JP7193345B2 - Polyester, method for producing same, and molded article made of same - Google Patents

Description

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

Polyesters such as polyethylene terephthalate are excellent in properties such as transparency, mechanical properties, gas barrier properties, and flavor barrier properties. Furthermore, polyester has little concern about residual monomers and harmful additives when formed into molded articles, and is excellent in sanitation and safety. Therefore, polyester has been widely used in recent years as a substitute for vinyl chloride, which has been used conventionally, as a hollow container for filling beverages, seasonings, oils, cosmetics, detergents, etc. .

As a molding method for manufacturing hollow molded articles made of polyester, melted plasticized resin is extruded through a die orifice as a cylindrical parison. There is known an extrusion blow molding method in which a fluid is blown to perform molding. Compared to the injection blow molding method, this method has a simpler process and does not require advanced technology for mold preparation and molding. Suitable for variety and small quantity production. Moreover, there is an advantage that it is possible to manufacture moldings having complex shapes such as thin, deep, large, and handles.

By the way, in addition to excellent properties such as chemical resistance and gas barrier properties, containers for cosmetics and oils are required to have excellent mechanical properties in order to prevent breakage due to impact such as dropping. be done. In addition, containers for cosmetics and the like are required to have appropriate hardness, have a scratch-resistant surface, and have a glass-like texture and appearance. In addition, ice packaging 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 frozen transport, It is required that it does not easily dent when drinking coffee.

However, unlike molded articles obtained by injection blow molding, molded articles obtained by extrusion molding general-purpose polyester are not oriented and crystallized. and mechanical properties such as hardness were insufficient.

A method of copolymerizing polyethylene terephthalate with other monomers is known as a method for improving the impact resistance of molded articles. In Patent Document 1, it is mainly composed of 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 pellets of a certain polyester (B) is described. Patent Literature 1 describes that a molded article obtained using such a resin composition has good chemical resistance, and the decrease in impact resistance after a long period of time is small. However, the molded article was still insufficient in chemical resistance and impact resistance after a long period of time. In addition, since the molded product is soft, the surface may be scratched or dented when picked up. In addition, when the molded article is used as a substitute for glass containers used for cosmetics, there is a problem because the texture and appearance when the container is soft is greatly different from that of the glass container when the container is soft.

Patent Document 2 describes a polyester resin containing 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. It is Patent Document 2 describes that the polyester resin is excellent in heat resistance, chemical resistance, impact resistance, transparency and moldability, and has a good appearance. However, the polyester resin has insufficient chemical resistance, especially durability against high-concentration alcohol. In addition, since the molded article obtained using the polyester resin is soft, there are problems as described above.

JP 2016-124966 A Japanese Patent Application Publication No. 2015-518916

The present invention has been made to solve the above problems, and has a moderate hardness, excellent chemical resistance, and good impact resistance even after a long period of time. An object of the present invention is to provide a polyester that can obtain a product and a method for producing the same.

The above problem is mainly composed of dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, and diol units mainly composed of linear aliphatic diol units, isosorbide units and cyclohexanedimethanol units, and isosorbide units relative to the total of the diol units. content is 1 to 14 mol % and the content of cyclohexanedimethanol units is 1 to 9 mol %.

In the polyester, the total content of isosorbide units and cyclohexanedimethanol units is preferably 15 mol % or less with respect to the total amount of diol units. The polyester further comprises a polyfunctional compound unit derived from a polyfunctional compound having 3 or more carboxyl groups, hydroxyl groups and/or their ester-forming groups, with respect to the total structural units, 0.00005 It is also preferable to contain up to 1 mol %. It is also preferred that the polyester has a limiting viscosity of 0.55 to 1.5 dl/g. It is also preferred that the diol units further contain units derived from bisphenol A ethylene oxide adducts 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 with respect to the total of the dicarboxylic acid units. % is also preferred.

A molded article obtained by extruding the above polyester is a preferred embodiment of the present invention. A more preferred embodiment of the present invention is a container comprising the molded article. A film or sheet made of the above molded article is also a more preferred embodiment of the present invention, and a thermoformed article obtained by thermoforming the above film or sheet is a further preferred embodiment.

A molded article obtained by thermoforming the above polyester is also a preferred embodiment of the present invention. A more preferred embodiment of the present invention is a container comprising the molded article.

The above object can also be solved by providing a method for producing the above polyester, wherein aromatic dicarboxylic acid, straight-chain aliphatic diol, isosorbide, and cyclohexanedimethanol are melt-kneaded to conduct polycondensation.

The above-mentioned problems are mainly composed of dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, and diol units mainly composed of units derived from linear aliphatic diol units, isosorbide units and bisphenol A ethylene oxide adducts, and the diol units The solution is also provided by providing a polyester having a content of isosorbide units of 1 to 25 mol % and a content of units derived from bisphenol A ethylene oxide adducts of 0.1 to 20 mol %, based on the total of . Further, the above-mentioned object is mainly composed of dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, 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 dicarboxylic acid units is 0.1 to 20 mol%, and the content of isosorbide units relative to the total diol units is 1 to 25 mol%. It is also solved by providing polyester.

Molded articles obtained using the polyester of the present invention have appropriate 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 is mainly composed of dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, and diol units mainly composed of linear aliphatic diol units, isosorbide units and cyclohexanedimethanol 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 called the 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'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, pamoic acid, anthracenedicarboxylic acid and the like. Among them, terephthalic acid unit, furandicarboxylic acid unit and isophthalic acid unit 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 units in the polyester is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, relative to the total dicarboxylic acid units in the polyester. .

It is preferable that the dicarboxylic acid units in the polyester further contain dimer acid (DA) units or hydrogenated dimer acid (H-DA) units, and among them, those having 36 carbon atoms or 44 carbon atoms are more preferable. The inclusion of dimer acid (DA) units or hydrogenated dimer acid (H-DA) units further improves drawdown resistance during extrusion molding of the polyester. 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 amount 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 resulting molded article is further improved. The content is more preferably 5 mol % or less, and even more preferably 2 mol % or less.

Linear aliphatic diol units in the polyester include ethylene glycol (EG) units, diethylene glycol (DEG) units, triethylene glycol units, 1,3-trimethylene glycol units, 1,4-butanediol units, 1, Examples include 5-pentanediol units, 1,6-hexanediol units, 1,9-nonanediol units, etc. Among them, ethylene glycol units and diethylene glycol units are preferred. These may be used alone or in combination of two or more. Usually, a polyester obtained by using ethylene glycol as a straight-chain aliphatic diol starting material contains 1 to 5 mol % of diethylene glycol units, which are a by-product of the polycondensation reaction, based on the total diol units.

The content of linear aliphatic diol units in the polyester is preferably 75 mol % or more with respect to the total diol units in the polyester. When the content is 75 mol% or more, solid phase polymerization can be performed at a high temperature when producing the polyester, so that productivity is improved and a molded product with a better color tone can be obtained. become. The linear aliphatic diol unit content is more preferably 80 mol % or more, still more preferably 85 mol % or more, and particularly preferably 86 mol % or more. On the other hand, the content of linear aliphatic diol units is 98 mol % or less. When the content is 98 mol % or less, the impact resistance of the obtained molded article is improved, and the transparency is also improved. The linear aliphatic diol unit content is preferably 96 mol % or less, more preferably 93 mol % or less, and even more preferably 90 mol % or less.

The content of isosorbide (ISB) units in the polyester is 1 mol % or more based on the total diol units in the polyester. When the content is 1 mol% or more, the glass transition point of the polyester increases and the enthalpy relaxation rate slows down, so that the resulting molded article has excellent impact resistance even after a long period of time. Become. In addition, since the molded article is moderately hardened, the surface is less likely to be scratched, and a glass-like texture and appearance can be obtained. The isosorbide unit content is preferably 2 mol % or more, more preferably 3 mol % or more, and even more 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 obtained molded article has good color tone. In addition, drawdown resistance is improved when the polyester is extruded. The isosorbide unit content is preferably 12 mol % or less.

The cyclohexanedimethanol (CHDM) unit in the polyester is at least one divalent unit selected from 1,2-cyclohexanedimethanol units, 1,3-cyclohexanedimethanol units and 1,4-cyclohexanedimethanol units. I wish I had. Among them, 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 obtained molded article. Preferably the units are 1,4-cyclohexanedimethanol units.

Cyclohexanedimethanol units exist in cis isomers and trans isomers, but the ratio of cis isomers to trans isomers in the cyclohexanedimethanol units in the polyester is not particularly limited. Among them, in the cyclohexanedimethanol unit in the polyester, the ratio of cis isomer: trans isomer is in the range of 0: 100 to 50: 50, the polyester is easy to be crystalline, during solid phase polymerization It is preferable from the viewpoint that agglutination between pellets hardly occurs and the impact resistance of the resulting molded product is further improved.

The content of cyclohexanedimethanol units in the polyester is 1 mol % or more with respect to the total diol units in the polyester. When the content is 1 mol % or more, the impact resistance at room temperature and low temperature of the obtained molded article is improved, and the transparency is also improved. The content is preferably 2 mol % or more, more preferably 4 mol % or more, and even more 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, especially the durability against high-concentration alcohol, is improved. In addition, since the molded article is moderately hardened, the surface is less likely to be scratched, and a glass-like texture and appearance can be obtained.

The total content of isosorbide units and cyclohexanedimethanol units is preferably 15 mol % or less with respect to the total of diol units in the polyester. When the content is 15 mol % or less, the polyester has appropriate crystallinity, so that the mechanical properties of the obtained molded article are further improved. In addition, by subjecting a polyester having a total content of isosorbide units and cyclohexanedimethanol units of 15 mol% or less to a pre-crystallization treatment, it becomes possible to dry at a temperature above the glass transition temperature, and the water content can be reduced. A decrease in intrinsic viscosity due to hydrolysis during molding can be suppressed. More preferably, the total content is 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 is Preferably, 95 mol % or more is more preferable.

It is preferable that the diol units in the polyester further contain units derived from bisphenol A ethylene oxide adduct (EOBPA) in an amount of 0.1 to 20 mol % based on the total diol units in the polyester. This further improves drawdown resistance during extrusion molding of the polyester. The bisphenol A ethylene oxide adduct is obtained by adding at least one ethylene oxide to each hydroxyl group of bisphenol A. The amount of ethylene oxide to be added is usually 2.0 to 4.0 mol per 1 mol of bisphenol A.

The content of the units derived from the bisphenol A ethylene oxide adduct in the polyester is preferably 0.1 mol % or more with respect to the total diol units in the polyester. When the content is 0.1 mol % or more, the above effects can be obtained. The content of the former is more preferably 0.5 mol % or more, more 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 moderate, and the impact resistance of the obtained molded article is further improved. The content is more preferably 10 mol % or less, and even 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 relative to the sum of all structural units in the polyester. When the content is 80 mol % or more, sticking due to softening of the resin is suppressed when the polyester is produced by solid phase polymerization, so that the degree of polymerization can be easily increased. The content is more preferably 90 mol % or more, more preferably 95 mol % or more.

The polyester optionally contains aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units, cyclohexanedimethanol units, dimer acid units, hydrogenated dimer acid units, and units other than units derived from bisphenol A ethylene oxide adducts. may contain other comonomer units.

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

Bifunctional compound units are mainly used as other comonomer units. The content of the other bifunctional compound units (the total when having two or more types of units) is preferably 20 mol% or less with respect to the total of all structural units constituting the polyester, and 10 It is more preferably mol % or less, and even more preferably 5 mol % or less. Other bifunctional 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 is other than units derived from ethylene oxide adducts. If other bifunctional compound units are dicarboxylic acid units, diol units, and hydroxycarboxylic acid units, they are aliphatic bifunctional compound units, alicyclic bifunctional compound units, and aromatic bifunctional compound units. may be either.

Aliphatic dicarboxylic acid units other than dimer acid units and hydrogenated dimer acid units, which are used as other comonomer units, include, for example, 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 and itaconic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, decahydronaphthalenedicarboxylic acid (decalindicarboxylic acid), tetralindicarboxylic acid, cyclobutenedicarboxylic acid, tricyclodecanedicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, etc. and units derived from aliphatic dicarboxylic acids or ester-forming derivatives thereof.

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. Units derived from aliphatic diols can be mentioned.

The polyester contains other comonomer units such as an aromatic dicarboxylic acid unit, a linear aliphatic diol unit, an isosorbide unit, a cyclohexanedimethanol unit, a dimer acid unit, and a hydrogenated dimer, as long as they do not impair the effects of the present invention. In addition to the acid units, the units derived from the bisphenol A ethylene oxide adduct and the other bifunctional compound units described above, other polyfunctional compound units may be included. Other polyfunctional compound units are polyfunctional compound units derived from polyfunctional compounds having 3 or more carboxyl groups, hydroxyl groups and/or their ester-forming groups. When the polyester contains such polyfunctional compound units, the inflation moldability is improved. The content of other polyfunctional compound units (the total when having two or more types of units) is preferably 0.00005 to 1 mol% with respect to the total structural units of the polyester, and 0 It is more preferably 0.00015 to 0.8 mol %, even more 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 polyvalent carboxylic acid units derived from trimellitic acid, trimesic acid, etc.; polyhydric alcohol units derived from trimethylolpropane, glycerin, etc.; preferable.

As the unit derived from the polyvalent ester, a carboxylic acid ester of a polyol having a valence of 3 or more, wherein the carboxylic acid has a hindered phenol group, is preferably derived from the polyvalent ester. Here, the units derived from polyvalent ester are those contained in the polyester by condensation polymerization of the polyvalent ester together with aromatic dicarboxylic acid, linear aliphatic diol, isosorbide and cyclohexanedimethanol. be. The polyol unit of the polyhydric ester and the carboxylic acid unit having a hindered phenol group are contained in the polyester by transesterification. The polyol unit is contained in the main chain, branched chain or end of the polyester. A part of the polyol units becomes a cross-linking point and acts as a cross-linking agent. On the other hand, some of the carboxylic acid units having hindered phenol groups are contained at the terminals of the polyester, and some of them are contained in the polyester together with the polyol units in a state of being bound to the polyol units. As described above, when the polyvalent ester-derived units are 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 improves. The polyvalent ester is preferably a carboxylic acid ester of a polyol having a valence of 3 or more and 5 or less. 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- di-tert-butyl-4-hydroxyphenyl)propanoyloxy]ethyl]hexahydro-1,3,5-triazine-2,4,6-trione and the like.

In addition, if necessary, the polyester comprises at least one monofunctional compound selected from monocarboxylic acids other than carboxylic acids having hindered phenol groups, monoalcohols, and ester-forming derivatives thereof as other comonomer units. It may have other monofunctional compound units from which it is derived. Other monofunctional compound units function as capping compound units to cap molecular chain end groups and/or branched chain end groups in the polyester to prevent excessive cross-linking and gel formation in the polyester. . When the polyester has such other monofunctional compound units, the content of other monofunctional compound units (the total if it has two or more units) is the total structural unit of the polyester. It is preferably 1 mol % or less, more preferably 0.5 mol % or less, relative to the total. If the content of the other monofunctional compound unit in the polyester exceeds 1 mol %, the polymerization rate during the production of the polyester is slowed down, and the productivity tends to be lowered. 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. .

The intrinsic viscosity of the polyester is preferably 0.55 dl/g or more, more preferably 0.65 dl/g or more, from the viewpoint of further improving the strength, impact resistance, melt moldability, and production stability of the resulting molded article. 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 even more preferably 1.3 dl/g or less.

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

From the viewpoint of improving drawdown resistance during extrusion blow molding, the melting point of the polyester is preferably 226° C. or higher. However, when the polyester contains the polyfunctional compound unit, it preferably has a melting point of 215° C. or higher. By containing the polyfunctional compound unit, the number of cross-linking points increases and the flow of the polyester is suppressed. Therefore, if the melting point is 215 ° C. or higher, the drawdown resistance at the time of extrusion blow molding is improved. . On the other hand, in extrusion blow molding, the melting point of the polyester is preferably 260° C. or lower from the viewpoint of keeping the cylinder temperature low and improving the color tone of the molded product.

As a method for producing the polyester, a method of melt-kneading an aromatic dicarboxylic acid, a linear aliphatic diol, cyclohexanedimethanol and isosorbide to conduct condensation polymerization is preferred.

The method of polycondensation by melt-kneading aromatic dicarboxylic acid, linear aliphatic diol, cyclohexanedimethanol and isosorbide is not particularly limited, but aromatic dicarboxylic acid or its ester-forming derivative, linear aliphatic diol, Cyclohexanedimethanol, isosorbide, and, if necessary, dimer acid, hydrogenated dimer acid, bisphenol A ethylene oxide adduct, polyvalent ester, and other comonomers were used as raw materials to conduct an esterification reaction or a transesterification reaction. A method of melt-polycondensing the obtained polyester oligomer is mentioned later. The polyvalent ester may be added before the esterification reaction or transesterification reaction, or may be added after these reactions. Raw materials other than the polyvalent ester can also be appropriately added before the esterification reaction or the transesterification reaction, or can be added after these reactions.

In the above-described esterification reaction or transesterification reaction, the above-described raw materials, a polymerization catalyst and, if necessary, additives such as a coloring inhibitor are charged into a reactor, and the reaction is performed under pressure of about 0.5 MPa or less in absolute pressure or under normal pressure. , 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 the transesterification reaction is performed by adding additives such as the above-described raw materials, polycondensation catalysts and anti-coloring agents to the obtained polyester oligomer, if necessary, to achieve a pressure of 1 kPa or less. It is preferable to carry 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 lower than 260°C, the polymerization activity of the polymerization catalyst is low, and there is a possibility that a polyester having a target polymerization degree cannot be obtained. On the other hand, when the reaction temperature of the melt polymerization reaction exceeds 290° C., the decomposition reaction tends to proceed, 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 carried out using, for example, a tank-type batch-type polycondensation apparatus, a continuous polycondensation apparatus comprising a biaxially rotating horizontal reactor, or the like.

As the polymerization catalyst used for the polycondensation, any catalyst that can be used for the production of polyester can be selected. Germanium, titanium, zirconium, hafnium, antimony, tin, magnesium, calcium, zinc, aluminum, Compounds containing metallic elements such as cobalt, lead, cesium, manganese, lithium, potassium, sodium, copper, barium, cadmium are preferred. Among them, compounds containing germanium element, antimony element and titanium element are preferable. As compounds containing antimony elements, antimony trioxide, antimony chloride, antimony acetate, etc. are used. As compounds containing germanium elements, germanium dioxide, germanium tetrachloride, germanium tetraethoxide, etc. are used. Tetraisopropyl titanate, tetrabutyl titanate and the like are used as the containing compound. Composite particles of hydrotalcite and titanium dioxide may also 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 weight based on the weight of the dicarboxylic acid component.

When an anti-coloring agent is used in the polycondensation, for example, a phosphoric acid compound such as phosphorous acid or an ester thereof can be used. These may be used alone or in combination of two or more. good. Examples of phosphoric acid compounds include phosphorous acid, phosphites, 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 sum of the dicarboxylic acid component and the diester component. Also, 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 within the range of 100 to 1000 ppm with respect to the total of the dicarboxylic acid component and the diester component. is more preferable.

In the polycondensation, an aromatic dicarboxylic acid ester may be used to form aromatic dicarboxylic acid units. The alcohol portion of the aromatic dicarboxylic acid ester is not particularly limited, and includes monools such as methanol and ethanol; polyols such as ethylene glycol, cyclohexanedimethanol, and bisphenol A ethylene oxide adducts, which are the constituent units of the polyester. be done.

Monoesters or diesters of linear aliphatic diols may be used in the polycondensation to form linear aliphatic diol units. The carboxylic acid moiety of the carboxylic acid ester is not particularly limited, and includes 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. As a result, 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 period of time, thereby improving productivity. The intrinsic viscosity is more preferably 0.55 dl/g or more, 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, in terms of easy removal of the polyester from the reactor and suppression of coloration due to thermal deterioration, 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 preferable to further subject the polyester obtained by melt polycondensation to solid phase polymerization. The solid phase polymerization will be described below.

The polyester obtained as described above is extruded into a shape such as a strand or sheet, cooled, and then cut by a strand cutter or sheet cutter to form a cylindrical shape, an elliptical columnar shape, a disk shape, a die shape, or the like. Produce intermediate pellets. The cooling after the extrusion described above can be performed, for example, by 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 carried out. It is preferable to preliminarily crystallize a part of the polyester by heating before solid phase polymerization. By doing so, sticking of the pellets during solid-phase polymerization can be prevented. The temperature of crystallization is preferably 100-180°C. As a crystallization method, crystallization may be performed in a vacuum tumbler, or may be performed by heating in an air circulation type heating apparatus. When heating in an air circulation type heating device, the internal temperature is preferably 100 to 160°C. When heating using an air circulation type heating apparatus, the time required for crystallization can be shortened and the apparatus is inexpensive as compared with the case of crystallization using a vacuum tumbler, because heat conduction is better. Although the time required for crystallization is not particularly limited, it 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 the solid state polymerization is preferably 170-250°C. If the solid phase polymerization temperature is lower than 170° C., the solid phase polymerization takes a long time, possibly reducing productivity. The temperature of solid phase polymerization is more preferably 175° C. or higher, and even more preferably 180° C. or higher. On the other hand, when the temperature of the solid phase polymerization exceeds 250°C, the pellets may stick together. The temperature of solid phase polymerization is more preferably 240° C. or lower, and even more preferably 230° C. or lower. The solid phase polymerization time is usually about 5 to 70 hours. Moreover, the catalyst used in the melt polymerization may coexist during the solid phase polymerization.

Further, solid phase polymerization is preferably carried out under reduced pressure or in an inert gas such as nitrogen gas. Moreover, it is preferable to carry out the solid phase polymerization while moving the pellets by a suitable method such as a tumbling method or a gas fluidized bed method so as not to cause sticking between the pellets. The pressure when solid phase polymerization is carried out under reduced pressure is preferably 1 kPa or less.

The polyester thus 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 performing 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, 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. This further improves drawdown resistance during extrusion blow molding of the polyester. The intrinsic viscosity is more preferably 1.0 dl/g or more, 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 articles can be obtained by melt-molding the obtained polyester. Molded articles obtained by melt-molding the polyester of the present invention have appropriate hardness and are excellent in chemical resistance, particularly resistance to high-concentration alcohol and the like. Moreover, the molded article has good impact resistance even after a long period of time, and is also excellent in low-temperature impact resistance. Furthermore, the molded article has moderate hardness, is hard to be scratched on the surface, and has a glass-like texture and appearance. In addition, a molded article can be obtained by further secondary processing the molten molded article.

The molding method is not particularly limited, but extrusion molding is preferably employed. A molded article obtained by extruding the above polyester is a preferred embodiment of the present invention. A more preferred embodiment of the present invention is a film or sheet obtained by extruding the polyester. A container formed by extruding the above polyester is also a more preferred embodiment of the present invention. Since the polyester has a high viscosity during melt molding, it is suitable for extrusion molding. The temperature of the resin composition during extrusion molding is preferably within the range of (melting point of polyester + 10 ° C.) to (melting point of polyester + 70 ° C.), and (melting point of polyester + 10 ° C.) to (melting point of polyester + 40 ° C. ° C.) is more preferred. Drawdown can be suppressed by extruding at a temperature relatively close to the melting point.

Using the polyester, for example, when producing a sheet or film by extrusion molding such as a T-die method or an inflation method, there is no drawdown, neck-in, film swaying, and unmelted spots, and a high-quality sheet Alternatively, films can be produced with high productivity. When the sheet or film thus obtained is subjected to secondary processing such as thermoforming, it can be used to mold deep-drawn molded products or large-sized molded products. It is possible to adjust the degree of crystallization of the molded product by adjusting the temperature of the mold. you can get the goods. A preferred embodiment of the present invention is a thermoformed product obtained by thermoforming such a sheet or film, particularly a container obtained by thermoforming the sheet or film. Since the molded article has excellent impact resistance even at low temperatures and moderate hardness, it is suitably used as an ice packaging container for iced coffee.

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

A molded article obtained by extrusion blow molding the above polyester is also a preferred embodiment of the present invention. The molded article has moderate hardness, excellent chemical resistance, particularly resistance to high-concentration alcohol, and good impact resistance even after a long period of time. In addition, the molded article has an appropriate hardness, a scratch-resistant surface, and a glass-like texture and appearance. Therefore, the molded article can be used for various purposes. A container made of the molded article is a preferred embodiment of the molded article. Such containers are suitably used as containers for cosmetics and oils. Also, a molded article having a laminate structure of the polyester and other thermoplastic resins may be used.

The second polyester, which is different in aspect from the first polyester, will be described below. The second polyester is mainly composed of 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 is 1 to 25 mol % and the content of units derived from bisphenol A ethylene oxide adduct is 0.1 to 20 mol % based on the total diol units. The second polyester has excellent chemical resistance. Further, when the polyester is extruded to produce a sheet or film, neck-in is less likely to occur. Therefore, it becomes possible to carry out extrusion molding at high speed, thereby improving productivity.

As the straight-chain aliphatic diol units in the second polyester, those mentioned above as the straight-chain aliphatic diol units contained in the first polyester are preferred. The content of linear aliphatic diol units in the second polyester is preferably 55 mol % or more with respect to the total diol units in the polyester. As a result, when the second polyester is produced, solid phase polymerization can be performed at a high temperature, so that the productivity is improved and a molded product with a better color tone can be obtained. The content of linear aliphatic diol units is more preferably 80 mol % or more. On the other hand, the said content is 98.9 mol% or less. As a result, the drawdown resistance of the resulting molded article is improved, and the coloration of the resin during polyester production is also suppressed. The content of linear aliphatic diol units is preferably 95 mol % or less.

The content of isosorbide units in the second polyester is 1 mol % or more based on the total diol units in the polyester. When the content is 1 mol% or more, the glass transition point of the polyester increases and the enthalpy relaxation rate slows down, so that the resulting molded article has excellent impact resistance even after a long period of time. Become. In addition, since the molded article is moderately hardened, the surface is less likely to be scratched, and a glass-like texture and appearance can be obtained. The isosorbide unit content is preferably 3 mol % or more. On the other hand, the content of isosorbide units is 25 mol % or less. This improves drawdown resistance during extrusion molding of the polyester. The isosorbide unit content is preferably 15 mol % or less, more preferably 10 mol % or less.

The second polyester contains units derived from bisphenol A ethylene oxide adducts. This improves drawdown resistance during extrusion molding of the polyester. In addition, neck-in is suppressed when the polyester is used to produce a film or sheet. The content of units derived from the bisphenol A ethylene oxide adduct in the second polyester is 0.1 mol% or more, preferably 0.5 mol% or more, relative to the total diol units in the polyester, 2 mol % or more is more preferable. On the other hand, the said content is 20 mol% or less. When the content is within the above range, the melt viscosity of the polyester becomes moderate and the impact resistance of the obtained molded article is improved. The content is preferably 10 mol % or less, more preferably 8 mol % or less.

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

The total content of units derived from aromatic dicarboxylic acid units, linear aliphatic diol units, isosorbide units and bisphenol A ethylene oxide adducts in the second polyester is, with respect to the total of all structural units in the polyester, 80 mol % or more is preferable. When the content is 80 mol % or more, sticking due to softening of the resin is suppressed when the polyester is produced by solid phase polymerization, so that the degree of polymerization can be easily increased. The content is more preferably 90 mol % or more, more preferably 95 mol % or more.

The constitution and physical properties of the second polyester are preferably the same as those of the above-described first polyester, except that the diol unit has the above-described structure.

The second polyester can be made in the same manner as the first polyester. 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 molding method of the first polyester is adopted, and among them, the T-die method and the inflation method are preferable. A molded article obtained by extruding the second polyester is a preferred embodiment of the polyester, and a container made from the molded article and a film or sheet made from the molded article are more preferred embodiments. A thermoformed article obtained by thermoforming the above film or sheet is also a more preferred embodiment of the second polyester.

The third polyester, which is different from the above-described first polyester and second polyester, will be described below. The third polyester mainly consists of dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units, 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 dicarboxylic acid units is 0.1 to 20 mol%, and the content of isosorbide units relative to the total diol units is 1 to 25 mol%. It is. The third polyester also has excellent chemical resistance. Further, when the polyester is extruded to produce a sheet or film, neck-in is less likely to occur. Therefore, it becomes possible to carry out extrusion molding at high speed, thereby improving productivity.

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

The third polyester contains dimer acid units or hydrogenated dimer acid units. This improves drawdown resistance during extrusion molding of the polyester. In addition, neck-in is suppressed when the polyester is used to produce a film or sheet. 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, relative to the total amount 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 moderate and the impact resistance of the obtained molded article is improved. The content is preferably 10 mol % or less, 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 and 90 mol % or more is preferable, and 95 mol % or more is more preferable.

As the linear aliphatic diol units in the third polyester, those mentioned above as the linear aliphatic diol units contained in the first polyester are preferred. The content of linear aliphatic diol units in the third polyester is preferably 75 mol % or more of the total diol units in the polyester. Thereby, when producing the third polyester, solid-phase polymerization can be performed at a high temperature, so that the productivity is improved and a molded article with a better color tone can be obtained. The linear aliphatic diol unit content is more preferably 80 mol % or more, still more preferably 85 mol % or more, and particularly preferably 90 mol % or more. On the other hand, the content of linear aliphatic diol units is 99 mol % or less. As a result, the drawdown resistance of the resulting molded product is improved, and the transparency is also improved. The content of linear aliphatic diol units is preferably 97 mol % or less.

The content of isosorbide units in the third polyester is 1 mol % or more with respect to the total diol units in the polyester. When the content is 1 mol% or more, the glass transition point of the polyester increases and the enthalpy relaxation rate slows down, so that the resulting molded article has excellent impact resistance even after a long period of time. Become. In addition, since the molded article is moderately hardened, the surface is less likely to be scratched, and a glass-like texture and appearance can be obtained. The isosorbide unit content is preferably 3 mol % or more. On the other hand, the content of isosorbide units is 25 mol % or less. This improves drawdown resistance during extrusion molding of the polyester. The isosorbide unit content is preferably 15 mol % or less, 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 amount of diol units in the polyester, and 95 mol% 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, with respect to the total of all structural units in the polyester, 80 mol % or more is preferable. When the content is 80 mol % or more, sticking due to softening of the resin is suppressed when the polyester is produced by solid phase polymerization, so that the degree of polymerization can be easily increased. The content is more preferably 90 mol % or more, more preferably 95 mol % or more.

The structure and physical properties of the third polyester are preferably the same as those of the first polyester described above, except that the dicarboxylic acid units and diol units have the structures described above.

The third polyester can be made in the same manner as the first polyester. 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 molding method of the first polyester is adopted, and among them, the T-die method and the inflation method are preferable. A molded article obtained by extruding the third polyester is a preferred embodiment of the polyester, and a container made from the molded article and a film or sheet formed from the molded article are more preferred embodiments. A thermoformed article obtained by thermoforming the above film or sheet is also a more preferred embodiment of the third polyester.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

(1) Intrinsic viscosity (IV)
The intrinsic viscosity of the polyester after melt polymerization and the polyester after solid phase polymerization was 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 Instruments Model TA Q2000). The melting point and melting enthalpy were determined by heating from 30°C to 280°C at a heating rate of 10°C/min. The melting peak at this time was taken as the melting point. Further, when the melting enthalpy of the polyester after melt polymerization was 3 J/g or more, it was judged to have crystallinity (A), and when it was less than 3 J/g, it was judged to have no crystallinity (B). The glass transition temperature (Tg) was raised from 30°C to 280°C at a heating rate of 10°C/min, then rapidly cooled to 30°C at -50°C/min, and then raised again at a heating rate of 10°C/min. Calculated from the data when warmed.

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

(4) Drop test After water (water temperature 20 to 25 ° C.) was added to the bottle immediately after molding so that the total weight was 263 g ± 0.5 g, it was passed through a vertically installed cylinder with a diameter of 10 cm, and It was alternately dropped from a height of 125 cm onto a horizontal concrete surface and a 45-degree inclined concrete surface. The number of cycles until cracks or cracks occurred in the bottle (per cycle, the bottle was dropped twice, once on a horizontal surface and once on a 45-degree slope) was measured. Up to 20 cycles were repeated. Five bottles were subjected to a drop test for each composition, and the average value was taken as the bottle drop strength. In addition, the molded bottle was stored in a constant temperature machine at 50° C. and 6% RH for 100 hours and subjected to an accelerated test, followed by a drop test by the method described above 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% ethanol aqueous solution at 50° C., and stored for 7 days. The haze values (%) of the samples before and after immersion were measured, and those with an increase in haze value of less than 5% after immersion were evaluated as A (good), and those with an increase of 5% or more were evaluated as B (bad).

(6) Rockwell hardness Pellets after solid-phase polymerization were vacuum-dried overnight at 120°C and pellets after melt-polymerization were vacuum-dried overnight at 70°C, respectively, and dumbbell-shaped test pieces (ISO20753 A1 type) were formed by injection molding. A sample was obtained by cutting a test piece gate-side grip portion (3 cm in length, 2 cm in width, and 4 mm in thickness) from the material. Using a hardness tester Rockwell Model 3R (manufactured by Imai Seiki), the Rockwell hardness was measured on the R scale. Each sample was measured 5 times at room temperature, and the average value was taken as the Rockwell hardness.

(7) Inflation moldability Pellets after solid-phase polymerization were dried to a moisture content of 50 ppm or less with a dehumidifying dryer. The pellets were put into the 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, and the extrusion temperature was 270° C. and the blow ratio (frost line diameter/die outer diameter) was 1. A film having a thickness of 50 μm was formed under two conditions of 0.5 and 2.0. Inflation moldability was evaluated by assigning A to those that could be molded at both blow ratios of 1.5 and 2.0, and B to those that could not be molded at a blow ratio of 2.0 but could be molded at a blow ratio of 1.5. . If molding is possible at a high blow ratio, it can be said that the inflation moldability is good.

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

Comparative example 11
(1) Melt polycondensation Terephthalic acid (TA) 100 parts by mass, ethylene glycol (EG) 40.3 parts by mass, 90% by mass isosorbide aqueous solution 5.9 parts by mass (5.3 parts by mass as isosorbide (ISB)), 1 , 4-cyclohexanedimethanol [CHDM, mixing ratio of cis and trans isomers (cis/trans) is 30/70] 2.6 parts by mass, germanium dioxide (GeO ₂ ) 0.017 parts by mass, phosphorous acid A slurry consisting of 0.012 parts by mass of cobalt acetate tetrahydrate and 0.012 parts by mass of cobalt acetate tetrahydrate is prepared and heated to a temperature of 250° C. under pressure (gauge pressure 0.25 MPa) to conduct 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. for 150 minutes under 0.1 kPa to produce a polyester having an intrinsic viscosity of 0.71 dL/g. The obtained polyester was extruded from a nozzle in the form of a strand, cooled with water, and then cut into cylinders (about 2.5 mm in diameter and about 2.5 mm in length) to obtain amorphous polyester pellets. When the ratio of the monomer components constituting the copolyester was confirmed by ¹ H-NMR spectrum (device: "JNM-GX-500" manufactured by JEOL Ltd., solvent: deuterated trifluoroacetic acid), TA 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 .

Comparative Examples 12-17 , Comparative Examples 1-3
Amorphous pellets were produced and evaluated in the same manner as in Comparative Example 11 , except that the amounts of the raw materials dicarboxylic acid and diol charged were changed as shown in Table 1. The results are summarized in Tables 2 and 3.

Example 8
(1) Pre-crystallization of amorphous pellets
The polyester amorphous pellets obtained in Comparative Example 11 were charged into a tumbling vacuum solid-phase polymerization apparatus, and pre-crystallization was performed at 120° C. under 0.1 kPa for 5 hours.

(2) Solid Phase Polymerization After the preliminary crystallization, the temperature was raised to carry out solid phase polymerization at 190 to 200° C. under 0.1 kPa for 100 hours to obtain crystal pellets. The intrinsic viscosity of the resulting copolyester was 1.1 dL/g. The ratio of the monomer components of the copolyester according to the ¹ H-NMR spectrum is TA unit: EG unit: ISB unit: CHDM unit: DEG = 50.0: 45.0: 2.5: 1.5: 1. .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 bottle After drying the obtained pellets at 120°C for 24 hours using a dehumidifying dryer, using an extrusion blow molding device ("MSE-40E model" manufactured by Tahara Co., Ltd.), the length of 14.5. A 5 cm, 220 mL volume clear bottle (27 g) was molded. At this time, the cylinder temperature was graded from 280.degree. C. to 240.degree. C., the die temperature was 240-250.degree. The resulting transparent bottle 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. Moreover, when the drawdown resistance of the obtained crystal pellet was measured, the evaluation was "A".

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

Comparative Example 18
Amorphous pellets were produced in the same manner as in Comparative Example 11 except that the types and amounts of the raw materials dicarboxylic acid and diol were changed as shown in Table 1, and the crystallinity was evaluated. A crystal pellet and a transparent bottle were produced and evaluated in the same manner as in Example 8 except that the obtained crystal pellet was used as a raw material. Results are shown in Tables 2 and 3.

Example 16
100 parts by mass of terephthalic acid, 41.4 parts by mass of ethylene glycol, 5.9 parts by mass of 90% by mass isosorbide aqueous solution (5.3 parts by mass as isosorbide), 1.3 parts by mass of bisphenol A ethylene oxide 2 mol adduct (EOBPA), Amorphous pellets were produced in the same manner as in Comparative Example 11 , except that a slurry containing 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 was used. to evaluate the crystallinity. Further, crystalline pellets were obtained in the same manner as in Example 8, except that the obtained amorphous pellets were used. The intrinsic viscosity of the resulting copolyester was 1.1 dL/g. The ratio of the monomer components of the copolyester according to the ¹ H-NMR spectrum is 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. 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. Moreover, when the drawdown resistance of the obtained crystal pellet was measured, the evaluation was "A".

Examples 17-20, 22, 23, Comparative Examples 4-10
Amorphous pellets, crystalline pellets, and transparent bottles were produced and evaluated in the same manner as in Example 16, except that the types and amounts of the dicarboxylic acids and diols used as raw materials were changed as shown in Table 1. Moreover, the inflation moldability of the crystal pellets obtained in Example 18 was evaluated. The results are summarized in Tables 2 and 3. Further, 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
In the same manner as in Example 16, except that the types and amounts of the raw material dicarboxylic acids and diols were changed as shown in Table 1, and the polyfunctional compound shown in Table 1 was further contained in the raw material slurry. Amorphous pellets, crystalline pellets and transparent bottles were produced and evaluated. Furthermore, the inflation moldability of the crystal pellets was evaluated. The results are summarized in Tables 2 and 3. In addition, when the drawdown resistance of the crystal pellets obtained in Examples 21 and 24 was measured, all evaluations were "A".

Claims (13)

A solid-phase polymerized polyester pellet obtained by subjecting an aromatic dicarboxylic acid, a linear aliphatic diol, isosorbide, and cyclohexanedimethanol to melt-kneading for polycondensation, followed by further solid-phase polymerization of the resulting polyester,
The solid phase polymerized polyester is composed of dicarboxylic acid units mainly composed of at least one aromatic dicarboxylic acid unit selected from the group consisting of terephthalic acid units, furandicarboxylic acid units and isophthalic acid units , ethylene glycol units and diethylene glycol units . Mainly composed of diol units mainly composed of at least one linear aliphatic diol unit, isosorbide unit and cyclohexanedimethanol unit selected from the group consisting of
In the solid phase polymerized polyester, the total content of terephthalic acid units, furandicarboxylic acid units and isophthalic acid units is 80 mol% or more with respect to the total of the dicarboxylic acid units, and ethylene glycol units and diethylene glycol with respect to the total of the diol units. The total content of units is 75 mol% or more, the content of isosorbide units is 1 to 14 mol%, the content of cyclohexanedimethanol units is 1 to 7 mol%,
The intrinsic viscosity of the solid-phase polymerized polyester is 1.05 dl/g or more ,
Solid-phase polymerized polyester pellets, wherein a test piece obtained by injection-molding the solid-phase polymerized polyester pellets has a Rockwell hardness of 115 or more as measured on the R scale . 2. The solid phase polymerized polyester pellets according to claim 1 , wherein the total content of isosorbide units and cyclohexanedimethanol units relative to the total of diol units in the solid phase polymerized polyester is 15 mol % or less. The polyfunctional compound unit derived from a polyfunctional compound in which the solid-phase polymerized polyester further has 3 or more carboxyl groups, hydroxyl groups and/or their ester-forming groups is added to the total number of structural units to 0. The solid-phase polymerized polyester pellets according to claim 1 or 2, containing from 0.00005 to 1 mol %. The solid phase polymerized polyester pellets according to any one of claims 1 to 3, wherein the intrinsic viscosity of the solid phase polymerized polyester is 1.5 dl/g or less. 5. Any one of claims 1 to 4 , wherein in the solid-phase polymerized polyester, the diol units further contain 0.1 to 20 mol% of units derived from bisphenol A ethylene oxide adducts with respect to the total of the diol units. Solid state polymerized polyester pellets as described. In the solid phase polymerized polyester, 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 based on the total of the dicarboxylic acid units , 0.1 to 20 mol %, the solid-phase polymerized polyester pellets according to any one of claims 1 to 5. A molded article obtained by extruding the solid phase polymerized polyester pellet according to any one of claims 1 to 6. A film or sheet comprising the molded article according to claim 7 . A thermoformed article obtained by thermoforming the film or sheet according to claim 8 . A container comprising the molded article according to claim 7 . 3. The solid state polymerization according to claim 1 or 2, wherein an aromatic dicarboxylic acid, a linear aliphatic diol, isosorbide, and cyclohexanedimethanol are melt-kneaded to cause condensation polymerization, and then the obtained polyester is further subjected to solid state polymerization . A method for producing polyester pellets . A solid-phase polymerized polyester pellet obtained by subjecting an aromatic dicarboxylic acid, a linear aliphatic diol, isosorbide, and a bisphenol A ethylene oxide adduct to melt-kneading for polycondensation, followed by further solid-phase polymerization of the obtained polyester. can be,
The solid phase polymerized polyester is composed of dicarboxylic acid units mainly composed of at least one aromatic dicarboxylic acid unit selected from the group consisting of terephthalic acid units, furandicarboxylic acid units and isophthalic acid units, ethylene glycol units and diethylene glycol units. At least one linear aliphatic diol unit selected from the group consisting mainly of diol units mainly composed of units derived from isosorbide units and bisphenol A ethylene oxide adducts,
In the solid phase polymerized polyester, the total content of terephthalic acid units, furandicarboxylic acid units and isophthalic acid units is 80 mol% or more with respect to the total of the dicarboxylic acid units, and ethylene glycol units and diethylene glycol with respect to the total of the diol units. The total content of units is 55 mol% or more, the content of isosorbide units is 1 to 25 mol%, the content of units derived from bisphenol A ethylene oxide adduct is 0.5 to 8 mol%,
Solid-phase polymerized polyester pellets , wherein the intrinsic viscosity of the solid-phase polymerized polyester is 1.05 dl/g or more. Solid-phase polymerized polyester pellets obtained by melt-kneading aromatic dicarboxylic acid, linear aliphatic diol, isosorbide, and dimer acid or hydrogenated dimer acid to cause polycondensation, followed by further solid-phase polymerization of the obtained polyester. and
The solid-phase polymerized polyester comprises at least one aromatic dicarboxylic acid unit selected from the group consisting of terephthalic acid units, furandicarboxylic acid units and isophthalic acid units, and dicarboxylic acid units or hydrogenated dimer acid units. Consists mainly of diol units mainly composed of acid units, and at least one linear aliphatic diol unit and isosorbide unit selected from the group consisting of ethylene glycol units and diethylene glycol units,
In the solid phase polymerized polyester, the total content of terephthalic acid units, furandicarboxylic acid units and isophthalic acid units relative to the total of dicarboxylic acid units is 80 mol% or more, and the total content of dimer acid units and hydrogenated dimer acid units is 0.4 to 8 mol%, the content of ethylene glycol units and diethylene glycol units is 75 mol% or more, and the content of isosorbide units is 1 to 25 mol% with respect to the total of the diol units,
Solid-phase polymerized polyester pellets , wherein the intrinsic viscosity of the solid-phase polymerized polyester is 1.05 dl/g or more.