JPH07276474A - Hollow molded product - Google Patents

Abstract

PURPOSE:To improve the dimensional stability and impact resistance by providing a polyester resin of a specified relative viscosity and polybutylene terephthalate within the range of a specified wt.% and specifying the ratio of a dimer acid component to the respective above-said components. CONSTITUTION:A hollow molded product is composed of a thermoplastic copolymerized polyester resin of 1-100wt.% which has a relative viscosity of 1.8-3.2 and polybutylene terephthalate of 0-99wt.%. The thermoplastic copolymerized polyester resin is a polymer prepared by containing terephthalic acid or its ester forming derivative or diameter acid or its ester forming derivative as an acid component and 1.4-butanediol as a main glycol component. The ratio of the dimer acid component is 0.5-30 molar% to the total acid content of the thermoplastic copolymerized polyester resin and polybutylene terephthalate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow molded article having excellent dimensional stability and impact resistance.

[0002]

2. Description of the Prior Art Conventionally, polypropylene, polyvinyl chloride, polystyrene, nylon, blow blow molding,
It is well known that hollow containers such as polyester and polycarbonate are widely used (for example, Japanese Patent Laid-Open No. 55-
12082, JP-A-57-5747, JP-B-5-70569, etc.).

However, with these high molecular weight polymers,
None of them satisfy all the points of dimensional stability, flexibility, impact resistance, chemical resistance, etc. For example, polypropylene and polystyrene have insufficient chemical resistance, and nylon has a high water absorption rate, resulting in insufficient dimensional stability and a decrease in elastic modulus over time. Further, the flexibility of polyesters such as polycarbonate and polyethylene terephthalate is insufficient. Further, plasticized polyvinyl chloride cannot be said to be an excellent soft material because of the problems of curing phenomenon due to elution of the plasticizer and toxicity of the plasticizer.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems of the prior art and to provide a blow hollow molded article excellent in dimensional stability and impact resistance.

The above-mentioned object consists of 1 to 100% by weight of a thermoplastic copolyester resin having a relative viscosity of 1.8 to 3.2 and 0 to 99% by weight of polybutylene terephthalate, which is a thermoplastic copolyester resin. Is a polymer obtained by using terephthalic acid or its ester-forming derivative and dimer acid or its ester-forming derivative as an acid component and 1,4-butanediol as a main glycol component, and the proportion of the dimer acid component is thermoplastic. This is achieved by a hollow molded article obtained by blow molding a thermoplastic resin composition characterized in that it accounts for 0.5 to 30 mol% of the total acid components of the copolymerized polyester resin and polybutylene terephthalate.

The present invention will be described in detail below. The acid component of the thermoplastic copolyester resin used in the present invention is
It consists of terephthalic acid and dimer acid or their ester-forming derivatives. The dimer acid is obtained after removing by-products such as trimer acid and monomer acid by separating unsaturated fatty acid from the low polymer by a clay catalyst, and the preferable purity is 99% by weight or more. Further, from the viewpoint of color tone, it is preferable that the dimer acid which is a constituent component of the thermoplastic copolyester resin used in the present invention is particularly hydrogenated, and a preferable iodination value is 10 g.
I is ₂ / 100g or less.

A preferred specific example is PRIPOL 1008 manufactured by Unichema {36 carbon atoms, aromatic type / alicyclic type / linear aliphatic type = 9/54/37.
(Mol%) dimer acid}, PRIPOL 1009
{Cymer 36, 13/64/23 (mol%) dimer acid}, and PRIPLAST 3008 {PRIPOL 10 manufactured by Unichema as an ester-forming derivative.
08 dimethyl ester}.

The copolymerization composition ratio of the dimer acid which is a constituent of the thermoplastic copolyester resin used in the present invention is not particularly limited, but it is 0.5 to the total of the acid components in the thermoplastic copolyester resin. It is preferably 30 mol%.

It is important that the glycol component of the thermoplastic copolyester resin contains 1,4-butanediol as the main component (70 mol% or more of the total glycol component).

The method for producing the thermoplastic copolyester resin used in the present invention is not particularly limited, and a known method can be used. For example, terephthalic acid or its ester-forming derivative, hydrogenated dimer acid or its ester-forming derivative, and 1,4-butanediol are directly or simultaneously esterified, or they are transesterified and then polymerized. The method can be adopted. Various known catalysts, stabilizers, modifiers or additives may be used in the polymerization, esterification reaction or transesterification reaction. Further, if necessary, solid phase polymerization may be carried out.

The thermoplastic copolyester resin has a relative viscosity η _rel of tetrachloroethane: phenol = 2:
1.8 to 3.2 as measured at 20 ° C. using the mixed solvent of No. 3
Is essential. If η _rel is less than 1.8,
Drawdown becomes remarkable and a good product cannot be obtained. On the other hand, if η _rel exceeds 3.2, molding becomes difficult.

The polybutylene terephthalate used in the present invention is a polyester obtained by polycondensing terephthalic acid and 1,4-butanediol. The PBT may be copolymerized with an acid component and / or a glycol component as long as the rigidity, toughness and moldability are not substantially lost.

Here, as the copolymerizable acid component, a dicarboxylic acid other than terephthalic acid, for example, isophthalic acid,
2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylethercarboxylic acid, diphenoxyethanedicarboxylic acid,
Diphenyl ketone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, succinic acid, adipic acid, sebacic acid, cyclohexane dicarboxylic acid, tetralin dicarboxylic acid,
Examples include decalin dicarboxylic acid, trimellitic acid, and pyromellitic acid. These dicarboxylic acids may have the carboxyl group esterified with a lower alcohol such as methanol or ethanol.

As the copolymerizable glycol component, glycols other than 1,4-butanediol, for example, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3 -Hexanediol, 2,5-hexanediol, 2,4-hexanediol, cyclohexanedimethanol, ethylene glycol, polyethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,4
-Butanediol, 2-methyl-2,4-butanediol, 1,3-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 2, 4-pentanediol, neopentyl glycol, tricyclodecane dimethylol, xylylene glycol, bisphenol A, bisphenol B, bishydroxyethoxy bisphenol A, glycerin, trimethylolpropane,
Pentaerythritol and the like are exemplified. As the copolymerization component, an acid component or glycol component may be used alone, an acid component and a glycol component may be used in combination, and two or more types of acid component and / or glycol component may be used.

The PBT is manufactured by a known method. That is, after the esterification or transesterification reaction, the polycondensation reaction is carried out under high vacuum. Also, if necessary, such PB
T may be further solid-state polymerized.

The thermoplastic resin composition used in the present invention is
It is essential that the thermoplastic copolyester resin having a relative viscosity of 1.8 to 3.2 be used in an amount of 1 to 100% by weight and polybutylene terephthalate to be used in an amount of 0 to 99% by weight. When the composition ratio of the thermoplastic copolyester resin is less than 1% by weight, impact resistance is insufficient.

The proportion of the dimer acid component in the thermoplastic resin composition used in the present invention is 0.5 with respect to the total of the acid components.
It is important to occupy 30 mol%, especially 1-2
0 mol% is preferable. If the proportion of the dimer acid component is less than 0.5 mol%, the impact resistance is insufficient, and 30 mol%
If it exceeds, drawdown becomes remarkable and a good product cannot be obtained.

The thermoplastic resin composition comprising the thermoplastic copolyester resin and polybutylene terephthalate used in the present invention has an isocyanate compound, an epoxy compound, ethylene and α, β as a method for preventing drawdown.
-A known drawdown improver such as a copolymer with an unsaturated glycidyl ester may be added.

The thermoplastic resin composition used in the present invention, which comprises the thermoplastic copolyester resin and polybutylene terephthalate, may be added with conventional additives such as reinforcing agents (for example, whiskers) within a range not impairing the object of the present invention. fiber,
Carbon fibers, etc.), antioxidants and heat stabilizers (eg hindered phenols, hydroquinones, phosphites, thioethers and their substitutions and combinations thereof),
UV absorbers (eg various resorcinols, salicylates, benzotriazoles, benzophenones, etc.), lubricants and mold release agents (eg montanic acid, stearic acid and its salts, stearyl alcohol, stearyl amides, etc.), dyes (eg nitrocin etc.) and pigments (Eg cadmium sulfide, phthalocyanine, carbon black, etc.) colorants, flame retardants (eg decabromodiphenyl ether,
Brominated polycarbonate, brominated polystyrene, halogenated compounds such as brominated epoxy oligomers, melamine or cyanuric acid, phosphorus, etc.), flame retardant aids (eg antimony trioxide, antimony pentoxide, etc.), antistatic agents (eg It is possible to add one or more kinds of sodium benzenesulfonate, polyalkyl glycol, etc., a crystallization accelerator (eg, polyethylene glycol, etc.), an additive impregnating liquid (silicone oil, etc.), and a small amount of another kind of polymer.

The blow hollow molded article of the present invention can be obtained by subjecting the resin composition obtained as described above to a known blow molding method, that is, basically, supplying the resin composition to an extruder to perform melt extrusion or injection molding. Form the parison with, and then the desired 2
It is obtained by forming a three-dimensional hollow molded body.

As typical examples of the blow molding method, a direct blow method, an injection blow method and the like can be mentioned, and the multilayer blow molding method and the exchange blow molding method used in combination with other materials can be applied. Of course, it is possible.

[0022]

The blow hollow molded article of the present invention has excellent dimensional stability and impact resistance, and is suitable for containers for foods, chemicals and the like.

[0023]

The present invention will be specifically described with reference to the following examples. The physical properties were evaluated according to the following methods. Relative viscosity η _rel : solvent tetrachloroethane: phenol = 2: 3 (weight ratio), measurement temperature 20 ° C. Concentration 1.000
g / dl Impact resistance: The container obtained by blow molding was filled with full water, the cap was closed, and the container was dropped onto a concrete floor from a height of 5 m, and the presence or absence of damage or cracks in the container was visually determined. The test was carried out at n = 20, the number of non-destructive products was counted, and the non-destructive ratio was expressed as a percentage of 100, which was used as a measure of impact resistance. Dimensional stability: The container obtained by blow molding was dipped in 23 ° C. water for 500 hours, and the change in the diameter of the lower part of the container body before and after the immersion was used as a measure of dimensional stability.

Production Example of Thermoplastic Copolymerized Polyester Resin Dimethyl terephthalate, hydrogenated dimer acid (PRIPLAST 3008 manufactured by Unichema), 1,4-butanediol, transesterification and tetra-n-as a polymerization catalyst.
Add butyl titanate with the composition shown in Table 1 and add 210 ° C.
The methanol produced by heating to 100 ° C. was distilled off from the system to carry out a transesterification reaction. After the distillation of methanol was almost completed, the reaction product was transferred to a polymerization vessel and the temperature was raised to 250
The temperature was brought to 0 ° C and the degree of vacuum to 0.5 mmHg, and then polycondensation was performed. Table 1 shows the sample names and relative viscosities η _rel of the obtained thermoplastic copolyester resins.

[0025]

[Table 1]

Examples 1-5, Comparative Examples 1-5 Thermoplastic copolymerized polyester resin and polybutylene terephthalate (PBT1 manufactured by Kanebo Co., Ltd.) obtained by the above-mentioned method.
19) in the composition shown in Table 2, and 0.2 parts by weight of a hindered phenolic compound (Irganox 1330 manufactured by Ciba-Geigy) as a heat stabilizer based on 100 parts by weight of the above resin mixture, and the mixture is injected after mixing. Molding was performed with a blow molding machine (screw diameter 25 mmφ).

Injection molding of the screw part (20 mmφ) of the container and the body part (20 m of the container) at a cylinder temperature of 240 to 260 ° C.
mφ) preform, blow mold temperature was 130 ° C. (parison bottom part) and 50 ° C. (parison shank part), and the barrel part was blow-molded to obtain an 80 mmφ cylindrical container. The physical properties of the obtained container were evaluated, and the results are shown in Table 2.

[0028]

[Table 2]

Example 6, Comparative Examples 6 and 7 Polyethylene terephthalate (EFG-manufactured by Kanebo Co., Ltd.
7), polyamide (Kanebo 6 nylon MC14
0) and a thermoplastic copolyester resin (sample name G) were used in the injection blow molding machine used in Example 1 to obtain a similar container. The physical properties of the obtained container were evaluated. The results are shown in Table 3.
Shown in.

[0030]

[Table 3]

Example 7 To 100 parts by weight of the thermoplastic copolyester resin (sample name G) obtained by the above method, 0.2 part by weight of the heat stabilizer used in Example 1 was blended, and after mixing Molding was performed using a direct blow molding machine (screw diameter 40 mmφ).

After the parison was extruded at a cylinder temperature of 250 to 270 ° C., a die diameter of 6.0 mm and a nozzle diameter of 5.0 mm, the parison was blown with a mold maintained at a temperature of 60 ° C. to obtain a 10 mmφ cylindrical container. It was The obtained molded product had good impact resistance and dimensional stability.

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Claims (1)

[Claims] 1. A thermoplastic copolymerized polyester resin having a relative viscosity of 1.8 to 3.2 and 1 to 100% by weight of polybutylene terephthalate and 0 to 99% by weight of the thermoplastic copolymerized polyester resin, wherein the thermoplastic copolymerized polyester resin is terephthalic acid. Or a polymer obtained by using an ester-forming derivative thereof and a dimer acid or an ester-forming derivative thereof as an acid component and 1,4-butanediol as a main glycol component, and a proportion of the dimer acid component being a thermoplastic copolyester 0.5 for all acid components of resin and polybutylene terephthalate
A hollow molded article obtained by blow molding a thermoplastic resin composition, characterized in that the blow molding is carried out.