KR102045392B1

KR102045392B1 - Thermoplastic resin composition and molded article made from same

Info

Publication number: KR102045392B1
Application number: KR1020150168419A
Authority: KR
Inventors: 이현진; 이종찬; 고춘원; 이언석
Original assignee: 주식회사 엘지화학
Priority date: 2015-11-30
Filing date: 2015-11-30
Publication date: 2019-11-15
Also published as: KR20170062798A

Abstract

The present disclosure relates to a thermoplastic resin composition and a molded article prepared therefrom, and more specifically, (a) 20 to 70 wt% of a polyphenylene sulfide resin having a melt index (300 ° C., 1.2 kg) of 60 to 100 g / 10 minutes. ; (b) 2 to 45 weight percent of polyamide resin; (c) 1 to 5% by weight of olefin rubber grafted with a reactive compound; (d) 20 to 40% by weight of glass fibers; And (e) 0 to 5% by weight of the additive; and a thermoplastic resin composition comprising a molded article prepared therefrom.
According to the present disclosure, there is an effect of providing a thermoplastic resin composition excellent in mechanical properties and whiteness and excellent in heat resistance and a molded article produced therefrom.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND MOLDED ARTICLE MADE FROM SAME}

The present disclosure relates to a thermoplastic resin composition and a molded article prepared therefrom, and more particularly, to a thermoplastic resin composition having excellent mechanical properties and whiteness and excellent heat resistance, and a molded article manufactured therefrom.

Polyphenylene sulfide resin has excellent heat resistance, excellent dimensional stability compared to other thermoplastic resins, and has characteristics of chemical resistance and flame retardancy, so that not only automotive and electronic parts but also electrical components and connectors requiring precision injection It can be applied to various industrial fields such as bobbins, optical pickup parts, gears, etc., but it has a disadvantage of brittleness due to high crystallinity.

Polyamide resin, a kind of engineering plastic, has excellent mechanical strength, abrasion resistance, heat resistance, chemical resistance, electrical insulation, arc resistance, etc. and is used in a wide range of applications such as automobiles, electrical / electronic parts, and industrial materials.

In order to develop a material having high heat resistance, a method of alloying a polyamide resin and a polyphenylene sulfide resin having superior heat resistance has been attempted.

Polyamide resins and polyphenylene sulfide resins have poor compatibility and poor extrusion properties, and phase separation may occur, resulting in poor appearance of molded products.

Compatibilizers are used to increase the compatibility of the two resins. The mechanical and thermal properties of the compatibilizers vary greatly depending on the type and content of the compatibilizers. On the other hand, when excessively used, the reaction between the matrix and the domain and the remaining compatibilizer reduce the area of the matrix, thereby reducing the mechanical and thermal properties.

In addition, since the polyphenylene sulfide resin itself has a yellow color, an excessive amount of a white pigment must be included in order to express white color. In this case, the mechanical properties decrease.

Therefore, it is necessary to develop a resin having high heat resistance and whiteness while maintaining mechanical properties.

Korean Patent Publication No. 2005-0064808

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties and whiteness and excellent heat resistance and a molded article manufactured therefrom.

The above and other objects of the present disclosure can be achieved by the present disclosure described below.

In order to achieve the above object, the present invention (a) 20 to 70% by weight of a polyphenylene sulfide resin having a melt index (300 ℃, 1.2kg) of 60 to 100 g / 10 minutes; (b) 2 to 45 weight percent of polyamide resin; (c) 1 to 5% by weight of olefin rubber grafted with a reactive compound; (d) 20 to 40% by weight of glass fibers; And (e) 0 to 5% by weight of an additive; provides a thermoplastic resin composition having excellent mechanical properties and whiteness and excellent heat resistance, and a method for producing the same.

The present invention also provides a molded article prepared from the thermoplastic resin composition.

As described above, according to the present disclosure, there is an effect of providing a thermoplastic resin composition having excellent mechanical properties and whiteness and excellent heat resistance and a molded article manufactured therefrom.

Hereinafter, the present description will be described in detail.

The thermoplastic resin composition of the present disclosure comprises: (a) 20 to 70 wt% of a polyphenylene sulfide resin having a melt index (300 ° C., 1.2 kg) of 60 to 100 g / 10 minutes; (b) 2 to 45 weight percent of polyamide resin; (c) 1 to 5% by weight of olefin rubber grafted with a reactive compound; (d) 20 to 40% by weight of glass fibers; And (e) 0 to 5% by weight of the additive; characterized in that, it is excellent in mechanical properties and whiteness within this range, there is an effect excellent in heat resistance.

Looking at each component constituting the thermoplastic resin composition of the present invention in detail as follows.

(a) Polyphenylene sulfide Suzy

The (a) polyphenylene sulfide resin may be, for example, 20 to 70% by weight, or 25 to 65% by weight, and has excellent heat resistance and whiteness while maintaining mechanical properties within this range.

The polyphenylene sulfide resin (a) may be, for example, a melt index (300 ° C., 1.2 kg) of 60 to 100 g / 10 minutes, 65 to 90 g / 10 minutes, or 70 to 90 g / 10 minutes. Excellent compatibility with the polyamide resin within the range has the effect of improving the whiteness while maintaining the heat resistance.

The polyphenylene sulfide resin (a) may contain, for example, 70 mol% or more, or 70 to 99.9 mol% of a unit having a structure of the following [Formula 1].

[Formula 1]

The polyphenylene sulfide resin may be, for example, a linear molecular structure having no branched or crosslinked structure, or may have a molecular structure having branched or crosslinked structure.

The polyphenylene sulfide resin may contain, for example, 30 mol% or less, or 0.1 to 30 mol%, of one or more selected from the group consisting of copolymer units having the structure of the following [Formula 2].

[Formula 2]

,

,

,

,

,

, or

(b) Polyamide Suzy

The polyamide resin (b) may be, for example, 2 to 45% by weight, or 5 to 40% by weight, and has excellent heat distortion temperature and whiteness within this range.

(B) the polyamide resin may have, for example, a melt index (270 ° C., 0.325 kg) of 5 to 25 g / 10 minutes, 10 to 20 g / 10 minutes, or 15 to 20 g / 10 minutes, within this range. Has an effect of excellent compatibility with the polyphenylene sulfide resin.

The polyamide resin (b) may be, for example, a relative viscosity measured in 96% sulfuric acid solvent of 2.3 to 2.8 dl / g, or 2.3 to 2.5 dl / g, and is compatible with the polyphenylene sulfide resin within this range. This has an excellent effect.

The polyamide resin (b) may be, for example, a polycondensation polymer of a ring structure lactam or w-amino acid, and may be a polymer in which diacids and diamines are condensation polymerized.

The polyamide resin (b) is, for example, poly caprolactam (nylon 6), poly hexamethylene diamine adipamide (nylon 6,6), poly hexamethylene seba amide (nylon 6,10), poly hexamethylenediamine la It may be at least one selected from the group consisting of uramide (nylon 6,12), polytetra methylenediamine adipamide (nylon 4,6), and polylaurolactam (nylon 12).

The (a) polyphenylene sulfide resin and the (b) polyamide resin may have, for example, a weight ratio of 30: 1 to 1: 2, 25: 1 to 1: 1.7, or 21: 1 to 1: 1.5, While maintaining mechanical properties within this range, there is an excellent effect of heat resistance and whiteness.

The melt index of the (a) polyphenylene sulfide resin and the (b) polyamide resin may satisfy the following Equation 1 or Equation 2 as an example, and the compatibility of the two resins within this range is excellent and mechanical Excellent physical properties.

[Equation 1]

20 ≤ | melt index of polyphenylene sulfide resin (300 ° C, 1.2kg)-melt index of polyamide resin (270 ° C, 0.325kg) | ≤ 90

[Equation 2]

30 ≤ | Melt Index of Polyphenylene Sulfade Resin (300 ℃, 1.2kg)-Melt Index of Polyamide Resin (270 ℃, 0.325kg) | ≤ 60

(c) the reactive compound is Grafted Olefin rubber

The olefin rubber grafted with the reactive compound (c) may be, for example, 1 to 5% by weight, or 2 to 4% by weight, and has excellent heat resistance while maintaining mechanical properties within this range.

In the olefin rubber in which the (c) reactive compound is grafted, the reactive compound may be, for example, glycidyl (meth) acrylate, maleic anhydride, or a mixture thereof, and a polyphenylene sulfide resin and a poly Excellent compatibility of the amide resin has the effect of improving the mechanical properties.

The olefin rubber grafted with the reactive compound (c) may be, for example, 1 to 10% by weight of the reactive compound is grafted to 90 to 99% by weight of the olefin rubber, polyphenylene sulfide resin and polyamide within this range Excellent compatibility of the resin has the effect of improving the mechanical properties.

The olefin rubber may be, for example, a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms, and as another example, an ethylene-propylene-diene monomer (EPDM) rubber, an ethylene-propylene monomer (EPM) rubber, and ethylene-1- It may be at least one selected from the group consisting of butene monomer rubber, ethylene-1-pentene monomer rubber, ethylene-1-hexene monomer rubber, and ethylene-1-octene monomer rubber.

(d) glass fiber

The glass fiber (d) may be 20 to 40% by weight, or 25 to 35% by weight, for example, and has an excellent extrudability within this range.

The glass fiber (d) may be, for example, a diameter of 5 to 20 μm, or 10 to 15 μm, a length of 1 to 10 mm, or 3 to 8 mm, and excellent mixing with the resin within this range to provide mechanical properties. It is effective to improve.

The glass fiber (d) may be, for example, surface-treated with an amino silane compound, in which case the mixing with the resin is excellent, thereby improving mechanical properties.

For example, the surface treatment of the amino silane-based compound may be a surface treatment of 0.5 to 2 parts by weight, or 1 to 1.5 parts by weight based on 100 parts by weight of the amino silane coupling agent.

The amino silane coupling agent may be a commercial amino silane coupling agent commercially available, and is not particularly limited.

(e) additives

The additive (e) may be, for example, 0 to 5% by weight, 0.1 to 3% by weight, or 0.5 to 3% by weight, and has an excellent balance of physical properties within this range.

The additive (e) may be at least one selected from the group consisting of, for example, antioxidants, lubricants, and pigments.

The thermoplastic resin composition is, for example, one kind selected from the group consisting of flame retardants, light stabilizers, hemoextension agents, catalysts, mold release agents, dyes, antistatic agents, antibacterial agents, processing aids, metal deactivators, fluorine-based anti-inflammatory agents, and anti-friction and anti-wear agents. It may further include the above.

For example, the thermoplastic resin composition may have a whiteness of 40 or more, 42 or more, or 42 to 55 based on ASTM E313, and may have an excellent whiteness and physical property balance within this range.

For example, the thermoplastic resin composition may have an impact strength of 50 J / m or more, 54 J / m or more, or 54 to 70 J / m based on ASTM D256, and excellent impact strength and physical property balance within this range. There is.

For example, the thermoplastic resin composition may have a bending strength of 150 MPa or more, 155 MPa or more, and 155 to 270 MPa based on ASTM D790, and has an excellent balance of bending strength and physical properties within this range.

For example, the thermoplastic resin composition may have a tensile strength of 100 MPa or more, 108 MPa or more, and 108 to 170 MPa based on ASTM D638, and has excellent balance of tensile strength and physical properties within this range.

For example, the thermoplastic resin composition may have a heat deformation temperature of 250 ° C. or more, 255 ° C. or more, and 255 to 280 ° C. in accordance with ASTM D648. The mechanical properties of the thermoplastic resin composition may be maintained while maintaining the mechanical properties within this range.

The method for producing a thermoplastic resin composition of the present disclosure includes, for example, (a) 20 to 70 wt% of a polyphenylene sulfide resin having a melt index (300 ° C., 1.2 kg) of 60 to 100 g / 10 minutes; (b) 2 to 45 weight percent of polyamide resin; (c) 1 to 5% by weight of olefin rubber grafted with a reactive compound; (d) 20 to 40% by weight of glass fibers; And (e) 0 to 5% by weight of additives; may comprise the step of extrusion after melt kneading.

For example, the melt kneading may be performed at 280 to 320 ° C, or at 290 to 310 ° C.

It provides a molded article characterized in that it is prepared comprising the thermoplastic resin composition of the present disclosure.

The molded article may be, for example, a connector or a nano molding molded article.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely to illustrate the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art, It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

The compound used in the following Example and the comparative example is as follows.

* PPS1: Polyphenylene sulfide resin of melt index (300 ℃, 1.2kg) 70 g / 10 minutes

* PPS2: polyphenylene sulfide resin with melt index (300 ° C., 1.2 kg) of 40 g / 10 minutes

* PA: polyamide resin with melt index (270 ° C, 0.325kg) 12g / 10min

* Olefin rubber: Rubber in which 6% by weight of glycidyl methacrylate is grafted to 94% by weight of ethylene (ethylene glycidyl methacrylate)

* Styrene rubber: Styrene rubber grafted with maleic anhydride

* Glass fiber: Glass fiber 10mm in diameter, 4mm long and surface-treated with amino silane

* Additives: lubricant WE-40PWD (Clariant), antioxidant 1 KY-445 (Chemtura) and antioxidant 2 IRGANOX-1098 (BASF)

Example 1 to 5 and Comparative example 1 to 6

As shown in Tables 1 and 2, each component was added to the corresponding content, mixed in a mixer, extruded using a twin-screw extruder under the conditions of 290 to 310 ° C, and prepared in pellet form to 80 ° C. After drying for more than 4 hours at injection molding to prepare a physical specimen.

[Test Example]

The properties of the thermoplastic resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

* Melt Index (g / 10min): measured according to ASTM D1238.

* Tensile strength (MPa): measured according to ASTM D638.

* Tensile Elongation (%): measured according to ASTM D638.

* Flexural Strength (MPa): measured according to ASTM D790 standard.

* Flexural modulus (MPa): measured according to ASTM D790 standard.

* Impact Strength (1/8 ", J / m): Measured according to ASTM D256 method.

* Heat deflection temperature (° C): measured according to ASTM D648.

* Whiteness: measured according to ASTM E313.

division Example 1 Example 2 Example 3 Example 4 Example 5 PPS1 59.8 53.1 46.5 39.8 26.6 PPS2 - - - - - Polyamide 6.6 13.3 19.9 26.6 39.8 Olefin rubber 3 3 3 3 3 Fiberglass 30 30 30 30 30 Additive ^* 0.6 0.6 0.6 0.6 0.6 The tensile strength 131 109 110 123 130 Elongation 1.6 1.3 1.4 1.6 2.6 Flexural strength 202 165 158 183 175 Flexural modulus 9801 8837 9247 8771 8135 Impact strength 63.3 54.8 57.4 59.8 67.2 Heat deflection temperature 269 264.5 258.4 257.3 257.1 Whiteness 42.3 49.5 53.4 54.7 57.3

(Additive ^* : 0.3 wt% of lubricant, 0.15 wt% of antioxidant 1, 0.15 wt% of antioxidant 2)

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PPS1 - - - - - - PPS2 39.8 26.6 33.8 22.6 75.5 75.5 Polyamide 26.6 39.8 22.6 33.8 18.9 18.9 Olefin rubber 3 3 3 3 - 5 Styrenic rubber - - - - 5 - Fiberglass 30 30 40 40 - - Additive ^* 0.6 0.6 0.6 0.6 0.6 0.6 Heat deflection temperature 254.5 256.0 250.3 251.4 94 95

As shown in Tables 1 and 2, the thermoplastic resin compositions (Examples 1 to 5) of the present substrate were excellent in mechanical properties while being excellent in heat resistance and whiteness.

On the other hand, Comparative Examples 1 to 6, including polyphenylene sulfide resins having a low melt index, had a lowered heat deformation temperature, and in particular, (c) did not include an olefin rubber grafted with a reactive compound, or (c) a reactive compound. Comparative Examples 5 and 6, in which styrene rubber was included instead of the grafted olefin rubber, had a very low heat distortion temperature.

Claims

(a) 20 to 70% by weight of a polyphenylene sulfide resin having a melt index (300 ° C., 1.2 kg) of 60 to 100 g / 10 minutes;
(b) 2 to 45 weight percent of polyamide resin;
(c) 1 to 5% by weight of olefin rubber grafted with a reactive compound;
(d) 20 to 40% by weight of glass fibers; And
(e) 0-5% by weight of additives;
Including,
(B) the polyamide resin has a melt index (270 ° C., 0.325 kg) of 10 to 20 g / 10 minutes,
The melt index of the (a) polyphenylene sulfide resin and the (b) polyamide resin satisfies Equation 2 below.
[Equation 2]
30 ≤ | Melt Index of Polyphenylene Sulfade Resin (300 ℃, 1.2kg)-Melt Index of Polyamide Resin (270 ℃, 0.325kg) | ≤ 60
Whiteness according to ASTM E313 is 42.3 to 57.3,
A thermoplastic resin composition according to ASTM D648, the heat distortion temperature is 255 to 280 ℃.

delete

The method of claim 1,
The (a) polyphenylene sulfide resin and the (b) polyamide resin have a weight ratio of 30: 1 to 1: 2, the thermoplastic resin composition.

delete

The method of claim 1,
In the olefin rubber in which the reactive compound is grafted (c), the reactive compound is glycidyl (meth) acrylate, maleic anhydride, or a mixture thereof.

The method of claim 1,
The glass fiber (d) is 5 to 20㎛ diameter, 1 to 10mm in length, the thermoplastic resin composition, characterized in that the surface treatment with an amino silane-based compound.

The method of claim 1,
The (e) additive is a thermoplastic resin composition, characterized in that at least one member selected from the group consisting of antioxidants, lubricants and pigments.

The method of claim 1,
The thermoplastic resin composition may be at least one selected from the group consisting of flame retardants, light stabilizers, hemoextension agents, catalysts, mold release agents, dyes, antistatic agents, antibacterial agents, processing aids, metal deactivators, fluorine-based anti-inflammatory agents, and anti-friction and anti-wear agents. It further comprises a thermoplastic resin composition.

delete

The method of claim 1,
The thermoplastic resin composition is a thermoplastic resin composition characterized in that the impact strength of 50 J / m or more based on ASTM D256.

The method of claim 1,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the flexural strength of 150 MPa or more based on ASTM D790.

The method of claim 1,
The thermoplastic resin composition has a tensile strength of 100 MPa or more according to ASTM D638.

delete

(a) 20 to 70% by weight of a polyphenylene sulfide resin having a melt index (300 ° C., 1.2 kg) of 60 to 100 g / 10 minutes; (b) 2 to 45 weight percent of polyamide resin; (c) 1 to 5% by weight of olefin rubber grafted with a reactive compound; (d) 20 to 40% by weight of glass fibers; And (e) extruding after melt kneading;
(B) the polyamide resin has a melt index (270 ° C., 0.325 kg) of 10 to 20 g / 10 minutes,
The melt index of the (a) polyphenylene sulfide resin and the (b) polyamide resin satisfies Equation 2 below.
[Equation 2]
30 ≤ | Melt Index of Polyphenylene Sulfade Resin (300 ℃, 1.2kg)-Melt Index of Polyamide Resin (270 ℃, 0.325kg) | ≤ 60
Whiteness according to ASTM E313 is 42.3 to 57.3,
Method for producing a thermoplastic resin composition, characterized in that the heat distortion temperature according to ASTM D648 is 255 to 280 ℃.

A molded article characterized in that it is made of the thermoplastic resin composition of any one of claims 1, 3, 5 to 8 or 10 to 12.

The method of claim 15,
The molded article is a molded article, characterized in that the connector or a nano-molded molded article.