KR20160038543A - Fiber reinforced thermoplastic resin composites including filler and method for preparing the same - Google Patents

Abstract

The present invention relates to a fiber-reinforced thermoplastic resin composite material containing filler, and to a production method thereof. the fiber-reinforced composite material which has improved mechanical properties and conductivity and is made of a filler, a polymeric resin, and a fibrous material. To this end, the production method comprises the following steps: producing a thermoplastic resin composition after dispersing and mixing a polymeric catalyst into a polymerizable thermoplastic resin; mixing the thermoplastic resin composition with the filler; spreading the same on the fibrous material; and in-situ polymerizing the same via heat application while impregnating the same into the fibrous material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced thermoplastic resin composite material containing a filler,

This specification describes a thermoplastic resin composite material in which a filler and a fiber fabric are simultaneously mixed, and a manufacturing method thereof.

Fiber-reinforced composites can be molded and manufactured in a variety of ways depending on the nature of the raw materials and the intended use, size and shape of the composite. Among them, Resin Transfer Molding (RTM) method is a typical method for molding a complex type of carbon fiber reinforced composite material.

In the resin transfer molding (RTM) method, a fiber mat or a fabric is placed in a mold cavity, and then a low viscosity resin is injected into the mold to form and cure the resin mat.

However, according to the conventional resin transfer molding (RTM) method, the production time of the product is delayed considerably depending on the resin injection time and the curing time. In particular, since the resin is required to be cured for a long time, there is a problem that product productivity is lowered. As a result, conventional resin transfer molding (RTM) methods have been limited to practical industries.

On the other hand, in a molding method such as a resin transfer molding (RTM) method, a fiber-reinforced thermosetting resin composite material produced by using a thermosetting resin as a resin does not melt again once cured, But it is difficult to apply it to a product having a complicated shape and has a disadvantage in that the product is inferior due to heat curing process and does not recycle.

On the other hand, a fiber-reinforced thermoplastic resin composite material using a thermoplastic resin as a resin is capable of injection molding or extrusion processing, so that various types of products can be processed and reproduced. However, the fiber-reinforced thermoplastic resin composite material is disadvantageous in that it is not properly impregnated into a fiber fabric or the like because the viscosity of the fiber-reinforced thermoplastic resin composite material is rapidly increased as the melt is cooled.

In order to overcome the disadvantages of the above-mentioned methods of producing a fiber-reinforced thermosetting and / or thermoplastic resin composite material, polymerizable CBT (Cyclic Butylene Terephthalate) or caprolactam or oligomer having a low melt viscosity of tens to hundreds of cps A method of manufacturing a carbon fiber reinforced composite material using the thermoplastic resin of the present invention has been proposed.

When the polymerizable thermoplastic resin is heated and melted, the viscosity of the polymerizable thermoplastic resin becomes low, resulting in a low-viscosity melt state of several tens to several hundreds of cps. Thereafter, the polymerized thermoplastic resin is polymerized by continuous heating. That is, the thermoplastic resin is impregnated into a fabric or the like in the state of a low-viscosity melt as described above, and then polymerized through continuous heating to form a fiber-reinforced thermoplastic resin composite material.

Korean Patent Publication No. 10-2014-0043519 Korean Patent Publication No. 10-2012-0062849

Composites Science and Technology 89 (2013) 29-37 Macromolecular Research 22 (2014) 528-533

In embodiments of the present invention, in a thermoplastic resin composite material comprising a filler, for example, a metal filler, a ceramic filler or a carbon filler, particularly a nano-carbon such as carbon nanotube or nano-graphene, in a thermoplastic resin and reinforced with a fiber, The content of the filler can be contained in the thermoplastic resin in a high content of 30 wt% or more, and the dispersion problem of the filler occurring in the complexation of such a high amount of filler and thermoplastic resin (especially in mass production) To provide a fiber-reinforced thermoplastic resin composite material containing a filler capable of completely impregnating a fiber material (a fiber mat or a fabric) and improving electrical and thermal conduction characteristics while mitigating problems such as incomplete adhesion and the like, and a manufacturing method thereof do.

Exemplary embodiments of the present invention include a first step of preparing a thermoplastic resin composition by dispersing and mixing a polymerization catalyst in a polymerizable thermoplastic resin; And a second step of mixing the filler with the thermoplastic resin composition, applying the composition to a fiber material, heating the mixture to in situ polymerize the polymerizable thermoplastic resin, and impregnating the fiber material with the filler and the thermoplastic resin composition. A composite material manufacturing method is provided.

Exemplary embodiments of the present invention also include a fiber-reinforced composite material comprising a filler, a polymeric resin, and a fiber material, wherein the polymeric resin is a polymerizable thermoplastic resin, and the polymerizable thermoplastic resin has a melt viscosity The present invention provides a fiber-reinforced composite material containing a filler which is deteriorated in heat resistance.

According to the embodiments of the present invention, even when the conductive filler is contained in the thermoplastic resin at a high content of 30 wt% or more, it is easy to disperse the filler uniformly and at the same time, the fiber material (fiber mat or fabric) This improved fiber-reinforced composite material can be produced easily and quickly.

In addition, the fiber-reinforced thermoplastic resin composite material containing the filler produced according to the embodiments of the present invention can improve not only the mechanical properties but also the electrical and thermal properties, especially the physical properties such as thermal conductivity.

FIG. 1 is a cross-sectional view of an embodiment of the present invention in which a filler (e.g., nano-carbon) according to an embodiment of the present invention is contained in a thermoplastic resin (e.g., CBT) Fig. 2 is a schematic view showing a composite material manufacturing process.
Fig. 2 is a photograph showing a fiber reinforced composite material improved in mechanical properties and conduction characteristics produced in embodiments of the present invention (Fig. 2A is a plan view, and Fig. 2B is a side view).

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is to be understood that the present invention is not limited thereto.

In the present specification, the polymerizable thermoplastic resin means a thermoplastic resin which is lowered in viscosity when heated and melted, and is polymerized when heated continuously to form a polymer resin.

In this specification, in-situ polymerization means that a polymerizable thermoplastic resin is melted by heating and polymerized to form a polymer resin.

In this specification, nano-carbon means a carbon-based material having a size in nanometers (1000 nm or less) and capable of bonding at a molecular level.

In this specification, a matrix means a matrix made of a thermoplastic resin.

According to the results of the inventors' study, the fiber-reinforced composite material composed of the fiber and the polymer resin has a continuous structure of the fiber mixture having a relatively good mechanical property, so that the mechanical properties of the composite material can be remarkably improved. However, Since the fiber is impregnated in the polymer resin regardless of the structure, the conductivity of the composite material is not excellent.

On the other hand, in the case of a composite material composed of a filler and a polymer resin, the composite material can exhibit excellent conduction characteristics when it is mixed with the conductive filler in an amount exceeding that of percolation induction. However, the improvement of the mechanical properties of such a composite material is limited, and in most cases, it is impossible to apply it as a structural material. On the other hand, when the filler is impregnated with the fibers, the problem of dispersion or agglomeration of the filler can be a bigger issue.

In the embodiments of the present invention, a filler (preferably a powder type filler) is mixed with a composition (preferably a powder type composition) in which a polymerization catalyst and a polymerizable thermoplastic resin are primarily dispersed and mixed, And at the same time, it is applied to a fiber material (for example, a fiber mat or a fabric) and then in-situ polymerized to provide a fiber-reinforced composite material having greatly improved mechanical properties and electrical conductivity and heat conduction properties.

Accordingly, even when the composite material of the filler, the thermoplastic resin and the fiber material is produced by the production, particularly the mass production, the filler content can be contained at a high content of at least 30% by weight or more, excluding the fibers. In addition, even if it is contained in such a high content and contained in the composite material together with the fiber material, it is possible to alleviate the dispersion problem of the filler and the problems such as cohesion or poor contact between the fillers, and the mechanical properties, And a fiber reinforced composite material improved in mechanical properties and conduction characteristics, in particular, thermal properties, can be obtained.

The method for producing a filler and a fiber-reinforced thermoplastic resin composite material according to embodiments of the present invention includes the steps of preparing a thermoplastic resin composition by dispersing and mixing a polymerization catalyst in a polymerizable thermoplastic resin, mixing the filler and the thermoplastic resin composition, (Which can be repeatedly laminated and thickened as necessary) to the material, and then heating to impregnate the fibers with the in situ polymer.

Each step will be described below. Since the nano-carbon in the filler is relatively difficult to induce particularly high content and high dispersion, the embodiments of the present invention may be usefully applied. In particular, the nano-carbon among the fillers will be mainly described below. However, other fillers such as fillers of other materials (e.g., metal fillers or ceramic fillers) other than carbon-based fillers and micro-sized fillers other than nano-sized fillers are contained in a high content in the polymer resin composite material Embodiments of the present invention may be suitably used for high dispersion. In addition, the fillers may use one or more combinations.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of a process for making fiber-reinforced thermoplastic resin composites containing fillers (e.g., nanocarbons) according to one illustrative embodiment of the present invention.

1, in one embodiment of the present invention, a polymerizable thermoplastic resin and a polymerization catalyst (1: a thermoplastic resin and a polymerization catalyst are represented by 1) are dispersed and mixed using a mixer (10) or the like to obtain a thermoplastic resin Composition (2) is prepared.

The polymerizable thermoplastic resin is then used to infiltrate the nanocarbon in the step of preparing the filler and the fiber-reinforced thermoplastic resin composite material and to have a low melt viscosity to facilitate impregnation into a fiber material (e.g., a fiber mat or fabric).

That is, the polymerizable thermoplastic resin has a low melt viscosity of, for example, several tens to several hundreds of cps, For example, CBT (Cyclic Butylene Terephthalate), Caprolactam, or Oligomer resin. The CBT may be polybutylene terephthalate (PBT) after polymerization, the caprolactam may be a polyamide resin (nylon resin) after polymerization, and the oligomer resin may be a polymer resin after polymerization. Particularly, CBT and caprolactam resins are excellent in heat resistance and mechanical strength, and are suitable as composite materials.

The thermoplastic resin may be in the form of a powder or pellets. However, it is preferable to conduct in situ polymerization after powder mixing in the production of a fiber-reinforced composite material to be described later, in order to highly disperse a high amount of filler (especially nano-carbon) It is preferable that the thermoplastic resin is in the form of a powder.

The polymerization catalyst is mixed with a polymerizable thermoplastic resin to form a thermoplastic resin composition, and is capable of inducing and promoting the polymerization reaction of the thermoplastic resin.

In an exemplary embodiment, Titanates and Stannoxanes may be used as the polymerization catalyst, and titanium tetraoxide (TiO ₄ ) may be used in particular.

The polymerization catalyst may be dispersed and mixed in, for example, about 0.02 to 1 mol%, more specifically about 0.5 mol%, of the thermoplastic resin composition to prepare a thermoplastic resin composition.

The thermoplastic resin composition (2) is mixed with the nano-carbon (3) and the thinky mixer (20).

The polymerizable thermoplastic resin of the thermoplastic resin composition (2) mixed with the nano-carbon (3) is impregnated with the nano-carbons so that the viscosity can be remarkably decreased upon melting, and at the same time, Etc.) and then polymerized to produce a fiber-reinforced composite material containing a high amount of nano-carbon in the matrix.

Accordingly, even when the nano-carbon is contained in a high content of 30% by weight or more with respect to the thermoplastic resin and the nano-carbon, the dispersion is satisfactory and the poor contact between the nano-carbons can be prevented and the fiber material such as a fiber mat or fabric is uniformly impregnated The physical properties of the composite material can be improved.

In an exemplary embodiment, the fiber material may be a fiber mat or a fiber fabric, for example, carbon fiber (Carbon fiber) or glass fiber mat (laminated one or more layers).

In an exemplary embodiment, the filler used with the thermoplastic resin is not limited to a material, but may be at least one selected from a metal filler, a ceramic filler, and a carbon filler, and may be a carbon filler.

The carbon filler may be of micrometer size, but may be nano-carbon. As described above, in particular, in the case of nano-carbon such as carbon nanotubes and nano-graphene, it is difficult to increase the dispersibility while allowing the polymeric resin composite material to have a high content. However, these problems can be solved by embodiments of the present invention.

In an exemplary embodiment, the nano-carbon may be at least one selected from a group of nano-carbon materials consisting of carbon nanotube (CNT), nano-graphene (Graphene) and nano-graphene oxide (Graphene Oxide). The nano-carbon may be one obtained by subjecting the nano-carbon such as the carbon nanotube, graphene or graphene oxide to heat treatment, hydrogen peroxide treatment, or water treatment.

In an exemplary embodiment, the nano-carbon is preferably in the form of a powder for even dispersion of the nano-carbon in the final composite material.

The method of mixing the thermoplastic resin composition and the nano-carbon is not particularly limited as long as the thermoplastic resin composition and the nano-carbon can be uniformly mixed.

In an exemplary embodiment, the mixing process may be performed using a Thinky mixer or a ball mill.

After the mixing, the in situ polymerization proceeds. That is, the mixture (4) obtained by mixing the thermoplastic resin composition (2) and the nano-carbon (3) is applied on a fiber material (5) such as a fiber mat or a fabric (evenly distributed / This is repeated to provide a laminate having a desired thickness (for example, several mm to several cm) to a molding machine (or polymerizer) 30 and to perform in situ polymerization to produce a composite material containing nano-carbon and polymer resin and reinforced with fibers . As described above, when the in situ polymerization is carried out, the polymer resin is uniformly penetrated between the nano-carbons and impregnated with the fiber mat or fabric, so that the nano-carbon is evenly dispersed.

The polymerizable thermoplastic resin undergoes polymerization at a high temperature at a high temperature and proceeds slowly at a low temperature. Therefore, the thermoplastic resin is heated to a temperature within the range of the polymerization initiation temperature and the pre-thermal decomposition temperature of the thermoplastic resin. Further, it is preferable that the polymerizable thermoplastic resin is heated to the polymerization initiation temperature within a short time and maintained at the polymerization initiation temperature to the pre-pyrolysis temperature for a certain period of time, followed by rapid cooling.

For example, CBT is melted at about 130 ° C. and polymerization proceeds at 150 ° C. or higher. As the temperature is higher, the polymerization proceeds faster. When the temperature exceeds 260 ° C., pyrolysis can occur. (For example, from 0 seconds to 60 seconds or less) after heating to a temperature range (e.g., 150 to 260 占 폚) and maintaining a certain time (for example, 1 to 24 hours, Of time).

In an exemplary embodiment, the heating and cooling processes for the in situ polymerization described above can be performed using temperature control of the mold. That is, the thermoplastic resin composition and the nano-carbon are mixed to prepare a mixture, the mixture is applied to a fiber material such as a fiber mat or a fabric, the mixture is introduced into a mold, and the mold is heated for a short period of time Rapidly heated to have a temperature in the range of 150 to 260 ° C, and then maintained within the temperature range for 1 minute to 24 hours. After the holding process, the mold may be rapidly cooled to room temperature for a time of more than 0 seconds to 60 seconds or less. The heating rate or cooling rate may be, for example, 40 ° C to 50 ° C per second.

In an exemplary embodiment, it is preferred that the mold is heated to a temperature of 230 캜 and maintained at the heating temperature for 10 minutes.

When the mold is rapidly heated and maintained for a predetermined period of time as described above and then cooled for a short time, it is advantageous to mass-produce the fiber-reinforced composite material in which a high content of nano-carbon is incorporated. In addition, since only the mold is rapidly cooled, it is possible to block factors that may affect the physical properties of the product, and it is advantageous to produce a composite material having uniform physical properties.

In an exemplary embodiment, hot pressing may be performed by applying pressure while heating to produce a fiber-reinforced composite material having a high content of the nano-carbon. Such thermocompression can be accomplished in a thermoforming mold.

The fiber-reinforced composite material in which the nano-carbon produced as described above is incorporated in a high content can be obtained by dispersing the nano-carbon (filler) evenly in the matrix of the composite material even when the content of the nano- . Particularly, when the nano-carbon and powder-type thermoplastic resin composition (the composition in which the polymerization catalyst and the polymerizable thermoplastic resin are dispersed and mixed) are mixed, that is, the powder is mixed and then the in situ polymerization is carried out, , It is particularly preferable to induce a very uniform dispersion in the matrix of the fiber-reinforced composite material. Accordingly, the physical properties of the fiber-reinforced composite material mixed with the nano-carbon to be produced at a high content can be greatly improved. It is possible to obtain a superior effect particularly in terms of thermal conductivity. For example, a fiber reinforced composite material having a high content of the nano-carbon produced may exhibit excellent thermal conductivity (20 W / m · K or more) and mechanical properties (for example, tensile strength of 500 Mpa or more) in the planar direction.

Further, the obtained composite material can be usefully used in various fields. For example, it can be usefully used in LED heat-radiating structure, notebook and cellular phone case, automobile parts requiring heat-dissipating characteristics, and structural parts requiring paintability by methods such as spray coating.

Hereinafter, exemplary embodiments of the present invention will be described in more detail by way of examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example

(1) Production of thermoplastic resin composition

For the production of the nano-carbon and polymer resin composite material according to the present embodiment, titanium tetraoxide (TiO ₄ ) as a polymerization catalyst was dispersed and mixed in 0.6 g of CBT supplied from Cyclics as a filler and a thermoplastic resin . The titanium tetraoxide was contained in an amount of 0.5 mol% of the thermoplastic composition.

As the filler, Graphene nano platelets (GNP, M5) supplied from XG science and not subjected to a special pretreatment process were prepared (Example 1).

In addition to the GNP as the filler, carbon black CB (Example 2), multiwall carbon nanotubes (MWCNT) (Example 3), graphite (Example 4), pitch carbon fiber (pitch CF) Example 5) was used. The contents of each example are shown in Table 1. In each of the examples, carbon fiber was commonly used in an amount of 76 wt%. (12 wt% or 3 wt%) and fiber content (76 wt%) and the remainder is thermoplastic resin (12 wt% or 21 wt%). On the other hand, as a comparative example, the case where only thermoplastic water was used (Comparative Example 1) and the case where only the fiber reinforcing was performed without adding a filler to the thermoplastic resin (Comparative Example 2) was prepared.

(2) Nano-carbon With high content  Manufacture of incorporated fiber-reinforced composites

The mixture of the nano-carbon and the thermoplastic resin composition was uniformly applied to a carbon fiber fabric (Korean Carbon, CF-3327EPC), laminated through repeated processes to adjust the thickness of the specimen, heated to 230 캜, The polymerization reaction was induced by compression molding at the pressure for 10 minutes (in situ polymerization), and the polymerization was completed.

2 is a photograph showing the conductive improved filler and fiber reinforced thermosetting resin composite material produced in Example 1 of the present invention (FIG. 2A is a plan view, and FIG. 2B is a side view).

(3) Nano-carbon With high content  Properties of Fiber-Reinforced Composites Contained

The electrical conductivity and thermal conductivity of the sheet were measured by the 4-point probe method and the hot-disk method, respectively. In addition, the filler and the fiber-reinforced thermoplastic resin composite material mixed with a high content of the nano- The mechanical properties were measured using a universal tensile tester.

Table 1 shows the electrical conductivity, thermal conductivity and tensile strength of the prepared filler and fiber-reinforced thermoplastic composite material prepared in the examples of the present invention.

Content (wt%) Thermal conductivity Electrical conductivity The tensile strength Isotropic (W / m · K) The surface (W / m · K) S / m (MPa) Comparative Example 1
(Including resin only) 0.18 - - 90 Comparative Example 2
(Fiber reinforced resin) 0.69 1.65 0 440 Example 1
GNP (12wt%) 5.12 35.42 2120 505 Example 2
CB
(3 wt%) 0.95 2.58 120 445 Example 3
MWCNT
(12 wt%) 0.57 2.26 1200 495 Example 4
Graphite
(12 wt%) 1.89 4.07 780 460 Example 5
Pitch CF
(12 wt%) 3.85 8.46 1350 500

As can be seen in Table 1, the electrical, thermal and mechanical properties of the finally produced composite strands increased in proportion to the content of nanocarbon fillers incorporated into the matrix, and 90 wt% The results showed excellent electrical conductivity, thermal conductivity and tensile strength of 2120 S / m, 35.42 W / m · K and 505 MPa, respectively.

Thus, through the exemplary embodiments of the present invention, the filler can be highly dispersed in the matrix with a high content to easily and quickly produce a fiber-reinforced composite material having excellent mechanical properties as well as improved electrical and thermal conduction characteristics.

Claims (23)

A first step of dispersing and mixing a polymerization catalyst in a polymerizable thermoplastic resin to prepare a thermoplastic resin composition;
And a second step of mixing the filler with the thermoplastic resin composition and applying the filler and the thermoplastic resin composition to a fiber material and heating the mixture to in situ polymerize the polymerizable thermoplastic resin and impregnating the filler and the thermoplastic resin composition into the fiber material. By weight based on the total weight of the fiber reinforced composite material.
The method according to claim 1,
Characterized in that a filler and a thermoplastic resin composition are impregnated between the fibers of the fiber material.
The method according to claim 1,
A method for producing a fiber-reinforced composite material containing a filler, which comprises mixing a thermoplastic resin composition in powder form and a filler in powder form.
The method according to claim 1,
Wherein the filler comprises at least 30% by weight based on the total weight of the filler and the thermoplastic resin.
The method according to claim 1,
Wherein the filler is contained in an amount of 30 wt% to 95 wt% based on the total weight of the filler and the thermoplastic resin.
The method according to claim 1,
Wherein the thermoplastic resin is melted and impregnated between the fillers at the time of producing the composite material, followed by heating to a temperature before pyrolysis of the thermoplastic resin at a polymerization initiation temperature or higher.
The method according to claim 6,
Characterized in that a pressure is further applied during heating to thermocompression.
The method according to claim 1,
Wherein the polymerizable thermoplastic resin is a cyclic butylene terephthalate (CBT), a caprolactam, or an oligomer resin.
The method according to claim 6,
The polymerizable thermoplastic resin is CBT,
A mixture of a filler and a thermoplastic resin composition is injected between fibers of a fiber material and then the in situ polymerization is carried out in the mold,
The mold is heated to a temperature of 150 to 260 ° C. within a time period of not less than 0 seconds but not longer than 30 seconds and the mold is maintained at a heating temperature for 1 minute to 24 hours, Wherein the fiber-reinforced composite material is cooled within a predetermined period of time.
The method according to claim 1,
Characterized in that titanium dioxide (TiO ₄ ) is used as a polymerization catalyst.
The method according to claim 1,
Wherein the filler is at least one selected from a metal filler, a ceramic filler, and a carbon filler.
The method according to claim 1,
Wherein the filler is nanocarbon. ≪ RTI ID = 0.0 > 11. < / RTI >
13. The method of claim 12,
The nano-carbon may be at least one selected from a nano-carbon group consisting of carbon nanotubes (CNT), nano-graphene and nano-graphene oxide (GO) Or more is treated with heat treatment, hydrogen peroxide treatment or regal water treatment.
The method according to claim 1,
Wherein the fiber material is a laminate of one or more mats made of a carbon fiber or a glass fiber.
A fiber-reinforced composite material comprising a filler, a polymer resin and a fiber material,
Wherein the polymer resin is a polymerizable thermoplastic resin, and the polymerizable thermoplastic resin has a lowered melt viscosity upon polymerization.
15. The method of claim 15,
Wherein the filler is contained in an amount of 30% by weight or more based on the total weight of the filler and the thermoplastic resin.
16. The method of claim 15,
Characterized in that a filler and a thermoplastic resin are distributed between the fibers of the fiber material.
16. The method of claim 15,
Wherein the fiber material comprises one or more layers of mats made of carbon fiber or glass fiber.
16. The method of claim 15,
Wherein the filler is at least one selected from a metal filler, a ceramic filler, and a carbon filler.
20. The method of claim 19,
Wherein the filler is a carbon filler.
21. The method of claim 20,
Wherein the carbon filler is a nano-carbon.
22. The method according to any one of claims 15 to 21,
Wherein the thermal conductivity of the composite material is 20 W / m · K or more.
22. The method according to any one of claims 15 to 21,
Wherein the composite material has a tensile strength of 500 MPa or more.

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