JP3192290B2 - Polyester heat-resistant bottle - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is to provide a transparent, tough, heat-resistant bottle which can be filled at a high temperature of 80 ° C. or higher, has excellent heat resistance, and is transparent and strong.

[0002]

2. Description of the Related Art Polyethylene terephthalate bottles are easily moldable and are containers having excellent transparency and mechanical properties, such as seasonings, edible oils, alcoholic drinks, carbonated drinks, fruit juice drinks, and mineral water. It is widely used in large quantities for applications and non-food applications such as detergents.
However, special treatment is required for the high-temperature filling field requiring heat resistance, for example, as shown in JP-A-55-12031, the mouth of a polyethylene terephthalate bottle is heat-treated to whiten (crystallize) the heat. It is necessary to prevent deformation due to

However, the provision of heat resistance by crystallization at the mouth is limited to the provision of heat resistance at the mouth, and not only the provision of heat resistance at the body and the bottom is required, but also the crystallization of the mouth is not necessarily uniform. In some cases, the unevenness in shrinkage during crystallization results in minute distortion of the shape, and the contents may leak even if the cap is capped.

[0004]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a bottle which can be easily molded, is transparent, has excellent mechanical strength and heat resistance, and can be filled even at a high temperature.

[0005]

An object of the present invention is to provide a dicarboxylic acid containing terephthalic acid or an ester-forming derivative thereof as a main component, and 5 to 15 mol% of a general formula

Embedded image (R ₁ is an alkyl group having 2 to 4 carbon atoms, and R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)
From a diol component containing a dihydroxy compound represented by
This is achieved by a polyester heat-resistant bottle made of a polyester copolymer having a glass transition temperature of 80 ° C. or higher.

The main component of the dicarboxylic acid component of the polyester copolymer is terephthalic acid or an ester-forming derivative thereof (eg, lower alkyl ester).
As other components, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as 1,5-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid are exemplified. Further, a part of the dicarboxylic acid can be replaced with p-oxybenzoic acid or the like.

[0007] In the present invention, the dihydroxy compound represented by the chemical formula 1 is 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene, 9,9-bis- (4-hydroxypropoxyphenyl) -fluorene, 9 And 9,9-bis- (4-hydroxybutoxyphenyl) -fluorene, and 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene is particularly preferred.

[0009] 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene is, for example, 9,9-bis- (4
-Hydroxyphenyl) -fluorene to which ethylene oxide (hereinafter referred to as EO) is added. At this time, ethylene oxide is added to both hydroxyl groups of phenol.
The 2EO adduct [9,9-bis- (4-
Hydroxyethoxyphenyl) -fluorene]
Further, impurities such as a 3EO adduct and a 4EO adduct which are added in excess of several molecules may be contained. When impurities such as 3EO and 4EO are increased, the heat resistance of the polyester polymer is lowered. At this time, the purity of the 2EO adduct may be 85% or more, but is preferably 95% or more.

9,9-bis- (4-hydroxypropoxyphenyl) -fluorene and 9,9-bis- (4-hydroxybutoxyphenyl) -fluorene are, for example, 9,9-bis- (4-hydroxybutoxyphenyl) -fluorene.
It is obtained by reacting 9-bis- (4-hydroxyphenyl) -fluorene with 3-chloro-propan-1-ol and 4-chloro-propan-1-ol, respectively, under alkaline conditions. The purity at this time may be 85% or more, preferably 95% or more.

Examples of the diol component other than the dihydroxy compound represented by Chemical Formula 1 include ethylene glycol, cyclohexane dimethanol, an ethylene oxide adduct of bisphenol A, and an ethylene oxide adduct of bisphenol S, with ethylene glycol being most preferred. .

[0011] The amount of the dihydroxy compound represented by Chemical Formula 1 contained in the polyester composition is calculated based on 100 parts of the diol component.
5 to 15 mol%, preferably 5 to 10 mol%. When the amount is less than 5 mol%, the glass transition temperature is greatly reduced, and no sufficient improvement in heat resistance is observed.
If the amount is larger, the crystallization speed becomes lower, and a strong bottle cannot be obtained by blow molding.

As the transesterification catalyst, the organic acid calcium salt is less colored than the titanium catalyst and the manganese catalyst and is safer for food hygiene and is preferred. For example, a method in which terephthalic acid is used as a dicarboxylic acid component and direct polymerization is performed without going through transesterification is advantageous because the steps are simplified and the cost is also advantageous. As a polymerization catalyst, a germanium oxide catalyst is preferable in that it is superior in color tone as compared with an antimony catalyst and a titanium catalyst, and is safer in food hygiene.

The polyester heat-resistant bottle of the present invention can be manufactured as follows. First, a low polymer is prepared by directly esterifying the above-mentioned dicarboxylic acid component and diol component according to a conventional method, or by transesterification in the presence of an organic acid calcium salt.

Next, a polycondensation reaction is carried out at 250 ° C. to 300 ° C. under reduced pressure using germanium oxide or the like as a polycondensation catalyst to produce a polyester copolymer having a desired viscosity.

The intrinsic viscosity of the polyester copolymer is 0.7
0 to 0.90 dl / g, preferably 0.70 dl
If it is less than / g, the moldability in blow molding is reduced, while if it exceeds 0.90 dl / g, the melt fluidity is reduced, and for example, molding of a parison is not preferable.

The intrinsic viscosity is measured at 25 ° C. using a solution obtained by melting 0.25 g of a polymer in 100 ml of a mixture of 60% by weight of phenol and 40% by weight of 1,1,2,2 tetrachloroethane. did.

[0017] The above polyester copolymer is prepared by
After drying to pm or less, preferably 50 ppm or less, it is injection molded into a bottomed parison (preform), and the preform is blow molded into a desired shape to form a heat resistant bottle. Alternatively, a hollow pipe may be formed by extrusion, one end may be sealed, and the other end may be formed with a cap-attachable neck, followed by blow molding.

[0018]

The polyester heat-resistant bottle of the present invention comprises:
It has excellent moldability, transparency and toughness, and can be filled at high temperatures. Further, there is an advantage that heat treatment after molding for imparting heat resistance is not required.

[0019]

The present invention will be described in more detail with reference to the following examples. The intrinsic viscosity, glass transition temperature, and NMR of the copolymer in the examples were measured by the following methods.

(1) Intrinsic viscosity 0.25 g in 100 ml of a mixed solution of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane
Was measured at 25 ° C. using a solution obtained by melting the polymer of (2) Glass transition temperature About 10 mg of a sample was measured with a differential scanning calorimeter (DSC-8230, manufactured by Rigaku Corporation) at a heating rate of 10 ° C./min. The glass transition temperature Tg was determined as defined in JIS-K7121. (3) NMR Using FT-NMR manufactured by Varian (300MG),
The composition of the new polyester copolymer was determined. As a solvent, a sample is dissolved in a mixed solution of trifluoroacetic acid and chloroform (1: 1), and tetramethylsilane is mixed as a standard, and then mixed.
The proton NMR spectrum was measured.

Example 1 1 mol of dimethyl terephthalate, 9,9-bis- (4-
0.1 mol of (hydroxyethoxyphenyl) -fluorene, 2.1 mol of ethylene glycol and 0.1 g of calcium acetate as an ester reaction catalyst are charged into a polymerization vessel having a rectification column, and then heated to 250 ° C. while flowing a slight amount of nitrogen. And stirred. By maintaining the rectification column temperature at 60 to 70 ° C. during this time, ethylene glycol was refluxed and only methanol was distilled out of the system.

[0022] calculated from the amount of collected methanol, where the transesterification rate reached about 90%, germanium oxide 0.05g as a polymerization catalyst, Li as a heat stabilizer
0.25 g of trimethyl acid was charged, and the pressure was gradually reduced while heating and stirring were continued.
The following high vacuum was used. During this time, the temperature was raised to 280 ° C. After the polymerization was continued for about 4 hours in this state, the pressure was returned to normal pressure and the mixture was extruded in a gut shape, cooled with water, and then cooled with a cutter.
A pellet-shaped polyester copolymer having a V = 0.75 was obtained.

The lightness (L), hue (a), and chroma (b) of the obtained polyester copolymer were measured by Suga Test Machine Co., Ltd.
When measured with a color meter, L / a / b = 83.
7 / -1.1 / -1.9.

Further, 9,9-bis- (4-hydroxyethoxyphenyl) contained in the polyester copolymer
Table 1 shows the results of analyzing fluorene by NMR. The values in the table are mol% when the whole diol component in the polyester copolymer is 100.

The polyester copolymer was placed under reduced pressure for 150 hours.
Dried at 100 ° C to a water content of 100 ppm or less.
Using a 0-type injection blow molding machine, at a polymer temperature of 285 ° C., a content of 1 liter, a basis weight of 40 g, and a cap diameter of 30 mmφ
Formed into a bottle of a book. Each container was filled with hot water at 80 ° C., and the results of inspection of deformation of the container appearance are shown in Table 1. The values in the table indicate the number of bottles with caps leaked out of 10 bottles. In addition, the glass transition temperature (T
Table 1 also shows the measurement results of g).

Example 2 Polymerization and bottle molding were performed under the same conditions as in Example 1 except that 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene was 0.05 mol and ethylene glycol was 2.15 mol. , Was measured. Table 1 shows the results.

Example 3 Bottle molding and measurement were performed in the same manner as in Example 1 except that terephthalic acid was used instead of dimethyl terephthalate for direct polymerization. Table 1 shows the results.

Comparative Example 1 Polymerization and bottle were prepared under the same conditions as in Example 1 except that 0.02 mol of 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene and 2.18 mol of ethylene glycol were used. Molding and measurement were performed. Table 1 shows the results.

Comparative Example 2 Polymerization, bottle molding, and the like were performed in the same manner as in Example 1 except that 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene was not used, and 2.2 mol of ethylene glycol was used. A measurement was made. Table 1 shows the results.

[0030]

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-186579 (JP, A) JP-A-7-149881 (JP, A) JP-A-7-188401 (JP, A) JP-A-1- 194904 (JP, A) JP-A-6-322087 (JP, A) JP-A-6-192408 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B29C 49/00-49 / 80 C08G 63/00-63/91

Claims (4)

(57) [Claims] 1. A dicarboxylic acid whose main component is terephthalic acid or an ester-forming derivative thereof, and 5 to 15 mol% of a general formula: (R ₁ is an alkyl group having 2 to 4 carbon atoms, and R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)
From a diol component containing a dihydroxy compound represented by
And a polyester heat-resistant bottle comprising a polyester copolymer having a glass transition temperature of 80 ° C. or higher. 2. The polyester heat-resistant bottle according to claim 1, wherein the polyester copolymer is polymerized after transesterification using a calcium salt of an organic acid as a catalyst. 3. The polyester heat-resistant bottle according to claim 1, wherein the polyester copolymer is directly polymerized. 4. The method according to claim 1, wherein the polyester copolymer is 0.70 to 0.1.
The polyester heat-resistant bottle according to claim 1, which has an intrinsic viscosity of 90 dl / g.