JP6036004B2 - Polyester resin - Google Patents

Description

  The present invention relates to an isosorbide copolymer polyester resin having excellent heat resistance.

In recent years, research and development of polyester resins using renewable raw materials derived from plant resources has been actively conducted for the purpose of considering limited petroleum resources and reducing environmental impact. Among these, polyesters obtained from isosorbide obtained by reducing glucose produced by hydrolysis of starch and intramolecular dehydration cyclization and dicarboxylic acid derivatives are known.
Further, isosorbide has attracted attention as a glycol component that enhances the heat resistance of the copolyester resin. Patent Documents 1 and 2 disclose crystalline resins obtained by copolymerizing isosorbide. However, there is little isosorbide copolymerization and heat resistance is insufficient. Patent Document 3 discloses an amorphous resin using diphenyl oxalate as an acid component. Although the heat resistance of this resin is superior to those of Patent Documents 1 and 2, since a deleterious phenol is by-produced during the reaction, there is a risk of adverse effects on the environment.

  Since isosorbide is a secondary alcohol, it has low reactivity. In particular, the greater the content of isosorbide in the glycol component, the greater the effect. Further, in the melt polymerization, when the content of isosorbide is increased, the melt viscosity increases as the reaction proceeds, and it becomes difficult to obtain a polyester resin having a high molecular weight and a high glass transition temperature. On the other hand, an isosorbide-containing polyester resin can be produced by solution polymerization or interfacial polymerization that is not easily affected by melt viscosity, but it is necessary to use an acid chloride compound as the dicarboxylic acid component, and an organic solvent that dissolves the resulting polyester resin. A solvent is required. Although it is possible to obtain an isosorbide-containing polyester resin having a high molecular weight and a high glass transition temperature by solution polymerization or interfacial polymerization, increasing the isosorbide content decreases the solubility in organic solvents. The polyester resin tends to precipitate inside. Furthermore, there are fears that chlorine and organic solvents derived from acid chloride remain in the polyester resin, and the use of a large amount of organic solvents may adversely affect the environment, which is not suitable for industrial production. In melt polymerization, solution polymerization, and interfacial polymerization for producing a general-purpose polyester such as polyethylene terephthalate, when the content of isosorbide is large, it is difficult to obtain a polyester resin having a high molecular weight and a high glass transition temperature. When trying to obtain a polyester having a high molecular weight and a high glass transition temperature by reducing the content of isosorbide, the glycol component must contain a compound that lowers the mobility of the molecular chain instead of isosorbide. . When the mobility of the molecular chain is high, it is difficult to achieve a high glass transition temperature even if high molecular weight is easy.

Japanese Patent No. 3399465 Japanese Patent No. 3413640 Japanese Patent No. 469057

  An object of the present invention is to provide an isosorbide-containing polyester resin that can be industrially produced and has improved heat resistance, which has been insufficient in the prior art.

  In order to solve this problem, the present inventors copolymerized a monomer having a polar group that imparts cohesive force to an isosorbide-containing polyester resin in melt polymerization, thereby obtaining an isosorbide-containing polyester resin having a high glass transition temperature. It was found that it was obtained.

The present invention has the following configuration.
[1] A polyester resin comprising a dicarboxylic acid component and a glycol component, wherein the dicarboxylic acid component contains 10 to 40 mol% of an aromatic dicarboxylic acid having a sulfonate group represented by the following formula (1), terephthalic acid , 90-60 mol% of one or more selected from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and alicyclic dicarboxylic acid, A polyester resin comprising 50 to 100 mol% of isosorbide.

[In the formula (1), Ar is a trivalent aromatic group having 6 to 12 carbon atoms, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms. Represents a group, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ]

[2] The polyester resin according to [1], which has a glass transition temperature of 190 ° C. or higher.
[3] The polyester resin according to [1] or [2], wherein the polyester resin contains a terminal blocking agent.
[4] The polyester resin according to [3], wherein the terminal blocking agent is an aromatic monocarboxylic acid having a sulfonate group represented by the following formula (2).

Wherein (2), Ar represents a divalent aromatic group, ^{R 3} represents a hydrogen atom, an alkyl group or an aryl group having 6 to 12 carbon atoms having 1 to 6 carbon atoms of 6 to 12 carbon atoms, ^{M +} Represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ]

[5] The polyester resin as described in [3] or [4], wherein the terminal blocking agent is contained in an amount of 1 to 25 mol% with respect to 100 mol% of the dicarboxylic acid component.
[6] A molded article using the polyester resin according to any one of [1] to [5].

  The polyester resin of the present invention is a polymer excellent in heat resistance because of its high glass transition temperature. By blending the polymer with another polymer to which heat resistance is to be imparted, it can be provided for molded articles, fibers, paints, coating agents and the like.

  The polyester resin in the present invention is mainly composed of a dicarboxylic acid component and a glycol component.

  The polyester resin of this invention needs to copolymerize the aromatic dicarboxylic acid which has a sulfonate group of Formula (1).

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ¹ and R ² are preferably alkyl groups having 1 to 3 carbon atoms such as a hydrogen atom, a methyl group, and an ethyl group.

In the above formula (1), M ⁺ represents an ion selected from metal ions, tetraalkylphosphonium ions, and tetraalkylammonium ions. M ⁺ includes alkali metal ions such as sodium ion, potassium ion and lithium ion, alkaline earth metal ions such as calcium ion and magnesium ion, zinc ion, tetrabutylphosphonium ion, tetramethylphosphonium ion, tetrabutylammonium ion, tetra Such as methylammonium ion. Of these ions, alkali metal ions and tetrabutylammonium ions are more preferred. However, in the case of a divalent metal ion, 1 mol of metal ion corresponds to 2 mol of sulfonic acid group.

  Ar in the above formula (1) is a trivalent aromatic group having 6 to 12 carbon atoms such as a benzene ring and a naphthalene ring, and these are also substituents such as an alkyl group, a phenyl group, a halogen, and an alkoxy group. You may have.

  As the aromatic dicarboxylic acid of the formula (1), 4-sodium sulfo-isophthalic acid, 5-sodium sulfo-isophthalic acid, 4-potassium sulfo-isophthalic acid, 5-potassium sulfo-isophthalic acid, 2-sodium sulfo-terephthalic acid Acid, 2-potassium sulfo-terephthalic acid, 4-sulfo-isophthalic acid zinc, 5-sulfo-isophthalic acid zinc, 2-sulfo-terephthalic acid zinc, 4-sulfo-isophthalic acid tetraalkylphosphonium salt, 5-sulfo-isophthalic acid Acid tetraalkylphosphonium salt, 4-sulfo-isophthalic acid tetraalkylammonium salt, 5-sulfo-isophthalic acid tetraalkylammonium salt, 2-sulfo-terephthalic acid tetraalkylphosphonium salt, 2-sulfo-terephthalic acid tetraalkylammonium salt, 4- Thorium sulfo-2, 6-naphthalenedicarboxylic acid, 4-sodium sulfo-2, 7-naphthalenedicarboxylic acid, 4-potassium sulfo-2, 6-naphthalenedicarboxylic acid, 4-sulfo-2, 6-naphthalenedicarboxylic acid zinc salt 4-sulfo-2,6-naphthalenedicarboxylic acid tetraalkylphosphonium salt, 4-sulfo-2,7-naphthalenedicarboxylic acid tetraalkylphosphonium salt, and the like. Examples of these ester-forming derivatives include dimethyl esters and diethyl esters of aromatic dicarboxylic acids specifically listed above.

Among these, R ¹ and R ² are both a hydrogen atom, a methyl group or an ethyl group, Ar is a benzene ring, and M ⁺ is an alkali metal ion such as sodium or potassium. More preferable in terms of mechanical properties, color tone, and the like.

  Specifically, for example, 4-sodium sulfo-isophthalate dimethyl, 5-sodium sulfo-isophthalate dimethyl, 4-potassium sulfo-isophthalate dimethyl, 5-potassium sulfo-isophthalate dimethyl, 2-sodium sulfo-terephthalic acid More preferred are dimethyl, 2-potassium sulfo-dimethyl terephthalate and the like.

  It is important that the aromatic dicarboxylic acid of the formula (1) is copolymerized in an amount of 10 to 40 mol% with respect to the total dicarboxylic acid component. 15-35 mol% is preferable and, as for the aromatic dicarboxylic acid of Formula (1), 20-30 mol% is more preferable. When the aromatic dicarboxylic acid of the formula (1) is less than 10 mol%, the effect of increasing the glass transition temperature is small, and the improvement in heat resistance is small. When the aromatic dicarboxylic acid of the formula (1) exceeds 40 mol%, the ion aggregation effect derived from the sulfonate group is large, for example, the melt viscosity at the time of melt polymerization becomes high and the condensation reaction or extrusion becomes difficult.

The polyester resin of the present invention is one or two selected from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and alicyclic dicarboxylic acid with respect to all dicarboxylic acid components. 90-60 mol% of seeds or more are contained. These derivatives (for example, dimethyl terephthalate) may be used. These may be anhydrides.
These are preferably copolymerized in an amount of 85 to 65 mol%, more preferably 80 to 70 mol%, based on the total dicarboxylic acid component. If the dicarboxylic acid content is less than 60 mol%, the resulting polyester resin has low heat resistance, which is not preferable. The total dicarboxylic acid component refers to the aromatic dicarboxylic acid of formula (1), terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and alicyclic dicarboxylic acid. The sum total of an aliphatic dicarboxylic acid component, a hydroxycarboxylic acid component, a monocarboxylic acid component other than the formula (2) described below, and a trivalent or higher carboxylic acid component is shown. However, when an aliphatic dicarboxylic acid having 4 or less carbon atoms (for example, oxalic acid, malonic acid, etc.) is used, the molecular chain of the polyester resin exhibits rigidity, so terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid One or two or more selected from acid, 4,4′-diphenyldicarboxylic acid, and alicyclic dicarboxylic acid may be less than 60 mol% based on the total dicarboxylic acid component.

  Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, and tetrahydrophthalic acid. Furthermore, these derivatives (for example, dimethyl 1,4-cyclohexanedicarboxylate) may be used. These may be anhydrides. As the alicyclic dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid is preferable.

  As another dicarboxylic acid component, an aliphatic dicarboxylic acid can be copolymerized as long as the heat resistance of the polyester resin is not impaired. Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, adipic acid, mazeleic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, octadecanoic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid An acid etc. are mentioned. Furthermore, these derivatives (for example, dimethyl oxalate) may be used. These may be anhydrides.

  The polyester resin of the present invention comprises, for all dicarboxylic acid components, an aromatic dicarboxylic acid of the formula (1), terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, And a total of one or more selected from alicyclic dicarboxylic acids, preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. .

  As the glycol component, it is necessary to use 1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”, which shows the chemical formula below). Isosorbide can be easily obtained from renewable resources such as sugars and starch. For example, isosorbide can be obtained by hydrogenating D-glucose and subjecting it to a dehydration reaction. Isosorbide can be obtained from Rocket Corporation.

Isosorbide must be copolymerized in an amount of 50 to 100 mol% with respect to the total glycol component. If it is less than 50 mol%, the effect of increasing the glass transition temperature is small, such being undesirable. In order to raise the heat resistance of a polyester resin, it is preferable to set it as 70 mol%-100 mol%, and 80 mol%-100 mol% are more preferable.
The “total glycol component” means the sum of a diol component, a hydroxycarboxylic acid component, a monoalcohol component, a trihydric or higher alcohol component, and the like that can be used as a constituent component of the polyester resin according to the present invention.

Other glycol components include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1 , 3-propanediol, 2,2-diethyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2 -Ethyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decandioe Aliphatic compounds such as 3 (4), 8 (9) -bis (hydroxymethyl) -tricyclo (5.2.1.1.2.6) decane, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol Aromatic glycols such as glycol, bisphenol A, bisphenol S, bisphenol C, bisphenol Z, bisphenol AP, ethylene oxide adduct or propylene oxide adduct of 4,4′-biphenol, 1,2-cyclohexanedimethanol, 1, Alicyclic glycols such as 3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol and the like, and 9,9-bis [4- (2-hydroxyethoxy) -phenyl] fluorene, 9 Bis [4- (3-hydroxypropoxy) - phenyl] fluorene such as 9,9-bis _{(4-hydroxy-C 2-4} alkoxy - phenyl) fluorene; 9,9-bis [3- (2-hydroxyethoxy) - 9,9-bis (3-hydroxyC _2-4 alkoxy-phenyl) fluorene such as phenyl] fluorene; 9,9-bis (9,9-bis [2- (2-hydroxyethoxy) -phenyl] fluorene, etc. _{2-hydroxy-C 2-4} alkoxy - phenyl) fluorene; 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) - 3-ethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-propylphenyl] fluorene, 9,9-bi 9,9-bis (4) such as s [4- (2-hydroxyethoxy) -3-n-butylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] fluorene - hydroxy _{C 2-4} alkoxy _{-C 1-4} alkylphenyl) fluorene; 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- ( 9,9-bis (4-hydroxy) such as 2-hydroxyethoxy) -3,5-diethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] fluorene C _2-4 alkoxy - di _{C 1-4} alkylphenyl) fluorene; 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene 9,9-bis [4- (2-hydroxyethoxy) -3-arylphenyl] fluorene; and 9,9-bis [4- (2-hydroxyethoxy) -3-benzylphenyl] fluorene -Bis [4- (2-hydroxyethoxy) -3-aralkylphenyl] fluorene and the like can be exemplified.
Among these, ethylene glycol, 1,4-cyclohexanedimethanol, and 9,9-bis [4- (2-hydroxyethoxy) -phenyl] fluorene are preferable.

  The glass transition temperature of the polyester resin according to the present invention is preferably 190 ° C. or higher. When the glass transition temperature is 190 ° C. or higher, it is possible to develop into a molded product that requires high heat resistance. In order to set the glass transition temperature to 190 ° C. or higher, for example, the aromatic dicarboxylic acid of the formula (1) is copolymerized in an amount of 10 to 40 mol% based on the total dicarboxylic acid component, and terephthalic acid, isophthalic acid, 2, 6 -One or two kinds selected from naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and alicyclic dicarboxylic acid are copolymerized in an amount of 60 to 90 mol% with respect to all dicarboxylic acid components, and isosorbide is all glycol components On the other hand, it can be obtained by copolymerization of 50 to 100 mol%. Moreover, when isosorbide is 50-70 mol% with respect to all the glycol components, isosorbide, 1,4-cyclohexanedimethanol, 9,9-bis [4- (2-hydroxyethoxy) with respect to all the glycol components. The total of glycols such as -phenyl] fluorene may be 90 mol% or more.

  In the polyester resin according to the present invention, a hydroxycarboxylic acid can be used depending on the purpose such as adjustment of the glass transition temperature.

  Examples of the hydroxycarboxylic acid component include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, lactic acid, oxirane, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε- Caprolactone, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxy Examples include valeric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, and 10-hydroxystearic acid.

If the amount is small, a tri- or higher functional carboxylic acid component or an alcohol component may be added as a copolymerization component.
Examples of the tri- or higher functional carboxylic acid component include aromatics such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, trimesic acid, and the like. Examples thereof include carboxylic acids and aliphatic carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid.
Examples of the tri- or higher functional alcohol component include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, α-methylglucose, mannitol, and sorbitol.

  These do not necessarily need to be used alone, and can be used in combination of two or more according to the properties desired to be imparted to the resin. At this time, the proportion of the tri- or higher functional monomer is suitably about 0.2 to 5 mol% with respect to the total carboxylic acid component or the total alcohol component. If the amount added is less than 0.2 mol%, the added effect is not manifested, and if the amount exceeds 5 mol%, the gelation may exceed the gel point during polymerization.

  The polyester resin according to the present invention can improve heat resistance by containing a terminal blocking agent. By blocking the end, thermal decomposition and hydrolysis derived from the end can be reduced. As the terminal blocking agent, general monocarboxylic acids and monoalcohols can be used.

  The polyester resin according to the present invention can be further improved in heat resistance by using the aromatic monocarboxylic acid of the formula (2) as a terminal blocking agent.

In the above formula (2), R ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, preferably 1 to 1 carbon atoms such as a hydrogen atom, a methyl group, or an ethyl group. 3 alkyl groups.

In the above formula (2), M ⁺ represents an ion selected from metal ions, tetraalkylphosphonium ions, and tetraalkylammonium ions. M ⁺ includes alkali metal ions such as sodium ion, potassium ion and lithium ion, alkaline earth metal ions such as calcium ion and magnesium ion, zinc ion, tetrabutylphosphonium ion, tetramethylphosphonium ion, tetrabutylammonium ion, tetra Such as methylammonium ion. Of these ions, alkali metal ions and tetrabutylammonium ions are more preferred. However, in the case of a divalent metal ion, 1 mol of metal ion corresponds to 2 mol of sulfonic acid group.

  Ar in the above formula (2) is a divalent aromatic group having 6 to 12 carbon atoms such as a benzene ring or a naphthalene ring, and these are also substituents such as an alkyl group, a phenyl group, a halogen, and an alkoxy group. You may have.

  Examples of the aromatic dicarboxylic acid represented by the formula (2) include sodium 2-sulfobenzoate, sodium 3-sulfobenzoate, sodium 4-sulfobenzoate, potassium 2-sulfobenzoate, potassium 3-sulfobenzoate, 4- Potassium sulfobenzoate, zinc 2-sulfobenzoate, zinc 3-sulfobenzoate, zinc 4-sulfobenzoate, 2-sulfobenzoic acid tetraalkylammonium salt, 3-sulfobenzoic acid tetraalkylammonium salt, 4-sulfobenzoic acid Acid tetraalkylammonium salt, 2-sulfobenzoic acid tetraalkylphosphonium salt, 3-sulfobenzoic acid tetraalkylphosphonium salt, 4-sulfobenzoic acid tetraalkylphosphonium salt, sodium sulfo-naphthalene monocarboxylic acid, potassium sulfo-naphthalene monocarboxylic acid Acid, sul - naphthalene dicarboxylic acid zinc salt, sulfo - naphthalene monocarboxylic acid tetraalkyl phosphonium salt, sulfo - can be exemplified naphthalene monocarboxylic acid tetraalkylphosphonium salts. Examples of these ester-forming derivatives include methyl esters and ethyl esters of aromatic dicarboxylic acids of the formula (2) specifically listed above.

Among these, R ³ is a hydrogen atom, a methyl group or an ethyl group, Ar is a benzene ring, and M ⁺ is an alkali metal ion such as sodium or potassium. Is more preferable.

  Specifically, for example, sodium 2-sulfobenzoate, sodium 3-sulfobenzoate, sodium 4-sulfobenzoate, potassium 2-sulfobenzoate, potassium 3-sulfobenzoate, potassium 4-sulfobenzoate, 2 -Zinc sulfobenzoate, zinc 3-sulfobenzoate, zinc 4-sulfobenzoate, 2-sulfobenzoic acid tetraalkylammonium salt, 3-sulfobenzoic acid tetraalkylammonium salt, 4-sulfobenzoic acid tetraalkylammonium salt, 2-sulfobenzoic acid tetraalkylphosphonium salt, 3-sulfobenzoic acid tetraalkylphosphonium salt, 4-sulfobenzoic acid tetraalkylphosphonium salt and the like are more preferable.

The aromatic monocarboxylic acid of the above formula (2) is preferably copolymerized in an amount of 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more with respect to 100 mol% of the dicarboxylic acid component. When the aromatic dicarboxylic acid of the formula (2) is less than 1 mol%, the decrease in the amount of hydroxyl groups in the polyester resin is small, and the improvement in hydrolysis resistance is also small. The aromatic dicarboxylic acid of the formula (2) with respect to the total dicarboxylic acid component is preferably 15 mol% or less, more preferably 10 mol% or less. When the aromatic monocarboxylic acid of the formula (2) is larger than 25 mol%, the ion aggregation effect derived from the sulfonate group is large, for example, the melt viscosity at the time of melt polymerization becomes high and the condensation reaction or extrusion becomes difficult.
The polyester resin according to the present invention contains a terminal blocking agent, but when the terminal blocking agent is excessive with respect to the terminal group of the polyester resin, the terminal blocking agent may be present in the polyester resin in an unreacted state. . In this case, although it is correct to call it a composition, in the present invention, for convenience, it is called a polyester resin.

  Moreover, monocarboxylic acid and monoalcohol other than Formula (2) may be copolymerized in the polyester resin according to the present invention. Monocarboxylic acids other than formula (2) include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxy acid. Examples of monoalcohols such as phenyl stearic acid include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-phenoxyethanol and the like.

The polyester resin according to the present invention can be produced in a known polymerization kettle by combining the above monomers. It can be produced by either a production method by direct esterification reaction and polycondensation reaction, or a production method by transesterification reaction and polycondensation reaction. The reaction may be carried out in a batch reactor or a continuous reactor.
In a continuous reaction apparatus (continuous polycondensation method), the esterification reaction, the transesterification reaction and the melt polycondensation reaction may each be performed in one stage, but are preferably performed in a plurality of stages. When the esterification reaction or transesterification reaction is performed in a plurality of stages, the number of reaction cans is preferably 2 to 3 cans. Further, when the melt polycondensation is performed in a plurality of stages, the number of reaction cans is preferably 3 to 7 cans.

  When produced by the continuous polycondensation method, it contains 1.02 to 3.5 mol, preferably 1.05 to 3.0 mol of all glycols per mol of all dicarboxylic acids or ester derivatives thereof. A slurry is prepared and continuously fed to the esterification reaction step containing the oligomer. Since isosorbide is a secondary alcohol, it is less reactive than a primary alcohol. Therefore, esterification reaction temperature is 180-270 degreeC, Preferably it is 200-265 degreeC. Further, the pressure in the reaction vessel is usually 0.4 MPaG, preferably 0.01 to 0.35 MPaG. The temperature of the polycondensation reaction is usually 255 to 320 ° C, preferably 260 to 300 ° C, and the pressure in the reaction vessel is usually 1.5 hPa abs. Hereinafter, preferably 0.5 hPa abs. It is as follows. The reaction time of the esterification reaction is preferably 5 hours or less, particularly preferably 2 to 4 hours. The reaction time for the polycondensation reaction is preferably 5 hours or less, particularly preferably 1 to 3 hours. The reaction time is the time from the desired reaction temperature to the subsequent polycondensation reaction.

  When manufacturing by a batch type polycondensation method, esterification reaction temperature is 180-170 degreeC, Preferably it is 200-265 degreeC. Moreover, the pressure in the reaction vessel is usually 0.2 to 0.4 MPaG, preferably 0.25 to 0.35 MPaG. Further, the polycondensation reaction may be performed in one stage or may be performed in a plurality of stages. When it is carried out in one stage, the pressure is gradually reduced and the temperature is raised, the final temperature is in the range of 255 to 320 ° C., preferably 260 to 300 ° C., and the final pressure is usually 3 hPa abs. Hereinafter, preferably 0.5 hPaabs. The following. The reaction time of the esterification reaction is preferably 4 hours or less, particularly preferably 2 to 3 hours. The reaction time for the polycondensation reaction is preferably 5 hours or less, particularly preferably 1 to 3 hours.

  In the case of producing a low polycondensate by continuous transesterification, 1.1 to 3.5 mol, preferably 1.2 to 3.0 mol, per 1 mol of a dicarboxylic acid derivative (for example, dimethyl terephthalate). A solution containing glycol is prepared and continuously fed to the transesterification step. The transesterification reaction temperature is usually 180 to 270 ° C, preferably 200 to 265 ° C. In the case of the transesterification method, it is necessary to use a transesterification catalyst in addition to the polycondensation catalyst. The obtained low polycondensate is reacted in the same manner as the above-mentioned continuous polycondensation.

  When a low polycondensate is produced by a batch transesterification reaction, 1.5 to 3.5 mol, preferably 2. 0 to 3.0 moles of glycol and a dicarboxylic acid derivative are added to carry out the reaction in the presence of a transesterification catalyst. The resulting low polycondensate is polycondensed in the same manner as in the above esterification reaction.

  Depending on the composition, isosorbide may be distilled off together with the glycol component, and isosorbide may be precipitated from the distillate. In that case, the distillation line is heated to 40 to 80 ° C. The precipitated isosorbide can be dissolved and discharged from the distillation line, which is preferable.

  In general, when a desired carboxyl group or hydroxyl group is imparted to a polyester resin, a polybasic acid component or a polyvalent glycol component is further added following the polycondensation reaction, and the mixture is dissolved in an inert atmosphere. Polymerization can be performed.

  As a catalyst for the esterification reaction or transesterification reaction and polycondensation reaction, at least one of an antimony compound, a germanium compound, a titanium compound, and an aluminum compound can be used. Examples of the antimony compound include antimony trioxide, antimony pentoxide, antimony acetate, and antimony glycoloxide. Among these, antimony trioxide, antimony acetate, and antimony glycoloxide are preferable, and antimony trioxide is particularly preferable. These antimony compounds are preferably contained in an amount of 50 to 400 ppm, more preferably 100 to 350 ppm, and particularly preferably 150 to 300 ppm with respect to the produced polyester. When the antimony compound is less than 50 ppm, the esterification reaction or transesterification reaction and the polycondensation reaction rate are slow, and the productivity is deteriorated. Moreover, each reaction time becomes long and quality deterioration, such as a color tone, arises. When the amount of the antimony compound is more than 400 ppm, an increase in foreign matters and a polyester decomposition reaction are promoted, resulting in deterioration of quality such as color tone.

  Examples of the germanium compound include crystalline germanium dioxide, amorphous germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, and phosphorous acid. Examples include compounds such as germanium. Among these, crystalline germanium dioxide and amorphous germanium dioxide are more preferable, and amorphous germanium dioxide is particularly preferable. These germanium compounds are preferably contained in an amount of 10 to 1000 ppm, more preferably 30 to 800 ppm, and particularly preferably 50 to 500 ppm with respect to the copolymerized polyester to be produced. If the germanium compound is less than 10 ppm, the esterification reaction or transesterification reaction and the polycondensation reaction rate are slow, and the productivity is deteriorated. Moreover, each reaction time becomes long and quality deterioration, such as a color tone, arises. If the germanium compound is more than 1000 ppm, the increase of foreign matters and the decomposition reaction of polyester are promoted, resulting in deterioration of quality such as color tone.

  Examples of the titanium compound include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, and tetra-n-butyl titanate, and partial hydrolysates thereof, titanium acetate, titanyl oxalate, and oxalic acid. Titanylammonium, sodium titanyl oxalate, potassium titanyl oxalate, titanyl calcium oxalate, titanyl oxalate compounds such as titanyl strontium oxalate, titanium trimellitic acid, titanium sulfate, titanium chloride, titanium halide hydrolyzate, titanium oxalate, titanium fluoride , Potassium hexafluorotitanate, ammonium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, titanium acetylacetonate, hydroxy polyvalent carboxylic acid or nitrogen-containing polyvalent potassium Titanium complex thereof with carbon acid, a complex oxide comprising titanium and silicon or zirconium, a reaction product of titanium alkoxide and the phosphorus compound. Among these, titanium tetraisopropoxide, titanium tetrabutoxide, and potassium titanyl oxalate are preferable, and titanium tetrabutoxide is particularly preferable. These titanium compounds are preferably contained in an amount of 10 to 500 ppm, more preferably 20 to 400 ppm, and particularly preferably 30 to 300 ppm with respect to the produced polyester. If the titanium compound is less than 10 ppm, the esterification reaction or transesterification reaction and the polycondensation reaction rate are slow, and the productivity is deteriorated. Moreover, each reaction time becomes long and quality deterioration, such as a color tone, arises. When the titanium compound is more than 400 ppm, an increase in foreign matters and a polyester decomposition reaction are promoted, resulting in deterioration in quality such as color tone.

Examples of the aluminum compound include carboxylates such as aluminum formate, aluminum acetate, aluminum propionate and aluminum oxalate, oxides, inorganic acid salts such as aluminum hydroxide, aluminum chloride, aluminum hydroxide chloride and aluminum carbonate, aluminum Aluminum alkoxide such as methoxide and aluminum ethoxide, aluminum acetylacetate, aluminum chelate compound with aluminum acetylacetate, etc., organoaluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysis thereof Thing etc. are mentioned. Among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate are particularly preferable. These aluminum compounds are preferably contained in an amount of 10 to 200 ppm, more preferably 15 to 150 ppm, and particularly preferably 15 to 100 ppm with respect to the produced polyester.
When the aluminum compound is less than 10 ppm, the esterification reaction or transesterification reaction and the polycondensation reaction rate are slow, and the productivity deteriorates. Moreover, each reaction time becomes long and quality deterioration, such as a color tone, arises. When the amount of the aluminum compound exceeds 200 ppm, the number of foreign matters increases and the quality such as color tone deteriorates.

  In the production of the polyester according to the present invention, an alkali metal compound or an alkaline earth metal compound may be used in combination. Examples of the alkali metal compound or alkaline earth metal compound include carboxylates such as acetates of these elements, alkoxides, and the like, which are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, or the like.

In the case of the direct esterification method, the polycondensation catalyst can be added at any time before the start of the esterification reaction or after the completion of the pressure esterification reaction and before the start of the initial polycondensation reaction. However, when an antimony compound or a titanium compound is used as a polycondensation catalyst, it is preferably added before the esterification reaction. Further, other polycondensation catalyst, heat stabilizer and additives are preferably added after the esterification reaction.
In the case of the transesterification method, the polycondensation catalyst can be added at an arbitrary time from the start of the transesterification reaction to the start of the initial polycondensation reaction. However, since the titanium compound has not only a function as a polycondensation catalyst but also a function as a transesterification catalyst, it is preferably added before the start of the transesterification reaction. Moreover, it is preferable to add other polycondensation catalysts, heat stabilizers, and additives after the end of the transesterification reaction. As the transesterification catalyst, titanium compounds such as manganese acetate, magnesium acetate and titanium tetrabutoxide are suitable. The transesterification catalyst needs to be added before the start of the transesterification reaction.

  Moreover, a phosphorus compound can be used as a stabilizer. Examples of the phosphorus compound include phosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Preferred examples include phosphoric acid, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphorous acid, trimethyl phosphite, phosphorus phosphite Examples include tributyl acid, methylphosphonic acid, dimethyl methylphosphonate, dimethyl ethylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, and diphenyl phenylphosphonate. Among these, trimethyl phosphate and phosphoric acid are particularly preferable. These phosphorus compounds are preferably contained in an amount of 10 to 200 ppm, more preferably 15 to 150 ppm, and particularly preferably 15 to 100 ppm with respect to the polyester to be produced. When the phosphorus compound is less than 10 ppm, the esterification reaction or transesterification reaction and the polycondensation reaction rate are slow, and the productivity is deteriorated. Moreover, each reaction time becomes long and quality deterioration, such as a color tone, arises. When the amount of the phosphorus compound is more than 200 ppm, an increase in foreign matters and a deterioration in quality such as color tone occur.

  A cobalt compound can be blended for improving the color tone of the polyester. By adding this cobalt compound, the color b value can be particularly reduced. The cobalt compound is preferably contained in the amount of 5 to 100 ppm as a cobalt atom, more preferably 10 to 80 ppm, and particularly preferably 10 to 50 ppm. If the cobalt atom content exceeds the above range, the reduction of cobalt metal causes the polyester to darken or bluish, resulting in a reduction in commercial value. Examples of the cobalt compound include cobalt acetate, cobalt chloride, cobalt benzoate, and cobalt chromate. Of these, cobalt acetate is preferred.

  The copolyester obtained by the above continuous polycondensation method or batch polycondensation method is usually extracted in a strand form from an extraction port provided at the bottom of the reaction can, and after water cooling, it is cut into chips.

Also in the production of the polyester resin according to the present invention, depolymerization can be performed in the same manner as in the case of producing a general polyester resin, and a desired carboxyl group amount or hydroxyl group amount can be imparted.
When the aromatic monocarboxylic acid of the formula (2) is added, the chip obtained after the polycondensation, after the polycondensation, after the completion of the polycondensation reaction or after the completion of the polycondensation and the aromatic monocarboxylic acid of the formula (2) It is preferable to mix and react in an extruder. If the aromatic monocarboxylic acid of the formula (2) is added during the esterification or transesterification reaction at the initial stage of the reaction, the reaction terminal is blocked and the molecular weight may not be increased.

  In the present invention, a crosslinking agent may be included to increase the molecular weight. As the crosslinking agent to be used, those capable of undergoing a crosslinking reaction with a functional group present in the above-described polyester, for example, a carboxyl group, a hydroxyl group or the like may be used. For example, carbodiimide crosslinking agent, melamine crosslinking agent, oxazoline crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, epoxy crosslinking agent, urea crosslinking agent, acrylamide crosslinking agent, polyamide resin, amide epoxy compound, Various silane coupling agents, various titanate coupling agents, and the like can be used.

  The reduced viscosity of the polyester resin of the present invention is preferably 0.10 dl / g or more. When the reduced viscosity is 0.10 dl / g or more, a polyester resin having a higher glass transition temperature can be obtained when an ion aggregation action is imparted. The reduced viscosity is preferably 0.70 dl / g or less. When the reduced viscosity is lower than 0.70 dl / g, the melt moldability is excellent.

The glass transition temperature of the polyester resin of the present invention is preferably 190 ° C. or higher. 195 ° C. or higher is more preferable, and 200 ° C. or higher is more preferable.
In order to set the glass transition temperature to 190 ° C. or higher, the polyester resin according to the present invention is obtained by the above composition.

  Further, in the polyester resin of the present invention, if necessary, pigments such as titanium oxide, zinc white, carbon black, dyes, polyester resins, urethane resins, olefin resins, acrylic resins, alkyd resins, cellulose derivatives, etc. Additives such as a pigment dispersant, an ultraviolet absorber, a release agent, and a lubricant can be blended.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. The characteristics of the polyester resin were measured according to the following method.

(1) Reduced viscosity (dl / g)
Using a Yamato Scientific vacuum dryer type DP61, 60 ° C., 12 hours, 130 Pa abs. Below, 0.05 g of polyester resin (composition) dried under vacuum was dissolved in 25 ml of a mixed solvent of phenol / 1,1,2,2-tetrachloroethane = 6/4 (mass ratio) at 90 ° C. and adjusted to 30 ° C. Then, it calculated | required from the solution viscosity in 30 degreeC using an Ostwald viscosity tube. The calculation was performed according to the following formula.
ηsp = (T1-To) / To
ηsp / c = ηsp / 4W
(Where ηsp: specific viscosity,
ηsp / c: reduced viscosity (dl / g)
T1: Sample solution drop seconds (seconds)
To: The number of seconds when the solvent only falls (seconds)
W: Polyester resin (composition) amount (g))

(2) Glass transition temperature (° C)
Using a Yamato Scientific vacuum dryer type DP61, 60 ° C., 12 hours, 130 Pa abs. The polyester resin 5-8 mg vacuum-dried below was put into the aluminum pan for DSC, and it measured using DSC2920 by TA Instruments. In a nitrogen atmosphere, the temperature was raised in the range of 30 to 300 ° C. at a rate of 20 ° C./min, and an intermediate value between two inflection points derived from the obtained glass transition was determined, and this was taken as the glass transition temperature.

(3) Calculation of composition ratio (mol%) of polyester resin The polyester resin was dissolved in deuterated chloroform solvent to which trifluoroacetic acid was added, 400 MHz 1H-NMR was measured, and the composition ratio was quantified from the integrated value of the peak.

(4) Heat resistance Judged from the glass transition temperature.
○: 190 ° C or higher ×: less than 190 ° C

Example 1
As a dicarboxylic acid component, 302.1 parts by mass (1.56 mol) of dimethyl terephthalate, 51.2 parts by mass of sodium 5-sulfoisophthalate (0. 17 mol), 721.7 parts by mass (4.94 mol) of isosorbide as a glycol component, and 0.71 parts by mass of tetrabutyl titanate as a catalyst were charged. Then, it heated up to 250 degreeC under normal pressure, and performed normal pressure transesterification for 120 minutes. Thereafter, the pressure was gradually reduced while raising the temperature to 280 ° C., and 10 Pa abs. It was. Thereafter, 280 ° C., 10 Pa abs. In the following, a polycondensation reaction was performed for 60 minutes. After returning to normal pressure with nitrogen gas, the polyester resin was extracted from the lower part of the autoclave after being pressurized, cooled with cooling water, and then cut into chips.
The properties of the obtained polyester resin were a reduced viscosity of 0.16 dl / g and a glass transition temperature of 190 ° C. Due to the ion aggregating action of the sulfonate group, it was possible to obtain an isosorbide-containing polyester resin having a high glass transition temperature that cannot be obtained by ordinary melt polymerization. The results are shown in Table 1.

(Example 2)
In a 2 L SUS autoclave having a stirrer, a thermometer, and a condenser, 257.0 parts by mass (1.32 mol) of dimethyl terephthalate and 98.0 parts by mass of sodium 5-sulfoisophthalate (0.0. 33 mol), 690.7 parts by mass (4.73 mol) of isosorbide as a glycol component, and 0.71 parts by mass of tetrabutyl titanate as a catalyst. Thereafter, as in Example 1, normal pressure transesterification and polycondensation were performed.
The properties of the obtained polyester resin were a reduced viscosity of 0.15 dl / g and a glass transition temperature of 204 ° C. An isosorbide-containing polyester resin having a high glass transition temperature that cannot be obtained by ordinary melt polymerization could be obtained. The results are shown in Table 1.

Example 3
As a dicarboxylic acid component, 215.6 parts by mass (1.11 mol) of dimethyl terephthalate and 140.9 parts by mass of sodium 5-sulfoisophthalate (0. 48 mol), 662.2 parts by mass (4.53 mol) of isosorbide as the glycol component, and 0.71 parts by mass of tetrabutyl titanate as the catalyst. Thereafter, as in Example 1, normal pressure transesterification and polycondensation were performed.
The characteristics of the obtained polyester resin were a reduced viscosity of 0.12 dl / g and a glass transition temperature of 198 ° C. An isosorbide-containing polyester resin having a high glass transition temperature that cannot be obtained by ordinary melt polymerization could be obtained. The results are shown in Table 1.

Example 4
As a dicarboxylic acid component, 302.1 parts by mass (1.56 mol) of dimethyl terephthalate, 51.2 parts by mass of sodium 5-sulfoisophthalate (0. 17 mol), 721.7 parts by mass (4.94 mol) of isosorbide as a glycol component, and 0.71 parts by mass of tetrabutyl titanate as a catalyst were charged. Then, it heated up to 250 degreeC under normal pressure, and performed normal pressure transesterification for 120 minutes. After completion of the normal pressure transesterification reaction, 38.1 parts by mass (0.17 mol) of sodium m-sulfobenzoate was added as a terminal blocking agent, and the mixture was stirred at normal pressure for 10 minutes. Thereafter, a polycondensation reaction was carried out in the same manner as in Example 1.
The properties of the obtained polyester resin were a reduced viscosity of 0.14 dl / g and a glass transition temperature of 195 ° C. Due to the ion aggregating action of the sulfonate group, it was possible to obtain an isosorbide-containing polyester resin having a high glass transition temperature that cannot be obtained by ordinary melt polymerization. Moreover, the glass transition temperature was able to be improved by adding the sulfonate group of monodicarboxylic acid. The results are shown in Table 1.

(Example 5)
In a 2 L SUS autoclave having a stirrer, a thermometer, and a condenser, 257.0 parts by mass (1.32 mol) of dimethyl terephthalate and 98.0 parts by mass of sodium 5-sulfoisophthalate (0.0. 33 mol), 690.7 parts by mass (4.73 mol) of isosorbide as a glycol component, and 0.71 parts by mass of tetrabutyl titanate as a catalyst. Then, it heated up to 250 degreeC under normal pressure, and performed normal pressure transesterification for 120 minutes. After completion of the normal pressure transesterification reaction, 19.1 parts by mass (0.085 mol) of sodium m-sulfobenzoate was added as a terminal blocking agent, and the mixture was stirred for 10 minutes under normal pressure. Thereafter, a polycondensation reaction was carried out in the same manner as in Example 1.
The properties of the obtained polyester resin were a reduced viscosity of 0.14 dl / g and a glass transition temperature of 208 ° C. Due to the ion aggregating action of the sulfonate group, it was possible to obtain an isosorbide-containing polyester resin having a high glass transition temperature that cannot be obtained by ordinary melt polymerization. Moreover, the glass transition temperature was able to be improved by adding the sulfonate group of monodicarboxylic acid. The results are shown in Table 1.

(Example 6)
As a dicarboxylic acid component, 174.3 parts by mass (0.90 mol) of dimethyl terephthalate and 66.5 parts by mass of sodium 5-sulfoisophthalate (0.05 mol) as a dicarboxylic acid component in a 2 L SUS autoclave having a stirrer, a thermometer and a condenser. 22 mol), 245.9 parts by mass (1.68 mol) of isosorbide as a glycol component, 147.6 parts by mass (0.336 mol) of bisphenoxyethanol fluorene, and 0.71 part by mass of tetrabutyl titanate as a catalyst. Then, it heated up to 250 degreeC under normal pressure, and performed normal pressure transesterification for 120 minutes. After the normal pressure transesterification reaction was completed, 6.72 parts by mass (0.03 mol) of sodium m-sulfobenzoate was added as a terminal blocking agent, and the mixture was stirred for 10 minutes under normal pressure. Thereafter, a polycondensation reaction was carried out in the same manner as in Example 1.
The characteristics of the obtained polyester resin were a reduced viscosity of 0.25 dl / g and a glass transition temperature of 190 ° C. Due to the ion aggregating action of the sulfonate group, it was possible to obtain an isosorbide-containing polyester resin having a high glass transition temperature that cannot be obtained by ordinary melt polymerization. Moreover, the glass transition temperature was able to be improved by adding the sulfonate group of monodicarboxylic acid. The results are shown in Table 1.

(Comparative Example 1)
The same procedure as in Example 1 was repeated except that 351.5 parts by mass (1.81 mol) of dimethyl terephthalate and 755.7 parts by mass (5.17 mol) of isosorbide were used as the glycol component.
The properties of the obtained polyester resin were a reduced viscosity of 0.38 dl / g and a glass transition temperature of 186 ° C. The glass transition temperature was low and the heat resistance was insufficient. The results are shown in Table 1.

(Comparative Example 2)
336.2 parts by mass (1.73 mol) of dimethyl terephthalate, 15.9 parts by mass (0.05 mol) of sodium 5-sulfoisophthalate, and 745.2 parts by mass (5.10 mol) of isosorbide as a glycol component The procedure was the same as in Example 1 except that.
The properties of the obtained polyester resin were a reduced viscosity of 0.27 dl / g and a glass transition temperature of 179 ° C. The glass transition temperature was low and the heat resistance was insufficient. The results are shown in Table 1.

(Comparative Example 3)
142.2 parts by mass (0.73 mol) of dimethyl terephthalate, 217.0 parts by mass (0.73 mol) of sodium 5-sulfoisophthalate, and 611.7 parts by mass (4.19 mol) of isosorbide as a glycol component The procedure was the same as in Example 1 except that. The ion aggregating action of sodium 5-sulfoisophthalate was strong, the melt viscosity increased significantly during polycondensation, and a polyester resin could not be obtained.

(Comparative Example 4)
116.2 parts by mass (0.60 mol) of dimethyl terephthalate, 75.6 parts by mass (0.26 mol) of sodium 5-sulfoisophthalate, and 356.0 parts by mass (0.81 mol) of bisphenoxyethanol fluorene as a glycol component ), Isosorbide was carried out in the same manner as in Example 1 except that the content was 131.1 parts by mass (0.90 mol).
The properties of the obtained polyester resin were a reduced viscosity of 0.14 dl / g and a glass transition temperature of 175 ° C. Since the amount of isosorbide copolymerization was small, a polyester resin having a high glass transition temperature could not be obtained. The results are shown in Table 1.

  The polyester resin composition of the present invention is a polymer excellent in heat resistance because of its high molecular weight and glass transition temperature, and is provided as a molded product, fiber, paint, coating agent, etc., and has high industrial utility value. .

Claims (5)

A polyester resin comprising a dicarboxylic acid component and a glycol component, wherein the dicarboxylic acid component is 10 to 40 mol% of an aromatic dicarboxylic acid having a sulfonate group represented by the following formula (1), terephthalic acid, isophthalic acid , 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 90 to 60 mol% of one or more selected from alicyclic dicarboxylic acid, and 50 parts of isosorbide as the glycol component 100 mol% seen containing, polyester resin, wherein the glass transition temperature of 190 ° C. or higher.

[In the formula (1), Ar is a trivalent aromatic group having 6 to 12 carbon atoms, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms. Represents a group, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ] The polyester resin according to claim 1, wherein the polyester resin contains a terminal blocking agent. The polyester resin according to claim 2 , wherein the terminal blocking agent is an aromatic monocarboxylic acid having a sulfonate group represented by the following formula (2).

Wherein (2), Ar represents a divalent aromatic group, ^{R 3} represents a hydrogen atom, an alkyl group or an aryl group having 6 to 12 carbon atoms having 1 to 6 carbon atoms of 6 to 12 carbon atoms, ^{M +} Represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ] The polyester resin according to claim 2 or 3 , wherein the terminal blocking agent is contained in an amount of 1 to 20 mol% with respect to 100 mol% of the dicarboxylic acid component. The molded article using the polyester resin in any one of Claims 1-4 .