JP2002037992A - Polyester resin composition and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition giving moldings excellent both in gas barrier property and mechanical property, and capable of being used suitably for films, packaging materials for food such as blown containers, packaging materials for electronic parts or the like, medical materials and the like, which need gas barrier property. SOLUTION: The polyester resin composition comprises (A) 1-70 pts.wt. of a succinic acid copolymer polyester and (B) 99-30 pts.wt. of a crystalline polyester. The succinic acid copolymer polyester contains 24-50 mol% of a succinic acid unit and 0-26 mol% of an aromatic dicarboxylic acid unit based on 100 mol% of the total constitutional units of the succinic acid copolymer polyester; the content of the succinic acid unit, the aromatic dicarboxylic acid unit and an ethylene glycol unit is >=90 mol%; and further, the succinic acid copolymer polyester contains 0.001-2 mol% of a monomer unit having >=3 of ester-forming functional groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition comprising a polyester obtained by copolymerizing succinic acid and a crystalline polyester, and a use thereof. Specifically, the present invention comprises a succinic acid copolymerized polyester (A) having a succinic acid unit and a monomer unit having a functionality of 3 or more, and a crystalline polyester (B), and is excellent in gas barrier properties and mechanical properties. The present invention relates to a resin composition, and a sheet, a film, and a hollow molded article made of the resin composition.

[0002]

BACKGROUND OF THE INVENTION When a polymer material is used for food packaging and the like, it is desired that the gas permeability is low in order to prevent deterioration of the contents. Among polyester resins, polyethylene terephthalate is often used for food packaging materials such as various kinds of beverage containers due to its excellent balance of moldability, mechanical properties, and gas barrier properties. However, especially for food packaging that requires long-term storage, even if a polyethylene terephthalate resin is used, gas barrier properties are not necessarily sufficient.

For this reason, Japanese Patent Publication No. 40444/1988 discloses that isophthalic acid and ethylene glycol and 1,3
A copolymer of bis (2-hydroxyethoxy) benzene has been proposed as a resin having low carbon dioxide and oxygen permeability. However, even if this polyester resin was added to a crystalline polyester such as polyethylene terephthalate as a gas barrier property improving agent, the effect was not sufficient.

The inventor of the present invention has conducted intensive studies to solve the above-mentioned situation, and has found that a polyester containing a specific amount of succinic acid has a gas barrier property improving performance, and has already proposed the same (Japanese Patent Application Flat 11-369732
issue). However, a polyester resin copolymerized mainly with succinic acid generally has a lower molecular weight than a polyester copolymerized mainly with an aromatic group such as terephthalic acid, and a resin composition comprising this and a crystalline polyester. The mechanical properties were also not satisfactory.

The inventor of the present invention has made intensive studies in view of the above circumstances, and has found that a resin composition comprising a specific polyester having a succinic acid unit and a crystalline polyester has excellent gas barrier properties and mechanical properties. And completed the present invention.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester resin composition comprising a polyester containing a succinic acid unit and a crystalline polyester and having excellent gas barrier properties and mechanical properties. Another object of the present invention is to provide a sheet, a film, and a hollow molded article comprising the polyester resin composition and having excellent gas barrier properties and mechanical properties.

[0007]

SUMMARY OF THE INVENTION The polyester resin composition of the present invention comprises:
(A) All the structural units of the succinic acid copolymerized polyester are 10
When 0 mol% is used, 24 to 50 mol% of succinic acid units are used.
0 to 26 mol% of aromatic dicarboxylic acid units, 90 mol% or more of succinic acid units, aromatic dicarboxylic acid units and ethylene glycol units in total, and a functional number of 3 having ester forming ability. It is characterized by comprising 1 to 70 parts by weight of a succinic acid copolymer polyester containing 0.001 to 2 mol% of the above monomer units and 99 to 30 parts by weight of a crystalline polyester (B).

In such a polyester resin composition, the aromatic dicarboxylic acid unit of the succinic acid copolymerized polyester (A) is preferably an isophthalic acid unit and / or a 2,6-naphthalenedicarboxylic acid unit. Further, the polyester resin composition of the present invention, when all the structural units of (A) succinic acid copolymerized polyester is 100 mol%,
It contains 24-49 mol% of succinic acid units and 1-226 mol% of isophthalic acid units and / or 2,6-naphthalenedicarboxylic acid units in total, and contains succinic acid units, isophthalic acid units, and 2,6-naphthalene. A succinic acid copolymer containing a total of 90 mol% or more of a dicarboxylic acid unit and an ethylene glycol unit and 0.001 to 2 mol% of a monomer unit having an ester-forming ability and having a functionality of 3 or more. Polyester: 1 to 70 parts by weight,
(B) Crystalline polyester: preferably 99 to 30 parts by weight.

In such a polyester resin composition of the present invention, it is also preferable that the monomer unit having a functionality of 3 or more having ester forming ability of the succinic acid copolymerized polyester (A) is a unit derived from a polyfunctional alcohol. A unit derived from at least one selected from the group consisting of glycerin, 1,1,1-tris (hydroxymethyl) ethane, 1,1,1-tris (hydroxymethyl) propane, pentaerythritol and dipentaerythritol Is also preferable.

[0010] In the polyester resin composition of the present invention, the crystalline polyester (B) is at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalate, and polyethylene isophthalate. One type of crystalline polyester is also preferable.

The polyester resin composition of the present invention is preferably algae in which the succinic acid copolymerized polyester (A) and the crystalline polyester (B) are compatible. The sheet or film of the present invention is obtained by molding the above-described polyester resin composition of the present invention. The hollow molded article of the present invention is obtained by blow molding the above-described polyester resin composition of the present invention.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. The polyester resin composition of the present invention contains a succinic acid copolymerized polyester (A) and a crystalline polyester (B). Succinic acid copolymerized polyester (A) The succinic acid copolymerized polyester (A) constituting the polyester resin composition of the present invention contains 100 mol% of all constituent units.
When it contains, 24-50 mol% of succinic acid units, 0-26 mol% of aromatic dicarboxylic acid units are contained, and 90 mol% or more of succinic acid units, aromatic dicarboxylic acid units and ethylene glycol units are contained in total. And a monomer unit having a functionality of 3 or more having an ester forming ability of 0.00
It contains 1 to 2 mol%.

The term "all structural units of the succinic acid copolymerized polyester" means all units obtained when the succinic acid copolymerized polyester is completely hydrolyzed with an acid or an alkali. As the succinic acid copolymer polyester (A) used in the present invention, when all the constituent units of the succinic acid copolymerized polyester are 100 mol%, the total of the succinic acid unit and the aromatic dicarboxylic acid unit is 48 to 50%. 5
0 mol%, containing 24 to 49 mol%, preferably 30 to 48 mol% of succinic acid units, 26 to 1 mol%, preferably 20 to 2 mol% of aromatic dicarboxylic acid units, and ethylene glycol. Containing at least 45 mol% of units,
0.01 to 0.3 mol% of a monomer unit having a functionality of 3 or more
It is preferred to contain.

As the aromatic dicarboxylic acid unit, isophthalic acid, 2,6-naphthalenedicarboxylic acid, terephthalic acid,
Phthalic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-sulfonebisbenzoic acid, 4,4'-
Examples include units derived from aromatic dicarboxylic acids such as biphenyldicarboxylic acid, 4,4'-sulfidebisbenzoic acid, 4,4'-oxybisbenzoic acid, diphenoxyethanedicarboxylic acid, and particularly, isophthalic acid units and / or 2,
6-Naphthalenedicarboxylic acid units are preferred.

The succinic acid copolymer polyester (A) used in the present invention has a succinic acid unit content of 24 mol% based on 100 mol% of all the structural units of the succinic acid copolymerized polyester.
~ 49 mol%, isophthalic acid units and / or
2,6-naphthalenedicarboxylic acid units in a total amount of 1 to 26 mol%, succinic acid units, isophthalic acid units, 2,6-naphthalenedicarboxylic acid units and ethylene glycol units in a total of 90 mol% or more; A monomer unit having a functionality of 3 or more having an ester forming ability of 0.001 to
It is also desirable to contain 2 mol%.

Particularly, when the total amount of the constituent units of the succinic acid copolymerized polyester is 100 mol%, the total amount of the units composed of succinic acid and isophthalic acid and / or 2,6-naphthalenedicarboxylic acid is 48 to 50%. 50 mol%, and the succinic acid unit is 24 to 49 mol%, preferably
30-48 mol%, isophthalic acid and / or 2,6
26 to 1 mol%, preferably 20 to 2 mol%, of units of naphthalenedicarboxylic acid, and 4 units of ethylene glycol.
5 mol% or more and a monomer unit having a functionality of 3 or more
Preferably, it is contained in an amount of about 0.3 mol%.

The succinic acid copolymerized polyester (A) comprises a monomer unit having an ester-forming ability and having a functionality of 3 or more which is a polyfunctional carboxylic acid having 3 or more carboxyl groups or 3 or more hydroxyl groups. And units derived from polyfunctional hydroxy acids having three or more carboxyl groups and hydroxyl groups.

Of these, units derived from polyfunctional alcohols having three or more hydroxyl groups are particularly preferred. Specifically, glycerin, diglycerin, tris (hydroxymethyl) methane, 1,1,1-tris (hydroxymethyl) ethane, 1,1,1-tris (hydroxymethyl) propane, pentaerthritol, dipentane Erythritol, sorbitol, glucose, lactose,
Examples include units derived from sugars such as galactose, fructose and saccharose, and nitrogen-containing polyhydric alcohols such as 1,3,5 trishydroxyethoxyisocyanurate.

In the succinic acid copolymerized polyester (A) used in the present invention, glycerin, 1,1,1-tris (hydroxymethyl) ethane, 1,1,1 1-tris (hydroxymethyl)
Units derived from one or more selected from propane, pentaerythritol and dipentaerythritol are more preferred.

The succinic acid copolymer polyester (A) used in the present invention contains other structural units in an amount of usually 10 mol% or less, preferably 5 mol% or less, as long as the above-mentioned constitution is satisfied. You may. Other structural units that the succinic acid copolymerized polyester (A) may contain include dicarboxylic acid units, diol units, and hydroxycarboxylic acid units other than those described above.

Specifically, the dicarboxylic acid units other than those described above include aliphatic acids such as malonic acid, glutaric acid, fumaric acid, maleic acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, and diglycolic acid. Units derived from a dicarboxylic acid, units derived from an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, and the like are included.

When the succinic acid copolymerized polyester (A) used in the present invention contains a unit derived from isophthalic acid and / or 2,6-naphthalenedicarboxylic acid, isophthalic acid and 2 , 6-
Needless to say, it may contain an aromatic dicarboxylic acid unit other than naphthalenedicarboxylic acid, specifically, terephthalic acid, phthalic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid From aromatic dicarboxylic acids such as 4,4'-sulfonebisbenzoic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfidebisbenzoic acid, 4,4'-oxybisbenzoic acid, diphenoxyethanedicarboxylic acid Units to be derived can be mentioned.

Specific examples of the diol unit include diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and dodecamethylene glycol. , Units derived from aliphatic diols such as triethylene glycol and tetraethylene glycol, units derived from alicyclic diols such as cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-
Bis (2-hydroxyethoxy) benzene, 1,4-bis (2-
Hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bisphenols,
Examples include units derived from diols containing an aromatic group such as hydroquinone and resorcin.

The units of hydroxycarboxylic acids include glycolic acid, lactic acid, 3-hydroxybutyric acid, p-
Hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxymethylbenzoic acid, m-hydroxymethylbenzoic acid, p-
And units derived from (2-hydroxyethyl) benzoic acid and m- (2-hydroxyethyl) benzoic acid. Although the molecular weight of the succinic acid copolymerized polyester (A) used in the present invention is arbitrary, the number average molecular weight is desirably 40,000 or less, preferably 20,000 or less, and more preferably 10,000 or less. With such a molecular weight,
When mixing with the crystalline polyester (B), the mixing time can be shortened, which is preferable.

Such a succinic acid copolymerized polyester (A) may be produced according to any of the methods generally used for producing polyesters. It is preferably produced by a reaction. When a succinic acid copolymerized polyester (A) is produced by a melt polycondensation reaction, copolymerized components such as isophthalic acid and naphthalenedicarboxylic acid can be easily introduced. Hereinafter, succinic acid copolymerized polyester (A)
Is produced by a melt polycondensation reaction.

As a method for producing the succinic acid copolymerized polyester (A) used in the present invention by a melt polycondensation reaction, a low polymer is produced using the above-mentioned monomer for each structural unit, and then the low polymer is produced. Any method of melt polycondensation is preferably mentioned. Examples of such a method include, for example, (i) a method of directly esterifying a dicarboxylic acid such as succinic acid and a diol such as ethylene glycol, followed by a melt polycondensation reaction, and (ii) a dicarboxylic acid such as dimethyl succinate. A method in which a transesterification of a diester and a diol such as ethylene glycol is performed, followed by a melt polycondensation reaction, and (iii) a method in which a dicarboxylic acid anhydride such as succinic anhydride is reacted with a diol such as ethylene glycol to perform a melt polycondensation reaction. And the like.

The production of the low polymer is carried out by using the above-mentioned dicarboxylic acid raw material for deriving the dicarboxylic acid unit, that is, a dicarboxylic acid raw material mainly composed of succinic acid or succinic anhydride, or a dicarboxylic acid raw material comprising a lower alcohol ester thereof. A diol raw material mainly composed of ethylene glycol,
The reaction is carried out by performing an esterification reaction or a transesterification reaction using the above-mentioned polyfunctional compound raw material such as a trifunctional alcohol which leads to a monomer unit having a functional number of 3 or more.

As a method of the esterification reaction for producing a low polymer, a predetermined amount of a dicarboxylic acid raw material, a predetermined amount of a diol raw material, and a predetermined amount of a polyfunctional compound raw material are mixed in 100 to 100%.
A method of performing dehydration condensation at a temperature of 230 ° C. under pressure or normal pressure may be used. In such esterification, the diol raw material is usually used in an amount of 1.01 to 3 mol, preferably 1.1 to 2.2, per 1 mol of the dicarboxylic acid raw material in total.
It is preferable to charge and react the raw materials of the polyfunctional compound at a ratio of usually 5 × 10 ^{−6 to} 0.01 mol, preferably 0.0001 to 0.005 mol.

Such an esterification reaction may be carried out in the presence of a catalyst or without a catalyst. Examples of the catalyst that can be used in the esterification reaction include an acid such as concentrated sulfuric acid and p-toluenesulfonic acid, and a catalyst such as a metal complex such as tin 2-ethyloctanoate. Further, as a method of transesterification reaction to produce a low polymer, as a dicarboxylic acid raw material, using a lower alcohol diester of dicarboxylic acid, or a lower alcohol diester of dicarboxylic acids other than succinic anhydride and succinic acid, A predetermined amount of a dicarboxylic acid raw material, a predetermined amount of a diol raw material, and a predetermined amount of a polyfunctional compound raw material are mixed with 100 to 230
A method of performing transesterification at a temperature of ° C. under normal pressure while distilling a lower monoalcohol.

In such transesterification, the diol raw material is usually added in an amount of 1.0 mol per mol of the dicarboxylic acid raw material.
1 to 3 mol, preferably 1.2 to 2.2 mol, the polyfunctional compound raw material is charged and reacted usually at a ratio of 5 × 10 ^{−6 to} 0.01 mol, preferably 0.0001 to 0.005 mol. Is preferred. Such an ester exchange reaction is preferably performed in the presence of a metal complex catalyst such as manganese acetate or magnesium acetate.

Next, the low polymer having a succinic acid unit obtained by the above method is subjected to melt polycondensation. Melt polycondensation is carried out in the presence of a polymerization catalyst at a temperature of usually 200 to 300 ° C, preferably 220 to 280 ° C, usually at 10 Torr.
The reaction is preferably performed under reduced pressure conditions of not more than r, preferably not more than 2 Torr, while distilling out a component mainly composed of ethylene glycol.

The polymerization catalyst used in the melt polycondensation includes alkali metals such as sodium, alkaline earth metals such as magnesium, aluminum, zinc, tin, titanium, and the like.
Organic complexes, oxides, and simple substances of metals such as copper, nickel, cobalt, zirconium, germanium, iron, antimony, and vanadium can be used. In particular, transition of zinc, tin, titanium, cobalt, germanium, antimony, and the like can be used. Organic complexes or oxides of metals are preferred, with germanium dioxide, antimony trioxide and antimony acetate being particularly preferred.

Further, these reactions may be carried out in the presence of various stabilizers and coloring inhibitors. Examples of the stabilizer and the coloring prevention agent include a phosphorus compound and a hindered phenol compound. Among these, it is particularly preferable to contain a phosphorus compound. Phosphorus compounds include phosphoric acid,
Inorganic phosphorus compounds such as phosphorous acid and polyphosphoric acid, phosphoric acid ester compounds such as trimethyl phosphoric acid and diphenyl phosphoric acid, and phosphite esters such as triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite And the like.

In producing the succinic acid copolymerized polyester (A), in such a melt polycondensation step, 3
In order to use a low polymer having a polyfunctional monomer unit such as a functional or higher alcohol, compared to the case where a low polymer containing no monomer unit having a functional number of 3 or more is melt-polycondensed,
It is preferable because the polymerization rate is high and a succinic acid copolymer polyester having a desired molecular weight can be efficiently obtained in a shorter time.

According to such a method, a succinic acid copolymerized polyester (A) having a desired molecular weight can be produced, and usually has a number average molecular weight of 40,000 or less, preferably 20,000 or less, more preferably 10,000 or less. Certain succinic acid copolyesters (A) can be suitably produced. Since the succinic acid copolymerized polyester (A) according to the present invention contains a monomer unit having a functionality of 3 or more, such as a polyfunctional alcohol, the polymerization rate is high and it can be efficiently produced.

The above-mentioned succinic acid copolymerized polyester (A) may be used alone or in combination of two or more. Crystalline Polyester (B) The crystalline polyester (B) used in the present invention has a crystallinity of usually 5% in a state where it is sufficiently annealed at a temperature in the range of 30 to 90 ° C. below the melting point for 24 hours or more.
As described above, a crystalline polyester of preferably 10 to 80% is desirable.

Specifically, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene 2,6 naphthalate, polytrimethylene 2,
Aromatic crystal of 6 naphthalate, polybutylene 2,6 naphthalate, polyhexamethylene 2,6 naphthalate, polyethylene isophthalate, polytrimethylene isophthalate, polybutylene isophthalate, polyhexamethylene isophthalate, poly 1,4 cyclohexane dimethanol terephthalate And aliphatic crystalline polyesters such as polylactic acid, polycaprolactone, polybutylene succinate, polyethylene adipate and polybutylene adipate.

The crystalline polyester (B) used in the present invention
Of these, crystalline polyesters selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate, and polyethylene isophthalate are particularly preferable. Hereinafter, these will be described in more detail.

<Polyethylene Terephthalate> The polyethylene terephthalate used as the crystalline polyester (B) includes a dicarboxylic acid unit derived from terephthalic acid or an ester derivative thereof, a diol (dihydroxy) unit derived from ethylene glycol or an ester derivative thereof, and other components. And a hydroxycarboxylic acid unit.

When the units of the polyethylene terephthalate such as dicarboxylic acid, diol and other hydroxycarboxylic acid are 100 mol% in total, the units other than the units of terephthalic acid and ethylene glycol are contained in the range of 20 mol% or less. It does not matter. The unit of the dicarboxylic acid that may be contained, specifically, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4 ′ -
Aromatic dicarboxylic acids such as sulfonbisbenzoic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfidebisbenzoic acid, 4,4'-oxybisbenzoic acid, diphenoxyethanedicarboxylic acid, malonic acid, succinic acid, Examples thereof include aliphatic dicarboxylic acids such as glutaric acid, fumaric acid, maleic acid, adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

Examples of the diols that may be contained include diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,
Aliphatic diols such as 1,6-hexanediol, neopentyl glycol, dodecamethylene glycol, triethylene glycol and tetraethylene glycol, alicyclic diols such as cyclohexanedimethanol, and 1,3-bis (2-hydroxyethoxy) benzene , 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 2,2-bis (4-β -Hydroxyethoxyphenyl) propane, bisphenols, hydroquinone, diols containing an aromatic group such as resorcin, and the like.

The units of the hydroxycarboxylic acids that may be contained include glycolic acid, diglycolic acid,
Lactic acid, 3 hydroxybutyric acid, p-hydroxybenzoic acid,
m-hydroxybenzoic acid, p-hydroxymethylbenzoic acid,
m-hydroxymethylbenzoic acid, p- (2-hydroxyethyl)
Benzoic acid and m- (2-hydroxyethyl) benzoic acid.

The polyethylene terephthalate used in the present invention may be a polyfunctional carboxylic acid having three or more carboxyl groups or a polyfunctional diol having three or more hydroxy groups as long as the object of the present invention is not impaired. May be contained, for example, polyfunctional carboxylic acids such as trimesic acid and pyromellitic anhydride, glycerin, trimethylolmethane, 1,1,1-trimethylolethane, and 1,1,1-trimethylolpropane And a unit derived from a polyfunctional alcohol such as pentaerythritol.

<Polytrimethylene terephthalate> The polytrimethylene terephthalate used as the crystalline polyester (B) is derived from a dicarboxylic acid unit derived from terephthalic acid or its ester derivative and a trimethylene glycol or its ester derivative. It comprises a diol (dihydroxy) unit and other hydroxycarboxylic acid units.

When the units of the polytrimethylene terephthalate such as dicarboxylic acid, diol and other hydroxycarboxylic acid are 100 mol% in total, the units other than the units of terephthalic acid and trimethylene glycol are not more than 20 mol%. May be contained. Specific examples of the dicarboxylic acid unit that may be contained include phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-
Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-sulfonebisbenzoic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfidebisbenzoic acid, 4,4'-oxybisbenzoic acid, Aromatic dicarboxylic acids such as phenoxyethane dicarboxylic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, maleic acid adipic acid, sebacic acid,
Examples include aliphatic dicarboxylic acids such as azelaic acid and decane dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

The diols that may be contained include, specifically, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,4-butanediol,
Aliphatic diols such as 6-hexanediol, neopentyl glycol, dodecamethylene glycol, triethylene glycol and tetraethylene glycol, alicyclic diols such as cyclohexanedimethanol, and 1,3-bis (2-
(Hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bisphenols, hydroquinone,
And diols containing an aromatic group such as resorcin.

The units of the hydroxycarboxylic acids which may be contained include glycolic acid, diglycolic acid,
Lactic acid, 3 hydroxybutyric acid, p-hydroxybenzoic acid,
m-hydroxybenzoic acid, p-hydroxymethylbenzoic acid,
m-hydroxymethylbenzoic acid, p- (2-hydroxyethyl)
Benzoic acid and m- (2-hydroxyethyl) benzoic acid.

The polytrimethylene terephthalate used in the present invention may be a polyfunctional carboxylic acid having three or more carboxyl groups or a polyfunctional diol having three or more hydroxy groups as long as the object of the present invention is not impaired. May be included, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic anhydride, glycerin, trimethylolmethane, 1,1,1-
It may contain units derived from polyfunctional alcohols such as trimethylolethane, 1,1,1-trimethylolpropane and pentaerthritol.

<Polybutylene terephthalate> The polybutylene terephthalate used as the crystalline polyester (B) includes a dicarboxylic acid unit derived from terephthalic acid or an ester derivative thereof, and a diol derived from 1,4 butanediol or an ester derivative thereof. Dihydroxy) units and other hydroxycarboxylic acid units.

When the units such as dicarboxylic acid, diol and hydroxycarboxylic acid of this polybutylene terephthalate are 100 mol% in total, the units other than the units of terephthalic acid and 1,4 butanediol are not more than 20 mol%. It is preferable to contain in the range. Specific examples of the dicarboxylic acid unit that may be contained include phthalic acid,
Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,
Aromatic dicarboxylic acids such as 4'-sulfonebisbenzoic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfidebisbenzoic acid, 4,4'-oxybisbenzoic acid, diphenoxyethanedicarboxylic acid, malonic acid, Succinic acid, glutaric acid,
Examples thereof include aliphatic dicarboxylic acids such as fumaric acid, maleic acid, adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

The diols that may be contained include, specifically, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol,
Aliphatic diols such as 1,6-hexanediol, neopentyl glycol, dodecamethylene glycol, triethylene glycol and tetraethylene glycol, alicyclic diols such as cyclohexanedimethanol, and 1,3-bis (2-hydroxyethoxy) benzene , 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 2,2-bis (4-β -Hydroxyethoxyphenyl) propane, bisphenols, hydroquinone, diols containing an aromatic group such as resorcinol, and the like.

The units of the hydroxycarboxylic acids that may be contained include glycolic acid, diglycolic acid,
Lactic acid, 3 hydroxybutyric acid, p-hydroxybenzoic acid,
m-hydroxybenzoic acid, p-hydroxymethylbenzoic acid,
m-hydroxymethylbenzoic acid, p- (2-hydroxyethyl)
Benzoic acid and m- (2-hydroxyethyl) benzoic acid.

The polybutylene terephthalate used in the present invention may be a polyfunctional carboxylic acid having three or more carboxyl groups or a polyfunctional diol having three or more hydroxy groups as long as the object of the present invention is not impaired. It may contain a derived unit, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic anhydride, glycerin, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylol It may contain a unit derived from polyfunctional alcohols such as propane and pentaerthritol.

<Polyethylene 2,6-naphthalate> Polyethylene 2,6-naphthalate used as crystalline polyester (B)
Naphthalate is composed of a dicarboxylic acid unit derived from 2,6-naphthalenedicarboxylic acid or an ester derivative thereof, a diol (dihydroxy) unit derived from ethylene glycol or an ester derivative thereof, and other hydroxycarboxylic acid units.

When the units of the polyethylene 2,6 naphthalate such as dicarboxylic acid, diol and other hydroxycarboxylic acid are 100 mol% in total, 20 mol of units other than the unit of 2,6 naphthalenedicarboxylic acid and the unit of ethylene glycol are used. % Is preferable. Specific units of the dicarboxylic acid that may be contained, specifically, phthalic acid, terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as 4,4'-sulfonebisbenzoic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfidebisbenzoic acid, 4,4'-oxybisbenzoic acid, diphenoxyethanedicarboxylic acid, and malon Acid, succinic acid, glutaric acid, fumaric acid, maleic acid, adipic acid, sebacic acid,
Examples include aliphatic dicarboxylic acids such as azelaic acid and decane dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

Examples of the diols that may be contained include diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,
Aliphatic diols such as 1,6-hexanediol, neopentyl glycol, dodecamethylene glycol, triethylene glycol and tetraethylene glycol, alicyclic diols such as cyclohexanedimethanol, and 1,3-bis (2-hydroxyethoxy) benzene , 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 2,2-bis (4-β -Hydroxyethoxyphenyl) propane, bisphenols, hydroquinone, diols containing an aromatic group such as resorcinol, and the like.

The units of the hydroxycarboxylic acids which may be contained include glycolic acid, diglycolic acid,
Lactic acid, 3 hydroxybutyric acid, p-hydroxybenzoic acid,
m-hydroxybenzoic acid, p-hydroxymethylbenzoic acid,
m-hydroxymethylbenzoic acid, p- (2-hydroxyethyl)
Benzoic acid and m- (2-hydroxyethyl) benzoic acid.

Further, the polyethylene 2, used in the present invention,
6-Naphthalate may contain a unit derived from a polyfunctional carboxylic acid having three or more carboxyl groups or a polyfunctional diol having three or more hydroxy groups as long as the object of the present invention is not impaired. Often, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic anhydride, glycerin, 1,1,1-trimethylolmethane, 1,
It may contain units derived from polyfunctional alcohols such as 1,1-trimethylolethane, 1,1,1-trimethylolpropane, and pentaerthritol.

<Polyethylene isophthalate> The crystalline polyester (B) includes a dicarboxylic acid unit derived from isophthalic acid or an ester derivative thereof, a diol (dihydroxy) unit derived from ethylene glycol or an ester derivative thereof, and other hydroxyl units. And carboxylic acid units.

When the units such as dicarboxylic acid, diol and other hydroxycarboxylic acid of the polyethylene isophthalate are 100 mol% in total, the units other than the units of isophthalic acid and ethylene glycol are contained in the range of 20 mol% or less. Is preferred. Specific examples of the dicarboxylic acid unit that may be contained include phthalic acid,
Terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,
Aromatic dicarboxylic acids such as 4'-sulfonebisbenzoic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfidebisbenzoic acid, 4,4'-oxybisbenzoic acid, diphenoxyethanedicarboxylic acid, malonic acid, Succinic acid, glutaric acid,
Examples thereof include aliphatic dicarboxylic acids such as fumaric acid, maleic acid, adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

The diols that may be contained include, specifically, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,
Aliphatic diols such as 1,6-hexanediol, neopentyl glycol, dodecamethylene glycol, triethylene glycol and tetraethylene glycol, alicyclic diols such as cyclohexanedimethanol, and 1,3-bis (2-hydroxyethoxy) benzene , 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 2,2-bis (4-β -Hydroxyethoxyphenyl) propane, bisphenols, hydroquinone, and diols containing an aromatic group such as resorcinol.

The units of the hydroxycarboxylic acids that may be contained include glycolic acid, diglycolic acid,
Lactic acid, 3 hydroxybutyric acid, p-hydroxybenzoic acid,
m-hydroxybenzoic acid, p-hydroxymethylbenzoic acid,
m-hydroxymethylbenzoic acid, p- (2-hydroxyethyl)
Benzoic acid and m- (2-hydroxyethyl) benzoic acid.

The polyethylene isophthalate used in the present invention may be a polyfunctional carboxylic acid having three or more carboxyl groups or a polyfunctional diol having three or more hydroxy groups as long as the object of the present invention is not impaired. It may contain a derived unit, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic anhydride, glycerin, 1,1,1-trimethylolmethane, 1,1,
It may contain a unit derived from polyfunctional alcohols such as 1-trimethylolethane, 1,1,1-trimethylolpropane, and pentaerthritol.

The crystalline polyester (B) as described above
May be used alone or in combination of two or more. Further, these crystalline polyesters (B) shown above may be those produced according to any method generally employed for producing ordinary polyester resins. It may be produced by polycondensation. Further, the above-mentioned crystalline polyester (B) may be a solid-phase polymerized one.

The intrinsic viscosity [η] of the crystalline polyester (B) measured in a mixed solution of tetrachloroethane / phenol at 1/1 at 25 ° C. is preferably 0.4 dl / g or more. More preferably, it is 0.5 to 2.0 dl / g. Further, the crystallinity of the crystalline polyester (B) can be known by a known method such as DSC and wide-angle X-ray diffraction.

The melting peak temperature of the crystalline polyester (B) measured by DSC (fingerprint scanning calorimeter) is 50 to 300.
It is preferably in the range of ° C. Here, the melting peak temperature of DSC is determined under a normal pressure of nitrogen or helium gas flow.
After the resin composition is once melted at a temperature at which melt molding can be performed, it is rapidly cooled to room temperature at a cooling rate of about −10 ° C./min and solidified, and then again at a heating rate of 10 ° C./min to the melting temperature. Obtained by measuring. The heat of fusion is determined from the area of the peak measured under the above conditions. The heat of fusion ΔHfb is preferably 1 (J / g) or more,
0 (J / g) is more preferable.

Further, as the above-mentioned crystalline polyester, a crystalline polyester which has been used once and then separated and recovered, particularly a recovered polyethylene terephthalate resin, can also be suitably used. Polyester Resin Composition The polyester resin composition of the present invention comprises the above-mentioned succinic acid copolymerized polyester (A): 1 to 70 parts by weight, preferably 3 to 65 parts by weight, more preferably 5 to 60 parts by weight,
Crystalline polyester (B) described above: 99 to 30 parts by weight, preferably 97 to 35 parts by weight, more preferably 95 to 95 parts by weight.
-40 parts by weight.

Such a polyester resin composition of the present invention is preferably obtained by melting and mixing a predetermined amount of the succinic acid copolymerized polyester (A) and the crystalline polyester (B). In addition, it is also preferable to obtain the composition by further performing solid phase polymerization after melt mixing. The temperature at which the melt mixing is performed may be any temperature as long as the temperature is equal to or higher than the flow temperature of the succinic acid copolymerized polyester (A) and equal to or higher than the melting point of the crystalline polyester (B).
Although it is not particularly limited, it is desirable that the temperature be in a temperature range of 180 to 300 ° C, and more preferably in a temperature range of 220 to 290 ° C. The time for performing the melt mixing is preferably between 30 seconds and 4 hours, and more preferably between 1 minute and 2 hours.

As a device for performing the melt mixing, a single screw extruder, a twin screw extruder, a plast mill, a kneader, or
Examples include a reactor equipped with a stirrer and a decompression device.
It is desirable that the melting and mixing be performed under an inert gas atmosphere and / or under reduced pressure. These melt mixing may be performed in the presence of a catalyst or a stabilizer in addition to the succinic acid copolymerized polyester (A) and the crystalline polyester (B). The catalyst and the stabilizer may be previously contained in the succinic acid copolymerized polyester (A) and the crystalline polyester (B), or may be added at the time of melt mixing.

Examples of the catalyst which can be used at the time of melt mixing include alkali metals, alkaline earth metals, metals such as manganese, zinc, tin, cobalt, titanium, antimony, and germanium, and organic and inorganic compounds containing them. You. Further, examples of the stabilizer and the coloring prevention agent include a phosphorus compound and a hindered phenol compound.

Of these, phosphorus compounds are particularly preferred. Examples of the phosphorus compound include inorganic phosphorus compounds such as phosphoric acid, phosphorous acid, and polyphosphoric acid, phosphoric acid ester compounds such as trimethyl phosphoric acid and diphenyl phosphoric acid, triphenyl phosphite, and tris (2,4-di-t-butylphenyl). Examples include phosphite compounds such as phosphite. It is preferable to contain such a phosphorus compound because a resin composition having at least a favorable hue can be obtained.

The melting temperature, melting time, melt mixing equipment, etc.
The selection of the melting conditions is based on the succinic acid copolymerized polyester (A).
Is appropriately selected depending on the mixing ratio and the molecular weight of the polymer and the crystalline polyester (B), and the presence or absence of a catalyst and a stabilizer. For example, a succinic acid / isophthalic acid / ethylene glycol copolymer having a number average molecular weight of 6,000 to 30,000 and an intrinsic viscosity [η] of 0.6 using a device that performs melt kneading under normal pressure conditions such as a laboplast mill. When 0.9 dl / g of polyethylene terephthalate is mixed in the presence of a catalyst,
In the temperature range of 270-290 ° C. for 2-15 minutes,
It is preferred to be melt mixed.

When the molecular weight of the succinic acid copolymerized polyester (A) and / or crystalline polyester (B) is larger than this, it is preferable that the succinic acid copolymerized polyester is further melt-mixed for a longer period of time. In such a case, it is preferable that the mixture is melt-mixed for a longer period of time. Even when a stabilizer such as a phosphate ester is present, the mixture is preferably melt-mixed for a longer period of time. When the mixing is performed under reduced pressure, it is preferable that the melt-mixing be performed in a shorter time, and under the condition of more intense kneading, it is preferable that the melt-mixing be performed in a shorter time.

The polyester resin composition obtained by melt mixing is further kept at a temperature not higher than its melting point under reduced pressure or under an inert gas flow for a period of 20 minutes to 100 hours to obtain a solid phase polymerized polymer. May be performed. The method of solid phase polymerization is
Known methods can be employed. For example, pellets of a polyester resin composition are mixed under an inert gas atmosphere.
1-3 ° C in a temperature range of 30 ° C to below the melting peak temperature.
After pre-crystallization by holding for 00 minutes,
Solid state polymerization can be performed by maintaining the temperature in a temperature range of 20 ° C. or lower to a melting peak temperature or lower for 1 to 100 hours. The resin subjected to solid-phase polymerization is preferable because the molecular weight is increased, the mechanical strength is improved, and the content of low-molecular components is reduced.

The polyester resin composition of the present invention obtained by melt-mixing the succinic acid copolymerized polyester (A) and the crystalline polyester (B) or by melt-mixing and then solid-phase polymerization by the method described above is used. Preferably, the succinic acid copolymerized polyester (A) and the crystalline polyester (B) are compatible. Whether or not compatible, for example, the glass state, or the transparency of the resin composition in a molten state,
Judgment can be made by electron microscope observation, observation of glass transition behavior in solid viscoelasticity, observation of glass transition behavior by DSC, and the like.

In the present invention, the state of being compatible means
It means that two or more of the following four events are simultaneously satisfied. This is a state in which the internal haze value of a 0.5 mm-thick pressed sheet in a glass state or a molten state in which the resin composition has no crystals is 5% or less. Area of resin composition observed by transmission electron microscope 0.1
The average number of discontinuous phases having a length of 1 μm or more in mm ² is 2 or less. The tan δ peak (not including the shoulder) accompanying the glass transition in solid viscoelasticity is one state. This is a state in which the specific heat change of the glass transition observed by DSC occurs in a single temperature range.

When the polyester resin composition is compatible, the resin composition molded article has a higher gas barrier property than the incompatible one and has transparency, so that it can be preferably used as a container or packaging material. Further, the polyester resin composition of the present invention comprises various compounding agents such as a heat stabilizer, a weather stabilizer, a crosslinking agent, a lubricant, a nucleating agent, a release agent, an inorganic filler, a pigment dispersant, a pigment or a dye. It may be contained within a range that does not impair the object of the invention.

Since the polyester resin composition of the present invention is excellent in gas barrier properties and mechanical properties, it is suitable for applications such as packaging materials for foods and machine parts, medical materials such as pharmaceutical containers, and the like. It can be suitably used for bottles or containers such as blow-molded bottles, multilayer bottles and ampoules, films such as gas barrier films, multilayer films and paper laminated films, and sheets such as wallpapers, floor sheets and sound insulation sheets. Further, it can be suitably used as a material such as a fiber, a nonwoven fabric, and a foam, and also as a material for a multilayer molded body with another polyester resin or another thermoplastic resin.

Films, Sheets and Hollow Molded Articles The films and sheets of the present invention are formed by molding the above-mentioned resin composition of the present invention comprising the succinic acid copolymerized polyester (A) and the crystalline polyester (B). Become. Since such films and sheets have excellent gas barrier properties and mechanical properties, they can be particularly suitably used for packaging materials such as foods and mechanical parts, and can be particularly suitably used as food packaging films. .

The film and sheet of the present invention may be stretched or unstretched, and may be formed by any known method for forming a film or sheet from a resin. As a method of molding the film and sheet of the present invention, specifically, extrusion molding, injection molding,
Examples include air-cooled or water-cooled inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding, and the like.

For example, when the film and sheet of the present invention are produced by extrusion molding, conventionally known extrusion equipment and molding conditions can be adopted. For example, a single screw extruder, a kneading extruder, a ram extruder By extruding the molten polyester resin composition of the present invention from a T-die or the like using a gear extruder or the like, an unstretched film or sheet can be formed.

Further, the film and sheet of the present invention are
In the case of manufacturing by injection molding, conventionally known injection molding equipment and molding conditions can be adopted, and the polyester resin composition of the present invention can be manufactured by injection molding into a desired shape and thickness. The film and sheet obtained by extrusion molding or injection molding may be further stretched and molded.

The stretched film or sheet can be obtained by converting an unstretched film or sheet, such as the above-mentioned extruded film or sheet, by a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method and the like. It can be obtained by stretching by a known stretching method. The stretching ratio when stretching an unstretched film or sheet depends on the thickness of the unstretched film or sheet, but is usually about 2 to 70 times in the case of biaxial stretching, and in the case of uniaxial stretching. Is preferably about 2 to 10 times. The thickness of the stretched film or sheet depends on its use, but is 5 to 2 mm.
It is preferably about 00 μm.

The film and sheet of the present invention may have a single-layer structure or a multilayer structure, and may have a multilayer structure with a sheet or film made of a resin other than the polyester resin composition of the present invention. There may be. Also,
The hollow molded article of the present invention is obtained by blow-molding the above-described resin composition of the present invention comprising the succinic acid copolymerized polyester (A) and the crystalline polyester (B). Examples of the hollow molded article include beverage bottles such as liquid filling bottles and carbonated beverage filling bottles, containers, tanks, pipes, and the like, and beverage bottles are particularly preferred.

The hollow molded article of the present invention is excellent in gas barrier properties and mechanical properties. The hollow molded article of the present invention may be molded by a method involving blow molding,
Extrusion molding of a preform, which is a precursor of a hollow molded product,
By forming the preform once by injection molding or the like and then blow-molding the formed preform, a desired hollow molded product can be suitably manufactured. According to this method,
This is preferable because a hollow molded article having a complicated shape can be formed.

Such a hollow molded article of the present invention may have a single layer, a multilayer structure, or a multilayer structure with a resin other than the polyester resin composition of the present invention. The conditions for blow molding are not particularly limited, and conventionally known conditions for blow molding a polyester resin can be appropriately employed.

[0087]

Since the polyester resin composition of the present invention comprises the specific succinic acid copolymerized polyester (A) and the crystalline polyester resin (B), the molding is excellent in both gas barrier properties and mechanical properties. Goods can be provided. The polyester resin composition of the present invention can be suitably used for food packaging materials such as films and blow containers that require gas barrier properties, packaging materials for electronic components, and medical materials.

Since the succinic acid copolymer polyester (A) constituting the polyester resin composition of the present invention contains a monomer having a functionality of 3 or more, the polymerization rate is high and the succinic acid copolymer is efficiently produced. Further, the film, sheet and hollow molded article of the present invention are excellent in gas barrier properties and mechanical properties, and are suitable as food packaging materials, surface materials such as electronic components, and medical materials.

[0089]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following Production Examples, Examples and Comparative Examples, the physical properties of each resin and resin composition were measured or evaluated by the following methods. [Composition of polyester] It was calculated from the spectrum of the ¹ H nucleus using a nuclear magnetic resonance apparatus (NMR; LA500, manufactured by JEOL Ltd.). [Molecular weight of polyester] The number average molecular weight in terms of polystyrene was measured using a gel permeation chromatograph (GPC). [Intrinsic viscosity [η] of polyester and resin composition] 2
The measurement was performed at 5 ° C. in a mixed solution of tetrachloroethane / phenol = 1/1. [Gas Barrier Property of Polyester and Resin Composition] A 100 μm-thick film obtained by a predetermined method was used for evaluation of carbon dioxide gas permeability. The carbon dioxide gas permeability coefficient at 25 ° C. was measured using a gas permeability measuring device GPM-250 (manufactured by GL Sciences), and the value was evaluated.
It is shown that the smaller the value of the transmission coefficient is, the more excellent the gas barrier property is. [Mechanical Properties of Polyester and Resin Composition] For a 0.5 mm-thick press sheet obtained by a predetermined method, 2
After being left for 3 days in a condition of 3 ° C. and a relative humidity of 50%, a dumbbell-shaped sample was cut out, and a tensile tester Instron 4 was used.
Using a 501 (manufactured by Instron), a tensile test was performed at 23 ° C. and a relative humidity of 50% at a strain rate of 100% / min, and evaluated by Young's modulus and tensile strength.

[0090]

[Production Example 1] Dimethyl succinate 131.5 g, dimethyl isophthalate 58.3 g, ethylene glycol 14
9.0 g, 1,1,1-tris (hydroxymethyl) ethane
0.29 g and manganese acetate tetrahydrate 0.15 g
Was charged into a glass reactor equipped with a stirrer and a distillation tube. The distilling tube is connected to a vacuum device including a vacuum pump and a decompression regulator, and has a structure capable of distilling off evaporated substances.

First, after the reactor was sufficiently purged with nitrogen, the temperature was raised with stirring from 160 ° C. to 220 ° C. over 3 hours in a nitrogen atmosphere at normal pressure, and further maintained for 1 hour to remove methanol. The transesterification reaction was performed while distilling off. Subsequently, germanium dioxide was added to the obtained compound.
After adding 0.034 g together with 3.16 g of ethylene glycol and sufficiently purging with nitrogen, 22
Stirred at 0 ° C. for 1 hour. After that, the vacuum pump was operated, and the temperature was raised to 240 ° C. over 1 hour, and the temperature was raised and reduced to 260 ° C. and 1 Torr over 1 hour.
Subsequently, the temperature was raised to 270 ° C. over 30 minutes, and in this state, stirring was continued for 3 hours to perform polycondensation.
After the above polycondensation reaction, nitrogen gas is introduced into the system to return to normal pressure, and the polyester resin (A
1) was taken out.

The composition of the obtained polyester was such that 37.3 mol% of succinic acid units, 12.8 mol% of isophthalic acid units, 46.7 mol% of ethylene glycol units, 3.2 mol% of diethylene glycol units, The 1,1,1-tris (hydroxymethyl) ethane unit was 0.1 mol%. The number average molecular weight measured by GPC is 240
00.

[0093]

[Production Example 2] 131.5 g of dimethyl succinate, 58.3 g of dimethyl isophthalate, 14 ethylene glycol
9.0 g, 1,1,1-tris (hydroxymethyl) ethane
A reactor was charged with 0.29 g and manganese acetate tetrahydrate 0.15 g, and transesterification was carried out in the same manner as in Production Example 1. Further, the same amounts of germanium dioxide and ethylene glycol as in Production Example 1 were added, and the holding time at 270 ° C. was 1
Polycondensation was carried out in the same manner as in Production Example 1 except that the time was changed to produce a polyester resin (A2). The number average molecular weight measured by GPC was 9,300. The composition is shown in Table 1.

[0094]

Production Example 3 131.5 g of dimethyl succinate, 73.2 g of dimethyl 2,6-naphthalenedicarboxylate, 149.0 g of ethylene glycol, 0.29 g of 1,1,1-tris (hydroxymethyl) ethane and manganese acetate tetrahydrate Japanese
0.15 g was charged into a reactor, and transesterification was carried out in the same manner as in Production Example 1. Further, the same amount of germanium dioxide and ethylene glycol as in Production Example 1 was added, and polycondensation was carried out in the same manner as in Production Example 1 except that the holding time at 270 ° C. was changed to 1 hour, to thereby prepare a polyester resin (A3). Manufactured. The number average molecular weight measured by GPC was 10,200. The composition is shown in Table 1.

[0095]

Production Example 4 175.4 g of dimethyl succinate, 149.0 g of ethylene glycol, 0.29 g of 1,1,1-tris (hydroxymethyl) ethane and manganese acetate tetrahydrate
0.15 g was charged into a reactor, and transesterification was carried out in the same manner as in Production Example 1. Further, the same amount of germanium dioxide and ethylene glycol as in Production Example 1 was added, and polycondensation was carried out in the same manner as in Production Example 1 except that the holding time at 270 ° C. was changed to 1 hour, to give a polyester resin (A4). Manufactured. The number average molecular weight measured by GPC was 8,100. The composition is shown in Table 1.

[0096]

[Comparative Production Example 1] 131.5 g of dimethyl succinate, 58.3 g of dimethyl isophthalate, ethylene glycol
149.0 g and 0.15 g of manganese acetate tetrahydrate were charged into a reactor, and transesterification was carried out in the same manner as in Production Example 1. Further, the same amounts of germanium dioxide and ethylene glycol as in Production Example 1 were added, and the holding time at 270 ° C. was 3 hours.
Polycondensation was carried out in the same manner as in Production Example 1 except that the time was changed to produce a polyester resin (D1). The number average molecular weight measured by GPC was 8,500. The composition is shown in Table 1. As a result, even if polycondensation was performed for the same time as in Production Example 1, the molecular weight was small and the productivity was poor.

[0097]

[Table 1]

[0098]

Example 1 80 parts by weight of a commercially available polyethylene terephthalate (B1; Tm = 252 ° C., intrinsic viscosity [η] = 0.82 dl / g) as a crystalline polyester and succinic acid copolymerized polyester in Production Example 1 After 20 parts by weight of the produced polyester (A1) was sufficiently dried with a vacuum dryer, it was charged into a glass reactor equipped with a stirrer and a distillation tube. The reactor was heated to 280 ° C., and after preheating for 20 minutes, the mixture was stirred for 10 minutes under a normal pressure nitrogen atmosphere, then reduced to 1 Torr, and stirred for 15 minutes. Then, the polyester resin composition (C
1) was taken out and pelletized. The obtained pellets were measured for intrinsic viscosity [η].

Next, the obtained polyester resin composition (C1) pellets were thoroughly dried with a vacuum drier, and then dried.
A predetermined amount is sandwiched between a brass plate, an aluminum plate and a release film, melted at 280 ° C., compressed at 10 MPa for 1 minute, and then compressed again at 10 ° C. with a compression molding machine set at 0 ° C.
a) A sheet having a thickness of 0.5 mm and a thickness of 1
A 00 μm film was formed.

A 100 μm thick film obtained by the above method was used for evaluation of carbon dioxide gas permeability, and a 0.5 mm thick press sheet was used for a tensile test. Table 2 shows the results of each evaluation.

[0101]

Example 2 The procedure of Example 2 was repeated except that 70 parts by weight of a commercially available polyethylene terephthalate (B1) was used as the crystalline polyester, and 30 parts by weight of the polyester (A1) produced in Production Example 1 was used as the succinic acid copolymerized polyester. A resin composition was produced in the same manner as in Example 1 and evaluated in the same manner. Table 2 shows the results of each evaluation.

[0102]

Example 3 The procedure was carried out except that 90 parts by weight of commercially available polyethylene terephthalate (B1) was used as the crystalline polyester and 10 parts by weight of the polyester (A1) produced in Production Example 1 was used as the succinic acid copolymerized polyester. A resin composition was produced in the same manner as in Example 1, and was evaluated in the same manner. Table 2 shows the results of each evaluation.

[0103]

Example 4 The procedure was carried out except that 80 parts by weight of commercially available polyethylene terephthalate (B1) was used as the crystalline polyester and 20 parts by weight of the polyester (A2) produced in Production Example 2 was used as the succinic acid copolymerized polyester. A resin composition was produced in the same manner as in Example 1, and was evaluated in the same manner. Table 2 shows the results of each evaluation.

[0104]

Example 5 The resin composition pellets obtained in Example 4 were maintained at 140 ° C. for 2 hours in a nitrogen atmosphere to crystallize, and then maintained at 190 ° C. for 6 hours under a nitrogen stream to carry out solid state polymerization. Carried out. About the obtained resin composition, Example 1
The evaluation was performed in the same manner as described above. Table 2 shows the results of each evaluation.

[0105]

Comparative Example 1 As a crystalline polyester, 20 parts by weight of a commercially available polyethylene terephthalate (B1) and 20 parts of a succinic acid copolymer polyester (D1) produced in Comparative Production Example 1 and containing no monomer unit having a functionality of 3 or more were used. A resin composition was manufactured in the same manner as in Example 1 except that the resin composition was used in parts by weight, and the evaluation was performed in the same manner. Table 2 shows the results of each evaluation. As a result, the tensile strength was particularly low due to the low molecular weight.

[0106]

Comparative Example 2 The resin composition pellets obtained in Comparative Example 1 were kept at 140 ° C. for 2 hours in a nitrogen atmosphere to be crystallized, and then kept at 190 ° C. for 6 hours under a nitrogen stream to carry out solid phase polymerization. Was carried out. The obtained resin composition was evaluated in the same manner as in Example 1. Table 2 shows the results of each evaluation. As a result, it was found that the elongation of the molecular weight was small even when the solid phase polymerization was performed, and the tensile strength was inferior to those of Examples 1 and 5.

[0107]

Example 6 The procedure of Example 6 was repeated except that 80 parts by weight of a commercially available polyethylene terephthalate (B1) was used as the crystalline polyester and 20 parts by weight of the polyester (A3) produced in Production Example 3 was used as the succinic acid copolymerized polyester. A resin composition was produced in the same manner as in Example 1, and was evaluated in the same manner. Table 2 shows the results of each evaluation.

[0108]

Example 7 The procedure was carried out except that 70 parts by weight of commercially available polyethylene terephthalate (B1) was used as the crystalline polyester and 30 parts by weight of the polyester (A3) produced in Production Example 3 was used as the succinic acid copolymerized polyester. A resin composition was produced in the same manner as in Example 1, and was evaluated in the same manner. Table 2 shows the results of each evaluation.

[0109]

Example 8 Example 1 was repeated except that 80 parts by weight of commercially available polyethylene terephthalate (B1) was used as the crystalline polyester and 20 parts by weight of the polyester (A4) produced in Production Example 4 was used as the succinic acid copolymerized polyester. A resin composition was produced in the same manner as in the above, and evaluated in the same manner. Table 2 shows the results of each evaluation.

[0110]

Example 9 Example 1 was repeated except that 70 parts by weight of a commercially available polyethylene terephthalate (B1) was used as the crystalline polyester and 30 parts by weight of the polyester (A4) produced in Production Example 4 was used as the succinic acid copolymerized polyester. A resin composition was produced in the same manner as in the above, and evaluated in the same manner. Table 2 shows the results of each evaluation.

[0111]

Example 10 Commercially available polybutylene terephthalate (B2; Tm = 224 ° C., [η]) as a crystalline polyester
= 0.87 dl / g) A resin composition was produced in the same manner as in Example 1 except that 70 parts by weight of the succinic acid copolymerized polyester and 30 parts by weight of the polyester (A1) produced in Production Example 1 were used. The evaluation was performed in the same manner. Table 2 shows the results of each evaluation.

[0112]

Example 11 Commercially available polytrimethylene terephthalate (B3; Tm = 227 ° C.,
[η] = 1.00 dl / g) A resin composition was prepared in the same manner as in Example 1 except that 70 parts by weight of the succinic acid copolymerized polyester and 30 parts by weight of the polyester (A1) produced in Production Example 1 were used. Was manufactured and evaluated similarly. Table 2 shows the results of each evaluation.

[0113]

Example 12 Dimethyl 2,6 naphthalenedicarboxylate 2
44.2 g, 124.2 g of ethylene glycol, and 0.12 g of manganese acetate tetrahydrate were heated while stirring from 160 ° C. to 220 ° C. over 3 hours under a nitrogen atmosphere at normal pressure, and held for 1 hour. Then, transesterification was carried out while distilling off methanol. Subsequently, 0.028 g of germanium dioxide was added to the obtained compound together with 2.63 g of ethylene glycol, and after sufficiently purging with nitrogen, the mixture was stirred at 220 ° C. for 1 hour under a normal pressure nitrogen stream. Thereafter, the vacuum pump is operated to raise the temperature to 260 ° C. over 2 hours, and further at 285 ° C. and 1 Torr over 1 hour.
The temperature was raised and the pressure was reduced to, and in this state, stirring was continued for 2 hours and 30 minutes to perform polycondensation. After the above polycondensation reaction,
Polyethylene 2,6 naphthalate (B4; Tm = 270
° C, intrinsic viscosity [η] = 0.57 dl / g).

Next, the commercially available polyethylene 2,6 naphthalate (B4) 70 obtained above as a crystalline polyester was prepared.
A resin composition was produced in the same manner as in Example 1 except that 30 parts by weight of the polyester (A1) produced in Production Example 1 was used as the succinic acid copolymerized polyester as the succinic acid copolymerized polyester, and the same evaluation was performed. Table 2 shows the results of each evaluation.

[0115]

Comparative Example 3 Evaluation was made in the same manner as in Example 1 for polyethylene terephthalate (B1). Table 2 shows the results of each evaluation.

[0116]

Comparative Example 4 Polybutylene terephthalate (B2) was evaluated in the same manner as in Example 1. Table 2 shows the results of each evaluation.

[0117]

Comparative Example 5 Polytrimethylene terephthalate (B3)
Was evaluated in the same manner as in Example 1. Table 2 shows the results of each evaluation.

[0118]

Comparative Example 6 Evaluation was made in the same manner as in Example 1 for polyethylene 2,6 naphthalate (B4). Table 2 shows the results of each evaluation.

[0119]

Comparative Example 7 As crystalline polyester, 80 parts by weight of commercially available polyethylene terephthalate (B1) and commercially available gas barrier polyester (B100 manufactured by Mitsui Chemicals, Inc .;
A resin composition was manufactured in the same manner as in Example 1 except that [η] = 0.814) was used in an amount of 20 parts by weight, and the evaluation was performed in the same manner. Table 2 shows the results of each evaluation.

[0120]

[Table 2]

[0121]

[Table 3]

Continued on the front page F term (reference) 3E033 AA20 BA10 BA17 BA18 BB01 BB04 BB08 CA03 CA16 FA02 FA03 4F071 AA43 AA44 AF08 AH04 BA01 BB05 BB06 BB07 BB09 BC01 BC04 4J002 CF00W CF01X CF02X CF03X CF04 CF07 CF08 CF04 CF08 GG00

Claims (9)

[Claims] (1) Assuming that the total constitutional units of the (A) succinic acid copolymerized polyester are 100 mol%, the succinic acid copolymer contains 24 to 50 mol% and the aromatic dicarboxylic acid unit has 0 to 26 mol%. A succinic acid containing 90 mol% or more in total of a succinic acid unit, an aromatic dicarboxylic acid unit and an ethylene glycol unit, and further containing 0.001 to 2 mol% of a monomer unit having a functionality of 3 or more and having an ester-forming ability. A polyester resin composition comprising: 1 to 70 parts by weight of a copolymerized polyester; and 99 to 30 parts by weight of a crystalline polyester (B). 2. The polyester resin composition according to claim 1, wherein the aromatic dicarboxylic acid unit of the succinic acid copolymerized polyester (A) is an isophthalic acid unit and / or a 2,6-naphthalenedicarboxylic acid unit. 3. When (A) 100 mol% of all the constituent units of the succinic acid copolymerized polyester are contained, the succinic acid unit is contained in an amount of 24 to 49 mol%, and isophthalic acid unit and / or 2,6-naphthalenedicarboxylic acid Contains a total of 1 to 26 mol% of units, and a total of 9 units of succinic acid units, isophthalic acid units, 2,6-naphthalenedicarboxylic acid units and ethylene glycol units
A succinic acid copolyester containing 0 mol% or more and 0.001 to 2 mol% of a monomer unit having a functionality of 3 or more having an ester forming ability: 1 to 70 parts by weight, and (B) a crystalline polyester : 99 to 30 parts by weight of a polyester resin composition. 4. The succinic acid copolymerized polyester (A), wherein the ester unit-forming monomer unit having a functionality of 3 or more is a unit derived from a polyfunctional alcohol.
The polyester resin composition according to any one of the above. 5. The succinic acid copolymerized polyester (A), wherein the monomer unit having an ester-forming ability and having a functionality of 3 or more is glycerin, 1,1,1-tris (hydroxymethyl) ethane,
The polyester resin composition according to any one of claims 1 to 3, which is a unit derived from at least one selected from the group consisting of 1,1,1-tris (hydroxymethyl) propane, pentaerythritol, and dipentaerythritol. . 6. The crystalline polyester (B) is at least one crystalline polyester selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6 naphthalate, and polyethylene isophthalate. The polyester resin composition according to claim 1. 7. The polyester resin composition according to claim 1, wherein the succinic acid copolymerized polyester (A) and the crystalline polyester (B) are compatible. 8. A sheet or film formed by molding the polyester resin composition according to claim 1. 9. A hollow molded article obtained by blow molding the polyester resin composition according to claim 1.