Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • 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

Definitions

• the present invention relates to a copolyester resin, a molded article thereof, and a method for producing a copolyester resin.
• Polyester especially polybutylene terephthalate (PBT), which is manufactured from terephthalic acid and 1,4-butanediol, has excellent chemical and physical properties and is used in a wide range of applications such as containers, films, sheets, and fibers. It is used for this purpose.
• PBT polybutylene terephthalate
• polyester resins which are made by copolymerizing adipic acid with 1,4-butanediol in addition to terephthalic acid, are known as crystalline PBT (Patent Documents) 1).
• Patent Document 1 a titanium compound is used as a polymerization catalyst, but the titanium compound is modified into titanium oxide and becomes a foreign substance during polymerization. It may be possible to remove foreign matter with a filter, but it is difficult to remove foreign matter with a small particle size (specifically, foreign matter with a particle size of 0.3 to 0.5 ⁇ m) with a filter, and it is difficult to remove foreign matter that remains in the resin. This leads to deterioration of product quality due to deterioration of operability during processing and appearance defects.
• An object of the present invention is to provide a copolyester resin with a particle size of 0.3 to 0.5 ⁇ m and less foreign matter.
• aliphatic dicarboxylic acid and terephthalic acid are used as the dicarboxylic acid component in a predetermined ratio, and 1,4-butanediol is used as the diol component. It has been found that by using an aluminum compound and a phosphorus compound as components and catalysts during polymerization, it is possible to reduce the amount of foreign matter in the copolymerized polyester resin.
• a copolyester resin characterized by satisfying the following (1) to (4).
• (1) Contains 20 to 80 mol% of units derived from aliphatic dicarboxylic acid in 100 mol% of dicarboxylic acid component, and 20 to 80 mol% of units derived from terephthalic acid
• 1,4-butanediol in 100 mol% of diol component
• (3) Contains 80 mol% or more of units derived from the above.
• (3) Contains aluminum atoms and phosphorus atoms.
• the copolymerized polyester resin has a particle size of 0.0.
• copolymerized polyester resin according to any one of [1] to [3].
• the mass reduction rate of the copolymerized polyester resin after decomposition relative to the copolymerized polyester resin before decomposition is 50 mass % or more of the copolymerized polyester resin according to any one of [1] to [6] above.
• the mass reduction rate of the resin after decomposition relative to the resin before decomposition is 50% by mass or more. Copolymerized polyester resin.
• Esterification reaction and/or transesterification of dicarboxylic acids containing 20 to 80 mol% of terephthalic acid and 20 to 80 mol% of aliphatic dicarboxylic acids and diols containing 80 mol% or more of 1,4-butanediol A first step of reacting and a second step of polycondensing the reactant obtained in the first step, and adding an aluminum compound and a phosphorus compound as a polymerization catalyst at the latest by the end of the first step.
• a method for producing a copolymerized polyester resin characterized by: [11] The manufacturing method according to [10] above, wherein addition of the aluminum compound and phosphorus compound is started before or during the first step.
• the particle size can be adjusted. It is possible to produce a copolyester resin with a small amount of foreign matter having a particle size of 0.3 to 0.5 ⁇ m. Therefore, the copolymerized polyester resin of the present invention can be widely used as a material for various molded products such as films, sheets, blow molded containers, engineering plastics, and fibers. Note that in this specification, foreign matter having a particle size of 0.3 to 0.5 ⁇ m may be simply referred to as "foreign matter.”
• the copolymerized polyester resin of the present invention has suppressed coloring. Furthermore, the copolyester resin of the present invention preferably has excellent biodegradability. Resins with excellent biodegradability and suppressed coloring are particularly preferred as materials for various molded products such as films, sheets, blow-molded containers, engineering plastics, and fibers.
• the copolyester resin of the present invention is a resin obtained by polycondensing a dicarboxylic acid component and a diol component.
• the copolymerized polyester resin of the present invention contains 20 to 80 mol% of units derived from aliphatic dicarboxylic acid and 20 to 80 mol% of units derived from terephthalic acid in 100 mol% of the dicarboxylic acid component. It preferably contains 30 to 70 mol%, more preferably 40 to 60 mol%, of units derived from aliphatic dicarboxylic acids. Further, it preferably contains 30 to 70 mol%, more preferably 40 to 60 mol%, of units derived from terephthalic acid.
• dicarboxylic acid component 100 mol% means that the total amount of units derived from all dicarboxylic acids is 100 mol%, and the same applies to components other than dicarboxylic acids (diol component, all carboxylic acid components, etc.) . Furthermore, when two or more types of aliphatic dicarboxylic acids are used, the proportion of "units derived from aliphatic dicarboxylic acids” means mol% of the total of all aliphatic dicarboxylic acids.
• the total amount of units derived from aliphatic dicarboxylic acid and units derived from terephthalic acid is preferably 80 mol% or more, more preferably 90 mol% or more, and preferably 95 mol% or more. More preferably, it is 97 mol% or more, particularly preferably 99 mol% or more, and most preferably 99 mol% or more.
• the aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer Saturated aliphatic dicarboxylic acids exemplified by acids; unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, ita
• At least one selected from succinic acid, glutaric acid, adipic acid, and sebacic acid is preferable, and at least one selected from succinic acid, glutaric acid, and adipic acid is more preferable. It is even more preferable that there be.
• the aliphatic dicarboxylic acid is preferably an aliphatic saturated dicarboxylic acid, more preferably an aliphatic saturated dicarboxylic acid having 3 to 12 carbon atoms, and preferably an aliphatic saturated dicarboxylic acid having 4 to 10 carbon atoms. More preferably, an aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms is particularly preferred, and an aliphatic saturated dicarboxylic acid having 6 carbon atoms is most preferred. Furthermore, the aliphatic saturated dicarboxylic acid is preferably an ⁇ , ⁇ -dicarboxylic acid, more preferably a linear ⁇ , ⁇ -dicarboxylic acid.
• the copolymerized polyester resin of the present invention may contain dicarboxylic acids other than aliphatic dicarboxylic acids and terephthalic acid.
• Dicarboxylic acids other than aliphatic dicarboxylic acids and terephthalic acid include orthophthalic acid, isophthalic acid, 5-(alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'-biphenylsulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid , 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid,
• units derived from dicarboxylic acids other than aliphatic dicarboxylic acids and terephthalic acid are preferably at most 30 mol%, more preferably at most 20 mol%, even more preferably at most 10 mol%, and especially Preferably it is 5 mol% or less, most preferably 1 mol% or less.
• the proportion of "units derived from aliphatic dicarboxylic acid and dicarboxylic acid other than terephthalic acid” is equal to the proportion of all dicarboxylic acids other than aliphatic dicarboxylic acid and terephthalic acid. It means mol% of the total dicarboxylic acid.
• units derived from terephthalic acid are preferably at least 60 mol%, more preferably at least 75 mol%, even more preferably at least 90 mol%, and even more preferably at least 95 mol%. It is particularly preferable, and most preferably 98 mol% or more.
• the copolyester resin of the present invention may contain a carboxylic acid-derived unit other than the dicarboxylic acid component as long as it is in a small amount.
• Carboxylic acids other than dicarboxylic acids may include trivalent or higher polyvalent carboxylic acids and hydroxycarboxylic acids, and the trivalent or higher polyvalent carboxylic acids are preferably trivalent to tetravalent polycarboxylic acids.
• trivalent or higher polyvalent carboxylic acids examples include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, and 3,4,3',4'-biphenyltetracarboxylic acid. Examples include acids.
• the unit derived from trivalent or higher polyhydric carboxylic acid is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 2 mol% or less.
• the proportion of "units derived from trivalent or more polyvalent carboxylic acids" means mol% of the total of all polyvalent carboxylic acids of trivalence or more. do.
• hydroxycarboxylic acids examples include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. It will be done.
• the unit derived from hydroxycarboxylic acid is preferably at most 10 mol%, more preferably at most 5 mol%, even more preferably at most 2 mol%.
• the ratio of "units derived from hydroxycarboxylic acid" means mol% of the total of all hydroxycarboxylic acids.
• Ester-forming derivatives of these dicarboxylic acids, trivalent or higher polycarboxylic acids, and hydroxycarboxylic acids may be used, such as their alkyl esters, acid chlorides, and acid anhydrides.
• unit derived from an acid includes not only a unit derived from the acid but also a unit derived from an ester-forming derivative of the acid.
• the copolymerized polyester resin of the present invention contains 80 mol% or more of units derived from 1,4-butanediol in 100 mol% of the diol component. It is preferable to contain 90 mol% or more of units derived from 1,4-butanediol, and more preferably 95 mol% or more.
• Diols other than 1,4-butanediol may be included as the diol component (glycol component).
• Diols other than 1,4-butanediol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 2 , 3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane Alkylene glycols such as dimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,10-decamethylene glyco
• units derived from diols other than 1,4-butanediol are 20 mol% or less, preferably 10 mol% or less, and more preferably 5 mol% or less.
• the proportion of "units derived from diols other than 1,4-butanediol" is the mol of the total of all diols other than 1,4-butanediol. means %.
• the copolymerized polyester resin of the present invention may contain a unit derived from a polyhydric alcohol other than the diol component as long as it is a small amount. That is, as the polyhydric alcohol other than the diol component, a trivalent or higher polyhydric alcohol may be used in combination.
• the polyhydric alcohol having a valence of 3 or more is preferably a polyhydric alcohol having a valence of 3 or 4.
• Examples of trivalent or higher polyhydric alcohols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like.
• the unit derived from trivalent or higher polyhydric alcohol is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 2 mol% or less.
• the ratio of "units derived from a polyhydric alcohol having a valence of 3 or more" means mol% of the total of all the polyhydric alcohols having a valence of 3 or more.
• Ester-forming derivatives of these may be used as 1,4-butanediol, glycols other than 1,4-butanediol, and trihydric or higher polyhydric alcohols.
• unit derived from 1,4-butanediol includes not only a unit derived from 1,4-butanediol but also a unit derived from an ester-forming derivative of 1,4-butanediol. shall be taken as a thing.
• a cyclic ester may be used as long as it is in a small amount.
• the cyclic ester include ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, glycolide, and lactide. Note that the cyclic ester does not correspond to either a carboxylic acid component or an alcohol component.
• the unit derived from the cyclic ester is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 2 mol% or less.
• the ratio of "units derived from cyclic esters" means mol% of the total of all cyclic esters.
• the copolymerized polyester resin of the present invention is produced using a polymerization catalyst consisting of an aluminum compound and a phosphorus compound, and as a result, the copolymerized polyester resin of the present invention contains a catalytic amount of an aluminum compound-derived component and a phosphorus compound-derived component. include. In other words, the copolyester resin of the present invention contains aluminum atoms and phosphorus atoms.
• the aluminum compound constituting the polymerization catalyst is not limited as long as it is soluble in a solvent, and any known aluminum compound can be used without limitation.
• Examples of aluminum compounds include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, citric acid.
• Carboxylic acid salts such as aluminum, aluminum tartrate, aluminum salicylate; Inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate; aluminum methoxide , aluminum alkoxides such as aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum t-butoxide; aluminum acetylacetonate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate diiso-propoxide, etc.
• Inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate; aluminum methoxide , aluminum alkoxides such as aluminum ethoxide, aluminum n-propoxide, aluminum is
• Chelate compounds organoaluminum compounds such as trimethylaluminum and triethylaluminum, and their partial hydrolysates, aluminum alkoxides and reaction products of aluminum chelate compounds and hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, Examples include composite oxides of aluminum and titanium, silicon, zirconium, alkali metals, alkaline earth metals, and the like.
• at least one selected from carboxylates, inorganic acid salts, and chelate compounds is preferred, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetate are preferred.
• At least one selected from aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate is more preferable, and aluminum acetate and a base At least one kind selected from basic aluminum acetate is particularly preferred, and basic aluminum acetate is most preferred.
• the above aluminum compound is preferably an aluminum compound that dissolves in water or glycol.
• Glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, trimethylene glycol, ditrimethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyl glycol, etc. It will be done. Preferred is butanediol. It is preferable to use a solution in which an aluminum compound is dissolved in water or butanediol because the effects of the present invention can be significantly exhibited. Note that the amount of the aluminum compound added will be described later.
• the phosphorus compound constituting the polymerization catalyst of the present invention is not particularly limited, but it is preferable to use a phosphonic acid-based compound or a phosphinic acid-based compound because it has a large effect of improving catalyst activity.
• phosphonic acid-based compounds are preferably used. This is more preferable because it has a particularly large effect of improving catalyst activity.
• phosphorus compounds having a phosphorus element and a phenol structure in the same molecule are preferred.
• phosphorus compounds There are no particular limitations on phosphorus compounds as long as they have a phosphorus element and a phenol structure in the same molecule, but phosphonic acid compounds have a phosphorus element and a phenol structure in the same molecule, and phosphines have a phosphorus element and a phenol structure in the same molecule.
• R 1 represents a hydrocarbon group having 6 to 50 carbon atoms containing a phenol moiety, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a hydrocarbon group having 6 to 50 carbon atoms containing a phenol structure.
• R 4 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
• R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a substituent such as a hydroxyl group or an alkoxyl group.
• the hydrocarbon group may include a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The ends of R 2 and R 4 may be bonded to each other.
• Examples of phosphorus compounds having a phosphorus element and a phenol structure in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis (p-hydroxyphenyl)phosphinic acid, methyl bis(p-hydroxyphenyl)phosphinate, phenyl bis(p-hydroxyphenyl)phosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, p-hydroxyphenyl Examples include phenyl phosphinate and dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate represented by the following (Formula 1).
• a phosphorus compound having a hindered phenol structure is particularly preferable, and among them, 3,5-di-tert-butyl shown below (Formula 1) is preferable. Dialkyl -4-hydroxybenzylphosphonate is preferred.
• X 1 and X 2 represent hydrogen and an alkyl group having 1 to 4 carbon atoms, respectively.
• the number of carbon atoms in the alkyl group of X 1 and X 2 is preferably 1 to 4, more preferably 1 to 2.
• the phosphorus compound since the ethyl ester having 2 carbon atoms is commercially available as Irganox 1222 manufactured by BASF, the phosphorus compound must be diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. is most preferred.
• the phosphorus compound in the present invention is preferably dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate shown in the above (Formula 1), but in addition to that, nine of the following chemical formulas are preferred. Also included are modified dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonates shown. The modified product will be explained below.
• dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate which is the phosphorus compound shown in the above (Formula 1)
• the phosphorus compound shown in the (Formula 1) is used.
• a part of dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, which is a phosphorus compound, undergoes a structural change. For example, the t-butyl group is eliminated, the ethyl ester group is hydrolyzed, and the structure changes to a hydroxyethyl transesterification structure (transesterification structure with ethylene glycol).
• the phosphorus compound includes not only the dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate shown in (Formula 1) but also structurally modified phosphorus compounds. Note that the elimination of the t-butyl group occurs significantly at high temperatures during the polymerization process.
• the content of antimony atoms in the copolymerized polyester resin of the present invention is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, even more preferably 20 mass ppm or less.
• the content of germanium atoms in the copolyester resin is preferably 40 mass ppm or less, more preferably 20 mass ppm or less, and the content of titanium atoms in the copolyester resin of the present invention is 10 mass ppm or less. It is preferably at most ppm, more preferably at most 5 ppm by mass.
• mass ppm means 10 -4 mass %.
• the method for producing the copolyester resin of the present invention includes using terephthalic acid, aliphatic dicarboxylic acid, and 1,4-butanediol as monomers in a predetermined ratio, and polyester polymerization using an aluminum compound and a phosphorus compound as a catalyst. It can be carried out by a method including known steps except for using a catalyst.
• the method for producing the copolymerized polyester resin of the present invention includes dicarboxylic acids (dicarboxylic acid component) containing 20 to 80 mol% of terephthalic acid and 20 to 80 mol% of aliphatic dicarboxylic acid, and 1,4-butanediol in an amount of 80 mol% or more. It has a first step of carrying out an esterification reaction and/or transesterification reaction with the diols (diol component) contained therein, and a second step of polycondensing the reaction product obtained in the first step.
• the method for producing the copolymerized polyester resin is not particularly limited as long as the first and second steps described above are satisfied.
• the esterification reaction for example, an aliphatic dicarboxylic acid, terephthalic acid, 1,4-butanediol, and other copolymerization components are directly reacted, water is distilled off, esterification is performed, and then the reaction is carried out under normal pressure or A direct esterification method in which polycondensation is carried out under reduced pressure can be mentioned.
• transesterification reaction for example, dimethyl terephthalate, an ester-forming derivative such as dimethyl ester of aliphatic dicarboxylic acid, 1,4-butanediol, and other copolymer components are reacted, and methyl alcohol is distilled off.
• ester-forming derivative such as dimethyl ester of aliphatic dicarboxylic acid, 1,4-butanediol, and other copolymer components are reacted, and methyl alcohol is distilled off.
• polycondensation is performed under normal pressure or reduced pressure.
• solid phase polymerization may be performed to increase the intrinsic viscosity.
• the esterification reaction or transesterification reaction may be carried out in one step or may be carried out in multiple steps.
• the polycondensation in the second step may be carried out in one step or may be carried out in multiple stages. Further, the polycondensation in the second step may be carried out only by melt polymerization, but the copolyester resin produced by melt polymerization may be additionally polymerized by solid phase polymerization.
• aliphatic dicarboxylic acids, terephthalic acid, dicarboxylic acids other than aliphatic dicarboxylic acids and terephthalic acid that may be added
• polycarboxylic acids of trivalent or higher valence that may be added in small amounts
• hydroxycarboxylic acids that may be added in small amounts.
• Acid and cyclic ester which may be added in small amounts, are not distilled out of the reaction system during polymerization, and almost 100% of the amount initially added to the system as a catalyst is a copolymerized polyester resin produced by polymerization. remain inside. Therefore, the mass of the "produced copolyester resin" can be calculated from the amount of these monomers charged.
• the amount of foreign matter is reduced compared to when a titanium compound or an antimony compound is used as a polymerization catalyst, but by the end of the first step, the amount of foreign matter is reduced. Compared to the case where a chemical compound and a phosphorus compound are added, the amount of foreign matter increases.
• the aluminum compound and phosphorus compound as polymerization catalysts may be added in their entirety at once, or may be added continuously. "Continuous addition” means to continue adding at a constant rate, and includes continuing to add a constant amount at regular intervals.
• Continuous addition means to continue adding at a constant rate, and includes continuing to add a constant amount at regular intervals.
• the addition of the aluminum compound and phosphorus compound as a polymerization catalyst is completed by the end of the first step at the latest, and the addition of the aluminum compound and phosphorus compound is preferably completed in the middle of the first step. It is more preferable that the addition of the aluminum compound and the phosphorus compound is completed before the start of the first step.
• a method for adding aluminum compounds and phosphorus compounds as catalysts it is preferable to add them in the form of a slurry or a solution, and it is more preferable to add a solution dissolved in a solvent such as water or glycol. More preferably, it is added, and most preferably, a solution dissolved in 1,4-butanediol is added.
• a complex having catalytic activity is functionally formed in the polymerization system, and sufficient polymerization activity can be exhibited. Further, the amount of foreign matter can be suppressed.
• the solution in which the aluminum compound is dissolved and the solution in which the phosphorus compound is dissolved it is preferable to add the solution in which the aluminum compound is dissolved and the solution in which the phosphorus compound is dissolved at the same time. It is more preferable to prepare a mixed liquid in advance and add the mixed liquid that has been made into one liquid. Examples of methods for making the solutions into one liquid in advance include a method of mixing each solution in a tank, and a method of merging the pipes for adding the catalyst in the middle and mixing them. By simultaneously adding a solution in which an aluminum compound is dissolved and a solution in which a phosphorus compound is dissolved, a complex formation reaction between the aluminum compound and the phosphorus compound occurs, and the complex of the aluminum compound and the phosphorus compound that brings about polymerization activity is quickly and efficiently produced. Can be generated.
• the copolyester resin of the present invention preferably contains 10 to 100 mass ppm of aluminum atoms, more preferably 20 to 80 mass ppm, and even more preferably 30 to 70 mass ppm.
• the aluminum atom content is 10 mass ppm or more, the polymerization activity is sufficiently exhibited.
• catalyst cost can be suppressed.
• the amount of aluminum atoms added to the copolymerized polyester resin to be produced is 10 to 100 mass ppm, more preferably 20 to 80 mass ppm. and more preferably 30 to 70 mass ppm. Note that, as described above, the mass of the "produced copolyester resin" can be calculated from the amount of monomers such as aliphatic dicarboxylic acid and terephthalic acid charged.
• the copolymerized polyester resin of the present invention preferably contains 20 to 250 mass ppm of phosphorus atoms, more preferably 30 to 200 mass ppm, still more preferably 40 to 150 mass ppm, particularly preferably 50 to 120 mass ppm. Mass ppm.
• the phosphorus atom content is 20 mass ppm or more, the polymerization activity is sufficiently exhibited and the amount of foreign substances can be suppressed. On the other hand, if it is 250 mass ppm or less, catalyst cost can be suppressed.
• the phosphorus compound which functions as a catalyst together with the aluminum compound, is partially (approximately 10 to 40%) of the amount initially added to the system as a catalyst when placed in a reduced pressure environment during polymerization of the copolyester resin.
• This removal ratio depends on the addition molar ratio of phosphorus atoms to aluminum atoms, the basicity and acidity of the aluminum-containing glycol solution and phosphorus-containing glycol solution, and the aluminum-containing solution and phosphorus-containing solution. It varies depending on the method of adding the solution (whether it is added as one liquid or added separately). Therefore, the amount of phosphorus atoms added to the copolymerized polyester resin to be produced is preferably 20 to 250 mass ppm, more preferably 30 to 200 mass ppm, and even more preferably 40 to 150 mass ppm.
• the content ratio of phosphorus atoms to aluminum atoms is preferably 1.1 to 2.1, more preferably 1.2 to 1.9, and still more preferably 1.3 to 1. .8.
• the aluminum atom and phosphorus atom in the copolyester resin are derived from the aluminum compound and phosphorus compound used as a polymerization catalyst for the copolyester resin, respectively.
• the content ratio of phosphorus atoms to aluminum atoms is 1.1 or more, thermal stability and thermal oxidation stability can be sufficiently exhibited, and the amount of foreign substances can also be suppressed.
• the content ratio of phosphorus atoms to aluminum atoms is 2.1 or less, the catalyst cost due to an increase in the amount of phosphorus compound added can be suppressed.
• the molar ratio of phosphorus atoms to aluminum atoms is preferably 1.3 to 2.5, more preferably 1.5 to 2.3, even more preferably 1. .7 to 2.2.
• the copolymerized polyester resin of the present invention may contain resins other than polyester resins as long as they do not impede the object of the present invention.
• Resins other than polyester resins are not particularly limited, and include, for example, polyolefin resins, polyamide resins, polyacetal resins, acrylic resins, and the like.
• the content of the resin other than the polyester resin in the copolymerized polyester resin is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and 3% by mass or less. It is particularly preferable that the amount is 1% by mass or less, and most preferably 1% by mass or less.
• the method of blending the above-mentioned resin with the polyester resin is not particularly limited, and examples thereof include methods that allow uniform mixing, such as addition during the manufacturing process of the polyester resin, dry blending with the polyester resin after manufacturing, etc. .
• the copolymerized polyester resin of the present invention may be modified using various chemical reactions. For example, modification such as epoxy modification using an epoxy compound or urethane modification using an isocyanate compound may be performed.
• Epoxy modification involves adding an acid anhydride such as trimellitic anhydride or phthalic anhydride to the terminal hydroxy group of a polyester resin to modify the terminal carboxy group, and then converting this carboxyl group and the epoxy resin into a catalyst such as triphenylphosphine. It can be synthesized by a known method such as a method of modifying with epoxy in the presence of epoxy. Furthermore, a carboxyl group may be introduced by using a carboxyl group-containing glycol such as dimethylolpropionic acid as a chain extender.
• the unit derived from the epoxy resin is preferably 5 mol% or less, more preferably 4 mol% or less, and even more preferably 3 mol% or less.
• the ratio of "units derived from epoxy” means mol% of the total of all epoxy resins.
• urethane modification it is synthesized by a known method such as blending a low molecular weight polyester diol with a chain extender if necessary and reacting it with a diisocyanate compound. Furthermore, a carboxyl group may be introduced into the side chain using a carboxyl group-containing diol such as dimethylolpropionic acid as a chain extender.
• the amount of units derived from diisocyanate is preferably 5 mol% or less, more preferably 4 mol% or less, and still more preferably 3 mol% or less.
• the ratio of "diisocyanate-derived units" means mol% of the total of all diisocyanates.
• the copolymerized polyester resin of the present invention may contain various known additives as appropriate, as long as they do not impede the purpose of the present invention.
• the additive include a leveling agent, an antifoaming agent, a dispersing agent for fine particles, an antioxidant, a bluing agent, an antistatic agent, a light stabilizer, a weatherability imparting agent, a coloring agent, and the like.
• a leveling agent may be added to improve the smoothness of the molded product obtained from the copolyester.
• leveling agents include silicone leveling agents, fluorine leveling agents, acrylic leveling agents, vinyl leveling agents, leveling agents that are a combination of fluorine and acrylic, and are used depending on the purpose. be able to.
• the leveling agent functions on the surface of the coating film and can lower the surface tension. If the purpose is to lower the surface tension, it is preferable to use a silicone leveling agent or a fluorine leveling agent, and if the purpose is to make wetting defects less likely to occur, it is preferable to use an acrylic leveling agent or a vinyl leveling agent. It is preferable to use an agent.
• silicone leveling agent for example, a copolymer of polyoxyalkylene and polydimethylsiloxane can be used.
• Commercially available silicone leveling agents include FZ-2118, FZ-77, FZ-2161, etc. manufactured by Dow Corning Toray; KP321, KP323, KP324, KP326, KP340, KP341, etc. manufactured by Shin-Etsu Chemical; and Momentive Performance. ⁇ TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, etc.
• BYK-300 manufactured by Materials Japan LLC, BYK-300, BYK-302, BYK-306, BYK-307, BYK-320, manufactured by BYK Chemie Japan, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-377, BYK-378, BYK- Examples include polyether-modified silicone oils (polyoxyalkylene-modified silicone oils) such as UV3500, BYK-3510, and BYK-3570.
• polyether-modified silicone oils polyoxyalkylene-modified silicone oils
• polyester-modified silicone oil or aralkyl-modified silicone oil having a benzene ring is suitable.
• Commercially available polyester-modified silicone oils include BYK-310, BYK-315, BYK-370 manufactured by BYK Chemie Japan.
• Commercially available aralkyl-modified silicone oils having benzene rings include BYK-322 and BYK-323 manufactured by BYK Chemie Japan.
• fluorine-based leveling agent for example, a copolymer of polyoxyalkylene and fluorocarbon can be used.
• fluorine leveling agents include the MEGAFAC series manufactured by DIC and the FC series manufactured by Sumitomo 3M.
• acrylic leveling agent commercially available vinyl leveling agents can be used.
• Commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-381, BYK-392 manufactured by BYK Chemie Japan, etc.
• Examples include BYK-340, which incorporates fluorine.
• vinyl leveling agent commercially available vinyl leveling agents can be used.
• examples of commercially available vinyl leveling agents include the Disparon series manufactured by Kusumoto Kasei Co., Ltd., and the like.
• the finished appearance of the molded product is improved and it can be applied evenly as a thin film.
• the amount of the leveling agent used is preferably 0.01 to 10% by weight, more preferably 0.02 to 5% by weight, based on the total amount of the composition.
• the leveling agent may be added at the time of preparing the composition for a molded object, it may be added to the composition immediately before forming the molded object, or the leveling agent may be added to the composition immediately before forming the molded object. It may be incorporated both at the stage of preparation and immediately before forming the shaped body.
• the copolymerized polyester resin of the present invention preferably has a reduced viscosity of 0.6 to 1.2 dL/g, more preferably 0.7 to 1.1 dL/g, and 0.8 to 1.0 dL. /g is more preferable.
• the details of the method for measuring reduced viscosity will be described later, but the method is based on JIS K7367-5.
• the reduced viscosity of the copolymerized polyester resin is within the above range, the molded product obtained from the resin can exhibit sufficient mechanical strength and impact resistance.
• the copolymerized polyester resin of the present invention preferably has an acid value of 3 to 80 eq/ton, more preferably 5 to 50 eq/ton, and even more preferably 8 to 20 eq/ton.
• the details of the method for measuring the acid value will be described later, but the method is based on JIS K0070.
• the number of particles with a particle size of 0.3 to 0.5 ⁇ m contained in a hexafluoro-2-propanol solution having a copolymerized polyester resin concentration of 0.15 g/L is 5500 particles/mL or less, and 4400 particles/mL. /mL or less is preferable, and it is more preferable that it is 4000 pieces/mL or less. It is preferable that the number of particles with a particle size of 0.3 to 0.5 ⁇ m (hereinafter sometimes referred to as "amount of foreign matter”) is as small as possible, but due to technical difficulties, the lower limit is, for example, 500 particles/mL, and preferably It is 1000 pieces/mL. Details of the method for measuring the amount of foreign matter will be described later.
• the b value in the L * a * b * color system of a solution obtained by dissolving 2g of copolyester resin in 18g of a mixed solvent with a mass ratio of phenol and tetrachloroethane of 60:40 is 10 or less. It is preferably 8 or less, more preferably 5 or less, and particularly preferably 3 or less.
• the b value of the solution shows the yellow/blue coordinate, positive values indicate yellow, negative values indicate blue, and the b value of the solution is affected by the amount of foreign matter in the copolyester resin. Conceivable. By reducing the amount of foreign matter in the copolymerized polyester resin, yellowing can be reduced and the b value of the solution can be 10 or less.
• the b value of the solution is as low as possible, but due to technical difficulties, the lower limit is, for example, 0 or more, preferably 1 or more.
• the b-value measurement method will be described later, but it is a measurement method based on JIS Z8701-1999.
• the b value of the copolymerized polyester resin pellets is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, and particularly preferably 3 or less.
• the b value of the pellet indicates the yellow/blue color coordinate, with positive values indicating yellow and negative values indicating blue. be.
• the lower limit is not particularly limited, but is, for example, 0 or more, preferably 1 or more. The details of the method for measuring the b value of pellets will be described later, but the method is based on JIS Z8722.
• the copolymerized polyester resin of the present invention preferably has a melting point, more preferably a melting point of 50°C or higher, from 70 to 180°C, from the viewpoint of increasing the mechanical strength of molded products obtained from the resin.
• the temperature is more preferably 90 to 150°C, particularly preferably 90 to 150°C. The details of the method for measuring the melting point will be described later, but the method is based on JIS K7121.
• the mass reduction rate of the resin after decomposition relative to the resin before decomposition was measured. Can determine gender. The larger the mass reduction rate, the better the biodegradability, and the mass reduction rate is preferably 50% or more, more preferably 65% or more, and even more preferably 80% or more. It is preferable that the mass reduction rate is as large as possible, but due to technical difficulties, the upper limit is, for example, 99%.
• esterase in the above enzymatic degradation test, it is preferable to use esterase, cutinase, or lipase, which are known as PET degrading enzymes.
• the cutinase is preferably Humicola insolens, Thermobifida cellulosityca, Thermobifida halotolerans, Thermobifida fusca, Thermobifida al. ba, Bacillus subtilis, Fusarium solanipisi, Sirococcus conigenus, Pseudomonas mendocina, Thielavia terrestris, or any functional variant thereof Microorganisms selected It is a cutinase produced by.
• Cutinases produced by Humicola insolens include, for example, the commercially available enzyme Novozym® 51032 or any functional variant thereof, and what is called A0A075B5G4 in Uniprot or any functional variant thereof. . Cutinases can also be obtained from metagenomic libraries, such as Sulaimanetal. , 2012, or esterases as described in EP3517608, or any functional variant thereof, including the degrading enzymes listed in WO2018/011284 or WO2018/011281. There may be.
• the lipase is preferably a lipase produced by Ideonella sakaiensis.
• an enzymatic degradation test was conducted using Novozym (registered trademark) 51032 manufactured by Strem Chemicals, which is a commercially available Humicola insolens-derived cutinase solution, and the It is preferable to determine the biodegradability of the resin by measuring the mass reduction rate of the resin. Details of the enzymatic degradation test (method for measuring biodegradability) using Novozym (registered trademark) 51032 will be described later.
• the mass reduction rate is preferably 50% or more, more preferably 65% or more, and 80%. It is more preferable that it is above. It is preferable that the mass reduction rate is as large as possible, but due to technical difficulties, the upper limit is, for example, 99%.
• a solution was prepared by dissolving 0.1 g of resin in 25 mL of a mixed solvent in which the mass ratio of phenol and tetrachloroethane was 60:40. Using an Ubbelohde viscometer whose temperature was adjusted to 30° C., the falling time of the solution and the mixed solvent was measured to determine the reduced viscosity.
• ⁇ Amount of foreign matter with a particle size of 0.3 to 0.5 ⁇ m> 3 mg of resin was dissolved in 20 mL of hexafluoro-2-propanol (HFIP) to prepare a hexafluoro-2-propanol solution having a resin concentration of 0.15 g/L.
• 2 mL of the above solution was discharged at a rate of 50 mL/min, and the number of particles with a particle size of 0.3 to 0.5 ⁇ m was measured using a Yamato Scientific particle counter "SLS-1200". The number of particles between 3 and 0.5 ⁇ m was calculated. The measurement and calculation were performed four times, the first calculation result was rejected, and the average value of the second to fourth calculation results was taken as the amount of foreign matter with a particle size of 0.3 to 0.5 ⁇ m.
• HFIP hexafluoro-2-propanol
• a solution was prepared by dissolving 2 g of resin in 18 g of a mixed solvent in which the mass ratio of phenol and tetrachloroethane was 60:40.
• the solution was placed in a glass cell with an optical path length of 10 mm, and measurement was performed using an ultraviolet-visible spectrophotometer (V-650 manufactured by JASCO Corporation) at a measurement wavelength of 350 to 800 nm to obtain a transmission spectrum. Thereafter, color analysis was performed in accordance with JIS Z8701-1999 using a data interval of 5 nm, a light source: D65, and a field of view of 2 deg, to calculate the b value of the solution.
• V-650 ultraviolet-visible spectrophotometer
• ⁇ Melting point> 5.0 mg of resin was added to an aluminum pan, the lid was pressed down and sealed, and measurement was performed using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science) under the following conditions. The temperature was raised from 20°C to 220°C at a rate of 20°C/min and held for 3 minutes to completely melt the sample. Next, it was cooled to -150°C at a rate of 50°C/min, held for 3 minutes, and then heated again to 220°C at a rate of 20°C/min. The melting point was calculated from the endothermic peak of the thermogram curve obtained when the temperature was raised for the second time.
• DSC7020 differential scanning calorimeter
• ⁇ Content of phosphorus atoms in resin The resin was subjected to wet decomposition with sulfuric acid, nitric acid, and perchloric acid, and then neutralized with aqueous ammonia. After adding ammonium molybdate and hydrazine sulfate to the prepared solution, the absorbance at a wavelength of 830 nm was measured using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1700). The phosphorus atom concentration in the resin was determined from a calibration curve prepared in advance.
• Example 1 Add 197.8 g of high-purity terephthalic acid, 173.8 g of adipic acid, and 385.8 g of 1,4-butanediol all at once to a 2L stainless steel autoclave equipped with a stirrer, and then add an aluminum-containing butanediol solution and a phosphorus-containing butanediol solution.
• the mixed solution obtained by mixing the solutions into one liquid was added, and the temperature was raised to 260° C. in a nitrogen atmosphere, and the reaction was continued until the mixture became transparent. After becoming transparent, the temperature was lowered to 250°C to obtain a polyester oligomer.
• the amount of copolyester resin produced can be calculated from the amounts of terephthalic acid, adipic acid, and 1,4-butanediol to be added, and in this example, 500 g of copolyester resin produced
• the above-mentioned liquid mixture is added so that aluminum atoms are 50 mass ppm and phosphorus atoms are 110 mass ppm. Thereafter, the system pressure was gradually reduced to 0.15 Pa over 1 hour, and a polycondensation reaction was carried out under these conditions to obtain a copolymerized polyester resin with a reduced viscosity of 0.91 dl/g and an acid value of 10 eq/ton. Ta.
• the copolyester resin contains 50 mass ppm of aluminum atoms and 88 mass ppm of phosphorus atoms, the b value of the copolyester resin solution is 2.2, and the amount of foreign matter with a particle size of 0.3 to 0.5 ⁇ m is 3000 pieces/mL, melting point was 126°C, and mass reduction rate was 89%.
• Examples 2 to 7, Comparative Examples 1 to 6) A copolymerized polyester resin was produced in the same manner as in Example 1, except that the aromatic dicarboxylic acid, aliphatic dicarboxylic acid, diol, and catalyst to be added were changed to the types and amounts listed in Table 1.
• Example 8 A copolymerized polyester resin was produced in the same manner as in Example 1, except that a polyester oligomer was obtained without adding the one-component mixed solution, and the one-component mixed solution was added to the obtained oligomer.
• Table 1 shows the physical properties of the copolyester resins obtained in Examples 1 to 8 and Comparative Examples 1 to 6.
• a catalyst is added before the esterification reaction
• a catalyst is added after an esterification reaction and before polycondensation
• aluminum atoms are Al
• phosphorus atoms are is written as P
• titanium atom is written as Ti.
• the b value of the copolyester resin pellets in Example 1 was 2.0, whereas isophthalic acid was used as the aromatic dicarboxylic acid.
• the b value of the copolymerized polyester resin pellets was 12.9.
• Comparative Example 1 which contained too little aliphatic dicarboxylic acid, had poor biodegradability. On the other hand, in Comparative Example 2, which contained too much aliphatic dicarboxylic acid, the melting point of the copolyester resin was low. In Comparative Examples 3 and 4 in which a titanium compound was used as a catalyst, the amount of foreign matter with a particle size of 0.3 to 0.5 ⁇ m was large, and the b value was large. In Comparative Example 5 in which isophthalic acid was used as the aromatic dicarboxylic acid, the resin had no melting point.

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• 2023
  • 2023-06-12 JP JP2023569746A patent/JPWO2023243609A1/ja active Pending
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