WO2018101320A1 - Polyester, method for producing polyester, molded article comprising polyester - Google Patents

Abstract

This polyester is mainly composed of: a dicarboxylic acid unit having an aromatic dicarboxylic acid unit as a main component; and a diol unit having a linear aliphatic diol unit, an isosorbide unit and a cyclohexanedimethanol unit as main components, wherein the content of the isosorbide unit is 1-14 mol%, and the content of the cyclohexanedimethanol unit is 1-9 mol% with respect to the total diol unit. By using such a polyester, a molded article having excellent chemical resistance and high hardness, and also having good impact resistance even after a long period of time has passed is provided.

Description

Polyester, method for producing the same, and molded article comprising the same

The present invention relates to a polyester suitable as a raw material for extrusion molding, a method for producing the same, and a molded product comprising the same.

Polyesters such as polyethylene terephthalate are excellent in properties such as transparency, mechanical properties, gas barrier properties, and flavor barrier properties. Furthermore, polyester has less concern about residual monomers and harmful additives when formed into molded articles, and is excellent in hygiene and safety. Therefore, polyester has been widely used in recent years as a hollow container for filling beverages, seasonings, oils, cosmetics, detergents, etc. as an alternative to the conventionally used vinyl chloride, taking advantage of these properties. .

As a molding method for producing a hollow molded product made of polyester, a resin melted and plasticized through a die orifice is extruded as a cylindrical parison, and the parison is sandwiched between molds while it is in a softened state. An extrusion blow molding method is known in which molding is performed by blowing a fluid. Compared with the injection blow molding method, this method is simpler and does not require advanced technology for the production and molding of the mold. Suitable for varieties and small volume production. In addition, there is an advantage that it is possible to manufacture a molded product having a complicated shape having a thin object, a deep object, a large object, a handle, and the like.

By the way, containers for cosmetics and oils are required to have excellent mechanical properties in order to prevent damage due to impact such as dropping in addition to excellent properties such as chemical resistance and gas barrier properties. It is done. In addition, cosmetic containers and the like are required to have an appropriate hardness, have a scratch-resistant surface, and have a glass-like texture and appearance. In addition, ice-packing containers for iced coffee sold at convenience stores, etc. have excellent impact resistance at low temperatures so that the containers are not damaged by sharp ice during refrigerated transportation, and the containers can be picked up by hand. When drinking coffee, it is required that it does not dent easily.

However, the molded product obtained by extrusion molding of general-purpose polyester is different from the molded product obtained using the injection blow molding method, because the polyester is not oriented and crystallized. And mechanical properties such as hardness were insufficient.

As a method for improving the impact resistance of a molded product, a method of copolymerizing polyethylene terephthalate with another monomer is known. Patent Document 1 mainly includes dicarboxylic acid units mainly composed of terephthalic acid units, and diol units mainly composed of ethylene glycol units and cyclohexanedimethanol units, and has an intrinsic viscosity of 0.85 to 1.5 dl / g. It consists mainly of polyester (A) pellets, dicarboxylic acid units mainly composed of terephthalic acid units and isophthalic acid units, and diol units mainly composed of ethylene glycol units, and has an intrinsic viscosity of 0.8 to 1.5 dl / g. A resin composition obtained by melt-kneading a polyester (B) pellet is described. Patent Document 1 describes that a molded product obtained by using such a resin composition has good chemical resistance, and that there is little decrease in impact resistance after a long period of time. However, the molded product still has insufficient chemical resistance and impact resistance after a long period of time. In addition, since the molded product is soft, there are cases where the surface is scratched or dents when picked up, which may be a problem. In addition, when the molded product is used as an alternative to a glass container used for cosmetics, it is a problem because the texture and appearance of the container when it is soft are very different from those of a glass container.

Patent Document 2 describes a polyester resin having a dicarboxylic acid component containing terephthalic acid and a diol component containing isosorbide, cyclohexanedimethanol and other diol compounds, and having an intrinsic viscosity of 0.5 to 1.0 dl / g. Has been. Patent Document 2 describes that the polyester resin is excellent in heat resistance, chemical resistance, impact resistance, transparency, moldability, and appearance. However, the polyester resin is insufficient in chemical resistance, particularly durability against a high concentration of alcohol. Moreover, since the molded product obtained using the said polyester resin is soft, it was a problem as mentioned above.

JP 2016-124966 A Special table 2015-518916

The present invention has been made to solve the above-mentioned problems, and is a molded product having moderate hardness, excellent chemical resistance, and good impact resistance even after a long period of time, especially extrusion molding. An object of the present invention is to provide a polyester capable of obtaining a product and a method for producing the same.

The above-mentioned problem is mainly composed of a dicarboxylic acid unit mainly composed of an aromatic dicarboxylic acid unit, and a diol unit mainly composed of a linear aliphatic diol unit, an isosorbide unit and a cyclohexanedimethanol unit, and an isosorbide unit relative to the total of the diol units. This is achieved by providing a polyester having a content of 1 to 14 mol% and a cyclohexanedimethanol unit content of 1 to 9 mol%.

In the polyester, the total content of isosorbide units and cyclohexanedimethanol units with respect to the total of the diol units is preferably 15 mol% or less. The polyester further comprises a polyfunctional compound unit derived from a polyfunctional compound having three or more carboxyl groups, hydroxyl groups and / or ester forming groups thereof, based on the total of the structural units. It is also preferable to contain ˜1 mol%. It is also preferable that the intrinsic viscosity of the polyester is 0.55 to 1.5 dl / g. It is also preferable that the diol unit further contains a unit derived from a bisphenol A ethylene oxide adduct in an amount of 0.1 to 20 mol% based on the total of the diol units. The dicarboxylic acid unit further contains a dimer acid unit or a hydrogenated dimer acid unit, and the total content of the dimer acid unit and the hydrogenated dimer acid unit is 0.1 to 20 mol relative to the total of the dicarboxylic acid units. % Is also preferred.

A molded product formed by extruding the polyester is a preferred embodiment of the present invention. A container made of the molded product is a more preferred embodiment of the present invention. Moreover, the film or sheet which consists of the said molded article is also a more suitable embodiment of this invention, and the thermoformed article formed by thermoforming the said film or sheet is a more suitable embodiment.

A molded product obtained by thermoforming the polyester is also a preferred embodiment of the present invention. A container made of the molded product is a more preferred embodiment of the present invention.

The above-mentioned problem can also be solved by providing a method for producing the polyester which is polycondensed by melt-kneading aromatic dicarboxylic acid, linear aliphatic diol, isosorbide, and cyclohexanedimethanol.

The above-mentioned problem is mainly composed of a dicarboxylic acid unit mainly comprising an aromatic dicarboxylic acid unit, and a diol unit mainly comprising a linear aliphatic diol unit, an isosorbide unit and a unit derived from a bisphenol A ethylene oxide adduct, and the diol unit This can also be solved by providing a polyester having an isosorbide unit content of 1 to 25 mol% and a bisphenol A ethylene oxide adduct content of 0.1 to 20 mol% with respect to the total of the above. In addition, the above-mentioned problem mainly consists of an aromatic dicarboxylic acid unit, a dicarboxylic acid unit mainly composed of a dimer acid unit or a hydrogenated dimer acid unit, and a diol unit mainly composed of a linear aliphatic diol unit and an isosorbide unit, The total content of dimer acid units and hydrogenated dimer acid units with respect to the total of the dicarboxylic acid units is 0.1 to 20 mol%, and the content of isosorbide units with respect to the total of the diol units is 1 to 25 mol%. It is also solved by providing polyester.

The molded product obtained using the polyester of the present invention has moderate hardness, excellent chemical resistance, and good impact resistance even after a long period of time. According to the production method of the present invention, such a polyester can be produced easily.

The polyester of the present invention mainly comprises dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, and diol units mainly composed of linear aliphatic diol units, isosorbide units and cyclohexane dimethanol units, and is based on the total of the diol units. The content of isosorbide units is 1 to 14 mol%, and the content of cyclohexanedimethanol units is 1 to 9 mol%. In the present invention, the polyester may be referred to as a first polyester.

The aromatic dicarboxylic acid units in the polyester include terephthalic acid (TA) units, furandicarboxylic acid (FDCA) units, isophthalic acid (IPA) units, phthalic acid units, 5- (alkali metal) sulfoisophthalic acid units, diphenine. Acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, and the like. Among them, terephthalic acid units, furandicarboxylic acid units, and isophthalic acid units are preferable. Terephthalic acid units are more preferred. These may be used alone or in combination of two or more.

The content of the aromatic dicarboxylic acid unit in the polyester is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more based on the total of the dicarboxylic acid units in the polyester. .

It is preferable that the dicarboxylic acid unit in the polyester further contains a dimer acid (DA) unit or a hydrogenated dimer acid (H-DA) unit, and among them, those having 36 or 44 carbon atoms are more preferable. By containing the dimer acid (DA) unit or the hydrogenated dimer acid (H-DA) unit, the drawdown resistance when the polyester is extruded is further improved. The total content of dimer acid units and hydrogenated dimer acid units in the polyester is preferably 0.1 mol% or more, more preferably 0.4 mol% or more, based on the total of dicarboxylic acid units in the polyester. . On the other hand, the content of the unit is preferably 20 mol% or less. When the content is within the above range, the melt viscosity of the polyester becomes appropriate, and the impact resistance of the obtained molded product is further improved. The content is more preferably 5 mol% or less, and further preferably 2 mol% or less.

Examples of the linear aliphatic diol unit in the polyester include an ethylene glycol (EG) unit, a diethylene glycol (DEG) unit, a triethylene glycol unit, a 1,3-trimethylene glycol unit, a 1,4-butanediol unit, 1, Examples thereof include 5-pentanediol units, 1,6-hexanediol units, 1,9-nonanediol, and among these, ethylene glycol units and diethylene glycol units are preferable. These may be used alone or in combination of two or more. Usually, a polyester obtained using ethylene glycol as a linear aliphatic diol as a raw material contains 1 to 5 mol% of diethylene glycol units, which are by-products during the condensation polymerization reaction, based on the total of diol units.

The content of the linear aliphatic diol unit in the polyester is preferably 75 mol% or more based on the total of diol units in the polyester. When the said content is 75 mol% or more, when manufacturing the said polyester, since solid-phase polymerization can be performed at high temperature, while improving productivity, a molded article with a better color tone is obtained. It becomes like this. The content of the linear aliphatic diol unit is more preferably 80 mol% or more, further preferably 85 mol% or more, and particularly preferably 86 mol% or more. On the other hand, the content of the linear aliphatic diol unit is 98 mol% or less. When the content is 98 mol% or less, the impact resistance of the obtained molded product is improved and the transparency is also improved. The content of the linear aliphatic diol unit is preferably 96 mol% or less, more preferably 93 mol% or less, and still more preferably 90 mol% or less.

The content of isosorbide (ISB) units in the polyester is 1 mol% or more based on the total of diol units in the polyester. When the content is 1 mol% or more, the glass transition point of the polyester is increased and the enthalpy relaxation rate is decreased, so that the obtained molded product has excellent impact resistance after a long period of time. Become. Moreover, since the said molded article becomes moderately hard, while being hard to get a damage | wound on the surface, the texture and external appearance like glass are obtained. The content of isosorbide units is preferably 2 mol% or more, more preferably 3 mol% or more, and further preferably 4 mol% or more. On the other hand, the content of isosorbide units is 14 mol% or less. When the content is 14 mol% or less, the color tone of the obtained molded product is improved. Moreover, the drawdown resistance at the time of extruding the polyester is improved. The content of isosorbide units is preferably 12 mol% or less.

The cyclohexanedimethanol (CHDM) unit in the polyester is at least one divalent unit selected from 1,2-cyclohexanedimethanol unit, 1,3-cyclohexanedimethanol unit and 1,4-cyclohexanedimethanol unit. I just need it. Among these, cyclohexanedimethanol is easy to obtain, easy to make the polyester crystalline, difficult to cause sticking between pellets during solid phase polymerization, and further improves the impact resistance of the resulting molded product. The unit is preferably 1,4-cyclohexanedimethanol unit.

There are cis and trans isomers in the cyclohexanedimethanol unit, but the ratio of the cis and trans isomers in the cyclohexanedimethanol unit in the polyester is not particularly limited. In particular, in the cyclohexanedimethanol unit in the polyester, the ratio of cis isomer: trans isomer is in the range of 0: 100 to 50:50, which makes it easy to make the polyester crystalline. This is preferable from the viewpoint that sticking between the pellets hardly occurs and the impact resistance of the obtained molded product is further improved.

The content of cyclohexanedimethanol units in the polyester is 1 mol% or more based on the total of diol units in the polyester. When the content is 1 mol% or more, impact resistance at normal temperature and low temperature of the obtained molded product is improved, and transparency is also improved. The content is preferably 2 mol% or more, more preferably 4 mol% or more, and further preferably 6 mol% or more. On the other hand, the content of cyclohexanedimethanol units is 9 mol% or less. When the content is 9 mol% or less, the chemical resistance of the obtained molded article, in particular, durability against a high concentration of alcohol is improved. Moreover, since the said molded article becomes moderately hard, while being hard to get a damage | wound on the surface, the texture and external appearance like glass are obtained.

It is preferable that the total content of isosorbide units and cyclohexanedimethanol units with respect to the total of the diol units in the polyester is 15 mol% or less. When the content is 15 mol% or less, since the polyester has appropriate crystallinity, the mechanical properties of the obtained molded product are further improved. In addition, since pre-crystallization treatment is performed on polyester having a total content of isosorbide units and cyclohexanedimethanol units of 15 mol% or less, drying at a temperature higher than the glass transition temperature can be performed, and moisture content can be reduced. It is possible to suppress a decrease in intrinsic viscosity due to hydrolysis during molding. The total content is more preferably 14 mol% or less.

The total content of linear aliphatic diol units, isosorbide units and cyclohexanedimethanol units in the polyester is usually 80 mol% or more, and 90 mol% or more based on the total of diol units in the polyester. Preferably, 95 mol% or more is more preferable.

It is preferable that the diol unit in the polyester further contains a unit derived from bisphenol A ethylene oxide adduct (EOBPA) in an amount of 0.1 to 20 mol% based on the total of diol units in the polyester. Thereby, the drawdown resistance at the time of extruding the polyester is further improved. The bisphenol A ethylene oxide adduct is obtained by adding at least one ethylene oxide to each hydroxyl group of bisphenol A. The addition amount of ethylene oxide is usually 2.0 to 4.0 mol with respect to 1 mol of bisphenol A.

The content of units derived from the bisphenol A ethylene oxide adduct in the polyester is preferably 0.1 mol% or more with respect to the total of diol units in the polyester. The effect mentioned above is acquired because the said content is 0.1 mol% or more. The initial content is more preferably 0.5 mol% or more, and further preferably 2 mol% or more. On the other hand, the content of the unit is preferably 20 mol% or less. When the content is 20 mol% or less, the melt viscosity of the polyester becomes appropriate, and the impact resistance of the obtained molded product is further improved. The content is more preferably 10 mol% or less, still more preferably 8 mol% or less.

The total content of aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units, and cyclohexanedimethanol units in the polyester is preferably 80 mol% or more based on the total of all structural units in the polyester. When the said content is 80 mol% or more, when the said polyester is manufactured by solid phase polymerization, since the sticking by softening of resin is suppressed, a polymerization degree can be raised easily. The content is more preferably 90 mol% or more, and still more preferably 95 mol% or more.

The polyester, if necessary, other than aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units, cyclohexane dimethanol units, dimer acid units, hydrogenated dimer acid units, and units derived from bisphenol A ethylene oxide adducts. Other comonomer units may be contained.

The other comonomer unit preferably has 5 or more carbon atoms. When the number of carbon atoms is less than 5, the comonomer boiling point of the raw material is lowered and volatilizes during the polycondensation reaction, which may make it difficult to recover a linear aliphatic diol such as ethylene glycol. The upper limit of the carbon number is not particularly limited, but is usually 50 or less. The other comonomer unit contained in the polyester may be one type or two or more types.

Bifunctional compound units are mainly used as other comonomer units. The content of other bifunctional compound units (the total when two or more units are included) is preferably 20 mol% or less with respect to the total of all structural units constituting the polyester. It is more preferably at most mol%, further preferably at most 5 mol%. Other difunctional compound units that can be contained in the polyester include aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units, cyclohexanedimethanol units, dimer acid units, hydrogenated dimer acid units, and bisphenols. A unit other than the unit derived from ethylene oxide adduct. If the other bifunctional compound unit is a dicarboxylic acid unit, a diol unit, or a hydroxycarboxylic acid unit, an aliphatic bifunctional compound unit, an alicyclic bifunctional compound unit, or an aromatic bifunctional compound unit Any of these may be used.

Examples of aliphatic dicarboxylic acid units other than dimer acid units and hydrogenated dimer acid units used as other comonomer units include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, Aliphatic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane For aliphatic dicarboxylic acids such as carboxylic acid, decahydronaphthalenedicarboxylic acid (decalin dicarboxylic acid), tetralin dicarboxylic acid, cyclobutene dicarboxylic acid, tricyclodecane dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid or their ester-forming derivatives Mention may be made of derived units.

Examples of aliphatic diol units other than linear aliphatic diol units, isosorbide units, and cyclohexanedimethanol units used as other comonomer units include 1,2-propanediol, neopentyl glycol (2,2-dimethyl-1, 3-propanediol), 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, tetramethylcyclobutanediol, dimer diol having 36 carbon atoms, dimer diol having 44 carbon atoms, etc. Mention may be made of units derived from aliphatic diols.

As long as the polyester does not impair the effects of the present invention, other comonomer units include aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units, cyclohexanedimethanol units, dimer acid units, hydrogenated dimers. In addition to the acid unit, the unit derived from the bisphenol A ethylene oxide adduct, and the other bifunctional compound unit described above, another polyfunctional compound unit may be included. Another polyfunctional compound unit is a polyfunctional compound unit derived from a polyfunctional compound having three or more carboxyl groups, hydroxyl groups and / or ester-forming groups thereof. When the polyester contains such a polyfunctional compound unit, inflation moldability is improved. The content of other polyfunctional compound units (the total when two or more units are included) is preferably 0.00005 to 1 mol% based on the total of the structural units of the polyester. The amount is more preferably 0.0015 to 0.8 mol%, and further preferably 0.00025 to 0.4 mol%. Among other polyfunctional compound units, trifunctional compound units and tetrafunctional compound units are preferred. Other polyfunctional compound units include polycarboxylic acid units derived from trimellitic acid, trimesic acid, etc .; polyhydric alcohol units derived from trimethylolpropane, glycerin, etc .; units derived from polyvalent esters preferable.

The unit derived from the polyvalent ester is preferably a carboxylic acid ester of a trivalent or higher polyol, wherein the carboxylic acid is derived from a polyvalent ester having a hindered phenol group. Here, the unit derived from a polyvalent ester is one contained in the polyester by polycondensing the polyvalent ester together with an aromatic dicarboxylic acid, a linear aliphatic diol, isosorbide, and cyclohexanedimethanol. is there. A polyol unit of the polyvalent ester and a carboxylic acid unit having a hindered phenol group are contained in the polyester by a transesterification reaction. The polyol unit is contained in the main chain, branched chain or terminal of the polyester. A part of the polyol unit becomes a crosslinking point and acts as a crosslinking agent. On the other hand, a part of the carboxylic acid unit having a hindered phenol group is contained at the terminal of the polyester, and a part is contained in the polyester together with the polyol unit in a state of being bonded to the polyol unit. As described above, when the unit derived from the polyvalent ester is contained in the polyester, in addition to the inflation moldability, the drawdown resistance at the time of extrusion blow molding is further improved, and the color tone of the molded product is also improved. Will improve. The polyvalent ester is preferably a carboxylic acid ester of a trivalent to pentavalent polyol. Examples of the polyvalent ester include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [2- [3- (3,5- And di-tert-butyl-4-hydroxyphenyl) propanoyloxy] ethyl] hexahydro-1,3,5-triazine-2,4,6-trione.

In addition, if necessary, the polyester comprises, as another comonomer unit, at least one monofunctional compound other than the carboxylic acid having a hindered phenol group, a monocarboxylic acid, a monoalcohol, and an ester-forming derivative thereof. It may have other monofunctional compound units derived. The other monofunctional compound unit functions as a sealing compound unit and seals molecular chain end groups and / or branched chain end groups in the polyester, thereby preventing excessive crosslinking and gel formation in the polyester. . When the polyester has such other monofunctional compound units, the content of other monofunctional compound units (the total when two or more units are included) is the total structural unit of the polyester. It is preferably 1 mol% or less, more preferably 0.5 mol% or less, based on the total. When the content of the other monofunctional compound unit in the polyester exceeds 1 mol%, the polymerization rate in producing the polyester becomes slow, and the productivity tends to decrease. Examples of other monofunctional compound units include units derived from monofunctional compounds selected from benzoic acid, 2,4,6-trimethoxybenzoic acid, 2-naphthoic acid, stearic acid and stearyl alcohol. .

From the viewpoint of further improving the strength, impact resistance, melt moldability, and production stability of the obtained molded product, the intrinsic viscosity of the polyester is preferably 0.55 dl / g or more, and more preferably 0.65 dl / g or more. On the other hand, from the viewpoint of improving melt moldability and productivity, the intrinsic viscosity is preferably 1.5 dl / g or less, more preferably 1.4 dl / g or less, and further preferably 1.3 dl / g or less.

From the viewpoint of further improving the impact resistance of the obtained molded article after a long period of time, the glass transition temperature of the polyester is preferably 81 ° C. or higher, more preferably 82 ° C. or higher. On the other hand, the glass transition temperature is preferably 100 ° C. or lower. In this case, when the polyester is extrusion blow molded, it is not necessary to heat the mold to room temperature or more, which is preferable.

From the viewpoint of improving the drawdown resistance during extrusion blow molding, the polyester preferably has a melting point of 226 ° C or higher. However, when the said polyester contains the said polyfunctional compound unit, it is preferable that melting | fusing point is 215 degreeC or more. By including the polyfunctional compound unit, the number of crosslinking points is increased and the flow of the polyester is suppressed. Therefore, if the melting point is 215 ° C. or more, the drawdown resistance at the time of extrusion blow molding is improved. . On the other hand, when extrusion blow molding is performed, the melting point of the polyester is preferably 260 ° C. or less from the viewpoint of suppressing the cylinder temperature low and improving the color tone of the molded product.

As a method for producing the polyester, a method of polycondensation by melting and kneading an aromatic dicarboxylic acid, a linear aliphatic diol, cyclohexane dimethanol and isosorbide is preferable.

A method for polycondensation by melt-kneading an aromatic dicarboxylic acid, a linear aliphatic diol, cyclohexanedimethanol and isosorbide is not particularly limited, but an aromatic dicarboxylic acid or an ester-forming derivative thereof, a linear aliphatic diol, Cyclohexanedimethanol, isosorbide, and dimer acid, hydrogenated dimer acid, bisphenol A ethylene oxide adduct, the polyvalent ester, and other comonomers as raw materials were used as raw materials to perform an esterification reaction or an ester exchange reaction. Then, the method of carrying out melt polycondensation of the obtained polyester oligomer is mentioned. The polyvalent ester may be added before performing the esterification reaction or transesterification reaction, or may be added after performing these reactions. In addition, raw materials other than the polyvalent ester can be appropriately added before the esterification reaction or transesterification reaction, or after these reactions have been performed.

In the above esterification reaction or transesterification reaction, the above-mentioned raw materials, polymerization catalyst and, if necessary, additives such as anti-coloring agents are charged into the reactor, and the absolute pressure is about 0.5 MPa or less under pressure or normal pressure. , Preferably at a temperature of 160 to 280 ° C. while distilling off the water or alcohol produced.

The melt polycondensation reaction following the esterification reaction or transesterification reaction is carried out by adding additives such as the above-mentioned raw materials, polycondensation catalyst and coloring inhibitor to the obtained polyester oligomer as necessary. It is preferably carried out under reduced pressure at a temperature of 260 to 290 ° C. until a polyester having a desired viscosity is obtained. When the reaction temperature of the melt polycondensation reaction is less than 260 ° C., the polymerization activity of the polymerization catalyst is low, and there is a possibility that a polyester having a target degree of polymerization cannot be obtained. On the other hand, when the reaction temperature of the melt polymerization reaction exceeds 290 ° C., the decomposition reaction easily proceeds, and as a result, there is a possibility that a polyester having a target degree of polymerization cannot be obtained. The melt polycondensation reaction can be performed using, for example, a tank-type batch polycondensation apparatus or a continuous polycondensation apparatus including a biaxial rotating horizontal reactor.

As the polymerization catalyst used for the condensation polymerization, any catalyst that can be used for the production of polyester can be selected, but germanium, titanium, zirconium, hafnium, antimony, tin, magnesium, calcium, zinc, aluminum, A compound containing a metal element such as cobalt, lead, cesium, manganese, lithium, potassium, sodium, copper, barium, cadmium is preferable. Of these, compounds containing germanium elements, antimony elements, and titanium elements are preferred. As the compound containing antimony element, antimony trioxide, antimony chloride, antimony acetate, etc. are used. As the compound containing germanium element, germanium dioxide, germanium tetrachloride, germanium tetraethoxide, etc. are used. As the compound to be contained, tetraisopropyl titanate, tetrabutyl titanate, or the like is used. In addition, composite particles of hydrotalcite and titanium dioxide may be used as the polymerization catalyst. Among these, antimony trioxide and germanium dioxide are preferable from the viewpoint of polymerization catalyst activity, physical properties of the resulting polyester, and cost. When a polycondensation catalyst is used, the amount added is preferably in the range of 0.002 to 0.8% by mass based on the mass of the dicarboxylic acid component.

When using an anti-coloring agent in the above condensation polymerization, for example, phosphoric acid compounds such as phosphorous acid or esters thereof can be used, and these can be used alone or in combination of two or more. Good. Examples of the phosphoric acid compound include phosphorous acid, phosphite, phosphoric acid, trimethyl phosphate, and triphenyl phosphate. The amount of the coloring inhibitor used is preferably in the range of 80 to 1000 ppm with respect to the total of the dicarboxylic acid component and the diester component. Further, in order to suppress coloring due to thermal decomposition of the polyester, it is preferable to add a cobalt compound such as cobalt acetate, and the amount used is in the range of 100 to 1000 ppm with respect to the total of the dicarboxylic acid component and the diester component. It is more preferable.

In the above condensation polymerization, an aromatic dicarboxylic acid ester may be used to form an aromatic dicarboxylic acid unit. The alcohol part of the aromatic dicarboxylic acid ester is not particularly limited, and examples include monools such as methanol and ethanol; polyols such as ethylene glycol, cyclohexane dimethanol, and bisphenol A ethylene oxide adduct, which are constituent units of the polyester. It is done.

In the above condensation polymerization, a mono- or diester of a linear aliphatic diol may be used in order to form a linear aliphatic diol unit. The carboxylic acid moiety of the carboxylic acid ester is not particularly limited, and examples thereof include monocarboxylic acids such as formic acid, acetic acid, and propionic acid.

The intrinsic viscosity of the polyester obtained by melt polycondensation is preferably 0.4 dl / g or more. Thereby, the handleability is improved and, when the polyester obtained by melt polycondensation is further solid-phase polymerized, the molecular weight can be increased in a short time, so that productivity is improved. The intrinsic viscosity is more preferably 0.55 dl / g or more, and still more preferably 0.65 dl / g or more. On the other hand, the intrinsic viscosity is preferably 0.9 dl / g or less, more preferably 0.85 dl / g or less, from the viewpoint that polyester can be easily taken out from the reactor and coloring due to thermal deterioration is suppressed. More preferably, it is 0.8 dl / g or less.

The polyester thus obtained is suitably used as a raw material for extrusion molding. It is also preferred to further solid-phase polymerize the polyester obtained by melt polycondensation. The solid phase polymerization will be described below.

The polyester obtained as described above is extruded into a strand shape, a sheet shape, and the like, cooled, and then cut with a strand cutter, a sheet cutter, or the like to have a shape such as a column shape, an elliptical column shape, a disk shape, or a die shape. Intermediate pellets are produced. The above-described cooling after extrusion can be performed by, for example, a water cooling method using a water tank, a method using a cooling drum, an air cooling method, or the like.

In order to further increase the degree of polymerization of the intermediate pellets thus obtained, solid phase polymerization is performed. It is preferable to crystallize a part of the polyester by heating before solid phase polymerization. By doing so, it is possible to prevent the pellets from sticking during solid phase polymerization. The crystallization temperature is preferably 100 to 180 ° C. As a crystallization method, crystallization may be performed in a vacuum tumbler, or crystallization may be performed by heating in an air circulation type heating apparatus. When heating in an air circulation heating device, the internal temperature is preferably 100 to 160 ° C. When heating using an air circulation type heating device, compared with crystallization using a vacuum tumbler, heat conduction is good, so the time required for crystallization can be shortened and the device is also inexpensive. The time required for crystallization is not particularly limited, but is usually about 30 minutes to 24 hours. It is also preferred to dry the pellets at a temperature below 100 ° C. prior to crystallization.

The temperature of solid phase polymerization is preferably 170 to 250 ° C. When the temperature of the solid phase polymerization is lower than 170 ° C., the time for the solid phase polymerization becomes long and the productivity may be lowered. The temperature of solid phase polymerization is more preferably 175 ° C. or higher, and further preferably 180 ° C. or higher. On the other hand, when the temperature of the solid phase polymerization exceeds 250 ° C., the pellets may be stuck. The temperature of the solid phase polymerization is more preferably 240 ° C. or lower, and further preferably 230 ° C. or lower. The time for solid phase polymerization is usually about 5 to 70 hours. Moreover, you may coexist the catalyst used by melt polymerization at the time of solid-phase polymerization.

Further, the solid phase polymerization is preferably performed under reduced pressure or in an inert gas such as nitrogen gas. Further, it is preferable to perform solid-state polymerization while moving the pellets by an appropriate method such as a rolling method or a gas fluidized bed method so that no sticking occurs between the pellets. The pressure when solid-state polymerization is performed under reduced pressure is preferably 1 kPa or less.

Thus, the polyester obtained by solid phase polymerization is suitably used as a raw material for extrusion molding, particularly extrusion blow molding.

As described above, the polyester obtained by performing melt polycondensation or further solid-phase polymerization may contain other additives as long as the effects of the present invention are not impaired. Colorants such as dyes and pigments, stabilizers such as ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, lubricants, plasticizers, inorganic fillers and the like. The content of these additives in the polyester is preferably 10% by mass or less, and more preferably 5% by mass or less.

The intrinsic viscosity of the polyester obtained by solid phase polymerization is preferably 0.9 dl / g or more. Thereby, the drawdown resistance at the time of carrying out extrusion blow molding of the said polyester further improves. The intrinsic viscosity is more preferably 1.0 dl / g or more, and still more preferably 1.05 dl / g or more. On the other hand, the intrinsic viscosity is preferably 1.5 dl / g or less.

Various molded products can be obtained by melt-molding the obtained polyester. A molded product obtained by melt-molding the polyester of the present invention has an appropriate hardness and excellent chemical resistance, particularly resistance to high-concentration alcohol. Moreover, the molded article has good impact resistance even after a long period of time, and is excellent in low-temperature impact resistance. Furthermore, the molded product has an appropriate hardness, is hardly scratched on the surface, and has a glass-like texture and appearance. Further, the melt molded product can be further subjected to secondary processing to obtain a molded product.

The molding method is not particularly limited, but an extrusion molding method is preferably employed. A molded product obtained by extrusion molding of the polyester is a preferred embodiment of the present invention. A film or sheet obtained by extruding the polyester is a more preferred embodiment of the present invention. A container formed by extrusion molding the polyester is also a more preferred embodiment of the present invention. The polyester is suitable for extrusion molding because of its high viscosity during melt molding. The temperature of the resin composition at the time of extrusion molding is preferably a temperature within the range of (polyester melting point + 10 ° C.) to (polyester melting point + 70 ° C.), and (polyester melting point + 10 ° C.) to (polyester melting point + 40). It is more preferable to set the temperature within the range of ° C. By extruding at a temperature relatively close to the melting point, drawdown can be suppressed.

For example, when a sheet or film is manufactured by extrusion molding such as T-die method or inflation method using the polyester, there is no generation of drawdown, neck-in, film sway, and unmelted fluff, and a high-quality sheet Or a film can be manufactured with high productivity. When secondary processing such as thermoforming is performed using the sheet or film thus obtained, when forming a deep-drawn molded product or a large molded product, By adjusting the temperature of the mold, the degree of crystallization of the molded product can be adjusted. Thickness and whitening are less likely to occur in the process of applying external force such as vacuum suction or compressed air, and the desired molding with good shaping properties Goods can be obtained. Such a thermoformed product formed by thermoforming a sheet or film, in particular, a container formed by thermoforming the sheet or film is a preferred embodiment of the present invention. Since the molded article has excellent impact resistance even at low temperatures and has an appropriate hardness, it is suitably used as an ice packaging container for iced coffee.

Of the extrusion molding, it is extrusion blow molding that is particularly suitable for using the polyester. The method of extrusion blow molding is not particularly limited, and can be performed in the same manner as conventionally known extrusion blow molding methods. For example, the polyester is melt-extruded to form a cylindrical parison, which is sandwiched between blow molds while the parison is in a softened state, and a gas such as air is blown to conform the parison to the mold cavity shape. It can be performed by a method of expanding into a predetermined hollow shape. When the polyester is used, the extruded parison has good drawdown resistance, and a hollow molded product can be produced with high productivity.

Thus, a molded product obtained by extrusion blow molding of the polyester is also a preferred embodiment of the present invention. The molded article has an appropriate hardness, is excellent in chemical resistance, particularly resistance to a high concentration of alcohol, and has good impact resistance even after a long period of time. Moreover, the said molded article has moderate hardness, the surface is hard to be damaged, and has a texture and external appearance like glass. Therefore, the molded product can be used for various applications. A container made of the molded product is a preferred embodiment of the molded product. Such a container is suitably used as a container for cosmetics or oil. Moreover, it can also be set as the molded article which has the laminated structure of the said polyester, another thermoplastic resin, etc.

Hereinafter, the second polyester having an aspect different from that of the first polyester will be described. The second polyester mainly comprises dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, and diol units mainly composed of linear aliphatic diol units, isosorbide units and units derived from bisphenol A ethylene oxide adducts, The content of isosorbide units relative to the total of diol units is 1 to 25 mol%, and the content of units derived from bisphenol A ethylene oxide adduct is 0.1 to 20 mol%. The second polyester has excellent chemical resistance. In addition, neck-in is unlikely to occur when the polyester is extruded to produce a sheet or film. Therefore, it is possible to perform extrusion molding at high speed, and productivity is improved.

As the linear aliphatic diol unit in the second polyester, those described above as the linear aliphatic diol unit contained in the first polyester are preferable. The content of the linear aliphatic diol unit in the second polyester is preferably 55 mol% or more with respect to the total of diol units in the polyester. Thereby, when manufacturing 2nd polyester, since solid state polymerization can be performed at high temperature, while improving productivity, a molded article with a more favorable color tone comes to be obtained. As for content of a linear aliphatic diol unit, 80 mol% or more is more preferable. On the other hand, the content is 98.9 mol% or less. Thereby, in addition to improving the drawdown resistance of the obtained molded product, coloring of the resin during polyester production is also suppressed. The content of the linear aliphatic diol unit is preferably 95 mol% or less.

The content of isosorbide units in the second polyester is 1 mol% or more based on the total of diol units in the polyester. When the content is 1 mol% or more, the glass transition point of the polyester is increased and the enthalpy relaxation rate is decreased, so that the obtained molded product has excellent impact resistance after a long period of time. Become. Moreover, since the said molded article becomes moderately hard, while being hard to get a damage | wound on the surface, the texture and external appearance like glass are obtained. The content of isosorbide units is preferably 3 mol% or more. On the other hand, the content of isosorbide units is 25 mol% or less. Thereby, the drawdown resistance at the time of extruding the said polyester improves. The content of isosorbide units is preferably 15 mol% or less, and more preferably 10 mol% or less.

The second polyester contains a unit derived from a bisphenol A ethylene oxide adduct. Thereby, the drawdown resistance at the time of extruding the said polyester improves. Moreover, the neck-in at the time of manufacturing the film and sheet | seat with the said polyester is suppressed. The content of the unit derived from the bisphenol A ethylene oxide adduct in the second polyester is 0.1 mol% or more, preferably 0.5 mol% or more, based on the total of diol units in the polyester, 2 mol% or more is more preferable. On the other hand, the content is 20 mol% or less. When the content is within the above range, the melt viscosity of the polyester becomes appropriate, and the impact resistance of the obtained molded product is improved. The content is preferably 10 mol% or less, and more preferably 8 mol% or less.

The total content of the linear aliphatic diol unit, isosorbide unit and unit derived from the bisphenol A ethylene oxide adduct in the second polyester is usually 80 mol% or more based on the total of diol units in the polyester. Yes, 90 mol% or more is preferable, and 95 mol% or more is more preferable.

The total content of aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units and units derived from bisphenol A ethylene oxide adduct in the second polyester is based on the total of all structural units in the polyester, 80 mol% or more is preferable. When the said content is 80 mol% or more, when the said polyester is manufactured by solid phase polymerization, since the sticking by softening of resin is suppressed, a polymerization degree can be raised easily. The content is more preferably 90 mol% or more, and still more preferably 95 mol% or more.

The configuration and physical properties of the second polyester are preferably the same as those of the first polyester described above, except that the diol unit is configured as described above.

The second polyester can be produced in the same manner as the first polyester. And various molded articles can be obtained by melt-molding the obtained polyester. As the molding method at this time, the method described above as the first polyester molding method is adopted, and among them, the T-die method and the inflation method are preferable. A molded product formed by extruding the second polyester is a preferred embodiment of the polyester, and a film or a sheet comprising the container from the molded product and the molded product is a more preferred embodiment. A thermoformed product formed by thermoforming the film or sheet is also a more preferable embodiment of the second polyester.

Hereinafter, a third polyester that is different from the first polyester and the second polyester will be described. The third polyester mainly comprises an aromatic dicarboxylic acid unit, a dicarboxylic acid unit mainly composed of a dimer acid unit or a hydrogenated dimer acid unit, and a diol unit mainly composed of a linear aliphatic diol unit and an isosorbide unit, The total content of dimer acid units and hydrogenated dimer acid units with respect to the total of the dicarboxylic acid units is 0.1 to 20 mol%, and the content of isosorbide units with respect to the total of the diol units is 1 to 25 mol%. Is. The third polyester is also excellent in chemical resistance. In addition, neck-in is unlikely to occur when the polyester is extruded to produce a sheet or film. Therefore, it is possible to perform extrusion molding at high speed, and productivity is improved.

As the aromatic dicarboxylic acid unit in the third polyester, those described above as the aromatic dicarboxylic acid unit contained in the first polyester are preferable. The content of the aromatic dicarboxylic acid unit in the third polyester is usually 80 mol% or more, preferably 90 mol% or more, preferably 95 mol% or more based on the total of the dicarboxylic acid units in the polyester. More preferred.

The third polyester contains dimer acid units or hydrogenated dimer acid units. Thereby, the drawdown resistance at the time of extruding the said polyester improves. Moreover, the neck-in at the time of manufacturing the film and sheet | seat with the said polyester is suppressed. The total content of dimer acid units and hydrogenated dimer acid units in the polyester is 0.1 mol% or more, preferably 0.4 mol% or more, based on the total of dicarboxylic acid units in the polyester. On the other hand, the content of the unit is 20 mol% or less. When the content is within the above range, the melt viscosity of the polyester becomes appropriate, and the impact resistance of the obtained molded product is improved. The content is preferably 10 mol% or less, and more preferably 8 mol% or less.

The total content of aromatic dicarboxylic acid units, dimer acid units and hydrogenated dimer acid units in the third polyester is usually 80 mol% or more based on the total of dicarboxylic acid units in the polyester, 90 The mol% or more is preferable, and 95 mol% or more is more preferable.

As the linear aliphatic diol unit in the third polyester, those described above as the linear aliphatic diol unit contained in the first polyester are preferable. The content of the linear aliphatic diol unit in the third polyester is preferably 75 mol% or more with respect to the total of diol units in the polyester. Thereby, when manufacturing 3rd polyester, since solid phase polymerization can be performed at high temperature, while improving productivity, a molded article with a more favorable color tone comes to be obtained. The content of the linear aliphatic diol unit is more preferably 80 mol% or more, further preferably 85 mol% or more, and particularly preferably 90 mol% or more. On the other hand, the content of the linear aliphatic diol unit is 99 mol% or less. Thereby, the draw-down resistance of the obtained molded product is improved and the transparency is also improved. The content of the linear aliphatic diol unit is preferably 97 mol% or less.

The content of isosorbide units in the third polyester is 1 mol% or more based on the total of diol units in the polyester. When the content is 1 mol% or more, the glass transition point of the polyester is increased and the enthalpy relaxation rate is decreased, so that the obtained molded product has excellent impact resistance after a long period of time. Become. Moreover, since the said molded article becomes moderately hard, while being hard to get a damage | wound on the surface, the texture and external appearance like glass are obtained. The content of isosorbide units is preferably 3 mol% or more. On the other hand, the content of isosorbide units is 25 mol% or less. Thereby, the drawdown resistance at the time of extruding the said polyester improves. The content of isosorbide units is preferably 15 mol% or less, and more preferably 10 mol% or less.

The total content of linear aliphatic diol units and isosorbide units in the third polyester is usually 80 mol% or more, preferably 90 mol% or more, based on the total of diol units in the polyester, 95 Mole% or more is more preferable.

The total content of aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units, dimer acid units and hydrogenated dimer acid units in the third polyester is based on the total of all structural units in the polyester, 80 mol% or more is preferable. When the said content is 80 mol% or more, when the said polyester is manufactured by solid phase polymerization, since the sticking by softening of resin is suppressed, a polymerization degree can be raised easily. The content is more preferably 90 mol% or more, and still more preferably 95 mol% or more.

The configuration and physical properties of the third polyester are preferably the same as those of the above-described first polyester except that the dicarboxylic acid unit and the diol unit are configured as described above.

The third polyester can be produced in the same manner as the first polyester. And various molded articles can be obtained by melt-molding the obtained polyester. As the molding method at this time, the method described above as the first polyester molding method is adopted, and among them, the T-die method and the inflation method are preferable. A molded product formed by extruding the third polyester is a preferred embodiment of the polyester, and a film or sheet comprising a container and the molded product from the molded product is a more preferred embodiment. A thermoformed product formed by thermoforming the film or sheet is also a more preferable embodiment of the third polyester.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

(1) Intrinsic viscosity (IV)
The intrinsic viscosity of the polyester after the melt polymerization and the polyester after the solid phase polymerization were measured at a temperature of 30 ° C. using an equal mass mixture of phenol and 1,1,2,2-tetrachloroethane as a solvent.

(2) Melting point (Tm), glass transition temperature (Tg) and melting enthalpy (ΔHm)
The melting point (Tm), melting enthalpy (ΔHm) and glass transition temperature (Tg) of the polyester after melt polymerization or solid phase polymerization were measured using a differential scanning calorimeter (TA Q2000 manufactured by TA Instruments). The melting point and melting enthalpy were determined by raising the temperature from 30 ° C. to 280 ° C. at a rate of temperature rise of 10 ° C./min. The melting peak at this time was defined as the melting point. Further, when the melt enthalpy of the polyester after melt polymerization was 3 J / g or more, it was judged that there was crystallinity (A), and when it was less than 3 J / g, it was judged that there was no crystallinity (B). The glass transition temperature (Tg) was raised from 30 ° C. to 280 ° C. at a temperature rising rate of 10 ° C./min, rapidly cooled to 30 ° C. at −50 ° C./min, and then increased again at a temperature rising rate of 10 ° C./min. It was calculated from the data when warmed.

(3) Low temperature IZOD impact strength The pellets after melt polymerization were vacuum-dried overnight at 70 ° C, and then a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was prepared by injection molding, and 10 samples were each notched. Went. After storing the test piece in a freezer at −20 ° C. for 24 hours, the IZOD impact strength was measured at a lifting angle of 150 degrees using a hammer with a nominal pendulum energy of 0.5 J immediately after taking out the test piece from the freezer. The average value of 10 test results for each sample was defined as low temperature IZOD impact strength, and impact resistance at low temperature was evaluated.

(4) Drop test After putting water (water temperature 20-25 ° C) into the bottle immediately after molding so that the total weight is 263 g ± 0.5 g, it is passed through a vertically installed cylinder of 10 cm in diameter, From 125 cm in length, it was dropped alternately on a horizontal concrete surface and a concrete surface inclined 45 degrees. The number of cycles until the bottle was cracked or cracked (the bottle was dropped twice in total, once on the horizontal surface and once on the 45 ° slope) was measured. Up to 20 cycles were repeated. A drop test of five bottles was performed per composition, and the average value was defined as the bottle drop strength. Further, the molded bottle was stored in a thermostat at 50 ° C. and 6% RH for 100 hours and subjected to an acceleration test, and then a drop test was performed by the above method to determine the drop strength of the bottle.

(5) Evaluation of chemical resistance A sample (3 cm long and 3 cm wide) was cut out from the body of the molded transparent bottle, immersed in a 50% aqueous ethanol solution at 50 ° C., and stored for 7 days. The haze value (%) of the sample before and after immersion was measured, and the increase in haze value after immersion was less than 5%, and the case where the haze value was 5% or more was evaluated as B (bad).

(6) Rockwell hardness The pellets after solid-phase polymerization were dried at 120 ° C. and the pellets after melt polymerization were dried overnight at 70 ° C., respectively, and then a dumbbell-shaped test piece (ISO20753 A1 type) was formed by injection molding. A sample obtained by cutting out the gate side grip (length: 3 cm, width: 2 cm, thickness: 4 mm) was used as a sample. Using a hardness tester Rockwell 3R (manufactured by Imai Seiki), Rockwell hardness was measured on an R scale. At room temperature, each sample was measured five times, and the average value was defined as Rockwell hardness.

(7) Inflation moldability The pellet after solid phase polymerization was dried to a moisture content of 50 ppm or less by a dehumidifying dryer. The pellets are put into a hopper of an air-cooled inflation film forming machine having a screw with a diameter of 20 mm and a compression ratio of 2.5, and a die with an outer diameter of 20 mm. The extrusion temperature is 270 ° C. and the blow ratio (frost line diameter / die outer diameter) is 1. A film having a thickness of 50 μm was formed under two conditions of .5 or 2.0. Inflation moldability was evaluated with A being able to be molded at both blow ratios of 1.5 and 2.0, and B being unable to be molded at a blow ratio of 2.0 but being able to be molded at a blow ratio of 1.5. . If molding is possible with a high blow ratio, it can be said that inflation moldability is good.

(8) Draw-down resistance When producing a transparent bottle, the length of the parison (target 20 cm) obtained 15 seconds after starting the discharge of the resin composition from the die outlet is measured to reduce the draw-down resistance. Evaluation was made according to the following criteria.
A: 15 cm or more and 21 cm or less B: Less than 15 cm C: More than 21 cm

Example 1
(1) Melt polycondensation 100 parts by mass of terephthalic acid (TA), 40.3 parts by mass of ethylene glycol (EG), 5.9 parts by mass of 90% by mass isosorbide aqueous solution (5.3 parts by mass as isosorbide (ISB)), 1 , 4-cyclohexanedimethanol [CHDM, mixing ratio of cis isomer to trans isomer (cis isomer / trans isomer) is 30/70] 2.6 parts by mass, germanium dioxide (GeO ₂ ) 0.017 parts by mass, phosphorous acid A slurry composed of 0.012 parts by mass and 0.012 parts by mass of cobalt acetate tetrahydrate is prepared, heated to a temperature of 250 ° C. under pressure (gauge pressure of 0.25 MPa), and subjected to an esterification reaction to form an oligomer. Manufactured. The obtained oligomer was transferred to a polycondensation tank and subjected to melt polycondensation at 260 ° C. to 280 ° C. under 0.1 kPa for 150 minutes to produce a polyester having an intrinsic viscosity of 0.71 dL / g. The obtained polyester was extruded into a strand form from a nozzle and cooled with water, and then cut into a cylindrical shape (diameter: about 2.5 mm, length: about 2.5 mm) to obtain an amorphous pellet of polyester. The ratio of the monomer components constituting the copolymerized polyester was confirmed by ¹ H-NMR spectrum (apparatus: “JNM-GX-500 type” manufactured by JEOL Ltd., solvent: deuterated trifluoroacetic acid). Unit: EG unit: ISB unit: CHDM unit: diethylene glycol (DEG) unit = 50.0: 45.0: 2.5: 1.5: 1.0 (molar ratio). The carboxyl group content was 30 μmol / g. The melting point (Tm) was 238 ° C., and the glass transition temperature (Tg) was 86 ° C. The Rockwell hardness was HHR116. The low temperature IZOD impact strength was 3.1 kJ / m ² .

Examples 2 to 7, Comparative Examples 1 to 3
Amorphous pellets were produced and evaluated in the same manner as in Example 1 except that the amounts of raw material dicarboxylic acid and diol were changed as shown in Table 1. The results are summarized in Tables 2 and 3.

Example 8
(1) Precrystallization of amorphous pellets The polyester amorphous pellets obtained in Example 1 were put into a rolling vacuum solid-phase polymerization apparatus, and precrystallization was performed at 120 ° C for 5 hours under 0.1 kPa. It was.

(2) Solid phase polymerization After the preliminary crystallization, the temperature was increased and solid phase polymerization was performed at 190 to 200 ° C. under 0.1 kPa for 100 hours to obtain crystal pellets. The intrinsic viscosity of the obtained copolyester was 1.1 dL / g. The ratio of the monomer component of the copolyester by ¹ H-NMR spectrum is as follows: TA unit: EG unit: ISB unit: CHDM unit: DEG = 50.0: 45.0: 2.5: 1.5: 1 0.0 (molar ratio). The melting point (Tm) was 235 ° C., and the glass transition temperature (Tg) was 84 ° C. The Rockwell hardness was HHR116.

(3) Production of bottles After the obtained pellets were dried at 120 ° C. for 24 hours using a dehumidifying dryer, the length was 14. A transparent bottle (27 g) having a size of 5 cm and a volume of 220 mL was formed. At this time, the cylinder temperature was graded from 280 ° C. to 240 ° C., the die temperature was 240 to 250 ° C., the molding cycle was 10 seconds, the screw rotation speed was 24 rpm, and the mold temperature was 20 ° C. The transparent bottle obtained had good chemical resistance. When the drop strength of the obtained bottle was examined, the bottle drop strength immediately after molding was 15, and the bottle drop strength after the acceleration test was 6. Further, when the draw-down resistance of the obtained crystal pellet was measured, the evaluation was “A”.

Examples 9-12, 14 and 15
Crystal pellets and transparent bottles were produced and evaluated in the same manner as in Example 8 except that amorphous pellets of polyester shown in Table 1 were used as raw materials. Furthermore, the inflation moldability of the crystal pellet obtained in Example 9 was evaluated. The results are summarized in Tables 2 and 3. Moreover, when the draw-down resistance of the crystal pellets obtained in Examples 9, 14, and 15 was measured, all the evaluations were “A”.

Example 13
Amorphous pellets were produced and crystallinity was evaluated in the same manner as in Example 1 except that the types and amounts of raw materials dicarboxylic acid and diol were changed as shown in Table 1. Moreover, production of crystal pellets and transparent bottles and evaluation thereof were performed in the same manner as in Example 8 except that the obtained crystal pellets were used as raw materials. The results are shown in Tables 2 and 3.

Example 16
100 parts by weight of terephthalic acid, 41.4 parts by weight of ethylene glycol, 5.9 parts by weight of 90% by weight isosorbide aqueous solution (5.3 parts by weight as isosorbide), 1.3 parts by weight of bisphenol A ethylene oxide 2-mol adduct (EOBPA), Amorphous pellets are produced in the same manner as in Example 1, except that a slurry composed of 0.017 parts by mass of germanium dioxide, 0.012 parts by mass of phosphorous acid and 0.012 parts by mass of cobalt acetate tetrahydrate is used. Then, crystallinity was evaluated. Further, crystal pellets were obtained in the same manner as in Example 8 except that the obtained amorphous pellets were used. The intrinsic viscosity of the obtained copolyester was 1.1 dL / g. The ratio of the monomer component of the copolyester by ¹ H-NMR spectrum is as follows: TA unit: EG unit: ISB unit: EOBPA unit: DEG unit = 50.0: 46.15: 2.5: 0.35: 1.0 (molar ratio). The melting point (Tm) was 238 ° C., and the glass transition temperature (Tg) was 84 ° C. The Rockwell hardness was HHR116. In addition, a transparent bottle was produced and evaluated in the same manner as in Example 8 except that the obtained crystal pellet was used as a raw material. The results are summarized in Tables 2 and 3. Further, when the draw-down resistance of the obtained crystal pellet was measured, the evaluation was “A”.

Examples 17 to 20, 22, 23, Comparative Examples 4 to 10
Amorphous pellets, crystal pellets and transparent bottles were prepared and evaluated in the same manner as in Example 16 except that the types and amounts of raw materials dicarboxylic acid and diol were changed as shown in Table 1. Further, the inflation moldability of the crystal pellet obtained in Example 18 was evaluated. The results are summarized in Tables 2 and 3. In addition, when the drawdown resistance of the crystal pellets obtained in Examples 17, 19, 20, and 22 was measured, all the evaluations were “A”.

Examples 21, 24, 25
Except having changed the kind and preparation amount of raw material dicarboxylic acid and diol as shown in Table 1, and having further added the polyfunctional compound shown in Table 1 in the raw material slurry, it carried out similarly to Example 16. Amorphous pellets, crystal pellets and transparent bottles were produced and evaluated. Furthermore, the blow moldability of the crystal pellet was evaluated. The results are summarized in Tables 2 and 3. Moreover, when the draw-down resistance of the crystal pellet obtained in Examples 21 and 24 was measured, all evaluations were “A”.

Claims (13)

1. A dicarboxylic acid unit mainly composed of an aromatic dicarboxylic acid unit, and a diol unit mainly composed of a linear aliphatic diol unit, an isosorbide unit and a cyclohexanedimethanol unit,
   Polyester having a content of isosorbide units of 1 to 14 mol% and a content of cyclohexanedimethanol units of 1 to 9 mol% based on the total of the diol units.
2. The polyester according to claim 1, wherein the total content of the isosorbide unit and the cyclohexanedimethanol unit with respect to the total of the diol units is 15 mol% or less.
3. Furthermore, the polyfunctional compound unit derived from the polyfunctional compound having three or more carboxyl groups, hydroxyl groups and / or ester forming groups thereof is used in an amount of 0.00005 to 1 mol% based on the total of the structural units. The polyester according to claim 1 or 2, which is contained.
4. The polyester according to any one of claims 1 to 3, wherein the intrinsic viscosity of the polyester is 0.55 to 1.5 dl / g.
5. The polyester according to any one of claims 1 to 4, wherein the diol unit further contains 0.1 to 20 mol% of a unit derived from a bisphenol A ethylene oxide adduct based on a total of the diol units.
6. The dicarboxylic acid unit further contains a dimer acid unit or a hydrogenated dimer acid unit, and the total content of the dimer acid unit and the hydrogenated dimer acid unit is 0.1 to 20 mol relative to the total of the dicarboxylic acid units. The polyester according to claim 1, which is%.
7. A molded product obtained by extrusion molding the polyester according to any one of claims 1 to 6.
8. A film or sheet comprising the molded product according to claim 7.
9. A thermoformed product obtained by thermoforming the film or sheet according to claim 8.
10. A container comprising the molded product according to claim 7.
11. The method for producing a polyester according to claim 1 or 2, wherein the polycondensation is performed by melt-kneading an aromatic dicarboxylic acid, a linear aliphatic diol, isosorbide, and cyclohexanedimethanol.
12. A dicarboxylic acid unit mainly composed of an aromatic dicarboxylic acid unit, and a diol unit mainly composed of a linear aliphatic diol unit, an isosorbide unit and a unit derived from a bisphenol A ethylene oxide adduct,
    Polyester having a content of isosorbide units of 1 to 25 mol% and a content of units derived from bisphenol A ethylene oxide adduct of 0.1 to 20 mol% based on the total of the diol units.
13. It consists mainly of aromatic dicarboxylic acid units, dicarboxylic acid units mainly composed of dimer acid units or hydrogenated dimer acid units, and diol units mainly composed of linear aliphatic diol units and isosorbide units,
    The total content of dimer acid units and hydrogenated dimer acid units relative to the total of the dicarboxylic acid units is 0.1 to 20 mol%;
    Polyester having a content of isosorbide units of 1 to 25 mol% based on the total of the diol units.