JPH07196900A - Hollow molding - Google Patents

Abstract

PURPOSE:To obtain a hollow molding excellent in dimensional stability and impact resistance and having high rigidity. CONSTITUTION:A hollow molding made from a thermoplastic resin composition obtained by mixing 100 pts.wt. polyester resin (A) consisting of 1-100wt.% thermoplastic copolyester resin (B) having a relative viscosity of 1.8 to 3.2 and 99-0wt.% polybutylene terephthalate (C) with 3-100 pts.wt. glass fibers (D). The copolyester resin B is a polymer obtained by using as the acid components terephthalic acid or its ester-forming derivative and a hydrogenated dimer acid or its ester-forming derivative and as the main glycol component 1,4- butanediol, and the dimer acid component in the polyester resin A accounts for 0 5-30mol% of all the acid components.

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 and high rigidity.

[0002]

2. Description of the Related Art Conventionally, a hollow molded article made of a polyamide resin composition mixed with glass fibers is known (Japanese Patent Publication No. 3-45691). However, this molded article has high water absorption, which is a characteristic of polyamide, and the dimensional stability of the molded article is poor.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to solve the above problems of the prior art and to provide a hollow molded article having excellent dimensional stability and impact resistance and high rigidity. .

[0004]

Means for Solving the Problems The above-mentioned objects are as follows: 1 to 100% by weight of a thermoplastic copolyester resin (A) having a relative viscosity of 1.8 to 3.2 and 99 to 0% by weight of polybutylene terephthalate (B). % To 100 parts by weight of the polyester resin (C), the glass fiber (D) 3 to 100
A hollow molded article made of a thermoplastic resin composition containing 1 part by weight of the thermoplastic copolymer polyester resin (A).
Is a polymer obtained by using terephthalic acid or its ester-forming derivative and hydrogenated dimer acid or its ester-forming derivative as an acid component and 1,4-butanediol as a main glycol component, and (A) and ( This is achieved by a hollow molded article characterized in that the proportion of the dimer acid component in the polyester resin (C) comprising B) accounts for 0.5 to 30 mol% with respect to the total of the acid components.

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 hydrogenated dimer acid or their ester-forming derivatives. Dimer acid is obtained after removal of by-products such as trimer acid and monomer acid by separation of unsaturated fatty acids from low polymers with clay catalysts,
The preferable purity is 99% by weight or more. Furthermore, from the hue plane, dimer acid is a constituent of the thermoplastic copolymerized polyester resin used in the present invention preferably has in particular hydrogenated, preferred iodination value or less 10gI ₂ / 100g.

As a preferred specific example, PRIPOL 1008 manufactured by Unichema [C36, aromatic type / alicyclic type / linear aliphatic type = 9/54/37
(Mol%) of dimer acid], PRIPOL 1009
[Cimera 36, 13/64/23 (mol%) dimer acid], and as an ester-forming derivative, PRILAST 3008 [PRIPOL 10 manufactured by Unichema Co., Ltd.
08 dimethyl ester].

The copolymerization composition ratio of the dimer acid, which is a constituent component of the thermoplastic copolyester resin used in the present invention, is not particularly limited, but it is 0.5 to the total of 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 can be carried out according to a known method. 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.

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 polyester resin 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 glass fiber used in the present invention is used for a usual glass fiber reinforced thermoplastic resin, and generally has a diameter of 5 to 20 μm and a length of 1 to 25 mm. In the present invention, the surface of the glass fiber is, for example, aminosilane, epoxysilane, borane, vinylsilane,
It may be surface-treated with methacrylosilane or the like.

The amount of the glass fiber of the thermoplastic resin composition used in the present invention is 3 to 100 parts by weight based on 100 parts by weight of the polyester resin composed of the thermoplastic copolyester resin and polybutylene terephthalate. It is essential, and preferably 5 to 80 parts by weight.

When the amount of glass fiber is less than 3 parts by weight, the rigidity is low and the object of the present invention cannot be achieved. On the other hand, if the amount of the glass fiber blended exceeds 100 parts by weight, moldability becomes poor.

The thermoplastic resin composition comprising the thermoplastic copolymerized polyester resin, polybutylene terephthalate and glass fiber used in the present invention has an isocyanate compound, an epoxy compound, ethylene and α, β-unsaturated as a method for preventing drawdown. It is also possible to add a known drawdown improver such as a copolymer with a saturated glycidyl ester.

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 materials (for example, whisker fibers) as long as the object of the present invention is not impaired. , Carbon fibers, etc.), antioxidants and heat stabilizers (including hindered phenols, hydroquinones, phosphites, thioethers and their substitutions and combinations thereof), UV absorbers (eg various resorcinols, salicylates, benzos). Triazole, benzophenone, etc., lubricants and mold release agents (eg montanic acid, stearic acid and its salts, stearyl alcohol, stearyl amide etc.), dyes (eg nitrocin etc.) and pigments (eg cadmium sulfide, phthalocyanine, carbon black etc.) Including coloring agents, flame retardants ( In example decabromodiphenyl ether, brominated polycarbonate, brominated polystyrene, halogen-based, such as brominated epoxy oligomer,
Melamine or cyanuric acid type, phosphorus type, etc., flame retardant aid (eg antimony trioxide, antimony pentoxide etc.), antistatic agent (eg sodium benzenesulfonate, polyalkyl glycol etc.), crystallization accelerator (eg polyethylene) It is possible to add one or more kinds of polymers such as glycol), an additive impregnating liquid (silicone oil, etc.), and a small amount of other polymer.

The hollow molded article of the present invention is preferably prepared by subjecting the resin composition obtained as described above to a known blow molding method,
That is, it is basically obtained by supplying a resin composition to an extruder, molding a parison by melt extrusion or injection molding, and then forming a desired two-dimensional 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.

[0024]

INDUSTRIAL APPLICABILITY The hollow molded article of the present invention is excellent in dimensional stability and impact resistance, has high rigidity, and is suitable for a container for foods, medicines and the like.

[0025]

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 from a height of 5 m onto the concrete floor, 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. Flexural modulus: 150 obtained by injection blow
12.7 mm from the body of a cylindrical container of mmH x 80 mmφ
A 127 mm rectangular test piece was punched out, and ASTM-
The flexural modulus was measured according to the D790 method.

Production Example of Thermoplastic Copolyester 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.

[0027]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 5 Thermoplastic copolymerized polyester resin and polybutylene terephthalate (PBT1 manufactured by Kanebo Co., Ltd.) obtained by the above 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 and 100 parts by weight of glass fiber (Japan). 15 parts by weight of T-187 manufactured by Denki Glass Co., Ltd. were mixed, melt-mixed by a kneading extruder, and then molded by an injection 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.

[0030]

[Table 2]

Examples 6 to 8 and Comparative Examples 6 and 7 100 parts by weight of the thermoplastic copolyester (sample name G) obtained by the above method was used as a heat stabilizer for a hindered phenol compound and a phosphorus compound. Mixture (Ciba Geigy Irganox B-225)
0.2 parts by weight and the glass fiber used in Example 1 are shown in Table 3.
The composition obtained by blending with the composition shown in 1 above and melt-mixing with a kneading extruder was molded in the same manner as in Example 1 to evaluate the physical properties. The results are also shown in Table 3.

[0032]

[Table 3]

Example 9, Comparative Example 8 6 parts by weight of 6 nylon (MC102 manufactured by Kanebo Co., Ltd.) to 1 part of glass fiber (T-24 manufactured by Nippon Electric Glass Co., Ltd.)
A composition obtained by blending 5 parts by weight and melt-mixing with a kneading extruder was molded in the same manner as in Example 1 to obtain a hollow molded product. The dimensional stability of this hollow molded product and the hollow molded product obtained in Example 6 were evaluated. The results are shown in Table 4.

[0034]

[Table 4]

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B29K 101: 12 309: 08 B29L 22:00

Claims (1)

[Claims] 1. A polyester resin (C) comprising 1 to 100% by weight of a thermoplastic copolyester resin (A) having a relative viscosity of 1.8 to 3.2 and 99 to 0% by weight of polybutylene terephthalate (B). ) In a hollow molded article made of a thermoplastic resin composition in which 3 to 100 parts by weight of glass fiber (D) is mixed with 100 parts by weight, the thermoplastic copolymer polyester resin (A) is terephthalic acid or its ester-forming derivative. And hydrogenated dimer acid or its ester-forming derivative as an acid component, 1,4-butanediol is a polymer obtained as a main glycol component,
Polyester resin (C) consisting of (A) and (B)
The ratio of the medium dimer acid component is 0.5 to the total of the acid components.
A hollow molded article comprising a thermoplastic resin composition, which accounts for 30 mol%.