JP2011084737A - Manufacturing method for polyester resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently manufacturing a polyester resin having high flowability. <P>SOLUTION: In the method for manufacturing the polyester resin by performing an esterification reaction of a dicarboxylic acid component consisting of dicarboxylic acid and a diol component or a transesterification reaction of a dicarboxylic acid component consisting of an ester forming derivative thereof and a diol component, and a subsequent polycondensation reaction, 0.1-2.0 pts.wt. compound having three or more functional groups is added in the polyester manufacturing step to 100 pts.wt. formed polyester resin, and a titanium compound and/or a tin compound are used as a reaction catalyst of the esterification reaction or the transesterification reaction. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for efficiently producing a polyester resin having high fluidity.

  Polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) have excellent mechanical properties, heat resistance, moldability and recyclability, and have high mechanical strength and chemical resistance. It is widely used for molded products, films, fibers, and the like. Among them, PBT is widely used as a material for industrial molded products such as connectors, relays, and switches for automobiles and electrical / electronic devices.

  In general, the polyester resin used for such applications is produced by a direct polymerization method or a transesterification method. The direct polymerization method is a method in which an oligomer which is a polyester precursor is formed by a direct esterification reaction of a dicarboxylic acid and a diol, and then the oligomer is polycondensed under normal pressure or reduced pressure. In the transesterification method, an ester-forming derivative of a dicarboxylic acid and a diol are transesterified to form an oligomer which is a polyester precursor, and then the oligomer is polycondensed under normal pressure or reduced pressure. is there.

  However, in recent years, there has been an increasing demand for miniaturization and weight reduction of industrial molded products, and it is desired to improve the mechanical strength and at the same time improve the fluidity at the time of melting. It has been desired to produce a resin efficiently.

  Conventionally, an aromatic polyester resin having a melt tension of 0.8 to 5.0 g containing a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol has been proposed (see Patent Document 1). However, the polyester resin obtained by this proposal can only obtain a resin that has increased viscosity and has decreased fluidity.

  Further, an efficient method for producing an aliphatic polyester resin containing a trifunctional or higher functional monomer unit has been proposed (see Patent Document 2). However, in this proposal, although it can be produced somewhat efficiently, there is a problem that it still takes a long time to obtain a high molecular weight product, and an efficient production method with a shorter reaction time is required. It was.

  In addition, a production method by a direct polymerization method using poly (alkylene oxide) glycol as a copolymerization component for polybutylene terephthalate, which is an aromatic polyester, has been proposed (see Patent Document 3). It is described that a polyfunctional component may be used. However, in this proposal, there is no disclosure of a specific addition method and addition conditions for the ester-forming polyfunctional component, and in addition, no effect on the copolymerization of the ester-forming polyfunctional component is disclosed. .

JP 2001-200038 A (Claims, Examples) JP 2006-328374 A (Claims, Examples) JP-A-6-128364 (Claims and Examples)

  Therefore, an object of the present invention is to provide a method for efficiently producing a polyester resin having high fluidity by adding a compound having three or more functional groups in the course of producing the polyester resin.

  As a result of intensive studies to solve the above problems, the present invention has found a method for efficiently producing a polyester resin having high fluidity, and has reached the present invention.

  The process for producing the polyester resin of the present invention comprises a dicarboxylic acid component (A-2) comprising an esterification reaction of a dicarboxylic acid component (A-1) comprising a dicarboxylic acid and a diol component (B) or an ester-forming derivative of a dicarboxylic acid. In the method for producing a polyester resin by performing a transesterification reaction between the diol component (B) and the subsequent polycondensation reaction, a compound having three or more functional groups per 100 parts by weight of the produced polyester resin ( C) 0.1 to 2.0 parts by weight are added in the course of producing the polyester resin, and the titanium compound (D-1) and / or tin compound (D-2) is used as a reaction catalyst for the esterification reaction or transesterification reaction. ) Is used for producing a polyester resin.

  According to the preferable aspect of the manufacturing method of the polyester resin of this invention, the said dicarboxylic acid component (A-1) is an aromatic dicarboxylic acid which contains 50 mol% or more of terephthalic acids and has this as a main component, The diol component (B) is an aliphatic diol containing 50 mol% or more of 1,4-butanediol and containing this as a main component.

  According to the preferable aspect of the manufacturing method of the polyester resin of this invention, the said compound (C) which has a 3 or more functional group is a polyfunctional compound which has a 3 or more functional group, Comprising: At least one of the terminal structures having a group is represented by the following formula (1)

(In the formula, R represents a hydrocarbon group having 1 to 15 carbon atoms, and n represents an integer of 1 to 10 and represents a repeating unit.).

  According to a preferred embodiment of the method for producing a polyester resin of the present invention, the esterification reaction or transesterification reaction is performed under a reduced pressure of 13.3 to 79.9 kPa, the diol component (B), The molar ratio ((B) / (A-1) or (B) / (A-2)) of the dicarboxylic acid component (A-1) or the dicarboxylic acid component (A-2) is 1.1 to 2.0. It is to be performed within the range.

  According to a preferred embodiment of the method for producing a polyester resin of the present invention, in the esterification reaction or transesterification reaction, the diol component (B) is added after the start of the esterification reaction or transesterification reaction, It is to add additionally at the stage until the start of the polycondensation reaction.

  According to the preferable aspect of the manufacturing method of the polyester resin of this invention, the said dicarboxylic acid component (C) which has the said 3 or more functional group at the start of the said esterification reaction or transesterification reaction ( A-1) or a dicarboxylic acid component (A-2) and the diol component (B) are mixed and added.

  According to the present invention, a polyester resin having a high molecular weight can be efficiently produced in a polycondensation reaction time shorter than that of the prior art, and moreover than a polyester resin having an equivalent weight average molecular weight obtained by the prior art. A polyester resin having a low melt viscosity at a temperature of 250 ° C. and high fluidity can be produced efficiently.

  Next, the form for implementing this invention is demonstrated in detail.

  The polyester resin targeted by the present invention includes an esterification reaction or transesterification reaction between a dicarboxylic acid component (A-2) comprising a dicarboxylic acid (A-1) or an ester-forming derivative thereof and a diol component (B), and In the method for producing a polyester resin by performing a subsequent polycondensation reaction, 0.1 to 2.0 parts by weight of the compound (C) having three or more functional groups is added to 100 parts by weight of the produced polyester resin. An ester in the main chain, which is produced by using a titanium compound (D-1) and / or a tin compound (D-2) as a reaction catalyst for the esterification reaction or transesterification reaction, which is added during the resin production process It is a polyester resin having a bond.

  The dicarboxylic acid component constituting the dicarboxylic acid unit used in the present invention includes a dicarboxylic acid component (A-1) comprising an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and a mixture thereof, and an ester-forming derivative of the dicarboxylic acid. The dicarboxylic acid component (A-2) which becomes.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4 Examples include '-diphenyl ether dicarboxylic acid and 5-sodium sulfoisophthalic acid. Examples of the ester-forming derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters.

  Examples of the aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and other aliphatic dicarboxylic acids, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexane. And alicyclic dicarboxylic acids such as dicarboxylic acids. Examples of the ester-forming derivatives of aliphatic dicarboxylic acids include lower alkyl esters of aliphatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters.

  Among these, it is preferable to use an aromatic dicarboxylic acid in terms of efficiently producing a polyester resin having high fluidity and excellent heat resistance and chemical resistance. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is particularly preferably used.

  In the present invention, when the dicarboxylic acid component is terephthalic acid, a polyester resin having excellent heat resistance, mechanical properties and chemical resistance can be produced. It is preferably at least mol%, more preferably at least 70 mol%, further preferably at least 90 mol%, particularly preferably at least 95 mol%, and most preferably at 100 mol%. is there. As an aromatic dicarboxylic acid component other than terephthalic acid, it is also a preferred embodiment to use one or more of isophthalic acid and 2,6-naphthalenedicarboxylic acid in combination.

  Examples of the diol component (B) used in the present invention include aromatic diols, aliphatic diols, and mixtures thereof.

  Examples of the aromatic diol include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.3) -2,2-bis (4-hydroxy Phenyl) propane, polyoxyethylene- (2.8) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (3.0) -2,2-bis (4-hydroxyphenyl) propane and the like Bisphenol A derivatives with addition of ethylene oxide and polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.3) -2,2-bis (4 -Hydroxyphenyl) propane, polyoxypropylene- (2.8) -2,2-bis (4-hydroxyphenyl) propane and poly Carboxymethyl propylene - (3.0) -2,2-bis (4-hydroxyphenyl) bisphenol A derivative obtained by adding propylene oxide such as propane.

  Examples of the aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,2-cyclohexanediol, 1, Examples include 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, isosorbide, isomannide, and isoidet.

  These diols may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic diol because a polyester resin having high fluidity and excellent heat resistance can be efficiently produced. As the aliphatic diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable, and particularly polyester having excellent crystallization characteristics, moldability, heat resistance, and chemical resistance. 1,4-butanediol is preferably used in that the resin can be efficiently produced.

  In the present invention, when the diol component (B) is 1,4-butanediol, a polyester resin having excellent crystallization characteristics, moldability, heat resistance and mechanical properties can be produced. On the other hand, it is preferable that 1,4-butanediol is 50 mol% or more as a main component, more preferably 70 mol% or more, still more preferably 90 mol% or more, and most preferably 100 mol%. It is an aspect. It is also a preferred embodiment that ethylene glycol, 1,3-propanediol and 1,4-cyclohexanedimethanol are used in combination of one or more as diol components other than 1,4-butanediol.

  The compound (C) having three or more functional groups used in the present invention is a component necessary for efficiently producing a polyester resin having high fluidity. The compound (C) having three or more functional groups has three or more functional groups in the molecule, and may be a low molecular compound or a polymer. In addition, examples of the compound (C) having three or more functional groups include compounds having three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound. A trifunctional compound or a tetrafunctional compound is preferable in that a polyester resin having excellent mechanical properties can be produced, and a trifunctional compound is particularly preferably used.

  Examples of the functional group in the compound (C) having three or more functional groups used in the present invention include a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, and an oxazoline. And at least one functional group selected from functional groups such as a group, an oxazine group, an ester group, an amide group, a silanol group, and a silyl ether group.

  These functional groups are preferably selected from the group consisting of hydroxyl group, carboxylic acid group, amino group, glycidyl group, isocyanate group, carbodiimide group, ester group, amide group and silanol group from the viewpoint of reactivity. In view of ease of control of polymerization, the group is particularly preferably selected from the group consisting of a hydroxyl group and a carboxylic acid group, and the hydroxyl group is most preferred as the functional group in the compound (C) having three or more functional groups.

  The functional group in the compound (C) having three or more functional groups used in the present invention may have three or more different functional groups. As the functional group in the compound (C) having the above functional group, it is preferable that two or more functional groups are the same functional group, and that three or more functional groups are the same functional group. It is particularly preferable that all functional groups are the same functional group in that a polyester resin having excellent mechanical properties, durability, and heat resistance can be produced.

  As a preferred example of the compound (C) having three or more functional groups, when the functional group is a hydroxyl group, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-to Xanthriol, 1,2,3,6-hexanetetrol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, triethanolamine, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tritrimethylol Propane, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, methyl glucoside, sorbitol, mannitol, sucrose, 1,3,5-trihydroxybenzene Oh Beauty 1,2,4 polymers such as polyhydric alcohol or a polyvinyl alcohol having a carbon number of 3 to 24, such as a trihydroxy benzene. Among them, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol having a branched structure are preferably used from the viewpoint that a polyester resin excellent in fluidity and mechanical properties can be efficiently produced.

  As a preferable example of the compound (C) having three or more functional groups, when the functional group is a carboxylic acid group, propane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3-tris Carboxylic acid, butane-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, cyclohexane 1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, naphthalene-2,5 , 7-tricarboxylic acid, pyridine-2,4,6-tricarboxylic acid, naphthalene-1,2,7,8-tetracarboxylic acid and naphthalene-1,4 , 8-tetracarboxylic polycarboxylic acids or polymers such as acrylic acid and methacrylic acid, such as acid and the like can also be used acid anhydrides thereof. Of these, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid and acid anhydrides having a branched structure are preferably used because a polyester resin excellent in fluidity can be efficiently produced.

  When the functional group of the compound (C) having three or more functional groups is an amino group, at least one of the three or more substituents is preferably a primary or secondary amine, both of which are primary Or it is more preferable that it is a secondary amine, and it is an especially preferable aspect that all are primary amines. As a preferred example of the compound (C) having three or more functional groups, when the functional group is an amino group, 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, , 2,4-triaminobutane, 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetramino Benzene, 1,2,4-triaminonaphthalene, 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene and 1,4,5,8 Tetra amino naphthalene. Among them, from the viewpoint that a polyester resin having excellent fluidity can be efficiently produced, 1,2,3-triaminopropane having a branched structure, 1,3,5-triaminocyclohexane and 1,3,5-trimethyl are preferred. Aminobenzene is preferably used.

  As a preferred example of the compound (C) having three or more functional groups, when the functional group is a glycidyl group, a monomer such as triglycidyl triazolidine-3,5-dione or triglycidyl isocyanurate, Examples include (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate, glycidyl group-containing acrylic polymer, and glycidyl group-containing acrylic / styrene polymer.

  As a preferable example of the compound (C) having three or more functional groups, when the functional group is an isocyanate group, nonane triisocyanate (for example, 4-isocyanatomethyl-1,8-octane diisocyanate (TIN)), decantrie Examples thereof include isocyanate, undecane triisocyanate, and dodecane triisocyanate.

  As a preferred example of the compound (C) having three or more functional groups, in the case of an oxycarboxylic acid having three or more functional groups, malic acid, hydroxyglutaric acid, hydroxymethylglutaric acid, tartaric acid, citric acid, hydroxyisophthalic acid and Examples thereof include hydroxyterephthalic acid, and these can be used alone or as a mixture of two or more. In particular, malic acid, tartaric acid and citric acid and mixtures thereof are preferably used because of their availability.

  As a preferable example of the compound (C) having three or more functional groups, when the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of the compound having three or more hydroxyl groups, And ester derivatives of compounds having a carboxylic acid group.

  As a preferable example of the compound (C) having three or more functional groups, when the functional group is an amide group, an amide derivative of the compound having three or more carboxylic acid groups may be mentioned.

  In addition, the compound (C) having three or more functional groups used in the present invention contains one or more alkylene oxide units from the viewpoint that a polyester resin excellent in fluidity and mechanical properties can be efficiently produced. Is preferred. In the present invention, the compound (C) having three or more functional groups is a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having a functional group is represented by the following formula (2).

(In the formula, R represents a hydrocarbon group having 1 to 15 carbon atoms, n represents an integer of 1 to 10 and represents a repeating unit, and X represents a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, or an amino group. And a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group, and a silyl ether group. Yes, when R in the formula (2) is an alkylene group, the structure represented by the formula (2) represents a structure containing an alkylene oxide unit.

  In particular, the compound (C) having three or more functional groups is a polyfunctional compound having three or more functional groups, and is an alkylene in that a polyester resin excellent in fluidity can be efficiently produced. The most preferred embodiment is a polyfunctional compound containing an oxide unit.

  In the present invention, preferred examples of the alkylene oxide unit include aliphatic alkylene oxide units having 1 to 4 carbon atoms. Specific examples include a methylene oxide unit, an ethylene oxide unit, a trimethylene oxide unit, a propylene oxide unit, and a tetramethylene. Examples thereof include an oxide unit, 1,2-butylene oxide unit, 2,3-butylene oxide unit, and isobutylene oxide unit. In the present invention, a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit is particularly preferable in that a polyester resin excellent in fluidity, recyclability, durability, heat resistance and mechanical properties can be efficiently produced. It is preferable to use a compound containing a propylene oxide unit from the viewpoint that a polyester resin excellent in hydrolysis resistance and toughness (tensile elongation at break) can be efficiently produced.

  In the compound (C) having three or more functional groups used in the present invention, the number of alkylene oxide units contained in the compound (C) having three or more functional groups is excellent in fluidity and mechanical properties. Is preferably 0 to 20, more preferably 0.5 to 10, still more preferably 1 to 5, and more preferably 1 to 5. Mole ratio ((B) / (A-1)) of diol component (B) and dicarboxylic acid component (A-1) mainly composed of 4-butanediol, or ester of diol component (B) and dicarboxylic acid When the molar ratio ((B) / (A-2)) of the dicarboxylic acid component (A-2) comprising the forming derivative is 1.5 or more, 1,4- during the esterification reaction or transesterification reaction From the viewpoint of reducing by-product tetrahydrofuran (THF) generation amount by cyclization of butanediol, and particularly preferably 1-3.

  As a preferable example of the compound (C) having three or more functional groups containing one or more alkylene oxide units, when the functional group is a hydroxyl group, (poly) oxymethylene glycerol, (poly) oxyethylene glycerol, (poly) Oxytrimethylene glycerol, (poly) oxypropylene glycerol, (poly) oxyethylene- (poly) oxypropylene glycerol, (poly) oxytetramethylene glycerol, (poly) oxymethylene diglycerol, (poly) oxyethylene diglycerol, ( Poly) oxytrimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylenetrimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, (poly) oxyp Pyrenetrimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethyleneditrimethylolpropane, (poly ) Oxytrimethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (Poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol, (poly) io Simethylenedipentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxytrimethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol, (poly) oxymethylene glucose, (poly) oxyethylene glucose, (poly ) Oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose and (poly) oxytetramethylene glucose.

  Further, as a preferred example of the compound (C) having three or more functional groups containing one or more alkylene oxide units, when the functional group is a carboxylic acid, propane-1, 2, 2 containing a (poly) methylene oxide unit 3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) trimethylene oxide units, (poly) propylene oxide units Propane-1,2,3-tricarboxylic acid containing, propane-1,2,3-tricarboxylic acid containing (poly) tetramethylene oxide units, 2-methylpropane-1,2,3 containing (poly) methylene oxide units -Triscarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) ethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing poly) trimethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) propylene oxide units, (poly) tetra 2-methylpropane-1,2,3-triscarboxylic acid containing methylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) methylene oxide units, butane-1 containing (poly) ethylene oxide units, 2,4-tricarboxylic acid, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, (poly) tetra Butane-1,2,4-tricarboxylic acid containing methylene oxide units, butane containing (poly) methylene oxide units 1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) ethylene oxide units, butane-1,2,3 containing (poly) trimethylene oxide units 4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly) tetramethylene oxide units , Trimellitic acid containing (poly) methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) trimethylene oxide units, trimellitic acid containing (poly) propylene oxide units, ( Trimellitic acid containing poly) tetramethylene oxide units, trimesic acid containing (poly) methylene oxide units, (poly Trimesic acid containing ethylene oxide units, trimesic acid containing (poly) trimethylene oxide units, trimesic acid containing (poly) propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, (poly) methylene oxide units Hemimellitic acid containing, hemimellitic acid containing (poly) ethylene oxide units, hemimellitic acid containing (poly) trimethylene oxide units, hemimellitic acid containing (poly) propylene oxide units, (poly) tetramethylene oxide units included Hemellitic acid, pyromellitic acid containing (poly) methylene oxide units, pyromellitic acid containing (poly) ethylene oxide units, pyromellitic acid containing (poly) trimethylene oxide units, pyromellitic acid containing (poly) propylene oxide units acid, Pyromellitic acid containing poly) tetramethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) methylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) ethylene oxide units, Cyclohexane-1,3,5-tricarboxylic acid containing poly) trimethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide units and cyclohexane-1 containing (poly) tetramethylene oxide units , 3,5-tricarboxylic acid and the like.

  Further, as a preferred example of the compound (C) having three or more functional groups containing one or more alkylene oxide units, when the functional group is an amino group, 1,2,3-containing a (poly) methylene oxide unit Triaminopropane, 1,2,3-triaminopropane containing (poly) ethylene oxide units, 1,2,3-triaminopropane containing (poly) trimethylene oxide units, 1,1 containing (poly) propylene oxide units 2,3-triaminopropane, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) methylene oxide units, (poly ) 1,2,3-triamino-2-methylpropane containing ethylene oxide units, 1,2 containing (poly) trimethylene oxide units 3-triamino-2-methylpropane, 1,2,3-triamino-2-methylpropane containing (poly) propylene oxide units, 1,2,3-triamino-2-methyl containing (poly) tetramethylene oxide units Propane, 1,2,4-triaminobutane containing (poly) methylene oxide units, 1,2,4-triaminobutane containing (poly) ethylene oxide units, 1,2,4 containing (poly) trimethylene oxide units 4-triaminobutane, 1,2,4-triaminobutane containing (poly) propylene oxide units, 1,2,4-triaminobutane containing (poly) tetramethylene oxide units, (poly) methylene oxide units 1,2,3,4-tetraminobutane containing, 1,2,3,4-tetraminobutane containing (poly) ethylene oxide units 1,2,3,4-tetraminobutane containing (poly) trimethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) propylene oxide units, 1 containing (poly) tetramethylene oxide units , 2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane containing (poly) methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, (poly) trimethylene 1,3,5-triaminocyclohexane containing oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triaminocyclohexane containing (poly) tetramethylene oxide units 1,2,4-triaminocyclohexane containing (poly) methylene oxide units, I) 1,2,4-triaminocyclohexane containing ethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) trimethylene oxide units, 1,2,4-trimethyl containing (poly) propylene oxide units Aminocyclohexane, 1,2,4-triaminocyclohexane containing a (poly) tetramethylene oxide unit, 1,2,4,5-tetraminocyclohexane containing a (poly) methylene oxide unit, 1,1 containing a (poly) ethylene oxide unit 2,4,5-tetraminocyclohexane, 1,2,4,5-tetraminocyclohexane containing (poly) trimethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) propylene oxide units, (poly ) 1,2,4,5-teto containing tetramethylene oxide units Minocyclohexane, 1,3,5-triaminobenzene containing (poly) methylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, 1,3 containing (poly) trimethylene oxide units , 5-triaminobenzene, 1,3,5-triaminobenzene containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, (poly) methylene oxide units 1,2,4-triaminobenzene containing 1,2,4-triaminobenzene containing (poly) ethylene oxide units, 1,2,4-triaminobenzene containing (poly) trimethylene oxide units, (poly ) 1,2,4-triaminobenzene and (poly) tetramethyleneoxy containing propylene oxide units Comprising units 1,2,4-triamino benzene and the like.

  In addition, as a preferable example of the compound (C) having three or more functional groups including one or more alkylene oxide units, when the functional group is an ester group, the compound having three or more hydroxyl groups including the alkylene oxide unit is used. Examples thereof include aliphatic acid esters or aromatic acid esters, and ester derivatives of compounds having three or more carboxylic acid groups containing the alkylene oxide unit.

  Further, as a preferred example of the compound (C) having three or more functional groups containing one or more alkylene oxide units, when the functional group is an amide group, it has three or more carboxylic acid groups containing the alkylene oxide units. Examples include amide derivatives of compounds.

  As a particularly preferred example of the compound (C) having three or more functional groups containing one or more alkylene oxide units from the viewpoint that a polyester resin excellent in fluidity can be produced efficiently, (Poly) oxyethylene glycerol, (poly) oxypropylene glycerol, (poly) oxyethylene diglycerol, (poly) oxypropylene diglycerol, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane, (poly ) Oxyethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol and (poly It includes oxypropylene dipentaerythritol.

  When the functional group is a carboxylic acid, propane-1,2,3-tricarboxylic acid containing a (poly) ethylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly) propylene oxide unit, (poly ) Trimellitic acid containing ethylene oxide units, trimellitic acid containing (poly) propylene oxide units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, cyclohexane containing (poly) ethylene oxide units -1,3,5-tricarboxylic acid and cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide units.

  When the functional group is an amino group, 1,2,3-triaminopropane containing a (poly) ethylene oxide unit, 1,2,3-triaminopropane containing a (poly) propylene oxide unit, (poly) ethylene oxide 1,3,5-triaminocyclohexane containing units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units and (poly ) 1,3,5-triaminobenzene containing propylene oxide units.

  As the compound (C) having three or more functional groups used in the present invention, the most preferable compound is a polyfunctional compound having three or more functional groups and having at least one hydroxyl group, At least one of the terminal structures having a hydroxyl group is represented by the following formula (1) in that a polyester having excellent properties and mechanical properties can be efficiently produced.

(In the formula, R represents a hydrocarbon group having 1 to 15 carbon atoms, and n is an integer of 1 to 10 and represents a repeating unit.).

  When the compound (C) having three or more functional groups is a polyfunctional compound having two or more hydroxyl groups, two terminal structures having a hydroxyl group in the compound (C) having three or more functional groups The above is more preferably a compound having a structure represented by the above formula (1), and when it is a polyfunctional compound having three or more hydroxyl groups, the compound (C) having three or more functional groups More preferably, three or more of the terminal structures having a hydroxyl group are compounds having the structure represented by the above formula (1), and the terminal structure having a hydroxyl group in the compound (C) having three or more functional groups is preferred. It is the most preferred embodiment that all are compounds having a structure represented by the above formula (1).

  In the present invention, R in the above formula (1) represents an alkylene group, and n is 1 to 1 in that a polyester resin excellent in fluidity, recyclability, durability, and mechanical properties can be efficiently produced. 7 is preferably a functional group representing an integer of 7, R represents an alkylene group, n is more preferably a functional group representing an integer of 1 to 5, R represents an alkylene group, and n is , A functional group representing an integer of 1 to 4 is more preferred, R represents an alkylene group, and n is a functional group representing an integer of 1 to 3 is particularly preferred.

  In the present invention, when R is an alkylene group, the structure represented by the above formula (1) represents a structure containing an alkylene oxide unit. As compounds having such a structure, Polyst R3611 manufactured by Perstorp, Polyol 3380 manufactured by Perstorp, PolyRR3530 manufactured by Perstorp, Polyol 3165 manufactured by Perstorp, Poly4290 manufactured by Perstorp, PNT-60U manufactured by Nihon Emulsifier Co., Ltd., TMP- manufactured by Nihon Emulsifier Co., Ltd. F32, Adeka T-400, etc. are mentioned.

  The viscosity of the compound (C) having three or more functional groups used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and can efficiently produce a polyester resin having excellent fluidity and mechanical properties. From the point, it is more preferably 5000 m · Pa or less, and still more preferably 2000 m · Pa or less. The lower limit of the viscosity is preferably 100 m · Pa or more from the viewpoint of bleeding property during molding. When the viscosity at 25 ° C. of the compound (C) having three or more functional groups is larger than 15000 m · Pa, it tends to be a polyester resin having an insufficient fluidity improving effect.

  The weight average molecular weight: Mw of the compound (C) having three or more functional groups used in the present invention is preferably in the range of 50 to 10,000 in that a polyester resin having excellent fluidity can be efficiently produced. More preferably, it is the range of 150-8000, More preferably, it is the range of 200-3000. In the present invention, Mw of the compound (C) having three or more functional groups is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent. .

  In the present invention, it is essential that the amount of the compound (C) having three or more functional groups to be added is in the range of 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the produced polyester resin. A polyester resin having excellent fluidity and mechanical properties can be efficiently produced, and the amount added is preferably in the range of 0.5 to 2 parts by weight, more preferably from the viewpoint of easy reaction control. Is in the range of 0.5 to 1.5 parts by weight, more preferably in the range of 0.5 to 1.0 parts by weight. When the addition amount is less than the range of 0.1 to 2.0 parts by weight, a polyester resin excellent in fluidity cannot be efficiently produced. When the addition amount is more than this range, the polyester excellent in fluidity Resin cannot be manufactured, and depending on the case, it becomes difficult to control reaction by gelation, and a polyester resin cannot be obtained.

  In the present invention, the dicarboxylic acid component (A-1) is mainly composed of terephthalic acid because it can efficiently produce a polyester resin having high fluidity and excellent crystallization properties, moldability, heat resistance and mechanical properties. A dicarboxylic acid as a component, a diol component (B) is a diol mainly composed of 1,4-butanediol, and a compound (C) having three or more functional groups has three or more hydroxyl groups It is a functional compound and is preferably a polyfunctional compound containing an alkylene oxide unit.

  In the present invention, a titanium compound (D-1) and / or a tin compound (D-2) is used as a reaction catalyst during an esterification reaction or a transesterification reaction. By using the reaction catalyst, the esterification reaction or the transesterification reaction can proceed more effectively. In the present invention, it is preferable to use a mixed catalyst of a titanium compound (D-1) and a tin compound (D-2) from the viewpoint of improving reactivity.

In the present invention, the titanium compound (D-1) used as a reaction catalyst during the esterification reaction or the transesterification reaction has the formula (R ₁ O) _n Ti (OR ₂ ) _4-n (wherein R ₁ and R ₂ represent an aliphatic, alicyclic or aromatic hydrocarbon group having ₁ to 10 carbon atoms, and n represents a number of 0 to 4 (including a decimal number). A condensate is preferred.

  Specific examples of the titanium compound (D-1) used in the present invention include methyl ester of titanic acid, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert- Examples thereof include butyl ester, cyclohexyl ester, phenyl ester, benzyl ester and tolyl ester, and mixed esters thereof. Among these, tetra-n-propyl titanate is preferred because polyester resin can be produced efficiently. Esters, tetra-n-butyl esters and tetraisopropyl esters are preferred, and tetra-n-butyl esters of titanic acid are particularly preferred.

  These titanium compounds (D-1) may be used alone or in combination of two or more.

  The added amount of these titanium compounds (D-1) is preferably in the range of 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the produced polyester resin from the viewpoint that the polyester resin can be efficiently produced. More preferably, it is the range of 0.02-0.2 weight part.

  In the present invention, the tin compound (D-2) used as a reaction catalyst during the esterification reaction or transesterification reaction is represented by the following formula (3):

(In the formula, R represents an alkyl group or aryl group having 1 to 15 carbon atoms, X _{1 to} X ₄ represent an alkyl group having 1 to 15 carbon atoms, an aryl group, an allyloxy group, a cyclohexyl group, a hydroxy group, a halogen, or the like. A monovalent group, which may be the same or different, and X ₅ represents a sulfur or oxygen atom) and a condensate thereof.

  Specific examples of the tin compound (D-2) include dibutyltin oxide, methylphenyltin oxide, tetraethyltin oxide, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, triethyl tin oxide, Examples thereof include phenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide. Among these, a monoalkyl tin compound is particularly preferably used because a polyester resin can be efficiently produced.

  Further, as the other tin compound (D-2), stannic acid can also be used. In this case, alkylstannic acid such as methylstannic acid, ethylstannic acid and butylstannic acid is preferably used. Is done.

  These tin compounds (D-2) may use only 1 type and can also use 2 or more types together.

  The addition amount of these tin compounds (D-2) is preferably in the range of 0.02 to 0.3 parts by weight with respect to 100 parts by weight of the produced polyester resin from the viewpoint that the polyester resin can be produced efficiently. More preferably, it is the range of 0.03-0.2 weight part.

  In the present invention, when a direct polymerization method is used in producing a polyester resin, a polyester resin is produced by performing a direct esterification reaction of a dicarboxylic acid and a diol to form an oligomer and then performing a polycondensation reaction. When the transesterification method is used, a polyester resin is produced by performing an ester exchange reaction between an ester-forming derivative of a dicarboxylic acid and a diol to obtain an oligomer, and then performing a polycondensation reaction.

  In the present invention, the pressure in the esterification reaction or transesterification reaction is usually 101 kPa or less, and the pressure is preferably in the range of 13.3 to 79.9 kPa from the viewpoint that the polyester resin can be efficiently produced. Preferably, it is performed under reduced pressure in the range of 13.3 to 53.3 kPa.

  The reaction temperature of the esterification reaction or transesterification reaction is preferably in the range of 140 to 290 ° C, more preferably in the range of 180 to 280 ° C. In addition, the reaction rate of the oligomer after the esterification reaction or the transesterification reaction is preferably 97% or more.

  In the present invention, the molar ratio of the diol component (B) to the dicarboxylic acid component (A-1) ((B) / (A-1)), or the dicarboxylic acid comprising the diol component (B) and an ester-forming derivative of the dicarboxylic acid. The molar ratio ((B) / (A-2)) of the acid component (A-2) is preferably in the range of 1.1 to 6.0, and a polyester resin having high fluidity is efficiently produced. More preferably, it is in the range of 1.1 to 3.0, more preferably in the range of 1.1 to 2.0. From the viewpoint of the effect of shortening the polycondensation reaction time, In particular, it is preferably within the range of 1.1 to 1.5.

  In the present invention, it is included as a preferred embodiment that the diol component (B) is additionally added in the esterification reaction or transesterification reaction.

  In the esterification reaction or transesterification reaction in the present invention, it is preferable to add the diol component (B) from the viewpoint of efficiently proceeding the reaction. After completion of the esterification reaction or transesterification reaction, polycondensation is performed. Although it may be carried out before the start of the reaction, it is a more preferred embodiment that it is additionally added at any stage from the start of the esterification reaction or transesterification reaction to the start of the polycondensation reaction from the viewpoint of shortening the polymerization time. is there. The additional addition of the diol component (B) may be performed at any one or a plurality of locations from the start of the esterification reaction or transesterification reaction to the start of the polycondensation reaction. From the viewpoint of operability, the diol component ( The additional addition of B) is preferably carried out at any one position from the start of the esterification reaction or transesterification reaction to the start of the polycondensation reaction.

  In the present invention, when additional addition of the diol component (B) is performed, from the diol component (B) at the start of the esterification reaction or transesterification reaction, and the dicarboxylic acid component (A-1) or the ester-forming derivative of the dicarboxylic acid. The dicarboxylic acid component (A-2) has a molar ratio ((B) / (A-1) or (B) / (A-2)) of preferably 0.7 to 1.1, more preferably It is in the range of 0.9 to 1.0.

  In the present invention, when the additional addition of the diol component (B) is performed in the esterification reaction stage or the transesterification reaction stage, the time from the additional addition of the diol component (B) to the start of the polycondensation reaction is the reaction time. In terms of efficient progress, it is preferably 30 to 150 minutes, more preferably 60 to 150 minutes, still more preferably 60 to 120 minutes, and particularly preferably 60 to 90 minutes. is there.

  The addition time of the compound (C) having three or more functional groups in the present invention is a polyester resin production process. The specific addition time in the polyester resin production process may be added at any stage from the start of the esterification reaction or transesterification reaction to just before the end of the polycondensation reaction, but has high fluidity. In terms of obtaining a polyester resin, the addition time is preferably added at any stage from the esterification reaction or before the ester exchange reaction to the start of the polycondensation reaction. At the start of the esterification reaction or transesterification reaction, the dicarboxylic acid component (A-1) or dicarboxylic acid component (A-2) composed of an ester-forming derivative of dicarboxylic acid and the diol component (B) are added to the mixture. Is the most preferred embodiment.

  Thus, in the present invention, the start of the esterification reaction or the start of the transesterification reaction is a stage where a reaction component such as a dicarboxylic acid component or a diol component is mixed to prepare the reaction, that is, before the esterification reaction or the ester It is used in the meaning including the start of the reaction before the exchange reaction. Further, the addition of the compound (C) having three or more functional groups may be performed once or a plurality of times. From the viewpoint that a polyester resin having high fluidity is obtained, the start of the esterification reaction or The addition is preferably performed once from the start of the transesterification reaction to just before the end of the polycondensation reaction.

  The oligomer obtained from the esterification reaction or transesterification reaction is then subjected to a polycondensation reaction, in which the polycondensation conditions used for the production of a normal polyester resin in a batch process or a continuous process are applied as they are. be able to. For example, it is a preferable embodiment to carry out the reaction under the reduced pressure of 230 to 260 ° C., preferably 240 to 255 ° C. and the pressure of 667 Pa or less, preferably 133 Pa or less.

  In the polycondensation reaction after the esterification reaction or the transesterification reaction in the present invention, a necessary catalyst can be separately added and used to effectively advance the polycondensation reaction. For example, a polyester resin that produces an antimony compound such as antimony trioxide or antimony acetate, a zirconia compound such as zirconium tetra-n-butoxide, the titanium compound (D-1), the tin compound (D-2), or the like. It is preferable to add in the range of 0.01 to 0.15 parts by weight with respect to 100 parts by weight, and it is particularly preferable to use a titanium compound.

  In the production of the polyester resin by the method of the present invention, the usual additives such as an ultraviolet absorber, a heat stabilizer, a lubricant, a release agent, a colorant containing a dye and a pigment, etc. are used within the range not impairing the object of the present invention. 1 type or 2 types or more can be added at the time of esterification reaction, transesterification reaction, or at the time of polycondensation reaction, and a polyester resin can be manufactured.

  In the present invention, particularly during the polycondensation reaction, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, phosphoric acid triamide, monoammonium phosphate, trimethyl phosphate, dimethyl phosphate, diphenyl phosphate, phosphoric acid When a phosphorus compound selected from triphenyl, diphenyl phosphite, triphenyl phosphite, dimethylphenyl phosphonate and the like is added, a preferable effect is obtained that the color tone of the polyester resin to be formed is remarkably improved.

  The polyester resin obtained by the production method of the present invention is a polyester resin having high fluidity, and can be widely used for molding materials such as electric parts and automobile parts, as well as for films, fibers and blow bottles. .

  Next, the production method of the polyester resin of the present invention will be specifically described with reference to examples. The measurement method and determination method used in the present invention are as follows.

(1) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) is a value of the weight average molecular weight in terms of standard polymethyl methacrylate measured by gel permeation chromatography (GPC). GPC measurement is performed using a WATERS differential refractometer WATERS410 as a detector, a MODEL510 high-performance liquid chromatography as a pump, and a column with Shodex GPC HFIP-806M and Shodex GPC HFIP-LG connected in series. It was. The measurement conditions were a flow rate of 1.0 mL / min, hexafluoroisopropanol was used as a solvent, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected. It shows that it has the outstanding mechanical strength, so that the value of this weight average molecular weight is large.

(2) Melt viscosity The melt viscosity was measured under the conditions of a temperature of 250 ° C, a shear rate of 100 (/ sec) to 3700 (/ sec), and an orifice diameter of 1 mm using a Toyo Seiki Capillograph Model 1C. It shows that it has high fluidity, so that the value of this melt viscosity is small.

[Example 1]
The molar ratio ((B) / (A-1)) of the diol component (B) to the dicarboxylic acid component (A-1) in the esterification reaction is 1.2, and terephthalic acid: 780 g as the dicarboxylic acid component (A), 1,4-butanediol as diol component (B): 390 g, polyoxypropylene trimethylolpropane having three hydroxyl groups as compound (C) having three or more functional groups (molecular weight 310, alkylene per functional group) Number of oxide units: 1, Perstorp PolyR3530: 10.6 g, titanium compound (D-1) (tetra-n-butyl titanate): 0.47 g as an esterification reaction catalyst, and tin compound as an esterification reaction catalyst ( D-2) (Monobutylhydroxytin oxide): 0.45 g was charged into a reactor equipped with a rectifying column. After starting the esterification reaction under a reduced pressure of 190 ° C. and a pressure of 60 kPa, the temperature was gradually raised and reduced, and finally the esterification reaction was carried out for 245 minutes at a temperature of 230 ° C. and a pressure of 30 kPa. The additional amount of 1,4-butanediol was 120 g, and the esterification reaction was completed 90 minutes after the addition was completed. Phosphoric acid: 0.18 g was added to the obtained reaction product, and then titanium compound (D-1) (tetra-n-butyl titanate): 5.2 g as a polycondensation reaction catalyst was added, and the temperature was 250 ° C. A polycondensation reaction was performed for 80 minutes under the condition of a pressure of 100 Pa to obtain a polyester resin.

[Example 2]
A polyester resin was obtained in the same manner as in Example 1 except that the polycondensation reaction time in Example 1 was changed to 100 minutes.

[Example 3]
A polyester resin is obtained in the same manner as in Example 2 except that the amount of the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 2 is changed to 5.2 g. It was.

[Example 4]
A polyester resin was obtained in the same manner as in Example 3 except that the polycondensation reaction time in Example 3 was changed to 140 minutes.
[Example 5]
Except that the molar ratio ((B) / (A-1)) of the diol component (B) to the dicarboxylic acid component (A) in Example 1 was changed to 1.5, and the polycondensation reaction time was changed to 115 minutes. Was carried out in the same manner as in Example 1 to obtain a polyester resin.

[Example 6]
The same procedure as in Example 5 was carried out except that the pressure reduction conditions in the esterification reaction in Example 5 were changed to normal pressure, the esterification reaction time was changed to 270 minutes, and the polycondensation reaction time was changed to 150 minutes. A resin was obtained.

[Example 7]
The timing of adding the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 1 was changed before the polycondensation reaction (after the esterification reaction), and the polycondensation reaction time was 140. A polyester resin was obtained in the same manner as in Example 1 except that the time was changed to minutes.

[Example 8]
Except that the compound (C) having three or more functional groups in Example 1 was changed to trimethylolpropane manufactured by Sigma-Aldrich having three hydroxyl groups, and the polycondensation reaction time was changed to 140 minutes. In the same manner as in Example 1, a polyester resin was obtained.

[Example 9]
As in Example 6, except that only the titanium compound (D-1) was added as the esterification reaction catalyst in Example 6, the esterification reaction time was 270 minutes, and the polycondensation reaction time was changed to 160 minutes. And a polyester resin was obtained.

[Example 10]
The compound (C) having three or more functional groups, the molar ratio ((B) / (A-1)) of the diol component (B) and the dicarboxylic acid component (A) in Example 9 being changed to 2.0 A polyester resin was obtained in the same manner as in Example 9 except that the amount of (polyoxypropylene trimethylolpropane) added was changed to 2.1 g and the polycondensation reaction time was changed to 175 minutes.

[Example 11]
Except that the addition amount of compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 10 was changed to 5.2 g and the polycondensation reaction time was changed to 165 minutes. In the same manner as in Example 10, a polyester resin was obtained.

[Example 12]
A polyester resin was obtained in the same manner as in Example 11 except that the polycondensation reaction time in Example 11 was changed to 220 minutes.

[Example 13]
Except that the addition amount of the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 10 was changed to 10.5 g and the polycondensation reaction time was changed to 200 minutes. In the same manner as in Example 10, a polyester resin was obtained.

[Example 14]
Except that the addition amount of the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 10 was changed to 15.8 g and the polycondensation reaction time was changed to 190 minutes. In the same manner as in Example 10, a polyester resin was obtained.

[Example 15]
Except that the addition amount of the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 10 was changed to 21.0 g and the polycondensation reaction time was changed to 180 minutes. In the same manner as in Example 10, a polyester resin was obtained.

[Example 16]
The compound (C) having three or more functional groups in Example 15 was converted into a polyoxypropylene pentaerythrole having four hydroxyl groups (molecular weight 600, number of alkylene oxide units per functional group of about 2, Poly 4360 manufactured by Perstorp). The polyester resin was obtained in the same manner as in Example 15 except that the polycondensation reaction time was changed to 130 minutes.

[Example 17]
The compound (C) having three or more functional groups in Example 13 was changed to trimethylolpropane, and the polycondensation reaction time was changed to 225 minutes. Obtained.

[Example 18]
The compound (C) having three or more functional groups in Example 13 was converted to polyoxypropylene glycerin having three hydroxyl groups (molecular weight 770, about 4 alkylene oxide units per functional group, G-700 manufactured by ADEKA). The polyester resin was obtained in the same manner as in Example 13 except that the polycondensation reaction time was changed to 225 minutes.

[Example 19]
Except that the compound (C) having three or more functional groups in Example 13 was changed to trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd. having three carboxylic acid groups, and the polycondensation reaction time was changed to 220 minutes. Was carried out in the same manner as in Example 13 to obtain a polyester resin.

[Example 20]
The compound (C) having three or more functional groups in Example 13 was converted to trimethylolpropane poly (oxypropylene) triamine having three amino groups (molecular weight 470, number of alkylene oxide units 2 per functional group, Mitsui Chemicals). A polyester resin was obtained in the same manner as in Example 13 except that the polycondensation reaction time was changed to 250 minutes.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 1 was not added and the polycondensation reaction time was changed to 150 minutes. A polyester resin was obtained.

[Comparative Example 2]
Except that the addition amount of the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 1 was changed to 0.5 g and the polycondensation reaction time was changed to 150 minutes. In the same manner as in Example 1, a polyester resin was obtained.

[Comparative Example 3]
Although it carried out similarly to Example 1 except having changed the addition amount of the compound (C) (polyoxypropylene trimethylol propane) which has a 3 or more functional group in Example 1 into 53 g, gelatinization generate | occur | produced. The polyester resin could not be obtained.

[Comparative Example 4]
The compound (C) having three or more functional groups in Example 1 was changed to trimethylolpropane, the addition amount of the compound (C) having three or more functional groups was changed to 0.5 g, and a polycondensation reaction A polyester resin was obtained in the same manner as in Example 1 except that the time was changed to 150 minutes.

[Comparative Example 5]
Except for changing the compound (C) having three or more functional groups in Example 1 to polyethylene glycol 200 manufactured by Tokyo Chemical Industry Co., Ltd. having two hydroxyl groups, and changing the polycondensation reaction time to 150 minutes, In the same manner as in Example 1, a polyester resin was obtained.

[Comparative Example 6]
The polyester resin obtained in Comparative Example 1 was subjected to solid phase polymerization. The conditions of the solid phase polymerization were a temperature of 200 ° C., a time of 1440 minutes (24 hours), and a nitrogen stream.

[Comparative Example 7]
Except that the addition amount of the compound (C) (polyoxypropylene trimethylolpropane) having three or more functional groups in Example 9 was changed to 0.5 g and the polycondensation reaction time was changed to 230 minutes. In the same manner as in Example 9, a polyester resin was obtained.
[Comparative Example 8]
A polyester resin was obtained in the same manner as in Comparative Example 7, except that the compound (C) having three or more functional groups in Comparative Example 7 was changed to trimethylolpropane and the polycondensation reaction time was changed to 250 minutes. It was.

[Comparative Example 9]
The same procedure as in Example 10 was carried out except that the compound (C) having three or more functional groups (polyoxypropylene trimethylolpropane) in Example 10 was not added and the polycondensation reaction time was changed to 190 minutes. A polyester resin was obtained.

[Comparative Example 10]
Except that the addition amount of the compound (C) (polyoxypropylene pentaerythrole) having three or more functional groups in Example 16 was changed to 23.3 g and the polycondensation reaction time was changed to 130 minutes. In the same manner as in Example 16, a polyester resin was obtained.

  About the obtained polyester resin, esterification reaction time, polycondensation reaction time, solid phase polymerization time, molecular weight characteristics and melt viscosity characteristics of the polyester resin are summarized in Tables 1 and 2 (Examples 1 to 8 and Comparative Examples 1 to 3). 6) and Tables 3 and 4 (Examples 9 to 20 and Comparative Examples 7 to 10).

  From the results of the above Examples and Comparative Examples, it can be seen that a polyester resin having high fluidity can be efficiently produced in the present invention. That is, a polyester resin 100 produced when a polyester resin is produced by performing an esterification reaction or transesterification reaction between a dicarboxylic acid component comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol component, and a subsequent polycondensation reaction. 0.1 to 2 parts by weight of a compound having three or more functional groups are added in the polyester resin production process with respect to parts by weight, and the titanium compound and / or tin compound is used as a reaction catalyst for the esterification reaction or transesterification reaction. By adopting a polyester resin production method that uses a polycondensation, the polycondensation reaction time is shortened and can be produced efficiently, and the resulting polyester resin has the same molecular weight, although it has the same molecular weight. Which has a low fluidity and has a high fluidity. A reester resin could be obtained.

  Furthermore, the following can be seen as preferred embodiments of the present invention.

  From the results of Example 1 to Example 4, Comparative Example 1 to Comparative Example 3, Example 10 to Example 16, Comparative Example 9 and Comparative Example 10, the amount of the compound having three or more functional groups was melted. It is preferable to blend in the range of 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the produced polyester resin, in that a polyester resin having low viscosity and excellent fluidity can be obtained. It can be seen that it is more preferable to add in the range of 1.0 part by weight.

  From the results of Example 2 and Example 7, as the addition time of the compound having three or more functional groups, at the start of the esterification reaction or transesterification reaction, the dicarboxylic acid component and It can be seen that it is most preferable to add the diol component to the mixture.

  From the results of Example 6 and Example 9, it is understood that it is preferable to use a mixed catalyst of a titanium compound and a tin compound as a reaction catalyst in the esterification reaction or the transesterification reaction in that the polymerization time is shortened. .

  From the results of Example 5 and Example 6, it can be seen that the esterification reaction or transesterification reaction is preferably performed under a reduced pressure of normal pressure or less in that the polymerization time is shortened.

  From the results of Example 2, Example 5, Example 9 and Example 13, the molar ratio of the diol component to the dicarboxylic acid component is particularly in the range of 1.1 to 1.5 in that the polymerization time is shortened. It can be seen that it is preferable to be within the range.

  From the results of Example 15 and Example 16, it can be seen that the number of functional groups is particularly preferably 3 in that a polyester resin having excellent fluidity can be obtained as a compound having three or more functional groups.

  From the results of Example 13 and Examples 18 to 20, as a compound having three or more functional groups, the polymerization time is shortened and a polyester resin having excellent fluidity is obtained. It can be seen that a hydroxyl group is particularly preferred.

  From the results of Example 13, Example 17 and Example 18, generation of tetrahydrofuran (THF) by cyclization of 1,4 butanediol, which is a side reaction at the time of esterification, as a compound having three or more functional groups It can be seen that the number of alkylene oxide units per functional group is particularly preferably in the range of 1 to 3 in that the amount can be reduced.

  In addition, from the results of Example 1, Comparative Example 1, Example 2 and Comparative Example 6, the compound having three or more functional groups used in the present invention is a polyester resin having high fluidity in a short reaction time. It turns out that it is a component required in order to manufacture efficiently.

Claims (8)

  Esterification reaction of dicarboxylic acid component (A-1) composed of dicarboxylic acid and diol component (B) or transesterification of dicarboxylic acid component (A-2) composed of ester-forming derivative of dicarboxylic acid and diol component (B) In the method for producing a polyester resin by performing the reaction and the subsequent polycondensation reaction, 0.1 to 2.0 weights of the compound (C) having three or more functional groups with respect to 100 weight parts of the produced polyester resin A polyester compound, wherein a titanium compound (D-1) and / or a tin compound (D-2) is used as a reaction catalyst for the esterification reaction or transesterification reaction. Production method of resin.   The method for producing a polyester resin according to claim 1, wherein the dicarboxylic acid component (A-1) is an aromatic dicarboxylic acid mainly composed of terephthalic acid.   The method for producing a polyester resin according to claim 1 or 2, wherein the diol component (B) is an aliphatic diol mainly composed of 1,4-butanediol. The compound (C) having three or more functional groups is a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having the functional group is represented by the following formula (1)

4. In the formula, R represents a hydrocarbon group having 1 to 15 carbon atoms, and n is an integer of 1 to 10 and represents a repeating unit. Of manufacturing polyester resin.   The method for producing a polyester resin according to any one of claims 1 to 4, wherein the esterification reaction or the transesterification reaction is carried out under a reduced pressure of 13.3 to 79.9 kPa.   The esterification reaction or transesterification reaction is carried out by subjecting the diol component (B) to the dicarboxylic acid component (A-1) or dicarboxylic acid component (A-2) molar ratio ((B) / (A-1) or (B). / (A-2)) is performed in the range of 1.1-2.0, The manufacturing method of the polyester resin in any one of Claims 1-5 characterized by the above-mentioned.   In the esterification reaction or transesterification reaction, the diol component (B) is additionally added in a stage from the start of the esterification reaction or transesterification reaction to the start of the polycondensation reaction. The manufacturing method of the polyester resin in any one.   Compound (C) having three or more functional groups is mixed with dicarboxylic acid component (A-1) or dicarboxylic acid component (A-2) and diol component (B) at the start of esterification reaction or transesterification reaction. The method for producing a polyester resin according to claim 1, wherein the polyester resin is added to the place.