WO2008001795A1 - Polyester resin aqueous dispersion, hybrid resin aqueous dispersion, and adhesive, coating material and painting material using them - Google Patents

Polyester resin aqueous dispersion, hybrid resin aqueous dispersion, and adhesive, coating material and painting material using them 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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French (fr)
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/en
Priority claimed from JP2006182170A external-priority patent/JP2008007720A/en
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Publication of WO2008001795A1 publication Critical patent/WO2008001795A1/en

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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

Disclosed is a resin aqueous dispersion which is suppressed in coloring due to poor thermal stability, while containing only a few extraneous substances which are derived from aluminum. This resin aqueous dispersion is obtained by using a copolymerized polyester resin having a resin acid value of 3-110 mgKOH/g and produced in the presence of a polymerization catalyst containing at least an aluminum compound, or alternatively by using a hybrid resin having an acid value of 20-400 mgKOH/g and composed of an acrylic resin and at least one of a copolymerized polyester resin produced in the presence of a polymerization catalyst containing at least an aluminum compound and a polyurethane resin containing the copolymerized polyester resin as a constituent.

Description

明 細 書  Specification
ポリエステル樹脂水分散体、ハイブリッド樹脂水分散体及びこれらを用い た接着剤、コーティング剤、塗料  Polyester resin water dispersion, hybrid resin water dispersion, and adhesives, coating agents and paints using these
技術分野  Technical field
[0001] 本発明は、スズィ匕合物、アンチモン化合物、ゲルマニウム化合物およびチタンィ匕合 物などのような金属重合触媒を用いず、主としてアルミニウム化合物からなる重合触 媒を用いたポリエステル樹脂水分散体、ポリエステル アクリルハイブリッド樹脂水分 散体及びこれらを用いたフィルム、布および金属用水性接着剤、水性コーティング剤 、水性塗料および製造方法に関する。  [0001] 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.
背景技術  Background art
[0002] 水性接着剤、水性コーティング剤、水性塗料は、 VOC規制とレ、う世の趨勢の要請 を受け開発が活発に行われている。これらの用途において用いられる樹脂としては、 フィルム、金属、布といった各種基材に対する幅広い接着性、耐熱性、耐候性、耐溶 剤性、顔料等各種添加剤の分散性等の性能が要求される。主としてチタン系重合触 媒 (特許文献 1、 2)、スズ系重合触媒 (特許文献 3)、アンチモン系重合触媒 (特許文 献 4)を用いた共重合ポリエステル系水分散体は、これらの要求性能のうち、良好な 接着性、耐熱性、耐候性、耐溶剤性を有するため、これらの特長を活かす分野で広 く利用されている。  [0002] Water-based adhesives, water-based coatings, and water-based paints have been actively developed in response to VOC regulations and the demands of the current trends. Resins used in these applications are required to have performance such as wide adhesion to various substrates such as films, metals, and cloth, heat resistance, weather resistance, solvent resistance, and dispersibility of various additives such as pigments. Copolymerized polyester-based aqueous dispersions mainly using titanium-based polymerization catalysts (Patent Documents 1 and 2), tin-based polymerization catalysts (Patent Document 3), and antimony-based polymerization catalysts (Patent Document 4) are required performances. Among them, they have good adhesion, heat resistance, weather resistance, and solvent resistance, and are widely used in the fields that make use of these features.
[0003] 特許文献 1 :特開 2005— 126619号公報  [0003] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2005-126619
特許文献 2：特開 2004— 292665号公報  Patent Document 2: Japanese Patent Application Laid-Open No. 2004-292665
特許文献 3 :特開 2005— 239869号公報  Patent Document 3: Japanese Patent Laid-Open No. 2005-239869
特許文献 4：特開 2004— 143326号公報  Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-143326
[0004] また、ポリエステル水分散体の樹脂分散性を安定性、長期の貯蔵安定性を付与す るために、さらに親水性のアクリル樹脂をグラフトすると効果があることが知られており (特許文献 5)、また架橋反応の反応点量を上げ緻密な効果塗膜を得るベぐポリエス テルに大量の官能基を導入する手段としてアクリル樹脂をポリエステルにグラフトする ことが有効であることが知られている（特許文献 6)。さらに、一度半乾燥したポリエス テル樹脂水分散体の再分散性能を上げるべく、疎水性ポリエステルに親水性ポリェ ステルをグラフトすることにより、力かるハイブリッド樹脂が水中でポリエステルをコア、 アクリルをシェルとしたコアシェル構造を取り、従来のポリエステル水分散体に比して 、大幅に再分散性が向上することが知られている（特許文献 7)。これらの発明におい ては、ポリエステル樹脂にアクリルグラフトの反応点として、不飽和結合を導入してい るが、チタン系触媒では重合活性が大きいため、導入された不飽和結合も熱的に不 安定でありゲルィ匕を起してしまう問題がある。ゲル化を抑制するために、大量の重合 安定剤を添加する必要があり、それらが樹脂の色相を大幅に低減するという問題が ある（特許文献 7)。またゲル化を抑制する手段として、一度高分子量のポリエステル を重合した後、フマル酸等の不飽和カルボン酸による解重合で不飽和基を導入する 試みがなされているが、分子量の低下、および分子量分布の制御が困難で、ポリエ ステル本来の可撓性を損ねてしまう（特許文献 5)。またポリエステル重合後、分子鎖 末端に、無水マレイン酸等の不飽和ジカルボン酸の無水物を付加する試みがなされ ているが、導入できる不飽和基の量が制限され、アクリルをハイブリッドする効果が薄 くなつてしまう（特許文献 6)。 [0004] Further, in order to impart stability and long-term storage stability of the resin aqueous dispersion of the polyester aqueous dispersion, it is known that grafting a hydrophilic acrylic resin further has an effect (Patent Documents). 5) In addition, it is known that grafting acrylic resin to polyester is effective as a means of introducing a large amount of functional groups into the polyester to increase the reaction site amount of the crosslinking reaction and obtain a dense effect coating film. (Patent Document 6). In addition, once semi-dried polyester In order to improve the re-dispersion performance of water dispersion of tellurium resin, hydrophilic polyester is grafted onto hydrophobic polyester, so that a powerful hybrid resin has a core-shell structure in which polyester is the core and acrylic is the shell in water. It is known that the redispersibility is greatly improved as compared with a polyester aqueous dispersion (Patent Document 7). In these inventions, unsaturated bonds are introduced into the polyester resin as reactive sites for acrylic grafting. However, since the titanium-based catalyst has a large polymerization activity, the introduced unsaturated bonds are also thermally unstable. There is a problem that causes gerui. 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).
特許文献 5 :特開平 9 216921号公報 Patent Document 5: JP-A-9 216921
特許文献 6 :特開 2004— 292751号公報 Patent Document 6: Japanese Unexamined Patent Application Publication No. 2004-292751
特許文献 7：特許第 3501234号公報 Patent Document 7: Japanese Patent No. 3501234
一方、従来の共重合ポリエステルの重合触媒としては、アンチモン系、チタン系、ゲ ノレマニウム系、スズ系などが知られている。し力 ながら、共重合ポリエステル系及び アクリルとのハイブリッド系水分散体の製造に関しては、これらの重合触媒種には、次 のような問題点が残されていた。  On the other hand, antimony-based, titanium-based, germanium-based, tin-based and the like are known as polymerization catalysts for conventional copolyesters. However, with respect to the production of aqueous dispersions of copolymerized polyesters and hybrids with acrylics, the following problems remain in these polymerization catalyst species.
(1)スズィヒ合物やアンチモン化合物等の重合触媒は重金属を含み、これらを含まな レ、ポリエステルが望まれてレ、ること。  (1) Polymerization catalysts such as suzuhi compounds and antimony compounds contain heavy metals, and should not contain these or polyesters.
(2)アンチモン化合物は、得られた共重合ポリエステル樹脂にくすみが見られること。 (2) The antimony compound is dull in the obtained copolymer polyester resin.
(3)チタン化合物を重合触媒として使用した場合、共重合ポリエステル樹脂の着色が あり、アジピン酸あるいはセバシン酸などの脂肪族ジカルボン酸などを共重合成分に 用いた場合は、耐熱性が劣るため樹脂の着色が著しぐ例えば白色塗料では、本来 の白色が得られないこと。また、透明な被着体を貼リ合わせる場合、接着層となる榭 脂の着色が問題となる場合があること。 (3) When a titanium compound is used as a polymerization catalyst, the copolymerized polyester resin is colored. When an aliphatic dicarboxylic acid such as adipic acid or sebacic acid is used as the copolymerization component, the resin is inferior in heat resistance. For example, with white paint, The white color cannot be obtained. In addition, when pasting transparent adherends, the coloring of the resin that becomes the adhesive layer may be a problem.
(4)ゲルマニウム化合物は上記重合触媒として有効に使用可能であるが、価格が著 しく高いこと。  (4) The germanium compound can be used effectively as the polymerization catalyst, but the price is extremely high.
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 力かる技術背景から、主としてアルミニウム化合物を重合触媒として用い、重合活 性が十分であり、得られた共重合ポリエステル樹脂の熱安定性不良に起因する着色 が抑制され、更にはアルミニウム由来の異物の少ない共重合ポリエステル水分散体 が求められている。 [0006] Because of the strong technical background, mainly an aluminum compound is used as a polymerization catalyst, the polymerization activity is sufficient, coloring due to poor thermal stability of the obtained copolyester resin is suppressed, and further, it is derived from aluminum. There is a need for an aqueous copolymerized polyester dispersion with less foreign matter.
また、共重合ポリエステル樹脂、および/または、そのポリエステルからなるウレタン 樹脂とアクリル樹脂とのハイブリッド樹脂の製造に当たって、アクリル樹脂をグラフトす る反応点となる不飽和結合を、共重合ポリエステル樹脂、および Zまたは、そのポリ エステルからなるウレタン樹脂に、安定にかつ色相を損ねることなぐ充分導入するこ とが可能であり、かつアルミニウム由来の異物の少なくすることが可能なアルミニウム 触媒を用いて、架橋剤等との高い反応性、高い接着性、高い加工性を有する、共重 合ポリエステルをベースにしてアクリルをハイブリッドした樹脂水分散体が求められて いる。  Further, in the production of a copolymerized polyester resin and / or a hybrid resin of urethane resin and acrylic resin made of the polyester, an unsaturated bond that becomes a reaction point for grafting the acrylic resin is introduced into the copolymerized polyester resin and Z Alternatively, 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.
課題を解決するための手段  Means for solving the problem
[0007] 発明者らは、こうした問題に鑑み、鋭意検討を重ねた結果、アルミニウム化合物から なる重合触媒および共重合ポリエステル、ポリウレタン、アクリルの各成分を下記のご とく特定することによって、重金属を含まず耐熱性に優れ、着色のない共重合ポリェ ステル系水分散体およびハイブリッド樹脂系水分散体が得られることを見出し本発明 に到達した。  [0007] In view of these problems, the inventors have made extensive studies and, as a result, specified the following components as a polymerization catalyst comprising an aluminum compound and copolymer polyester, polyurethane, and acrylic, thereby including heavy metals. The present inventors have found that copolymer polyester water dispersions and hybrid resin water dispersions having excellent heat resistance and no coloring can be obtained.
すなわち、本発明は、以下の特性を有するポリエステル樹脂水分散体、ハイブリッド 樹脂系水分散体及びこれらを用いた水性接着剤、水性コーティング剤、水性塗料で ある。  That is, 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.
[0008] (1)少なくともアルミニウム化合物を含有する重合触媒の存在下に製造された、樹脂 酸価が 3〜110mgK〇H/gである共重合ポリエステル樹脂を用いることを特徴とす るポリエステル樹脂水分散体。 (1) 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.
(2)樹脂酸価の 80%以上がカルボキシル基及び/またはスルホン基によるものである ことを特徴とする（1)に記載のポリエステル樹脂水分散体。  (2) The polyester resin aqueous dispersion according to (1), wherein 80% or more of the resin acid value is derived from a carboxyl group and / or a sulfone group.
(3)上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、リ ン化合物から選ばれる少なくとも 1種からなることを特徴とする（1)〜（2)のレ、ずれか に記載のポリエステル樹脂水分散体。  (3) The above (1) to (2), wherein the polymerization catalyst comprises at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds. The polyester resin aqueous dispersion as described.
(4)上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、 アルカリ金属および/またはアルカリ土類金属とからなることを特徴とする請求項（1) 〜（2)のレ、ずれかに記載のポリエステル樹脂水分散体。  (4) The 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 polyester resin aqueous dispersion according to any one of the above.
(5)上記アルミニウム化合物がカルボン酸含有化合物であることを特徴とする（1)〜（ 4)のレ、ずれかに記載のポリエステル樹脂水分散体。  (5) The polyester resin aqueous dispersion according to (1) to (4), wherein the aluminum compound is a carboxylic acid-containing compound.
(6)上記リンィヒ合物が芳香族ホスホン酸およびその誘導体からなる群から選ばれる 少なくとも 1種であることを特徴とする（3)または（5)に記載のポリエステル樹脂水分 散体。  (6) The polyester resin water dispersion according to (3) or (5), wherein the Linich compound is at least one selected from the group consisting of aromatic phosphonic acids and derivatives thereof.
(7)上記アルカリ金属およびアルカリ土類金属力 SLi, Na, Mgないしその化合物から 選択される少なくとも 1種であるであることを特徴とする（4)〜（6)のいずれかに記載 のポリエステル樹脂水分散体。  (7) The polyester according to any one of (4) to (6), wherein the polyester is at least one selected from the above-mentioned alkali metal and alkaline earth metal forces SLi, Na, Mg or a compound thereof Resin water dispersion.
(8)共重合ポリエステル樹脂に不溶なアルミニウム系異物が明細書に記載の方法で 測定した場合、 5時間未満であることを特徴とする（1)〜（7)のいずれかに記載のポリ エステル樹脂水分散体。  (8) The polyester according to any one of (1) to (7), characterized in that the aluminum-based foreign matter insoluble in the copolymerized polyester resin is less than 5 hours when measured by the method described in the specification. Resin water dispersion.
(9)被接着材がフィルム、布および金属のいずれかであることを特徴とする（1)〜（8) のいずれかに記載のポリエステル樹脂水分散体を用いた水性接着剤。  (9) The aqueous adhesive using the polyester resin aqueous dispersion according to any one of (1) to (8), wherein the adherend is any one of a film, a cloth and a metal.
(10) (1)〜（8)のいずれかに記載のポリエステル樹脂水分散体を用いた水性コーテ イング剤。  (10) An aqueous coating agent using the polyester resin aqueous dispersion according to any one of (1) to (8).
(11) (1)〜（8)のいずれかに記載のポリエステル樹脂水分散体を用いた水性塗料。  (11) A water-based paint using the aqueous polyester resin dispersion according to any one of (1) to (8).
(12)少なくともアルミニウム化合物を含有する重合触媒の存在下に製造された共重 合ポリエステル樹脂、および、該共重合ポリエステル樹脂を構成成分として含むポリ ウレタン樹脂のうち少なくとも一方と、アクリル樹脂とのハイブリッド樹脂を用いるハイ ブリツド樹脂水分散体であって、ハイブリッド樹脂の酸価が 20〜400mgKOH/gで あることを特徴とするハイブリッド樹脂水分散体。 (12) a copolyester resin produced in the presence of a polymerization catalyst containing at least an aluminum compound, and a polyester containing the copolyester resin as a constituent component A hybrid resin aqueous dispersion using a hybrid resin of at least one of urethane resins and an acrylic resin, wherein the hybrid resin has an acid value of 20 to 400 mgKOH / g.
(13)共重合ポリエステル樹脂、および、該共重合ポリエステル樹脂を構成成分として 含むポリウレタン樹脂のうち少なくとも一方の重量力 S、ハイブリッド樹脂の重量の 10% 以上 90%以下であることを特徴とする（12)に記載のハイブリッド樹脂水分散体。  (13) 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).
(14)共重合ポリエステル樹脂、および、該共重合ポリエステル樹脂を構成成分として 含むポリウレタン樹脂のうち少なくとも一方に、不飽和結合を導入し、それを反応点と してアクリルグラフトすることを特徴とする（12)または（13)に記載のハイブリッド樹脂 水分散体。  (14) 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).
(15)上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、 リンィ匕合物から選ばれる少なくとも 1種からなることを特徴とする（12)〜（14)のいず れかに記載のハイブリッド樹脂水分散体。  (15) Any of (12) to (14), wherein the polymerization catalyst comprises at least one selected from the group consisting of aluminum compounds and at least one selected from a phosphorus compound. The hybrid resin aqueous dispersion described in 1.
(16)上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、 アルカリ金属および/またはアルカリ土類金属とからなることを特徴とする（12)〜（14 )のレ、ずれかに記載のハイブリッド樹脂水分散体。  (16) The above (12) to (14), 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 hybrid resin aqueous dispersion described in 1.
(17)上記アルミニウム化合物がカルボン酸含有化合物であることを特徴とする（12) 〜（16)のいずれかに記載のハイブリッド樹脂水分散体。  (17) The hybrid resin water dispersion according to any one of (12) to (16), wherein the aluminum compound is a carboxylic acid-containing compound.
(18)上記リンィヒ合物が芳香族ホスホン酸およびその誘導体からなる群から選ばれる 少なくとも 1種であることを特徴とする（15)または（17)に記載のハイブリッド樹脂水分 散体。  (18) The hybrid resin moisture dispersion according to (15) or (17), wherein the Linich compound is at least one selected from the group consisting of aromatic phosphonic acids and derivatives thereof.
(19)上記アルカリ金属およびアルカリ土類金属力 SLi， Na, Mgないしその化合物か ら選択される少なくとも 1種であることを特徴とする（16)〜（18)のいずれかに記載の ハイブリッド樹脂水分散体。  (19) The 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.
(20)共重合ポリエステル樹脂に不溶なアルミニウム系異物が明細書に記載の方法 で測定した場合、 5時間未満であることを特徴とする（12)〜（： 19)のいずれかに記載 のハイブリッド樹脂水分散体。  (20) The hybrid according to any one of (12) to (: 19), characterized in that the aluminum-based foreign matter insoluble in the copolymerized polyester resin is less than 5 hours when measured by the method described in the specification. Resin water dispersion.
(21)被接着材がフィルム、布および金属のいずれかであることを特徴とする（12)〜 (20)のいずれかに記載のノ、イブリツド樹脂水分散体を用いた水性接着剤。 (21) 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).
(22) (12)〜（20)のいずれかに記載のハイブリッド樹脂水分散体を用いた水性コー ティング斉 IJ。  (22) Aqueous coating simultaneous IJ using the hybrid resin water dispersion according to any one of (12) to (20).
(23) (12)〜（20)のいずれかに記載のハイブリッド樹脂水分散体を用いた水性塗料  (23) Water-based paint using the hybrid resin water dispersion according to any one of (12) to (20)
発明の効果 The invention's effect
[0010] 本発明のポリエステル樹脂組成物、ポリエステル アクリルハイプリッド樹脂組成物 は従来のものに比べて、優れた色相を示すとともに、耐熱性に優れており、各種ブラ スチックフィルム同士の接着、各種プラスチックフィルムと木質ボード、布あるいは金 属との接着、各種基材のコーティング剤、塗料として有用である。また、本発明のポリ エステル樹脂水分散体、ポリエステル アクリルハイブリッド樹脂水分散体は優れた 透明性を有し、低着色であるためフィルムに成形して使用することにも好適である。 発明を実施するための最良の形態  [0010] 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. In addition, 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. BEST MODE FOR CARRYING OUT THE INVENTION
[0011] 本発明に用いられる重合触媒を構成するアルミニウム化合物としては、金属アルミ 二ゥムのほか、公知のアルミニウム化合物は限定なく使用できる。  [0011] As the aluminum compound constituting the polymerization catalyst used in the present invention, known aluminum compounds can be used without limitation in addition to metal aluminum.
[0012] アルミニウム化合物としては、具体的には、ギ酸アルミニウム、酢酸アルミニウム、塩 基性酢酸アルミニウム、プロピオン酸アルミニウム、蓚酸アルミニウム、アクリル酸アル ミニゥム、ラウリン酸アルミニウム、ステアリン酸アルミニウム、安息香酸アルミニウム、ト リクロロ酢酸アルミニウム、乳酸アルミニウム、クェン酸アルミニウム、サリチル酸アルミ ニゥムなどのカルボン酸塩、塩化アルミニウム、水酸化アルミニウム、水酸化塩化アル ミニゥム、炭酸アルミニウム、リン酸アルミニウム、ホスホン酸アルミニウムなどの無機酸 塩、アルミニウムメトキサイド、アルミニウムェトキサイド、アルミニウム n-プロポキサイド 、アルミニウム iso-プロポキサイド、アルミニウム n-ブトキサイド、アルミニウム tーブトキ サイドなどアルミニウムアルコキサイド、アルミニウムァセチルァセトネート、アルミニゥ ムァセチルアセテート、アルミニウムェチルァセトアセテート、アルミニウムェチルァセ トアセテートジ iso-プロポキサイドなどのアルミニウムキレート化合物、トリメチルアルミ 二ゥム、トリェチルアルミニウムなどの有機アルミニウム化合物およびこれらの部分カロ 水分解物、酸化アルミニウムなどが挙げられる。これらのうちカルボン酸塩、無機酸塩 およびキレートイ匕合物が好ましぐこれらの中でもさらに酢酸アルミニウム、塩基性酢 酸アルミニウム、塩化アルミニウム、水酸化アルミニウム、水酸化塩化アルミニウムお よびアルミニウムァセチルァセトネートが特に好ましい。 [0012] Specific examples of 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. And organoaluminum compounds of these and their partial carohydrates, aluminum oxide and the like. Of these, 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.
[0013] 本発明に用いるアルミニウム化合物の使用量としては、得られるポリエステルのジカ ルボン酸や多価カルボン酸などのカルボン酸成分の全構成ユニットのモル数に対し て 0. 001〜： 1.0モノレ0 /0力 S好ましく、さらに好ましくは、 0. 005〜0. 5モノレ0 /0である。こ のようにアルミニウム成分の添加量は、使用する多価カルボン酸およびジオールの種 類やその組合せ、さらには重合方法によって大きく触媒活性が変動するため広い範 囲が求められる。このことは他の重合触媒でも同様の傾向を示す。特に減圧下で重 合を実施しない場合は重合触媒量を大幅に増加する必要がある。本発明の重合触 媒は十分な触媒活性を示すため、その結果、得られるポリエステルの熱安定性や熱 酸化安定性、耐加水分解性が優れ、アルミニウムに起因する異物の発生や着色が抑 制される。 [0013] 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. Thus, 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.
[0014] 以下に、アルミニウム化合物として、塩基性酢酸アルミニウムを用いた同溶液の調 製方法の具体例を示す。  [0014] A specific example of a method for preparing the same solution using basic aluminum acetate as the aluminum compound is shown below.
塩基性酢酸アルミニウムの水溶液の調製例としては、下記の通りである。すなわち、 塩基性酢酸アルミニウムに水を加え室温で十分拡散させた後、室温〜 100°Cで溶解 させることで水溶液を調製する。この場合の温度は低い方が好ましぐ加熱は短い方 が好ましい。水溶液の濃度は、 10〜30g/lが好ましぐとくに 15〜20g/lが好ましい。  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.
[0015] さらに、触媒添カ卩時のヒートショックを抑制するために、塩基性酢酸アルミニウム水 溶液を同エチレングリコール溶液にすることが好ましい態様である。すなわち、上述 の水溶液に対してエチレングリコールを加える。エチレングリコールの添加量は水溶 液に対して容量比で 0. 5〜5. 0倍量が好ましい。より好ましくは 0. 8〜2. 0倍量であ る。該溶液を攪拌することで均一な水/エチレングリコール混合溶液を得た後、該溶 液を加熱し、水を留去することでエチレングリコール溶液を得ることができる。温度は 70°C以上が好ましぐ 130°C以下が好ましい。より好ましくは 80〜： 120°Cで加熱-攪 拌して水を留去することが好ましい。さらに好ましくは、減圧下および/または窒素、ァ ルゴンなどの不活性ガス雰囲気下で加熱し、水を留去し触媒溶液を調製することで ある。 [0015] Further, in order to suppress heat shock during catalyst addition, it is a preferred embodiment that 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. After stirring the solution to obtain a uniform water / ethylene glycol mixed solution, 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.
上記エチレングリコールは一例であって、他のアルキレングリコールも同様にして使 用できる。  The above ethylene glycol is an example, and other alkylene glycols can be used in the same manner.
[0016] 上述の塩基性酢酸アルミニウムは水ゃグリコールなどの溶媒に可溶ィ匕したもの、とく に水および Zまたはエチレングリコールに可溶化したものを用いることが触媒活性や 得られる共重合ポリエステルの異物低減の観点からも好ましい。  [0016] 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.
[0017] 本発明に用いる重合触媒を構成するリンィ匕合物としては、特に限定はされないが、 リン酸ならびにトリメチルリン酸、トリェチルリン酸、フヱニルリン酸、トリフヱニルリン酸 等のリン酸エステル、亜リン酸ならびにトリメチルホスファイト、トリェチルホスファイト、ト リフエニルホスファイト、トリス（2,4-ジ- tert-ブチルフエニル）ホスファイト、テトラキス（2， 4-ジ -tert-ブチルフエニル） 4,4' _ビフヱ二レンジホスファイト等の亜リン酸エステルな どが挙げられる。  [0017] 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.
[0018] 本発明に用いるより好ましいリン化合物は、ホスホン酸系化合物、ホスフィン酸系化 合物、ホスフィンオキサイド系化合物、亜ホスホン酸系化合物、亜ホスフィン酸系化合 物、ホスフィン系化合物からなる群より選ばれる少なくとも一種のリン化合物である。こ れらのリン化合物を用いることで触媒活性の向上効果が見られるとともに、ポリエステ ルの熱安定性等の物性が改善する効果が見られる。これらの中でも、ホスホン酸系 化合物を用いると物性改善効果や触媒活性の向上効果が大きく好ましい。上記した リン化合物の中でも、芳香環構造を有する化合物を用いると物性改善効果や触媒活 性の向上効果が大きく好ましい。  [0018] 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.
[0019] 本発明で言うホスホン酸系化合物、ホスフィン酸系化合物、ホスフィンオキサイド系 化合物、亜ホスホン酸系化合物、亜ホスフィン酸系化合物、ホスフィン系化合物とは、 それぞれ下記式 (化 1)〜 (化 6)で表される構造を有する化合物のことを言う。  [0019] 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).
[0020] [化 1]
Figure imgf000009_0001
[0020] [Chemical 1]
Figure imgf000009_0001
[0021] [化 2]
Figure imgf000010_0001
[0021] [Chemical 2]
Figure imgf000010_0001
[0022] [化 3] [0022] [Chemical 3]
ΟΡΠΜΙ  ΟΡΠΜΙ
[0023] [化 4]
Figure imgf000010_0002
[0024] [化 5] [0023] [Chemical 4]
Figure imgf000010_0002
[0024] [Chemical 5]
— p— o- — P— o-
[0025] [化 6] [0025] [Chemical 6]
-P -P
[0026] 本発明に用いるホスホン酸系化合物としては、例えば、メチルホスホン酸ジメチル、 メチルホスホン酸ジフエニル、フエニルホスホン酸ジメチル、フエニルホスホン酸ジェ チル、フエニルホスホン酸ジフエニル、ベンジルホスホン酸ジメチル、ベンジルホスホ ン酸ジェチルなどが挙げられる。本発明のホスフィン酸系化合物としては、例えば、 ジフエニルホスフィン酸、ジフエニルホスフィン酸メチル、ジフエニルホスフィン酸フエ ニル、フエニルホスフィン酸、フエニルホスフィン酸メチル、フエニルホスフィン酸フエ二 ルなどが挙げられる。本発明のホスフィンオキサイド系化合物としては、例えば、ジフ ェニルホスフィンオキサイド、メチルジフエニルホスフィンオキサイド、トリフエニルホス オキサイドなどが挙げられる。 [0027] ホスフィン酸系化合物、ホスフィンオキサイド系化合物、亜ホスホン酸系化合物、亜 ホスフィン酸系化合物、ホスフィン系化合物の中では、本発明のリンィ匕合物としては、 下記式 (化 7)〜（化 12)で表される化合物が好ましレ、。 [0026] 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. Can be mentioned. Examples of the phosphine oxide compound of the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Among the phosphinic acid-based compounds, phosphine oxide-based compounds, phosphonous acid-based compounds, phosphinic acid-based compounds, and phosphine-based compounds, the phosphorus compound of the present invention includes the following formulas (Chemical Formula 7) to ( The compound represented by Chemical formula 12) is preferred.
[0028] [化 7]  [0028] [Chemical 7]
[0029] [化 8] [0029] [Chemical 8]
[0030] [化 9] [0030] [Chemical 9]
[0031] [化 10] [0031] [Chemical 10]
Figure imgf000011_0001
Figure imgf000011_0001
[0032] [化 11] [0032] [Chemical 11]
Figure imgf000012_0001
Figure imgf000012_0001
[0033] [化 12] [0033] [Chemical 12]
[(C¾) (CH2)7〗 3P [(C¾) (CH2) 7〗 3P
[0034] 上記したリン化合物の中でも、芳香環構造を有する化合物を用いると物性改善効 果ゃ触媒活性の向上効果が大きく好ましい。 [0034] Among the phosphorus compounds described above, it is preferable to use a compound having an aromatic ring structure because the physical property improving effect and the catalytic activity improving effect are great.
[0035] また、本発明に用いるリン化合物としては、下記一般式 (化 13)〜（化 15)で表され る化合物を用いると物性改善効果や触媒活性の向上効果が特に大きく好ましい。 [0035] In addition, as the phosphorus compound used in the present invention, 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.
[0036] [化 13] [0036] [Chemical 13]
PC^R1 (OR2) (OR3) PC ^ R 1 (OR 2 ) (OR 3 )
[0037] [化 14]  [0037] [Chemical 14]
P(=0)FTR4(0R2) P (= 0) FTR 4 (0R 2 )
[0038] [化 15] [0038] [Chemical 15]
[0039] (式 (化 13)
Figure imgf000012_0002
R6はそれぞれ独立に水素、炭素数:!〜 50の 炭化水素基、水酸基またはハロゲン基またはアルコキシル基またはアミノ基を含む炭 素数:!〜 50の炭化水素基を表す。 R2、 R3はそれぞれ独立に水素、炭素数:!〜 50の 炭化水素基、水酸基またはアルコキシル基を含む炭素数 1〜 50の炭化水素基を表 す。ただし、炭化水素基はシクロへキシル等の脂環構造やフエニルゃナフチル等の 芳香環構造を含んでいてもよい。 ) [0039] (Formula 13)
Figure imgf000012_0002
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. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl and an aromatic ring structure such as phenyl naphthyl. )
[0040] 本発明に用いるリン化合物としては、上記式 (化 13)〜（化 15)中、 R6 が芳香環構造を有する基である化合物がとくに好ましい。 [0040] 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.
[0041] 本発明に用いるリン化合物としては、例えば、メチルホスホン酸ジメチル、メチルホ スホン酸ジフエニル、フエニルホスホン酸ジメチル、フエニルホスホン酸ジェチル、フエ ニルホスホン酸ジフエニル、ベンジルホスホン酸ジメチル、ベンジルホスホン酸ジェチ ノレ、ジフエニルホスフィン酸、ジフエニルホスフィン酸メチル、ジフエニルホスフィン酸 フエニル、フエニルホスフィン酸、フエニルホスフィン酸メチル、フエニルホスフィン酸フ ェニル、ジフエ二ルホスフィンオキサイド、メチルジフエニルホスフィンオキサイド、トリフ ヱニルホスフィンオキサイドなどが挙げられる。これらのうちで、フヱニルホスホン酸ジ メチル、ベンジルホスホン酸ジェチルがとくに好ましレ、。  [0041] 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. Acid, methyl diphenylphosphinate, diphenylphosphinic acid phenyl, phenylphosphinic acid, methyl phenylphosphinate, phenylphosphinic acid phenyl, diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, etc. Is mentioned. Of these, dimethyl phenylphosphonate and jetyl benzylphosphonate are particularly preferred.
[0042] 上述したリン化合物の中でも、本発明では、リン化合物としてリンの金属塩化合物が とくに好ましレ、。リンの金属塩ィヒ合物とは、リン化合物の金属塩であれば特に限定は されないが、ホスホン酸系化合物の金属塩を用いると本発明の課題であるポリエステ ルの物性改善効果や触媒活性の向上効果が大きく好ましい。リン化合物の金属塩と しては、モノ金属塩、ジ金属塩、トリ金属塩などが含まれる。  [0042] Among the phosphorus compounds described above, in the present invention, 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. However, when a metal salt of a phosphonic acid compound is used, 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. Examples of metal salts of phosphorus compounds include monometal salts, dimetal salts, and trimetal salts.
[0043] また、上記したリン化合物の中でも、金属塩の金属部分が、 Li、 Na、 K、 Be、 Mg、 Sr、 Ba、 Mn、 Ni、 Cu、 Znから選択されたものを用いると触媒活性の向上効果が大 きく好ましい。これらのうち、 Li、 Na、 Mgがとくに好ましい。  [0043] Among the above phosphorus compounds, 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. Of these, Li, Na, and Mg are particularly preferable.
[0044] 本発明に用いるリンの金属塩化合物としては、下記一般式 (化 16)で表される化合 物から選択される少なくとも一種を用いると物性改善効果や触媒活性の向上効果が 大きく好ましい。  [0044] As 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.
[0045] [化 16]  [0045] [Chemical 16]
Figure imgf000013_0001
Figure imgf000013_0001
(式 (化 16)中、 R1は水素、炭素数 1〜50の炭化水素基、水酸基またはハロゲン基ま たはアルコキシノレ基またはアミノ基を含む炭素数 1〜50の炭化水素基を表す。 は 、水素、炭素数 1〜50の炭化水素基、水酸基またはアルコキシル基を含む炭素数 1 〜50の炭化水素基を表す。 R3は、水素、炭素数 1〜50の炭化水素基、水酸基また はアルコキシノレ基またはカルボニルを含む炭素数 1〜50の炭化水素基を表す。 1は 1 以上の整数、 mは 0または 1以上の整数を表し、 1+mは 4以下である。 Mは (1+m)価の金 属カチオンを表す。 nは 1以上の整数を表す。炭化水素基はシキロへキシル等の脂 環構造や分岐構造やフエニルゃナフチル等の芳香環構造を含んでレ、てもよレ、。 ) [0047] 上記の R1としては、例えば、フエニル、 1一ナフチル、 2—ナフチル、 9 _アンスリル、 4—ビフエニル、 2—ビフエニルなどが挙げられる。上記の R2としては例えば、水素、メ チノレ基、ェチル基、プロピル基、イソプロピル基、 n_ブチル基、 see—ブチル基、 ter t一ブチル基、長鎖の脂肪族基、フヱニル基、ナフチル基、置換されたフヱニル基ゃ ナフチル基、 _CH CH OHで表される基などが挙げられる。 R3〇—としては例えば、 (In the formula (Chemical Formula 16), 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. Represents a hydrocarbon group having 1 to 50 carbon atoms, including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and 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. 1 represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and 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. [0047] Examples of R 1 include phenyl, 1-naphthyl, 2-naphthyl, 9_anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R 2 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. Groups, substituted phenyl groups, naphthyl groups, groups represented by —CH 2 CH 2 OH, and the like. For example, R 3 〇—
2 2  twenty two
水酸化物イオン、アルコラ一トイオン、アセテートイオンゃァセチルアセトンイオンなど が挙げられる。  Examples include hydroxide ions, alcoholate ions, acetate ions and cetylacetone ions.
[0048] 上記一般式 (化 16)で表される化合物の中でも、下記一般式 (化 17)で表される化 合物から選択される少なくとも一種を用いることが好ましい。  [0048] Among the compounds represented by the above general formula (Formula 16), it is preferable to use at least one selected from compounds represented by the following general formula (Formula 17).
[0049] [化 17] [0049] [Chemical 17]
Figure imgf000014_0001
Figure imgf000014_0001
[0050] (式 (化 17)中、 は水素、炭素数:!〜 50の炭化水素基、水酸基またはハロゲン基ま たはアルコキシノレ基またはアミノ基を含む炭素数 1〜50の炭化水素基を表す。 R3は 、水素、炭素数:!〜 50の炭化水素基、水酸基またはアルコキシル基またはカルボ二 ルを含む炭素数 1〜50の炭化水素基を表す。 1は 1以上の整数、 mは 0または 1以上 の整数を表し、 1+mは 4以下である。 Mは (1+m)価の金属カチオンを表す。炭化水素基 はシキロへキシル等の脂環構造や分岐構造やフエニルゃナフチル等の芳香環構造 を含んでいてもよい。 ) [0050] (In the formula (Chemical Formula 17), 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.)
[0051] 上記の R1としては、例えば、フエニル、 1 ナフチル、 2—ナフチル、 9 アンスリル、 4_ビフヱニル、 2—ビフヱニルなどが挙げられる。 R3〇—としては例えば、水酸化物ィ オン、アルコラ一トイオン、アセテートイオンゃァセチルアセトンイオンなどが挙げられ る。 [0052] 上記したリン化合物の中でも、芳香環構造を有する化合物を用いると物性改善効 果ゃ触媒活性の向上効果が大きく好ましい。 [0051] Examples of R 1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. Examples of R 3 O— include hydroxide ions, alcohol ions, acetate ions and acetylacetone ions. [0052] Among the phosphorus compounds described above, it is preferable to use a compound having an aromatic ring structure because the physical property improving effect and the catalytic activity improving effect are great.
[0053] 上記式（ィ匕 17)の中でも、 Mが、 Li, Na、 K、 Be、 Mg、 Sr、 Ba、 Mn、 Ni、 Cu、 Zn から選択されたものを用レ、ると触媒活性の向上効果が大きく好ましレ、。これらのうち、 Li、 Na、 Mgがとくに好ましい。  [0053] Among the above formulas (I 匕 17), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, Zn, catalytic activity The improvement effect is greatly preferred. Of these, Li, Na, and Mg are particularly preferable.
[0054] 本発明に用いるリンの金属塩化合物としては、リチウム ナフチル)メチルホス ホン酸ェチル]、ナトリウム ナフチル）メチルホスホン酸ェチル]、マグネシウムビ ス [ ( 1 _ナフチル）メチルホスホン酸ェチル]、カリウム [ (2 _ナフチル）メチルホスホン 酸ェチル]、マグネシウムビス [ (2 _ナフチル）メチルホスホン酸ェチル]、リチウム [ベ ンジルホスホン酸ェチル]、ナトリウム [ベンジルホスホン酸ェチル]、マグネシウムビス [ベンジルホスホン酸ェチル]、ベリリウムビス [ベンジルホスホン酸ェチル]、ストロン チウムビス [ベンジルホスホン酸ェチノレ]、マンガンビス [ベンジルホスホン酸ェチル] 、ベンジルホスホン酸ナトリウム、マグネシウムビス [ベンジルホスホン酸]、ナトリウム [ (9 アンスリル）メチルホスホン酸ェチル]、マグネシウムビス [ (9 アンスリル）メチル ホスホン酸ェチル]、ナトリウム [4ーヒドロキシベンジルホスホン酸ェチル]、マグネシ ゥムビス [4ーヒドロキシベンジルホスホン酸ェチル]、ナトリウム [4 クロ口ベンジルホ スホン酸フエ二ル]、マグネシウムビス [4 クロ口べンジルホスホン酸ェチル]、ナトリウ ム [4—ァミノべンジルホスホン酸メチル]、マグネシウムビス [4 -ァミノべンジルホスホ ン酸メチル]、フエニルホスホン酸ナトリウム、マグネシウムビス [フエニルホスホン酸ェ チル]、亜鉛ビス [フエニルホスホン酸ェチル]などが挙げられる。これらの中で、リチウ ム [ (1 ナフチル）メチルホスホン酸ェチル]、ナトリウム [ (1 ナフチル）メチルホスホ ン酸ェチル]、マグネシウムビス ナフチル）メチルホスホン酸ェチル]、リチウム [ ベンジルホスホン酸ェチル]、ナトリウム [ベンジルホスホン酸ェチル]、マグネシウム ビス [ベンジルホスホン酸ェチル]、ベンジルホスホン酸ナトリウム、マグネシウムビス [ ベンジノレホスホン酸]がとくに好ましレ、。  [0054] 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-chlorobenzyl phosphonate], magnesium bis [Ethyl benzyl phosphonate], sodium [methyl 4-aminobenzyl phosphonate], magnesium bis [methyl 4-amino benzyl phosphonate], sodium phenylphosphonate, magnesium bis [phenyl phosphonate], zinc bis [Ethyl phenylphosphonate] and the like. Among these, lithium [(1 naphthyl) methylphosphonate], sodium [(1 naphthyl) methylphosphonate], magnesium bisnaphthyl) methylphosphonate], lithium [benzylphosphonate], sodium [benzylphosphone] Particularly preferred are acid ethyl], magnesium bis [benzyl phosphonate], sodium benzyl phosphonate, and magnesium bis [benzenorephosphonic acid].
[0055] 上述したリン化合物の中でも、本発明では、リンィ匕合物として P_〇H結合を少なく とも一つ有するリン化合物がとくに好ましい。これらのリン化合物を含有することでポリ エステルの物性改善効果がとくに高まることにカ卩えて、ポリエステルの重合時に、これ らのリン化合物を本発明のアルミニウム化合物と共存して用いることで触媒活性の向 上効果が大きく見られる。 [0055] Among the phosphorus compounds described above, in the present invention, a phosphorus compound having at least one P_OH bond as the phosphorus compound is particularly preferable. By containing these phosphorus compounds, the effect of improving the physical properties of the polyester is particularly enhanced. When these phosphorus compounds are used together with the aluminum compound of the present invention, the effect of improving the catalytic activity is greatly seen.
P— OH結合を少なくとも一つ有するリン化合物とは、分子内に P— OHを少なくとも 一つ有するリン化合物であれば特に限定はされなレ、。これらのリン化合物の中でも、 P— OH結合を少なくとも一つ有するホスホン酸系化合物を用いるとアルミニウム化合 物との錯体形成が容易になり、ポリエステルの物性改善効果や触媒活性の向上効果 が大きく好ましい。  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. Among these phosphorus compounds, 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.
[0056] 上記したリン化合物の中でも、芳香環構造を有する化合物を用いると物性改善効 果ゃ触媒活性の向上効果が大きく好ましい。  [0056] Among the phosphorus compounds described above, it is preferable to use a compound having an aromatic ring structure because the physical property improving effect and the catalytic activity improving effect are great.
[0057] 本発明に用いる P_〇H結合を少なくとも一つ有するリンィ匕合物としては、下記一般 式 (化 18)で表される化合物から選択される少なくとも一種を用レ、ると物性改善効果 や触媒活性の向上効果が大きく好ましい。 [0057] As the 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.
[0058] [化 18]
Figure imgf000016_0001
[0058] [Chemical 18]
Figure imgf000016_0001
[0059] (式 (化 18)中、 R1は水素、炭素数:!〜 50の炭化水素基、水酸基またはハロゲン基ま たはアルコキシノレ基またはアミノ基を含む炭素数 1〜50の炭化水素基を表す。 R2は 、水素、炭素数 1〜50の炭化水素基、水酸基またはアルコキシル基を含む炭素数 1 〜50の炭化水素基を表す。 nは 1以上の整数を表す。炭化水素基はシキロへキシル 等の脂環構造や分岐構造やフエニルゃナフチル等の芳香環構造を含んでいてもよ い。） [0059] (In the formula (Chemical Formula 18), 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.)
[0060] 上記の R1としては、例えば、フエニル、 1 ナフチル、 2 ナフチル、 9 アンスリル、 4—ビフエニル、 2—ビフエニルなどが挙げられる。上記の R2としては例えば、水素、メ チノレ基、ェチル基、プロピル基、イソプロピル基、 n ブチル基、 sec ブチル基、 ter t ブチル基、長鎖の脂肪族基、フエ二ル基、ナフチル基、置換されたフエ二ル基ゃ ナフチル基、 _CH CH OHで表される基などが挙げられる。 [0060] Examples of R 1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R 2 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. A substituted phenyl group, a naphthyl group, a group represented by —CH 2 CH 2 OH, and the like.
2 2  twenty two
[0061] 上記したリン化合物の中でも、芳香環構造を有する化合物を用いると物性改善効 果ゃ触媒活性の向上効果が大きく好ましい。 [0061] Among the phosphorus compounds described above, the use of a compound having an aromatic ring structure can improve the physical properties. As a result, the effect of improving the catalytic activity is large and preferable.
[0062] 本発明の P— OH結合を少なくとも一つ有するリン化合物としては、 （1 ナフチル） メチルホスホン酸ェチル、 （1 ナフチル）メチルホスホン酸、（2—ナフチノレ）メチルホ スホン酸ェチル、ベンジルホスホン酸ェチル、ベンジルホスホン酸、（9—アンスリル） メチルホスホン酸ェチル、 4—ヒドロキシベンジルホスホン酸ェチル、 2_メチルベンジ ノレホスホン酸ェチル、 4 _クロ口べンジルホスホン酸フエニル、 4—ァミノべンジルホス ホン酸メチル、 4—メトキシベンジルホスホン酸ェチルなどが挙げられる。これらの中 で、 （1—ナフチル）メチルホスホン酸ェチル、ベンジルホスホン酸ェチルがとくに好ま しい。  [0062] 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.
[0063] 本発明に用いる好ましいリン化合物としては、化学式 (化 19)であらわされるリンィ匕 合物が挙げられる。  [0063] A preferable phosphorus compound used in the present invention is a phosphorus compound represented by the chemical formula (Chemical Formula 19).
[0064] [化 19] [0064] [Chemical 19]
R^C¾-P(-0) (0R8) (QHS) R ^ C¾-P (-0) (0R 8 ) (QH S )
[0065] (式 (化 19)中、 R1は炭素数 1〜49の炭化水素基、または水酸基またはハロゲン基ま たはアルコキシノレ基またはアミノ基を含む炭素数 1〜49の炭化水素基を表し、 R2,R3 はそれぞれ独立に水素、炭素数：!〜 50の炭化水素基、水酸基またはアルコキシル 基を含む炭素数 1〜50の炭化水素基を表す。炭化水素基は脂環構造や分岐構造 や芳香環構造を含んでいてもよい。 ) In the 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.)
[0066] また、更に好ましくは、化学式 (化 19)中の 1^ 2 3の少なくとも一つが芳香環構造 を含む化合物である。 [0066] Furthermore, more preferably, at least one of 1 ^ 2 3 in the chemical formula (Chemical Formula 19) is a compound containing an aromatic ring structure.
[0067] これらのリン化合物の具体例を以下に示す。  [0067] Specific examples of these phosphorus compounds are shown below.
[0068] [化 20]
Figure imgf000017_0001
[0068] [Chemical 20]
Figure imgf000017_0001
[0069] [化 21]
Figure imgf000018_0001
[0069] [Chemical 21]
Figure imgf000018_0001
[0070] [化 22]
Figure imgf000018_0002
[0070] [Chemical 22]
Figure imgf000018_0002
[0071] [化 23]  [0071] [Chemical 23]
Figure imgf000018_0003
Figure imgf000018_0003
[0072] [化 24]
Figure imgf000018_0004
[0072] [Chemical 24]
Figure imgf000018_0004
[0073] [化 25]  [0073] [Chemical 25]
¾ H2— 。C2HS ¾ H 2 —. C 2 H S
OC2Hs OC 2 H s
[0074] また、本発明に用いるリン化合物は、分子量が大きいものの方が重合時に留去され にくいため効果が大きく好ましレ、。 [0074] In addition, the phosphorus compound used in the present invention has a large effect because it is less likely to be distilled off during polymerization.
[0075] 本発明に用いるリン化合物は、フエノール部を同一分子内に有するリンィ匕合物であ ることが好ましい。フエノール部を同一分子内に有するリン化合物を含有することでポ リエステルの物性改善効果が高まることに加えて、ポリエステルの重合時にフエノー ル部を同一分子内に有するリン化合物を用いることで触媒活性を高める効果がより 大きぐ従ってポリエステルの生産性に優れる。 [0076] フエノール部を同一分子内に有するリンィ匕合物としては、フエノール構造を有するリ ン化合物であれば特に限定はされないが、フエノール部を同一分子内に有する、ホ スホン酸系化合物、ホスフィン酸系化合物、ホスフィンオキサイド系化合物、亜ホスホ ン酸系化合物、亜ホスフィン酸系化合物、ホスフィン系化合物からなる群より選ばれる 一種または二種以上の化合物を用いるとポリエステルの物性改善効果や触媒活性 の向上効果が大きく好ましい。これらの中でも、一種または二種以上のフエノール部 を同一分子内に有するホスホン酸系化合物を用いるとポリエステルの物性改善効果 や触媒活性の向上効果がとくに大きく好ましい。 [0075] The phosphorus compound used in the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. In addition to enhancing the physical properties of the polyester by containing a phosphorus compound having a phenol moiety in the same molecule, 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. [0076] 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. Among these, 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.
[0077] 本発明に用いるフエノール部を同一分子内に有するリンィ匕合物としては、下記一般 式 (化 26)〜（化 28)で表される化合物が好ましレ、。  [0077] As the phosphorus compound having a phenol moiety in the same molecule for use in the present invention, compounds represented by the following general formulas (Chemical Formula 26) to (Chemical Formula 28) are preferable.
[0078] [化 26]  [0078] [Chemical 26]
PC^R^OR^ COR3 ( U PC ^ R ^ OR ^ COR 3 (U
[0079] [化 27] [0079] [Chemical 27]
PC^R^COR2) (2 ) - PC ^ R ^ COR 2 ) (2)-
[0080] [化 28] [0080] [Chemical 28]
PC^R1^^ C 3 ) PC ^ R 1 ^^ C 3)
[0081] (式 (化 26)〜（化 28)中、 R1はフエノール部を含む炭素数 1〜50の炭化水素基、水 酸基またはハロゲン基またはアルコキシノレ基またはアミノ基などの置換基およびフエ ノール部を含む炭素数:!〜 50の炭化水素基を表す。 R4,R5,R6はそれぞれ独立に水素 、炭素数:!〜 50の炭化水素基、水酸基またはハロゲン基またはアルコキシノレ基また はァミノ基などの置換基を含む炭素数：!〜 50の炭化水素基を表す。 R2,R3はそれぞれ 独立に水素、炭素数：!〜 50の炭化水素基、水酸基またはアルコキシル基などの置換 基を含む炭素数 1〜50の炭化水素基を表す。ただし、炭化水素基は分岐構造ゃシ クロへキシノレ等の脂環構造やフエニルゃナフチル等の芳香環構造を含んでいてもよ レ、。 R2と R4の末端どうしは結合していてもよい。 ) [0082] 本発明に用いるフエノール部を同一分子内に有するリンィ匕合物としては、例えば、 p —ヒドロキシフエニルホスホン酸、 p—ヒドロキシフエニルホスホン酸ジメチル、 p—ヒド ロキシフエニルホスホン酸ジェチル、 p—ヒドロキシフエニルホスホン酸ジフエニル、ビ ス（p—ヒドロキシフエニル）ホスフィン酸、ビス（p—ヒドロキシフエニル）ホスフィン酸メ チル、ビス（p—ヒドロキシフエニル）ホスフィン酸フエニル、 p—ヒドロキシフエユルフェ ニルホスフィン酸、 p—ヒドロキシフエユルフェニルホスフィン酸メチル、 p—ヒドロキシフ ェユルフェニルホスフィン酸フエニル、 p—ヒドロキシフエニルホスフィン酸、 p—ヒドロキ シフエニルホスフィン酸メチル、 p—ヒドロキシフエニルホスフィン酸フエニル、ビス（p— ヒドロキシフエニル）ホスフィンオキサイド、トリス（p—ヒドロキシフエニル）ホスフィンォキ サイド、ビス（p—ヒドロキシフエニル）メチルホスフィンオキサイド、および下記式（化 2 9)〜（化 32)で表される化合物などが挙げられる。これらのうちで、下記式 (化 31)で 表される化合物および p—ヒドロキシフヱニルホスホン酸ジメチルがとくに好ましい。 [0081] (In the formulas (Chemical Formula 26) to (Chemical Formula 28), 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. Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a group, provided that the hydrocarbon group includes an alicyclic structure such as a branched structure cyclohexynole or an aromatic ring structure such as phenyl naphthyl. 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 (Chemical Formula 31) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.
[0083] [化 29]  [0083] [Chemical 29]
Figure imgf000020_0001
Figure imgf000020_0001
[0084] [化 30]  [0084] [Chemical 30]
Figure imgf000020_0002
Figure imgf000020_0002
[0085] [化 31] [0085] [Chemical 31]
Figure imgf000020_0003
[0086]
Figure imgf000020_0003
[0086]
Figure imgf000021_0001
Figure imgf000021_0001
[0087] 上記の式 (化 31)にて示される化合物としては、 SANKO-220 (三光株式会社製）が あり、使用可能である。 [0087] As a compound represented by the above formula (Chemical Formula 31), SANKO-220 (manufactured by Sanko Co., Ltd.) is available and can be used.
[0088] 本発明に用いるフエノール部を同一分子内に有するリンィ匕合物の中でも、下記一 般式 (化 33)で表される特定のリンの金属塩化合物から選択される少なくとも一種が とくに好ましい。 [0088] Among the 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. .
[0089] [化 33]  [0089] [Chemical 33]
Figure imgf000021_0002
[0090] ( (式 (化 33)中、
Figure imgf000021_0003
R2はそれぞれ独立に水素、炭素数 1〜30の炭化水素基を表す 。 R3は、水素、炭素数：!〜 50の炭化水素基、水酸基またはアルコキシル基を含む炭 素数:!〜 50の炭化水素基を表す。 R4は、水素、炭素数:!〜 50の炭化水素基、水酸 基またはアルコキシル基またはカルボニルを含む炭素数 1〜50の炭化水素基を表 す。 R4〇—としては例えば、水酸化物イオン、アルコラ一トイオン、アセテートイオンや ァセチルアセトンイオンなどが挙げられる。 1は 1以上の整数、 mは 0または 1以上の整 数を表し、 l+mは 4以下である。 Mは (l+m)価の金属カチオンを表す。 nは 1以上の整数 を表す。炭化水素基はシキロへキシル等の脂環構造や分岐構造やフエニルゃナフ チル等の芳香環構造を含んでいてもよい。 )
Figure imgf000021_0002
[0090] ((Formula (Chemical Formula 33)
Figure imgf000021_0003
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. Examples of R 4 O— include hydroxide ions, alcohol ions, acetate ions, acetylacetone ions, and the like. 1 represents an integer of 1 or more, m represents an integer of 0 or 1 and l + m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl. )
[0091] これらの中でも、下記一般式 (化 34)で表される化合物から選択される少なくとも一 種が好ましい。  Among these, at least one selected from compounds represented by the following general formula (Formula 34) is preferable.
[0092]
Figure imgf000022_0001
[0092]
Figure imgf000022_0001
[0093] (式（ィ匕 34)中、 M は n価の金属カチオンを表す。 nは 1， 2, 3または 4を表す。）  [0093] (In the formula (I 匕 34), M represents an n-valent metal cation. N represents 1, 2, 3 or 4).
[0094] 上記式（ィ匕 33)または（ィ匕 34)の中でも、 Mが、 Li， Na、 K、 Be、 Mg、 Sr、 Ba、 Mn 、 Ni、 Cu、 Znから選択されたものを用いると触媒活性の向上効果が大きく好ましい。 これらのうち、 Li、 Na、 Mgがとくに好ましい。  [0094] Among the above formulas (匕) 33) or (匕 匕 34), M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, Zn The effect of improving the catalytic activity is large and preferable. Of these, Li, Na, and Mg are particularly preferable.
[0095] 本発明に用いる特定のリンの金属塩ィ匕合物としては、リチウム [3,5—ジ一 tert—ブ チル _4—ヒドロキシベンジルホスホン酸ェチル]、ナトリウム [3,5—ジ一 tert ブチル 4ーヒドロキシベンジルホスホン酸ェチル]、ナトリウム [3, 5—ジ tert ブチノレー 4 ーヒドロキシベンジルホスホン酸]、カリウム [3,5—ジ tert ブチルー 4ーヒドロキシ ベンジルホスホン酸ェチル]、マグネシウムビス [3, 5—ジ tert ブチルー 4ーヒドロキ シベンジルホスホン酸ェチノレ]、マグネシウムビス [3,5—ジ tert ブチルー 4 ヒドロ キシベンジルホスホン酸]、ベリリウムビス [ 3 , 5—ジ tert ブチル 4ーヒド口キシべ ンジルホスホン酸メチル]、ストロンチウムビス [3, 5—ジ tert ブチルー 4ーヒドロキシ ベンジルホスホン酸ェチル]、バリウムビス [3,5—ジー tert ブチルー 4ーヒドロキシべ ンジノレホスホン酸フエ二ノレ]、マンガンビス [3,5—ジー tert ブチノレー 4 ヒドロキシべ ンジルホスホン酸ェチル]、ニッケルビス [ 3 , 5—ジ tert ブチル 4ーヒドロキシベン ジルホスホン酸ェチル]、銅ビス [3,5—ジ一 tert ブチル _4—ヒドロキシベンジルホ スホン酸ェチル]、亜鉛ビス [3， 5 _ジ一 tert -ブチル _ 4 _ヒドロキシベンジルホスホ ン酸ェチル]などが挙げられる。これらの中で、リチウム [3，5 _ジ一 tert ブチル _4 —ヒドロキシベンジルホスホン酸ェチル]、ナトリウム [3,5—ジ一 tert—ブチノレ _4—ヒ ドロキシベンジルホスホン酸ェチノレ]、マグネシウムビス [3,5—ジ一 tert ブチル _4 —ヒドロキシベンジルホスホン酸ェチル]がとくに好ましい。  [0095] 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 phosphonate phenolate], manganese bis [3,5-di-tert-butynoleyl 4-hydroxybenzyl phosphonate], nickel bis [3,5-di-tert-butyl 4-hydroxybenzyl phosphonate], copper bis [3,5 —Di-tert-butyl_4-hydroxybenzylphosphonate], zinc bis [3,5-di-tert-butyl_4-hydroxybenzylphosphonate]. Among these, 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.
[0096] 本発明に用いるフエノール部を同一分子内に有するリンィ匕合物の中でも、下記一 般式 (化 35)で表される P-OH結合を少なくとも一つ有する特定のリンィ匕合物から選 択される少なくとも一種がとくに好ましい。 [0097] [化 35] [0096] Among the phosphorus compounds having the phenol moiety used in the present invention in the same molecule, a specific phosphorus compound having at least one P-OH bond represented by the following general formula (Formula 35) is used. At least one selected is particularly preferred. [0097] [Chemical 35]
[0098] (式
Figure imgf000023_0001
2はそれぞれ独立に水素、炭素数 1 30の炭化水素基を表す。 [0098] (expression
Figure imgf000023_0001
2 independently represents hydrogen and a hydrocarbon group having 130 carbon atoms.
R3は、水素、炭素数:!〜 50の炭化水素基、水酸基またはアルコキシル基を含む炭素 数:!〜 50の炭化水素基を表す。 nは 1以上の整数を表す。炭化水素基はシキロへキ シノレ等の脂環構造や分岐構造やフエニルゃナフチル等の芳香環構造を含んでいて もよレヽ。） 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. )
[0099] これらの中でも、下記一般式 (化 36)で表される化合物から選択される少なくとも一 種が好ましい。  Among these, at least one selected from compounds represented by the following general formula (Formula 36) is preferable.
[0100] [化 36] [0100] [Chemical 36]
Figure imgf000023_0002
Figure imgf000023_0002
[0101] (式 (化 36)中、 R3は、水素、炭素数：!〜 50の炭化水素基、水酸基またはアルコキシ ル基を含む炭素数：!〜 50の炭化水素基を表す。炭化水素基はシキロへキシル等の 脂環構造や分岐構造やフエニルゃナフチル等の芳香環構造を含んでレ、てもよレ、。 )[0101] In the formula (Chemical Formula 36), 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.)
[0102] 上記の R3としては例えば、水素、メチル基、ェチル基、プロピル基、イソプロピル基 n—ブチル基、 sec—ブチル基、 tert—ブチル基、長鎖の脂肪族基、フエニル基、 ナフチル基、置換されたフヱニル基ゃナフチル基、 _CH CH〇Hで表される基など [0102] Examples of R 3 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
2 2  twenty two
が挙げられる。  Is mentioned.
[0103] 本発明に用いる P_〇H結合を少なくとも一つ有する特定のリン化合物としては、 3, 5 _ジ一 tert _ブチル一 4—ヒドロキシベンジルホスホン酸ェチル、 3 , 5 _ジ一 tert—ブ チル _4—ヒドロキシベンジルホスホン酸メチル、 3,5—ジ一 tert—ブチル _4—ヒドロ キシベンジルホスホン酸イソプロピル、 3 5—ジ一 tert -ブチル一 4 -ヒドロキシベンジ ノレホスホン酸フエニル、 3,5—ジ一 tert -ブチル 4—ヒドロキシベンジルホスホン酸ォ クタデシル、 3, 5—ジー tert ブチル 4ーヒドロキシベンジルホスホン酸などが挙げら れる。これらの中で、 3, 5—ジ tert ブチルー 4ーヒドロキシベンジルホスホン酸ェチ ノレ、 3，5 _ジ一 tert ブチル _4—ヒドロキシベンジルホスホン酸メチルがとくに好まし レ、。 [0103] 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.
[0104] 本発明に用いるフエノール部を同一分子内に有するリンィ匕合物の中でも、下記一 般式 (化 37)で表される特定のリンィ匕合物から選ばれる少なくとも一種のリン化合物 が好ましい。  [0104] Among the 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. .
[0105] [化 37]  [0105] [Chemical 37]
Figure imgf000024_0001
Figure imgf000024_0001
[0106] (上記式 (化 37)中、 R\ R2はそれぞれ独立に水素、炭素数 1〜30の炭化水素基を 表す。 R3、 R4はそれぞれ独立に水素、炭素数 1〜50の炭化水素基、水酸基またはァ ルコキシノレ基を含む炭素数 1〜50の炭化水素基を表す。 nは 1以上の整数を表す。 炭化水素基はシクロへキシル等の脂環構造や分岐構造やフエニルゃナフチル等の 芳香環構造を含んでいてもよい。 ) [In the above formula (Chemical Formula 37), 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. Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group, a hydroxyl group, or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group represents an alicyclic structure such as cyclohexyl, a branched structure, or phenyl. It may contain an aromatic ring structure such as naphthyl.)
[0107] 上記一般式 (化 37)の中でも、下記一般式 (化 38)で表される化合物から選択され る少なくとも一種を用いるとポリエステルの物性改善効果や触媒活性の向上効果が 高く好ましい。  [0107] Among the above general formulas (Chemical formula 37), it is preferable to use at least one compound selected from the compounds represented by the following general formula (Chemical formula 38) because the effect of improving the physical properties and the catalytic activity of the polyester are high.
[0108] [化 38]  [0108] [Chemical 38]
Figure imgf000024_0002
Figure imgf000024_0002
(上記式 (化 38)中、 R3、 R4はそれぞれ独立に水素、炭素数 1〜50の炭化水素基、 水酸基またはアルコキシル基を含む炭素数 1〜50の炭化水素基を表す。炭化水素 基はシクロへキシル等の脂環構造や分岐構造やフエニルゃナフチル等の芳香環構 造を含んでいてもよい。 ) (In the above formula (Chemical Formula 38), 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. )
[0110] 上記の R3、 R4としては例えば、水素、メチル基、ブチル基等の短鎖の脂肪族基、ォ クタデシル等の長鎖の脂肪族基、フエニル基、ナフチル基、置換されたフエ二ル基ゃ ナフチル基等の芳香族基、 -CH CH〇Hで表される基などが挙げられる。 [0110] Examples of 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. Examples of the phenyl group include aromatic groups such as a naphthyl group, and a group represented by -CH CHOH.
2 2  twenty two
[0111] 本発明に用いる特定のリン化合物としては、 3,5—ジ一 tert—ブチル _4—ヒドロキシ ベンジルホスホン酸ジイソプロピル、 3，5_ジ一 tert—ブチル _4—ヒドロキシベンジル ホスホン酸ジ _n—ブチル、 3,5—ジ一 tert—ブチル _4—ヒドロキシベンジルホスホン 酸ジォクタデシル、 3，5 _ジ一 tert _ブチル一 4—ヒドロキシベンジルホスホン酸ジフエ ニルなどが挙げられる。これらの中で、 3，5_ジ一 tert—ブチル _4—ヒドロキシベンジ ノレホスホン酸ジォクタデシル、 3， 5 _ジ一 tert -ブチル _ 4 _ヒドロキシベンジルホスホ ン酸ジフエニルがとくに好ましレ、。  [0111] 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. Among these, 3,5-di-tert-butyl_4-hydroxybenzenorephosphonate dioctadecyl and 3,5-di-tert-butyl_4-hydroxybenzylphosphonate diphenyl are particularly preferred.
[0112] 本発明に用いるフエノール部を同一分子内に有するリンィ匕合物の中でも、本発明 でとくに望ましい化合物は、化学式 (化 39)、（化 40)で表される化合物から選ばれる 少なくとも一種のリン化合物である。  [0112] Among the phosphorus compounds having a phenol moiety in the same molecule used in the present invention, 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.
[0113] [化 39]  [0113] [Chemical 39]
Figure imgf000025_0001
Figure imgf000025_0001
[0114] [化 40] [0114] [Chemical 40]
Figure imgf000025_0002
上記の化学式（化 39)にて示される化合物としては、 Irganoxl222 (チバ 'スぺシャ ルティ'ケミカルズ社製）が市販されており、また化学式 (化 40)にて示される化合物と しては Irganoxl425 (チバ'スペシャルティ'ケミカルズ社製）が市販されており、使用 可能である。
Figure imgf000025_0002
As a compound represented by the above chemical formula (Chemical Formula 39), Irganoxl222 (manufactured by Ciba 'Specialty' Chemicals) is commercially available, and a compound represented by the chemical formula (Chemical Formula 40) Irganoxl425 (manufactured by Ciba 'Specialty' Chemicals) is commercially available and can be used.
[0116] 本発明で使用することが好ましいその他のリン化合物としては、下記する（化 41)、 ( 化 42)で表される連結基 (X)を有するホスホン酸系化合物あるいは (化 43)で表される 連結基 (X)を有さないホスホン酸系化合物などが挙げられる。  [0116] Other phosphorus compounds that are preferably used in the present invention include phosphonic acid compounds having a linking group (X) represented by the following (Chemical Formula 41) and (Chemical Formula 42), or (Chemical Formula 43). Examples thereof include phosphonic acid compounds having no linking group (X).
[0117] (化 41) R1 - X - (P = 0)(OR2) (OR3) [0117] (Chemical 41) R 1 -X-(P = 0) (OR 2 ) (OR 3 )
[式 (化 41)中、 R1は炭素数 6〜50の芳香環構造あるいは炭素数 4〜50の複素環構 造を表し、該芳香環構造あるいは複素環構造は置換基を有していてもよい。 Xは連 結基であり、炭素数 1〜： 10の脂肪族炭化水素（直鎖状あるいは分岐構造あるいは脂 環構造であってもかまわない）、あるいは置換基を含有する炭素数 1〜： 10の脂肪族 炭化水素（直鎖状あるいは分岐構造あるいは脂環構造であってもかまわなレ、）、 _ o 一、 -OCH一、 - SO一、一 C〇一、 -COCH一、 -CH OCO—、 -NHCO-[Wherein, 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. Also good. 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-
2 2 2 2 2 2 2 2
NH— NHCONH— NHSO NHC H OCH CH O—から選ば  Choose from NH—NHCONH—NHSO NHC H OCH CH O—
2 3 6 2 2  2 3 6 2 2
れる。また、 R2および R3はそれぞれ独立に、水素原子、炭素数 1 20の炭化水素基 、水酸基またはアルコキシル基を含む炭素数 1 20の炭化水素基を表す。炭化水 素基は脂環構造や分岐構造や芳香環構造を有してレ、てもよレ、。 ] It is. 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. ]
[0118] 式 (化 41)で表されるリン化合物の芳香環構造および複素環構造の置換基が、炭素 数 1〜50の炭化水素基 (直鎖状であっても脂環構造、分岐構造、芳香環構造であつ てもよく、これらがハロゲン置換されたものであってもよい）または水酸基またはハロゲ ン基または炭素数 1〜： 10のアルコキシル基またはアミノ基（炭素数 1〜： 10のアルキル あるいはアル力ノール置換されてレヽてもかまわなレ、）あるいはニトロ基あるいはカルボ キシル基あるいは炭素数 1〜： 10の脂肪族カルボン酸エステル基あるいはホルミル基 あるいはァシル基あるいはスルホン酸基、スルホン酸アミド基（炭素数 1〜10のアルキ ルあるいはアル力ノール置換されていてもかまわない）、ホスホリル含有基、二トリル基 、シァノアノレキノレ基、力 選ばれる 1種もしくは 2種以上である。  [0118] 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.
[0119] 式 (化 41)で表されるリン化合物には次のようなものが挙げられる。具体的には、ベ ンジルホスホン酸、ベンジルホスホン酸モノェチルエステル、 1 _ナフチルメチルホス ホン酸、 1 _ナフチルメチルホスホン酸モノェチルエステル、 2 _ナフチルメチルホス ホン酸、 2—ナフチルメチルホスホン酸モノェチルエステル、 4 フエ二ノレ，ベンジルホ スホン酸、 4 フエ二ノレ，ベンジルホスホン酸モノェチルエステル、 2 フエニル,ベンジ ルホスホン酸、 2 フエニル,ベンジルホスホン酸モノェチルエステル、 4-クロノレ，ベン ジルホスホン酸、 4-クロノレ，ベンジルホスホン酸モノェチルエステル、 4-クロノレ，ベンジ ルホスホン酸ジェチルエステル、 4—メトキシ,ベンジルホスホン酸、 4—メトキシ，ベン ジルホスホン酸モノェチルエステル、 4—メトキシ,ベンジルホスホン酸ジェチルエステ ノレ、 4—メチノレ，ベンジルホスホン酸、 4—メチノレ，ベンジルホスホン酸モノェチルエス テル、 4—メチノレ，ベンジルホスホン酸ジェチルエステル、 4_ニトロ，ベンジルホスホン 酸、 4 _ニトロ,ベンジノレホスホン酸モノェチノレエステノレ、 4_ニトロ，ベンジルホスホン 酸ジェチルエステル、 4—ァミノ,ベンジルホスホン酸、 4—ァミノ,ベンジルホスホン酸 モノェチルエステル、 4—ァミノ,ベンジルホスホン酸ジェチルエステル、 2—メチル， ベンジルホスホン酸、 2—メチノレ，ベンジルホスホン酸モノェチルエステル、 2—メチ ノレ，ベンジルホスホン酸ジェチルエステル、 10—アンスラエルメチルホスホン酸、 10 アンスラニルメチルホスホン酸モノェチルエステル、 10—アンスラニルメチルホスホ ン酸ジェチルエステル、 （4ーメトキシフエエル-,エトキシ -)メチルホスホン酸、 （4ーメ トキシフエ二ル-,エトキシ -)メチルホスホン酸モノメチルエステル、 （4ーメトキシフエ二 ル-,エトキシ -)メチルホスホン酸ジメチルエステル、 （フエ二ル-,ヒドロキシ-)メチル ホスホン酸、（フエ二ル-,ヒドロキシ-)メチルホスホン酸モノェチルエステル、 （フエ二 ル-，ヒドロキシ-)メチルホスホン酸ジェチルエステル、 （フエ二ル-,クロル-)メチルホス ホン酸、（フエエル-,クロル-)メチルホスホン酸モノェチルエステル、 （フエ二ル-,クロ ル-)メチルホスホン酸ジェチルエステル、 （4 クロルフエニル） -ィミノホスホン酸、（4 -クロルフエ二ノレ） -ィミノホスホン酸モノェチルエステル、 （4—クロルフエ二ノレ） -ィミノ ホスホン酸ジェチルエステル、 （4—ヒドロキシフエ二ル-，ジフエ二ル-）メチルホスホン 酸、（4—ヒドロキシフエ二ル-,ジフエ二ル-)メチルホスホン酸モノェチルエステル、 （4 —ヒドロキシフエ二ル-，ジフエ二ル-）メチルホスホン酸ジェチルエステル、 （4一クロノレ フエ二ル-，ヒドロキシ-）メチルホスホン酸、（4—クロルフエ二ル-，ヒドロキシ-）メチル ホスホン酸モノメチルエステル、 （4—クロルフエ二ル-,ヒドロキシ-)メチルホスホン酸 ジメチルエステル、その他、複素環を含有するリン化合物としては、 2_ベンゾフラ二 ノレメチルホスホン酸ジェチルエステル、 2—べンゾフラニルメチルホスホン酸モノェチ ノレエステノレ、 2—ベンゾフラエルメチルホスホン酸、 2— (5—メチル）ベンゾフラニルメ チルホスホン酸ジェチルエステル、 2—（5—メチノレ）ベンゾフラエルメチルホスホン酸 モノェチルエステル、 2— (5—メチル）ベンゾフラニルメチルホスホン酸などが挙げら れる。上記の連結基を有するリン化合物は、重合活性の点で好ましい態様である。 [0119] 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-methoxy, benzylphosphonic acid, 4-methoxy, benzylphosphonic acid mono Ethyl ester, 4-methoxy, benzylphosphonic acid jetyl ester, 4-methinole, benzylphosphonic acid, 4-methinole, benzylphosphonic acid monoethyl ester, 4-methinole, benzylphosphonic acid jetyl ester, 4-nitro, benzylphosphonic acid 4_nitro, ben Dinorephosphonic acid monoethylenoestenole, 4-nitro, benzylphosphonic acid jetyl ester, 4-amino, benzylphosphonic acid, 4-amino, benzylphosphonic acid monoethyl ester, 4-amino, benzylphosphonic acid jetyl ester 2-methyl, benzylphosphonic acid, 2-methylol, benzylphosphonic acid monoethyl ester, 2-methylol, benzylphosphonic acid jetyl ester, 10-anthrael methylphosphonic acid, 10 anthranilmethylphosphonic acid monoethyl ester, 10-anthranylmethylphosphonic acid jetyl ester, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid, (4-methoxyphenyl-, ethoxy-) methylphosphonic acid monomethyl ester, (4-methoxyphenyl-, Ethoxy-) methylphosphonic acid dimethyl ester (Phenyl-, hydroxy-) methylphosphonic acid, (phenyl-, hydroxy-) methylphosphonic acid monoethyl ester, (phenyl-, hydroxy-) methylphosphonic acid jetyl ester, (phenyl-, Chloro-) methylphosphonic acid, (phenyl-, chloro-) methylphosphonic acid monoethyl ester, (phenyl-, chloro-) methylphosphonic acid jetyl ester, (4 chlorophenyl) -iminophosphonic acid, (4-chlorophenyl) Nole) -iminophosphonic acid monoethyl ester, (4-chlorophenyl) -iminophosphonic acid jetyl ester, (4-hydroxyphenyl-, diphenyl-) methylphosphonic acid, (4-hydroxyphenyl- , Diphenyl-) methylphosphonic acid monoethyl ester, (4 —hydroxyphenyl-, diphenyl-) methylphosphonic acid jetyl ester (4 monochlorophenol-, hydroxy-) methylphosphonic acid, (4-chlorophenyl-, hydroxy-) methylphosphonic acid monomethyl ester, (4-chlorophenyl-, hydroxy-) methylphosphonic acid dimethyl ester, etc. 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.
[0120] 本発明で使用することが好ましい連結基 (X)を有するその他の化合物としては式（ 化 42)で表されるリン化合物が挙げられる。  [0120] Other compounds having a linking group (X) that are preferably used in the present invention include phosphorus compounds represented by the formula (Formula 42).
[0121] (化 42) (R。） 一 Rl— (CH ) — (P = 0) (〇R2) (〇R3) [0121] (Chem. 42) (R.) One Rl— (CH) — (P = 0) (〇R 2 ) (〇R 3 )
m 2 n  m 2 n
[式（ィ匕 42)中、 R°は、水酸基、 C1〜C10のアルキル基、 _ C〇〇H基あるいは一 C〇 OR4 (R4は、 C1〜C4のアルキル基を表す）、アルキレングリコール基あるいはモノア ルコキシアルキレングリコール基を表す（モノアルコキシは C1〜C4を、アルキレングリ コールは C1〜C4のグリコールを表す）。 R1はベンゼン、ナフタレン、ビフエニル、ジフ ェニルエーテル、ジフエ二ルチオエーテル、ジフエニルスルホン、ジフエニルメタン、 ジフエニルジメチルメタン、ジフエ二ルケトン、アントラセン、フエナントレンおよびピレ ンなどの芳香環構造を表す。 R2および R3は、それぞれ独立に、水素原子、 C1〜C4 の炭化水素基、水酸基またはアルコシキル基を有する C1〜C4の炭化水素基を表す 。 mは 1〜5の整数を表し、 が複数個の場合、同一置換基あるいは異なる置換基の 組合せであってもかまわなレ、。 nは 0あるいは 1〜5の整数を表す。 ] In formula (I spoon 42), R ° represents a hydroxyl group, an alkyl group of C1 -C10, _ C_〇_〇_H group or single C_〇 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. ]
[0122] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がベンゼンであるリン化合物としては次のようなものが挙げられる。すなわち、 2—ヒド ロキシベンジルホスホン酸ジェチルエステル、 2—ヒドロキシベンジルホスホン酸モノ ェチルエステル、 2—ヒドロキシベンジルホスホン酸、 4—ヒドロキシベンジルホスホン 酸ジェチルエステル、 4—ヒドロキシベンジルホスホン酸モノェチルエステル、 4—ヒド ロキシベンジルホスホン酸、 6—ヒドロキシベンジルホスホン酸ジェチルエステル、 6 _ ヒドロキシベンジルホスホン酸モノェチルエステル、 6 -ヒドロキシベンジルホスホン酸 などのベンゼン環に水酸基を導入したベンジノレホスホン酸類が挙げられるがこれらに 限定されるものではない。  [0122] Among the phosphorus compounds represented by the formula (Formula 42) used in the present invention, examples of the phosphorus compounds having a substituent aromatic ring structure as benzene include the following. That is, 2-hydroxybenzylphosphonic acid jetyl ester, 2-hydroxybenzylphosphonic acid monoethyl ester, 2-hydroxybenzylphosphonic acid, 4-hydroxybenzylphosphonic acid jetyl ester, 4-hydroxybenzylphosphonic acid monoethyl ester, 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 However, it is not limited to these.
[0123] また、 2 _n-ブチルベンジルホスホン酸ジェチルエステル、 2 _n_ブチルベンジル ホスホン酸モノメチルエステル、 2 n-ブチルベンジルホスホン酸、 3 n-ブチルベン ジルホスホン酸ジェチルエステル、 3— n-ブチルベンジルホスホン酸モノェチルエス テル、 3— n-ブチルベンジルホスホン酸、 4 n-ブチルベンジルホスホン酸ジェチル エステル、 4 _n_ブチルベンジルホスホン酸モノェチルエステル、 4 _n-ブチルベン ジルホスホン酸、 2, 5 _n-ジブチルベンジルホスホン酸ジェチルエステル、 2， 5-n- ジブチルベンジルホスホン酸モノェチルエステル、 2， 5 _n-ジブチルベンジルホスホ ン酸、 3， 5 _n -ジブチルベンジルホスホン酸ジェチルエステル、 3， 5 _n -ジブチル ベンジルホスホン酸モノェチルエステル、 3, 5 _n -ジブチルベンジルホスホン酸など のベンゼン環にアルキルを導入したベンジルホスホン酸類が挙げられるがこれらに限 定されるものではない。 [0123] Also, 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, 3,5_n-dibutylbenzylphosphonic acid monoethyl ester, 3,5_n-dibutylbenzylphosphonic acid Examples include benzylphosphonic acids with alkyl introduced in the ring. It is not limited to.
さらに、 2 _カルボキシベンジルホスホン酸ジェチルエステル、 2_カルボキシベン ジルホスホン酸モノェチルエステル、 2 _カルボキシベンジルホスホン酸、 3_カルボ キシベンジルホスホン酸ジェチルエステル、 3—カルボキシベンジルホスホン酸モノ ェチルエステル、 3—カルボキシベンジルホスホン酸、 4 カルボキシベンジルホスホ ン酸ジェチルエステル、 4 カルボキシベンジルホスホン酸モノェチルエステル、 4 カルボキシベンジルホスホン酸、 2, 5 ジカルボキシベンジルホスホン酸ジェチルェ ステル、 2, 5 ジカルボキシベンジルホスホン酸モノェチルエステル、 2, 5 ジカル ボキシベンジルホスホン酸、 3, 5—ジカルボキシベンジルホスホン酸ジェチルエステ ノレ、 3, 5—ジカルボキシベンジルホスホン酸モノェチルエステル、 3, 5—ジカルボキ シベンジルホスホン酸、 2—メトキシカルボエルベンジルホスホン酸ジェチルエステル 、 2—メトキシカルボニルベンジルホスホン酸モノェチルエステル、 2—メトキシカルボ ニルベンジルホスホン酸、 3—メトキシカルボニルベンジルホスホン酸ジェチルエステ ノレ、 3—メトキシカルボニルベンジルホスホン酸モノェチルエステル、 3—メトキシカル ボニルベンジルホスホン酸、 4—メトキシカルボニルベンジルホスホン酸ジェチルエス テル、 4—メトキシカルボニルベンジルホスホン酸モノェチルエステル、 4—メトキシカ ノレボニルベンジルホスホン酸、 2， 5—ジメトキシカルボニルベンジルホスホン酸ジェ チルエステル、 2， 5—ジメトキシカルボニルベンジルホスホン酸モノェチルエステル、 2, 5—ジメトキシカルボニルベンジルホスホン酸、 3, 5—ジメトキシカルボニルベンジ ノレホスホン酸ジェチルエステル、 3, 5—ジメトキシカルボニルベンジルホスホン酸モノ ェチルエステル、 3, 5—ジメトキシカルボエルベンジルホスホン酸などのベンゼン環 にカルボキル基あるいはカルボン酸エステル基を導入したベンジルホスホン酸類が 挙げられるがこれらに限定されるものではない。 Furthermore, 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 benzylphosphonic acid jetyl ester, 2-methoxycarbonylbenzylphosphonic acid monoethyl ester, 2-methoxycarbonylbenzylphosphonic acid, 3-methoxycarbonylbenzylphosphonic acid jetyl ester, 3 —Methoxycarbonylbenzylphosphonic acid monoethyl ester, 3-methoxycarbonylbenzylphosphonic acid, 4-methoxycarbonylbenzylphosphonic acid jetyl ester, 4-methoxycarbonylbenzylphosphonic acid monoethyl ester, 4-methoxycarbonylbenzylphosphonic acid, 2,5-Dimethoxycarbonylbenzylphosphonic acid ethyl ester, 2,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester, 2,5-dimethoxycarbonyl Njiruhosuhon acid, 3, 5-dimethoxy carbonyl benzylidene Examples include benzylphosphonic acids in which a carbocycle group or a carboxylic acid ester group is introduced into a benzene ring, such as norephosphonic acid jetyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester, and 3,5-dimethoxycarbobenzylbenzylphosphonic acid. It is not limited to these.
さらに、 2_(2—ヒドロキシエトキシ)ベンジルホスホン酸ジェチルエステル、 2_(2_ ヒドロキシエトキシ)ベンジルホスホン酸モノェチルエステル、 2 _ (2 _ヒドロキシェトキ シ)ベンジルホスホン酸、 3 _ (2—ヒドロキシエトキシ)ベンジルホスホン酸ジェチルエス テル、 3 _ (2—ヒドロキシエトキシ)ベンジルホスホン酸モノェチルエステル、 3 _(2—ヒ ドロキシエトキシ)ベンジルホスホン酸、 4 _ (2—ヒドロキシエトキシ)ベンジルホスホン 酸ジェチルエステル、 4 _ (2 _ヒドロキシエトキシ)ベンジルホスホン酸モノェチルエス テル、 4_(2—ヒドロキシエトキシ)ベンジルホスホン酸、 2, 5—ジ (2—ヒドロキシェトキ シ)ベンジルホスホン酸ジェチルエステル、 2， 5—ジ (2—ヒドロキシエトキシ)ベンジル ホスホン酸モノェチルエステル、 2, 5—ジ (2—ヒドロキシエトキシ)ベンジルホスホン酸 、 3, 5—ジ (2—ヒドロキシエトキシ)ベンジルホスホン酸ジェチルエステル、 3, 5—ジ（ 2—ヒドロキシエトキシ)ベンジルホスホン酸モノェチルエステル、 3, 5—ジ (2—ヒドロ キシエトキシ)ベンジルホスホン酸、 2—（2—メトキシェトキシ）ベンジルホスホン酸ジェ チルエステル、 2—（2—メトキシエトキシ)ベンジルホスホン酸モノェチルエステル、 1 一（2—メトキシェトキシ)ベンジルホスホン酸、 3—（2—メトキシエトキシ)ベンジルホス ホン酸モノメチルエステル、 3—（2—メトキシエトキシ)ベンジルホスホン酸ジェチルェ ステル、 3—（2—メトキシェトキシ)ベンジルホスホン酸モノェチルエステル、 3—（2—メ トキシエトキシ)ベンジルホスホン酸、 4ー（2—メトキシエトキシ)ベンジルホスホン酸ジ ェチルエステル、 4_(2—メトキシエトキシ)ベンジルホスホン酸モノェチルエステル、 4_(2—メトキシェトキシ)ベンジルホスホン酸、 2， 5—ジ (2—メトキシェトキシ)ベンジ ノレホスホン酸ジェチルエステル、 2, 5—ジ (2—メトキシェトキシ)ベンジルホスホン酸 モノェチルエステル、 2， 5—ジ (2—メトキシエトキシ)ベンジルホスホン酸、 3， 5—ジ (2 —メトキシエトキシ)ベンジルホスホン酸ジェチルエステル、 3, 5—ジ (2—メトキシエト キシ)ベンジルホスホン酸モノェチルエステル、 3， 5—ジ (2—メトキシェトキシ)ベンジ ノレホスホン酸などのベンゼン環にァノレキレングリコーノレ基あるいはモノアノレコキシィ匕 アルキレングリコール基を導入したベンジルホスホン酸類が挙げられる。 In addition, 2_ (2-hydroxyethoxy) benzylphosphonic acid jetyl ester, 2_ (2_hydroxyethoxy) benzylphosphonic acid monoethyl ester, 2_ (2_hydroxyethoxy) benzylphosphonic acid, 3_ (2-hydroxyethoxy) ) Benzylphosphonic acid jetyl ester, 3_ (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 3_ (2-hydroxyethoxy) benzylphosphonic acid, 4_ (2-hydroxyethoxy) benzylphosphonic acid jetyl Ester, 4_ (2_hydroxyethoxy) benzylphosphonic acid monoethyl ester, 4_ (2-hydroxyethoxy) benzylphosphonic acid, 2,5-di (2-hydroxyethoxy) benzylphosphonic acid jetyl ester, 2,5- Di (2-hydroxyethoxy) benzyl phosphonic acid monoethyl ester, 2,5-di (2-hydride) Loxyethoxy) benzylphosphonic acid, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid jetyl ester, 3,5-di (2-hydroxyethoxy) benzylphosphonic acid monoethyl ester, 3,5-di ( 2-hydroxyethoxy) benzylphosphonic acid, 2- (2-methoxyethoxy) benzylphosphonic acid ethyl ester, 2- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 1 (2-methoxyethoxy) benzyl Phosphonic acid, 3- (2-methoxyethoxy) benzylphosphonic acid monomethyl ester, 3- (2-methoxyethoxy) benzylphosphonic acid jetyl ester, 3- (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 3- (2-Methoxyethoxy) benzylphosphonic acid, 4- (2-methoxyethoxy) benzylphosphone Diethyl ester, 4_ (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 4_ (2-methoxyethoxy) benzylphosphonic acid, 2,5-di (2-methoxyethoxy) benzenorephosphonic acid jetyl ester, 2 , 5-Di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 2,5-di (2-methoxyethoxy) benzylphosphonic acid, 3,5-di (2-methoxyethoxy) benzylphosphonic acid jetyl Esters, 3,5-di (2-methoxyethoxy) benzylphosphonic acid monoethyl ester, 3,5-di (2-methoxyethoxy) benzenorephosphonic acid, etc. Anolecoxi 匕 Examples thereof include benzylphosphonic acids into which an alkylene glycol group has been introduced.
[0126] (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がベンゼンであるリ ン化合物としては、上述した単一置換基種に限定されるものではなぐ上述した置換 基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒドロ キシエトキシ基、 2—メトキシェトキシ基の混成されたものも使用できる。  [0126] Among the phosphorus compounds represented by (Chemical Formula 42), 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.
[0127] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がナフタレンであるリンィ匕合物としては次のようなものが挙げられる。すなわち、 1 _ (5 —ヒドロキシ）ナフチルメチルホスホン酸ジェチルエステル、 1 _ (5—ヒドロキシ）ナフ チルメチルホスホン酸モノェチルエステル、 1 _ (5—ヒドロキシ）ナフチルメチルホス ホン酸、 1 _ (5—ヒドロキシ）ナフチルメチルホスホン酸ジェチルエステル、 1 _ (5—ヒ ドロキシ）ナフチルメチルホスホン酸モノェチルエステル、 1 _ (5 _ヒドロキシ）ナフチ ノレメチルホスホン酸、 1 _ (5 _n—ブチノレ）ナフチルメチルホスホン酸ジェチルエステ ノレ、 1一（5—n—ブチル）ナフチルメチルホスホン酸モノェチルエステル、 1 （5—n ーブチル）ナフチルメチルホスホン酸、 1一（4 カルボキシ）ナフチルメチルホスホン 酸ジェチルエステル、 1一（4 カルボキシ）ナフチルメチルホスホン酸モノエチルェ ステル、 1一（4一カルボキシ）ナフチルメチルホスホン酸、 1一（4ーメトキシカルボ二 ノレ）ナフチルメチルホスホン酸ジェチルエステル、 1一（4ーメトキシカルボ二ノレ）ナフ チルメチルホスホン酸モノェチルエステル、 1一（4ーメトキシカルボ二ノレ）ナフチルメ チルホスホン酸、 1 - [4 - (2 ヒドロキシェトキシ）]ナフチルメチルホスホン酸ジェチ ノレエステノレ、 1 [4一（2—ヒドロキシェトキシ）]ナフチルメチルホスホン酸モノェチル エステル、 1 [4一（2—ヒドロキシェトキシ）]ナフチルメチルホスホン酸、 1一（4ーメト キシエトキシ）ナフチルメチルホスホン酸ジェチルエステル、 1 _ (4—メトキシェトキシ[0127] Among the phosphorus compounds represented by the formula (Formula 42) used in the present invention, 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, 1 (4 carboxy) naphthylmethylphosphonic acid jetyl ester, 1 (4 carboxy) naphthylmethylphosphonic acid Acid monoethyl ester, 1 (4 carboxy) 1- (4-methoxycarboninole) naphthylmethylphosphonic acid jetyl ester, 1- (4-methoxycarboninole) naphthylmethylphosphonic acid monoethyl ester, 1- (4-methoxycarboninole) naphthylmethylphosphonic acid, 1 -[4- (2 hydroxyethoxy)] naphthylmethylphosphonic acid jetty lesenoestole, 1 [4 (2-hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 1 [4 (2-hydroxyethoxy)] naphthylmethylphosphonic acid 1- (4-Methoxyethoxy) naphthylmethylphosphonic acid jetyl ester, 1_ ( 4 -methoxyethoxy
)ナフチルメチルホスホン酸モノェチルエステル、 1 _ (4—メトキシエトキシ）ナフチル メチルホスホン酸、 1 _ (5—ヒドロキシ）ナフチルメチルホスホン酸ジェチルエステル、 2 - (6—ヒドロキシ）ナフチルメチルホスホン酸ジェチルエステル、 2— (6—ヒドロキシ )ナフチルモノェチルホスホン酸、 2 _ (6—ヒドロキシ）ナフチルメチルホスホン酸、 2 - (6 _n—ブチノレ）ナフチルメチルホスホン酸ジェチルエステル、 2 _ (6 _n—ブチ ノレ）ナフチルメチルホスホン酸モノェチルエステル、 2— (6 _n—ブチル）ナフチルメ チルホスホン酸、 2—（6—カルボキシ）ナフチルメチルホスホン酸ジェチルエステル、 2—（6—カルボキシ）ナフチルメチルホスホン酸モノェチルエステル、 2—（6—力ノレ ボキシ）ナフチルメチルホスホン酸、 2—（6—メトキシカルボ二ノレ）ナフチルメチルホス ホン酸ジェチルエステル、 2_ (6—メトキシカルボ二ノレ）ナフチルメチルホスホン酸モ ノエチルエステル、 2 _ (6—メトキシカルボニル）ナフチルメチルホスホン酸、 2_ [6 _ (2—ヒドロキシェトキシ）]ナフチルメチルホスホン酸ジェチルエステル、 2_ [6 _ (2— ヒドロキシェトキシ）]ナフチルメチルホスホン酸モノェチルエステル、 2_ [6 _ (2—ヒド 口キシェトキシ）]ナフチルメチルホスホン酸、 2_ (6—メトキシェトキシ）ナフチルメチ ルホスホン酸ジェチルエステル、 2_ (6—メトキシエトキシ）ナフチルメチルホスホン酸 モノェチルエステル、 2_ (6—メトキシェトキシ）ナフチルメチルホスホン酸などのナフ タレン環にアルキル基、カルボキキシル基、カルボン酸エステル基、アルキレングリコ ール基、モノアルコキシアルキレングリコール基などが導入されたホスホン酸類などが 挙げられるがこれらに限定されるものではない。 ) 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-force-reoxy) naphthylmethylphosphonic acid, 2- (6- Methoxycarboninole) naphthylmethylphosphonic acid jetyl ester, 2_ (6-methoxycarbonyliniole) naphthylmethylphosphonic acid monoethyl ester, 2 _ (6-methoxycarbonyl) naphthylmethylphosphonic acid, 2_ [6 _ (2— Hydroxyethoxy)] naphthylmethylphosphonic acid jetyl ester, 2_ [6 _ (2-hydroxyethoxy)] naphthylmethylphosphonic acid monoethyl ester, 2_ [6 _ (2-hydroxymethoxy)] naphthylmethylphosphonic acid, 2_ ( 6-Methoxyethoxy) naphthylmethylphosphonic acid jetyl ester, 2_ (6-Methyl Toxiethoxy) naphthylmethylphosphonic acid monoethyl ester, 2_ (6-methoxyethoxy) naphthylmethylphosphonic acid, etc., naphthalene ring, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monoalkoxyalkylene glycol group Examples thereof include, but are not limited to, phosphonic acids having introduced therein.
[0128] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がナフタレンで あるリン化合物は、上述した単一置換基種に限定されるものではなぐ上述した置換 基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒドロ キシエトキシ基、 2—メトキシェトキシ基の混成されたものも使用できる。  Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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.
[0129] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がビフヱニルであるリン化合物としては次のようなものが挙げられる。すなわち、 4一 ( 4—ヒドロキシフエニル）ベンジルホスホン酸ジェチルエステル、 4— (4—ヒドロキシフ ェニル）ベンジルホスホン酸モノェチルエステル、 4一（4ーヒドロキシフエニル）ベンジ ノレホスホン酸、 4- (4 _n_ブチルフエ二ノレ）ベンジルホスホン酸ジェチルエステル、 4- (4 _n_ブチルフエ二ノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4_n_ ブチルフエ二ノレ）ベンジルホスホン酸、 4_ (4—カルボキシフエ二ノレ）ベンジルホスホ ン酸ジェチルエステル、 4_ (4—カルボキシフエ二ノレ）ベンジルホスホン酸モノェチ ノレエステノレ、 4— (4—カルボキシフエ二ノレ）ベンジルホスホン酸、 4— (4—メトキシカ ノレボユルフェ二ノレ）ベンジルホスホン酸ジェチルエステル、 4_ (4—メトキシカルボ二 ノレフエ二ノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキシカルボニルフ ェニル）ベンジルホスホン酸、 4- (4—ヒドロキシエトキシフエ二ノレ）ベンジルホスホン 酸ジェチルエステル、 4— (4—ヒドロキシエトキシフエ二ノレ）ベンジルホスホン酸モノエ チルエステル、 4— (4—ヒドロキシエトキシフエ二ノレ）ベンジルホスホン酸、 4— (4—メ トキシェトキシフエ二ノレ）ベンジルホスホン酸ジェチルエステル、 4_ (4—メトキシエト キシフエ二ノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキシェトキシフエ ニル）ベンジルホスホン酸などのビフヱニル環にアルキル基、カルボキキシル基、力 ルボン酸エステル基、アルキレングリコール基、モノメトキシアルキレングリコール基な どが導入されたホスホン酸類などが挙げられるがこれらに限定されるものではない。 [0129] Among the phosphorus compounds represented by the formula (Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is biphenyl 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, 4- (4-methoxycanole fenorenore) Benzylphosphonic acid jetyl ester, 4_ (4-methoxycarbonyl 2-phenol) benzyl Suhon acid mono E chill ester, 4_ (4-methoxycarbonylphenyl Benzyl) phosphonic acid, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid jetyl ester, 4- (4-hydroxyethoxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyethoxyphenyl) Nole) benzylphosphonic acid, 4- (4-methoxyphenoxy) benzylphosphonic acid jetyl ester, 4_ (4-methoxyethoxyphenyl) benzylphosphonic acid monoethyl ester, 4_ (4-methoxyethoxy) Examples thereof include, but are not limited to, phosphonic acids in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, etc. are introduced into a biphenyl ring such as phenyl) benzylphosphonic acid. It is not a thing.
[0130] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がビフエニルで あるリン化合物は、上述した単一置換基種に限定されるものではなぐ上述した置換 基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒドロ キシエトキシ基、 2—メトキシェトキシ基の混成されたものも使用できる。  [0130] Among the phosphorus compounds represented by the formula (Formula 42), 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.
[0131] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がジフエニルエーテルであるリン化合物としては次のようなものが挙げられる。すなわ ち、 4— (4—ヒドロキシフエニルォキシ）ベンジルホスホン酸ジェチルエステル、 4— ( 4—ヒドロキシフエニルォキシ）ベンジルホスホン酸モノェチルエステル、 4— (4—ヒド ロキシフエニルォキシ）ベンジルホスホン酸、 4一（4 n ブチルフエニルォキシ）ベ ンジルホスホン酸モノェチルエステル、 4一（4 n—ブチルフエニルォキシ）ベンジル ホスホン酸モノェチルエステル、 4一（4 ブチルフエニルォキシ）ベンジルホスホン酸 、 4一（4 カルボキシフエニルォキシ）ベンジルホスホン酸モノェチルエステル、 4一 ( 4 カルボキシフエニルォキシ）ベンジルホスホン酸モノェチルエステル、 4一（4一力 ノレボキシフエニルォキシ）ベンジルホスホン酸、 4_ (4—メトキシカルボユルフェニル ォキシ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキシカルボユルフェ二 ノレォキシ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキシカルボユルフェ ニルォキシ）ベンジルホスホン酸、 4_ (4—ヒドロキシエトキシフエニルォキシ）ベンジ ノレホスホン酸モノェチルエステル、 4_ (4—ヒドロキシメトキシフエニルォキシ）ベンジ ノレホスホン酸モノェチルエステル、 4_ (4—ヒドロキシメトキシフエニルォキシ）ベンジ ノレホスホン酸、 4- (4—メトキシェトキシフエ二ルォキシ）ベンジルホスホン酸モノェチ ノレエステノレ、 4— (4—メトキシェトキシフエニルォキシ）ベンジルホスホン酸モノェチル エステノレ、 4一（4ーメトキシェトキシフエニノレオキシ）ベンジノレホスホン酸などのジフエ ニルエーテル環にアルキル基、カルボキキシル基、カルボン酸エステル基、アルキレ ングリコール基、モノメトキシアルキレングリコール基などが導入されたホスホン酸類な どが挙げられるがこれらに限定されるものではない。 [0131] Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenyl ether 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 Noreboxyphenyloxy) benzylphosphonic acid, 4_ (4-methoxycarbophenylphenyloxy) benzylphosphonic acid monoethyl ester 4_ (4-Methoxycarbophenylphenoxy) benzylphosphonic acid monoethyl ester, 4_ (4-methoxycarbophenyloxy) benzylphosphonic acid, 4_ (4-hydroxyethoxyphenyloxy) benzenolephosphonic acid mono Ethyl ester, 4_ (4-hydroxymethoxyphenyl) benzenophosphonic acid monoethyl ester, 4_ (4-hydroxymethoxyphenyl) benzenophosphonic acid, 4- (4-methoxyethoxyphenyloxy) Benzylphosphonic acid monoethyl Noreestenole, 4- (4-methoxyethoxyphenyloxy) benzyl phosphonate monoethyl ester, 4- (4-methoxyethoxyphenyl) benzenorephosphonic acid, diphenyl ether ring, alkyl group, carboxy group, carboxylic acid Examples thereof include, but are not limited to, phosphonic acids into which an ester group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like has been introduced.
[0132] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がジフエニルェ 一テルであるリン化合物は、上述した単一置換基種に限定されるものではなぐ上述 した置換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒドロキシエトキシ基、 2—メトキシエトキシ基の混成されたものも使用できる。  [0132] Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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.
[0133] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がジフヱニチォエーテルであるリン化合物としてはには次のようなものが挙げられる。 すなわち、 4- (4—ヒドロキシフヱ二ルチオ）ベンジルホスホン酸ジェチルエステル、 4 一（4ーヒドロキシフエ二ルチオ）ベンジルホスホン酸モノェチルエステル、 4一（4ーヒ ドロキシフエ二ルチオ）ベンジルホスホン酸、 4— (4— n—ブチルフエ二ルチオ）ベン ジルホスホン酸モノェチルエステル、 4一（4 n—ブチルフエ二ルチオ）ベンジルホス ホン酸モノェチルエステル、 4一（4 ブチルフエ二ルチオ）ベンジルホスホン酸、 4 (4 カルボキシフエ二ルチオ）ベンジルホスホン酸モノェチルエステル、 4一（4一力 ノレボキシフエ二ルチオ）ベンジルホスホン酸モノェチルエステル、 4一（4一カルボキ シフエ二ルチオ）ベンジルホスホン酸、 4一（4ーメトキシカルボエルフェ二ルチオ）ベ ンジルホスホン酸モノェチルエステル、 4一（4ーメトキシカルボエルフェ二ルチオ）ベ ンジルホスホン酸モノェチルエステル、 4一（4ーメトキシカルボエルフェ二ルチオ）ベ ンジルホスホン酸、 4- (4—ヒドロキシエトキシフエ二ルチオ）ベンジルホスホン酸モノ ェチルエステル、 4_ (4—ヒドロキシメトキシフエ二ルチオ）ベンジルホスホン酸モノエ チルエステル、 4_ (4—ヒドロキシメトキシフエ二ルチオ）ベンジルホスホン酸、 4_ (4 —メトキシエトキシフエ二ルチオ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メ トキシェトキシフエ二ルチオ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキ シェトキシフエ二ルチオ）ベンジルホスホン酸などのジフエ二ルチオエーテル環にァ ノレキノレ基、カルボキキシル基、カルボン酸エステル基、アルキレングリコール基、モノ メトキシアルキレングリコール基などが導入されたホスホン酸類などが挙げられるがこ れらに限定されるものではない。 [0133] Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenyl ether 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 ester, 4-one (4 carboxyphenylthio) benzylphosphonic acid, 4-one (4- Methoxycarbophenylphenylthio) benzylphosphonic acid monoethyl ester, 4-one (4-methoate) Cicarboylphenylthio) benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbophenylthio) benzylphosphonic acid, 4- (4-hydroxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4_ (4- Hydroxymethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4_ (4-hydroxymethoxyphenylthio) benzylphosphonic acid, 4_ (4-methoxyethoxyphenylthio) benzylphosphonic acid monoethyl ester, 4_ (4-methoxy Shetoxyphenylthio) benzylphosphonic acid monoethyl ester, 4_ (4-methoxyoxyphenylthio) benzylphosphonic acid and other diphenylthioether rings with an alkenole group, a carboxy group, a carboxylic ester group, an alkylene glycol group, mono Examples thereof include, but are not limited to, phosphonic acids into which a methoxyalkylene glycol group is introduced.
[0134] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がジフエニルチ ォエーテルであるリンィ匕合物は、上述した単一置換基種に限定されるものではなぐ 上述した置換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステノレ 基、 2—ヒドロキシエトキシ基、 2—メトキシェトキシ基の混成されたものも使用できる。  [0134] Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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.
[0135] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がジフヱニルスルホンであるリン化合物としてはには次のようなものが挙げられる。 4 - (4—ヒドロキシフエニルスルホニノレ）ベンジルホスホン酸ジェチルエステル、 4_ (4 —ヒドロキシフエニルスルホニノレ）ベンジルホスホン酸モノェチルエステル、 4一（4一 ヒドロキシフエニルスルホニノレ）ベンジルホスホン酸、 4_ (4_n_ブチルフエニルス ノレホニノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4_n_ブチルフエニルスル ホニル）ベンジルホスホン酸モノェチルエステル、 4一（4 ブチルフエニルスルホニ ノレ）ベンジルホスホン酸、 4— (4—カルボキシフエニルスルホニル）ベンジルホスホン 酸モノェチルエステル、 4一（4 カルボキシフエニルスルホニル）ベンジルホスホン酸 モノェチルエステル、 4一（4 カルボキシフエニルスルホニル）ベンジルホスホン酸、 4一（4ーメトキシカルボエルフェニルスルホニル）ベンジルホスホン酸モノェチルエス テル、 4一（4ーメトキシカルボニルフエニルスルホニル）ベンジルホスホン酸モノェチ ノレエステノレ、 4— (4—メトキシカルボニルフエニルスルホニノレ）ベンジルホスホン酸、 4 一（4ーヒドロキシエトキシフエニルスルホニノレ）ベンジルホスホン酸モノェチルエステ ノレ、 4一（4ーヒドロキシメトキシフエニルスルホニノレ）ベンジルホスホン酸モノエチルェ ステル、 4_ (4—ヒドロキシメトキシフエニルスルホニノレ）ベンジルホスホン酸、 4_ (4 —メトキシエトキシフエニルスルホニノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキシエトキシフエニルスルホニノレ）ベンジルホスホン酸モノェチルエステル、 4 - (4—メトキシエトキシフエニルスルホニノレ）ベンジルホスホン酸などのジフエニルス ノレホン環にアルキル基、カルボキキシル基、カルボン酸エステル基、アルキレングリコ ール基、モノメトキシアルキレングリコール基などが導入されたホスホン酸類などが挙 げられるがこれらに限定されるものではない。 [0136] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がジフエニルス ルホンであるリンィヒ合物は、上述した単一置換基種に限定されるものではなぐ上述 した置換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒドロキシエトキシ基、 2—メトキシエトキシ基の混成されたものも使用できる。 [0135] Among the phosphorus compounds represented by the formula (Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenylsulfone 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 monoethyl ester, 4 (4 carboxyphenylsulfonyl) benzylphosphonic acid monoethyl ester, 4 (4 carboxyphenylsulfonyl) benzylphosphonic acid, 4 One (4-methoxycarbophenylphenylsulfonyl) Monoethyl ester of benzyl phosphonate, 4- (4-methoxycarbonylphenylsulfonyl) benzylphosphonate monoesterol, 4- (4-methoxycarbonylphenylsulfonole) benzylphosphonic acid, 4- (4-hydroxyethoxyphenylsulfonole) Monoethyl ester of benzylphosphonate, 4-one (4-hydroxymethoxyphenylsulfoninole) monoethyl ester of benzylphosphonate, 4_ (4-hydroxymethoxyphenylsulfoninole) benzylphosphonic acid, 4_ (4-methoxyethoxyphenylsulfoninole) Benzylphosphonic acid monoethyl ester, 4_ (4-methoxyethoxyphenylsulfoninole) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenylsulfoninole) benzylphosphonic acid Of Jifuenirusu Norehon ring alkyl group, Karubokikishiru group, a carboxylic acid ester group, an alkylene glycol group, such as phosphonic acids, such as is introduced monomethoxy polyalkylene glycol group is not intended but be mentioned up as being limited thereto. [0136] Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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.
[0137] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がジフヱニルメタンであるリン化合物としては次のようなものが挙げられる。すなわち、 4- (4—ヒドロキシベンジル）ベンジルホスホン酸ジェチルエステル、 4_ (4ーヒドロ キシベンジル）ベンジルホスホン酸モノェチルエステル、 4_ (4—ヒドロキシベンジル )ベンジルホスホン酸、 4- (4 _n_ブチルベンジル）ベンジルホスホン酸モノェチル エステル、 4_ (4 _n_ブチルベンジル）ベンジルホスホン酸モノェチルエステル、 4 - (4—ブチルベンジル）ベンジルホスホン酸、 4_ (4—カルボキシベンジル）ベンジ ノレホスホン酸モノェチルエステル、 4_ (4—カルボキシベンジル）ベンジルホスホン 酸モノェチルエステル、 4一（4 カルボキシベンジル）ベンジルホスホン酸、 4一（4 ーメトキシカルボエルベンジル）ベンジルホスホン酸モノェチルエステル、 4一（4ーメ トキシカルボエルベンジル）ベンジルホスホン酸モノェチルエステル、 4一（4ーメトキ シカルボニルベンジル）ベンジルホスホン酸、 4一（4ーヒドロキシエトキシベンジル）ベ ンジルホスホン酸モノェチルエステル、 4— (4—ヒドロキシメトキシベンジル）ベンジル ホスホン酸モノェチルエステル、 4一（4ーヒドロキシメトキシベンジル）ベンジルホスホ ン酸、 4— (4—メトキシェトキシベンジル）ベンジルホスホン酸モノェチルエステル、 4 一（4ーメトキシェトキシベンジル）ベンジルホスホン酸モノェチルエステル、 4一（4 メトキシエトキシベンジノレ）ベンジノレホスホン酸などのジフエ二ノレメタン環にァノレキノレ基 [0137] Among the phosphorus compounds represented by the formula (Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenylmethane 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, 4- (4-methoxycarboylbenzyl) benzylphosphonic acid monoethyl ester, 4- (4-me Toxicarbol benzyl) benzylphosphonate monoethyl ester 4- (4-methoxycarbonylbenzyl) benzylphosphonic acid, 4- (4-hydroxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxybenzyl) benzylphosphonic acid monoethyl ester, 4 Mono (4-hydroxymethoxybenzyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4 mono (4-methoxyethoxybenzyl) benzylphosphonic acid monoethyl ester, 4 One (4 methoxyethoxybenzenole) benzenorephosphonic acid or other diphenolinomethane ring with an anolequinole group
、カルボキキシル基、カルボン酸エステル基、アルキレングリコール基、モノメトキシァ ルキレングリコール基などが導入されたホスホン酸類などが挙げられるがこれらに限 定されるものではない。 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.
[0138] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がジフエニルメタ ンであるリン化合物は、上述した単一置換基種に限定されるものではなぐ上述した 置換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2 - ヒドロキシエトキシ基、 2—メトキシエトキシ基の混成されたものも使用できる。 [0139] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がジフエニルジメチルメタンであるリン化合物としてはには次のようなものが挙げられ る。すなわち、 4- (4ーヒドロキシフエ二ルジメチルメチル）ベンジルホスホン酸ジェチ ノレエステノレ、 4_ (4—ヒドロキシフエニルジメチルメチノレ）ベンジルホスホン酸モノェチ ノレエステノレ、 4_ (4—ヒドロキシフエニルジメチルメチノレ）ベンジルホスホン酸、 4_ (4 _n_ブチルフエニルジメチルメチノレ）ベンジルホスホン酸モノェチルエステル、 4_ ( 4 _n_ブチルフエニルジメチルメチノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4—ブチルフエニルジメチルメチノレ）ベンジルホスホン酸、 4_ (4—カルボキシフエ二 ノレジメチルメチノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4—カルボキシフエ ニルジメチルメチノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4—カルボキシフ ェニルジメチルメチノレ）ベンジルホスホン酸、 4_ (4—メトキシカルボユルフェ二ルジメ チルメチノレ）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキシカルボニルフ ェニルジメチルメチル）ベンジルホスホン酸モノェチルエステル、 4一（4ーメトキシカ ノレボニルフエ二ルジメチルメチル）ベンジルホスホン酸、 4一（4ーヒドロキシエトキシフ ェニルジメチルメチル）ベンジルホスホン酸モノェチルエステル、 4一（4ーヒドロキシメ トキシフエ二ルジメチルメチル）ベンジルホスホン酸モノェチルエステル、 4一（4ーヒド 口キシメトキシフエ二ルジメチルメチル）ベンジルホスホン酸、 4一（4ーメトキシエトキシ フエ二ルジメチルメチル）ベンジルホスホン酸モノェチルエステル、 4一（4ーメトキシェ トキシフエ二ルジメチルメチル）ベンジルホスホン酸モノェチルエステル、 4一（4ーメト キシエトキシフエニルジメチルメチノレ）ベンジルホスホン酸などのジフエニルメタン環に アルキル基、カルボキキシル基、カルボン酸エステル基、アルキレングリコール基、モ ノメトキシアルキレングリコール基などが導入されたホスホン酸類などが挙げられるが これらに限定されるものではない。 Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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. [0139] Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenyldimethylmethane include the following. . 4- (4-Hydroxyphenyldimethylmethyl) benzylphosphonic acid jettyreesterol, 4_ (4-hydroxyphenyldimethylmethylenol) benzylphosphonic acid monoethylenole, 4_ (4-hydroxyphenyldimethylmethylenol) benzylphosphonic acid, 4_ (4 _n_Butylphenyldimethylmethinole) benzylphosphonic acid monoethyl ester, 4_ (4 _n_butylphenyldimethylmethinole) benzylphosphonic acid monoethyl ester, 4_ (4-butylphenyldimethylmethylenole) ) Benzylphosphonic acid, 4_ (4-carboxyphenyl dimethylmethinole) benzylphosphonic acid monoethyl ester, 4_ (4-carboxyphenyldimethylmethinole) benzylphosphonic acid monoethyl ester, 4_ (4-carboxyph Nenyldimethylmethinole) benzylho Phosphonic acid, 4_ (4-methoxycarbonylphenyldimethylmethinoyl) benzylphosphonic acid monoethyl ester, 4_ (4-methoxycarbonylphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxycanolphenylphenyl) (Dimethylmethyl) benzylphosphonic acid, 4- (4-hydroxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxymethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4 -Hydroxymethoxyphenyldimethylmethyl) benzylphosphonic acid, 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxyphenyldimethylmethyl) benzylphosphonic acid monoethyl ester Esters, phosphones in which alkyl groups, carboxyxyl groups, carboxylic acid ester groups, alkylene glycol groups, monomethoxyalkylene glycol groups, etc. have been introduced into diphenylmethane rings such as esters, 4- (4-methoxyethoxyphenyldimethylmethinoyl) benzylphosphonic acid Examples include acids, but are not limited thereto.
[0140] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がジフエニルジ メチルメタンであるリン化合物は、上述した単一置換基種に限定されるものではなぐ 上述した置換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステノレ 基、 2—ヒドロキシエトキシ基、 2—メトキシェトキシ基の混成されたものも使用できる。  Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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.
[0141] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がジフエ二ルケトンであるリン化合物としては次のようなものが挙げられる。すなわち、[0141] Among the 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,
4— (4—ヒドロキシベンゾィル）ベンジルホスホン酸ジェチルエステル、 4— (4ーヒドロ キシベンゾィノレ）ベンジルホスホン酸モノェチルエステル、 4一（4ーヒドロキシベンゾィ ノレ）ベンジルホスホン酸、 4_ (4 _n_ブチルベンゾィノレ）ベンジルホスホン酸モノエ チルエステル、 4_ (4 _n_ブチルベンゾィノレ）ベンジルホスホン酸モノェチルエステ ノレ、 4- (4—ブチルベンゾィノレ）ベンジルホスホン酸、 4_ (4—カルボキシベンゾィル )ベンジルホスホン酸モノェチルエステル、 4_ (4—カルボキシベンゾィノレ）ベンジル ホスホン酸モノェチルエステル、 4_ (4—カルボキシベンゾィノレ）ベンジルホスホン酸 、 4- (4—メトキシカルボニルベンゾィノレ）ベンジルホスホン酸モノェチルエステル、 4 - (4—メトキシカルボニルベンゾィル）ベンジルホスホン酸モノェチルエステル、 4_ (4—メトキシカルボニルベンゾィル）ベンジルホスホン酸、 4_ (4—ヒドロキシエトキシ ベンゾィル）ベンジルホスホン酸モノェチルエステル、 4_ (4—ヒドロキシメトキシベン ゾィル）ベンジルホスホン酸モノェチルエステル、 4一（4ーヒドロキシメトキシベンゾィ ノレ）ベンジルホスホン酸、 4一（4ーメトキシェトキシベンゾィノレ）ベンジルホスホン酸モ ノエチルエステル、 4一（4ーメトキシェトキシベンゾィル）ベンジルホスホン酸モノェチ ノレエステノレ、 4— (4—メトキシェトキシベンゾィル）ベンジルホスホン酸などのジフエ二 ルケトン環にアルキル基、カルボキキシル基、カルボン酸エステル基、アルキレングリ コール基、モノメトキシアルキレングリコール基などが導入されたホスホン酸類などが 挙げられるがこれらに限定されるものではない。 4- (4-hydroxybenzoyl) benzylphosphonic acid jetyl ester, 4- (4-hydroxybenzoinole) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid, 4_ (4 _n _Butylbenzoinole) benzylphosphonic acid monoethyl ester, 4_ (4 _n_butylbenzoinole) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzoinole) benzylphosphonic acid, 4_ (4-carboxybenzoyl) ) Benzylphosphonic acid monoethyl ester, 4_ (4-carboxybenzoinole) benzylphosphonic acid monoethyl ester, 4_ (4-carboxybenzoinole) benzylphosphonic acid, 4- (4-methoxycarbonylbenzoinole) Benzylphosphonic acid monoethyl ester, 4- (4-methoxycarbonylbenzoyl) benzene Diethylphosphonic acid monoethyl ester, 4_ (4-methoxycarbonylbenzoyl) benzylphosphonic acid, 4_ (4-hydroxyethoxy benzoyl) benzylphosphonic acid monoethyl ester, 4_ (4-hydroxymethoxybenzoyl) benzylphosphonic acid mono Ethyl ester, 4- (4-hydroxymethoxybenzoyl) benzylphosphonic acid, 4- (4-methoxyethoxybenzoino) benzylphosphonic acid monoethyl ester, 4- (4-methoxyethoxybenzoyl) ) Benzylphosphonic acid monoesterolene, 4- (4-methoxyethoxybenzoyl) diphenyl ketone ring such as benzylphosphonic acid, alkyl group, carboxyl group, carboxylic acid ester group, alkylene glycol group, monomethoxyalkylene glycol group Etc. Examples thereof include, but are not limited to, phonic acids.
[0142] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がジフエ二ルケ トンであるリン化合物は、上述した単一置換基種に限定されるものではなぐ上述した 置換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2 - ヒドロキシエトキシ基、 2—メトキシエトキシ基の混成されたものも使用できる。  [0142] Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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.
[0143] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がアンスラセンであるリン化合物としては次のようなものが挙げられる。すなわち、 9 _ (10—ヒドロキシ）アンスリルメチルホスホン酸ジェチルエステル、 9_ (10—ヒドロキシ )アンスリルメチルホスホン酸モノェチルエステル、 9_ (10—ヒドロキシ）アンスリルメ チルホスホン酸、 9 - (10 _n—ブチノレ）アンスリルメチルホスホン酸ジェチルエステ ノレ、 9- (10— n—ブチル）アンスリルメチルホスホン酸モノェチルエステル、 9— (10 —n—ブチル）アンスリルィルメチルホスホン酸、 9一（10—カルボキシ）アンスリルメチ ノレホスホン酸ジェチルエステル、 9一（10—カルボキシ）アンスリルメチルホスホン酸 モノェチルエステル、 9 _ (10—カルボキシ）アンスリルメチルホスホン酸、 9 _ (10_ カルボキシ） 9 _ (2—ヒドロキシエトキシ）アンスリルメチルホスホン酸ジェチルエステ ノレ、 9 _ (2—ヒドロキシエトキシ）アンスリルメチルホスホン酸モノェチルエステル、 9_ (2—ヒドロキシエトキシ）アンスリルメチルホスホン酸、 9— (2—メトキシェトキシ）アンス リルメチルホスホン酸ジェチルエステル、 9 _ (2—メトキシェトキシ）アンスリルメチル ホスホン酸モノェチルエステル、 9_ (2—メトキシエトキシ）アンスリルメチルホスホン 酸、 9_ (2—メトキシカルボニル）アンスリルメチルホスホン酸ジェチルエステル、 9 _ (2—メトキシカルボ二ノレ）アンスリルメチルホスホン酸モノェチルエステル、 9_ (2—メ トキシカルボニル）アンスリルメチルホスホン酸などのアンスラセン環にアルキル基、力 ルボキキシル基、カルボン酸エステル基、アルキレングリコール基、モノメトキシアル キレングリコール基などが導入されたホスホン酸類などが挙げられるがこれらに限定 されるものではない。 [0143] Among the phosphorus compounds represented by the formula (Formula 42) used in the present invention, examples of the phosphorus compounds having an anthracene substituted aromatic ring structure 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-hydroxyethoxy) anthrylmethylphosphonic acid jetyl ester, 9 _ (2-hydroxyethoxy) anthrylmethylphosphonic acid monoethyl ester, 9_ (2-hydroxyethoxy) anthrylmethylphosphonic acid, 9- (2-methoxyethoxy) anthrylmethylphosphonic acid jetyl ester, 9_ (2-methoxy Ethoxy) anthrylmethyl phosphonic acid monoethyl ester, 9_ ( 2-Methoxyethoxy) anthrylmethylphosphonic acid, 9_ (2-methoxycarbonyl) anthrylmethylphosphonic acid jetyl ester, 9_ (2-methoxycarboninole) anthrylmethylphosphonic acid monoethyl ester, 9_ (2-methoxy Examples thereof include, but are not limited to, phosphonic acids in which an alkyl group, a strong ruxoxyl group, a carboxylic ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, etc. are introduced into an anthracene ring such as carbonyl) anthrylmethylphosphonic acid. It is not a thing.
[0144] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がアンスラセン であるリン化合物は、上述した単一置換基種に限定されるものではなぐ上述した置 換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒド ロキシエトキシ基、 2—メトキシェトキシ基の混成されたものも使用できる。  [0144] Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compounds in which the aromatic ring structure having a substituent is anthracene 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.
[0145] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 力 Sフエナントレンであるリン化合物としては次のようなものが挙げられる。すなわち、 1 [0145] Among the phosphorus compounds represented by the formula (Formula 42) used in the present invention, examples of the phosphorus compound having an aromatic ring structure force S phenanthrene having a substituent include the following. Ie 1
- (7 _n—ブチノレ）フエナントリルメチルホスホン酸ジェチルエステル、 1 _ (7_n_ ブチノレ）フエナントリルメチルホスホン酸モノェチルエステル、 1 _ (7_n—ブチル）フ ェナントリルメチルホスホン酸、 1 _ (7—カルボキシ）フエナントリルメチルホスホン酸 ジェチルエステル、 1 _ (7—カルボキシ）フエナントリルメチルホスホン酸モノェチル エステル、 1 _ (7—カルボキシ）フエナントリルメチルホスホン酸、 1 _ (7—ヒドロキシ エトキシ）フエナントリルメチルホスホン酸ジェチルエステル、 1 _ (7—ヒドロキシェトキ シ）フエナントリルメチルホスホン酸モノェチルエステル、 1 _ (7—ヒドロキシエトキシ） フエナントリルメチルホスホン酸、 1一（7—メトキシェトキシ）フエナントリルメチルホスホ ン酸ジェチルエステル、 1一（7—メトキシエトキシ）フエナントリルメチルホスホン酸モノ ェチルエステル、 1— (7—メトキシェトキシ）フエナントリルメチルホスホン酸、 1 7— メトキシカルボ二ノレ）フエナントリルメチルホスホン酸ジェチルエステル、 1 _ (7—メトキ シカルボ二ノレ）フエナントリルメチルホスホン酸モノェチルエステル、 1 _ (7—メトキシ カルボニル）フエナントリルメチルホスホン酸などのフエナントレン環にアルキル基、力 ルボキキシル基、カルボン酸エステル基、アルキレングリコール基、モノメトキシアル キレングリコール基などが導入されたホスホン酸類などが挙げられるがこれらに限定 されるものではない。 -(7_n-butynole) phenanthrylmethylphosphonic acid jetyl ester, 1_ (7_n_butynole) phenanthrylmethylphosphonic acid monoethyl ester, 1_ (7_n-butyl) phenanthrylmethylphosphonic acid, 1_ (7- Carboxy) phenanthrylmethylphosphonic acid jetyl ester, 1_ (7-carboxy) phenanthrylmethylphosphonic acid monoethyl ester, 1_ (7-carboxy) phenanthrylmethylphosphonic acid, 1_ (7-hydroxyethoxy) phenanthryl Methylphosphonic acid jetyl ester, 1_ (7-hydroxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1_ (7-hydroxyethoxy) Phenanthrylmethylphosphonic acid, 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid jetyl ester, 1- (7-methoxyethoxy) phenanthrylmethylphosphonic acid monoethyl ester, 1- (7-methoxyethoxy ) Phenanthrylmethylphosphonic acid, 1 7-methoxycarboninole) Phenanthrylmethylphosphonic acid jetyl ester, 1 _ (7-methoxycarbonyl) Phenanthrylmethylphosphonic acid monoethyl ester, 1 _ (7-methoxy) Examples thereof include, but are not limited to, phosphonic acids such as carbonyl) phenanthrylmethylphosphonic acid in which an alkyl group, a strong carboxy group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, etc. are introduced. It is not something.
[0146] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がフエナントレン であるリン化合物は、上述した単一置換基種に限定されるものではなぐ上述した置 換基、ヒドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒド ロキシエトキシ基、 2—メトキシェトキシ基の混成されたものも使用できる。  [0146] Among the phosphorus compounds represented by the formula (Chemical Formula 42), the phosphorus compounds in which the aromatic ring structure having a substituent is phenanthrene 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.
[0147] 本発明に用いる式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造 がピレンであるリン化合物としては次のようなものが挙げられる。すなわち、 1ー（5—ヒ ドロキシ）ピレニルメチルホスホン酸ジェチルエステル、 1一（5—ヒドロキシ）ピレニルメ チルホスホン酸モノェチルエステル、 1一（5—ヒドロキシ）ピレニルメチルホスホン酸、 1一（5— n-ブチル）ピレニリルメチルホスホン酸ジェチルエステル、 1一（5— n-ブチ ノレ）ピレニルメチルホスホン酸モノェチルエステル、 1ー（5— n-ブチル）ピレニルメチ ノレホスホン酸、 1— (5—カルボキシ）ピレニルメチルホスホン酸ジェチルエステル、 1 一（5—カルボキシ）ピレニルメチルホスホン酸モノェチルエステル、 1一（5—カルボ キシ）ピレニルメチルホスホン酸、 1 _ (5—ヒドロキシエトキシ）ピレニルメチルホスホン 酸ジェチルエステル、 1 _ (5—ヒドロキシエトキシ）ピレニルメチルホスホン酸モノェチ ノレエステル、 1 _ (5—ヒドロキシエトキシ）ピレニルメチルホスホン酸、 1 _ (5—メトキシ エトキシ）ピレニルメチルホスホン酸ジェチルエステル、 1 _ (5—メトキシエトキシ）ピレ ニルメチルホスホン酸モノェチルエステル、 1 _ (5—メトキシェトキシ）ピレニルメチル ホスホン酸、 1 _ (5—メトキシカルボ二ノレ）ピレニルルメチルホスホン酸ジェチルエス テル、 1 _ (5—メトキシカルボ二ノレ）ピレニルメチルホスホン酸モノェチルエステル、 1 一（5—メトキシカルボ二ノレ）ピレニルメチルホスホン酸などのピレン環にアルキル基、 カルボキキシル基、カルボン酸エステル基、アルキレングリコール基、モノメトキシァ ルキレングリコール基などが導入されたホスホン酸類などが挙げられるがこれらに限 定されるものではない。 [0147] Among the phosphorus compounds represented by the formula (Chemical Formula 42) used in the present invention, examples of the phosphorus compounds in which the aromatic ring structure having a substituent is pyrene 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_ (5-hydroxyethoxy) pyrenylmethylphosphone Acid jetyl ester, 1_ (5-hydroxyethoxy) pyrenylmethylphosphonate monoethylenoles 1_ (5-hydroxyethoxy) pyrenylmethylphosphonic acid, 1_ (5-methoxyethoxy) pyrenylmethylphosphonic acid jetyl ester, 1_ (5-methoxyethoxy) pyrenylmethylphosphonic acid monoethyl ester, 1_ (5-methoxyethoxy) pyrenylmethylphosphonic acid, 1 _ (5-methoxycarboninole) pyrenyllmethylphosphonic acid jetyl ester, 1 _ (5-methoxycarboninole) pyrenylmethylphosphonic acid monoethyl ester, 1 Examples include phosphonic acids in which an alkyl group, a carboxy group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, etc. are introduced into a pyrene ring such as one (5-methoxycarbonyleno) pyrenylmethylphosphonic acid. It is not limited to these.
[0148] 式 (化 42)で表されるリン化合物の内、置換基を有する芳香環構造がピレンであるリ ン化合物は、上述した単一置換基種に限定されるものではなぐ上述した置換基、ヒ ドロキシル基、アルキル基、カルボキシル基、カルボキシエステル基、 2—ヒドロキシェ トキシ基、 2—メトキシエトキシ基の混成されたものも使用できる。  Among the phosphorus compounds represented by the formula (Chemical Formula 42), 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.
[0149] 上記一連の芳香環に導入されるヒドロキシル基、アルキル基、カルボキシル基、力 ルボキシエステル基、 2—ヒドロキシエトキシ基、 2—メトキシエトキシ基などの置換基 は、ポリエステルの重合時のアルミニウム原子との錯体形成に深く関わるものと推定さ れる。また、ポリエステル形成時の官能基であるカルボキシル基あるいは水酸基と類 似のものも含まれており、ポリエステルマトリックス中に溶解または取り込まれやすい ため、重合活性、異物低減などに特に有効であると考えられる。 [0149] 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. .
[0150] 芳香環構造 (R1)に結合した R°が水素原子である未置換基に比べ、本発明の C1 〜C10のアルキル基、— COOH基あるいは— C〇OR4 (R4は、 C1〜C4のアルキル 基を表す）、アルキレングリコール基あるいはモノアルコキシアルキレングリコール基（ モノアルコキシは C1〜C4を、アルキレングリコールは C1〜C4のグリコールを表す） で置換されたリン化合物は、触媒活性を改善するだけでなぐ異物低減効果の点で 好ましい。 [0150] 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_〇_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.
芳香環構造に結合した置換基は、 C1〜C10のアルキル基、カルボキシルおよび力 ノレボキシルエステル基、アルキレングリコールおよびモノアルコキシアルキレングリコ ールなどが挙げられる。異物低減効果の点でより好ましくは、カルボキシルおよび力 ノレボキシルエステル基、アルキレングリコールおよびモノアルコキシアルキレングリコ ールである。その理由は不明であるが、ポリエステルおよび触媒の媒体であるアルキ レンダリコールとの相溶性が改善されることによると推測している。  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.
[0151] 本発明で使用することが好ましい連結基 (X)を持たなレ、リン化合物（化 43)は次のよ うなものである。 [0152] (化 43) R1— (P = 0)(OR2) (OR3) [0151] The phosphorus compound (Chemical Formula 43) having no linking group (X) preferably used in the present invention is as follows. [0152] (Chemical 43) R 1 — (P = 0) (OR 2 ) (OR 3 )
(R1は炭素数 6〜50の芳香環構造あるいは炭素数 4〜50の複素環構造を表し、該 芳香環構造あるいは複素環構造は置換基を有してレ、てもよレ、。 R2および R3はそれぞ れ独立に、水素原子、炭素数 1〜20の炭化水素基、水酸基またはアルコキシル基を 含む炭素数 1〜20の炭化水素基を表す。炭化水素基は脂環構造や分岐構造ゃ芳 香環構造を有していてもよい。 ) (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.)
式 (化 43)で表されるリンィ匕合物の芳香環構造および複素環構造の置換基が、炭素 数 1〜50の炭化水素基 (直鎖状であっても脂環構造、分岐構造、芳香環構造であつ てもよく、これらがハロゲン置換されたものであってもよレ、）または水酸基またはハロゲ ン基または炭素数 1〜10のアルコキシル基またはアミノ基（炭素数 1〜10のアルキル あるいはアル力ノール置換されてレヽてもかまわなレ、）あるいはニトロ基あるいはカルボ キシル基あるいは炭素数 1〜： 10の脂肪族カルボン酸エステル基あるいはホルミル基 あるいはァシル基あるいはスルホン酸基、スルホン酸アミド基（炭素数 1〜： 10のアルキ ルあるいはアル力ノール置換されていてもかまわない）、ホスホリル含有基、二トリル基 、シァノアルキル基から選ばれる 1種もしくは 2種以上である。また、前記（化 43)の芳 香環構造がベンゼン、ナフタレン、ビフエニル、ジフエニルエーテル、ジフエ二ルチオ エーテル、ジフエニルスルホン、ジフエニルメタン、ジフエニルジメチルメタン、アントラ セン、フエナントレンおよびピレンから選ばれる。および前記複素環構造がフラン、ベ ンゾフラン、イソべンゾフラン、ジベンゾフラン、ナフタランおよびフタリドから選ばれる 。また、上記式 (化 43)中の R2および R3の少なくとも一方が水素原子であることが好ま しい。 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). Or 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. And the heterocyclic structure is selected from furan, benzofuran, isobenzofuran, dibenzofuran, naphthalane and phthalide. In addition, it is preferable that at least one of R 2 and R 3 in the above formula (Formula 43) is a hydrogen atom.
[0153] 本発明で使用できる式 (化 43)で表されるリン化合物としては、下記のリン化合物な どが挙げられる。すなわち、 （3—ニトロ， 5—メチル） -フヱニルホスホン酸ジェチルエス テル、（3—ニトロ, 5—メチル) -フエニルホスホン酸モノェチルエステル、 （3—ニトロ， 5 —メチル） -フエニルホスホン酸、（3—ニトロ, 5—メトキシ) -フエニルホスホン酸ジェチ ノレエステノレ、 （3—ニトロ, 5—メトキシ） -フエニルホスホン酸モノェチルエステル、 （3— ニトロ， 5—メトキシ） -フエニルホスホン酸、（4—クロル） -フエニルホスホン酸ジェチル エステル、 （4—クロル，） -フヱニルホスホン酸モノェチルエステル、 （4—クロル）-フエ ニルホスホン酸、 （5—クロル,） -フエニルホスホン酸ジェチルエステル、 （5—クロル，） - フエニルホスホン酸モノェチルエステル、 （5—クロル，） -フエ二ルホスホン酸、 （3—二 トロ, 5—メチル） -フエニルホスホン酸ジェチルエステル、（3—ニトロ， 5—メチル) -フエ ニルホスホン酸モノェチルエステル、（3—ニトロ, 5—メチル) -フエニルホスホン酸、 （4 —ニトロ） -フエニルホスホン酸ジェチルエステル、 （4 _ニトロ） -フエニルホスホン酸モ ノエチルエステル、（4—ニトロ) -フヱニルホスホン酸、（5—ニトロ) -フヱニルホスホン酸 ジェチルエステル、（5 _ニトロ) - フエニルホスホン酸モノェチルエステル、（5—ニトロ)-フエニルホスホン酸、（6—ニトロ )-フエニルホスホン酸ジェチルエステル、（6—ニトロ)-フエニルホスホン酸モノェチル エステル、（6—ニトロ) -フエニルホスホン酸、（4—ニトロ, 6—メチル) -フエ二ルホスホン 酸ジェチルエステル、（4—ニトロ， 6—メチル) - フエニルホスホン酸モノェチルエステル、（4—ニトロ， 6—メチル)-フエニルホスホン酸 、その他、式（化 42)で表されるリン化合物において、上述のベンゼン、ナフタレン、ビ フエニル、ジフエニルエーテル、ジフエ二ルチオエーテル、ジフエニルスルホン、ジフ ェニルメタン、ジフエニルジメチルメタン、ジフエ二ルケトン、アントラセン、フエナントレ ンおよびピレンなどの芳香環構造を有するそれぞれの構造式から連結基であるメチ レン鎖すなわち、 -CH を取り除いたリン化合物群、さらに複素環含有リン化合物 [0153] 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,)-phenylphosphonic acid monoethyl ester, (5-chloro,)-phenylphosphonic acid, (3-nitro, 5- Methyl) -phenylphosphonic acid jetyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3-nitro, 5-methyl) -phenylphosphonic acid, (4-nitro) -phenylphosphonic acid jetyl Esters, (4_nitro) -phenylphosphonic acid monoethyl ester, (4-nitro) -phenylphosphonic acid, (5-nitro) -phenylphosphonic acid jetyl ester, (5_nitro) -phenylphosphonic acid monoethyl ester, ( 5-nitro) -phenylphosphonic acid, (6-nitro) -phenylphosphonic acid jetyl ester, (6-nitro) -phenylphosphonic acid Phosphonic acid monoethyl ester, (6-nitro) -phenylphosphonic acid, (4-nitro, 6-methyl) -phenylphosphonic acid jetyl ester, (4-nitro, 6-methyl) -phenylphosphonic acid monoethyl ester, ( 4-nitro, 6-methyl) -phenylphosphonic acid, and other phosphorous compounds represented by the formula (Chemical Formula 42), benzene, naphthalene, biphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenyl Each of the structural formulas having an aromatic ring structure such as phenylmethane, diphenyldimethylmethane, diphenylketone, anthracene, phenanthrene, and pyrene has a methylene chain as a linking group, i.e., a phosphorus compound group from which -CH is removed, and a heterocyclic ring. Containing phosphorus compound
2  2
として、 5—べンゾフラニルホスホン酸ジェチルエステル、 5—べンゾフラニルホスホン 酸モノェチルエステル、 5 べンゾフラニルホスホン酸、 5—（2 メチノレ）ベンゾフラ二 ノレホスホン酸ジェチルエステル、 5—（2 メチノレ）ベンゾフラニルホスホン酸モノェチ ルエステル、 5—（2 メチル）ベンゾフラエルホスホン酸などが挙げられる。上述の連 結基を有しなレ、リン化合物は、前述の連結基を有するリン化合物に比べ重合活性は 若干劣る場合もあるが、本発明の触媒調製法を使用した場合、共重合ポリエステル 重合触媒として使用することは可能である。 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. However, when the catalyst preparation method of the present invention is used, a copolymerized polyester is polymerized. It can be used as a catalyst.
リン化合物は、ポリエステルの熱安定剤としては知られていた力 これらの化合物を 従来の金属含有ポリエステル重合触媒と組み合わせて使用しても、溶融重合を大き く促進することはこれまで知られていなかった。実際に、ポリエステル重合の代表的な 触媒であるアンチモンィ匕合物、チタン化合物、スズィ匕合物あるいはゲルマニウム化合 物を重合触媒としてポリエステルを溶融重合する際に、本発明のリン化合物を添加し ても、実質的に有用なレベルまで重合が促進されることは認められない。 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.
[0155] 本発明に用いるリン化合物の使用量としては、得られる共重合ポリエステルのポリ力 ルボン酸成分の全構成ユニットのモル数に対して 0. 001~2. 0モル％が好ましぐ 0 . 005〜1. 0モル0 /0であることがさらに好ましレ、。リン化合物の添加量が 0. 001モノレ %未満の場合には添加効果が発揮されない場合があり、 2. 0モル％を超えて添カロ すると逆に共重合ポリエステル重合触媒としての触媒活性が低下する場合があり、そ の低下の傾向は、アルミニウムの使用量等により変化する。 [0155] 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.
[0156] また一方で、本発明においてアルミニウムもしくはその化合物に加えて少量のアル カリ金属、アルカリ土類金属並びにその化合物から選択される少なくとも 1種を第 2金 属含有成分として共存させることが好ましレ、態様である。力、かる第 2金属含有成分を 触媒系に共存させることは、触媒活性を高め、従って反応速度をより高めた触媒成分 が得られ、生産性向上に有効である。  [0156] On the other hand, in the present invention, in addition to aluminum or a compound thereof, it is preferable that 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.
[0157] アルカリ金属、アルカリ土類金属並びにその化合物を添加する場合、その使用量 M (モル0 /0)は、ポリエステルを構成する全ポリカルボン酸ユニットのモル数に対して、 1 X 10— 6以上 1. 0モル％未満であることが好ましぐより好ましくは 5 X 10— 6〜0. 5モ ノレ0 /0であり、さらに好ましくは 1 X 10— 5〜0· 3モル0 /0であり、特に好ましくは、 1 X 10—5 〜0. 1モル％である。アルカリ金属、アルカリ土類金属の添加量が少量であるため、 熱安定性低下、異物の発生、着色、耐加水分解性の低下等の問題を発生させること なぐ反応速度を高めることが可能である。アルカリ金属、アルカリ土類金属並びにそ の化合物の使用量 Μが 1. 0モル％以上になると熱安定性の低下、異物発生や着色 の増加、並びに耐加水分解性の低下が製品加工上問題となる場合が発生する。 Μ 力^ X 10— 6未満では、添加してもその効果が明確ではない。 [0157] 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. . When 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 Μ force ^ X 10- 6, the effect is not clear also be added.
[0158] 本発明においてアルミニウムもしくはその化合物に加えて使用することが好ましレヽ 第 2金属含有成分を構成するアルカリ金属、アルカリ土類金属としては、 Li, Na， K, Rb, Cs， Be, Mg， Ca， Sr， Baから選択される少なくとも 1種であることが好ましぐこ のうち Li， Na, Mgないしその化合物から選択される少なくとも 1種の使用がより好ま しい。アルカリ金属やアルカリ土類金属の化合物としては、例えば、これら金属のギ 酸、酢酸、プロピオン酸、酪酸、蓚酸などの飽和脂肪族カルボン酸塩、アクリル酸、メ タクリル酸などの不飽和脂肪族カルボン酸塩、安息香酸などの芳香族カルボン酸塩 、トリクロ口酢酸などのハロゲン含有カルボン酸塩、乳酸、クェン酸、サリチル酸などの ヒドロキシカルボン酸塩、炭酸、硫酸、硝酸、リン酸、ホスホン酸、炭酸水素、リン酸水 素、硫化水素、亜硫酸、チォ硫酸、塩酸、臭化水素酸、塩素酸、臭素酸などの無機 酸塩、 1 _プロパンスルホン酸、 1 _ペンタンスルホン酸、ナフタレンスルホン酸などの 有機スルホン酸塩、ラウリル硫酸などの有機硫酸塩、メトキシ、エトキシ、 n—プロポキ シ、 iso _プロポキシ、 n—ブトキシ、 tert—ブトキシなどのアルコキサイド、ァセチルァ セトネートなどとのキレートイ匕合物、水素化物、酸化物、水酸化物などが挙げられる。 [0158] In the present invention, it is preferably used in addition to aluminum or a compound thereof. 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. Examples of 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 —Propoxy, iso_propoxy, n-butoxy, tert-butoxy and other alkoxides, chelating compounds with acetylacetonate, etc., hydrogen And oxides, hydroxides and the like.
[0159] これらのアルカリ金属、アルカリ土類金属またはそれらの化合物のうち、水酸化物等 のアルカリ性の強いものを用いる場合、これらはエチレングリコール等のジオールもし くはアルコール等の有機溶媒に溶解しにくい傾向があるため、水溶液で重合系に添 カロしなければならず重合工程上問題となる場合が有る。さらに、水酸化物等のアル力 リ性の強レ、ものを用いた場合、重合時にポリエステルが加水分解等の副反応を受け 易くなるとともに、重合したポリエステルは着色し易くなる傾向があり、耐加水分解性も 低下する傾向がある。従って、本発明のアルカリ金属またはそれらの化合物あるいは アルカリ土類金属またはそれらの化合物として好適なものは、アルカリ金属あるいは アルカリ土類金属の飽和脂肪族カルボン酸塩、不飽和脂肪族カルボン酸塩、芳香族 カルボン塩、ハロゲン含有カルボン酸塩、ヒドロキシカルボン酸塩、硫酸、硝酸、リン 酸、ホスホン酸、リン酸水素、硫化水素、亜硫酸、チォ硫酸、塩酸、臭化水素酸、塩 素酸、臭素酸から選ばれる無機酸塩、有機スルホン酸塩、有機硫酸塩、キレートイ匕 合物、及び酸化物である。これらの中でもさらに、取り扱い易さや入手のし易さ等の 観点から、アルカリ金属あるいはアルカリ土類金属の飽和脂肪族カルボン酸塩、特に 酢酸塩の使用が好ましい。  [0159] Among these alkali metals, alkaline earth metals or their compounds, when using 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. In addition, when using 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. Accordingly, 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 An inorganic acid salt, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide selected from the group consisting of Among these, from the viewpoints of ease of handling and availability, use of saturated aliphatic carboxylates of alkali metals or alkaline earth metals, particularly acetates is preferred.
[0160] 本発明に用いる重合触媒は、アンチモン化合物、ゲルマニウム化合物、チタン化合 物、スズ化合物などの他の重合触媒を、これらの成分の添加が前述のようなポリエス テルの特性、加工性、色調等製品に問題を生じない添加量の範囲内において共存 させて用いることは、重合時間の短縮による生産性を向上させる際に有効であり、好 ましい。 [0160] 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. When these components are added, the characteristics, processability, and color tone of the polyester as described above are used. It is effective to improve the productivity by shortening the polymerization time. Good.
[0161] 本発明に用いるリン化合物を併用することにより、ポリエステル重合触媒中のアルミ ニゥムとしての添加量が少量でも十分な触媒効果を発揮する触媒が得られる。  [0161] By using the phosphorus compound used in the present invention in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even if the amount of aluminum added to the polyester polymerization catalyst is small.
[0162] 以下に、アルミニウム化合物として、塩基性酢酸アルミニウムを用いた場合の、同溶 液の調製方法の具体例を示す。  [0162] Specific examples of the method for preparing the same solution when basic aluminum acetate is used as the aluminum compound are shown below.
[0163] (1)アルミニウム化合物のエチレングリコール溶液の調製例  [0163] (1) Preparation example of ethylene glycol solution of aluminum compound
塩基性酢酸アルミニウム（ヒドロキシアルミニウムジアセテート；アルドリッチ社製）を 2 Og/1の濃度で蒸留水に分散させ、攪拌下 95°Cで 2時間加熱処理をして溶解させた。 該水溶液に対して等量 (容量比）のエチレングリコールを共にフラスコへ仕込み、減 圧（133Pa)下、 70〜90°Cで攪拌しながら系から水を留去し、 20g/lのアルミニウム 化合物のエチレングリコール溶液を調製した。  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.
[0164] (2)リンィ匕合物のエチレングリコール溶液の調製例  [0164] (2) Preparation example of ethylene glycol solution of phosphorus compound
リン化合物として Irganox 1222 (チノく'スペシャルティー'ケミカルズ社製）をェチ レンダリコールと共にフラスコへ仕込み、窒素置換下攪拌しながら液温 160°Cで 12時 間加熱し、 30g/lのリンィ匕合物のエチレングリコール溶液を調製した。  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.
[0165] (3)アルミニウム化合物のエチレングリコール溶液/リン化合物のエチレングリコール 溶液の混合物の調製例 [0165] (3) Preparation example of a mixture of ethylene glycol solution of aluminum compound / ethylene glycol solution of phosphorus compound
上記アルミニウム化合物の調製例 1および上記リン化合物の調製例 1で得られたそ れぞれのエチレングリコール溶液をフラスコに仕込み、アルミニウム原子とリン原子が モル比で 1： 2となるように室温で混合し、 5時間攪拌して触媒溶液を調製した。  The respective ethylene glycol solutions obtained in Preparation Example 1 of the above-mentioned aluminum compound and Preparation Example 1 of the above-mentioned phosphorus compound are charged into a flask, and at room temperature so that the molar ratio of aluminum atoms to phosphorus atoms is 1: 2. The mixture was mixed and stirred for 5 hours to prepare a catalyst solution.
[0166] (4)アルカリ金属化合物のエチレングリコール溶液の調製例 [0166] (4) Preparation example of ethylene glycol solution of alkali metal compound
アルカリ金属化合物として酢酸リチウム（ナカライ (株)製、試薬特級)をエチレンダリ コールと共にフラスコへ仕込み、窒素置換下攪拌しながら室温で 30g/lのアルカリ 金属化合物のエチレングリコール溶液を調製した。  Lithium acetate (manufactured by Nacalai Co., Ltd., reagent grade) as an alkali metal compound was charged into the flask together with ethylene glycol, and an ethylene glycol solution of an alkali metal compound at 30 g / l was prepared at room temperature while stirring under nitrogen substitution.
[0167] 本発明に用いる重合触媒の別の態様として、上記アルミニウム化合物のエチレング リコール溶液/リンィ匕合物のエチレングリコール溶液にアルカリ金属化合物および/ま たはアルカリ土類金属のエチレングリコール溶液を併用して使用することも可能であ ることはいうまでもない。 [0168] 以下、本発明のポリエステル樹脂水分散体について説明する。 [0167] As another embodiment of the polymerization catalyst used in the present invention, 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. [0168] Hereinafter, the polyester resin aqueous dispersion of the present invention will be described.
本発明のポリエステル樹脂水分散体を構成する共重合ポリエステル樹脂における 樹脂酸価は、 3〜： 110mgK〇H/g、好ましくは 4〜： 105mgKOH/g、より好ましくは 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
5〜： 100mgKOHZg、さらに好ましくは 6〜95mgK〇H/gである。樹脂酸価が 3mg5-: 100 mg KOHZg, more preferably 6-95 mg KH / g. Resin acid value is 3mg
KOHZg未満であると分散安定性が悪くなる。一方 l lOmgKOHZgを超えると、樹 脂分散体力 得られる塗膜の耐水性が悪くなつてしまい、実用に耐えなレ、。 If it is less than KOHZg, the dispersion stability will deteriorate. On the other hand, if it exceeds lOmgKOHZg, the water dispersion of the resulting resin dispersion will deteriorate and the water resistance of the resulting coating will be unusable.
[0169] 本発明の共重合ポリエステル樹脂の酸価を示す官能基のうち、カルボキシノレ基及 び/またはスルホン酸基は 80%以上、好ましくは 85%以上、より好ましくは 90%以 上、更に好ましくは 95%以上である。カルボキシル基及び/またはカルボン酸基が 8 0%未満の場合、酸価を示す官能基の 20%超が、燐酸基またはフエノール性水酸基 である場合、水分散体の経時安定性が悪くなつたり、着色を起すことがあり、実用に 耐えない。  [0169] Among the functional groups showing the acid value of the copolyester resin of the present invention, 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. When the 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.
[0170] 本発明に用いるポリエステルとしては上記の範囲内であれば、様々な原料を使用 すること力 Sできる。  [0170] The polyester used in the present invention can use various raw materials within the above range.
[0171] 共重合ポリエステル樹脂の多価カルボン酸成分としては、例えばテレフタル酸、イソ フタル酸、オルソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸、コハク 酸、グルタル酸、アジピン酸、ァゼライン酸、セバシン酸、ドデカンジオン酸、ダイマー 酸等の脂肪族ジカルボン酸、（無水）マレイン酸、フマル酸、テルペン マレイン酸付 加体などの不飽和ジカルボン酸、 1 , 4ーシクロへキサンジカルボン酸、テトラヒドロフ タル酸、へキサヒドロイソフタル酸、 1 , 2—シクロへキセンジカルボン酸などの脂環族 ジカルボン酸、（無水）トリメリト酸、（無水）ピロメリト酸、メチルシクロへキセントリカルボ ン酸等の 3価以上のカルボン酸等が挙げられ、これらの中から 1種または 2種以上を 選択し使用できる。  [0171] 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. 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.
[0172] 本発明に用いる共重合ポリエステル樹脂に使用されるポリアルコール成分としては 、エチレングリコール、プロピレングリコール（1 , 2_プロパンジオール）、 1 , 3 _プロ パンジォーノレ、 1 , 4 _ブタンジォーノレ、 1， 2 _ブタンジォーノレ、 1 , 3 _ブタンジォー ノレ、 2_メチル一1 , 3 _プロパンジオール、ネオペンチルグリコール、 1 , 5_ペンタン ジオール、 1， 6—へキサンジオール、 3_メチル_ 1 , 5 _ペンタンジオール、 2—ェ チルー 2—ブチルー 1, 3—プロパンジオール、 2, 4—ジェチルー 1, 5—ペンタンジ オール、 1ーメチルー 1 , 8—オクタンジオール、 3—メチルー 1, 6—へキサンジォー ノレ、 4ーメチノレー 1 , 7—ヘプタンジオール、 4ーメチルー 1, 8—オクタンジオール、 4 —プロピル— 1， 8_オクタンジオール、 1 , 9—ノナンジオール等の脂肪族グリコール 、ジエチレングリコーノレ、トリエチレングリコーノレ、ポリエチレングリコーノレ、ポリプロピレ ングリコール、ポリテトラメチレングリコール等のエーテルグリコール類、 1， 4—シクロ へキサンジメタノール、 1， 3—シクロへキサンジメタノール、 1， 2—シクロへキサンジメ タノ一ノレ、トリシクロデカングリコール類、水素添カ卩ビスフヱノール類等の脂環族ポリア ノレコーノレ等、トリメチローノレプロパン、トリメチローノレエタン、ペンタエリスリトーノレ等の 3 価以上のポリアルコール等が挙げることができ、これらの中から 1種、又はそれ以上を 選び使用できる。 [0172] 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-1,8-octanediol, 4-propyl-1,8_octanediol, 1,9-nonanediol, diethylene glycolanol, triethyleneglycolanol, polyethyleneglycolanol, polypropylene glycol Ether glycols such as polytetramethylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane glycol, hydrogenated Trimethyl, such as alicyclic polyols such as carbphenols Norepuropan, trimethylolpropane low Honoré ethane, pentaerythritol tri- or higher can polyalcohol is exemplified such Honoré, one from among them, or more select available.
[0173] スルホン酸塩基を分子内に導入する場合は、例えば 5 _Naスルホイソフタル酸、 5 —アンモニゥムスルホイソフタル酸、 4— Naスルホイソフタル酸、 4—メチルアンモニゥ ムスルホイソフタル酸、 2— Naスルホテレフタル酸、 5— Kスルホイソフタル酸、 4— K スルホイソフタル酸、 2— Kスルホイソフタル酸、 Naスルホコハク酸等のスルホン酸ァ ルカリ金属塩系またはスルホン酸アミン塩系化合物、スルホン酸 Na塩含有ビスフヱノ ール A—アルキレンオキサイド付加物、スルホン酸 K塩基含有ハイドロキノンアルキレ ンオキサイド付加物等を共重合することが出来る。  [0173] In the case of introducing a sulfonate group into the molecule, 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.
[0174] フエノール性水酸基を分子内に導入する場合は、例えば 5—ヒドロキシイソフタル酸 、ジフヱノール酸等を共重合することが出来る。  [0174] When a phenolic hydroxyl group is introduced into the molecule, for example, 5-hydroxyisophthalic acid, diphenolic acid or the like can be copolymerized.
[0175] カルボキシル基を導入する方法は、ポリエステル樹脂を重合した後に常圧、窒素雰 囲気下、無水トリメリット酸、無水フタル酸、無水ピロメリット酸、無水コハク酸、無水 1 , 8_ナフタル酸、無水 1 , 2—シクロへキサンジカルボン酸、シクロへキサン一 1， 2, 3 , 4—テトラカルボン酸一3, 4_無水物、エチレングリコールビスアンヒドロトリメリテー ト、 5 - (2, 5—ジォキソテトラヒドロ一 3—フラニル） _ 3_メチル _ 3—シクロへキセン - 1 , 2—ジカルボン酸無水物、ナフタレン 1， 8 : 4， 5—テトラカルボン酸二無水物な どから 1種または 2種以上を選択し、後付加して酸価を付与する方法やポリエステル を高分子量化する前のオリゴマー状態のものにこれらの酸無水物を投入し、次いで 減圧下の重縮合により高分子量化することで、ポリエステルに酸価を導入する方法な どがある。この場合、 目標とする酸価が得られやすいとして前者の方法が好ましい。 [0175] 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. , Anhydrous 1,2-cyclohexanedicarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid-1,4_anhydride, ethylene glycol bisanhydro trimellitate, 5-(2, 5 —Dioxotetrahydro-1-3-furanyl) _ 3_Methyl _ 3-Cyclohexene-1, 2,2-dicarboxylic anhydride, naphthalene 1,8: 4, 5-tetracarboxylic dianhydride, etc. Or select two or more kinds, add these acid anhydrides to the method of adding the acid value by post-addition or the oligomer state before high molecular weight polyester, There is a method of introducing an acid value into polyester by increasing the molecular weight by polycondensation under reduced pressure. In this case, the former method is preferable because the target acid value is easily obtained.
[0176] また、ポリエステル重合時に、トリェチルァミン、トリー n—ブチルァミン、ベンジルジ メチルァミンなどの第 3級ァミン、水酸化テトラエチルアンモニゥム、水酸化テトラ— n —ブチルアンモニゥム、水酸化トリメチルベンジルアンモニゥムなどの水酸化第 4級ァ ンモニゥムおよび炭酸リチウム、炭酸ナトリウム、炭酸カリウム、酢酸ナトリウムなどの塩 基性化合物を少量添加して実施すると、グリコール成分同士の縮合物の発生が低く 抑えられるので好ましい。  [0176] Further, during polyester polymerization, 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.
[0177] カルボキシル基を導入したポリエステル樹脂の水分散体を作成する場合、分散した 微粒子の安定化のために、当該粒子表面のカルボキシノレ基などの極性基を部分的 に、あるいは全面的に塩基性物質でもって中和することが好ましい。  [0177] When preparing an aqueous dispersion of a polyester resin into which a carboxyl group has been introduced, in order to stabilize the dispersed fine particles, 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.
[0178] ここで、中和に使用できる塩基性物質としては、アンモニアゃトリエチルァミンなどに 代表されるァミン類、あるいは水酸化ナトリウム、水酸化カリウム、水酸化リチウムなど に代表される無機塩基類の使用が可能である。揮発性の問題や、逆に塗膜にした際 の塗膜中への残存の問題などを考慮して、用途に応じて選択すると良い。  [0178] Here, 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.
[0179] 揮発性アミン類として特に代表的なもののみを例示するにとどめれば、アンモニア、 モノメチルァミン、ジメチルァミン、トリメチルァミン、モノェチルァミン、ジェチルァミン 、トリェチルァミン、モノー n—プロピルァミン、ジメチル n—プロピルァミン、モノエタノ ールァミン、ジエタノールァミンまたはトリエタノールアミンをはじめ、 N—メチルェタノ ーノレアミン、 N—アミノエチルエタノールァミン、 N—メチルジェタノールァミン、モノィ ソプロパノールァミン、ジイソプロパノールァミン、トリイソプロパノールァミン、 N, N— ジメチルエタノールァミンまたは N, N—ジメチルプロパノールァミン等の各種のァミン 類などである。特に好ましいのは、トリエチノレアミン、 N， N—ジメチルエタノールァミン または N， N—ジメチルプロパノールァミンなどである。また、これらの有機塩基性化 合物から選ばれる 2種以上の併用を、決して妨げるものではない。  [0179] If only typical examples of volatile amines are exemplified, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, jetylamine, triethylamine, mono-n-propylamine, dimethyl n-propylamine, Monoethanolamine, diethanolamine or triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methylethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, Various amines such as N, N-dimethylethanolamine or N, N-dimethylpropanolamine. Particularly preferred are triethylenoamine, N, N-dimethylethanolamine or N, N-dimethylpropanolamine. Moreover, it does not prevent the combined use of two or more selected from these organic basic compounds.
[0180] 水分散体の製造方法としては、公知の方法をとることができる力 例えば、ブチルセ 口ソルブ等の高沸点有機溶剤に溶解した後に温水を加え水分散させることができる。 また、ブチルセルソルブ、メチルェチルケトン、イソプロピルアルコール等極性溶剤と 水の混合溶剤に、直接溶解/分散させることができる。また、水よりも沸点の低い溶 媒を使用して、溶解/分散させた系では、有機溶剤を溜去すれば完全水系の水分 散体を得ること力 Sできる。 [0180] As a method for producing an aqueous dispersion, power capable of taking a publicly known method can be used. For example, hot water can be added and dispersed in water after dissolving in a high-boiling organic solvent such as butylcerosolve. Also, polar solvents such as butyl cellosolve, methyl ethyl ketone, isopropyl alcohol It can be directly dissolved / dispersed in a mixed solvent of water. In addition, in a system in which 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.
[0181] また共重合ポリエステル樹脂と、必要に応じて保水剤、分散助剤などを加圧ニーダ 一、加熱 3本ロール、 2軸押出混練機などを用いて溶融混練して樹脂溶融体を製造 し、共重合ポリエステル樹脂の溶融温度以上の温度に加熱し、塩基性化合物を含有 し加熱された水性媒体中に、必要により加圧下で、溶融状態で機械的手段により分 散させる製造方法等が挙げられる。  [0181] Also, 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. Can be mentioned.
[0182] カルボキシル基の中和は、この方法に限定されるものではなぐ例えば、カルボキシ ル基の塩基性化合物による中和を行った後、樹脂溶融体を水性媒体中に機械的手 段で分散させる方法や、樹脂溶融体を水性媒体中に機械的手段で分散させたのち 、攪拌下で塩基性化合物を加えて中和する方法であっても良い。  [0182] Neutralization of carboxyl groups is not limited to this method. For example, after neutralization of a carboxyl group with a basic compound, the resin melt is dispersed mechanically in an aqueous medium. Or a method in which a resin melt is dispersed in an aqueous medium by mechanical means and then neutralized by adding a basic compound under stirring.
[0183] 水性媒体は、加熱時に必要に応じて加圧してもよレ、。樹脂溶融体の溶融温度が低 い場合は、必ずしも加圧は必要ないが、溶融温度が 100°C以上の場合には、水性媒 体が沸騰しなレ、ように加圧する必要がある。  [0183] The aqueous medium may be pressurized as necessary during heating. When the melting temperature of the resin melt is low, 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.
[0184] 本発明に用いる有機溶剤としては、例えば、 n—ブタノール、イソプロピルアルコー ノレ、ジアセトンアルコール、 2—ェチルへキサノール、メチルェチルケトン、ァセトニトリ ノレ、ジメチルァセトアミド、ジメチルホルムアミド、 n メチルピロリドン、テトラヒドロフラ ン、 1 , 4 ジォキサン、 1 , 3—ォキソラン、メチルソロソルブ、ェチルソロソルブ、ブチ ノレセロソルブ、ェチノレカノレビトーノレ、ブチルカルビトール、プロピレングリコールモノプ 口ピルエーテル、プロピレングリコールモノプチルエーテルなどの両親媒性溶媒を必 要に応じて用いても良い。  [0184] 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. Pyrrolidone, tetrahydrofuran, 1,4 dioxane, 1,3-oxolane, methyl solosolve, ethyl solosolve, butinorecellosolve, ethinorecanolebitonore, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monoptil ether An amphiphilic solvent such as may be used as necessary.
[0185] このうちイソプロピルアルコール、ブチルセ口ソルブ、プロピレングリコールモノプロ ピノレエーテノレ、プロピレングリコーノレモノブチノレエーテノレ、ブチノレカノレビトーノレが特に 好ましレ、。またこれらの有機溶剤は、溶媒に水以外のものを用いなレ、、完全水系のポ リエステル樹脂水分散体を製造するときは、水分散体を有機溶剤の沸点以上に加熱 し、有機溶剤を揮発、脱有機溶剤する必要がある。そうでない場合はこれらの有機溶 剤はポリエステル樹脂水分散体中に含有してレ、ても良レ、。 [0186] 以下、本発明のハイブリッド樹脂水分散体について説明する。 [0185] Of these, isopropyl alcohol, butylcetosolve, propylene glycol monopropinoreateol, propyleneglycololebutynoreatenore and butinorecanolebitonore are particularly preferred. When these organic solvents are prepared using a solvent other than water, or when producing a completely aqueous polyester resin aqueous dispersion, 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. [0186] The hybrid resin aqueous dispersion of the present invention will be described below.
本発明のハイブリッド樹脂水分散体に用いられる、共重合ポリエステル樹脂、およ び/または、その共重合ポリエステル樹脂を構成成分として含むポリウレタン樹脂と、 アクリル樹脂とのハイブリッド樹脂の酸価は、 20〜400mgKOH/g、好ましくは 25〜 350mgKOHZg、より好まし <は 30〜300mgK〇H さらに好まし <は 35〜250 mgKOHZgである。樹脂酸価が 20mgK〇H/g未満であると、水分散体としたとき に分散安定性が悪くなる。一方 400mgKOHZgを超えると、樹脂分散体から得られ る塗膜の耐水性が悪くなつてしまい、実用に耐えなレ、。  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. When the resin acid value is less than 20 mgK0H / g, the dispersion stability becomes poor when an aqueous dispersion is obtained. On the other hand, if it exceeds 400 mgKOHZg, the water resistance of the coating film obtained from the resin dispersion will deteriorate, and it will be unusable.
ハイブリッド樹脂の酸価は、下記測定法で記載する通り、水分散体で測定し、樹脂 固形分重量当たりに換算した値である。  As described in the following measurement method, 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.
[0187] 本発明のハイブリッド樹脂のうち、共重合ポリエステル樹脂、および Zまたは、その 共重合ポリエステル樹脂を構成成分として含むポリウレタン樹脂の重量は 10%以上 90%以下、好ましくは 15%以上 88%以下、より好ましくは 20%以上 86%以下、更 に好ましくは 25%以上 85%以下である。共重合ポリエステル樹脂、および/または、 その共重合ポリエステル樹脂を構成成分として含むポリウレタン樹脂の重量が 10% 未満の場合、得られる塗膜の可撓性が悪くなり、 90%超の場合、アクリル部分で導入 できる官能基量が少なくなる等、ハイブリッド樹脂にするメリットがなくなってしまう。特 に、共重合ポリエステル樹脂、および/または、その共重合ポリエステル樹脂を構成 成分として含むポリウレタン樹脂が疎水性で、アクリル樹脂部分で水分散機能を付与 する場合、得られる水分散体の安定性を損ねてしまう。  [0187] Among the hybrid resins of the present invention, 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. In particular, when 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.
[0188] 共重合ポリエステル樹脂、および/または、その共重合ポリエステル樹脂を構成成 分として含むポリウレタン樹脂とアクリル樹脂とのハイブリッド樹脂を製造するには、 [0188] To produce a copolyester resin and / or a hybrid resin of a polyurethane resin and an acrylic resin containing the copolyester resin as a constituent component,
(1)高分子量の共重合ポリエステル樹脂、および Zまたは、その共重合ポリエステル 樹脂を構成成分として含むポリウレタン樹脂と、高分子量のアクリル樹脂を、直接およ び/または架橋剤等を用いて化学的結合させる方法 (1) 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
(2)高分子量の共重合ポリエステル樹脂、および Zまたは、その共重合ポリエステル 樹脂を構成成分として含むポリウレタン樹脂に、アクリル樹脂を形成するモノマーと反 応可能な官能基を導入し、その存在下でアクリル樹脂を重合する方法 (3)アクリル樹脂ェマルジヨン中で、共重合ポリエステル樹脂を水中重合する方法 などが挙げられる力 共重合ポリエステル樹脂、および/または、その共重合ポリェ ステル樹脂を構成成分として含むポリウレタン樹脂のもつ物性を活力しながら、機能 性付与のためにアクリル樹脂をハイブリッドするには、（2)の方法が適当である。 (2) 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 On the other hand, the method (2) is suitable for hybridizing an acrylic resin for imparting functionality.
[0189] 本発明に用いる共重合ポリエステル樹脂としては上記の範囲内であれば、様々な 原料を使用することができる。  [0189] As the copolyester resin used in the present invention, various raw materials can be used as long as they are within the above range.
[0190] 共重合ポリエステル樹脂のジカルボン酸成分としては、例えば芳香族ジカルボン酸 としてはテレフタル酸、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸、ビフ ヱニルジカルボン酸等を挙げることができる。脂肪族ジカルボン酸としては、コハク酸 [0190] Examples of the dicarboxylic acid component of the copolyester resin include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like as aromatic dicarboxylic acid. Aliphatic dicarboxylic acids include succinic acid
、アジピン酸、ァゼライン酸、セバシン酸、ドデカンジオン酸、ダイマー酸等を挙げるこ とができ、脂環族ジカルボン酸としては、 1 , 4—シクロへキサンジカルボン酸、 1， 3- シクロへキサンジカルボン酸、 1 , 2—シクロへキサンジカルボン酸とその酸無水物等 を挙げることができる。 , Adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and the like. Examples of alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid. Examples thereof include acids, 1,2-cyclohexanedicarboxylic acid and acid anhydrides thereof.
[0191] さらに、 P-ヒドロキシ安息香酸、 p-(2 ヒドロキシエトキシ）安息香酸、あるいはヒドロ キシビバリン酸、 γ—ブチ口ラタトン、 ε—力プロラタトン等のヒドロキシカルボン酸類も 必要により使用できる。  [0191] Furthermore, P-hydroxybenzoic acid, p- (2 hydroxyethoxy) benzoic acid, or hydroxycarboxylic acids such as hydroxybivalic acid, γ-butyral rataton, and ε-force prolataton can be used as necessary.
[0192] 共重合ポリエステル樹脂のジカルボン酸成分としては、重合性不飽和二重結合を 含有するジカルボン酸を用いることができ、その例としては、 ひ， 一不飽和ジカル ボン酸類としてフマル酸、マレイン酸、無水マレイン酸、ィタコン酸、シトラコン酸、不 飽和二重結合を有する脂環族ジカルボン酸として 2, 5 ノルボルナンジカルボン酸 無水物、テトラヒドロ無水フタル酸等を挙げることができる。  [0192] As the 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.
[0193] 共重合ポリエステル樹脂にアクリルモノマーをグラフトすることにより、ポリエステル —アクリルハイブリッド樹脂を作製する場合、重合性不飽和二重結合を含有するジカ ルボン酸の使用量は、全酸成分に対して 2〜7モル％である。重合性不飽和二重結 合を含有するジカルボン酸が 2モル％未満の場合、共重合ポリエステル樹脂に対す るラジカル重合性単量体の効率的なグラフト化が行なわれにくぐ水系媒体中での分 散粒子径が大きくなる傾向があり、分散安定性が低下する傾向がある。  [0193] When a polyester-acrylic hybrid resin is produced by grafting an acrylic monomer to a copolyester resin, the amount of dicarboxylic acid containing a polymerizable unsaturated double bond is based on the total acid component. 2 to 7 mol%. When 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.
重合性不飽和二重結合を含有するジカルボン酸が 7モル％を超える場合、グラフト 化反応の後期に余りにも粘度が上昇し反応の均一な進行をさまたげるので望ましく ない。 If 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.
[0194] 一方、共重合ポリエステル樹脂のグリコール成分は炭素数 2〜： 10の脂肪族グリコー ルおよびまたは炭素数力 〜： 12の脂環族グリコールおよび Zまたはエーテル結合含 有グリコールよりなる力 炭素数 2〜： 10の脂肪族グリコールとしては、エチレングリコ ール、 1 , 2 _プロピレングリコ一ノレ、 1 , 3 _プロパンジォ一ノレ、 1 , 4 _ブタンジォー ノレ、 1 , 5 _ペンタンジオール、ネオペンチルグリコール、 1 , 6—へキサンジオール、 3 —メチノレ一 1 , 5 _ペンタンジオール、 1 , 9—ノナンジオール、 2 _ェチル _ 2—ブチ ノレプロパンジオール、ヒドロキシピバリン酸ネオペンチルグリコールエステル、ジメチ口 ールヘプタン等を挙げることができ、炭素数 6〜： 12の脂環族グリコールとしては、 1， 4—シクロへキサンジメタノール、トリシクロデカンジメタノール等を挙げることができる  [0194] On the other hand, 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.
[0195] エーテル結合含有グリコールとしては、ジエチレングリコール、トリエチレングリコー ノレ、ジプロピレングリコール、さらにビスフエノール類の 2つのフエノール性水酸基にェ チレンオキサイド又はプロピレンオキサイドをそれぞれ 1〜数モル付カ卩して得られるグ リコーノレ類、例えば 2, 2—ビス（4ーヒドロキシエトキシフエニル）プロパンなどを挙げる こと力 S出来る。その他のグリコールとして、公知のポリオールが使用でき、例えば、ポリ エチレングリコールやポリプロピレングリコールやポリテトラメチレングリコール等のポリ エーテルポリオール類、ラタトン系化合物の重合体やポリエチレンアジペート等のポリ エステルポリオール類、ポリカーボネートポリオール類、ポリオレフインポリオール類等 が使用できる力 そのほかに、ジカルボン酸化合物ゃジァミン化合物にエポキシ化合 物を反応させて得られるポリオール等も使用できる。ポリエチレングリコール、ポリプロ ピレンダリコール、ポリテトラメチレングリコールも必要により使用しうる。 [0195] 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. As other glycols, known polyols can be used. For example, 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 In addition, the ability to use polyolefin polyols, etc. In addition, 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.
[0196] 本発明の共重合ポリエステル樹脂中に 0〜5モル％の 3官能以上のポリカルボン酸 および/又はポリオールが共重合することができる力 S、 3官能以上のポリカルボン酸と しては（無水）トリメリット酸、（無水）ピロメリット酸、（無水）ベンゾフエノンテトラカルボン 酸、トリメシン酸、エチレンダルコールビス（アンヒドロトリメリテート）、グリセロールトリス (アンヒドロトリメリテート）等が使用される。一方 3官能以上のポリオ一ルとしてはグリセ リン、トリメチ口一ルェタン、トリメチロールプロパン、ペンタエリスリトール等が使用され る。 [0196] In the copolymerized polyester resin of the present invention, 0 to 5 mol% of tricarboxylic or higher polycarboxylic acid and / or polyol can be copolymerized with S, and trifunctional or higher polycarboxylic acid. (Anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene dalcol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), etc. used. On the other hand, as a polyol with more than 3 functional groups, Phosphorus, trimethyl mouthfuls, trimethylol propane, pentaerythritol, etc. are used.
[0197] 3官能以上のポリカルボン酸またはポリオールは、全酸成分または全グリコール成 分に対し 0〜5モル％、望ましくは、 0〜3モル％の範囲で共重合されるが、 5モル0 /0 を越えると充分な加工性が付与できに《なる。 [0197] 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.
[0198] 本発明の共重合ポリエステル樹脂は必要により、スルホン酸基、フエノール性水酸 基が導入されてもよい。  [0198] In the copolymerized polyester resin of the present invention, a sulfonic acid group or a phenolic hydroxyl group may be introduced, if necessary.
[0199] スルホン酸塩基を分子内に導入する場合は、例えば 5 _Naスルホイソフタル酸、 5 —アンモニゥムスルホイソフタル酸、 4— Naスルホイソフタル酸、 4—メチルアンモニゥ ムスルホイソフタル酸、 2 _Naスルホテレフタル酸、 5— Kスルホイソフタル酸、 4— K スルホイソフタル酸、 2— Kスルホイソフタル酸、 Naスルホコハク酸等のスルホン酸ァ ルカリ金属塩系またはスルホン酸アミン塩系化合物、スルホン酸 Na塩含有ビスフヱノ ール A—アルキレンオキサイド付加物、スルホン酸 K塩基含有ハイドロキノンアルキレ ンオキサイド付加物等を共重合することが出来る。  [0199] When 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.
[0200] フエノール性水酸基を分子内に導入する場合は、例えば 5—ヒドロキシイソフタル酸 、ジフヱノール酸等を共重合することが出来る。  [0200] When a phenolic hydroxyl group is introduced into the molecule, for example, 5-hydroxyisophthalic acid, diphenolic acid or the like can be copolymerized.
[0201] 本発明の共重合ポリエステル樹脂に添加される酸化防止剤としては、フエノール系 酸化防止剤、リン系酸化防止剤、アミン系酸化防止剤、硫黄系酸化防止剤などが例 示できる。  [0201] Examples of the antioxidant added to the copolyester resin of the present invention include phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, and the like.
[0202] フエノール系酸化防止剤としてはイソアミルガレート、ブチル化ヒドロキシァ二ソール 、ブチル化ヒドロキシトノレェン、 4,4'ーブチルデンビス (3—メチル -6-t-ブチルフエノー ノレ）、 2，4-ジォクチルチオ- 6-(4 '—ヒドロキシ- 3',5 '—ジ -t—ブチルァニリノ)- 1,3，5-トリ ァジン、ドデシルガレート、 2，6-ジ -t_ブチル -4—ヒドロキシメチルフヱノール、プロ口 カテチュ酸ェチル、 2，2 '—メチレン（ビス- 4_メチル _6_t-ブチルフエノール）、ォクタ デシル -3-(4-ヒドロキシ -3，5—ジ _t_ブチルフエニル）プロピオネート、ォクチルガレ ート、プロピルガレート、 4,4' _イソプロピリデンビス (2—イソプロピルフエノール）、ソル ビン酸、ソルビン酸カリウム、テトラキス [メチレン (3，5—ジ _t_ブチル -4—ヒドロキシフ ェニル）プロピオネート]メタン、テレフタロイル―ジ (2, 6—ジメチル -4-t_ブチル -3— ヒドロキシベンジルスルファイト、 4,4'ーチォビス (6-t ブチル -m クレゾ一ル）、トリス( 3,5—ジ -t ブチル -4 -ヒドロキシフエニル）イソシァヌレート、トリス [ベータ- 3, 5—ジ (t ブチル -4ーヒドロキシフエ二ノレ）プロピオ二ルォキシェチノレ]イソシァヌレート、グァ ャク脂、ノルジヒドログアヤンチック酸、トコフエノール、エリソルビン酸、 2，5-ジクロロ- p —ベンゾキノン、 2, 6 -ジクロ口 _p—ベンゾキノン、 p-ベンゾキノン、テトラメチルベンゾ キノン、ピクリン酸、メチル _p—ベンゾキノン、メトキシ- p—ベンゾキノン， 2，4,6 -トリ- 1_ ブチルフエノール、 n-ォクタデシル- 3_(4 '—ヒドロォキシ -3'，5' _ジ- 1—ブチルフエノ ール）プロピオネート、スチレン化フエノール、 4 -ヒドロォキメチル -2,6—ジ _t_ブチル フエノーノレ， 2,5-ジ -t_ブチルハイドロキノン、シクロへキシフエノール、 2，2 '—メチレン (ビス- 4_ェチル _6_t_ブチルフエノール）、 4，4，_イソプロピリデンビスフェノール、 1, 1'—ビス（4-ヒドロキシフエニル）シクロへキサン、 4，4' メチレンビス（2，6-ジ -t ブチ ルフヱノール）、 2,6-ビス（2 '—ヒドロキシ -3'- -ブチル -5しメチルベンジル） 4-メチルフ エノーノレ、 1, 1, 3-トリス（2-メチル -4ーヒドロキシ -5-t ブチルフエニル）ブタン、 1，3，5- トリスーメチル -2, 4,6 トリス（3,5-ジ -t-ブチル -4-ヒドロキシベンジル）ベンゼン、 4，4'- チォビス（3-メチル -6-t-ブチルフエノーノレ）、 4,4,しチォビス（4-メチル -6-t-ブチルフ 工ノール）、 4，4'-チォビス（2-メチル -6-t-ブチルフエノール）など、またはそれらの誘 導体などが挙げられる。なかでも好ましいものとして 2,4,6-トリ- 1-ブチルフエノール、 4 -ヒドロォキメチル -2,6-ジ -t-ブチルフエノール， 2, 5-ジ -t-ブチルハイドロキノン、 2,2'- メチレン（ビス- 4-ェチル -6-t-ブチルフエノール）、 4，4'-イソプロピリデンビスフエノー ノレ、 4，4'-ブチルデンビス（3-メチル -6-t-ブチルフエノーノレ）、 1，1'-ビス（4-ヒドロキシ フエニル）シクロへキサン、 4,4'-メチレンビス (2,6-ジ- 1-ブチルフエニール），2,6-ビス（ 2'-ヒドロキシ _3'-t-ブチル -5'-メチルベンジル） 4-メチルフエノール、 1，1，3_トリス（2-メ チル -4-ヒドロキシ -5-t-ブチルフヱニル）ブタン、 1,3, 5-トリス-メチル -2,4,6-トリス（3，5 -ジ -t_ブチル -4-ヒドロキシベンジル）ベンゼン、テトラキス〔メチレン (3，5-ジ -t_ブチル -4-ヒドロキシフエニル）プロピオネート〕メタン、トリス（3，5-ジ -t-ブチル -4-ヒドロキシフ ヱニル）イソシァヌレート、トリス〔ベータ- 3，5-ジ（t-ブチル 4-ヒドロキシフヱニル）プロピ ォニルォキシェチル〕イソシァヌレート、 4,4'-チォビス（3-メチル -6-t-ブチルフエノー ル）、 4，4， -チォビス（2-メチル -6-t-ブチルフエノール）などがあげられ、さらに好まし いものとして、 2,5-ジ -t-ブチルハイドロキノン、 4，4'-ブチルデンビス（3-メチル -6-t-ブ チルフエノール）、 1, 1,3-トリス（2-メチル -4-ヒドロキシ -5-t-ブチルフエニル）ブタン、 1， 3,5-トリス-メチル -2,4,6-トリス（3,5-ジ -t-ブチル -4-ヒドロキシベンジル）ベンゼン、トリ ス（3，5-ジ -t_ブチル -4-ヒドロキシフエニル）イソシァヌレートなど、またはそれらの誘 導体等が挙げられる。 [0202] 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 (3,5-di-t_butyl-4-hydroxyphenyl) propionate G] methane, terephthaloyl-di (2,6-dimethyl-4-t_butyl-3 Hydroxybenzyl sulfite, 4,4'-thiobis (6-t butyl-m cresol), tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [beta-3,5-di (t-Butyl-4-hydroxyphenenole) propionyloxychettinole] isocyanurate, guaiac fat, nordihydroguayantic acid, tocophenol, erythorbic acid, 2,5-dichloro-p-benzoquinone, 2, 6-dichloro _p —Benzoquinone, p-benzoquinone, tetramethylbenzoquinone, picric acid, methyl _p-benzoquinone, methoxy-p-benzoquinone, 2,4,6-tri-1_butylphenol, n-octadecyl-3_ (4'-hydroxy-3 ', 5' _di-1-butylphenol) propionate, styrenated phenol, 4-hydroxymethyl-2,6-di-t_butylphenol, 2,5- -t_Butylhydroquinone, cyclohexenyl, 2,2'-methylene (bis-4-ethyl _6_t_butylphenol), 4,4, _isopropylidenebisphenol, 1,1'-bis (4-hydroxyphenyl) ) Cyclohexane, 4,4 'methylenebis (2,6-di-t-butylphenol), 2,6-bis (2'-hydroxy-3'-butyl-5 and methylbenzyl) 4-methylphenol, 1 , 1, 3-Tris (2-methyl-4-hydroxy-5-tbutylphenyl) butane, 1,3,5-trismethyl-2,4,6 tris (3,5-di-t-butyl-4-hydroxybenzyl ) Benzene, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4, thiobis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol) and the like or derivatives thereof. Among them, 2,4,6-tri-1-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,5-di-t-butylhydroquinone, 2,2'-methylene are preferable. (Bis-4-ethyl-6-t-butylphenol), 4,4'-isopropylidenebisphenol, 4,4'-butyldenbis (3-methyl-6-t-butylphenol), 1, 1'-bis (4-hydroxyphenyl) cyclohexane, 4,4'-methylenebis (2,6-di-1-butylphenyl), 2,6-bis (2'-hydroxy_3'-t-butyl -5'-methylbenzyl) 4-methylphenol, 1,1,3_tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris-methyl-2,4 , 6-Tris (3,5-di-t_butyl-4-hydroxybenzyl) benzene, tetrakis [methylene (3,5-di-t_butyl-4-hydroxyphenyl) propionate] methane , Tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [beta-3,5-di (t-butyl 4-hydroxyphenyl) propionyloxychetyl] isocyanurate 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4, -thiobis (2-methyl-6-t-butylphenol), etc. 2,5-di-t-butylhydroquinone, 4,4'-butyldenbis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy) -5-t-butylphenyl) butane, 1,3,5-tris-methyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5 -Di-t_butyl-4-hydroxyphenyl) isocyanurate, or derivatives thereof.
[0203] リン系酸化防止剤としては、トリ（ノユルフェニル）ホスファイト、トリフエニルホスフアイ ト、ジフヱ二ルイソデシルホスファイト、トリオクタデシルホスフアイト、トリデシルホスファ イト、ジフヱニルデシルホスフアイト、 4,4'-ブチリデン-ビス（3-メチル _6_t-ブチルフエ ニルジトリデシルホスフアイト）、ジステアリル-ペンタエリスリトールジホスフアイト、トリラ ゥリルトリチォホスファイトなど、またはそれらの誘導体等が挙げられるなど、またはそ れらの誘導体等が挙げられる。  [0203] 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.
[0204] アミン系酸化防止剤としては、 1，3-ジメチルブチル- N-フエニル- n_フエ二レンジアミ ン、 Ν,Ν'-ジ (1,4-ジメチルペンチル) -n-フエ二レンジァミン、 N-フエニル- Ν'-イソプロ ピル- ρ-フエ二レンジァミン、 6-エトキシ -2,2,4-トリメチル -1,2-ジヒドロキノリン、フエノ チアジン、フエニル-アルファ-ナフチルァミン、フエニル-ベータ-ナフチルァミン、 Ν,Ν '-ジフエニル -ρ-フエ二レンジァミン、 Ν,Ν'-ジ-ベータナフチル -ρ-フエ二レンジァミン 、 Ν-シクロへキシル Ν'-フエニル -ρ -フエ二レンジァミン、アルドール -アルファ-ナフチ ノレアミン、 2,2,4-トリメチル -1,2-ジハイド口キノリンポリマーなど、またはそれらの誘導 体等が挙げられる。中でも好ましいものとしてはフエニル-ベータ-ナフチルァミン、フ エノチアジン、 Ν,Ν'-ジフエニル -ρ-フエ二レンジァミン、 -ジ-べータナフチル- _ フエ二レンジァミン、 Ν-シクロへキシル -Ν'-フエニル -ρ-フエ二レンジァミン、ァノレドー ル-アルファ-ナフチルァミン、 2, 2,4-トリメチル -1,2 -ジハイド口キノリンポリマーなど、ま たはそれらの誘導体等が挙げられる。  [0204] Amine-based antioxidants include 1,3-dimethylbutyl-N-phenyl-n_phenylenediamine, Ν, Ν'-di (1,4-dimethylpentyl) -n-phenylenediamine, N-phenyl-Ν'-isopropyl-ρ-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, phenylthiazine, phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, Ν, Ν '-Diphenyl-ρ-phenylenediamine, Ν, Ν'-Di-beta-naphthyl-ρ-phenylenediamine, シ ク ロ -cyclohexyl Ν'-phenyl-ρ-phenylenediamine, aldol-alpha-naphthy Examples thereof include noreamine, 2,2,4-trimethyl-1,2-dihydrate quinoline polymer, and derivatives thereof. Among them, preferred are phenyl-beta-naphthylamine, phenothiazine, Ν, Ν'-diphenyl-ρ-phenylenediamine, -di-betanaphthyl- _phenylenediamine, Ν-cyclohexyl-Ν'-phenyl-ρ -Fenylenediamine, ananolol-alpha-naphthylamine, 2,2,4-trimethyl-1,2-dihydred quinoline polymer, or derivatives thereof.
[0205] 硫黄系酸化防止剤としてはチォジプロピオン酸、ジラウリルチオジプロピオネート、 ジステアリルチオジプロピオネート、ラウリルステアリルチオジプロピオネート、ジミリス チノレチォジプロピオネート、ジステアリノレ-ベータ、ベータ， -チォジブチレート、チオビ ス（ベータナフトール）、チォビス（Ν -フエニル-ベータ-ナフチルァミン、 2-メルカプト ベンゾチアゾール、 2_メルカプトべンゾイミダゾール、ドデシルメルカプタン、テトラメチ チォカルバメート、ニッケルイソプロピルキサンテート、ジラウリルチオジプロピオネー トなど、又はそれらの誘導体が挙げられる。なかでも好ましいものとしては、チォビス（ N-フエニル-ベータ-ナフチルァミン、 2_メルカプトベンチァゾール、 2_メルカプトベン ゾイミダゾール、テトラメチルチウラムジサルファイド、ニッケルイソプロピルキサンテー トなど、又はそれらの誘導体が挙げられる。 [0205] Sulfuric antioxidants include thiodipropionic acid, dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristino thiodipropionate, distearino re-beta, beta, -Thiodibutyrate, thiobis (beta-naphthol), thiobis (Ν-phenyl-beta-naphthylamine, 2-mercaptobenzothiazole, 2_mercaptobenzozoimidazole, dodecyl mercaptan, tetramethi Examples include thiocarbamate, nickel isopropyl xanthate, dilauryl thiodipropionate, and the like, or derivatives thereof. Among them, thiobis (N-phenyl-beta-naphthylamine, 2_mercaptobendazole, 2_mercaptobenzazoimidazole, tetramethylthiuram disulfide, nickel isopropyl xanthate, etc., or their derivatives are preferable. It is done.
[0206] ニトロ化合物系酸化防止剤としては、 1，3，5_トリニトロベンゼン、 p -ニトロソジフヱニル ァミン、 p-ニトロソジメチルァ二リン、 1-クロ口- 3_ニトロベンゼン、 0-ジニトロベンゼン、 m-ジニトロベンゼン、 p-ジニトロベンゼン、 p-ニトロ安息香酸、ニトロベンゼン、 2-ニト 口- 5-シァノチォフェンなど、又はそれらの誘導体が挙げられる。無機化合物系酸化 防止斉 IJとしては、 FeCl、 Fe(CN)、 CuCl、 CoCl、 Co(C10 )、 Co(NO )、 Co (S〇）等 が挙げられる。 [0206] 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. Examples of inorganic compound-based antioxidant IJ include FeCl, Fe (CN), CuCl, CoCl, Co (C10), Co (NO), and Co (SO).
[0207] これらの酸化防止剤の中で、フエノール系酸化防止剤、アミン系酸化防止剤が熱 安定性の点で好ましぐ融点が 120°C以上で分子量が 200以上のものがより好ましく 、融点が 170°C以上のものがさらに好ましい。酸化防止剤の使用される量としては、 榭月旨に対し、 10〜5000ppmであり、望ましくは 100〜2000ppmであり、さらに望まし くは 100〜： !OOOppmである。 5000ppmを越えると、ポリエステル中の二重結合を利 用した反応を阻害する恐れがある。 lOppm以下では、熱安定性が低ぐゲル化が進 行する恐れがある。  [0207] Among these antioxidants, 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.
[0208] 得られた共重合ポリエステル樹脂の分子量は、還元粘度測定により代用的に知るこ とができる。樹脂の還元粘度は、 0.：!〜 2. 0dl/gであり、望ましくは 0. 2〜： 1. 5dl/ g、さらに望ましくは 0. 3〜： 1. 3dl/gである。 0. ldlZg以下では、望ましい機械的物 性が得られない。  [0208] 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.
[0209] ポリウレタン樹脂に二重結合を含む重合性単量体をグラフトして、ポリウレタンーァ クリルハイブリッド樹脂を作製する場合、当該樹脂は、上に記載したポリエステル重合 用モノマー類を重合することにより得られるポリエステルポリオール (a)、有機ジィソシ ァネート化合物 (b)、及び必要に応じて活性水素基を有する鎖延長剤 (c)より構成され る。 [0210] アクリル樹脂とハイブリッドさせ、充分な物性を達成するには、ポリウレタン樹脂の分 子量は 5000〜： 100000、ウレタン結合含有量は 500〜4000当量/ 106g、重合性 二重結合含有量は一分子当たり平均 1.5〜30個であることが好ましい。 [0209] When 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 resulting polyester polyol (a), an organic disoocyanate compound (b), and, if necessary, a chain extender (c) having an active hydrogen group. [0210] In order to achieve sufficient physical properties by hybridizing with acrylic resin, 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.
また、ポリエーテルポリオール、ポリオレフインポリオールなども必要に応じて、これら ポリエステルポリオールと共に使用することができる。  Moreover, polyether polyol, polyolefin polyol, etc. can be used with these polyester polyols as needed.
[0211] 本発明で用いる有機ジイソシァネートイ匕合物 (b)としては、へキサメチレンジイソシァ ネート、テトラメチレンジイソシァネート、 3, 3 '—ジメトキシ一4, 4 '—ビフエ二レンジィ  [0211] The organic diisocyanate compound (b) used in the present invention includes hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-1,4'-biphenol. Two range
—ジイソシァネートメチルシクロへキサン、 4， 4 '—ジイソシァネートジシクロへキサン 、 4, 4 '—ジイソシァネートシクロへキシルメタン、イソホロンジイソシァネート、 2, 4—ト リレンジイソシァネート、 2, 6 _トリレンジイソシァネート、 p—フエ二レンジイソシァネー ト、ジフエニルメタンジイソシァネート、 m—フエ二レンジイソシァネート、 2, 4_ナフタ レンジイソシァネート、 3, 3， 一ジメチルー 4, 4'ービフエ二レンジイソシァネート、 4, 4 ，ージイソシァネートジフエニルエーテル、 1 , 5—ナフタレンジイソシァネート等が挙 げられる。 —Diisocyanate methylcyclohexane, 4,4′-diisocyanate dicyclohexane, 4,4′-diisocyanate cyclohexylmethane, isophorone diisocyanate, 2,4-tolylene Isocyanate, 2, 6_tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2, 4_naphtha diisocyanate 3, 3, 1-dimethyl-4,4'-biphenyl diisocyanate, 4,4, -diisocyanate diphenyl ether, 1,5-naphthalene diisocyanate, and the like.
[0212] 本発明において、ポリウレタン樹脂を得るのに必要に応じて使用する活性水素基を 有する鎖延長剤 (c)としては、例えば、エチレングリコール、プロピレングリコール、ネ ォペンチルグリコール、 2, 2—ジェチルー 1 , 3—プロパンジオール、ジエチレングリ コール、スピログリコール、ポリエチレングリコールなどのグリコール類、へキサメチレ ンジァミン、プロピレンジァミン、へキサメチレンジァミンなどのアミン類が挙げられる。  [0212] In the present invention, 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.
[0213] 本発明に用いるポリウレタン樹脂は、ポリエステルポリオール (a)、有機ジイソシァネ ート (b)、及び必要に応じて活性水素基を有する鎖延長剤 (c)とを、（a)+(c)の活性水素 基/イソシァネート基の比で 0.8〜1.3 (当量比）の配合比で反応させて得られるポリウ レタン樹脂であることが必要である。  [0213] 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).
(a)+(c)の活性水素基/イソシァネート基の比がこの範囲外であるとき、ウレタン樹脂 は充分高分子量ィヒすることが出来ず、所望の塗膜物性を得ることが出来ない。  When the ratio of active hydrogen groups / isocyanate groups of (a) + (c) is outside this range, the urethane resin cannot sufficiently have a high molecular weight, and the desired coating film properties cannot be obtained.
[0214] 本発明で使用するポリウレタン樹脂は、公知の方法、溶剤中で 20〜150°Cの反応 温度で触媒の存在下あるいは無触媒で製造される。この際に使用する溶剤としては 、例えば、メチルェチルケトン、メチルイソブチルケトン、シクロへキサノン等のケトン類 、トルエン、キシレンなどの芳香族炭化水素、酢酸ェチル、酢酸ブチルなどのエステ ル類が使用できる。反応を促進するための触媒としては、アミン類、有機錫化合物等 が使用される。 [0214] 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. As 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. As the catalyst for promoting the reaction, amines, organotin compounds and the like are used.
また、溶融状態でポリエステルポリオールと有機ジイソシァネートを混練りする事に よっても製造すること力 Sできる。  It can also be produced by kneading polyester polyol and organic diisocyanate in a molten state.
[0215] 本発明で使用するポリウレタン樹脂はラジカル重合性単量体によるグラフ Hヒ反応 の効率を高めるために重合性二重結合をポリウレタン鎖一本当たり平均 1.5〜30個、 望ましくは 2〜20個、更に望ましくは 3〜10個含有していることが必要である。 [0215] 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.
[0216] この重合性二重結合の導入については、下記の 4つの方法があり、これらの単独ま たは組み合わせにおレ、て実施可能である。 [0216] There are the following four methods for introducing the polymerizable double bond, and these methods can be used alone or in combination.
1)ポリエステルポリオール中にフマル酸、ィタコン酸、ノルボルネンジカルボン酸など の不飽和ジカルボン酸を含有せしめる。  1) An unsaturated dicarboxylic acid such as fumaric acid, itaconic acid or norbornene dicarboxylic acid is incorporated into the polyester polyol.
2)ポリエステルポリオール中に、ァリルエーテル基含有グリコールを含有せしめる。 2) Incorporate aryl ether group-containing glycol in the polyester polyol.
3)鎖延長剤として、ァリルエーテル基含有グリコールを用いる。 3) As the chain extender, a glycol containing an aryl ether group is used.
4)固相重合にぉレ、て飽和共重合ポリエステルポリオールと不飽和共重合ポリエステ ルポリオールの混合物を有機ジイソシァネートィヒ合物と反応させる。  4) A mixture of a saturated copolymerized polyester polyol and an unsaturated copolymerized polyester polyol is reacted with an organic diisocyanate compound before solid phase polymerization.
[0217] 本発明の高分子量の共重合ポリエステル樹脂、および/または、その共重合ポリェ ステル樹脂を構成成分として含むポリウレタン樹脂に、アクリル樹脂を形成するモノマ 一と反応可能な官能基を導入し、その存在下でアクリル樹脂を重合する方法にぉレヽ て、使用できる重合性単量体（アクリル樹脂を形成するモノマー）としてはアクリル酸、 メタクリル酸のエステル類としてアクリル酸メチル、アクリル酸ェチル、アクリル酸イソプ ロピノレ、アクリル酸 n—ブチル、アクリル酸 2—ェチルへキシル、アクリル酸 2—ヒドロキ シェチル、アクリル酸ヒドロキプロピル、メタクリル酸メチル、メタクリル酸ェチル、メタク リル酸イソプロピル、メタクリル酸 n—ブチル、メタクリル酸イソブチル、メタクリル酸 n_ へキシル、メタクリル酸ラウリル、メタクリル酸 2—ヒドロキシェチル、メタクリノレ酸ヒドロキ シルプロピル、アクリロニトリル、メタタリロニトリノレ、アクリルアミド、 N—メチロールアタリ ノレアミド、ジアセトンアクリルアミド、酢酸ビュル、ビュルエーテル類、 N-ビュルピロリド ン、スチレン、 α—メチルスチレン、 t—ブチルスチレン、ビエルトルエン、アクリル酸、 メタクリル酸、マレイン酸、フマル酸、ィタコン酸、シトラコン酸、マレイン酸無水物、ィ タコン酸無水物、メタクリル酸無水物、などを例示することができ、これらの中から一種 または複数種を選んで用いることができる。 [0217] 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, As a polymerizable monomer (a monomer for forming an acrylic resin) that can be used in the method of polymerizing an acrylic resin in the presence thereof, 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 methacrylate, 2-hydroxy E chill, Metakurinore acid hydroxy Shirupuropiru, acrylonitrile, methacrylonitrile Tali Roni Turin les, acrylamide, N- methylol Atari Noreamido, diacetone acrylamide, acetic Bulle, Bulle ethers, N- Byurupirorido , Styrene, α-methylstyrene, t-butylstyrene, vinyltoluene, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, methacrylic anhydride , Etc., and one or more of these can be selected and used.
[0218] ポリエステル系グラフト重合体は、共重合ポリエステル樹脂、および Zまたは、その 共重合ポリエステル樹脂を構成成分として含むポリウレタン樹脂の重合性不飽和二 重結合に、ラジカル重合性単量体をグラフト重合させることにより効率的に得られる。  [0218] 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.
[0219] 本発明では一般には共重合ポリエステル樹脂、および Zまたは、その共重合ポリェ ステル樹脂を構成成分として含むポリウレタン樹脂を有機溶剤中に溶解させた状態 におレ、て、ラジカル開始剤およびラジカル重合性単量体混合物を反応せしめること により実施される。グラフト化反応終了后の反応生成物は、所望のポリエステル—ラ ジカル重合性単量体混合物間のグラフト重合体の他にグラフトを受けなかったポリエ ステルおよびポリエステルとグラフト化しなかったラジカル重合体をも含有していると 考えられる力 反応生成物中のグラフト重合体比率が低ぐ非グラフトポリエステル及 び非グラフトラジカル重合体の比率が高い場合は、安定性良好分散体を得ることが 出来ない。  [0219] In the present invention, 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.
[0220] 共重合ポリエステル樹脂、および/または、その共重合ポリエステル樹脂を構成成 分として含むポリウレタン樹脂に対するラジカル重合性単量体のグラフ Hヒ反応の実 施に際しては、溶媒に加温下溶解されている共重合ポリエステル樹脂、および/また は、その共重合ポリエステル樹脂を構成成分として含むポリウレタン樹脂に対し、ラジ カル重合性単量体混合物とラジカル開始剤を一時に添加して行なってもよレ、し、別 々に一定時間を要して滴下した後、更に一定時間撹拌下に加温を継続して反応を 進行せしめてもよレ、。また、モノマーの一部をさきに一時に添カ卩しておいてから残りの モノマー、開始剤を別々に一定時間を要して滴下した後、更に一定時間撹拌下に加 温を継続して反応を進行させることも必要に応じて行なわれる。  [0220] Graph of radical polymerizable monomer for polyurethane resin containing copolyester resin and / or copolyester resin as constituent component When H-reaction is carried out, it is dissolved in a solvent under heating. This may be carried out by adding a radically polymerizable monomer mixture and a radical initiator to a copolyester resin and / or a polyurethane resin containing the copolyester resin as constituents. Alternatively, after dropwise addition over a certain period of time, the reaction may be allowed to proceed by further heating with stirring for a certain period of time. In addition, after adding a part of the monomer at a time, the remaining monomer and initiator are separately added dropwise over a certain period of time, and then the heating is continued with stirring for a certain period of time. The reaction is allowed to proceed as needed.
[0221] 反応に先立って、共重合ポリエステル樹脂、および Zまたは、その共重合ポリエス テル樹脂を構成成分として含むポリウレタン樹脂と溶剤を反応機に投入し、撹拌下に 昇温して樹脂を溶解させる。共重合ポリエステル樹脂、および/または、その共重合 ポリエステル樹脂を構成成分として含むポリウレタン樹脂と溶媒の重量比率は 70/3 0なレ、し 30/70の範囲であることが望ましレ、。 [0221] Prior to the reaction, 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.
この場合、重量比率は後述する共重合ポリエステルとラジカル重合性モノマーの反 応性ゃ溶剤溶解性を考慮して、重合工程中均一に反応が行える重量比率に調節さ れる。  In this case, 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.
[0222] グラフトイ匕反応温度は 50°Cないし 120°Cの範囲で行なわれることが望ましい。  [0222] The graft reaction temperature is preferably in the range of 50 ° C to 120 ° C.
[0223] 本発明で使用されるラジカル重合開始剤としては、良く知られた有機過酸化物類 や有機ァゾ化合物類を利用しうる。すなわち有機過酸化物としてべンゾィルバ—ォキ サイド、 t—ブチルバ一ォキシピバレ一ト、有機ァゾ化合物として 2. 2'—ァゾビスイソ ブチロニトリル、 2. 2'—ァゾビス（2. 4—ジメチルバレロニトリル）などを例示すること が出来る。 As the radical polymerization initiator used in the present invention, well-known organic peroxides and organic azo compounds can be used. In other words, 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.
[0224] ラジカル開始剤化合物の選定については、その化合物の反応実施温度におけるラ ジカル生成速度すなわち半減期（Half— life)を考慮して行なわれる必要がある。一 般に、その温度における半減期の値が 1分ないし 2時間の範囲にあるようなラジカル 開始剤を選定することが望ましい。  [0224] 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.
グラフ H匕反応を行なうためのラジカル開始剤の使用量は、ラジカル重合性単量体 に対して少なくとも 0. 2重量％以上が必要であり、望ましくは 0. 5重量％以上使用さ れることが必要である。  Graph 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.
連鎖移動剤、例えばォクチルメルカプタン、メルカプトエタノールの添加もグラフト鎖 長調節のため必要に応じて使用される。その場合、ラジカル重合性単量体に対して 0 〜5重量％の範囲で添加されるのが望ましい。  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.
[0225] 本発明の実施のためのグラフトイ匕反応溶媒は沸点が 50〜250°Cの水性有機溶媒 力 構成されることが好ましい。ここで水性有機溶媒とは 20°Cにおける水に対する溶 解性が少なくとも 10g/L以上、望ましくは 20g/L以上であるものをいう。沸点が 25 0°Cを越えるものは、余りに蒸発速度がおそぐ塗膜の高温焼付によっても充分に取 り除くことが出来ないので不適当である。また沸点が 50°C以下では、それを溶媒とし てグラフト化反応を実施する場合、 50°C以下の温度でラジカルに解裂する開始剤を 用いねばならないので取扱上の危険が増大し、好ましくない。 [0226] 共重合ポリエステル樹脂、および/または、その共重合ポリエステル樹脂を構成成 分として含むポリウレタン樹脂をよく溶解しかつカルボキシノレ基含有重合性単量体を 含む重合性単量体混合物およびその重合体を比較的良く溶解する第一群の水性有 機溶媒としては、エステル類例えば酢酸ェチル、ケトン類例えばメチルェチルケトン、 メチルイソブチルケトン、シクロへキサノン、環状ェ一テル類例えばテトラヒドロフラン、 ジォキサン、 1,3 -ジォキソラン、グリコールエーテル類例えばエチレングリコールジメ チノレエーテノレ、プロピレングリコ一ノレメチノレエ一テノレ、プロピレングリコ一ノレプロピノレ エーテノレ、エチレングリコーノレエチノレエーテノレ、エチレングリコ一ノレブチノレエ一テノレ 、カルビトール類例えばメチルカルビトール、ェチノレカノレビトーノレ、ブチルカルビト一 ノレ、グリコール類若しくはグリコ—ルェ—テルの低級エステル類例えばエチレングリコ —ルジアセテート、エチレングリコールェチルエーテルアセテート、ケトンアルコール 類例えばダイアセトンアルコール、更には N _置換アミド類例えばジメチルホルムアミ ド、ジメチルァセトアミド、 N—メチルピロリドン等を例示する事が出来る。 [0225] 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. Here, 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. Also, when the boiling point is 50 ° C or lower, when the grafting reaction is carried out using it as a solvent, an initiator that cleaves into radicals at a temperature of 50 ° C or lower must be used, which increases the handling risk and is preferable. Absent. [0226] A polymerizable monomer mixture containing a copolymerized polyester resin and / or a polyurethane resin containing such a copolymerized polyester resin as a constituent component and containing a carboxylate-containing polymerizable monomer and its weight Examples of 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, carbitol Such as methyl carbitol, ethinorecanolbitonole, butyl carbitol, glycols or lower esters of glycol ether such as ethylene glycol diacetate, ethylene glycol ether ether acetate, ketone alcohol such as diacetone alcohol Furthermore, N_substituted amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be exemplified.
[0227] これに対し、共重合ポリエステル樹脂をほとんど溶解しないがカルボキシノレ基含有 重合性単量体を含む重合性単量体混合物およびその重合体を比較的よく溶解する 第二群の水性有機溶媒として、水、低級アルコール類、低級カルボン酸類、低級アミ ン類などを挙げることが出来る力 本発明の実施に特に好ましいものとしては炭素数 1〜4のアルコール類およびダリコール類である。  [0227] In contrast, a polymerizable monomer mixture containing a carboxylate group-containing polymerizable monomer that hardly dissolves the copolyester resin, and a polymer that dissolves the polymer relatively well. Second group of aqueous organic solvents Examples of such a power 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.
[0228] グラフト化反応を単一溶媒で行なう場合は、第一群の水性有機溶媒からただ一種 を選んで行なうことが出来る。混合溶媒で行なう場合は第一群の水性有機溶媒から のみ複数種選ぶ場合と、第一群の水性有機溶媒力 少なくとも一種を選びそれに第 二群の水性有機溶媒から少なくとも一種を加える場合がある。  [0228] When the grafting reaction is performed with a single solvent, only one of the first group of aqueous organic solvents can be selected. When using 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.
グラフト重合反応溶媒を第一群の水性有機溶媒からの単一溶媒とした場合と、第一 群および第二群の水性有機溶媒のそれぞれ一種力 なる混合溶媒とした場合のい ずれにおいてもグラフト重合反応を行なうことができる。しかし、グラフト化反応の進行 挙動、グラフト化反応生成物およびそれから導かれる水分散体の外観、性状などに 差異がみられ、第一群および第二群の水性有機溶媒のそれぞれ一種からなる混合 溶媒を使用する方が好ましレ、。 [0229] すなわち第一群の水性有機溶媒に属し、ポリエステル樹脂、カルボキシル基含有 重合性単量体を含む単量体混合物およびそれから導かれる重合体に対して最も強 力な溶解力を示すテトラヒドロフランを単一溶媒とする場合には、グラフ H匕反応は終 始透明な外観をもって進行する。系の粘度は次第に上昇し、グラフト化反応の後期 には著しく増粘し、反応を継続しえない場合もある。そのような場合反応生成物は溶 媒を取り込んだまま透明なゴム状であり、強力な溶剤に対しても溶解しなレ、ゲルの生 成を示す。それを回避するには大幅な樹脂濃度の低下などが必要となり、製造上合 理的な方法とはいえない。これに対して、第一群の水性有機溶媒力 メチルェチル ケトンを選定し、第二群の水性有機溶媒力 イソプロピルアルコールを選定して両者 を 75Z25の重量比で混合して得た混合溶媒系を使用し共重合ポリエステルの溶解 性を調節した場合には、テトラヒドロフランの場合と全く同一のポリエステル樹脂、同 一のラジカル重合性単量体組成比、同一のポリエステル/ラジカル重合性単量体比 、同一の樹脂固形分で反応を行なってもグラフ H匕反応の進行にともなう系の増粘も ゲル化も観察されない。また、それに続く水系化により良好な水系分散体を与える。 このことから混合溶媒系の使用は、製造時の樹脂固形分濃度を高めることができ、製 造時に使用する有機溶媒量を低減できる合理的なプロセスであることがわかる。 Graft polymerization in both cases where 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. However, 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. That is, 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. When a single solvent is used, the graph H 匕 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. In such a case, 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. In contrast, 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. When 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.
[0230] 第一群の溶媒中では共重合ポリエステル分子鎖は広がりの大きい鎖ののびた状態 にあり、一方第一群/第二群の混合溶媒中では広がりの小さい糸まり状に絡まった 状態にあることがこれら溶液中の共重合ポリエステルの粘度測定により確認された。 共重合ポリエステルの溶解状態を調節し分子間架橋を起こりに《することがゲル化 防止に有効である。効率の高いグラフト化とゲル化抑制の両立は後者の混合溶媒系 において達成される。  [0230] In the first group of solvents, 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.
[0231] 第 1群/第 2群の混合溶媒の重量比率はより望ましくは 95Z5〜： 10Z90さらに望 ましくは 90ZlO〜20/80、最も望ましくは 85Zl5〜30/70の範囲である。最適の 混合比率は使用するポリエステルの溶解性などに応じて決定される。  [0231] 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.
[0232] (水分散化）  [0232] (Water dispersion)
本発明にかかわるグラフトイヒ反応生成物は塩基性化合物で中和することが好ましく 、中和することによって容易に平均粒子径 500nm以下の分散状態の安定した微粒子 に水分散化することが出来る。塩基性化合物としては塗膜形成時、或は硬化剤配合 による焼付硬化時に揮散する化合物が望ましぐアンモニア、有機アミン類などが好 適である。望ましい化合物の例としては、トリェチルァミン、 Ν,Ν-ジェチルエタノーノレ ァミン、 Ν,Ν-ジメチルエタノールァミン、アミノエタノールァミン、 Ν-メチル -Ν，Ν -ジエタ ノーノレアミン、イソプロピルァミン、イミノビスプロピルァミン、ェチルァミン、ジェチルァ ミン、 3_エトキシプロピルァミン、 3—ジェチルァミノプロピルアミン、 sec-ブチルァミン、 プロピルァミン、メチルァミノプロピルァミン、ジメチルァミノプロピルアミン、メチルイミ ノビスプロピルァミン、 3—メトキシプロピルァミン、モノエタノールァミン、ジエタノール ァミン、トリエタノールァミンなどを挙げることが出来る。塩基性化合物は、グラフトイ匕反 応生成物中に含まれるカルボキシル基含有量に応じて、少くとも部分中和、若しくは 、完全中和によって水分散体の PH値が 5. 0 - 9. 0の範囲であるように使用するの が望ましい。 The grafted reaction product according to the present invention is preferably neutralized with 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. As 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, Ν, Ν-jetylethanolamine, Ν, Ν-dimethylethanolamine, aminoethanolamine, Ν-methyl-Ν, Ν-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.
[0233] 水分散化の実施に際してはグラフトイ匕反応生成物中に含有される溶媒をあらかじめ 減圧下のェクストルダ—などにより除去してメルト状、若しくは固体状 (ペレット、粉末 など）のグラフトイヒ反応生成物を塩基性化合物を含有する水中へ投じて加熱下撹拌 して水分散体を作成することも出来るが、最も好適には、グラフ H匕反応を終了した時 点で直ちに塩基性化合物を含有する水を投入し、さらに加熱撹拌を継続して水分散 体を得る方法（ワン'ポット法）が望ましい。更に溶媒の沸点が 100°C以下の場合、ダラ フトイヒ反応に用いた溶媒を蒸留によって一部又は全部を容易に取り除くことが出来る  [0233] When carrying out the water dispersion, 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. Most preferably, however, water containing a basic compound is immediately prepared after completion of the graph H 匕 reaction. A method (one'pot method) in which an aqueous dispersion is obtained by continuing heating and stirring is further desirable. In addition, when 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.
[0234] 本発明により製造される水系分散体の固形分濃度は 20〜60重量％であり、必要に 応じて水を添カ卩し希釈して用いることができる。 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.
[0235] 本発明にかかわる水系分散体は塗料、インキ、コーティング材、接着剤などのべヒク ノレとして、あるいは繊維、フイノレム、紙製品の加工剤として利用される。本発明の水系 分散体はそのままでも使用されるが、架橋剤 (硬化用樹脂）を配合して焼付硬化を行 なうことにより、高度の耐水性を発現することができる。架橋剤としては、フヱノールホ ルムアルデヒド樹脂、ァミノ樹脂、多官能エポキシ化合物、多官能イソシァネート化合 物およびその各種ブロックイソシァネートイ匕合物、多官能アジリジン化合物などを挙 げること力 S出来る。 [0235] 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. Although the aqueous dispersion of the present invention is used as it is, a high degree of water resistance can be expressed by blending a crosslinking agent (curing resin) and baking and curing. Examples of the crosslinking agent include phenol formaldehyde resin, amino resin, polyfunctional epoxy compound, polyfunctional isocyanate compound, various block isocyanate compounds, and polyfunctional aziridine compound. The ability to boil S
[0236] フエノール樹脂としてはたとえばアルキル化フエノール類、タレゾール類のホルムァ ルデヒド縮合物を挙げることが出来る。具体的にはアルキル化 (メチル、ェチル、プロ ピル、イソプロピル、ブチノレ）フエノール、 p- tert -ァミルフエノール、 4、 4'- sec-ブチリデ ンフエノーノレ、 p— tert—ブチノレフエノーノレ、 0— ,m-，p-クレゾ一ノレ、 p-シクロへキシノレフエ ノール、 4，4'_イソプロピリデンフエノール、 p_ノニルフエノール、 p -ォクチルフエノール 、 3-ペンタデシルフェノール、フエノール、フエニル 0_クレゾール、 p-フエニルフエノー ノレ、キシレノールなどのホルムアルデヒド縮合物が挙げられる。  [0236] Examples of 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.
[0237] ァミノ樹脂としては、例えば尿素、メラミン、ベンゾグアナミンなどのホルムアルデヒド 付加物、さらにこれらの炭素原子数が 1〜6のアルコールによるアルキルエーテル化 合物を挙げることができる。具体的にはメトキシ化メチロール尿素、メトキシ化メチロー ル N，N -エチレン尿素、メトキシ化メチロールジシアンジアミド、メトキシ化メチロールメ ラミン、メトキシ化メチロールべンゾグアナミン、ブトキシ化メチロールメラミン、ブトキシ 化メチロールべンゾグアナミンなどが挙げられるが好ましくはメトキシ化メチロールメラ ミン、ブトキシ化メチロールメラミン、およびメチロール化べンゾグアナミンであり、それ ぞれ単独または併用して使用することができる。  [0237] 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. Are preferably methoxylated methylol melamine, butoxylated methylol melamine, and methylolated benzoguanamine, each of which can be used alone or in combination.
[0238] エポキシ化合物としてはビスフエノーノレ Aのジグリシジルエーテルおよびそのオリゴ マー、水素化ビスフエノール Aのジグリシジルエーテルおよびそのオリゴマー、オルソ フタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグ リシジルエステル、 P-ォキシ安息香酸ジグリシジルエステル、テトラハイド口フタル酸ジ グリシジルエステル、へキサハイドロフタル酸ジグリシジルエステル、コハク酸ジグリシ ジノレエステノレ、アジピン酸ジグリシジノレエステノレ、セバシン酸ジグリシジノレエステノレ、 エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテ ノレ、 1、 4_ブタンジオールジグリシジルエーテル、 1，6 -へキサンジオールジグリシジル エーテルおよびポリアルキレングリコールジグリシジルエーテル類、トリメリット酸トリグ リシジルエステル、トリグリシジルイソシァヌレート、 1，4-ジグリシジルォキシベンゼン、 ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールプロ パントリグリシジルエーテル、ペンタエリスリトールトリグリシジルエーテル、グリセロー ルアルキレンオキサイド付加物のトリグリシジルエーテルなどを挙げることができる。 [0238] 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 ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropan triglycidyl ether, Pentaerythritol triglycidyl ether, glycero And triglycidyl ether of a alkylene oxide adduct.
[0239] さらにイソシァネートイ匕合物としては芳香族、脂肪族のジイソシァネート、 3価以上の ポリイソシァネートがあり、低分子化合物、高分子化合物のいずれでもよい。たとえば ネート、ジフヱニルメタンジイソシァネート、水素化ジフヱニルメタンジイソシァネート、 キシリレンジイソシァネート、水素化キシリレンジイソシァネート、イソホロンジイソシァ ネートあるいはこれらのイソシァネート化合物の 3量体、およびこれらのイソシァネート 化合物の過剰量と、たとえばエチレングリコール、プロピレングリコール、トリメチロー ルプロパン、グリセリン、ソノレビトーノレ、エチレンジァミン、モノエタノールァミン、ジエタ ノーノレアミン、トリエタノールァミンなどの低分子活性水素化合物または各種ポリエス テルポリオール類、ポリエーテルポリオール類、ポリアミド類の高分子活性水素化合 物などとを反応させて得られる末端イソシァネート基含有化合物が挙げられる。  [0239] Further, 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. For example, nate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or 3 amounts of these isocyanate compounds And 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. Examples thereof include terminal isocyanate group-containing compounds obtained by reacting terpolyols, polyether polyols, polymer active hydrogen compounds of polyamides and the like.
[0240] イソシァネート化合物としてはブロック化イソシァネートであってもよい。イソシァネー トブロック化剤としては、例えばフエノール、チオフヱノール、メチルチオフエノール、ク レゾーノレ、キシレノーノレ、レゾノレシノーノレ、ニトロフエノーノレ、クロ口フエノーノレ等のフエ ノーノレ類、ァセトキシム、メチルェチルケトォキシム、シクロへキサノンォキシムなどの ォキシム類、メタノール、エタノール、プロパノール、ブタノールなどのアルコール類、 エチレンクロルヒドリン、 1,3-ジクロロ- 2-プロパノールなどのハロゲン置換アルコール 類、 t-ブタノール、 t-ペンタノールなどの第 3級アルコール類、 ε -カプロラタタム、 δ 一バレロラタタム、 Ί一ブチロラタタム、 β一プロピルラタタムなどのラタタム類が挙げ られ、その他にも芳香族ァミン類、イミド類、ァセチルアセトン、ァセト酢酸エステル、 マロン酸ェチルエステルなどの活性メチレンィ匕合物、メルカプタン類、イミン類、尿素 類、ジァリール化合物類重亜硫酸ソーダなども挙げられる。ブロック化イソシァネート は上記イソシァネートイ匕合物とイソシァネートイ匕合物とイソシァネートブロック化剤とを 従来公知の適宜の方法より付加反応させて得られる。 [0240] 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 β one propyl rata Tam and the like, other aromatic Amin of any kind, imides, § cetyl acetone, Aseto acetate S. Le, active Mechireni 匕合 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.
[0241] 架橋剤の配合方法としては（1)架橋剤が水性である場合、直接水系分散体中に溶 解もしくは分散せしめられ、（2)架橋剤が油性である場合グラフトイヒ反応終了後水分 散化の前または後に架橋剤を加えてコア部にポリエステルと共存せしめる方法が用 いられ、架橋剤の種類、性状により任意に選択することができる。これらの架橋剤に は硬化剤あるいは促進剤を併用することもできる。 [0241] 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.
[0242] 硬化反応は、一般に本発明の水系分散体 100部（固形分）に対して硬化用樹脂 5 〜40部（固形分）が配合され硬化剤の種類に応じて 60〜250°Cの温度範囲で 1〜6 0分間程度加熱することにより行われる。必要の場合、反応触媒や促進剤も併用され る。本発明の水系分散体には、顔料、染料、各種添加剤などを配合することが出来る 。本発明の水系分散体は、他の水性樹脂、水系分散体と混合使用することができ、 その加工性を向上せしめることが出来る。  [0242] 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.
[0243] さらに本発明にかかわる水系分散体を基材とした塗料、インキ、コーティング剤、接 着剤、各種加工剤は、再分散性に優れているので、ディップコート法、はけ塗り法、口 ールコート法、スプレー法、各種印刷法のすべてに適用可能性を有している。  [0243] Furthermore, 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.
[0244] 本発明により得られるポリエステル樹脂水分散体、ノ、イブリツド樹脂水分散体は、各 種増粘剤を使用することにより、作業性に適した粘性、粘度に調整することができる。 増粘剤添加による系の安定性から、メチルセルロース、ポリアルキレングリコール誘導 体のノニオン性のもの、ポリアクリル酸塩、アルギン酸塩等のァニオン性のものが好ま しい。  [0244] 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. In view of the stability of the system due to the addition of a thickener, nonionic ones such as methylcellulose and polyalkylene glycol derivatives, and polyanilates, alginates and other anionic ones are preferred.
[0245] 本発明により得られるポリエステル樹脂水分散体、ノ、イブリツド樹脂水分散体は、各 種表面張力調整剤を使用することにより、塗布性をさらに向上させることができる。添 加量は水分散体の安定性等の面から、樹脂に対して好ましくは lwt%以下、さらに 好ましくは 0. 5wt%の添カ卩を制限することが好ましい。  [0245] 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. From the viewpoint of the stability of the aqueous dispersion, the addition amount is preferably limited to 1 wt% or less, more preferably 0.5 wt%, relative to the resin.
[0246] 本発明により得られるポリエステル樹脂水分散体、ノ、イブリツド樹脂水分散体は、そ の製造時、または得られた水分散体中に酸化チタン、シリカなどの公知の無機顔料、 各種染料、表面平滑剤、消泡剤、酸化防止剤、分散剤、潤滑剤等の公知の添加剤 を配合しても良い。  [0246] 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. In addition, known additives such as a surface smoothing agent, an antifoaming agent, an antioxidant, a dispersant, and a lubricant may be blended.
[0247] 本発明により得られるポリエステル樹脂水分散体、ノ、イブリツド樹脂水分散体は、そ の用途に応じて、各種紫外線吸収剤、酸化防止剤、光安定剤を添加することができ る。紫外線吸収剤としては、ベンゾトリアゾール系、ベンゾフヱノン系、トリアジン系等 各種有機系のもの、酸化亜鉛等無機系のもののいずれも使用可能である。また酸ィ匕 防止剤としては、ヒンダードフエノール、フエノチアジン、ニッケル化合物等一般的に ポリマー用のもの、各種が使用可能である。光安定剤もポリマー用のもの各種が使用 可能である力 特にヒンダードァミン系のものが有効である。 [0247] 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. As the ultraviolet absorber, various organic types such as benzotriazole type, benzophenone type, triazine type, and inorganic type such as zinc oxide can be used. Also 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.
実施例  Example
[0248] 以下本発明を実施例によりさらに詳細に説明する。なお、各樹脂、各樹脂水分散 体の物性値測定は以下の方法により実施した。なお、「部」は「重量部」を表す。  [0248] Hereinafter, the present invention will be described in more detail with reference to Examples. The physical properties of each resin and each aqueous resin dispersion were measured by the following method. “Part” means “part by weight”.
[0249] 1.共重合ポリエステル樹脂の組成  [0249] 1. Composition of copolymer polyester resin
共重合ポリエステル樹脂を重クロ口ホルム溶媒中でヴアリアン社製、核磁気共鳴分 析計（NMR)ジヱミニ— 200を用いて、 ifi— NMR分析を行い、その積分比より決定 した。なお、共重合ポリエステル樹脂は重縮合反応終了後、窒素雰囲気下で真空を 破壊し、減圧後、得られた溶融状態の共重合ポリエステル樹脂を反応釜から少量取 り出し、冷却したものを測定に供した。  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.
[0250] 2.共重合ポリエステル樹脂のガラス転移温度  [0250] 2. Glass transition temperature of copolyester resin
上述のようにして得たポリエステル樹脂サンプル 5mgをアルミニウム製サンプルパ ンに入れて密封し、セイコーインスツルメンッ社製、示差走査熱量分析計 (DSC) DS C_ 220を用いて、 200°Cまで、昇温速度 20°CZ分にて測定し、ガラス転移温度以 下のベースラインの延長線と遷移部分での最大傾斜を示す接線との交点の温度で 求めた。  5 mg of the polyester resin sample obtained as described above is put in an aluminum sample pan and sealed, and up to 200 ° C using a differential scanning calorimeter (DSC) DS C_220 manufactured by Seiko Instruments Inc. The temperature was measured at a heating rate of 20 ° CZ, and the temperature was obtained at the intersection of the baseline extension below the glass transition temperature and the tangent indicating the maximum slope at the transition.
[0251] 3.樹脂の還元粘度 [0251] 3.Reduced viscosity of resin
樹脂 0. 10gをフエノール/テトラクロロェタン（質量比 6/4)の混合溶媒 25cm3に 溶かし、ウベローデ粘度管を用いて 30°Cで測定した。 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.
[0252] 4.樹脂酸価の測定 [0252] 4. Measurement of resin acid value
[ポリエステル樹脂水分散体に用いられる樹脂]  [Resin used in polyester resin aqueous dispersion]
(1)カルボキシル基、フエノール性水酸基  (1) Carboxyl group, phenolic hydroxyl group
ポリエステル樹脂 0· 2gを 20mlのクロ口ホルムに溶解し、 0. 1Nの KOHエタノール 溶液で滴定し、フエノールフタレイン溶液の変色点をもって中和点として、酸価を求 めた（mgK〇H/g)  2 g of polyester resin 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〇H / g)
(2)スルホン酸基 原子吸光法でポリエステル樹脂中の硫黄原子濃度を求め、その 100%がスルホン 酸基由来として、スルホン酸価（mgKOH/g)とした。 (2) Sulfonic acid group The sulfur atom concentration in the polyester resin was determined by the atomic absorption method, and 100% of the concentration was derived from the sulfonic acid group and the sulfonic acid value (mgKOH / g).
樹脂の酸価は、（1)カルボキシル基、フエノール性水酸基と（2)スルホン酸基の合 計量として算出した (mgKOHZg)  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)
レ、イブリツド樹脂水分散体に用いられる樹脂]  Les, resins used in hybrid resin water dispersions]
樹脂 0. 2gを 20mlのクロ口ホルムまたはジメチルホルムアミドに溶解し、 0. 1Nの K OHエタノール溶液で滴定し、フエノールフタレイン溶液の変色点をもって中和点とし て、酸価を求めた（mgKOHZg)  0.2 g of the resin was dissolved in 20 ml of chloroform or dimethylformamide, titrated with 0.1 N KOH ethanol solution, and the acid value was determined as the neutralization point using the discoloration point of the phenolphthalein solution (mgKOHZg )
[0253] 5.樹脂に不溶なアルミニウム系異物の評価法 [0253] 5. Evaluation method for aluminum insolubles in resin
樹脂 30gおよびパラクロロフヱノール/テトラクロロェタン（3/1 :重量比）混合溶液 30 0mlを攪拌機付き丸底フラスコに投入し、該樹脂を混合溶液に 100〜105°C、 2時間 で攪拌'溶解した。該溶液を室温になるまで放冷し、直径 47mm/孔径 1. 0 μ mのポ リテトラフルォロエチレン製のメンブレンフィルター（Advantec社製 PTFEメンブレン フィルター、品名： T100A047A)を用レ、、全量を 0. 15MPaの加圧下、有効ろ過直 径 37. 5mmで異物をろ別した。  30 g of resin and 30 ml of parachlorophenol / tetrachloroethane (3/1: weight ratio) mixed solution are put into a round bottom flask equipped with a stirrer, and the resin is stirred in the mixed solution at 100 to 105 ° C for 2 hours. 'Dissolved. Allow the solution to cool to room temperature and use a polytetrafluoroethylene membrane filter (Advantec PTFE membrane filter, product name: T100A047A) with a diameter of 47 mm / pore size of 1.0 μm. The foreign matter was filtered out with an effective filtration diameter of 37.5 mm under a pressure of 0.15 MPa.
[0254] 異物評価は、以下のように濾過時間で行った。 [0254] The evaluation of foreign matters was performed by filtration time as follows.
〇：ろ過時間 5時間未満  ○: Filtration time less than 5 hours
△：ろ過時間 5時間〜 24時間  Δ: Filtration time 5-24 hours
：ろ過時間1日超  : Filtration time over 1 day
上記ろ過時間が 1日を超えた場合は、共重合ポリエステル樹脂に不溶性の微細な 異物含有量が多くなり、重合工程や成型工程での共重合ポリエステル樹脂のろ過時 のフィルター詰まりが多くなるという課題に繋力 Sり好ましくなレ、。また、被着体への濡れ 性低下に伴う接着性不良などに繋がり好ましくない。  If 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.
[0255] 6.樹脂の外観着色の程度 [0255] 6. Appearance coloring of resin
樹脂をほぼ同一厚みの板状のまま目視判定した。  The resin was visually judged as a plate having substantially the same thickness.
〇：ほとんど着色なし  Y: Almost no coloring
△:やや着色あり  △: Slightly colored
X：著しく着色あり [0256] 7.ゲル分率 X: Remarkably colored [0256] 7.Gel fraction
樹脂 10gをソックスレー抽出機を使用し、メチルェチルケトンに対する不溶物を回収 した。 30Pa減圧下、 70°C X 3時間乾燥し、得られた乾燥物の重量を A (g)として、以 下に示す式を用レ、てゲル分率を算出した。  Using a Soxhlet extractor, 10 g of resin was recovered insoluble matter with respect to methyl ethyl ketone. The gel fraction was calculated using the following formula using the weight of the obtained dried product as A (g) under reduced pressure of 30 Pa at 70 ° C. for 3 hours.
(ゲル分率％) = (A/10) * 100  (Gel fraction%) = (A / 10) * 100
[0257] 8.水分散体酸価の測定 [0257] 8. Measurement of acid value of aqueous dispersion
樹脂水分散体 lgを 30mlのジォキサンに溶解し、 0. 1Nの KOHエタノール溶液で 滴定し、フエノールフタレイン溶液の変色点をもって中和点として、酸価を求めた（mg KOHZg)。ただし、水分散体中の樹脂固形分 lg当たりに換算した値で算出した。  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.
[0258] 9.水分散体安定性 [0258] 9. Water dispersion stability
作製した水分散体を、室温で 1週間静置し目視判定した。  The prepared aqueous dispersion was allowed to stand at room temperature for 1 week and visually judged.
〇 ：ほとんど沈殿なし  ○: Almost no precipitation
△ ：わずかに沈殿あり  Δ: Slight precipitation
X ：沈殿物多い  X: Many precipitates
[0259] 10.塗膜耐水性 [0259] 10.Water resistance of paint film
作製した樹脂水分散体を、 PETフィルム上に塗布し、 120°C X 2時間熱風乾燥機 にて乾燥し、膜厚約 10 μの樹脂層を得た。 PETフィルムごと樹脂を 25°Cの水中に 4 時間放置し、樹脂層の変化を目視判定した。  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 μm. 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.
〇 ： 樹脂層にほとんど変化が見られない  ○: Almost no change in resin layer
△ ： 樹脂層の若干膨潤が見られる  Δ: Slight swelling of resin layer is observed
X ： 樹脂層の溶解が見られる  X: Dissolution of resin layer is observed
[0260] (実施例 1)本発明樹脂の合成例：（A) Example 1 Synthesis Example of Resin of the Present Invention: (A)
攪拌機、コンデンサー、温度計を装備したステンレス製反応釜に表 1に記載の各成 分モル％になるように酸成分としてテレフタル酸、イソフタル酸、 5 _ナトリウムスルホ イソフタル酸のエチレングリコールジエステル体、グリコール成分としてエチレングリコ ール、ネオペンチルグリコール、前記アルミニウム化合物のエチレングリコール溶液/ リンィ匕合物のエチレングリコール溶液の混合物の調製例からなる重合触媒溶液、ダリ コール同士の縮合物抑制のためトリェチルアミンを全酸成分に対して 0. 2モル％仕 込み、窒素下 150°C〜220°Cでエステル化反応を行なった後、次いで 260°Cまでカロ 温しながら徐々に減圧し 60分間で 13. 3Pa減圧とし、この温度ならびに減圧条件下 で 1時間重合を行なレ、共重合ポリエステル (A)を得た。得られた共重合ポリエステル の組成および特性値を表 1に示す。 In a stainless steel reaction kettle equipped with a stirrer, condenser and thermometer, terephthalic acid, isophthalic acid, 5_sodiumsulfo ethylene glycol diester, glycol as the acid component so that each component mol% listed in Table 1 Polymerization catalyst solution consisting of ethylene glycol solution, neopentyl glycol, ethylene glycol solution of the above aluminum compound / ethylene glycol solution mixture of the above-mentioned aluminum compounds as components, and triethylamine in order to suppress condensates of dallicol. 0.2 mol% of acid component After the esterification reaction was performed at 150 ° C to 220 ° C under nitrogen, the pressure was gradually reduced to 260 ° C while maintaining the temperature at 13.3 Pa in 60 minutes. Time polymerization was carried out to obtain a copolyester (A). Table 1 shows the composition and characteristic values of the obtained copolyester.
[0261] 樹脂水分散体の製造例 [0261] Production Example of Resin Water Dispersion
共重合ポリエステル樹脂 A 100重量部、メチルェチルケトン 120重量部、 2_プロ パノール 30重量部、水 10重量部を、攪拌機、コンデンサー、温度計を装備した反応 缶に仕込み、 50rpmで攪拌しながら、 70°Cまで昇温した。さらに 3時間攪拌すること により、樹脂を完全に溶解した。そこに、 70°Cの温水を 300重量部添加し、水分散体 を作製、さらに容器内を温度を徐々に昇温し、有機溶剤を蒸留溜去した。残留溶剤 をガスクロマトグラフィー法で測定したところ、 0. 08wt。/oであった。反応缶内温度を、 室温まで冷却し、さらに 200メッシュフィルターでろ過することにより、樹脂水分散体 A を得た。 Copolymerized polyester resin A 100 parts by weight, methyl ethyl ketone 120 parts by weight, 2_propanol 30 parts by weight, water 10 parts by weight were charged into a reaction vessel equipped with a stirrer, condenser and thermometer and stirred at 50 rpm. The temperature was raised to 70 ° C. The resin was completely dissolved by further stirring for 3 hours. Thereto, 300 parts by weight of 70 ° C. warm water was added to prepare an aqueous dispersion, and the temperature inside the container was gradually raised, and the organic solvent was distilled off. The residual solvent was measured by gas chromatography and found to be 0.08 wt. / o . The temperature inside the reaction vessel was cooled to room temperature, and further filtered through a 200 mesh filter to obtain a resin water dispersion A.
[0262] (実施例 2、 3) (比較例:!〜 3)  [0262] (Examples 2 and 3) (Comparative examples:! To 3)
上記本発明の共重合ポリエステル樹脂 (A)の合成に準じた方法で、各重合触媒種 を用いた本発明樹脂'水分散体 (B)、（C)および比較樹脂'水分散体 (D)， （E)， (F )を得た。得られた各共重合ポリエステル樹脂の組成と特性値を表 1に示す。  Resin of the present invention using each polymerization catalyst species (B), (C) and comparative resin (Aqueous dispersion (D)) using a method according to the synthesis of the copolymer polyester resin (A) of the present invention , (E), (F) were obtained. Table 1 shows the composition and characteristic values of each obtained copolyester resin.
アルミニウム化合物単独系触媒の場合 (C)は、複合系 (A)、 (B)に比べて重合活 性がやや低ぐ異物が若干多い以外は、着色の少ない良好な外観を示した。アンチ モン系重合触媒 (D)は着色に加えて濁っていた。チタン系触媒 (E)は得られた樹脂 の着色が著しぐまた、スズ系重合触媒 (F)は比較的着色も少ないものであったがァ ンチモン系重合触媒同様にこれらを含まなレ、ポリエステルが望まれてレ、る。  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.
[0263] (実施例 4)本発明樹脂の合成例：（G) [0263] (Example 4) Synthesis example of resin of the present invention: (G)
攪拌機、コンデンサー、温度計を装備したステンレス製反応釜に表 1に記載の各成 分モル％になるように酸成分としてテレフタル酸、イソフタル酸、トリメリット酸、グリコー ノレ成分としてエチレングリコール、ネオペンチルグリコール、表 2記載のアルミニウム 化合物のエチレングリコール溶液/リン化合物のエチレングリコール溶液の混合物の 調製例からなる重合触媒溶液を仕込み、窒素下 150°C〜220°Cでエステルイ匕反応 を行なった後、次いで 240°Cまで加温しながら徐々に減圧し 60分間で 13. 3Pa減圧 とした。さらに系を 220°Cに保ち、窒素ガスで真空を破壊、窒素雰囲気下、所定の無 水トリメリット酸、エチレングリコールビスアンヒドトリメリテートを添加、 30分攪拌してポ リエステル Gを得た。得られた共重合ポリエステルの組成および特性値を表 2に示す In a stainless steel reaction kettle equipped with a stirrer, condenser and thermometer, terephthalic acid, isophthalic acid, trimellitic acid as the acid component and ethylene glycol, neopentyl as the glycol component so that each component mol% shown in Table 1 is obtained. Glycol, a polymerization catalyst solution consisting of a mixture of an ethylene glycol solution of an aluminum compound listed in Table 2 and an ethylene glycol solution of a phosphorus compound was charged, and the esterification reaction was carried out at 150 ° C to 220 ° C under nitrogen After that, the pressure was gradually reduced while heating to 240 ° C, and the pressure was reduced to 13.3 Pa in 60 minutes. Furthermore, the system was maintained at 220 ° C, the vacuum was broken with nitrogen gas, and the prescribed anhydrous trimellitic acid and ethylene glycol bisanhydride trimellitate were added under a nitrogen atmosphere and stirred for 30 minutes to obtain polyester G. . Table 2 shows the composition and characteristic values of the obtained copolyester.
[0264] 樹脂水分散体の製造例 [0264] Production Example of Resin Water Dispersion
共重合ポリエステル樹脂 G 100重量部、メチルェチルケトン 120重量部を、攪拌 機、コンデンサー、温度計を装備した反応缶に仕込み、 50rpmで攪拌しながら、 70 °Cまで昇温した。さらに 3時間攪拌することにより、樹脂を完全に溶解した。そこに、 2 —プロパノール 30重量部、トリエチノレアミン 25部、 70°Cの温水を 300重量部添加し 、水分散体を作製、さらに容器内を温度を徐々に昇温し、有機溶剤を蒸留溜去した。 残留溶剤をガスクロマトグラフィー法で測定したところ、 1. 2wt%であった。反応缶内 温度を、室温まで冷却し、さらに 200メッシュフィルターでろ過することにより、樹脂水 分散体 Gを得た。  100 parts by weight of copolymer polyester resin G and 120 parts by weight of methyl ethyl ketone were charged into a reaction can equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 70 ° C. while stirring at 50 rpm. By further stirring for 3 hours, the resin was completely dissolved. Thereto, 30 parts by weight of 2-propanol, 25 parts of triethylenoleamine, and 300 parts by weight of warm water at 70 ° C were added to prepare an aqueous dispersion. Further, the temperature inside the container was gradually raised, and the organic solvent was removed. Distilled off. The residual solvent was measured by gas chromatography and found to be 1.2 wt%. The internal temperature of the reaction can was cooled to room temperature, and further filtered through a 200 mesh filter to obtain a resin water dispersion G.
[0265] (実施例 5〜9) (比較例 4〜6)  [0265] (Examples 5 to 9) (Comparative Examples 4 to 6)
実施例 4で用いたモノマーの代わりに、表 2および 3に示した種々のモノマーを用い る以外は実施例 4と同様にして本発明樹脂 ·比較樹脂 (H)〜（〇）を合成した。得られ た樹脂の組成および特性値を表 2および 3に示す。  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.
[0266] 水分散体製造例 H  [0266] Water dispersion production example H
共重合ポリエステル樹脂 H 100重量部、イソプロピルアルコール 100重量部、ィォ ン交換水 1 15重量部、アンモニア水（28%) 3重量部を、攪拌機、コンデンサー、温 度計を装備した反応缶に仕込み、 50rpmで攪拌しながら、 70°Cまで昇温した。さら に 3時間攪拌することにより、樹脂を完全に分散した。反応缶内温度を、室温まで冷 却し、さらに 200メッシュフィルターでろ過することにより、樹脂水分散体 Hを得た。  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.
[0267] 水分散体製造例 I  [0267] Example of water dispersion production I
共重合ポリエステル樹脂 I 100重量部、イソプロピルアルコール 60重量部、トリエ チルァミン 7. 8重量部およびイオン交換水 170重量部を、密閉式ガラス容器 (プライ ミクス株式会社製、 T. K.ロボミックス）に仕込み、ホモディスパーを用いて、 7000pp mで攪拌した。徐々に昇温し 70°Cで 30分間攪拌を続けた。その後、攪拌速度を 350 Oppmに下げ、室温まで冷却、 300メッシュのフィルターでろ過することにより、樹脂水 分散体 Iを得た。 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.
[0268] 水分散体製造例 J  [0268] Example of water dispersion production J
共重合ポリエステル樹脂 J 100重量部、イソプロピルアルコール 60重量部、アンモ ニァ水（28%) 4重量部およびイオン交換水 170重量部を、密閉式ガラス容器 (プライ ミクス株式会社製、 T. K.ロボミックス）に仕込み、ホモディスパーを用いて、 7000pp mで攪拌した。徐々に昇温し 70°Cで 30分間攪拌を続けた。その後、攪拌速度を 350 Oppmに下げ、室温まで冷却、 300メッシュのフィルターでろ過することにより、樹脂水 分散体 Jを得た。  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.
[0269] 水分散体製造例 K  [0269] Example of water dispersion production K
共重合ポリエステル樹脂 K 100重量部を 2軸押出混練機を用いて 150°C溶融混 練して樹脂溶融体を製造し、トリエタノールァミン 30重量部、蒸留水 300重量部から なる液体を徐々に添加しながら練り、水分散体を得、さらに室温まで冷却した後、 20 0メッシュのフィルターでろ過することにより、樹脂水分散体 Kを得た。  100 parts by weight of copolyester resin K 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.
[0270] 水分散体製造例 L  [0270] Example of water dispersion production L
共重合ポリエステル樹脂 L 100重量部、ノルマルプチルセ口ソルブ 20重量部、トリ エタノールァミン 20重量部を、攪拌機、コンデンサー、温度計を装備した反応缶に仕 込み、 50rpmで攪拌しながら、 130°Cまで昇温した。さらに 30分攪拌することにより、 樹脂を完全に分散した。反応缶内温度を 90°Cまで冷却し、 200重量部の 80°Cのィ オン交換水を添加し 1時間攪拌後、室温まで冷却し、さらに 200メッシュフィルターで ろ過することにより、樹脂水分散体 Lを得た。  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.
[0271] 水分散体製造例 M、 N、 O  [0271] Examples of water dispersion production M, N, O
水分散体 Gを製造するのと同様の方法で製造した。  A water dispersion G was produced in the same manner as that for the production.
[0272] 比較例 4の樹脂 Mは酸価が 3mgK〇H/gよりも小さぐ製造時は水中に樹脂は分 散するが、経時の安定性が保てない。一方、比較例 5の樹脂 Nは酸価が 110mgK〇 H/gよりも大きぐ水分散体は安定に製造できるが、得られる塗膜の耐水性がなぐ 実用に適さない。また比較例 6の樹脂 Oは樹脂酸価のうち、フエノール性水酸基に拠 る量が大きぐ樹脂そのもの、特に一度水分散したものから乾固して得られる塗膜の 着色が大きぐアルミ系触媒からなる樹脂の色相のよさを減じてしまう。 [0272] Resin M of Comparative Example 4 has an acid value of less than 3 mg KH / g. During production, the resin is dispersed in water, but stability over time cannot be maintained. On the other hand, 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.
[表 1] [table 1]
Figure imgf000074_0001
Figure imgf000074_0001
[表 2] [Table 2]
実施例 4 実施例 5 実施例 6 実施例 7 実施例 8 実施例 9 共重合ホ'リエステル樹脂 G H [ J K し 多価カルホ'ン酸成分 τレフタル酸 50 48 50 52 48Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Copolyester resin G H [J K and polyvalent carboxylic acid component τ Rephthalic acid 50 48 50 52 48
(モル％) イソフタル酸 42 30 40 42 45 (Mol%) Isophthalic acid 42 30 40 42 45
5-ナトリウムスルホイソフタル酸 4 2.5 5-sodium sulfoisophthalic acid 4 2.5
5-ヒト'ロキシイソフタル酸 1 2.5 ァシ'ピン酸 50 8 セ Λ V- 50 16 5-Human 'roxyisophthalic acid 1 2.5 Basic' Pinic acid 50 8C Λ V-50 16
トリ リット酸 8 2 3 ピロメリット酸 1 3 2 多価アルコ-ル成分 エチレンク 'リコール 50 50 50 50 Trilitnic acid 8 2 3 Pyromellitic acid 1 3 2 Polyhydric alcohol component Ethylene alcohol Recall 50 50 50 50
(モル％) ジエチレンゲリコ—ル 55 50 53 50 (Mol%) Diethylene gel 55 50 53 50
ネオへ'ンチルク'リコ-ル 50 45 50 47 Neohe 'Nilch' recall 50 45 50 47
1.4ーフ'タンシ'オール 1.4?
ホ'リ亍トラメチレンク'リコ-ル（分子量： 1 ,000)  Holy tramethylene cup (Molecular weight: 1,000)
付加酸成分 無水トリ刈ツト酸 10 4 15 12Additional acid component Anhydrous tri-cutting acid 10 4 15 12
(モル0/。） 無水マレイン酸 1 (Mole 0 /.) Maleic anhydride 1
エチレンゲリコ-ルビスアンヒト'トリメリ亍-ト 10 2 3 触媒  Ethylene gericorubisanhit trimellito 10 2 3 catalyst
(全酸成分に対する 塩基性酢酸アルミニウム 0.02 0.02 0.02 0.02 0.02 0.02 モル0 Irf;anox1222 0.04 0.04 0.04 0.04 0.04 0.04 特性 還元粘度（dl/g)) 0.14 0.45 0.23 0.31 0.15 0.17 ガラス転移点温度 (°C) 46 -22 35 51 43 51 酸価 (mgKOH/g) 94 12 29.2 18.7 76 71 酸価中カルホ'キシル基/スルホン基の割合 (W 100 100 100 86 100 91 外観 着色の程度 0 0 O 0 0 0(Basic aluminum acetate for all acid components 0.02 0.02 0.02 0.02 0.02 0.02 mol 0 Irf; anox1222 0.04 0.04 0.04 0.04 0.04 0.04 Properties Reduced viscosity (dl / g)) 0.14 0.45 0.23 0.31 0.15 0.17 Glass transition temperature (° C) 46 -22 35 51 43 51 Acid value (mgKOH / g) 94 12 29.2 18.7 76 71 Ratio of carboxyl group / sulfone group in acid value (W 100 100 100 86 100 91 Appearance Degree of color 0 0 O 0 0 0
AI由来の異物（ろ過時間） 0 0 O 0 0 0 水分散体安定性 〇 〇 〇 〇 〇 〇 塗膜耐水性 O O O O O O [表 3]Foreign matter derived from AI (filtration time) 0 0 O 0 0 0 Water dispersion stability ○ ○ ○ ○ ○ ○ Paint water resistance O O O O O O [Table 3]
Figure imgf000075_0001
Figure imgf000075_0001
本発明ポリエステル樹脂の合成例：（AA) Synthesis example of the polyester resin of the present invention: (AA)
攪拌機、コンデンサー、温度計を装備したステンレス製反応釜に表 4に記載の各成 分モル0 /0になるように酸成分としてテレフタル酸、イソフタル酸、フマル酸、グリコール 成分としてエチレングリコール、ネオペンチルグリコール、前記アルミニウム化合物の エチレングリコール溶液/リンィヒ合物のエチレングリコール溶液の混合物の調製例か らなる重合触媒溶液、熱安定剤としてフヱノチアジンを出来上力 ^樹脂量に対して 20 Oppm仕込み、窒素下 150°C〜220°Cでエステル化反応を行なった後、次いで 250 °Cまで加温しながら徐々に減圧し 60分間で 13. 3Pa減圧とし、この温度ならびに減 圧条件下で 1時間重合を行ない共重合ポリエステル (AA)を得た。得られた共重合ポ リエステルの組成および特性値を表 4に示す。 Each stainless steel reaction kettle equipped with a stirrer, condenser and thermometer is listed in Table 4. Min mole 0/0 so as terephthalic acid as the acid component, isophthalic acid, fumaric acid, ethylene glycol as a glycol component, neopentyl glycol, the preparation of a mixture of ethylene glycol solution of an ethylene glycol solution / Rinihi compound of the aluminum compound Polymerization catalyst solution consisting of an example, Funothiazine as a heat stabilizer, and the resulting power ^ 20 Oppm of the amount of resin, esterified at 150 ° C to 220 ° C under nitrogen, then up to 250 ° C While heating, the pressure was gradually reduced to 13.3 Pa in 60 minutes, and polymerization was carried out for 1 hour under this temperature and reduced pressure to obtain a copolyester (AA). Table 4 shows the composition and characteristic values of the obtained copolymer polyester.
[0277] 上記本発明の共重合ポリエステル樹脂 (AA)の合成に準じた方法で、ポリエステル 樹脂（BB)、（CC)、（DD)、 (EE) , (FF)を得た。得られた各共重合ポリエステル樹脂 の組成と特性値、を表 4に示す。 [0277] 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.
アルミニウム化合物単独系触媒の場合 (CC)は、複合系 (AA)、 (BB)に比べて重合 活性がやや低ぐ異物が若干多い以外は、着色の少ない良好な外観を示した。アン チモン系重合触媒 (DD)は着色に加えて濁っていた。チタン系触媒 (EE)は得られた 樹脂の着色が著しぐかつゲル分率が大きぐ重合中に不飽和結合基が反応したも のと考えられる。チタン系触媒はポリエステル重合能は大きいが、ゲル化反応も助長 すること力 S分力る。また、スズ系重合触媒 (FF)は比較的着色も少ないものであつたが アンチモン系重合触媒同様にこれらを含まなレ、ポリエステルが望まれてレ、る。  In the case of an aluminum compound-only catalyst (CC), 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 (AA) and (BB). Antimony polymerization catalyst (DD) was cloudy in addition to coloring. The 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.
アルミニウム化合物系触媒は、色相も良好で、かつ不飽和基由来のゲルィヒ反応を 抑制する効果のあることが分かる。  It can be seen that the aluminum compound-based catalyst has a good hue and has an effect of suppressing the Gerich reaction derived from the unsaturated group.
[0278] 本発明ウレタン樹脂の合成例：（GG) [0278] Synthesis Example of Urethane Resin of the Present Invention: (GG)
攪拌機、コンデンサー、温度計を装備したステンレス製反応釜に表 5に記載の各成 分モル％になるように酸成分としてテレフタル酸、イソフタル酸、フマル酸、グリコール 成分としてエチレングリコール、ネオペンチルグリコール、前記アルミニウム化合物の エチレングリコール溶液/リンィ匕合物のエチレングリコール溶液の混合物の調製例か らなる重合触媒溶液、熱安定剤としてフヱノチアジンを出来上力 ^樹脂量に対して 20 Oppm仕込み、窒素下 150°C〜220°Cでエステル化反応を行なった後、次いで 250 °Cまで加温しながら徐々に減圧し 60分間で 13. 3Pa減圧とし、この温度ならびに減 圧条件下で 20分重合を行ない、還元粘度が 0. 3dl/gの共重合ポリエステル樹脂を 得た。 In a stainless steel reaction kettle equipped with a stirrer, condenser, and thermometer, terephthalic acid, isophthalic acid, fumaric acid, glycol components as ethylene components, neopentyl glycol, Polymerization catalyst solution consisting of a mixture of an ethylene glycol solution of the above-mentioned aluminum compound / ethylene glycol solution of a phosphorus compound, and phenothiazine as a heat stabilizer. After the esterification reaction was performed at ° C to 220 ° C, the pressure was gradually reduced to 250 ° C while heating to 13.3 Pa in 60 minutes. Polymerization was carried out under pressure for 20 minutes to obtain a copolyester resin having a reduced viscosity of 0.3 dl / g.
[0279] 当該ポリエステル 100部を温度計、撹拌機、還流式冷却器を具備した反応器中に メチルェチルケトン 120部と共に仕込み溶解後、ネオペンチルダリコール 1. 5部、ィ ソホロンジイソシァネート 5部、ジブチル錫ラウレート 0. 02部を仕込み、 60〜70°Cで 6時間反応させた。次いで、反応系を 70°Cまで冷却し、反応を停止した。得られたポ リウレタン樹脂 Gの還元粘度は 0. 56dl/gであった。物性測定結果を表 5に示す。  [0279] 100 parts of the polyester was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser together with 120 parts of methyl ethyl ketone, dissolved, and then 1.5 parts of neopentyldarlicol, isophorone diisocyanate. 5 parts of nate and 0.02 part of dibutyltin laurate were charged and reacted at 60 to 70 ° C. for 6 hours. Subsequently, the reaction system was cooled to 70 ° C. to stop the reaction. The reduced viscosity of the obtained polyurethane resin G was 0.56 dl / g. Table 5 shows the physical property measurement results.
[0280] 上記本発明のウレタン樹脂（GG)の合成に準じた方法で、ウレタン樹脂（HH)、 (II) 、（JJ)、を得た。得られたウレタン樹脂の組成と特性値、を表 5に示す。  [0280] 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.
アルミニウム化合物触媒の場合、いずれも外観良好で、ゲル分率は見られなかった 。チタン系触媒 (JJ)は得られた樹脂の着色が著しぐかつゲル分率が大きぐ重合中 に不飽和結合基が反応したものと考えられる。チタン系触媒はポリエステル重合能は 大きいが、ゲルィ匕反応も助長することが分かる。  In the case of the aluminum compound catalyst, all had good appearance and no gel fraction was observed. It is considered that 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.
[0281] (実施例 la)  [0281] (Example la)
撹拌器、温度計、還流装置と定量滴下装置を備えた反応器に共重合ポリエステル 樹脂 (AA)のメチルェチルケトン溶液（固形分 50%) 200部、イソプロピルアルコール 3 0部をいれ、 65°Cに加熱後、アクリル酸 12部とアクリル酸ェチル 8部の混合物と、 AI BN1. 2部、ォクチルメルカプタン 1部を 20部のメチルェチルケトンと 7部のイソプロピ ルアルコールの混合溶液に溶解した溶液とを 2時間掛けて徐々にポリエステル溶液 中に滴下し、さらに 2時間撹拌を続けた。その後、水 300部とトリェチルァミン 25部を 反応溶液に加え、 1時間撹拌した。その後、分散体の温度を 100°Cに上げ、メチルェ チルケトン、イソプロピルアルコール、過剰のトリェチルァミンを蒸留により溜去、室温 まで冷却したのち、 200メッシュフィルターでろ過して、乳白色の水分散体を得た。得 られた水分散体の特性値を表 6に示す。  In a reactor equipped with a stirrer, thermometer, refluxing device and quantitative dropping device, put 200 parts of methyl ethyl ketone solution of copolyester resin (AA) (solid content 50%), 30 parts of isopropyl alcohol, 65 ° After heating to C, dissolve 12 parts of acrylic acid and 8 parts of ethyl acrylate, 1.2 parts of AI BN, 1 part of octyl mercaptan in a mixed solution of 20 parts of methyl ethyl ketone and 7 parts of isopropyl alcohol. The solution was gradually added dropwise to the polyester solution over 2 hours, and stirring was continued for another 2 hours. Thereafter, 300 parts of water and 25 parts of triethylamine were added to the reaction solution and stirred for 1 hour. Thereafter, the temperature of the dispersion was raised to 100 ° C, methyl ethyl ketone, isopropyl alcohol and excess triethylamine were distilled off, cooled to room temperature, and then filtered through a 200 mesh filter to obtain a milky white aqueous dispersion. . Table 6 shows the characteristic values of the obtained water dispersion.
[0282] (実施例 2a) [0282] (Example 2a)
撹拌器、温度計、還流装置と定量滴下装置を備えた反応器に共重合ポリエステル 樹脂 (BB)のメチルェチルケトン溶液（固形分 50%) 200部、イソプロピルアルコール 3 0部をいれ、 65°Cに加熱後、無水マレイン酸 11部を添カ卩し、溶解させた。別途、スチ レン 9部と、 AIBN1. 2部、ォクチルメルカプタン 1部を 20部のメチルェチルケトンと 7 部のイソプロピルアルコールの混合溶液に溶解した溶液とを 2時間掛けて徐々にポリ エステル/無水マレイン酸溶液中に滴下し、さらに 2時間撹拌を続けた。その後、ェ タノールを 25部、トリェチルァミン 25部を反応溶液に加え 30分攪拌、さらに水 300部 を反応溶液に加え、 30分撹拌した。その後、分散体の温度を 100°Cに上げ、メチル ェチルケトン、イソプロピルアルコール、エタノール、過剰のトリェチルァミンを蒸留に より溜去、室温まで冷却したのち、 200メッシュフィルターでろ過して、乳白色の水分 散体を得た。得られた水分散体の特性値を表 6に示す。 In a reactor equipped with a stirrer, thermometer, refluxing device and quantitative dropping device, put 200 parts of methyl ethyl ketone solution of copolyester resin (BB) (solid content 50%), 30 parts of isopropyl alcohol, 65 ° After heating to C, 11 parts of maleic anhydride was added and dissolved. Separately, Polyester / maleic anhydride over a period of 2 hours with 9 parts of LEN, 1.2 parts of AIBN and 1 part of octyl mercaptan in a mixed solution of 20 parts of methyl ethyl ketone and 7 parts of isopropyl alcohol The solution was added dropwise to the solution, and stirring was continued for another 2 hours. Thereafter, 25 parts of ethanol and 25 parts of triethylamine were added to the reaction solution and stirred for 30 minutes. Further, 300 parts of water was added to the reaction solution and stirred for 30 minutes. Thereafter, the temperature of the dispersion was raised to 100 ° C, methyl ethyl ketone, isopropyl alcohol, ethanol and excess triethylamine were distilled off, cooled to room temperature, filtered through a 200 mesh filter, and milky white water dispersion. Got. Table 6 shows the characteristic values of the obtained water dispersion.
[0283] (実施例 3a、 4a、 6a) (比較例 la、 3a、 4a、 5a、 6a)  [0283] (Examples 3a, 4a, 6a) (Comparative Examples la, 3a, 4a, 5a, 6a)
実施例 laと同様の方法で水分散体を作製した。得られた水分散体の物性は表 6に 示す。  An aqueous dispersion was prepared in the same manner as in Example la. Table 6 shows the physical properties of the resulting water dispersion.
[0284] (実施例 5a)  [0284] (Example 5a)
実施例 2aと同様の方法で水分散体を作製した。得られた水分散体の物性は表 6に 示す。  A water dispersion was prepared in the same manner as in Example 2a. Table 6 shows the physical properties of the resulting water dispersion.
[0285] (比較例 2a) [0285] (Comparative Example 2a)
実施例 laと同様の方法で水分散体の作製を試みた。しかしながら、水を添加した 段階で樹脂は水分散せず、析出してしまった。これは、ポリエステルの重合段階で、 不飽和結合が熱劣化のため潰れたため、充分にグラフト反応ができず、水分散体に 充分な酸価が得られなかったためである。  An 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.
[0286] 比較例 la、 3a、 4aでは、水分散体としては分散性も安定で、塗膜の耐水性も充分 ではあるが、ベースとなるポリエステル、ウレタンの色相の悪さが影響を及ぼし、アタリ ル樹脂のハイブリッドとなっても色相が悪い。 [0286] In Comparative Examples la, 3a, and 4a, the water dispersion is stable in dispersibility and the water resistance of the coating film is sufficient, but the bad hue of the polyester and urethane as the base affects it. Even if it becomes a hybrid of resin, the hue is bad.
[0287] 比較例 5aにおいては、水分散体の酸価が大きぐ得られた塗膜の耐水性が不良で ある。 [0287] In Comparative Example 5a, the water resistance of the obtained coating film having a high acid value of the aqueous dispersion is poor.
[0288] 比較例 6aにおいては、製造工程では水分散はするものの、酸価が低いため、経時 による析出が起こった。  [0288] In Comparative Example 6a, although water was dispersed in the production process, precipitation with time occurred because the acid value was low.
[0289] [表 4] 共重合ホ'リエステル樹脂 AA BB GG DD EE FF 多価カルホ'ン酸成分 亍レフタル酸 47 50 50 47 47 47 (モル <½) イソフタル酸 47 29 45 47 47 47 セ Λ'シン 16 [0289] [Table 4] Copolyester resin AA BB GG DD EE FF Multivalent carboxylic acid component 亍 Lephthalic acid 47 50 50 47 47 47 (mol <½) Isophthalic acid 47 29 45 47 47 47
フマル酸 6 5 6 6 6 ィタコン酸 5  Fumaric acid 6 5 6 6 6 Itaconic acid 5
多価アルコ-ル成分 エチレンク'リコール 48 55 50 50 50 50Polyhydric alcohol component Ethylene alcohol recall 48 55 50 50 50 50
(モル％) ネオべ 'ンチルク'リコール 52 45 50 50 50 (Mole%) Neo-Benchiru recall 52 45 50 50 50
2,2-ビス (4 -ヒド Πキシ Iトキシフェニ  2,2-Bis (4-Hydroxy I Toxipheny
50  50
ル)プロ/ ン  E) Pro /
熱安定剤 フエノチアシ 'ン 100 100 100 100Thermal stabilizer Phenothicin 100 100 100 100
(樹脂全量に対する 2,5-シ '- ί-プチル Λ仆'ロキノン 300 (2,5-Si'- ί-Ptyl Λ 仆 'roquinone with respect to the total amount of resin 300
Mm. ppm) Ρ-ベ'ンソキノン 100  Mm.ppm) ベ -Bensoquinone 100
触媒 三酸化アンチモン 0.02 Catalyst Antimony trioxide 0.02
(全酸成分に対する 亍トラプチルチタネ-ト 0.02 モル％) ヒト'ロキシプチルスス'オキサイド 0.02  (亍 Trappyl titanate 0.02 mol% with respect to all acid components) Human 'Roxyptylus' oxide 0.02
塩基性齚酸アルミニウム 0.02 0.02 0.1  Basic aluminum oxalate 0.02 0.02 0.1
Irganox1222 0.04  Irganox1222 0.04
酢酸リチウム 0.04  Lithium acetate 0.04
特性 還元粘度（dl/g) 0.55 0.63 0.45 0.53 0.57 0.54 ガラス転移点温度 C) 63 40 78 62 66 64 酸価 (mgKOH/g) 0.4 0.8 0.6 0.5 0.7 0.6 外観 着色の程度 〇 Δ 〇 X X XCharacteristic Reduced viscosity (dl / g) 0.55 0.63 0.45 0.53 0.57 0.54 Glass transition temperature C) 63 40 78 62 66 64 Acid value (mgKOH / g) 0.4 0.8 0.6 0.5 0.7 0.6 Appearance Degree of color ○ Δ ○ X X X
AI由来の異物（ろ過時間） 〇 〇 Δ~〇 Foreign matter derived from AI (filtration time) 〇 △ Δ ~ 〇
ゲル分率 ( 0 0 0 4 18 1 表 5]  Gel fraction (0 0 0 4 18 1 Table 5)
ウレタン樹脂 GG HH 1 1 JJ Urethane resin GG HH 1 1 JJ
亍レフタル酸 47 30 48 47 イソフタル酸 47 30 47 47 多価カル木'ン酸  亍 Lephthalic acid 47 30 48 47 Isophthalic acid 47 30 47 47
セ Λ'シン酉 ¾ 36  S Λ 'Shin 酉 36
成分 (モル <½〉  Ingredients (mol <½>
フマル酸 6 5 6 ィタコン酸 4  Fumaric acid 6 5 6 Itaconic acid 4
エチレンク'リコ-ル 50 50 50 多価アルコ―ル ネオへ 'ンチルゲリコール 50 55 50 50 成分 (モル½) 2,2-ビス (4-ヒト'ロキシ Iトキシフ I  Ethylene alcohol 50 50 50 Polyhydric alcohol Neohexyl glycol 50 55 50 50 Ingredients (mol ½) 2,2-bis (4-human'loxy I Toxif I
ポリエステル 45  Polyester 45
ニル)プロ ン  Nyl) prone
熱安定剤 フエ/チアシ 'ン 100 100 (樹脂全量に対 2,5—シ'一 ί—フ'チル Λイト'ロキ /ン 200  Heat Stabilizer Hue / Thiashi 100 100
する 星 ppm) ρ ンソキゾン 1 00 fid] A甘 f 3i ハ 亍トラブチルチタネ-ト 0.02  Yes star ppm) ρ Nsokison 1 00 fid] A sweet f 3i Ha 亍 trabutyl titanate 0.02
塩基性酢酸アルミニウム 0.02 0.02 0.02 に対するモル <½ )  Basic aluminum acetate 0.02 0.02 mol to 0.02 <½)
Irganox1222 0.04 0.04 0.04 ホ 'リエステル還元粘度 (dl/g) 0.3 0.2 0.2 0.3 ジオール（重量 <½、 ネオへ 'ンチルゲリコール 1.5 1.5 ホ 'リエステ』! 1.2-プロピレンゲリコ—ル 3  Irganox1222 0.04 0.04 0.04 Polyester reduced viscosity (dl / g) 0.3 0.2 0.2 0.3 Diol (weight <½, neohexylgelol 1.5 1.5 e-Rieste)! 1.2-propylene gelol 3
100とした値） へキサンシ'ォ―ル 3 ジイソシァネート  Hexanediol 3 diisocyanate
重量 <½、木'リエス亍ルをイソホロンシ'イソシァネート 5 8 8 5 100とした値） Weight <½, wood 'ressle' as isophoron'isocyanate 5 8 8 5 100)
還元粘度 (dl/g)) 0.56 0.50 0.51 0.56 外観 (着色の程度） 〇 〇 〇 X 特性 酸価 (mgKOH/g) 0.4 0.8 0.6 0.5  Reduced viscosity (dl / g)) 0.56 0.50 0.51 0.56 Appearance (degree of coloration) ○ ○ ○ X characteristics Acid value (mgKOH / g) 0.4 0.8 0.6 0.5
AI由来の異物（ろ過時間） 〇 〇 〇 ゲル分率 (％) 0 0 0 3 [0291] [表 6] AI-derived foreign matter (filtration time) 〇 〇 〇 Gel fraction (%) 0 0 0 3 [0291] [Table 6]
Figure imgf000080_0001
Figure imgf000080_0001
産業上の利用可能性  Industrial applicability
[0292] 上記の結果から、本発明の共重合ポリエステル樹脂及びその水分散体、並びにハ イブリツド樹脂及びその水分散体は、重金属や錫を含まず、従来のアンチモンあるい はチタン系重合触媒を用いたものに比べ着色が少なく良好な外観を示した。さらに 得られる塗膜は耐水性に優れることが分かった。これらの本発明の共重合ポリエステ ル樹脂水分散体、ハイブリッド樹脂水分散体は、水性接着剤、水性コーティング剤、 水性塗料組成などに優れた特性を示す。  [0292] From the above results, 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.

Claims

請求の範囲 The scope of the claims
[I] 少なくともアルミニウム化合物を含有する重合触媒の存在下に製造された、樹脂酸 価が 3〜110mgK〇H/gである共重合ポリエステル樹脂を用いることを特徴とする ポリエステル樹脂水分散体。  [I] A polyester resin aqueous dispersion characterized by using a copolymerized polyester resin having a resin acid value of 3 to 110 mgKH / g, which is produced in the presence of a polymerization catalyst containing at least an aluminum compound.
[2] 樹脂酸価の 80%以上がカルボキシル基及び Zまたはスルホン基によるものであるこ とを特徴とする請求項 1に記載のポリエステル樹脂水分散体。  [2] The polyester resin aqueous dispersion according to [1], wherein 80% or more of the resin acid value is attributed to a carboxyl group and a Z or sulfone group.
[3] 上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、リン 化合物から選ばれる少なくとも 1種からなることを特徴とする請求項 1〜2のいずれか に記載のポリエステル樹脂水分散体。 [3] The polyester resin water according to any one of claims 1 to 2, wherein the polymerization catalyst comprises at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds. Dispersion.
[4] 上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、ァ ルカリ金属および/またはアルカリ土類金属からなることを特徴とする請求項 1〜2の いずれかに記載のポリエステル樹脂水分散体。 [4] The polyester according to any one of claims 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. Resin water dispersion.
[5] 上記アルミニウム化合物がカルボン酸含有化合物であることを特徴とする請求項 1[5] The aluminum compound is a carboxylic acid-containing compound.
〜4のいずれかに記載のポリエステル樹脂水分散体。 The polyester resin aqueous dispersion according to any one of -4.
[6] 上記リンィ匕合物が芳香族ホスホン酸およびその誘導体からなる群から選ばれる少 なくとも 1種であることを特徴とする請求項 3または 5に記載のポリエステル樹脂水分 散体。 6. The polyester resin water dispersion according to claim 3 or 5, wherein the phosphorus compound is at least one selected from the group consisting of aromatic phosphonic acids and derivatives thereof.
[7] 上記アルカリ金属およびアルカリ土類金属が Li, Na， Mgないしその化合物から選 択される少なくとも 1種であることを特徴とする請求項 4〜6のいずれかに記載のポリ エステル樹脂水分散体。  7. The polyester resin water according to any one of claims 4 to 6, wherein the alkali metal and alkaline earth metal are at least one selected from Li, Na, Mg or a compound thereof. Dispersion.
[8] 共重合ポリエステル樹脂に不溶なアルミニウム系異物が明細書に記載の方法で測 定した場合、 5時間未満であることを特徴とする請求項 1〜7のいずれかに記載のポリ エステル樹脂水分散体。 [8] The polyester resin according to any one of claims 1 to 7, wherein the aluminum-based foreign matter insoluble in the copolyester resin is less than 5 hours when measured by the method described in the specification. Water dispersion.
[9] 被接着材がフィルム、布および金属のいずれかであることを特徴とする請求項 1〜8 のレヽずれかに記載のポリエステル樹脂水分散体を用いた水性接着剤。 [9] The aqueous adhesive using the polyester resin aqueous dispersion according to any one of [1] to [8], wherein the adherend is any one of a film, cloth and metal.
[10] 請求項 1〜8のいずれかに記載のポリエステル樹脂水分散体を用いた水性コーティ ング剤。 [10] An aqueous coating agent using the aqueous polyester resin dispersion according to any one of claims 1 to 8.
[II] 請求項 1〜8のいずれかに記載のポリエステル樹脂水分散体を用いた水性塗料。 [II] A water-based paint using the polyester resin aqueous dispersion according to any one of claims 1 to 8.
[12] 少なくともアルミニウム化合物を含有する重合触媒の存在下に製造された共重合ポ リエステル樹脂、および、該共重合ポリエステル樹脂を構成成分として含むポリウレタ ン樹脂のうち少なくとも一方と、アクリル樹脂とのハイブリッド樹脂を用いるハイブリッド 樹脂水分散体であって、ハイブリッド樹脂の酸価が 20〜400mgK〇H/gであること を特徴とするハイブリッド樹脂水分散体。 [12] A hybrid of at least one of a copolymer polyester resin produced in the presence of a polymerization catalyst containing at least an aluminum compound, and a polyurethane resin containing the copolymer polyester resin as a constituent, and an acrylic resin A hybrid resin aqueous dispersion using a resin, wherein the hybrid resin has an acid value of 20 to 400 mgKH / g.
[13] 共重合ポリエステル樹脂、および、該共重合ポリエステル樹脂を構成成分として含 むポリウレタン樹脂のうち少なくとも一方の重量力 S、ハイブリッド樹脂の重量の 10%以 上 90%以下であることを特徴とする請求項 12に記載のハイブリッド樹脂水分散体。  [13] It is characterized by having a weight force S of at least one of the copolyester resin and a polyurethane resin containing the copolyester resin as a constituent, and not less than 10% and not more than 90% of the weight of the hybrid resin. The hybrid resin water dispersion according to claim 12.
[14] 共重合ポリエステル樹脂、および、該共重合ポリエステル樹脂を構成成分として含 むポリウレタン樹脂のうち少なくとも一方に、不飽和結合を導入し、それを反応点とし てアクリルグラフトすることを特徴とする請求項 12または 13に記載のハイブリッド樹脂 水分散体。  [14] 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. The hybrid resin aqueous dispersion according to claim 12 or 13.
[15] 上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、リン 化合物から選ばれる少なくとも 1種からなることを特徴とする請求項 12〜： 14のいずれ 力に記載のハイブリッド樹脂水分散体。  15. The hybrid resin according to any one of claims 12 to 14, wherein the polymerization catalyst comprises at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds. Water dispersion.
[16] 上記重合触媒が、アルミニウム化合物からなる群から選ばれる少なくとも 1種と、ァ ルカリ金属および/またはアルカリ土類金属とからなることを特徴とする請求項 12〜116. The polymerization catalyst according to claim 12, wherein the polymerization catalyst comprises at least one selected from the group consisting of aluminum compounds, and alkali metal and / or alkaline earth metal.
4のいずれかに記載のハイブリッド樹脂水分散体。 5. The hybrid resin water dispersion according to any one of 4 above.
[17] 上記アルミニウム化合物がカルボン酸含有化合物であることを特徴とする請求項 117. The aluminum compound is a carboxylic acid-containing compound.
2〜： 16のいずれかに記載のハイブリッド樹脂水分散体。 2 to: The hybrid resin water dispersion according to any one of 16.
[18] 上記リンィヒ合物が芳香族ホスホン酸およびその誘導体からなる群から選ばれる少 なくとも 1種であることを特徴とする請求項 15または 17に記載のハイブリッド樹脂水分 散体。 18. The hybrid resin moisture dispersion according to claim 15 or 17, wherein the Linich compound is at least one selected from the group consisting of aromatic phosphonic acids and derivatives thereof.
[19] 上記アルカリ金属およびアルカリ土類金属が Li, Na， Mgないしその化合物から選 択される少なくとも 1種であることを特徴とする請求項 16〜： 18のいずれかに記載のハ イブリツド樹脂水分散体。  [19] The hybrid resin according to any one of [16] to [18], wherein the alkali metal and alkaline earth metal are at least one selected from Li, Na, Mg or a compound thereof. Water dispersion.
[20] 共重合ポリエステル樹脂に不溶なアルミニウム系異物が明細書に記載の方法で測 定した場合、 5時間未満であることを特徴とする請求項 12〜： 19のいずれかに記載の ハイブリッド樹脂水分散体。 [20] The aluminum foreign matter insoluble in the copolyester resin is less than 5 hours when measured by the method described in the specification, wherein the foreign material is less than 5 hours. Hybrid resin water dispersion.
[21] 被接着材がフィルム、布および金属のいずれかであることを特徴とする請求項 12〜 20のレ、ずれかに記載のハイブリッド樹脂水分散体を用いた水性接着剤。  21. The aqueous adhesive using the hybrid resin water dispersion according to any one of claims 12 to 20, wherein the adherend is any one of a film, a cloth and a metal.
[22] 請求項 12〜20のいずれかに記載のハイブリッド樹脂水分散体を用いた水性コー ティング斉 1J。  [22] Aqueous coating simultaneous 1J using the hybrid resin water dispersion according to any one of claims 12 to 20.
[23] 請求項 12〜20のいずれかに記載のハイブリッド樹脂水分散体を用いた水性塗料  [23] A water-based paint using the hybrid resin water dispersion according to any one of claims 12 to 20
PCT/JP2007/062854 2006-06-30 2007-06-27 Polyester resin aqueous dispersion, hybrid resin aqueous dispersion, and adhesive, coating material and painting material using them WO2008001795A1 (en)

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JP2006182170A JP2008007720A (en) 2006-06-30 2006-06-30 Water dispersion for hybrid resin, adhesive using the same, coating agent and coating
JP2006-182170 2006-06-30

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