JP2003327806A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition containing a polytrimethylene terephthalate resin, having improved crystallization rate to increase the productivity of molded articles and giving molded articles having high quality and provide a molded article produced by using the thermoplastic resin composition. <P>SOLUTION: The 1st invention comprises a thermoplastic resin composition containing a polytrimethylene terephthalate and 0.001-20 wt.% ionomer and 0-50 wt.% glass fiber based on the resin composition and the 2nd invention comprises a molded article produced by using the thermoplastic resin composition of the 1st invention. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition and a molded article. More specifically, the crystallization rate of a polytrimethylene terephthalate resin (hereinafter abbreviated as PTT) is improved, and when a molded product (product) is manufactured by an injection molding method, the productivity is excellent and the crystallinity is high. The present invention relates to a thermoplastic resin composition from which a molded article is obtained, and a molded article obtained from this thermoplastic resin composition.

[0002]

2. Description of the Related Art In recent years, PTT resins have been used in many industrial products such as fibers and carpets because of their excellent elastic recovery characteristics and chemical resistance. Recently, its use as a material for film production and as an engineering plastic for the production of various industrial parts has also been investigated. However, when it is used as a molding material, its crystallization rate is important. The PTT-based resin has a drawback that the crystallization rate is still slower than that of the polybutylene terephthalate-based resin.

Since the PTT-based resin has a relatively low crystallization rate during molding, a thick-walled molded article manufactured by an injection molding method has a difference in crystallization rate between the outer surface side and the inner side of the molded article. Occurs. The molded product has a non-uniform crystallinity as a whole, resulting in uneven heat resistance, mechanical properties, dimensional stability, etc., and it is difficult to obtain an excellent molded product. For this reason,
There is a demand to make the crystallinity of the PTT resin molded product uniform and to increase the crystallization speed.

As one method for making the crystallinity of a molded product uniform, the property of increasing the crystallization rate at high temperature is utilized.
There is a method of raising the temperature of the injection mold. However, the method of increasing the mold temperature not only requires a special device for increasing the mold temperature, but also has a drawback that the molding cycle becomes long and the productivity is lowered. Another method to make the crystallinity of the molded product uniform is to add a crystal nucleating agent, but the crystallization promoting effect is not always sufficient, and in some cases, the PTT resin is decomposed to lower the melt viscosity. , Which causes deterioration of mechanical properties. Therefore, problems such as strand breakage during compound production by an extruder and molded article cracking during the production of molded articles occur.

[0005]

The present invention has been completed as a result of intensive studies to solve the above problems. That is, the objects of the present invention are as follows. 1. To provide a PTT resin composition having a high crystallization rate and capable of high cycle molding. 2. To provide a molded article made of a PTT-based resin composition having excellent mechanical properties.

[0006]

In order to solve the above-mentioned problems, in the first invention, 0.001 to 20% by weight of an ionomer and a glass are contained in the entire resin composition containing a polytrimethylene terephthalate resin. Fiber 0-50% by weight
There is provided a thermoplastic resin composition comprising:

Further, in the second invention, a thermoplastic resin composition containing 0.001 to 20% by weight of an ionomer and 0 to 50% by weight of glass fiber based on the entire resin composition containing a polytrimethylene terephthalate resin. Provided is a molded article, which is manufactured by using a material as a raw material.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
In the present invention, the PTT-based resin means a polymer or copolymer obtained by a polycondensation reaction containing terephthalic acid and propylene glycol as main components. In this polymer, a part of terephthalic acid may be replaced with other dicarboxylic acids or ester derivatives thereof, and a part of propylene glycol may be replaced with other diols and / or triols.

Examples of dicarboxylic acids capable of substituting a part of terephthalic acid include isophthalic acid, orthophthalic acid, 1,
5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-
Dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid,
Aromatic dicarboxylic acids such as bis (4,4'-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and fats such as 1,4-cyclohexanedicarboxylic acid and 4,4'-dicyclohexyldicarboxylic acid Examples thereof include aliphatic dicarboxylic acids such as cyclic dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, and ester derivatives thereof.

Examples of diols capable of substituting a part of propylene glycol include aliphatic or alicyclic diols having 2 to 20 carbon atoms and bisphenol derivatives. Specific examples include ethylene glycol, tetramethylene glycol, 1,5-pentanediol, 1,6
-Hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,
4'-dicyclohexyl hydroxymethane, 4,4'-
Examples thereof include dicyclohexylhydroxypropane and ethylene oxide addition diol of bisphenol A.
Examples of triols include glycerin and trimethylolpropane.

The amount of other dicarboxylic acids used for substituting a part of terephthalic acid is preferably 30 mol% or less,
More preferably, it is less than 10 mol%. The amount of other diols and / or triols used when substituting a part of propylene glycol is preferably 30 mol% or less, more preferably less than 10 mol%.

PTT constituting the resin composition according to the present invention
The resin is a usual production method, for example, a melt polycondensation reaction,
It can be produced by a solid phase polycondensation reaction or a method combining these. For example, terephthalic acid, or terephthalic acid and other diols or ester derivatives thereof,
Propylene glycol, or propylene glycol and other diols and / or triols are heated and reacted in the presence of a catalyst, and a glycol ester of terephthalic acid obtained by the reaction is polymerized to a predetermined degree of polymerization in the presence of a catalyst. It can be manufactured by a method.

The PTT resin has an intrinsic viscosity of at least 0.4-when measured at a temperature of 30 ° C. using a mixed solution in which methylene chloride and trifluoroacetic acid are mixed in a weight ratio of 1: 1. The range of 1.6 is preferable, and the range of 0.6 to 1.3 is particularly preferable.

The resin composition according to the present invention comprises the PTT resin and an ionomer. In the present invention, the ionomer means an olefin such as ethylene and / or
Alternatively, it means a copolymer of styrene and an unsaturated carboxylic acid in which at least a part of the unsaturated carboxylic acid group is neutralized with a metal ion.

The copolymer constituting the above ionomer is
80 to 99 of styrene component and / or ethylene component
Mol%, unsaturated carboxylic acid components, that is, unsaturated carboxylic acids and salts thereof are 1 to 20 mol%, and among them, the former is preferably 80 to 95 mol%, and the latter is 5 to 50 mol%.
It is 20 mol%. As the unsaturated carboxylic acid,
Examples thereof include acrylic acid and methacrylic acid. In these copolymers, at least a part of the unsaturated carboxylic acid group contained therein is neutralized with a metal ion such as an alkali metal, an alkaline earth metal or a transition metal. Examples of the alkali metal include lithium, sodium and potassium, examples of the alkaline earth metal include magnesium and calcium, and examples of the transition metal include manganese, cobalt, nickel, copper and zinc. Alkali metals are preferred, and sodium is most preferred. The degree of neutralization is at least 10% or more, preferably 40 to 100%.

The content of the ionomer in the resin composition can be appropriately changed depending on the kind of unsaturated carboxylic acid group, the proportion of the copolymer, and the kind and proportion of the metal ion used for neutralization. It is selected in the range of 0.001 to 20% by weight with respect to the entire composition. When the content is less than 0.001% by weight, the crystallization promoting effect is insufficient, and when it exceeds 20% by weight, the crystallization promoting effect is not only saturated but also the mechanical properties of the resin composition are deteriorated. However, both are not preferable. The preferable range of the content is 0.01 to 15% by weight, and more preferably 0.1 to 10% by weight.

If desired, a thermoplastic resin other than the PTT resin can be added to the resin composition according to the present invention. The resin component of the resin composition according to the present invention is PTT.
Mainly based resin. Further, other crystal nucleating agent can be added if necessary. Furthermore, if necessary,
Reinforcing materials such as glass fiber, mica and whiskers, fillers such as glass beads and talc, brominated compounds such as brominated polycarbonate and brominated epoxy compounds, and flame retardants such as phosphorus compounds such as phosphoric acid ester and phosphazene. Can be included. Furthermore, if necessary, various kinds of additives that do not impair the effects of the resin composition according to the present invention, for example, release agents, lubricants, stabilizers such as antioxidants, colorants, ultraviolet absorbers, An impact strength improving material for improving the properties of the resin composition, a compatibilizing component, etc., such as a molecular chain terminal modifier, can be contained. When glass fiber is included, the molded product has dimensional stability,
It is preferable because it has excellent rigidity. The glass fiber is 0 to 50% by weight, preferably 5 to the whole resin composition.
It can be contained in the range of ~ 45% by weight, more preferably 10-40% by weight. The content of the release agent is preferably 0.05 to 1% by weight with respect to the entire resin composition.

To produce the resin composition according to the present invention,
It can be performed by melt kneading, and can be melt kneaded by a kneading device such as a Banbury mixer, an extruder and various kneaders which are generally used. In addition,
The kneading order of the constituent components in producing the resin composition according to the present invention is not particularly limited, (1) a mixture obtained by weighing each component in a predetermined amount and mixing them, the resulting mixture at once. Any method such as kneading, (2) supplying ionomer from a side feeder of an extruder, or the like may be used.

The resin composition according to the present invention can be used as a material for producing a film or an engineering plastic material for producing various industrial parts. The applicable molding method is the injection molding method, extrusion molding method, rotational molding method, hollow molding method, compression molding method, or other molding method that is applied when a molded product is manufactured from a thermoplastic resin molding material. it can. The resin composition according to the present invention does not reduce the melt viscosity during the production of a molded article, has a high crystallization rate, can be molded by setting the mold temperature at a low temperature, and improves the productivity during the production of a molded article, It is preferably manufactured by an injection molding method. The obtained molded product has excellent mechanical properties. Examples of molded products include automobile parts, OA equipment parts, and household electric appliance parts.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

The raw materials used in the examples described below have the following characteristics. (1) Component A: Polytrimethylene terephthalate (PT
T, manufactured by Shell Chemicals, trade name: Cortera CP50
9200), using a mixture of methylene chloride and trifluoroacetic acid in a weight ratio of 1: 1 as a solvent,
It has an intrinsic viscosity of 0.92 when measured at a temperature of 30 ° C. (2) Component B: An ionomer (ethylene / methacrylic acid copolymer neutralized with sodium ions, manufactured by Mitsui DuPont, trade name: HIMILAN1707). (3) C component: glass fiber (reinforcing material, manufactured by Nippon Electric Glass Co., Ltd.,
The product name is ECS03T-187 / PL). (4) Component D: Low molecular weight polyethylene (release agent, manufactured by Mitsui Chemicals, Inc., trade name: HW100P). (5) E component: Talc (crystal nucleating agent, manufactured by Nippon Talc Co., Ltd., trade name: Mistron Vapor). (6) F component: sodium benzoate (crystal nucleating agent, reagent manufactured by Wako Pure Chemical Industries, Ltd.).

[Examples 1 to 3 and Comparative Examples 1 to 4] <Preparation of Resin Composition> The components A to F were weighed in the proportions shown in Table 1 and mixed with a blender. The mixture was melted and kneaded into pellets by using a 30 mmφ twin-screw extruder (manufactured by Japan Steel Works, model: TEX30C) with the resin composition at a substantial temperature of 270 ° C. A molded article was manufactured using the obtained pellets by an injection molding method. A test piece for an evaluation test of mechanical properties was prepared by drying the above pellets at a temperature of 120 ° C. for 4 hours or more with a dryer, and then measuring the cylinder temperature with an injection molding machine (manufactured by Japan Steel Works, model: J75ED). 250 ° C
The mold temperature was set to 80 ° C. for the resin composition containing no C component (glass fiber), and the mold temperature was set to 20 ° C. for the resin composition containing the C component.

[0023]

[Table 1]

<Various Evaluation Tests> The test pieces prepared by the above method were subjected to evaluation tests by the methods described below, and the results are shown in Table 1. (a) Tc and ΔTc: prepare a sample from the pellet,
Using a differential calorimeter (DSC200, manufactured by Seiko Instruments Inc.), the temperature was raised from room temperature at a rate of 20 ° C./min to 280 ° C.
After being held for 3 minutes, it is cooled at a rate of 20 ° C./minute, and the crystallization peak in the temperature decreasing process is measured to determine the crystallization temperature Tc.
(° C.) and the full width at half maximum ΔTc (° C.) of the crystallization peak were measured. The higher Tc (° C.) is preferable, and ΔTc is a parameter indicating the crystallization rate, and the lower the better.

(B) Melt viscosity (Pa · s): using a Caprograph manufactured by Toyo Seiki, at a temperature of 270 ° C., shear rate γ = 912
The melt viscosity corresponding to s ^-1 was measured. (c) Tensile strength (MPa) and tensile elongation (%): ASTM-D63
It measured based on 8. (d) Flexural modulus (GPa): Measured according to ASTM-D790. (e) Izod impact strength (J / m): Based on ASTM-D-256, it was measured on a 1/8 "test piece with a notch.

[0026]

[Table 2]

From Table-1 and Table-2, the following is clarified. (1) The Tc of the resin composition containing the ionomer (Examples 1 and 2) is the same as that of the resin composition of Comparative Example 1 containing no E component or F component (both are crystal nucleating agents). The temperature was higher than Tc (183.2 ° C.) by 6.5 ° C. or more, and ΔTc was improved to less than half that of Comparative Example 1. (2) The resin composition containing the ionomer (Examples 1 and 2) has the same melt viscosity as that of the resin composition of Comparative Example 1 in which the crystal nucleating agent is not added. Is equivalent. (3) In Comparative Example 2 in which the E component (talc) was blended as the crystal nucleating agent, compared with Comparative Example 1 in which it was not blended, the melt viscosity was not decreased, but Tc was slightly increased and ΔTc was changed. No, the tensile elongation at break is significantly reduced. This is
Talc means that the performance as a crystal nucleating agent is not remarkable and mechanical properties are impaired. (4) In Comparative Example 3 in which the F component (sodium benzoate) was blended as the crystal nucleating agent, Tc and ΔTc were preferable values, but the tensile elongation at break of mechanical properties showing melt viscosity and toughness was lowered. Fierce. This means that the addition of sodium benzoate as a crystal nucleating agent accelerates the thermal decomposition of the PTT resin.

(5) Ionomer and C component (glass fiber)
The Tc of the resin composition (Example 3) in which
Tc of Comparative Example 4 (18
5 ° C higher than that of 4.7 ° C), and ΔTc
Comparative Example 4 is also significantly improved. (6) Comparative Example 4 containing no crystal nucleating agent has a low ΔTc, a large Tc, a slow crystallization, and a low-temperature molding manageable to produce a molded product, but the crystallization is insufficient, so that the mechanical properties are low. Has low tensile strength. (7) As described above, also in the resin composition containing glass fiber, the ionomer as the crystal nucleating agent makes the crystallization rate of the PTT resin very high.

[0029]

As described above in detail, the present invention has the following particularly advantageous effects, and its industrial utility value is extremely large. 1. The thermoplastic resin composition according to the first invention of the present invention comprises P
Since the TT resin is blended with the ionomer, the crystallization rate at the time of molding is high, the crystallization can be sufficiently and uniformly performed, and an excellent molded product can be obtained. 2. The thermoplastic resin composition according to the first invention of the present invention has a higher crystallization rate during molding than a resin composition containing a conventional crystal nucleating agent, and molding using a low temperature mold, high cycle molding. It is possible to produce molded products with high efficiency. 3. Since the melt viscosity of the thermoplastic resin composition according to the first invention of the present invention does not decrease at the time of manufacturing a molded product, the excellent mechanical properties of the PTT resin itself are not sacrificed. 4. The molded product according to the second invention of the present invention has a uniform crystallinity as a whole, is excellent in heat resistance, mechanical properties, dimensional stability, and the like, and has high commercial value.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) (C08L 67/02 25:08) (72) Inventor Ryo Saito 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in Technical Center of Sanryo Engineering Plastics Co., Ltd. (Reference) 4F071 AA45 AA78 AA81 AF11 AH00 BB05 BC07 4J002 BB232 BC042 CF051 DL006 FA046 FD016

Claims (6)

[Claims] 1. An ionomer of the resin composition containing a polytrimethylene terephthalate resin is 0.
A thermoplastic resin composition comprising 001 to 20% by weight and 0 to 50% by weight of glass fiber. 2. The ionomer is a copolymer of an olefin and / or styrene and an unsaturated carboxylic acid,
The thermoplastic resin composition according to claim 1. 3. The thermoplastic resin composition according to claim 1 or 2, wherein at least a part of the unsaturated carboxylic acid group contained in the ionomer is neutralized with a metal ion. 4. The thermoplastic resin composition according to claim 3, wherein the metal ion is an alkali metal. 5. The thermoplastic resin composition according to claim 1, wherein the polytrimethylene terephthalate resin has an intrinsic viscosity of 0.4 to 1.6. 6. An ionomer of the resin composition containing a polytrimethylene terephthalate resin is 0.
A molded article, which is produced from a thermoplastic resin composition containing 001 to 20% by weight and 0 to 50% by weight of glass fiber as a raw material.