have also been made to add unsaturated dicarboxylic acid anhydrides such as maleic anhydride to the molecular chain ends after polyester polymerization, but the amount of unsaturated groups that can be introduced is limited, and the effect of hybridizing acrylic is low. (Patent document 6).
  • Patent Document 5 JP-A-9 216921
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2004-292751
  • Patent Document 7 Japanese Patent No. 3501234
  • antimony-based, titanium-based, germanium-based, tin-based and the like are known as polymerization catalysts for conventional copolyesters.
  • polymerization catalysts for conventional copolyesters.
  • the following problems remain in these polymerization catalyst species.
  • Polymerization catalysts such as suzuhi compounds and antimony compounds contain heavy metals, and should not contain these or polyesters.
  • the copolymerized polyester resin is colored.
  • an aliphatic dicarboxylic acid such as adipic acid or sebacic acid
  • the resin is inferior in heat resistance.
  • white paint The white color cannot be obtained.
  • the coloring of the resin that becomes the adhesive layer may be a problem.
  • the germanium compound can be used effectively as the polymerization catalyst, but the price is extremely high.
  • an unsaturated bond that becomes a reaction point for grafting the acrylic resin is introduced into the copolymerized polyester resin and Z
  • an aluminum catalyst that can be sufficiently introduced into the urethane resin composed of the polyester without causing any loss of hue stably and using an aluminum catalyst that can reduce foreign matters derived from aluminum is used. Therefore, there is a demand for an aqueous resin dispersion in which acrylic is hybridized on the basis of a copolymer polyester, which has high reactivity, high adhesion, and high processability.
  • the present invention is a polyester resin water dispersion, a hybrid resin water dispersion, and a water-based adhesive, water-based coating agent, and water-based paint using these.
  • a resin produced in the presence of a polymerization catalyst containing at least an aluminum compound A polyester resin aqueous dispersion characterized by using a copolyester resin having an acid value of 3 to 110 mg KH / g.
  • the polymerization catalyst comprises at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds.
  • polymerization catalyst according to (1) to (2) wherein the polymerization catalyst comprises at least one selected from the group consisting of aluminum compounds and an alkali metal and / or an alkaline earth metal.
  • the weight strength S of at least one of the copolyester resin and the polyurethane resin containing the copolyester resin as a constituent component is 10% or more and 90% or less of the weight of the hybrid resin ( The hybrid resin water dispersion according to 12).
  • An unsaturated bond is introduced into at least one of the copolyester resin and the polyurethane resin containing the copolyester resin as a constituent component, and acrylic grafting is performed using the unsaturated bond as a reaction point. (12) or the hybrid resin water dispersion according to (13).
  • hybrid resin according to any one of (16) to (18), wherein the hybrid resin is at least one selected from the above-mentioned alkali metal and alkaline earth metal forces SLi, Na, Mg or a compound thereof. Water dispersion.
  • the material to be adhered is any one of a film, a cloth and a metal (12) to (20) A water-based adhesive using the aqueous dispersion of hybrid resin in any one of (20).
  • the polyester resin composition and the polyester acrylic hybrid resin composition of the present invention exhibit superior hue and heat resistance compared to conventional ones, adhesion between various plastic films, and various plastics. It is useful as an adhesive between film and wood board, cloth or metal, and as a coating agent or paint for various substrates.
  • the aqueous polyester resin dispersion and the aqueous polyester acrylic hybrid resin dispersion of the present invention have excellent transparency and are low in color, so that they are suitable for use after being formed into a film.
  • aluminum compound constituting the polymerization catalyst used in the present invention known aluminum compounds can be used without limitation in addition to metal aluminum.
  • 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 E butoxide, aluminum n- propoxide, aluminum i so - propoxide, aluminum n- butoxide, aluminum t Butoki Sai Aluminum alkoxides, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate di-iso-propoxide, etc., trimethylaluminum bismuth, triethylaluminum, etc.
  • organoaluminum compounds of these and their partial carohydrates, aluminum oxide and the like are particularly preferred.
  • carboxylates and inorganic acid salts Of these preferred are chelate compounds, and aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylylacetonate are particularly preferred.
  • the amount of aluminum compound used in the present invention with respect to the moles of all the structural units of the carboxylic acid component such as deer carboxylic acid or polycarboxylic acid of the polyester obtained 0. 001: 1.0 Monore 0 / 0 force S preferably, more preferably 0.005 to 0.5 Monore 0/0.
  • the addition amount of the aluminum component is required to be in a wide range because the catalytic activity varies greatly depending on the type and combination of polyvalent carboxylic acid and diol used, and the polymerization method. This shows the same tendency with other polymerization catalysts. In particular, when polymerization is not carried out under reduced pressure, the amount of polymerization catalyst needs to be greatly increased. Since the polymerization catalyst of the present invention exhibits sufficient catalytic activity, as a result, the resulting polyester has excellent thermal stability, thermal oxidation stability, and hydrolysis resistance, and suppresses the generation and coloring of foreign matters due to aluminum. Is done.
  • 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 amount of ethylene glycol added is preferably 0.5 to 5.0 times the volume ratio of the aqueous solution. More preferably, the amount is 0.8 to 2.0 times.
  • the solution is heated and water is distilled off to obtain an ethylene glycol solution.
  • the temperature is preferably 70 ° C or higher, preferably 130 ° C or lower. More preferably, the water is distilled off by heating and stirring at 80 to 120 ° C. More preferably, heating is performed under reduced pressure and / or an inert gas atmosphere such as nitrogen or argon, and water is distilled off to prepare a catalyst solution. is there.
  • 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 a solvent such as water glycol, and particularly used in water and Z or ethylene glycol so that the catalytic activity and the copolymer polyester obtained can be obtained. This is also preferable from the viewpoint of reducing foreign matter.
  • the phosphorus compound constituting the polymerization catalyst used in the present invention is not particularly limited, but phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid, triphenyl phosphoric acid, phosphorous acid and Trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4 ' Examples include phosphites such as phosphites.
  • More preferable phosphorus compounds for use in the present invention are from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is at least one phosphorus compound selected. By using 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. Of these, the use of phosphonic acid compounds is preferable because of their great effects of improving physical properties and catalytic activity. Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because it is effective in improving physical properties and improving catalyst activity.
  • a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound, as used in the present invention are represented by the following formulas This refers to a compound having the structure represented by 6).
  • Examples of the phosphonic acid compounds used in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, dimethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, and benzyl phosphonate phosphonate. It is done.
  • Examples of the phosphinic acid-based compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, diphenylphosphinic acid phenyl, phenylphosphinic acid, phenylphenylphosphinic acid methyl, phenylphosphinic acid phenyl, and the like.
  • Examples of the phosphine oxide compound of the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.
  • the phosphorus compound of the present invention includes the following formulas (Chemical Formula 7) to ( The compound represented by Chemical formula 12) is preferred.
  • the compounds represented by the following general formulas (Chemical Formula 13) to (Chemical Formula 15) are preferably used because the physical property improving effect and the catalytic activity improving effect are particularly large.
  • R 6 each independently represents hydrogen, a hydrocarbon group having carbon atoms:! To 50, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having! To 50 carbon atoms.
  • R 2 and R 3 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.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl and an aromatic ring structure such as phenyl naphthyl.
  • the phosphorus compound used in the present invention includes R 6 in the above formulas (Chem. 13) to (Chem. 15).
  • a compound in which is a group having an aromatic ring structure is particularly preferred.
  • Examples of the phosphorus compound used in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, dimethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, dimethylphosphonate benzylphosphonate, and diphenylphosphine.
  • a metal salt compound of phosphorus is particularly preferable as the phosphorus compound.
  • the phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus compound.
  • the physical property improving effect and catalytic activity of the polyester which are the problems of the present invention, are not limited. The improvement effect is 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.
  • the phosphorus metal salt compound used in the present invention it is preferable to use at least one compound selected from compounds represented by the following general formula (Chemical Formula 16) because the physical property improving effect and the catalytic activity improving effect are large.
  • R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxy group or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or Represents an alkoxy group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl.
  • R 1 represents an integer of 1 or more
  • m represents 0 or an integer of 1 or more
  • 1 + m is 4 or less
  • M represents a (1 + m) -valent metal cation
  • n represents an integer of 1 or more.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as a branched structure or phenyl naphthyl.
  • R 1 include phenyl, 1-naphthyl, 2-naphthyl, 9_anthryl, 4-biphenyl, 2-biphenyl, and the like.
  • R 2 examples include hydrogen, methylol group, ethyl group, propyl group, isopropyl group, n_butyl group, see-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group.
  • Examples include hydroxide ions, alcoholate ions, acetate ions and cetylacetone ions.
  • [0050] represents a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having a carbon number of! To 50, a hydroxyl group, a halogen group, an alkoxy group, or an amino group.
  • 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, an alkoxyl group, or a carbocyclic group, 1 is an integer of 1 or more, m is 0 or an integer of 1 or more, 1 + m is 4 or less, M represents a (1 + m) -valent metal cation, and the hydrocarbon group is an alicyclic structure such as cyclohexyl, a branched structure, phenyl or the like. It may contain an aromatic ring structure such as naphthyl.)
  • R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like.
  • R 3 O— examples include hydroxide ions, alcohol ions, acetate ions and acetylacetone ions.
  • Phosphorus metal salt compounds used in the present invention include lithium naphthyl) methyl phosphonate], sodium naphthyl) methyl phosphonate], magnesium bis [(1_naphthyl) methylphosphonate], potassium [(2 _Naphthyl) methylphosphonate], magnesium bis [(2_naphthyl) methylphosphonate], lithium [benzylphosphonate], sodium [benzylphosphonate], magnesium bis [benzylphosphonate], beryllium bis [benzyl Phosphonate], strontium bis [benzylphosphonate], manganese bis [benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonate], sodium [(9 anthryl) methylphosphonate], Nesium bis [(9 anthryl) methyl phosphonate], sodium [4-hydroxybenzyl phosphonate], magnesium [4-hydroxybenzyl phosphonate], sodium [4-chloro
  • acid ethyl magnesium bis [benzyl phosphonate]
  • sodium benzyl phosphonate sodium benzyl phosphonate
  • magnesium bis [benzenorephosphonic acid particularly preferred are acid ethyl]
  • a phosphorus compound having at least one P_OH bond as the phosphorus compound is particularly preferable.
  • the effect of improving the physical properties of the polyester is particularly enhanced.
  • these phosphorus compounds are used together with the aluminum compound of the present invention, the effect of improving the catalytic activity is greatly seen.
  • 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.
  • use of a phosphonic acid compound having at least one P—OH bond facilitates formation of a complex with an aluminum compound, and is highly preferable for improving the physical properties and improving the catalytic activity of the polyester.
  • phosphorus compound having at least one P_OH bond used in the present invention physical properties can be improved by using at least one compound selected from the compounds represented by the following general formula (Formula 18).
  • the effect and the improvement effect of catalyst activity are large and preferable.
  • R 1 is hydrogen, a hydrocarbon having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxy 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. May contain alicyclic structures such as cyclohexyl, 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, methylol group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group.
  • the phosphorus compound having at least one P-OH bond of the present invention includes (1 naphthyl) methylphosphonate, (1 naphthyl) methylphosphonate, (2-naphthinole) methylphosphonate, benzylphosphonate, Benzylphosphonic acid, (9-anthryl) methylphosphonic acid ethyl, 4-hydroxybenzylphosphonic acid ethyl, 2_methylbenzenolephosphonic acid ethyl, 4_cyclopentyl phosphonic acid phenyl, 4-aminobenzilphosphonic acid methyl, 4-methoxybenzyl Examples include ethyl phosphonate. Of these, (1-naphthyl) methylphosphonate and benzylphosphonate are particularly preferred.
  • a preferable phosphorus compound used in the present invention is a phosphorus compound represented by the chemical formula (Chemical Formula 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 alkoxy 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. It may contain a branched structure or an aromatic ring structure.
  • At least one of 1 ⁇ 2 3 in the chemical formula (Chemical Formula 19) is a compound containing an aromatic ring structure.
  • the phosphorus compound used in the present invention has a large effect because it is less likely to be distilled off during polymerization.
  • the phosphorus compound used in the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule.
  • catalytic activity can be increased by using a phosphorus compound having a phenol moiety in the same molecule during polyester polymerization. The effect of increasing is greater and therefore the productivity of polyester 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 phosphonic acid compound, phosphine having a phenol moiety in the same molecule.
  • Using one or more compounds selected from the group consisting of acid-based compounds, phosphine oxide-based compounds, phosphonous acid-based compounds, phosphinic acid-based compounds, and phosphine-based compounds can improve the physical properties and catalytic activity of polyester.
  • the improvement effect is large and preferable.
  • the use of a phosphonic acid compound having one or two or more phenol moieties in the same molecule is particularly preferable because of the effect of improving the physical properties and the catalytic activity of the polyester.
  • R 1 is a substituent having a phenol moiety, such as a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxy group, or an amino group. And a hydrocarbon group having a phenol moiety:! To 50.
  • R 4 , R 5 and R 6 are each independently hydrogen, a hydrocarbon group having a carbon number:! To 50, a hydroxyl group, a halogen group or an alkoxy group.
  • a hydrocarbon group containing a substituent such as a nore group or an amino group: represents a hydrocarbon group having from! To 50.
  • R 2 and R 3 are each independently hydrogen, a hydrocarbon group having a carbon number:! To 50, a hydroxyl group or an alkoxyl.
  • Rye, the ends of R 2 and R 4 may be joined together.
  • Examples of phosphorus compounds having a phenol moiety used in the present invention in the same molecule include p-hydroxyphenylphosphonic acid, p-hydroxyphenylphosphonic acid dimethyl, and p-hydroxyphenylphosphonic acid jetyl.
  • P-hydroxyphenyl phosphonate diphenyl bis (p-hydroxyphenyl) phosphinic acid, bis (p-hydroxyphenyl) phosphinic acid methyl, bis (p-hydroxyphenyl) phosphinic acid phenyl, p-hydroxy Phenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphenylphosphinic acid phenyl, p-hydroxyphenylphosphinic acid, p-hydroxyphenylphosphinic acid methyl, p-hydroxyphenyl Phenyl phosphinate, bis (p-hydro Ciphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis (p-hydroxyphenyl) methylphosphine oxide, and compounds represented by the following formulas (Chemical 29) to (Chemical 32) . Among these, a compound represented by the following formula
  • SANKO-220 manufactured by Sanko Co., Ltd. is available and can be used.
  • phosphorus compounds having the phenol moiety used in the present invention in the same molecule at least one selected from a metal salt compound of a specific phosphorus represented by the following general formula (Chemical Formula 33) is particularly preferable. .
  • R 2 independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
  • R 3 represents hydrogen, a hydrocarbon group having a carbon number:! To 50, a hydrocarbon group having a carbon number:! To 50, including a hydroxyl group or an alkoxyl group.
  • R 4 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a carbonyl group containing 1 to 50 carbon atoms.
  • R 4 O— include hydroxide ions, alcohol ions, acetate ions, acetylacetone ions, and the like.
  • n 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 compounds represented by the following general formula (Formula 34) is preferable.
  • M 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, Zn
  • Li, Na, and Mg are particularly preferable.
  • Specific phosphorus metal salt compounds used in the present invention include lithium [3,5-di-tert-butyl-ethyl 4-hydroxybenzylphosphonate], sodium [3,5-di-tert Butyl 4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butynole 4-hydroxybenzylphosphonate], potassium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5 —Di-tert-butyl-4-hydroxybenzylphosphonate ethynole], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], beryllium bis [3,5-di-tert-butyl 4-hydroxybutyrylphosphonate methyl] , Strontium bis [3,5-di-tert-butyl-4-hydroxybenzyl phosphonate], barium bis [3,5-di-tert-butyl-4- Droxybenzidine
  • lithium [3,5_di-tert-butyl _4-hydroxybenzylphosphonate] sodium [3,5-di-tert-butynole_4-hydroxybenzylphosphonate]
  • magnesium bis [3 , 5-di-tert-butyl _4-hydroxybenzylphosphonate] is particularly preferred.
  • expression 2 independently represents hydrogen and a hydrocarbon group having 130 carbon atoms.
  • R 3 represents hydrogen, a hydrocarbon group having carbon atoms:! To 50, a hydrocarbon group having carbon atoms:! To 50 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 cyclohexinole, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • At least one selected from compounds represented by the following general formula (Formula 36) is preferable.
  • R 3 represents hydrogen, a hydrocarbon group having a carbon number:! To 50, a hydrocarbon group having a carbon number:! To 50, including a hydroxyl group or an alkoxyl group.
  • the group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as a branched structure or phenyl 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, phenyl group, naphthyl Groups, substituted phenyl groups, naphthyl groups, groups represented by _CH CHOH
  • Specific phosphorus compounds having at least one P_OH bond used in the present invention include 3, 5_di-tert-butyl-1-hydroxybenzylphosphonate, 3,5_di-tert- Butyl _Methyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl _4-Hydroxybenzylphosphonate isopropyl, 35-di-tert-butyl 4-hydroxyhydroxy Examples thereof include phenyl benzoate, 3,5-di-tert-butyl 4-hydroxybenzylphosphonate octadecyl, 3,5-di-tert-butyl 4-hydroxybenzylphosphonate, and the like. Of these, 3,5-ditertbutyl-4-hydroxybenzylphosphonate methyl ester and 3,5_ditertbutylbutyl-4-hydroxybenzylphosphonate methyl ester are particularly preferred.
  • phosphorus compounds having the phenol moiety used in the present invention in the same molecule, at least one phosphorus compound selected from the specific phosphorus compounds represented by the following general formula (Chemical Formula 37) is preferable. .
  • R ⁇ R 2 independently represents hydrogen and a hydrocarbon group having 1 to 30 carbon atoms.
  • R 3 and R 4 each independently represent hydrogen and 1 to 50 carbon atoms.
  • R 3 and R 4 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.
  • 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.
  • the phenyl group include aromatic groups such as a naphthyl group, and a group represented by -CH CHOH.
  • Specific phosphorus compounds used in the present invention include 3,5-di-tert-butyl _4-hydroxybenzylphosphonate diisopropyl, 3,5-di-tert-butyl _4-hydroxybenzyl phosphonate di_n-butyl 3,5-di-tert-butyl_4-hydroxybenzylphosphonate dioctadecyl, 3,5-di-tert-butyl-1-4-hydroxybenzylphosphonate diphenyl, and the like.
  • 3,5-di-tert-butyl_4-hydroxybenzenorephosphonate dioctadecyl and 3,5-di-tert-butyl_4-hydroxybenzylphosphonate diphenyl are particularly preferred.
  • a particularly desirable compound in the present invention is at least one selected from compounds represented by the chemical formulas (Chemical Formula 39) and (Chemical Formula 40).
  • the phosphorus compound is at least one selected from compounds represented by the chemical formulas (Chemical Formula 39) and (Chemical Formula 40).
  • 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 (which may be a straight chain, branched structure or alicyclic structure), or a substituent containing 1 to 10 carbon atoms. Aliphatic hydrocarbons (straight, branched or alicyclic structures may be used), _ o one, -OCH one,-SO one, one C 0, -COCH one, -CH OCO —, -NHCO-
  • R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 120 carbon atoms, a hydrocarbon group having 120 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) Or an aromatic ring structure, which may be halogen-substituted), a hydroxyl group or a halogen group, or an alkoxyl group or amino group having 1 to 10 carbon atoms (1 to 10 carbon atoms).
  • Alkyl or alkanol substituted and nitro groups carboxyl groups, aliphatic carboxylic acid ester groups having 1 to 10 carbon atoms, formyl groups, acyl groups, sulfonic acid groups, sulfonic acids Amido group (which may be substituted with an alkyl or alkyl group having 1 to 10 carbon atoms), phosphoryl-containing group, nitrile group, cyano-anorequinole group, force Or more than two.
  • 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_naphthylmethylphosphine Phosphonic acid, 2-naphthylmethylphosphonic acid monoethyl ester, 4 phenylol, benzylphosphonic acid, 4 phenylole, benzylphosphonic acid monoethyl ester, 2 phenyl, benzylphosphonic acid, 2 phenyl, benzylphosphonic acid monoester Tyl ester, 4-chronole, benzylphosphonic acid, 4-chronole, benzylphosphonic acid monoethyl ester, 4-chronole, benzylphosphonic acid jetyl ester, 4-
  • Phosphorus compounds containing heterocycles include 2_benzofuran di Noremethylphosphonic acid jetyl ester, 2-Benzofuranylmethylphosphonic acid monoethylesterol, 2-benzofurerylmethylphosphonic acid, 2- (5-methyl) benzofuranyl methylphosphonic acid jetyl ester, 2- (5-methinole) benzofuran Examples include ermethylphosphonic acid monoethyl ester and 2- (5-methyl) benzofuranylmethylphosphonic acid.
  • the phosphorus compound which has said coupling group is a preferable aspect at the point of polymerization activity.
  • R ° represents a hydroxyl group, an alkyl group of C1 -C10, _ C_ ⁇ _ ⁇ _H group or single C_ ⁇ OR 4 (R 4 represents an alkyl group C1 -C4), alkylene It represents a glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, and alkylene glycol represents C1-C4 glycol).
  • R 1 represents an aromatic ring structure such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, diphenyl ketone, anthracene, phenanthrene, and pyrene.
  • 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, the same substituent or a combination of different substituents may be used.
  • n represents 0 or an integer of 1 to 5.
  • examples of the phosphorus compounds represented by the formula (Formula 42) used in the present invention 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, Benzenorephosphonic acids with hydroxyl groups introduced into the benzene ring, such as 4-hydroxybenzylphosphonic acid, 6-hydroxybenzylphosphonic acid jetyl ester, 6_hydroxybenzylphosphonic acid monoethyl ester, 6-hydroxybenzylphosphonic acid
  • 2_n-butylbenzylphosphonic acid jetyl ester 2_n_butylbenzyl Phosphonic acid monomethyl ester, 2 n-butylbenzylphosphonic acid, 3 n-butylbenzylphosphonic acid jetyl ester, 3-n-butylbenzylphosphonic 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-dibutylbenzylphosphonic acid jetyl ester, 2,5-n-dibutylbenzylphosphonic acid monoethyl ester, Benzene such as 2,5_n-dibutylbenzylphosphonic acid, 3,5_n-dibutylbenzylphosphonic acid jetyl ester,
  • 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 dicarboxybenzyl Phosphonic acid monoethyl ester, 2,5-dicarboxybenzylphosphonic acid, 3,5-dicarboxybenzylphosphonic acid jetyl ester, 3,5-dicarboxybenzylphosphonic acid monoethyl ester, 3,5-di Carboxybenzyl phosphonic acid, 2-methoxycarbonyl benzyl
  • the phosphorus compound having an aromatic ring structure having a substituent as benzene is not limited to the above-mentioned single substituent species, but is substituted as described above.
  • a mixture of a 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. 1_ (5-hydroxy) naphthylmethylphosphonic acid jetyl ester, 1_ (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1_ (5-hydroxy) naphthylmethylphosphonic acid, 1_ (5— Hydroxy) naphthylmethylphosphonic acid jetyl ester, 1 _ (5-hydroxy) naphthylmethylphosphonic acid monoethyl ester, 1 _ (5 _hydroxy) naphthylenomethylphosphonic acid, 1 _ (5 _n-butynole) naphthylmethylphosphonic acid jetyl ester 1 (5-n-butyl) naphthylmethylphosphonic acid monoethyl ester, 1 (5-n-butyl) naphthylmethylphosphonic acid
  • Naphtylmethylphosphonic acid monoethyl ester 1_ (4-methoxyethoxy) naphthyl methylphosphonic acid, 1_ (5-hydroxy) naphthylmethylphosphonic acid jetyl ester, 2- (6-hydroxy) naphthylmethylphosphonic acid jetyl ester, 2 — (6-Hydroxy) naphthylmonoethylphosphonic acid, 2 _ (6-hydroxy) naphthylmethylphosphonic acid, 2- (6 _n-butynole) naphthylmethylphosphonic acid jetyl ester, 2 _ (6 _n-butynole) naphthylmethylphosphone Acid monoethyl ester, 2- (6 _n-butyl) naphthylme Tylphosphonic acid, 2- (6-carboxy) naphthylmethylphosphonic acid jetyl ester, 2- (6-carboxy) naphthylmethylphosphonic acid monoethyl ester, 2- (6-car
  • the phosphorus compound in which the aromatic ring structure having a substituent is naphthalene is not limited to the above-mentioned single substituent species.
  • 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 compounds represented by the formula (Formula 42) used in the present invention are as follows. That is, 4- (4-hydroxyphenyl) benzylphosphonic acid jetyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid monoethyl ester, 4 (4-hydroxyphenyl) benzenorephosphonic acid, 4- (4 _n_Butylphenol) Benzylphosphonic acid jetyl ester, 4- (4 _n_Butylphenol) benzylphosphonic acid monoethyl ester, 4_ (4_n_ butylphenol) benzylphosphonic acid, 4_ (4-carboxyphenol Ninore) Benzylphosphonic acid jetyl ester, 4_ (4-carboxyphenenole) benzylphosphonic acid monoethenore, 4- (4-carboxyphenenole) benzylphosphonic acid monoethenore, 4- (4-carboxyphenenole) benzylphosphonic acid mono
  • the phosphorus compound whose aromatic ring structure having a substituent is biphenyl is not limited to the above-mentioned single substituent species.
  • 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 compounds represented by the formula (Chemical Formula 42) used in the present invention include the following. That is, 4- (4-hydroxyphenyl) benzylphosphonic acid jetyl ester, 4- (4-hydroxyphenyloxy) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyl) Oxy) benzylphosphonic acid, 4- (4 n-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4 n-butylphenyloxy) benzyl phosphonic acid monoethyl ester, 4- (4 Butylphenyl) benzylphosphonic acid, 4- (4-carboxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4 Noreboxyphen
  • the phosphorus compounds whose aromatic ring structure having a substituent is diphenyl ether 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 compounds represented by the formula (Chemical Formula 42) used in the present invention include the following. . 4- (4-hydroxyphenylthio) benzylphosphonic acid jetyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylthio) benzylphosphonic acid, 4- (4-n-butylphenylthio) benzilphosphonic acid monoethyl ester, 4- (4 n-butylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4 butylphenylthio) benzylphosphonic acid, 4 (4 Carboxyphenylthio) benzylphosphonic acid monoethyl ester, 4-one (4 trout norboxoxyphenylthio) benzylphosphonic acid monoethyl este
  • 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 carboxyesterol group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can be used.
  • examples of the phosphorus compounds represented by the formula (Formula 42) used in the present invention include the following. 4- (4-Hydroxyphenylsulfoninole) benzylphosphonic acid jetyl ester, 4_ (4-hydroxyphenylsulfoninole) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylsulfoninole) benzylphosphonic acid , 4_ (4_n_Butylphenyl nonenophonyl) benzylphosphonic acid monoethyl ester, 4_ (4_n_butylphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4 (4-butylphenylsulfoninole) benzylphosphonic acid 4- (4-carboxyphenylsulfonyl) benzylphosphonic acid 4- (4-carboxyphenylsulfonyl)
  • the Linyig compound in which the aromatic ring structure having a substituent is diphenylsulfone is 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 compounds represented by the formula (Formula 42) used in the present invention include the following. That is, 4- (4-hydroxybenzyl) benzylphosphonic acid jetyl ester, 4_ (4-hydroxybenzyl) benzylphosphonic acid monoethyl ester, 4_ (4-hydroxybenzyl) benzylphosphonic acid, 4- (4_n_butylbenzyl ) Benzylphosphonic acid monoethyl ester, 4_ (4_n_butylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzyl) benzylphosphonic acid, 4_ (4-carboxybenzyl) benzenorephosphonic acid monoethyl ester, 4_ (4-Carboxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxybenzyl)
  • Phosphonic acids into which a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group and the like have been introduced are not limited thereto.
  • the phosphorus compound whose aromatic ring structure having a substituent is diphenylmethane is not limited to the above-mentioned single substituent species.
  • a hybrid of a 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 compounds in which the aromatic ring structure having a substituent is diphenyldimethylmethane include the following. .
  • the phosphorus compound whose aromatic ring structure having a substituent is diphenyldimethylmethane is not limited to the above-mentioned single substituent species.
  • a mixture of a substituent, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyesterol group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.
  • phosphorus compounds represented by the formula (Formula 42) used in the present invention an aromatic ring structure having a substituent
  • Examples of phosphorus compounds in which is diphenyl ketone include the following. That is,
  • the phosphorus compounds whose aromatic ring structure having a substituent is diphenylketone are not limited to the above-mentioned single substituent species.
  • a hybrid 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 compounds represented by the formula (Formula 42) used in the present invention 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-butinole) Anthryl methylphosphonate Jetyl Este Nole, 9- (10- n-butyl) anthrylmethylphosphonic acid monoethyl ester, 9- (10 —n-butyl) anthrylmethylphosphonic acid, 9- (10-carboxy) anthrylmethyl nitrophosphonic acid jetyl ester, 9 Mono (10-carboxy) anthrylmethylphosphonic acid monoethyl ester, 9 _ (10-carboxy) anthrylmethylphosphonic acid, 9 _ (10_carboxy) 9 _ (2-hydroxye
  • the phosphorus compounds represented by the formula (Chemical Formula 42) are not limited to the above-mentioned single substituent species.
  • a mixture of a 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 having an aromatic ring structure force S phenanthrene having a substituent include the following. Ie 1
  • the phosphorus compounds represented by the formula (Chemical Formula 42) are not limited to the above-mentioned single substituent species.
  • a mixture of a 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 compounds represented by the formula (Chemical Formula 42) used in the present invention include the following. 1- (5-hydroxy) pyrenylmethylphosphonic acid jetyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid, 1- (5- n-butyl) pyrenylylmethylphosphonic acid jetyl ester, 1- (5-n-butynole) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) pyrenylmethinorephosphonic acid, 1- (5- Carboxy) pyrenylmethylphosphonic acid jetyl ester, 1 mono (5-carboxy) pyrenylmethylphosphonic acid monoethyl ester, 1 mono (5-carboxy) pyrenylmethylphosphonic acid, 1
  • the phosphorus compound in which the aromatic ring structure having a substituent is pyrene is not limited to the above-mentioned single substituent species.
  • a hybrid of a 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.
  • Substituents such as hydroxyl group, alkyl group, carboxyl group, force carboxy ester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group introduced into the above-described series of aromatic rings are aluminum at the time of polymerization of polyester. It is presumed to be deeply involved in complex formation with atoms. In addition, some of them are similar to carboxyl groups or hydroxyl groups that are functional groups at the time of polyester formation, and are easily dissolved or incorporated in the polyester matrix. .
  • R ° bonded to the aromatic ring structure (R 1) is compared to the unsubstituted groups are hydrogen atom, an alkyl group of C1 -C10 the present invention, - COOH group or - C_ ⁇ _OR 4 (R 4 is C1-C4 alkyl group), an alkylene glycol group or a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, alkylene glycol represents C1-C4 glycol) It is preferable in terms of the effect of reducing foreign matter that can be improved only.
  • Examples of the substituent bonded to the aromatic ring structure include a C1-C10 alkyl group, a carboxyl and a strong carboxyl ester group, an alkylene glycol, and a monoalkoxyalkylene glycol. From the viewpoint of the effect of reducing foreign matter, carboxyl and power carboxyl ester groups, alkylene glycols and monoalkoxy alkylene glycols are more preferable. The reason for this is unknown, but it is presumed to be due to improved compatibility with the polyester and the catalyst medium, alkylendalycol.
  • 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 the heterocyclic structure may have a substituent.
  • 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 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 linear, an alicyclic structure, a branched structure, An aromatic ring structure, which may be halogen-substituted, or 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).
  • a nitro group a carboxyl group, an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, a formyl group, a acyl group, a sulfonic acid group, or a sulfonic acid amide. 1 or 2 selected from a group (which may be substituted with an alkyl or alkyl group having 1 to 10 carbon atoms), a phosphoryl-containing group, a nitrile group, or a cyanoalkyl group Or more.
  • the aromatic ring structure of (Chemical Formula 43) is selected from benzene, naphthalene, biphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenylmethane, diphenyldimethylmethane, anthracene, phenanthrene, and pyrene.
  • 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-nitro, 5-methyl) -phenylphosphonic acid jetyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, (3- Nitro, 5-methoxy) -phenylphosphonic acid jetty lesestole, (3-nitro, 5-methoxy) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methoxy) -phenylphosphonic acid, (4-chloro) -phenylphosphonic acid Jetyl ester, (4-chloro,)-phenylphosphonic acid monoethyl ester, (4-chloro) -hue Nylphosphonic acid, (5-chloro,)-phenylphosphonic acid jetyl ester, (5-chloro,)-
  • 5-Benzofuranylphosphonic acid jetyl ester As: 5-Benzofuranylphosphonic acid jetyl ester, 5-Benzofuranylphosphonic acid monoethyl ester, 5 Benzofuranylphosphonic acid, 5- (2 methinore) benzofuraninophosphophosphonic acid jetyl Examples include esters, 5- (2methyleno) benzofuranylphosphonic acid monoethyl ester, and 5- (2 methyl) benzofurerphosphonic acid.
  • the phosphorus compound having no linking group described above may have a slightly lower polymerization activity than the phosphorus compound having the linking group described above.
  • a copolymerized polyester is polymerized. It can be used as a catalyst.
  • Phosphorus compounds are known as heat stabilizers for polyesters. It has not been known so far that even when these compounds are used in combination with conventional metal-containing polyester polymerization catalysts, melt polymerization is greatly promoted. It was. In fact, antimony compounds, titanium compounds, tin compounds, and germanium compounds that are typical catalysts for polyester polymerization When the polyester is melt-polymerized using the product as a polymerization catalyst, it is not recognized that the polymerization is accelerated to a substantially useful level even if the phosphorus compound of the present invention is added.
  • the amount of the phosphorus compound used in the present invention is preferably 0.001 to 2.0 mol% with respect to the number of moles of all constituent units of the polystrengthen rubonic acid component of the copolymer polyester obtained. . 005 to 1.0 mole 0/0, it is further preferable les. If the addition amount of the phosphorus compound is less than 0.001%, the effect of addition may not be exhibited. If the addition amount exceeds 2.0 mol%, the catalytic activity as a copolymerized polyester polymerization catalyst is reduced. In some cases, the downward trend varies depending on the amount of aluminum used.
  • a small amount of an alkali metal, an alkaline earth metal and at least one selected from the compound coexist as a second metal-containing component. It is a mode.
  • the coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity, and thus provides a catalyst component with a higher reaction rate, which is effective in improving productivity.
  • 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 mode Honoré 0/0, more preferably 1 X 10- 5 ⁇ 0 ⁇ 3 moles 0 / 0, particularly preferably 1 X 10- 5 ⁇ 0. 1 mol%. Since the addition amount of alkali metal and alkaline earth metal is small, it is possible to increase the reaction rate without causing problems such as deterioration of thermal stability, generation of foreign substances, coloring, deterioration of hydrolysis resistance, etc. .
  • the amount of alkali metal, alkaline earth metal and its compound used is 1.0 mol% or more, the heat stability decreases, the generation of foreign matter and coloring, and the hydrolysis resistance decrease. A case occurs. If it is less than ⁇ force ⁇ X 10- 6, the effect is not clear also be added.
  • the alkali metal and alkaline earth metal constituting the second metal-containing component include Li, Na, K, Rb, Cs, Be, Of these, at least one selected from Mg, Ca, Sr, and Ba is preferred, and at least one selected from Li, Na, Mg, or a compound thereof is more preferable.
  • the alkali metal or alkaline earth metal compound include, for example, these metal compounds.
  • Saturated aliphatic carboxylates such as acid, acetic acid, propionic acid, butyric acid, and succinic acid, unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid, aromatic carboxylates such as benzoic acid, Halogen-containing carboxylates, hydroxycarboxylates such as lactic acid, citrate, and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, odor Inorganic acid salts such as hydrofluoric acid, chloric acid and bromic acid, 1_propanesulfonic acid, 1_pentanesulfonic acid, organic sulfonates such as naphthalenesulfonic acid, organic sulfates such as laurylsulfuric acid, methoxy, ethoxy, n
  • alkali metals alkaline earth metals or their compounds
  • a strongly alkaline one such as a hydroxide
  • these are dissolved in a diol such as ethylene glycol or an organic solvent such as an alcohol. Since it tends to be difficult, it must be added to the polymerization system with an aqueous solution, which may cause a problem in the polymerization process.
  • a strong alcoholic material such as hydroxide
  • the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be easily colored. Hydrolyzability also tends to decrease.
  • the alkali metal of the present invention or a compound thereof or the alkaline earth metal or a compound thereof is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, an aroma of an alkali metal or an alkaline earth metal.
  • Group Carboxyl salt halogen-containing carboxylate, hydroxy carboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloroacid, bromic acid
  • the polymerization catalyst used in the present invention is another polymerization catalyst such as an antimony compound, a germanium compound, a titanium compound, or a tin compound.
  • an antimony compound such as aluminum, copper, copper, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium
  • 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' Chemicals Co., Ltd.) as a phosphorus compound is charged into the flask together with the ethylene glycol and heated at 160 ° C for 12 hours with stirring under nitrogen purge. An ethylene glycol solution of the compound was prepared.
  • Lithium acetate manufactured by Nacalai Co., Ltd., reagent grade
  • ethylene glycol ethylene glycol
  • 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 polyester resin aqueous dispersion of the present invention will be described.
  • the resin acid value in the copolyester resin constituting the aqueous polyester resin dispersion of the present invention is 3 to: 110 mgKH / g, preferably 4 to 105 mgKOH / g, more preferably
  • Resin acid value is 3mg
  • carboxynole groups and / or sulfonic acid groups are 80% or more, preferably 85% or more, more preferably 90% or more, and further Preferably it is 95% or more.
  • carboxyl group and / or carboxylic acid group is less than 80%, when the functional group showing an acid value exceeds 20% is a phosphoric acid group or a phenolic hydroxyl group, the temporal stability of the aqueous dispersion may be deteriorated, It may cause coloring and is not practical.
  • the polyester used in the present invention can use various raw materials within the above range.
  • Examples of the polyvalent carboxylic acid component of the copolyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid.
  • Aliphatic dicarboxylic acids such as acid, dodecanedioic acid and dimer acid, unsaturated dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid and terpene maleic acid adduct, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid
  • Alicyclic dicarboxylic acids such as hexahydroisophthalic acid, 1,2-cyclohexene dicarboxylic acid, trivalent or higher carboxylic acids such as (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, methylcyclohexycentric carboxylic acid, etc. Acids and the like are listed, and one or more of these can be selected and used.
  • Examples of the polyalcohol component used in the copolymerized polyester resin used in the present invention include ethylene glycol, propylene glycol (1,2_propanediol), 1,3_propanodiole, 1,4_butanediole, 1, 2_butanediol, 1,3_butanediol, 2_methyl-1,3_propanediol, neopentylglycol, 1,5_pentanediol, 1,6-hexanediol, 3_methyl_1,5_pentane Diol, 2— Thiru 2-butyl-1- 1,3-propanediol, 2,4-jetyl 1,5-pentanediol, 1-methyl-1,8-octanediol, 3-methyl-1,6-hexanediol, 4-methinole 1,7-heptane Diol, aliphatic glycols such as 4-methyl-1
  • 5_Na sulfoisophthalic acid for example, 5_Na sulfoisophthalic acid, 5—ammonium sulfoisophthalic acid, 4-Na sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, 2— Sodium sulfoterephthalic acid, 5-K sulfoisophthalic acid, 4-K sulfoisophthalic acid, 2-K sulfoisophthalic acid, Na sulfosuccinic acid and other sulfonic acid alkali metal salts or sulfonic acid amine salt compounds, sulfonic acid Na salt
  • a bisphenol A-alkylene oxide adduct, a sulfonic acid K base-containing hydroquinone alkylene oxide adduct, and the like can be copolymerized.
  • a phenolic hydroxyl group is introduced into the molecule, for example, 5-hydroxyisophthalic acid, diphenolic acid or the like can be copolymerized.
  • the carboxyl group is introduced by polymerizing the polyester resin, followed by atmospheric pressure and nitrogen atmosphere, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8_naphthalic anhydride.
  • tertiary amines such as triethylamine, tri-n-butylamine, benzyldimethylamine, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide are used. It is preferable to add a small amount of a quaternary hydroxide such as lithium carbonate, a basic compound such as lithium carbonate, sodium carbonate, potassium carbonate, or sodium acetate, since the generation of condensates between glycol components can be suppressed low.
  • a quaternary hydroxide such as lithium carbonate, a basic compound such as lithium carbonate, sodium carbonate, potassium carbonate, or sodium acetate
  • a polar group such as a carboxyl group on the surface of the particle is partially or wholly a base. It is preferable to neutralize with an organic substance.
  • basic substances that can be used for neutralization include ammonia such as triethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. Can be used. Considering the volatility problem and the problem of remaining in the coating film when it is turned into a coating film, it is better to select it according to the application.
  • aqueous dispersion power capable of taking a publicly known method can be used.
  • hot water can be added and dispersed in water after dissolving in a high-boiling organic solvent such as butylcerosolve.
  • polar solvents such as butyl cellosolve, methyl ethyl ketone, isopropyl alcohol It can be directly dissolved / dispersed in a mixed solvent of water.
  • a solvent having a boiling point lower than that of water is used for dissolution / dispersion, it is possible to obtain a completely water-based water dispersion by distilling off the organic solvent.
  • a resin melt is produced by melt-kneading a copolyester resin and, if necessary, a water retention agent, a dispersion aid, etc., using a pressure kneader, heating 3-roll, twin-screw extrusion kneader, And a production method in which it is heated to a temperature equal to or higher than the melting temperature of the copolymerized polyester resin, and dispersed in a molten state in a heated aqueous medium containing a basic compound, if necessary under pressure, by mechanical means.
  • a pressure kneader heating 3-roll, twin-screw extrusion kneader
  • Neutralization of carboxyl groups is not limited to this method.
  • the resin melt is dispersed mechanically in an aqueous medium.
  • the aqueous medium may be pressurized as necessary during heating.
  • pressurization is not necessarily required, but when the melt temperature is 100 ° C or higher, it is necessary to pressurize so that the aqueous medium does not boil.
  • Examples of the organic solvent used in the present invention include n-butanol, isopropyl alcohol, diacetone alcohol, 2-ethylhexanol, methyl ethyl ketone, acetonitrile, dimethylacetamide, dimethylformamide, and n methyl.
  • isopropyl alcohol, butylcetosolve, propylene glycol monopropinoreateol, propyleneglycololebutynoreatenore and butinorecanolebitonore are particularly preferred.
  • the aqueous dispersion is heated to the boiling point of the organic solvent or higher. It is necessary to volatilize and remove organic solvents. If this is not the case, these organic solvents should be contained in the polyester resin aqueous dispersion.
  • the hybrid resin aqueous dispersion of the present invention will be described below.
  • the acid value of the hybrid resin of the copolymer resin and / or acrylic resin used in the hybrid resin aqueous dispersion of the present invention and a polyurethane resin containing the copolymer polyester resin as a constituent component is 20 to 400 mg KOH / g, preferably 25 to 350 mg KOHZg, more preferably ⁇ is 30 to 300 mg KOH, more preferably ⁇ is 35 to 250 mg KOHZg.
  • the resin acid value is less than 20 mgK0H / g, the dispersion stability becomes poor when an aqueous dispersion is obtained.
  • it exceeds 400 mgKOHZg the water resistance of the coating film obtained from the resin dispersion will deteriorate, and it will be unusable.
  • the acid value of the hybrid resin is a value measured with an aqueous dispersion and converted to the weight of the resin solid content.
  • the weight of the copolyester resin and Z or the polyurethane resin containing the copolyester resin as a constituent component is 10% or more and 90% or less, preferably 15% or more and 88% or less. More preferably, it is 20% or more and 86% or less, and further preferably 25% or more and 85% or less. If the weight of the copolyester resin and / or the polyurethane resin containing the copolyester resin as a constituent component is less than 10%, the resulting coating film becomes inflexible. The advantages of using a hybrid resin are lost, such as the amount of functional groups that can be introduced with a small amount.
  • the copolyester resin and / or the polyurethane resin containing the copolyester resin as a constituent component is hydrophobic and imparts a water dispersion function in the acrylic resin portion, the stability of the resulting water dispersion is improved. It will be damaged.
  • High molecular weight copolyester resin and Z or polyurethane resin containing the copolyester resin as a constituent component and high molecular weight acrylic resin are chemically and directly and / or using a crosslinking agent. How to join
  • a functional group capable of reacting with a monomer forming an acrylic resin is introduced into a high molecular weight copolyester resin and polyurethane resin containing Z or the copolyester resin as a constituent component, and in the presence thereof.
  • Method for polymerizing acrylic resin (3) The ability to polymerize copolyester resins in acrylic resin emulsions in water, etc. The physical properties of copolyester resins and / or polyurethane resins containing such copolyester resins as structural components are vital
  • the method (2) is suitable for hybridizing an acrylic resin for imparting functionality.
  • copolyester resin used in the present invention various raw materials can be used as long as they are within the above range.
  • dicarboxylic acid component of the copolyester resin examples include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like as aromatic dicarboxylic acid.
  • Aliphatic dicarboxylic acids include succinic acid
  • Adipic acid Adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and the like.
  • alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid. Examples thereof include acids, 1,2-cyclohexanedicarboxylic acid and acid anhydrides thereof.
  • P-hydroxybenzoic acid p- (2 hydroxyethoxy) benzoic acid, or hydroxycarboxylic acids such as hydroxybivalic acid, ⁇ -butyral rataton, and ⁇ -force prolataton can be used as necessary.
  • a dicarboxylic acid component of the copolyester resin a dicarboxylic acid containing a polymerizable unsaturated double bond can be used.
  • examples thereof include fumaric acid and maleic acid as monounsaturated dicarboxylic acids.
  • examples of the acid, maleic anhydride, itaconic acid, citraconic acid, and alicyclic dicarboxylic acids having an unsaturated double bond include 2,5 norbornane dicarboxylic acid anhydride and tetrahydrophthalic anhydride.
  • the amount of dicarboxylic acid containing a polymerizable unsaturated double bond is based on the total acid component. 2 to 7 mol%.
  • the amount of dicarboxylic acid containing a polymerizable unsaturated double bond is less than 2 mol%, it is difficult to efficiently graft the radically polymerizable monomer onto the copolymerized polyester resin in an aqueous medium.
  • the dispersed particle size tends to increase, and the dispersion stability tends to decrease.
  • the dicarboxylic acid containing a polymerizable unsaturated double bond exceeds 7 mol%, This is not desirable because the viscosity increases too much in the later stage of the chemical reaction, preventing the uniform progress of the reaction.
  • the glycol component of the copolyester resin has an aliphatic glycol of 2 to 10 carbon atoms and / or a carbon number power of ⁇ : a force consisting of an alicyclic glycol of 12 and Z or an ether bond-containing glycol.
  • 2 to 10 aliphatic glycols include ethylene glycol, 1,2_propylene glycol, 1,3_propanediol, 1,4_butanediol, 1,5_pentanediol, neopentyl glycol 1,6-hexanediol, 3-methinole 1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-propanediol, hydroxypivalic acid neopentyl glycol ester, dimethyoxyl heptane, etc.
  • Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol, Mention may be made of Rodez Kanji methanol, etc.
  • the glycol containing ether bond is obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of diethylene glycol, triethylene glycol, dipropylene glycol, and bisphenols.
  • examples of the glyconoles that can be used include 2,2-bis (4-hydroxyethoxyphenyl) propane.
  • known polyols can be used.
  • polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol
  • polymer polyols of rataton compounds and polyether polyols such as polyethylene adipate
  • polycarbonate polyols polycarbonate polyols
  • polyols obtained by reacting dicarboxylic acid compounds and diamine compounds with epoxy compounds can also be used.
  • Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used as necessary.
  • 0 to 5 mol% of tricarboxylic or higher polycarboxylic acid and / or polyol can be copolymerized with S, and trifunctional or higher polycarboxylic acid.
  • Phosphorus trimethyl mouthfuls, trimethylol propane, pentaerythritol, etc. are used.
  • trifunctional or higher polycarboxylic acids or polyols 0-5 mol% relative to the total acid component or total glycol Ingredient desirably but are copolymerized in the range of 0 to 3 mol%, 5 mol 0 If it exceeds 0 , sufficient workability can be imparted.
  • a sulfonic acid group or a phenolic hydroxyl group may be introduced, if necessary.
  • a sulfonate group is introduced into the molecule, for example, 5_Na sulfoisophthalic acid, 5—ammonium sulfoisophthalic acid, 4-Na sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, 2_Na Sulfoterephthalic acid, 5-K sulfoisophthalic acid, 4-K sulfoisophthalic acid, 2-K sulfoisophthalic acid, Na sulfosuccinic acid and other sulfonic acid metal salt compounds or sulfonic acid amine salt compounds, sulfonic acid Na salt included Bisphenol A-alkylene oxide adducts, sulfonic acid K-base-containing hydroquinone alkylene oxide adducts, and the like can be copolymerized.
  • a phenolic hydroxyl group is introduced into the molecule, for example, 5-hydroxyisophthalic acid, diphenolic acid or the like can be copolymerized.
  • antioxidant added to the copolyester resin of the present invention examples include phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, and the like.
  • Phenolic antioxidants include isoamyl gallate, butylated hydroxydiazole, butylated hydroxytonolene, 4,4'-butyldenbis (3-methyl-6-tert-butylphenol), 2,4-dioctylthio -6- (4'-hydroxy-3 ', 5'-di-t-butylanilino)-1,3,5-triazine, dodecyl gallate, 2,6-di-t_butyl -4-hydroxymethyl ester Nol, Pro-Methyl catechuate, 2,2'-methylene (bis-4-methyl-6_t-butylphenol), Octadecyl-3- (4-hydroxy-3,5-di-t_butylphenyl) propionate, Octyl gallate , Propyl gallate, 4,4 'isopropylidenebis (2-isopropylphenol), sorbic acid, potassium sorbate, tetrakis [methylene (3-tert
  • 2,4,6-tri-1-butylphenol 4-hydroxymethyl-2,6-di-t-butylphenol, 2,5-di-t-butylhydroquinone, 2,2'-methylene are preferable.
  • Phosphorous antioxidants include tri (noylphenyl) phosphite, triphenyl phosphite, diphenylisodecyl phosphite, trioctadecyl phosphite, tridecyl phosphite, diphenyl decyl phosphite, 4,4'-butylidene-bis (3-methyl _6_t-butylphenyl ditridecyl phosphite), distearyl-pentaerythritol diphosphite, trilauryl trithiophosphite, or their derivatives, etc. Or derivatives thereof.
  • Amine-based antioxidants include 1,3-dimethylbutyl-N-phenyl-n_phenylenediamine, ⁇ , ⁇ '-di (1,4-dimethylpentyl) -n-phenylenediamine, N-phenyl- ⁇ '-isopropyl- ⁇ -phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, phenylthiazine, phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, ⁇ , ⁇ '-Diphenyl- ⁇ -phenylenediamine, ⁇ , ⁇ '-Di-beta-naphthyl- ⁇ -phenylenediamine, ⁇ ⁇ ⁇ -cyclohexyl ⁇ '-phenyl- ⁇ -phenylenediamine, aldol-alpha-naphth
  • phenyl-beta-naphthylamine preferred are phenyl-beta-naphthylamine, phenothiazine, ⁇ , ⁇ '-diphenyl- ⁇ -phenylenediamine, -di-betanaphthyl- _phenylenediamine, ⁇ -cyclohexyl- ⁇ '-phenyl- ⁇ -Fenylenediamine, ananolol-alpha-naphthylamine, 2,2,4-trimethyl-1,2-dihydred quinoline polymer, or derivatives thereof.
  • Sulfuric antioxidants include thiodipropionic acid, dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristino thiodipropionate, distearino re-beta, beta, -Thiodibutyrate, thiobis (beta-naphthol), thiobis ( ⁇ -phenyl-beta-naphthylamine, 2-mercaptobenzothiazole, 2_mercaptobenzozoimidazole, dodecyl mercaptan, tetramethi Examples include thiocarbamate, nickel isopropyl xanthate, dilauryl thiodipropionate, and the like, or derivatives thereof.
  • thiobis N-phenyl-beta-naphthylamine, 2_mercaptobendazole, 2_mercaptobenzazoimidazole, tetramethylthiuram disulfide, nickel isopropyl xanthate, etc., or their derivatives are preferable. It is done.
  • Nitro compound-based antioxidants include 1,3,5_trinitrobenzene, p-nitrosodiphenylamine, p-nitrosodimethylaniline, 1-black-mouth-3_nitrobenzene, 0-dinitrobenzene M-dinitrobenzene, p-dinitrobenzene, p-nitrobenzoic acid, nitrobenzene, 2-nitro-5-cyanothiophene, etc., or derivatives thereof.
  • inorganic compound-based antioxidant IJ include FeCl, Fe (CN), CuCl, CoCl, Co (C10), Co (NO), and Co (SO).
  • phenol-based antioxidants and amine-based antioxidants preferably have a melting point of 120 ° C or higher and a molecular weight of 200 or higher, which are preferable in terms of thermal stability. More preferably, the melting point is 170 ° C or higher.
  • the amount of the antioxidant used is from 10 to 5000 ppm, preferably from 100 to 2000 ppm, more preferably from 100 to: OOOOppm with respect to the effect of the moon. If it exceeds 5000 ppm, the reaction utilizing the double bond in the polyester may be hindered. Below lOppm, there is a risk of gelation with low thermal stability.
  • the molecular weight of the obtained copolyester resin can be known as a substitute by measuring the reduced viscosity.
  • the reduced viscosity of the resin is from 0.:! To 2.0 dl / g, preferably from 0.2 to: 1.5 dl / g, more preferably from 0.3 to: 1.3 dl / g. 0. Less than ldlZg, the desired mechanical properties cannot be obtained.
  • a polyurethane-acrylic hybrid resin is produced by grafting a polymerizable monomer containing a double bond to a polyurethane resin, the resin is obtained by polymerizing the above-mentioned polyester polymerization monomers.
  • the molecular weight of polyurethane resin is 5000-: 100,000
  • urethane bond content is 500-4000 equivalent / 10 6 g
  • polymerizable double bond content The amount is preferably 1.5 to 30 on average per molecule.
  • polyether polyol polyolefin polyol, etc. can be used with these polyester polyols as needed.
  • the organic diisocyanate compound (b) used in the present invention includes hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-1,4'-biphenol. Two range
  • examples of the chain extender (c) having an active hydrogen group used as necessary to obtain a polyurethane resin include ethylene glycol, propylene glycol, neopentyl glycol, 2, 2- Examples include glycols such as jetyl-1,3-propanediol, diethylene glycol, spiroglycol and polyethylene glycol, and amines such as hexamethylenamine, propylenediamine and hexamethylenediamine.
  • the polyurethane resin used in the present invention comprises a polyester polyol (a), an organic diisocyanate (b), and, if necessary, a chain extender (c) having an active hydrogen group. It is necessary to be a polyurethane resin obtained by reacting at a compounding ratio of 0.8 to 1.3 (equivalent ratio) in the ratio of active hydrogen group / isocyanate group).
  • the polyurethane resin used in the present invention is produced by a known method in a solvent at a reaction temperature of 20 to 150 ° C in the presence or absence of a catalyst.
  • a solvent used at this time For example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used.
  • the catalyst for promoting the reaction amines, organotin compounds and the like are used.
  • polyester polyol and organic diisocyanate in a molten state.
  • the polyurethane resin used in the present invention has an average of 1.5 to 30 polymerizable double bonds per polyurethane chain, preferably 2 to 20 in order to increase the efficiency of the graph H reaction by the radically polymerizable monomer. It is necessary to contain 3 to 10 pieces, more desirably.
  • An unsaturated dicarboxylic acid such as fumaric acid, itaconic acid or norbornene dicarboxylic acid is incorporated into the polyester polyol.
  • a glycol containing an aryl ether group is used.
  • a functional group capable of reacting with a monomer forming an acrylic resin is introduced into a polyurethane resin containing the high molecular weight copolymer polyester resin of the present invention and / or the copolymer polyester resin as a constituent component
  • a polymerizable monomer a monomer for forming an acrylic resin
  • acrylic acid, methacrylic acid esters such as methyl acrylate, ethyl acrylate, acrylic Isopropylenolic acid, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxychetyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Isobutyl acid, n_hexyl methacrylate, methacryl Lauryl me
  • methacrylic acid esters such as methyl acrylate, ethy
  • the polyester-based graft polymer is obtained by graft polymerization of a radically polymerizable monomer to a polymerizable unsaturated double bond of a copolymerized polyester resin and Z or a polyurethane resin containing the copolymerized polyester resin as a constituent component. Can be obtained efficiently.
  • a radical initiator and a radical initiator are generally prepared by dissolving a copolymer polyester resin and Z or a polyurethane resin containing the copolymer polyester resin as a constituent component in an organic solvent. It is carried out by reacting a polymerizable monomer mixture. After completion of the grafting reaction, the reaction product contains not only the graft polymer between the desired polyester-radical polymerizable monomer mixture but also the ungrafted polyester and the radical polymer not grafted with the polyester. The force considered to be contained When the ratio of the non-grafted polyester and the non-grafted radical polymer in the reaction product is low, a dispersion with good stability cannot be obtained.
  • a copolyester resin and a polyurethane resin containing Z or a copolyester resin as a constituent component and a solvent are charged into the reactor, and the temperature is increased with stirring to dissolve the resin.
  • Copolyester resin and / or copolymerization thereof The weight ratio between the polyurethane resin containing the polyester resin as a constituent and the solvent is 70/30, preferably 30/70.
  • the weight ratio is adjusted to a weight ratio at which the reaction can be carried out uniformly during the polymerization step, taking into account the solvent solubility of the copolymerized polyester and radical polymerizable monomer described later.
  • the graft reaction temperature is preferably in the range of 50 ° C to 120 ° C.
  • organic peroxides and organic azo compounds can be used as the radical polymerization initiator used in the present invention.
  • benzoyl peroxide, t-butyl oxypivalate as organic peroxides, 2.2'-azobisisobutyronitrile, 2.2'-azobis (2.4-dimethylvaleronitrile) as organic azo compounds, etc. Can be illustrated.
  • the selection of the radical initiator compound needs to be performed in consideration of the radical generation rate at the reaction temperature of the compound, that is, the half-life. In general, it is desirable to select a radical initiator that has a half-life value at that temperature in the range of 1 minute to 2 hours.
  • the amount of radical initiator used for carrying out the H-reaction must be at least 0.2% by weight, preferably 0.5% by weight or more, based on the radical polymerizable monomer. is necessary.
  • Addition of a chain transfer agent such as octyl mercaptan or mercaptoethanol is also used as needed for graft chain length control. In that case, it is desirable to add in the range of 0 to 5% by weight with respect to the radical polymerizable monomer.
  • the Grafty reaction solvent for carrying out the present invention is preferably composed of an aqueous organic solvent having a boiling point of 50 to 250 ° C.
  • the aqueous organic solvent means a solvent having a solubility in water at 20 ° C of at least 10 g / L or more, preferably 20 g / L or more. Those having a boiling point exceeding 250 ° C are not suitable because they cannot be sufficiently removed even by high-temperature baking of a coating film having a too slow evaporation rate.
  • the first group of aqueous organic solvents that dissolve the polymer relatively well include esters such as ethyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclic ethers such as tetrahydrofuran, dioxane, 1,3-dioxolane, glycol ethers such as ethylene glycol dimethyloleatenore, propylene glycol monoremethinore tenole, propylene glycol monorepropinore etherenore, ethylene glyconoreethinoreatenore, ethylene glycol monolebutinoreene tenole
  • Second group of aqueous organic solvents examples include water, lower alcohols, lower carboxylic acids, and lower amines. Particularly preferred for the practice of the present invention are alcohols having 1 to 4 carbon atoms and dallicols.
  • the grafting reaction is performed with a single solvent, only one of the first group of aqueous organic solvents can be selected.
  • a mixed solvent there are a case where plural kinds are selected only from the first group of aqueous organic solvents and a case where at least one kind of the first group of aqueous organic solvents is selected and at least one kind is added thereto from the second group of aqueous organic solvents.
  • the graft polymerization reaction solvent is a single solvent from the first group of aqueous organic solvents and a mixed solvent of one kind each of the first group and the second group of aqueous organic solvents.
  • the reaction can be performed.
  • there are differences in the progress of the grafting reaction the appearance and properties of the grafting reaction product and the aqueous dispersion derived therefrom, and a mixed solvent consisting of each of the first group and second group aqueous organic solvents. I prefer to use it.
  • tetrahydrofuran which belongs to the first group of aqueous organic solvents and has the strongest dissolving power for the polyester resin, the monomer mixture containing the carboxyl group-containing polymerizable monomer, and the polymer derived therefrom.
  • the graph H ⁇ reaction proceeds with a transparent appearance throughout.
  • the viscosity of the system gradually increases and may increase significantly later in the grafting reaction and may not be able to continue.
  • the reaction product is a transparent rubber-like material with the solvent taken in, and forms a gel or gel that does not dissolve in a strong solvent. In order to avoid this, it is necessary to drastically reduce the resin concentration, which is not a reasonable method for manufacturing.
  • the first group of aqueous organic solvent strength methylethyl ketone was selected
  • the second group of aqueous organic solvent strength isopropyl alcohol was selected, and both were mixed at a weight ratio of 75Z25.
  • the solubility of the copolyester is adjusted, the same polyester resin, the same radical polymerizable monomer composition ratio, the same polyester / radical polymerizable monomer ratio, the same as in the case of tetrahydrofuran are used. Even when the reaction is carried out with resin solids, neither thickening nor gelation of the system is observed as the reaction proceeds. Moreover, a favorable aqueous dispersion is given by subsequent aqueous formation. This shows that the use of a mixed solvent system is a rational process that can increase the resin solids concentration during production and reduce the amount of organic solvent used during production.
  • the copolyester molecular chains are in a state of extended chains, while in the mixed solvents of the first group / second group, they are in a state of entangled in the form of small threads. It was confirmed by measuring the viscosity of the copolyester in these solutions. It is effective in preventing gelation by adjusting the dissolved state of the copolyester to cause intermolecular crosslinking. High efficiency grafting and gelling suppression can be achieved in the latter mixed solvent system.
  • the weight ratio of the mixed solvent of the first group / second group is more desirably in the range of 95Z5 to 10Z90, more desirably 90ZlO to 20/80, and most desirably 85Zl5 to 30/70.
  • the optimum mixing ratio is determined according to the solubility of the polyester used.
  • the grafted reaction product according to the present invention is preferably neutralized with a basic compound.
  • a basic compound By neutralization, stable fine particles having an average particle diameter of 500 nm or less can be easily obtained. Can be dispersed in water.
  • the basic compound ammonia, organic amines, etc., which are desirable as compounds that volatilize when forming a coating film or baking and curing with a curing agent, are suitable.
  • Examples of desirable compounds include triethylamine, ⁇ , ⁇ -jetylethanolamine, ⁇ , ⁇ -dimethylethanolamine, aminoethanolamine, ⁇ -methyl- ⁇ , ⁇ -diethananolamine, isopropylamine, iminobis Propylamine, Ethylamine, Jetylamine, 3_Ethoxypropylamine, 3-Gethylaminopropylamine, sec-Butylamine, Propylamine, Methylaminopropylamine, Dimethylaminopropylamine, Methyliminobispropylamine, Examples include 3-methoxypropylamine, monoethanolamine, diethanolamine, and triethanolamine.
  • the basic compound has a PH value of 5.0 to 9.0 depending on the carboxyl group content contained in the graft-i reaction product, at least by partial neutralization or complete neutralization. It should be used as a range.
  • the solvent contained in the Grafty soot reaction product is removed in advance by using an extruder under reduced pressure, etc., and the Grafty reaction product in the form of a melt or solid (pellet, powder, etc.) Can be poured into water containing a basic compound and stirred under heating to prepare an aqueous dispersion.
  • water containing a basic compound is immediately prepared after completion of the graph H ⁇ reaction.
  • a method one'pot method in which an aqueous dispersion is obtained by continuing heating and stirring is further desirable.
  • the boiling point of the solvent is 100 ° C or less, the solvent used in the Darafutohi reaction can be easily removed partly or entirely by distillation.
  • the aqueous dispersion produced according to the present invention has a solid content concentration of 20 to 60% by weight, and can be used after diluting with water if necessary.
  • the aqueous dispersion according to the present invention is used as a binder for paints, inks, coating materials, adhesives and the like, or as a processing agent for fibers, vinylomes and paper products.
  • a high degree of water resistance can be expressed by blending a crosslinking agent (curing resin) and baking and curing.
  • the crosslinking agent include phenol formaldehyde resin, amino resin, polyfunctional epoxy compound, polyfunctional isocyanate compound, various block isocyanate compounds, and polyfunctional aziridine compound.
  • phenol resins include formaldehyde condensates of alkylated phenols and talesols. Specifically, alkylation (methyl, ethyl, propyl, isopropyl, butynole) phenol, p-tert-amylphenol, 4, 4'-sec-butylidene phenol, p-tert-butinolev phenol, 0— , m-, p-cresolenoleol, p-cyclohexenolephenol, 4,4'_isopropylidenephenol, p_nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl 0_cresol, Examples include formaldehyde condensates such as p-phenylphenol and xylenol.
  • Examples of the amino resin include formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkyl ether compounds of these alcohols having 1 to 6 carbon atoms.
  • Specific examples include methoxylated methylol urea, methoxylated methylol N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like.
  • Examples of the epoxy compound include diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of hydrogenated bisphenol A and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester , P-oxybenzoic acid diglycidyl ester, tetrahydride phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidino estenole, adipic acid diglycidino lesenore, sebacic acid diglycidino lesenore, ethylene Glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and Polyalkylene glycol diglycidyl
  • the isocyanate compounds include aromatic and aliphatic diisocyanates and polyisocyanates having a valence of 3 or more, and may be either low molecular compounds or high molecular compounds.
  • excess amounts of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylol propane, glycerin, sonorebitole, ethylenediamine, monoethanolamine, diethylanolamine, triethanolamine, or various polyesters.
  • terminal isocyanate group-containing compounds obtained by reacting terpolyols, polyether polyols, polymer active hydrogen compounds of polyamides and the like.
  • the isocyanate compound may be a blocked isocyanate.
  • Isocyanate blocking agents include, for example, phenols such as phenol, thiophenol, methylthiophenol, cresonole, xylenore, resonoresinole, nitrophenol, and black mouth phenol, etc., acetooxime, methyl ethyl ketoxime, Oximes such as xanone oxime, alcohols such as methanol, ethanol, propanol and butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, t-butanol and t-pentanol.
  • tertiary alcohols epsilon - Kapuroratatamu, [delta] one Bareroratatamu, I one Buchiroratatamu, Ratatamu such as ⁇ one propyl rata Tam and the like, other aromatic Amin of any kind, imides, ⁇ cetyl acetone, Aseto acetate S. Le, active Mechireni ⁇ of malonic acid Echiruesuteru, mercaptans, imines, ureas, and also such Jiariru compounds sodium bisulfite.
  • the blocked isocyanate is obtained by subjecting the above isocyanate compound, the isocyanate compound and the isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.
  • the cross-linking agent is blended as follows: (1) When the cross-linking agent is aqueous, it is dissolved or dispersed directly in the aqueous dispersion. Use a method in which a cross-linking agent is added before or after conversion to coexist with polyester in the core. It can be arbitrarily selected depending on the type and properties of the crosslinking agent. These crosslinking agents can be used in combination with a curing agent or an accelerator.
  • the curing reaction is generally carried out at a temperature of 60 to 250 ° C. depending on the type of curing agent in which 5 to 40 parts (solid content) of a curing resin is blended with 100 parts (solid content) of the aqueous dispersion of the present invention. It is performed by heating in the temperature range for about 1 to 60 minutes. If necessary, a reaction catalyst and a promoter are also used in combination.
  • the aqueous dispersion of the present invention can contain pigments, dyes, various additives and the like.
  • the aqueous dispersion of the present invention can be used by mixing with other aqueous resins and aqueous dispersions, and the processability can be improved.
  • paints, inks, coating agents, adhesives, and various processing agents based on the aqueous dispersion according to the present invention are excellent in redispersibility, so that the dip coating method, the brush coating method, Applicable to all of the coat coating method, spraying method, and various printing methods.
  • the polyester resin aqueous dispersion, No. and hybrid resin aqueous dispersion obtained by the present invention can be adjusted to viscosity and viscosity suitable for workability by using various thickeners.
  • nonionic ones such as methylcellulose and polyalkylene glycol derivatives, and polyanilates, alginates and other anionic ones are preferred.
  • the water dispersion of polyester resin, the aqueous dispersion of hybrid resin, and the hybrid resin obtained by the present invention can be further improved in coating properties by using various surface tension adjusting agents.
  • the addition amount is preferably limited to 1 wt% or less, more preferably 0.5 wt%, relative to the resin.
  • the polyester resin aqueous dispersion, noble and hybrid resin aqueous dispersion obtained by the present invention are known inorganic pigments such as titanium oxide and silica, various dyes at the time of production or in the obtained aqueous dispersion.
  • known additives such as a surface smoothing agent, an antifoaming agent, an antioxidant, a dispersant, and a lubricant may be blended.
  • the polyester resin water dispersion, the hybrid resin, and the hybrid resin water dispersion obtained by the present invention can be added with various ultraviolet absorbers, antioxidants, and light stabilizers depending on the application.
  • various ultraviolet absorber various organic types such as benzotriazole type, benzophenone type, triazine type, and inorganic type such as zinc oxide can be used.
  • acid As the inhibitor hindered phenols, phenothiazines, nickel compounds, etc., generally used for polymers and various types can be used.
  • the ability to use various types of light stabilizers for polymers is particularly effective for hindered amines.
  • the copolymer polyester resin was subjected to ifi-NMR analysis using a nuclear magnetic resonance analyzer (NMR) dimini-200 manufactured by Varian, in a heavy chloroform solvent, and determined from its integration ratio. After the polycondensation reaction, the copolyester resin was broken under a nitrogen atmosphere, and after decompression, a small amount of the molten copolyester resin obtained was taken out of the reaction kettle and cooled to measure. Provided.
  • NMR nuclear magnetic resonance analyzer
  • 0.1 g of the resin was dissolved in 25 cm 3 of a mixed solvent of phenol / tetrachloroethane (mass ratio 6/4) and measured at 30 ° C. using an Ubbelohde viscometer.
  • polyester resin 2 g was dissolved in 20 ml of black mouth form, titrated with 0.1 N KOH ethanol solution, and the acid value was determined as the neutralization point with the discoloration point of phenolphthalein solution (mgK ⁇ H / g)
  • the acid value of the resin was calculated as the total weight of (1) carboxyl group, phenolic hydroxyl group and (2) sulfonic acid group (mgKOHZg)
  • the filtration time exceeds 1 day, the content of fine foreign matter insoluble in the copolymer polyester resin will increase, and the filter will become clogged during filtration of the copolymer polyester resin in the polymerization process and molding process.
  • the power that is connected to S is favorable. Further, it is not preferable because it leads to poor adhesion due to a decrease in wettability to the adherend.
  • the resin was visually judged as a plate having substantially the same thickness.
  • the resin aqueous dispersion lg was dissolved in 30 ml of dioxane, titrated with a 0.1N KOH ethanol solution, and the acid value was determined as the neutralization point using the discoloration point of the phenolphthalein solution (mg KOHZg). However, it calculated with the value converted per resin solid content lg in an aqueous dispersion.
  • the prepared aqueous dispersion was allowed to stand at room temperature for 1 week and visually judged.
  • the prepared resin water dispersion was applied onto a PET film and dried with a hot air dryer at 120 ° C. for 2 hours to obtain a resin layer having a thickness of about 10 ⁇ m.
  • the resin together with the PET film was left in water at 25 ° C for 4 hours, and the change in the resin layer was visually judged.
  • an aluminum compound-only catalyst (C) In the case of an aluminum compound-only catalyst (C), it showed a good appearance with little coloration, except that there were a few foreign substances with slightly lower polymerization activity than the composite systems (A) and (B).
  • the antimony polymerization catalyst (D) was cloudy in addition to coloring.
  • the titanium-based catalyst (E) is markedly colored in the resulting resin, and the tin-based polymerization catalyst (F) is relatively less colored, but like the antimony-based polymerization catalyst, I want polyester.
  • Resins of the present invention and comparative resins (H) to ( ⁇ ) were synthesized in the same manner as in Example 4 except that various monomers shown in Tables 2 and 3 were used instead of the monomers used in Example 4.
  • Tables 2 and 3 show the composition and characteristic values of the obtained resin.
  • Copolyester resin H 100 parts by weight, isopropyl alcohol 100 parts by weight, ion exchanged water 1 15 parts by weight, ammonia water (28%) 3 parts by weight are charged into a reaction can equipped with a stirrer, condenser and thermometer. The temperature was raised to 70 ° C. while stirring at 50 rpm. The resin was completely dispersed by stirring for 3 hours. The internal temperature of the reaction vessel was cooled to room temperature, and further filtered through a 200 mesh filter to obtain a resin water dispersion H.
  • Copolymerized polyester resin I 100 parts by weight, isopropyl alcohol 60 parts by weight, triethylamine 7.8 parts by weight and ion-exchanged water 170 parts by weight were charged into a sealed glass container (Primics Co., Ltd., TK Robomix). 7000pp using a disper Stir at m. The temperature was gradually raised and stirring was continued at 70 ° C for 30 minutes. Thereafter, the stirring speed was reduced to 350 Oppm, cooled to room temperature, and filtered through a 300 mesh filter to obtain Resin Water Dispersion I.
  • Copolymerized polyester resin J 100 parts by weight, isopropyl alcohol 60 parts by weight, ammonia water (28%) 4 parts by weight and ion exchange water 170 parts by weight in a sealed glass container (Primics Co., Ltd., TK Robotics)
  • the mixture was stirred and stirred at 7000 ppm using a homodisper.
  • the temperature was gradually raised and stirring was continued at 70 ° C for 30 minutes. Thereafter, the stirring speed was lowered to 350 Oppm, cooled to room temperature, and filtered through a 300 mesh filter, to obtain a resin water dispersion J.
  • copolyester resin K 100 parts by weight was melt-kneaded at 150 ° C using a twin-screw extruder kneader to produce a resin melt, and a liquid consisting of 30 parts by weight of triethanolamine and 300 parts by weight of distilled water was gradually added. The resulting mixture was kneaded while being added to obtain an aqueous dispersion, further cooled to room temperature, and then filtered through a 200 mesh filter to obtain an aqueous resin dispersion K.
  • Copolyester resin L 100 parts by weight, normal ptylcetone solve 20 parts by weight, triethanolamine 20 parts by weight were charged into a reaction vessel equipped with a stirrer, condenser and thermometer, and stirred at 50 rpm, 130 ° The temperature was raised to C. By further stirring for 30 minutes, the resin was completely dispersed. Cool the reaction can to 90 ° C, add 200 parts by weight of 80 ° C ion exchange water, stir for 1 hour, cool to room temperature, and filter with a 200 mesh filter to disperse the resin water. Body L was obtained.
  • a water dispersion G was produced in the same manner as that for the production.
  • Resin M of Comparative Example 4 has an acid value of less than 3 mg KH / g.
  • the resin is dispersed in water, but stability over time cannot be maintained.
  • the resin N of Comparative Example 5 can stably produce an aqueous dispersion having an acid value greater than 110 mgKH / g, but is not suitable for practical use because the resulting coating film has poor water resistance.
  • Resin O of Comparative Example 6 is based on phenolic hydroxyl groups in the resin acid value. The resin itself made of a large amount of resin, especially an aluminum-based catalyst with a high coloration of the coating film obtained by drying from a water-dispersed resin, will be reduced.
  • Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Copolyester resin G H [J K and polyvalent carboxylic acid component ⁇ Rephthalic acid 50 48 50 52 48
  • Trilitnic acid 8 2 3 Pyromellitic acid 1 3 2 Polyhydric alcohol component Ethylene alcohol Recall 50 50 50 50
  • Polyester resins (BB), (CC), (DD), (EE), and (FF) were obtained by a method according to the synthesis of the copolymer polyester resin (AA) of the present invention.
  • Table 4 shows the composition and characteristic values of each obtained copolyester resin.
  • titanium-based catalyst (EE) is considered to be one in which unsaturated bonding groups reacted during the polymerization, in which the obtained resin was markedly colored and the gel fraction was large. Titanium-based catalysts have a high polyester polymerization ability, but they also contribute to the gelation reaction. In addition, tin-based polymerization catalysts (FF) have relatively little coloration, but like antimony-based polymerization catalysts, polyesters containing these are desired.
  • the aluminum compound-based catalyst has a good hue and has an effect of suppressing the Gerich reaction derived from the unsaturated group.
  • Urethane resins (HH), (II) and (JJ) were obtained by a method according to the synthesis of the urethane resin (GG) of the present invention.
  • Table 5 shows the composition and characteristic values of the obtained urethane resin.
  • the titanium-based catalyst JJ was obtained by the reaction of unsaturated bonding groups during the polymerization, in which the obtained resin was markedly colored and the gel fraction was large. It can be seen that the titanium-based catalyst has a large polyester polymerization ability, but also promotes the gelling reaction.
  • a water dispersion was prepared in the same manner as in Example 2a.
  • Table 6 shows the physical properties of the resulting water dispersion.
  • aqueous dispersion was prepared in the same manner as in Example la. However, when water was added, the resin did not disperse in water and precipitated. This is because in the polymerization stage of the polyester, the unsaturated bond was crushed due to thermal deterioration, so that the graft reaction could not be carried out sufficiently and a sufficient acid value could not be obtained for the aqueous dispersion.
  • Ethylene alcohol 50 50 Polyhydric alcohol Neohexyl glycol 50 55 50 50 50 Ingredients (mol 1 ⁇ 2) 2,2-bis (4-human'loxy I Toxif I
  • the copolymerized polyester resin of the present invention and the aqueous dispersion thereof, and the hybrid resin and the aqueous dispersion thereof do not contain heavy metals and tin, and the conventional antimony or titanium-based polymerization catalyst is used. It was less colored than the one used and had a good appearance. Furthermore, it was found that the obtained coating film was excellent in water resistance.
  • These copolymer polyester resin aqueous dispersions and hybrid resin aqueous dispersions of the present invention exhibit excellent properties in aqueous adhesives, aqueous coating agents, aqueous paint compositions and the like.

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Abstract

L'invention concerne une dispersion aqueuse de résine présentant une coloration limitée en raison d'une stabilité thermique médiocre mais ne contient que quelques substances étrangères provenant de l'aluminium. Cette dispersion aqueuse de résine est obtenue par l'utilisation d'une résine polyester copolymérisée ayant un indice d'acide de résine de 3-110 mgKOH/g ; ladite résine est obtenue en présence d'un catalyseur de polymérisation contenant au moins un composé de l'aluminium, ou en variante, par l'utilisation d'une résine hybride dont l'indice d'acide est de 20-400 mgKOH/g ; ladite résine est composée d'une résine acrylique et d'au moins une résine polyester copolymérisée obtenue en présence d'un catalyseur de polymérisation contenant au moins un composé de l'aluminium ou une résine de polyuréthane contenant la résine polyester copolymérisée comme constituant.
PCT/JP2007/062854 2006-06-30 2007-06-27 Dispersion aqueuse de résine polyester, dispersion aqueuse de résine hybride, et adhésif, matière de revêtement et matière de peinture les utilisant WO2008001795A1 (fr)

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JP2006182169A JP2008007719A (ja) 2006-06-30 2006-06-30 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
JP2006-182170 2006-06-30
JP2006182170A JP2008007720A (ja) 2006-06-30 2006-06-30 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
JP2006-182169 2006-06-30

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