KR102482344B1 - Polycarbonate resin composition and article produced therefrom - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition and a molded article manufactured therefrom, and the polycarbonate resin composition according to an embodiment of the present invention includes 50 to 80 parts by weight of polycarbonate; 5 to 40 parts by weight of carbon fiber; 0 to 10 parts by weight of carbon nanotubes; and 0.2 to 3 parts by weight of a coupling agent; and the polycarbonate resin composition according to the present invention may have excellent mechanical properties and high productivity.

Description

Polycarbonate resin composition and molded article manufactured therefrom {Polycarbonate resin composition and article produced therefrom}

The present invention relates to a polycarbonate resin composition and a molded article manufactured therefrom, and more particularly, to a polycarbonate resin composition having excellent mechanical properties and high productivity, and a molded article manufactured therefrom.

Thermoplastic resin compositions have a wide range of applications and can be used to produce a variety of molded parts. Among them, engineering plastics have high strength, excellent heat resistance, impact resistance, and chemical resistance, and can be used in various fields such as household goods, electric and electronic parts, automobiles, and aircraft.

In particular, polycarbonate is an amorphous thermoplastic resin with excellent mechanical properties such as high impact resistance at room temperature, excellent thermal properties such as flame retardancy and heat resistance, and high dimensional stability. It is applied to various fields such as parts.

In order to realize better physical properties, studies are being conducted to mix various fillers such as inorganic fillers, carbon fibers, glass fibers, and carbon nanotubes with polycarbonate resins. In addition, there is a method of blending a polyester resin and a polycarbonate resin, but since the melt viscosity and molecular structure of the polyester resin and the polycarbonate resin are different from each other, there is a certain limit to improving mechanical properties by simply blending them. there is.

In addition, various methods have been used to increase physical properties while maintaining conductivity, tensile force, and flexural strength of polycarbonate, but the degree of improvement in physical properties has not been sufficient for practical industrial application, and the appearance characteristics of manufactured products are There was a problem with deterioration.

Recently, molded products are gradually becoming thinner and larger, and a high level of appearance quality is required. In particular, in the case of large parts such as housings of TVs and refrigerators, post-shrinkage of resin occurs after injection molding and product assembly, resulting in dimensional change and increased stress due to contact with metal materials, resulting in poor fastening and cracks Problems such as occurrence occur, and development of a material capable of reducing post-shrinkage is continuously required.

Korean Patent Registration No. 10-2043095 discloses 50 to 80% by weight of polycarbonate resin, 5 to 20% by weight of an aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer, 5 to 30% by weight of a phosphorus-based flame retardant, and plate-shaped, spherical Or, a polycarbonate resin composition containing 0.1 to 7% by weight of a mixed inorganic filler and a molded product including the same are disclosed.

Korean Patent Publication No. 2019-0123168 discloses a polycarbonate-based resin composition comprising a methyl methacrylate-butadiene copolymer as an impact modifier along with polycarbonate and a styrene-acrylonitrile copolymer.

Korean Patent Publication No. 2019-0125583 discloses a polycarbonate resin composition including a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, silicone gum, a metal inorganic compound, a phosphorus-based flame retardant, and an inorganic filler.

KR 10-2043095 B KR 10-2019-0123168 A KR 10-2019-0125583 A

An object of the present invention is to provide a polycarbonate resin composition having excellent conductivity, mechanical properties and high productivity, and a composition prepared therefrom.

One embodiment of the present invention is 50 to 80 parts by weight of polycarbonate; 5 to 40 parts by weight of carbon fiber; 0 to 10 parts by weight of carbon nanotubes; It provides a polycarbonate resin composition comprising; and 0.2 to 3 parts by weight of a coupling agent.

The carbon fiber may have a length of 15 to 30 mm.

The carbon fibers may be polyacrylonitrile-based.

The carbon fiber may have a particle diameter of 5 to 10 μm.

The carbon nanotubes may be MWCNTs or SCNTs.

The coupling agent may include 0.1 to 1.5 parts by weight of the first titanium-based coupling agent and 0.1 to 1.5 parts by weight of the second polymeric ethylene-based coupling agent.

The coupling agent may include a titanium-based coupling agent represented by Formula 1 below.

[Formula 1]

The coupling agent may include a polymerizable ethylene-based coupling agent, and the polymerizable ethylene-based coupling agent may include 50 to 70 mgKOH/g of an acid radical.

The polycarbonate may be prepared by reacting bisphenol A (bisphenol A, 2,2-bis (4-hydroxyphenyl) propane) with phosgene.

Another embodiment of the present invention provides a composition formed of the polycarbonate resin composition according to one embodiment of the present invention.

The composition can be used as an interior and exterior material for precision machinery, automobiles, electrical and electronic devices, home appliances, office equipment, or daily necessities.

The polycarbonate resin composition according to an embodiment of the present invention may have excellent mechanical properties and high productivity.

The polycarbonate resin composition according to an embodiment of the present invention has increased fluidity, thereby lowering the load value of the production machine generated when polycarbonate and carbon fiber are mixed, thereby increasing productivity, and increasing the tensile strength of polycarbonate resin molded products. It may have excellent properties in strength, flexural strength, impact strength, and flexural modulus.

According to one embodiment of the present invention, free electrons can be increased at the interface between polycarbonate and polyacrylonitrile-based carbon fibers by the titanium-based coupling agent, so that strong bonding force is induced and excellent mechanical properties can be exhibited.

In addition, the polymerizable ethylene-based coupling can lower the load value of the production machine generated when polycarbonate and carbon fiber are mixed, increase dispersibility, and increase the toughness of polycarbonate. Accordingly, it is possible to improve impact strength, increase productivity that may be reduced due to the use of long carbon fibers, and improve quality uniformity.

The polycarbonate resin composition according to an embodiment of the present invention is expected to be able to replace expensive imported products, and accordingly, cost reduction is expected to be possible.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Accordingly, the embodiments of the present invention can be modified in many different forms, and the scope of the present invention is not limited to the embodiments described below.

Throughout the specification of the present invention, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

Throughout the specification of the present invention, when a step is said to be located "on" or "before" another step, this means that a step is in a direct time-series relationship with another step, as well as the mixing step after each step. As such, the order of the two steps may include the same rights as in the case of an indirect time-series relationship in which the time-series order may change.

The term "step of (doing)" or "step of" used throughout the specification of the present invention does not mean "step for".

The present invention relates to a polycarbonate resin composition and a material made of the composition.

The polycarbonate resin composition according to an embodiment of the present invention has increased fluidity, thereby lowering the load value of the production machine generated when polycarbonate and carbon fiber are mixed, thereby increasing productivity, and increasing the tensile strength of polycarbonate resin molded products. It may have excellent properties in strength, flexural strength, impact strength, and flexural modulus.

One aspect of the present invention is 50 to 80 parts by weight of polycarbonate and 5 to 40 parts by weight of carbon fiber (Carbon Fiber); It relates to a polycarbonate resin composition comprising 0 to 10 parts by weight of carbon nanotubes and 0.2 to 3 parts by weight of a coupling agent.

The polycarbonate is a thermoplastic resin, and since it is amorphous, it is transparent, has high mechanical strength, and has excellent heat resistance and electrical insulation properties. It is an engineering plastic that has the highest impact strength among thermoplastic resins, has little dimensional change due to moisture absorption, and is resistant to environmental changes with stable physical properties according to temperature changes.

In one embodiment of the present invention, polycarbonate prepared by reacting bisphenol A (bisphenol A, 2,2-bis (4-hydroxyphenyl) propane) and phosgene may be used.

In the present invention, excellent mechanical properties can be obtained by inducing strong bonding force between polycarbonate, carbon fiber, and filler by using a coupling agent.

50 to 80 parts by weight of the polycarbonate may be used. If the content is less than 50 parts by weight, appearance quality may be deteriorated, and if the content exceeds 80 parts by weight, mechanical properties may be deteriorated.

According to one embodiment of the present invention, the carbon fiber may have a particle diameter of 5 to 10 μm. Also, the carbon fibers may be 15 to 30 mm in length.

When carbon fibers having a short length, that is, short chips (eg, 3 to 6 mm) are used, productivity may be stabilized and quality stability may be secured, but it may be difficult to obtain excellent physical properties.

However, the use of long carbon fibers shows higher physical properties than the case of using relatively short carbon fibers, but production becomes very unstable and the uniformity of overall physical properties is low, which may be vulnerable to quality stability. In addition, the molded part surface may be very rough and uneven. That is, it may be difficult to secure quality stability together with high physical properties.

However, according to one embodiment of the present invention, long fibers of 15 to 30 mm may be used. Even if a long carbon fiber is used, by combining a polymerizable ethylene-based coupling agent and a titanium-based coupling agent, the fluidity (MFI) and strong crystallization are increased by heteroatoms at the interface, thereby reducing the overload of the extruder and maintaining high productivity. , can provide excellent mechanical properties.

If the length of the carbon fiber is less than 15 mm, it may be difficult to achieve excellent mechanical properties, and if it exceeds 30 mm, overload of the extruder or deterioration in appearance quality may occur. In addition, if the particle diameter of the carbon fiber is out of the range of 5 to 10 μm, an overload of the extruder may occur or the appearance quality may deteriorate.

Also, according to one embodiment of the present invention, the carbon fibers may be polyacrylonitrile (PAN) carbon fibers.

The polyacrylonitrile-based carbon fiber may be a polyacrylonitrile-based carbon fiber prepared by carbonization with heat of 1000° C. to 1500° C. in an inactive state in which no chemical reaction occurs.

The physical properties of polycarbonate resin molded products are affected by the physical properties of polycarbonate and carbon fibers used as reinforcing materials, but the chemical bond between polycarbonate and carbon fibers, carboxyl (-COOH), carbonyl (C=O), hydroxyl ( -OH), etc., and the interface of the interface plays an important role in determining the mechanical properties.

According to one embodiment of the present invention, free electrons can be increased at the interface between polycarbonate and polyacrylonitrile-based carbon fibers by the titanium-based coupling agent, and strong bonding force can be induced to exhibit excellent mechanical properties.

According to one embodiment of the present invention, 5 to 40 parts by weight of the carbon fiber may be used. If the content is less than 5 parts by weight, it may be difficult to obtain excellent mechanical properties, and if it exceeds 40 parts by weight, the appearance quality of the molded product may be deteriorated.

According to one embodiment of the present invention, 0 to 10 parts by weight of the carbon nanotubes may be used.

According to one embodiment of the present invention, 0.2 to 3 parts by weight of the coupling agent may be used.

According to one embodiment of the present invention, two types of coupling agents can be used. The first coupling agent may be a titanium-based coupling agent.

0.1 to 1.5 parts by weight of the first coupling agent may be used.

The titanium-based coupling agent can induce strong bonding force at the interface between polycarbonate and polyacrylonitrile (PAN)-based carbon fibers by activating heteroatoms.

According to an embodiment of the present invention, the titanium-based coupling agent may be represented by Formula 1 below.

Also, according to one embodiment of the present invention, the molecular formula of the titanium-based coupling agent may be C ₆₀ H ₁₂₃ O ₁₅ P ₃ Ti.

The second coupling agent according to an embodiment of the present invention may be polymerized ethylene. In addition, the second coupling agent may include 50 to 70 mgKOH/g, specifically 60 mgKOH/g of an acid radical.

The second coupling agent is a nucleating agent and can lower the load value of the production machine generated when polycarbonate and carbon fiber are mixed, increase dispersibility, and increase toughness of polycarbonate. Accordingly, it is possible to improve impact strength, increase productivity that may be reduced due to the use of long carbon fibers, and improve quality uniformity.

In addition, the polycarbonate resin composition of the present invention may further include an antioxidant or lubricant commonly used in the manufacture of polycarbonate resin compositions in addition to the above components.

Although not limited thereto, for example, a phosphite-based antioxidant may be used, and a monoglyceride-based lubricant, a stearate-based lubricant, or a fatty acid-based lubricant may be used.

Another aspect of the present invention relates to a composition made of a polycarbonate resin composition.

As described above, the polycarbonate resin composition according to an embodiment of the present invention may have excellent mechanical properties and high productivity.

More specifically, the polycarbonate resin composition according to an embodiment of the present invention can increase productivity by lowering the load value of a production machine due to increased fluidity, and can have excellent tensile strength, flexural strength, impact strength, and flexural modulus.

Although not limited thereto, a molded article may be manufactured by extruding and injecting the polycarbonate resin composition according to an embodiment of the present invention. The extrusion and injection methods may use methods commonly used in the art.

The molded article is not limited thereto, but may be, for example, internal and external parts for precision machinery, automobiles, electrical and electronic devices, home appliances, office equipment, or daily necessities.

Hereinafter, the present invention will be described in detail by examples and experimental examples. However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the contents of the present invention are not limited to the following Examples and Experimental Examples.

[Example]

A test piece was prepared by mixing 67.8% by weight of polycarbonate, 30% by weight of carbon fiber, 0.2% of carbon nanotube, and 2% of a coupling agent.

The extruder used a twin twin screw extruder, and the extrusion temperature was set to 240 ℃ ~ 260 ℃ at the inlet, 260 ℃ ~ 290 ℃ in the mixing zone, 290 ℃ ~ 320 ℃ in the die, and the input of carbon fiber was carried out throughout the extruder Side feeding at the 2/3 point of the carbon fiber was prevented from breaking, and the internal screw combination was arranged softly from the side zone section, and the screw speed speed) was maintained at 300 rpm and produced with 250 kg/hrs Capability.

Example 1

In Example 1, 15 mm of carbon fiber and a coupling agent were applied in the same manner as in Example 1.

Example 2

Example 2 was carried out in the same manner as in Example 1 except for the difference in which 30 mm of carbon fiber was applied.

[Comparative Example]

The test pieces of Comparative Examples 1 to 6 were prepared as in the above examples, but the length of the carbon fiber used and whether or not the coupling agent was used are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 carbon fiber 15mm 30mm 3mm 6mm 15mm 30mm 3mm 6mm coupling agent apply apply Unapplied Unapplied Unapplied Unapplied apply apply

[Results and evaluation]

1. Physical property measurement

The physical properties of the specimens obtained in the Examples and Comparative Examples were measured by the ASTM method, and are shown in Table 2 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 The tensile strength
(kgf/cm²) 1,880 2,320 1,100 1,250 1,520 1,800 1,250 1,510 flexural strength
(kgf/cm²) 2,940 3,270 1,850 2,480 2,760 2,920 2,450 2,670 impact strength
(kgf.cm/cm) 13 15 6 8 10 12 7 11 Appearance form
(Visual inspection) ◎ ◎ ◎ ○ △ X ◎ ◎

Referring to Table 2, it can be seen that the mechanical properties and appearance are excellent when a long fiber of 15 mm to 30 mm and a coupling are used. More specifically, Comparative Examples 3 and 4 used long fibers, but did not use a coupling agent, so the mechanical properties were excellent, but the appearance was poor. In addition, Comparative Example 5 and Comparative Example 6 used a coupling agent, but sufficient mechanical properties were not obtained due to the short length of the carbon fiber. In addition, Comparative Example 1 and Comparative Example 2 use short fibers and have excellent appearance, but poor mechanical properties.

2. Comparison with other products

Examples 1 and 2 were compared with foreign products (RTP PC CF30, RTP, USA).

Example 1 Example 2 Company R Specific Gravity (kg/㎥) 1.32 1.32 1.32 Tensile strength (kgf/㎠) 1,880 2,320 1,620 Flexural strength (kgf/㎠) 2,940 3,270 2,455 Impact strength (kgf.cm/cm) 13 15 11 Appearance (visual inspection) ◎ ◎ ○

Referring to Table 3, it can be seen that the products of Examples 1 and 2 are very excellent in tensile strength, flexural strength and impact strength compared to the products of R company. Company R's products are known in the industry to have world-class quality and are widely used.

The polycarbonate resin composition according to an embodiment of the present invention is expected to be able to replace expensive imported products, and accordingly, cost reduction is expected to be possible.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be covered by the following claims. All changes or modifications derived from the meaning and scope of the claims described later and equivalent concepts thereof may be interpreted as being included in the scope of the present invention.

Claims (11)

50 to 80 parts by weight of polycarbonate; 5 to 40 parts by weight of carbon fiber; 0 to 10 parts by weight of carbon nanotubes; and 0.2 to 3 parts by weight of a coupling agent;
The carbon fiber has a length of 15 to 30 mm,
The coupling agent comprises 0.1 to 1.5 parts by weight of a titanium-based coupling agent represented by Formula 1 below and 0.1 to 1.5 parts by weight of a polymerizable ethylene-based coupling agent having 50 to 70 mgKOH/g of an acid radical. A polycarbonate resin composition.
[Formula 1]

delete According to claim 1,
The carbon fiber is a polycarbonate resin composition, characterized in that the polyacrylonitrile-based.
According to claim 1,
The carbon fiber is a polycarbonate resin composition, characterized in that the particle size of 5 to 10㎛.
According to claim 1,
The carbon nanotube is a polycarbonate resin composition, characterized in that MWCNT (Multi-Walled Carbon NanoTube) or SCNT (semiconducting carbon nanotube) to prevent contamination and increase blackness.
delete delete delete According to claim 1,
The polycarbonate is a polycarbonate resin composition, characterized in that prepared by reacting bisphenol A (bisphenol A, 2,2-bis (4-hydroxyphenyl) propane) and phosgene (phosgene).
Claim 1, claim 3, claim 4, claim 5, characterized in that the molded article formed of the polycarbonate resin composition according to any one of claims 9.
According to claim 10,
The molded article is characterized in that the molded article is an internal and external parts for precision machinery, automobiles, electrical and electronic devices, home appliances, office equipment or daily necessities.