JP2003020330A - Polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polyester resin that exhibits excellent molding processability and gives a molded article excellent in impact resistance. SOLUTION: The polyester resin primarily comprises a dicarboxylic acid unit comprising a terephthalic acid unit (I) and a 1,4-cyclohexane dicarboxylic acid unit (II) and/or an isophthalic acid unit (III) and a diol unit comprising an ethylene glycol unit (IV) and a 1,4-cyclohexane dimethanol unit (V) and has a melting point of 210-250 deg.C and an intrinsic viscosity of 0.6-1.5 dl/g wherein a molar ratio of the constitutional units is given alternatively as A : I: (II +III)=97:3-90:10 and IV:V=97:3-88:12 or as B : I: (II+III)=95:5-80:20 and IV:V=20:80-5:95.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyester resin and a molded product thereof. More specifically, a polyester resin having excellent moldability and excellent impact resistance, a film made of the resin, a laminate including a layer made of the film, a container in a bag-in-box made of the laminate, etc. Regarding molded products.

[0002]

2. Description of the Related Art The function required for a flexible laminated packaging material is basically preservation of the packaged material, that is, prevention of deterioration. Pinhole property is required. Among them, so-called bag-in-box or bag-in-carton (hereinafter, these are collectively referred to as bag-in-box)
When it is used as an inner container, it is required to have various high performances. Here, the bag-in-box is a container in which a foldable plastic thin-walled inner container and an outer corrugated cardboard box having stackability, portability, and printability are combined.

Since the bag-in-box container always has a heat-sealing portion, the material for the bag-in-box container is mainly a heat-sealable polyethylene resin, particularly a soft polyethylene resin.
However, the polyethylene-based resin is inferior in flavor and aroma and is not preferable as a container in a bag-in-box. On the other hand, polyethylene terephthalate resin, which has good flavor and aroma retention, generally has low mechanical strength as a film, and is not particularly resistant to transport vibration and bending fatigue. There is.

[0004]

As a means for improving the impact resistance of a polyester resin such as polyethylene terephthalate, the polyester resin after melt polymerization is usually pelletized and then crystallized so that the pellets do not stick to each other. A method is known in which solid-state polymerization is performed below the melting point of the polyester resin to increase the molecular weight. It is also known that the impact resistance of the polyester resin is further improved by copolymerizing, for example, cyclohexanedimethanol or the like with a polyester resin component and increasing the molecular weight by solid-phase polymerization.

However, polyethylene terephthalate is brought into a low crystallized state or an amorphous state by copolymerizing a specific amount of cyclohexanedimethanol. In this case, since crystallinity that can be used for solid phase polymerization cannot be obtained, impact resistance cannot be further improved by increasing the molecular weight.

Therefore, the object of the present invention is not to impair the excellent moldability and originality of the polyester resin, and to preserve the flavor and aroma, and to have excellent impact resistance, and to bend during transportation and transportation. The object is to provide a novel polyester resin which gives a molded product with less generation of pinholes caused by vibration. Another object of the present invention is to provide a molded article such as a film having excellent impact resistance and pinhole resistance, a flexible laminate including a layer made of the film, and a bag-in-box container made of the laminate. To do.

[0007]

The present inventors have found that a terephthalic acid unit and a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and / or isophthalic acid units in a specific ratio, an ethylene glycol unit and 1 unit. , 4-
It was found that a polyester resin mainly composed of a diol unit containing a cyclohexanedimethanol unit in a specific ratio is suitable for the above purpose, and as a result of further studies, the present invention has been completed.

That is, the present invention relates to the terephthalic acid unit (I) and the 1,4-cyclohexanedicarboxylic acid unit (I).
I) and / or a dicarboxylic acid unit mainly composed of an isophthalic acid unit (III) and a glycol resin mainly composed of an ethylene glycol unit (IV) and a 1,4-cyclohexanedimethanol unit (V). And the molar ratio of the above structural units is [terephthalic acid unit (I)]: [1,4-cyclohexanedicarboxylic acid unit (II) + isophthalic acid unit (III)] = 97: 3 to 90:10, and [Ethylene glycol unit (IV)]: [1,4-cyclohexanedimethanol unit (V)] = 97: 3 to 88:12, the melting point is 210 to 250 ° C., and the intrinsic viscosity is 0.
Polyester resin having 6 to 1.5 dl / g (hereinafter, may be abbreviated as polyester resin A), or terephthalic acid unit (I) and 1,4-cyclohexanedicarboxylic acid unit (II) and / or isophthalic acid A polyester resin mainly composed of a dicarboxylic acid unit mainly composed of a unit (III) and a glycol unit mainly composed of an ethylene glycol unit (IV) and a 1,4-cyclohexanedimethanol unit (V), wherein The molar ratio is [terephthalic acid unit (I)]:
[1,4-Cyclohexanedicarboxylic acid unit (II) +
Isophthalic acid unit (III)] = 95: 5 to 80: 2
0, and [ethylene glycol unit (IV)]: [1,
4-Cyclohexanedimethanol unit (V)] = 20:
80-5: 95 and a melting point of 210-25
Provided is a polyester resin having an intrinsic viscosity of 0.6 to 1.5 dl / g at 0 ° C. (hereinafter sometimes abbreviated as polyester resin B).

The present invention also provides a molded article such as a film made of the above polyester resin, a laminate having at least one layer made of the film, and a bag-in-box container made of the laminate.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The dicarboxylic acid unit constituting the polyester resin of the present invention comprises a terephthalic acid unit (I) and a 1,4-cyclohexanedicarboxylic acid unit (II) or an isophthalic acid unit (III) in a specific ratio. contains. The diol units constituting the polyester resin of the present invention include ethylene glycol units (IV) and 1,4-
Cyclohexanedimethanol unit (V) is contained in a specific ratio.

In the polyester resin A, the molar ratio of these constituent units is [terephthalic acid unit (I)]: [1,4
-Cyclohexanedicarboxylic acid unit (II) + isophthalic acid unit (III)] = 97: 3 to 90:10, and [ethylene glycol unit (IV)]: [1,4-cyclohexanedimethanol unit (V)] = 97 : 3-8
8:12, and in the polyester resin B, [terephthalic acid unit (I)]: [1,4-cyclohexanedicarboxylic acid unit (II) + isophthalic acid unit (III)] = 9
It is 5: 5 to 80:20 and [ethylene glycol unit (IV)]: [1,4-cyclohexanedimethanol unit (V)] = 20:80 to 5:95. A molar ratio of 1,4-cyclohexanedicarboxylic acid unit (II) and / or isophthalic acid unit (III), and 1,4-
When the molar ratio of the cyclohexanedimethanol unit (V) is within the above range, a polyester resin excellent in mechanical strength and impact resistance can be obtained.

From the viewpoint of impact resistance, polyester resin A
Then, 1,4-cyclohexanedicarboxylic acid unit (I
The molar ratio of I) and / or the isophthalic acid unit (III) is [terephthalic acid unit (I)]: [1,4-cyclohexanedicarboxylic acid unit (II) + isophthalic acid unit (III)] = 96: 4 to It is preferably 91: 9, and the molar ratio of 1,4-cyclohexanedimethanol units (V) is [ethylene glycol units (IV)]:
[1,4-Cyclohexanedimethanol unit (V)] =
It is preferably 96: 4 to 89:11. In the polyester resin A, 1,4-cyclohexanedicarboxylic acid unit (II) and / or isophthalic acid unit (II
It is more preferable from the viewpoint of impact resistance of the polyester resin that both the molar ratio of I) and the molar ratio of 1,4-cyclohexanedimethanol unit (V) are within the above preferable ranges.

From the viewpoint of impact resistance, the polyester resin B contains 1,4-cyclohexanedicarboxylic acid unit (II) and / or isophthalic acid unit (II).
The molar ratio of I) is [terephthalic acid unit (I)]: [1,
4-cyclohexanedicarboxylic acid unit (II) + isophthalic acid unit (III)] = 94: 6 to 81:19 is preferable, and the molar ratio of 1,4-cyclohexanedimethanol unit (V) is [ethylene glycol Unit (I
V)]: [1,4-cyclohexanedimethanol unit (V)] = 19:81 to 6:94 is preferable. In the polyester resin B, both the molar ratio of the 1,4-cyclohexanedicarboxylic acid unit (II) and / or the isophthalic acid unit (III) and the molar ratio of the 1,4-cyclohexanedimethanol unit (V) are as described above. It is more preferable that it is within the preferable range from the viewpoint of impact resistance of the polyester resin.

The polyester resin of the present invention can be produced according to a method generally employed in producing a general-purpose polyester resin such as polyethylene terephthalate. For example, the polyester resin of the present invention,
A dicarboxylic component mainly consisting of terephthalic acid, 1,4-cyclohexanedicarboxylic acid and / or isophthalic acid, and a diol component mainly consisting of ethylene glycol and 1,4-cyclohexanedimethanol are mixed,
It can be produced by melt polycondensation through an esterification reaction or a transesterification reaction. Then, the obtained polyester resin may be pelletized into an arbitrary shape and further solid-phase polymerized if desired. In the production of the polyester resin of the present invention, terephthalic acid, 1,4-
The molar ratio of cyclohexanedicarboxylic acid and / or isophthalic acid and the molar ratio of ethylene glycol and 1,4-cyclohexanedimethanol are preferably the same as those of the respective constituent units.

The polyester resin of the present invention is terephthalic acid, isophthalic acid, 1,4
-Can contain dicarboxylic acid units other than cyclohexanedicarboxylic acid. Examples of such a dicarboxylic acid unit include 2,6-naphthalenedicarboxylic acid, 2,
Dicarboxylic acid units derived from aromatic dicarboxylic acids such as 7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid; 1,3- Dicarboxylic acid units derived from alicyclic dicarboxylic acids such as cyclopentanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid; malonic acid, dimethylmalonic acid, succinic acid, 3,3
-Derived from aliphatic dicarboxylic acids such as diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid Examples include dicarboxylic acid units.

The polyester resin of the present invention is derived from the above-mentioned dicarboxylic acid unit and, in a small amount, from a trifunctional or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid and tricarballylic acid. It may contain a small amount of units. The amount is preferably 1 mol% or less of all dicarboxylic acid units.

The polyester resin of the present invention may contain a diol unit other than 1,4-cyclohexanedimethanol and ethylene glycol within the range not impairing the object of the invention. Examples of such diol units include diol units derived from aliphatic diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentadiol, and 1,6-hexanediol;
A diol unit derived from an alicyclic diol such as 1,1-cyclohexanedimethanol; 2,2-bis (4-β
-Hydroxyethoxydiphenyl) propane, bis (4
Examples include diol units derived from aromatic diols such as -β-hydroxyethoxydiphenyl) sulfone.

In addition to the above-mentioned diol units, the polyester resin of the present invention includes, for example, trifunctional or higher polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, 1,2-hexanetriol and pentaerythritol. May contain units derived from The amount is preferably 1 mol% or less of all diol units.

A polymerization catalyst can be used in the production of the polyester resin of the present invention. Examples of the polymerization catalyst include antimony compounds such as antimony trioxide and antimony acetate; titanium compounds such as isopropyl titanate and titanium acetate; germanium compounds such as germanium dioxide, germanium tetraethoxide and germanium tetra-n-butoxide. . No decrease in molecular weight even in extrusion molding with long melt residence time,
Since a polyester resin excellent in aroma retention is obtained,
It is preferable to use a germanium compound as a polymerization catalyst. The amount of the polymerization catalyst used is not particularly limited, but the content in the polyester resin is usually 50 to 3
The range is 00 ppm.

When the polyester resin of the present invention is produced, the polycondensation reaction is carried out in the presence of a phosphorus compound such as phosphoric acid, phosphorous acid, trimethyl phosphate, tributyl phosphate, trioctyl phosphate or triphenyl phosphate. It is possible to prevent coloring of the obtained polyester resin due to thermal decomposition and reduction of the molecular weight during melt molding.

The polyester resin in the present invention must have a melting point within the range of 210 to 250 ° C.
If the melting point of the polyester resin is outside this range, the molding processability of the polyester resin and the impact resistance of the molded product obtained from the polyester resin will be reduced. From the viewpoint of the moldability of the polyester resin and the impact resistance of the molded product obtained from the polyester resin, the melting point of the polyester resin is preferably in the range of 215 to 245 ° C.

The intrinsic viscosity of the polyester resin of the present invention must be within the range of 0.6 to 1.5 dl / g. Intrinsic viscosity of polyester resin is 0.6dl / g
If it is less than 100, the impact resistance of the molded product obtained from the polyester resin is poor. On the other hand, when the intrinsic viscosity of the polyester resin exceeds 1.5 dl / g, the moldability of the polyester resin deteriorates. From the viewpoint of impact resistance of the molded product obtained from the polyester resin and molding processability of the polyester resin, the intrinsic viscosity of the polyester resin is 0.7 to
It is preferably within the range of 1.2 dl / g.

The polyester resin of the present invention may contain additives such as stabilizers, lubricants, fillers, antistatic agents and pigments for improving heat aging resistance and light resistance as long as the effects of the present invention are not impaired. You may add in.

The polyester resin of the present invention is produced by extrusion molding,
By a molding method such as injection molding, it can be molded into an arbitrary shape such as a film, a sheet and a tube. Also,
For example, a layer made of the polyester resin of the present invention and a layer made of another material are formed by using a generally used molding method such as a T-die molding method, an inflation molding method, a coextrusion molding method, and a dry laminate molding method. It is also possible to manufacture a laminate having the above. The laminated body has a two-layer structure in which a layer made of a polyester resin and a layer made of another material are laminated one by one, and a three-layer structure in which a layer made of another material is laminated on both sides of a layer made of a polyester resin. Examples include a body, a multilayer structure in which a layer made of a polyester resin and a plurality of layers made of other materials are laminated. There is no particular limitation on the number of layers in the laminate and the layer configuration, and an appropriate configuration may be used according to the application. Further, the laminated body may have any shape such as a film, a sheet, a tube and the like. When forming the layer made of the polyester resin of the present invention, it is preferable to use the film made of the polyester of the present invention. A crystalline polyester resin is desirable as a material for forming the other layers in the laminate.

The crystalline polyester resin is mainly composed of terephthalic acid units and isophthalic acid units,
The molar ratio of terephthalic acid units to isophthalic acid units is 99:
It is composed of a diol unit consisting of a dicarboxylic acid unit of 1 to 80:20 and an ethylene glycol unit, and has a melting point of 210 to 250 ° C. and an intrinsic viscosity of 0.6 to 1.5 dl / g.
Are preferred. The molar ratio of the terephthalic acid unit to the isophthalic acid unit in the dicarboxylic acid unit constituting the crystalline polyester resin is 95: 5 to 85:
It is more preferably within the range of 15. Further, when the melting point of the crystalline polyester resin is less than 210 ° C., the crystalline polyester resin is inferior in heat resistance and may not be able to withstand heating during heat sealing, which is not preferable. On the other hand, when the melting point of the crystalline polyester resin exceeds 250 ° C., the crystalline polyester resin is inferior in heat sealability, which is not preferable. The melting point of the crystalline polyester resin is more preferably 215 to 245 ° C. When the intrinsic viscosity of the crystalline polyester resin is less than 0.6 dl / g, the impact resistance of the molded product formed of the laminate tends to be impaired, while the intrinsic viscosity of the crystalline polyester resin is 1 If it exceeds 0.5 dl / g, the melt moldability of the laminate tends to be impaired, which is not preferred in any case. The intrinsic viscosity of the crystalline polyester resin is more preferably in the range of 0.7 to 1.2 dl / g.

The diol unit constituting the crystalline polyester resin is, for example, in addition to the ethylene glycol unit,
A small amount of a unit derived from a trifunctional or higher-functional polyhydric alcohol such as trimethylolethane, trimethylolpropane, glycerin, 1,2,6-hexanetriol, and pentaerythritol can be contained in a small amount, but the units are all diol units. Is preferably 1 mol% or less.

The crystalline polyester resin can be produced by the same method as the polyester resin of the present invention. When a germanium compound is used as a polymerization catalyst in the production of crystalline polyester, a crystalline polyester resin excellent in aroma retention is obtained. Further, when the polycondensation reaction is carried out in the presence of a phosphorus compound such as phosphoric acid, phosphorous acid, trimethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, the molecular weight at the time of coloration and melt molding due to thermal decomposition A crystalline polyester resin without deterioration is obtained. Also, for crystalline polyester resin, heat aging resistance during molding,
Additives such as stabilizers, lubricants, fillers, antistatic agents and pigments for improving light resistance can be added.

The laminate of the present invention having at least one layer of a film made of a polyester resin and at least one layer of a film made of a crystalline polyester resin is suitable for producing a bag-in-box container. .
Although the layer structure in such a laminate is not particularly limited, it is preferably a structure having a crystalline polyester resin layer on one surface of the layer comprising the polyester resin of the present invention, and the crystalline polyester resin layer is a content. It is preferable that it is a contact surface with an object and that the laminate can be heat-sealed.

The thickness of the laminate having a layer made of the polyester resin of the present invention is not particularly limited,
In the case of a laminate having a structure having a crystalline polyester resin layer on one surface of the layer made of the polyester resin of the present invention, the total thickness is preferably in the range of 30 to 200 μm, and in the range of 40 to 150 μm. More preferably. When the total thickness exceeds 200 μm, the flexibility of the laminate is lowered, and when the inner container of the bag-in-box is formed from the laminate, the weight of the container becomes large, which is not preferable in terms of cost. . When the total thickness is less than 30 μm, the laminate has low mechanical strength and is easily broken, and pinholes are easily generated in the layer made of the polyester resin of the present invention. The produced bag-in-box container cannot adequately protect the contents and is not suitable for the intended purpose. The thickness of the crystalline polyester resin layer is 5 to
It is preferably in the range of 30 μm, and 5 to 20 μm
Is more preferably within the range. When the thickness of the crystalline polyester resin layer is more than 30 μm, the flexibility of the laminate is poor, while when the thickness of the crystalline polyester resin layer is less than 5 μm, a bag having good aroma retention property. In-box containers cannot be manufactured.

The bag-in-box container obtained from such a laminate has excellent flavor and aroma retention, impact resistance and portability, and is required to be preserved in drinking water, wine, edible oil, soy sauce, sauce and the like. It is particularly useful as a material for a container in a bag-in-box that uses the liquid as a content.

[0031]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, various physical property evaluations were performed as follows.

(A) Intrinsic viscosity Phenol / tetrachloroethane mixed solvent (weight ratio:
1/1) in 30 degreeC.

(A) Melting point The endothermic peak temperature due to melting of the resin observed when measured with a DSC30 (trade name) manufactured by METTLER CORPORATION under the conditions of a sample amount of 10 mg and a heating rate of 10 ° C./min. I asked.

(C) By film-forming extrusion molding, a two-layer melt-extruded film comprising a layer (thickness: 50 μm) made of the polyester resin of the present invention and a crystalline polyester resin layer (thickness: 10 μm) is produced. The film forming property was evaluated according to the following criteria. ◯: Stable film formation with almost no film breakage. ×: gel and lumps were generated, many film breakages occurred,
Poor film formability.

(D) Impact resistance Layer comprising the polyester resin of the present invention (thickness: 50 μ
m) and a crystalline polyester resin layer (thickness: 10 μm) from a two-layer melt-extruded film, 100 × 100 m
A test piece having a size of m is cut out, and a film impact tester (manufactured by Toyo Seiki Co., Ltd.) is used to obtain a temperature of 20 ° C. and a relative humidity of 65
%, The 10 test pieces were measured and the average value was obtained. The larger the value, the better the impact resistance.

(E) Pinhole resistance It was measured using a Gelbo flex tester (manufactured by Rigaku Kogyo Co., Ltd.). 30.5 cm × 20.3 cm (12 inches × 8 inches) from a two-layer melt-extruded film composed of a layer (thickness: 50 μm) of the polyester resin of the present invention and a crystalline polyester resin layer (thickness: 10 μm)
Cut out a test piece of 8.9 cm (3.5 inch) in diameter
It has a cylindrical shape. Grasp both ends and set initial gripping interval 1
7.8 cm (7 inches), gripping interval 2.5 at maximum bending
cm (1 inch), first 8.9 cm of stroke
(3.5 inches), add a twist of 440 °,
After that, a 6.4 cm (2.5 inch) is a linear horizontal motion. Using a Gelbo flex tester that performs reciprocating reciprocating motion at a speed of 40 times / minute, under the condition of 20 ° C. and 65% relative humidity. The occurrence of pinholes in the test piece was observed. The larger the number of reciprocations until one pinhole occurs, the better the pinhole resistance.

Example 1 (1) Production of polyester resin (a) Terephthalic acid 157.8 parts by weight, 1,4-cyclohexanedicarboxylic acid 8.6 parts by weight, ethylene glycol 6
0.04 parts by weight of phosphorous acid was added to a slurry composed of 7.0 parts by weight and 14.4 parts by weight of 1,4-cyclohexanedimethanol.
1 part by weight, and as a catalyst germanium dioxide 0.0
3 parts by weight was added, the mixture was heated to an internal temperature of 260 ° C. under a pressure of 2.5 kg / cm ² , and an esterification reaction was carried out until the esterification rate reached 95%, to produce a low polymerization composition. Further, this low-polymerization composition was melt-polymerized at a temperature of 280 ° C. under a reduced pressure of 133 Pa (1 torr) in absolute pressure, and then extruded from a nozzle in a strand shape and cut to manufacture polyester chips. The intrinsic viscosity of this polyester was 0.8 dl / g. Further, the chips obtained above were dried at 120 ° C. for 4 hours and then dried under reduced pressure at 200 ° C.
Solid-state polymerization for 23 hours at ℃, terephthalic acid unit 95 mol%
And 1,4-cyclohexanedicarboxylic acid unit 5 mol% dicarboxylic acid unit, and ethylene glycol unit 90
A polyester resin (a) consisting of mol% and 1,4-cyclohexanedimethanol unit of 10 mol% of diol unit was produced. The polyester resin (a) had an intrinsic viscosity of 1.04 dl / g and a melting point of 218.6 ° C.

(2) Production of Crystalline Polyester Resin A slurry containing 157.8 parts by weight of terephthalic acid, 8.3 parts by weight of isophthalic acid and 74.5 parts by weight of ethylene glycol, 0.01 part by weight of phosphorous acid, and Add 0.03 parts by weight of germanium dioxide as a catalyst, and add 2.5
Under an applied pressure of kg / cm ² , the internal temperature is heated to 260 ° C., and the esterification reaction is performed until the esterification rate reaches 95%,
A low polymerization composition was produced. Furthermore, this low-polymerization composition was subjected to a pressure reduction of 133 Pa (1 torr) at 280 ° C.
Were melt-polymerized at a temperature of 1, and then extruded from a nozzle into a strand and cut to produce polyester chips. The intrinsic viscosity of this polyester was 0.75 dl / g. Further, the obtained chips were dried at 120 ° C. for 4 hours and then solid-state polymerized at 200 ° C. for 18 hours under reduced pressure to obtain 95 mol% of terephthalic acid and 5 mol% of isophthalic acid and 100 mol of ethylene glycol units. A crystalline polyester resin consisting of mol% diol units was prepared. The crystalline polyester resin thus obtained had an intrinsic viscosity of 0.92 dl / g and a melting point of 222.0 ° C.

(3) Manufacture of Laminated Body Two extruders having a melt channel in which the polyester resin (a) and the crystalline polyester resin obtained above are connected to a T die [Osaka Seiki Kogaku KK, "EXT""
(Commercial name); polyester resin (a) having a diameter of 65 cm and crystalline polyester resin having a diameter of 40 cm] were used to melt at 265 ° C.
Melt extrusion was carried out simultaneously at 0 ° C. to produce a laminate (film) composed of a layer (thickness: 50 μm) made of the polyester resin (a) and a crystalline polyester resin layer (thickness: 10 μm). Table 1 shows the physical properties of the polyester resin (a) and the crystalline polyester resin, and Table 2 shows the evaluation results of the physical properties of the laminate.
Shown in.

Example 2 In Example 1, 157.8 parts by weight of terephthalic acid, 8.3 parts by weight of isophthalic acid, and 67.0 ethylene glycol.
Parts by weight and 1,4-cyclohexanedimethanol 1
The same operation as in Example 1 was carried out except that a slurry of 4.4 parts by weight was used and the solid-phase polymerization was carried out at 200 ° C. for 25 hours to obtain 95 mol% of terephthalic acid unit and 5 mol% of isophthalic acid unit. A polyester resin (b) comprising 90 mol% of ethylene glycol units and 10 mol% of 1,4-cyclohexanedimethanol units of diol units was prepared. Polyester resin (b) has an intrinsic viscosity of 1.05 dl / g and a melting point of 21.
It was 8.4 ° C. Using this polyester resin (b) and the above crystalline polyester resin, a laminate (film) was produced in the same manner as in Example 1. Table 1 shows the physical properties of the polyester resin (b), and Table 2 shows the evaluation results of the physical properties of the laminate.
Shown in.

Example 3 In Example 1, 141.2 parts by weight of terephthalic acid,
25.8 parts by weight of 1,4-cyclohexanedicarboxylic acid,
The same operation as in Example 1 was carried out except that a slurry consisting of 14.9 parts by weight of ethylene glycol and 115.4 parts by weight of 1,4-cyclohexanedimethanol was used and the solid phase polymerization was carried out at 200 ° C. for 22 hours. A polyester comprising 85 mol% of terephthalic acid units and 15 mol% of 1,4-cyclohexanedicarboxylic acid units and 20 mol% of ethylene glycol units and 80 mol% of 1,4-cyclohexanedimethanol units of diol units. Resin (c) was produced. Polyester resin (c) has an intrinsic viscosity of 1.05 dl / g and a melting point of 22.
It was 7.6 ° C. Using this polyester resin (c) and the above crystalline polyester resin, a laminate (film) was produced in the same manner as in Example 1. Table 1 shows the physical properties of the polyester resin (c), and Table 2 shows the evaluation results of the physical properties of the laminate.
Shown in.

Example 4 In Example 1, 149.5 parts by weight of terephthalic acid, 16.6 parts by weight of isophthalic acid, ethylene glycol 14.
9 parts by weight and 1,4-cyclohexanedimethanol 1
The same operation as in Example 1 was carried out except that a slurry containing 15.4 parts by weight was used and the solid phase polymerization was carried out at 200 ° C. for 24 hours, and 90 mol% of terephthalic acid units and 10 mol% of isophthalic acid units were used. A polyester resin (d) comprising 20 mol% of ethylene glycol units and 80 mol% of 1,4-cyclohexanedimethanol units of diol units was produced. Polyester resin (d) has an intrinsic viscosity of 1.00 dl / g and a melting point of 2
It was 29.0 ° C. Using this polyester resin (d) and the above crystalline polyester resin, a laminate (film) was produced in the same manner as in Example 1. Table 1 shows the physical properties of the polyester resin (d), and Table 2 shows the evaluation results of the physical properties of the laminate.

Comparative Example 1 In Example 1, a slurry consisting of 166.1 parts by weight of terephthalic acid, 67.0 parts by weight of ethylene glycol and 14.4 parts by weight of 1,4-cyclohexanedimethanol was used, and solid-state polymerization was carried out. Was carried out at 200 ° C. for 26 hours, and the same operation as in Example 1 was carried out to obtain 100 mol% of terephthalic acid units, 90 mol% of ethylene glycol units and 10 mol of 1,4-cyclohexanedimethanol units. A polyester resin (e) consisting of% diol units was prepared. The intrinsic viscosity of the polyester resin (e) is 1.05 dl / g, and the melting point is 225.
It was 1 ° C. Using this polyester resin (e) and the above crystalline polyester resin, a laminate (film) was produced in the same manner as in Example 1. Table 1 shows the physical properties of the polyester resin (e), and Table 2 shows the evaluation results of the physical properties of the laminate.

Comparative Example 2 In Example 1, a slurry comprising 166.1 parts by weight of terephthalic acid, 14.9 parts by weight of ethylene glycol and 115.4 parts by weight of 1,4-cyclohexanedimethanol was used and solid-state polymerization was carried out. Was carried out at 200 ° C. for 26 hours, and the same operation as in Example 1 was carried out to obtain a dicarboxylic acid unit having 100 mol% of terephthalic acid unit, 20 mol% of ethylene glycol unit and 80 mol of 1,4-cyclohexanedimethanol unit. A polyester resin (f) consisting of% diol units was prepared. The intrinsic viscosity of the polyester resin (f) is 1.05 dl / g, and the melting point is 236.
It was 5 ° C. Using this polyester resin (f) and the above crystalline polyester resin, a laminate (film) was produced in the same manner as in Example 1. Table 1 shows the physical properties of the polyester resin (f), and Table 2 shows the evaluation results of the physical properties of the laminate.

Comparative Example 3 The same procedure as in Example 1 was carried out except that a slurry comprising 166.1 parts by weight of terephthalic acid, 43.4 parts by weight of ethylene glycol and 43.3 parts by weight of 1,4-cyclohexanedimethanol was used and solid-state polymerization was carried out. Was carried out at 200 ° C. for 26 hours, and the same operation as in Example 1 was carried out to obtain 100 mol% terephthalic acid unit dicarboxylic acid unit, 70 mol% ethylene glycol unit and 30 mol 1,4-cyclohexanedimethanol unit. A polyester resin (g) consisting of% diol units was prepared. The intrinsic viscosity of the polyester resin (g) was 1.00 dl / g. Also,
The polyester resin (g) was amorphous. Using this polyester resin (g) and the above crystalline polyester resin, a laminate (film) was produced in the same manner as in Example 1. Table 1 shows the physical properties of the polyester resin (g), and Table 2 shows the evaluation results of the physical properties of the laminate.

[0046]

[Table 1]

[0047]

[Table 2]

As is clear from the results of Table 2, Examples 1 to 1
No. 4 polyester resin (a) to (d) of the present invention
All have excellent film forming properties. A laminate (film) having a layer made of the same polyester resin has good impact resistance and pinhole resistance.

[0049]

INDUSTRIAL APPLICABILITY The polyester resin of the present invention exhibits excellent moldability and gives a molded article excellent in impact resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 3E086 AD01 BA04 BA15 BB15 BB90                       CA11                 4F071 AA44 AF23 BA01 BB06 BC01                       BC04                 4F100 AK41A AK41B AK41K BA02                       BA07 BA16 GB16 JA04A                       JA04B JA06A JA06B JA11B                       JK10 JK14 YY00A YY00B                 4J029 AA03 AB01 AC02 AD01 AD06                       AE03 BA03 BD04A CB05A                       CB06A CD03

Claims (5)

[Claims] 1. A dicarboxylic acid unit mainly consisting of a terephthalic acid unit (I) and a 1,4-cyclohexanedicarboxylic acid unit (II) and / or an isophthalic acid unit (III), an ethylene glycol unit (IV) and 1,4. −
Cyclohexanedimethanol unit (V) is mainly composed of glycol units and has a melting point of 210 to 210.
A polyester resin having an intrinsic viscosity of 0.6 to 1.5 dl / g at 250 ° C. and a molar ratio of the above structural units is [terephthalic acid unit (I)]: [1,4-cyclohexanedicarboxylic acid unit (II ) + Isophthalic acid unit (III)]
= 97: 3 to 90:10, and [ethylene glycol unit (IV)]: [1,4-cyclohexanedimethanol unit (V)] = 97: 3 to 88:12, or [terephthalic acid unit (I )]: [1,4-cyclohexanedicarboxylic acid unit (II) + isophthalic acid unit (II
I)] = 95: 5 to 80:20, and [ethylene glycol unit (IV)]: [1,4-cyclohexanedimethanol unit (V)] = 20:80 to 5:95. 2. A film made of the polyester resin according to claim 1. 3. A laminate having at least one layer comprising the film according to claim 2 and at least one layer comprising a crystalline polyester resin film. 4. The crystalline polyester resin is mainly composed of terephthalic acid units and isophthalic acid units, and the molar ratio of terephthalic acid units to isophthalic acid units is 99: 1 to 1.
It is composed of dicarboxylic acid units of 80:20 and diol units of ethylene glycol units, and has a melting point of 2
The laminate according to claim 3, which is a polyester resin having an intrinsic viscosity of 0.6 to 1.5 dl / g at 10 to 250 ° C. 5. A bag-in-box container comprising the laminate according to claim 3 or 4.