KR102723133B1 - Manufacturing method for thermoplastic resin composite material, thermoplastic resin composite material and article comprising same - Google Patents

Abstract

The present invention relates to a method for producing a thermoplastic resin composite including an additive, comprising the steps of: forming additive layers each including an additive on a thermoplastic resin film to produce two or more composite preforms; and supplying the two or more composite preforms to an extruder and melt-extruding them. The present invention also relates to a method for producing a thermoplastic resin composite, a thermoplastic resin composite, and a molded article including the same.

Description

MANUFACTURING METHOD FOR THERMOPLASTIC RESIN COMPOSITE MATERIAL, THERMOPLASTIC RESIN COMPOSITE MATERIAL AND ARTICLE COMPRISING SAME}

The present invention relates to a method for producing a thermoplastic resin composite, a thermoplastic resin composite, and a molded article comprising the same.

In general, polymer nanocomposites are heterogeneous materials in which nanomaterials with a size of 1 to 100 nanometers are dispersed into a polymer matrix. It is a material that physically/chemically hybridizes different materials to overcome the limitations of the properties of the raw materials and to obtain synergistic effects of multifunctionality and high performance. The characteristic of nanocomposites is that the particle size of the existing inorganic filler or reinforcing agent (generally micron or larger) is dispersed to the nano level, thereby maximizing the surface area compared to the past, minimizing the input amount, and minimizing the deterioration of properties due to the input of additives, thereby imparting the characteristics of the reinforcing agent to the polymer. In other words, stiffness, flame retardancy, wear resistance, electrical conductivity, thermal conductivity, etc. can be significantly improved without loss of the impact resistance and tensile properties of the existing resin. Representative examples of these nanomaterials include clay, carbon nanotubes (CNT), graphene, carbon nanofibers (CNF), gold nanoparticles, and silver nanoparticles, which each have excellent properties such as high aspect ratio, physical rigidity, strength, electrical conductivity, thermal conductivity, and barrier properties. When these nanomaterials are added to a polymer matrix to form a composite, a material can be manufactured that has improved physical strength, rigidity, electrical conductivity, thermal conductivity, hygroscopicity, waterproofness, and other properties compared to the properties of the polymer itself.

On the other hand, existing nanomaterials have difficulty in sufficiently securing the desired effect due to the agglomeration of nanomaterials that occurs during dispersion. In addition, in the case of metal nanoparticles, there is a risk of dust explosion when used directly, so there are many restrictions on their use.

Japanese Publication Patent No. 1999-217524 A

The present invention provides a method for manufacturing a thermoplastic resin composite, a thermoplastic resin composite, and a molded article comprising the same.

The present invention provides a method for producing a thermoplastic resin composite including an additive, comprising the steps of: producing two or more composite preforms by forming additive layers each including an additive on a thermoplastic resin film; and supplying the two or more composite preforms to an extruder and melt-extruding them.

In addition, the present invention provides a thermoplastic resin composite manufactured by the method for manufacturing a thermoplastic resin composite described above.

In addition, the present invention provides a molded article comprising the thermoplastic resin composite described above.

Since the method for manufacturing a thermoplastic resin composite of the present invention can include two or more types of additives, it can be applied to a method for manufacturing a composite requiring various physical properties.

In addition, since it can be used in processes where the particle size of the additive is very small, the processability can be improved.

In addition, since the thickness of the additive layer is nano-sized but the length and width are micro-sized, there is almost no risk of dust explosion. Therefore, it can be safely used in processes where the use of nano-sized metals is difficult due to the risk of dust explosion, and thus new product development is possible.

Figure 1 shows the composite viscosity measurement values of resin composites of examples and comparative examples.
Figure 2 shows the elongation viscosity measurement values of resin composites of examples and comparative examples.
Figure 3 shows the appearance of resin composites of examples and comparative examples.

Hereinafter, the present invention will be described in more detail.

The present invention provides a method for producing a thermoplastic resin composite including an additive, comprising the steps of: producing two or more composite preforms by forming additive layers each including an additive on a thermoplastic resin film; and supplying the two or more composite preforms to an extruder and melt-extruding them.

When the diameter size of the above additive is nano-sized (nm), the thermoplastic resin composite can be called a nanocomposite. Dispersion of nanomaterials has emerged as a very important issue in increasing the physical properties by using nanocomposite materials. In particular, the improvement of nanomaterial dispersion in melting processes for mass production such as extrusion and injection has been more difficult to solve than the solution process approach. In addition, in the case of metal particles below a certain size, the difficulty of the process increases, and there was a problem that it was difficult to apply to the process because there was a possibility of explosion in the atmosphere.

The method for manufacturing a thermoplastic resin composite of the present invention comprises forming an additive layer on a thermoplastic resin film in advance before a melting and extrusion process to manufacture a composite preform, and then melting and extruding the manufactured composite preform to manufacture a thermoplastic resin composite. Accordingly, it has the advantage of improving the dispersibility of an additive material forming an additive layer and improving mechanical properties. In addition, by separately manufacturing two or more composite preforms and then feeding them into an extruder, the dispersibility of the additive material can be further improved.

In addition, the step of supplying the two or more composite preforms to the extruder and melt-extruding them may be supplying the two or more composite preforms to the extruder simultaneously.

Below, the steps for manufacturing the composite preform are described.

The above composite preform refers to a composite form before being supplied to an extruder, melted, and extruded. In the past, a method was used in which already melted resin material and additives were simultaneously supplied to an extruder, or in which resin material was supplied to a main stream and additives were supplied to a sub stream, thereby dispersing the additives on a resin matrix. However, in this case, there was a problem in that the additives were not well dispersed on the resin. Therefore, in the present invention, a composite preform is manufactured by forming an additive layer on a thermoplastic resin film that has already been formed into a film, and the manufactured composite preform is supplied to an extruder so that the additives can be well dispersed in the resin.

In particular, the present invention can control the effects or properties of each composite preform by individually manufacturing two or more composite preforms and then feeding them into an extruder. For example, when a first composite preform and a second composite preform are manufactured and then fed into an extruder to manufacture a resin composite, the final manufactured resin composite has properties intermediate between the properties of the first composite preform and the second composite preform. In addition, when the weight ratio of the first composite preform and the second composite preform is adjusted, a composite having desired properties can be easily manufactured.

For example, the method for producing the thermoplastic resin composite includes a step of producing a first composite preform and a second composite preform, wherein the first composite preform and the second composite preform include different additive layers, and the weight ratio of the first composite preform and the second composite preform may be 10:1 to 1:10, preferably 5:1 to 1:5, and more preferably 3:1 to 1:3. When the weight ratio is adjusted, the properties due to the unique characteristics of the additive layers included in each composite preform can be adjusted. For example, when the weight ratio of the first composite preform and the second composite preform is the same, the composite preform has an intermediate form between the properties of the additive layer included in the first composite preform and the additive layer included in the second composite preform.

When two or more composite preforms are manufactured separately, the additive layer formed on each composite preform may be the same or different from each other for each composite preform. For example, when a first composite preform and a second composite preform are manufactured separately, the additive included in the additive layer formed on the first composite preform and the additive layer formed on the second composite preform may be the same or different from each other.

In particular, when two or more types of additives having different adhesive strengths with the resin are used, the adhesive strength between the resin and the additive layer can be improved by controlling the thickness of the additive layer, the content of the additive, and the stacking order of the additive layers. Improving the adhesive strength between the resin and the additive layer can improve phase separation or cracking phenomena that may occur in the composite preform.

The formation of the above additive layer can be by deposition or coating. That is, the additive material included in the additive layer can be deposited on a thermoplastic resin film, or a composition including the additive included in the additive layer can be coated on a thermoplastic resin film.

The above deposition can be by chemical vapor deposition (CVD) or physical vapor deposition (PVD). The chemical vapor deposition (CVD) is a method in which a gaseous metal source and a gas that reacts with it are heated or converted into plasma to form highly reactive radicals and cause a chemical reaction on a high-temperature substrate to form a metal thin film, and the physical vapor deposition (PVD) is a method in which energy applied to a desired metal material is converted into kinetic energy to cause the material to move and accumulate on the substrate to form a thin film. The physical vapor deposition surface has a thickness of several nanometers to several thousand nanometers and can be deposited regardless of the substrate size. Physical vapor deposition is divided into thermal evaporation vacuum deposition, sputtering, and ion-assisted deposition depending on the gas generation method.

The above sputtering method refers to the phenomenon in which atoms are ejected from the surface when ionized atoms are accelerated and collide with a material and the collision energy is greater than the binding energy of the material surface. The sputtering method uses this principle to collide ionized particles (ex. Ar ⁺ ) with a metal source in a vacuum and deposit the ejected atoms on a substrate.

The above sputtering method can be performed in a chamber containing plasma gas. The plasma gas can be argon (Ar) gas.

The above sputtering method may be a reactive sputtering method and may be performed in a chamber containing a plasma gas and a reactive gas. The reactive gas is oxygen (O ₂ ) and nitrogen (N ₂ ), and is a gas for providing oxygen or nitrogen atoms, and is distinguished from the plasma gas.

In one embodiment of the present invention, the flow rate of the plasma gas may be 10 sccm or more and 300 sccm or less, preferably 20 sccm or more and 200 sccm or less. The sccm means Standard Cubic Centimeer Per minute.

In one embodiment of the present invention, the step of forming an additive layer including two or more additives on the thermoplastic resin film is performed at a process pressure of 0.01 mTorr to 100 mTorr and a driving power of 10 W to 100,000 W.

The step of pulverizing the composite preform may be further included before the step of melt-extruding the composite preform. That is, before feeding the composite preform into the extruder, the composite preform may be pulverized and formed into a pulverized product. The size of the pulverized product may be adjusted by the diameter and size of the extruder input port or the performance of the extruder so as to be easily pulverized for feeding into the extruder. For example, the diameter of the pulverized product may be 10 mm or more and 100 mm or less.

The above thermoplastic resin film refers to a thermoplastic resin film that has already been manufactured into a film form using a thermoplastic resin, and is different from a thermoplastic resin in a molten form.

In general, the extrusion process is a molding method that converts a continuous body with a certain cross-section by supplying raw materials to an extruder and extruding them through a heated cylinder-shaped structure, and is a major molding method for thermoplastic resins. The raw materials supplied to the extruder are heated, softened, and melted in the cylinder, and are transported while being kneaded and compressed by the rotation of the screw. The flow of raw materials in the form of a uniform melt is continuously extruded to the outside through the opening of a mold made into the desired shape, and then the extrusion result is obtained after a cooling process.

The step of melt-extruding the above composite preform uses an extruder, and the extruder may be a single-screw extruder or a twin-screw extruder.

In this extrusion process, the raw material may change its properties while undergoing a kneading process under mechanical pressure in a heated state. Therefore, it is desirable to proceed with the extrusion process while maintaining the properties of the raw material. To this end, it is necessary to appropriately control the extrusion conditions of the extruder. Specifically, it is intended to control the resin composition, feed speed, operating temperature, extruder screw RPM, residence time, heating zone length, and extruder torque and/or pressure.

In order to suppress damage to the raw material, the rotation speed of the screw equipped in the extruder can be controlled to 50% or less of the maximum speed of the equipment, for example, 10 to 40%. The speed of the screw can be, for example, 350 rpm or less, or 300 rpm or less, or 250 rpm or less, or 200 rpm or less. On the other hand, if the speed of the screw equipped in the extruder is too small, the throughput per unit time decreases, which deteriorates productivity and also deteriorates mixing performance. Therefore, the speed of the screw can be controlled to 10% or more of the maximum speed of the equipment, for example, 10 rpm or more, or 20 rpm or more.

The screw of the extruder may have a diameter of 5 to 50 mm, preferably 10 to 30 mm. If the screw diameter of the extruder is less than 5 mm, the productivity efficiency may decrease, the extruder shaft may bend, and if it is more than 50 mm, the motor may be overloaded.

In addition, the main speed of the screw equipped in the extruder can be appropriately determined by the diameter and rotational speed of the screw equipped in the extruder, but in order to suppress thermal deterioration such as reduction in molecular weight of the thermoplastic resin, a range of usually 10 m/sec or less, for example, 6 m/sec or less, or 4 m/sec or less can be used.

The screw of such an extruder is composed of multiple elements (screw elements) in order to provide various functions. Generally, it is composed of a full flight consisting of only a spiral screw (flight) mainly for the purpose of returning the resin, and a kneading disk for the purpose of mixing the resin. Depending on the purpose, a reverse flight in which the screw is arranged in the opposite direction to the direction of returning the resin can also be used.

In the present invention, the configuration of these screw elements is not limited, but one having a kneading disk can be used, and one or more kneading disks can be used, and a heating area can be distinguished by the kneading disk. In the structure of such an extruder, the total length of the kneading disk can be 20% or less, for example, 15% or less, of the entire length of the screw. If the total length of the kneading disk is too long, local heat generation due to shearing of the resin increases, which may cause a color change phenomenon of the thermoplastic resin, which is not preferable.

If the total length of the above-described kneading discs is too short, the mixing performance described above may deteriorate, so the total length of the above-described kneading discs may be in a range of 3% or more, for example, 5% or more, of the total length of the screw.

The above-mentioned kneading discs are of the forward, orthogonal, and reverse transport types with respect to the direction of return of the resin, but can be appropriately selected depending on the viscosity of the resin used or the required performance.

By changing the heating conditions inside the extruder, the degree to which the resin is melted and the degree to which the additive is dispersed in the resin can be controlled. The extruder may include a plurality of heating zones, and the plurality of heating zones may have a temperature gradient.

The extruder may have a plurality of heating zones and extrusion dies, and the plurality of heating zones may be distinguished by the positions of the kneading discs. That is, a region in which only a heating zone exists before the first kneading disc may be distinguished as a first heating zone, a flight region between the second and third kneading discs may be distinguished as a second heating zone, etc. The heating zones may have, but are not limited to, the first to fifth heating zones. A composite preform supplied to the extruder may be melted by the heating zones.

The heating temperature of such a heating zone can be controlled by a heater provided on the outside of the barrel. Since the heater can be controlled independently, the heating zones can be individually temperature-controlled.

The temperature of the first heating zone can be set to a range below the melting temperature of the thermoplastic resin, and in this range, a rapid temperature rise of the raw material can be prevented, thereby suppressing changes in the properties or shape. For example, the temperature of the first heating zone can have a gradient form. Through the temperature gradient, the dispersibility of the additive can be improved, thereby improving the mechanical properties such as tensile strength. The melt mixing can be performed at a processing temperature of 160°C to 500°C, but preferably 200 to 330°C. When the processing temperature is less than 160°C, the resin may not be sufficiently melted, so that excessive shear force may be applied, making processing difficult. When the processing temperature exceeds 500°C, the resin may deteriorate, resulting in a deterioration in the properties and characteristics of the product, making it difficult to use as a product.

An example of such a temperature gradient is a case where the temperature gradually increases from the front end of the first heating region to the bottom end, that is, in the direction of travel of the raw material. The temperature control of such a first heating region can be regulated by individually controlling the temperature of the heater installed on the outside of the barrel as described above. The maximum temperature of such a first heating region can have a range of, for example, 180 to 330°C, for example, 200 to 325°C. The maximum temperature of the first heating region refers to the temperature of the bottom end of the first heating region.

The temperature of the second heating zone, that is, after the first heating zone, may have a range higher than the melting temperature of the thermoplastic resin. That is, the composite preform that has passed through the first heating zone can be sufficiently melt-mixed by heating it in the subsequent heating zone to a temperature higher than the melting temperature of the resin. The highest temperature of the heating zone after the first heating zone may have a range of, for example, 180 to 330°C, for example, 200 to 325°C. The highest temperature of the heating zone after the first heating zone means the highest temperature among all heating zones that exist after the second heating zone.

If the above maximum temperature is less than 180°C, it is difficult to obtain sufficient mixing, and if it exceeds 330°C, thermal decomposition of the thermoplastic resin may occur.

The L/D of the extruder according to the present invention is the ratio of the length (“L”) to the diameter (“D”) of the screw. The L/D value of the extruder according to the present invention may be 5 to 80, preferably 10 to 60. The extruder may preferably have an L/D of 30 or more in order to implement various screw combinations suitable for the present invention and secure dispersibility, and may preferably have an L/D of 80 or less in order to prevent motor capacity limitations and deterioration of the resin.

When the composite preform is extruded using a twin-screw extruder having an L/D of 50 or more, the extrusion amount may be 0.01 kg/h or more per 1 rpm of the screw, for example, in a range of 0.05 kg/h to 1 kg/h, or 0.08 to 0.5 kg/h. Here, the extrusion amount means the weight (kg) per hour of the molten mixture discharged from the twin-screw extruder having a screw diameter of 41 mm.

The residence time within the above extrusion can range from 1 to 30 minutes, for example, from 5 to 10 minutes. This residence time is a value representing the average residence time from the time the raw material is supplied to the extruder until the time it is discharged. The above residence time is the time from the position of the bottom of the screw where the raw material is supplied to the time it is discharged from the discharge port of the extruder when the molten mixture is in a normal molten mixture state in which the molten mixture is adjusted to a predetermined extrusion amount.

When a twin-screw extruder is used as the above extruder, there is no particular limitation on the screw of the twin-screw extruder, and a screw of a completely meshed type, an incompletely meshed type, a non-meshed type, etc. can be used. From the viewpoints of mixing properties and reactivity, a completely meshed screw is preferable. Also, the rotation direction of the screw may be either co-rotation or counter-rotation, but co-rotation is preferable from the viewpoints of mixing properties and reactivity. A co-rotation completely meshed screw is most preferable.

In order to suppress deterioration of the resin in the above extrusion process, an inert gas may be introduced into the raw material input section to perform melting and mixing. Nitrogen, etc. may be exemplified as the inert gas at this time.

The above additives are intended to impart the properties of each additive to a resin composite having the inherent properties of a thermoplastic resin. For example, the properties may be appearance properties such as the inherent gloss of a metal, or magnetic properties such as surface resistance or electrical conductivity. In other words, the resin composite may have various properties depending on the inclusion of the additives. Examples of the additives may include a material selected from the group consisting of metals such as indium (In), titanium (Ti), tin (Sn), silicon (Si), germanium (Ge), aluminum (Al), copper (Cu), nickel (Ni), vanadium (V), tungsten (W), tantalum (Ta), molybdenum (Mo), neodymium (Nb), iron (Fe), chromium (Cr), cobalt (Co), gold (Au), or silver (Ag), oxides of the metals, nitrides of the metals, oxynitrides of the metals, and carbon nanotubes.

The thickness ratio of the thermoplastic resin film to the additive layer may be 100,000:1 to 10:1, preferably 10,000 to 50:1, and more preferably 5,000 to 100:1. The additive included in the additive layer has a network structure within the matrix of the thermoplastic resin-containing composite, and when it is within the above range, it is more advantageous for forming the above-described network structure.

The weight ratio of the additive layer to the entire composite preform may be 30 wt% or less, preferably 25 wt% or less, and more preferably 20 wt% or less. The additive included in the additive layer has a network structure within the matrix of the thermoplastic resin-containing composite, and when it is within the above range, it is more advantageous for forming the above-described network structure. When the additive layer is a multilayer additive layer, the thickness means the content ratio of the additive layer including all layers.

The thermoplastic resin is a vinyl polymer or copolymer resin obtained by polymerizing or copolymerizing at least one vinyl monomer selected from the group consisting of polycarbonate resin, polypropylene resin, polyamide resin, aramid resin, aromatic polyester resin, polyolefin resin, polyester carbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyarylene resin, cycloolefin resin, polyether imide resin, polyacetal resin, polyvinyl acetal resin, polyketone resin, polyether ketone resin, polyether ether ketone resin, polyaryl ketone resin, polyether nitrile resin, liquid crystal resin, polybenzimidazole resin, polyparavanic acid resin, aromatic alkenyl compound, methacrylic acid ester, acrylic acid ester, and vinyl cyanide compound. It may be at least one selected from the group consisting of alkenyl compound copolymer resin, vinyl cyanide-diene-aromatic alkenyl compound copolymer resin, aromatic alkenyl compound-diene-vinyl cyanide-N-phenylmaleimide copolymer resin, vinyl cyanide-(ethylene-diene-propylene (EPDM))-aromatic alkenyl compound copolymer resin, polyolefin, vinyl chloride resin, and chlorinated vinyl chloride resin.

The polyolefin resin may be, but is not limited to, polypropylene, polyethylene, polybutylene, and poly(4-methyl-1-pentene), and combinations thereof. The polyolefin is selected from the group consisting of polypropylene homopolymers (e.g., atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene), polypropylene copolymers (e.g., polypropylene random copolymers), and mixtures thereof. Suitable polypropylene copolymers include, but are not limited to, random copolymers prepared by polymerizing propylene in the presence of a comonomer selected from the group consisting of ethylene, but-1-ene (i.e., 1-butene), and hex-1-ene (i.e., 1-hexene). In these polypropylene random copolymers, the comonomer may be present in any suitable amount, but is typically present in an amount of about 10 wt % or less (e.g., about 1 to about 7 wt %, or about 1 to about 4.5 wt %).

The above polyester resin refers to a homopolyester or copolymer polyester which is a polycondensation product of a dicarboxylic acid component skeleton and a diol component skeleton. Here, representative examples of the homopolyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene diphenylate. In particular, polyethylene terephthalate is preferable because it is inexpensive and can be used for a wide range of applications. In addition, the copolymer polyester is defined as a polycondensation product composed of at least three or more components selected from the following components having a dicarboxylic acid skeleton and a component having a diol skeleton. Components having a dicarboxylic acid skeleton include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylsulfonic dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexanedicarboxylic acid, and their ester derivatives. Components having a glycol skeleton include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2,2-bis(4'-β-hydroxyethoxyphenyl)propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol, etc.

As the above polyamide resin, nylon resin, nylon copolymer resin, and mixtures thereof can be used. As the nylon resin, polyamide-6 (nylon 6) obtained by ring-opening polymerization of lactams commonly known as ε-caprolactam and ω-dodecalactam; nylon polymers obtained from amino acids such as aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; Aliphatic, alicyclic or aromatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonahexamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexane)methane, bis(4-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperidine, and adipic acid, sebacic acid, Nylon polymers obtainable from polymerization of aliphatic, cycloaliphatic or aromatic dicarboxylic acids, such as azelaic acid, terephthalic acid, 2-chloroterephthalic acid and 2-methylterephthalic acid; copolymers or mixtures thereof can be used. Examples of nylon copolymers include copolymers of polycaprolactam (nylon 6) and polyhexamethylene sebacamide (nylon 6,10), copolymers of polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 66), and copolymers of polycaprolactam (nylon 6) and polylauryllactam (nylon 12).

The above polycarbonate resin can be manufactured by reacting diphenols with phosgene, halogen formate, carbonic ester or a combination thereof. Specific examples of the above diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also called 'bisphenol-A'), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfoxide, Bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ether, etc. can be mentioned. Among these, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or 1,1-bis(4-droxyphenyl)cyclohexane can be used preferably, and 2,2-bis(4-hydroxyphenyl)propane can be used more preferably.

The above polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. In addition, the polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like.

Examples of the linear polycarbonate resin include bisphenol-A polycarbonate resins. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride or trimellitic acid with diphenols and carbonates. The polyfunctional aromatic compound may be included in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those prepared by reacting a difunctional carboxylic acid with diphenols and carbonates. In this case, the carbonate may be a diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like.

As the above cycloolefin polymer, there can be mentioned a norbornene polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and a hydride thereof. Specific examples thereof include APPEL (ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals, Inc.), ATON (norbornene polymer manufactured by JSR), and ZEONOR (norbornene polymer manufactured by Nippon Zeon Corporation).

The step of supplying the above composite preform to an extruder and melt-extruding it may further include a step of supplying a second additive selected at least one from the group consisting of a flame retardant, an impact modifier, a flame retardant, a flame retardant auxiliary agent, a lubricant, a plasticizer, a heat stabilizer, an anti-dripping agent, an antioxidant, a compatibilizer, a light stabilizer, a pigment, a dye, an inorganic additive, and an anti-drip agent.

The present invention provides a thermoplastic resin composite manufactured by the method for manufacturing a thermoplastic resin composite described above.

In addition, the present invention provides a molded article comprising the thermoplastic resin composite described above. Through the processing method of the thermoplastic resin composite described above, a composite in the form of a pellet or film can be manufactured.

The molded product obtained through the above method not only has no decrease in mechanical strength, but also has no problems in the production process and secondary processability, and a thermoplastic resin composite having sufficient physical properties can be obtained even if it contains a small amount of additives.

The above composite material can be molded by any method, such as injection molding, blow molding, press molding, or spinning, which is commonly known, and can be processed into various molded products and used. As molded products, they can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, etc.

As a method for manufacturing the above film, a known melt film-forming method can be employed, and examples thereof include a method in which raw materials are melted in a single-screw or twin-screw extruder, then extruded from a film die and cooled on a cooling drum to create an unstretched film, or a single-screw stretching method or twin-screw stretching method in which the film thus created is appropriately stretched lengthwise and crosswise by a roller-type longitudinal stretching device and a transverse stretching device called a tenter.

The above fibers can be used as various types of fibers such as undrawn yarn, drawn yarn, and superdrawn yarn, and as a method for manufacturing a fiber using the thermoplastic resin composite, a known melt spinning method can be applied. For example, a method can be adopted in which chips made of a resin composite preform as a raw material are supplied to a single-screw or twin-screw extruder while being kneaded, and then the fibers are extruded from a spinneret through a polymer flow line switcher, a filter layer, or the like installed at the tip of the extruder, and then cooling, drawing, and heat setting are performed.

The above-mentioned various molded products can be used for various purposes such as automobile parts, electrical and electronic parts, and construction materials. Specific applications include air flow meters, air pumps, automatic temperature control unit housings, engine mounts, ignition bobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotation sensors, acceleration sensors, distributor caps, coil bases, actuator cases for ABS, tops and bottoms of radiator tanks, cooling fans, fan shrouds, engine covers, cylinder head covers, oil caps, oil pans, oil filters, fuel caps, fuel strainers, distributor caps, vapor canister housings, air cleaner housings, timing belt covers, brake booster parts, automotive under-hood parts such as various cases, various tubes, various tanks, various hoses, various clips, various valves, and various pipes, torque control levers, seat belt parts, register blades, washer levers, wind regulator handles, knobs for wind regulator handles, passing light levers, Examples include automotive interior parts such as sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grille apron cover frames, lamp reflectors, lamp bezels, door handles, automotive exterior parts such as wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, notebook PC housings and internal parts, LED display housings and internal parts, printer housings and internal parts, portable terminal housings and internal parts such as mobile phones, mobile PCs, and portable mobiles, housings and internal parts of recording media (CD, DVD, PD, FDD, etc.) drives, housings and internal parts of copiers, housings and internal parts of facsimile machines, and electrical and electronic components such as parabolic antennas.

Also, examples include VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, video cameras, projectors and other imaging equipment parts, optical recording media substrates such as laser discs (registered trademarks), compact discs (CDs), CD-ROMs, CD-Rs, CD-RWs, DVD-ROMs, DVD-Rs, DVD-RWs, DVD-RAMs and Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts and word processor parts, and household and office electrical appliance parts.

In addition, it is particularly useful as electrical and electronic components such as housings or internal parts of electronic musical instruments, home game consoles, portable game consoles, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, condensers, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, transformer members, coil bobbins, or various automotive connectors such as wire harness connectors, SMJ connectors, PCB connectors, and door gremet connectors.

In addition, the thermoplastic resin composite and the molded article of the present invention can be recycled. For example, the thermoplastic resin composite obtained by crushing the composite and the molded article, preferably making them into powder, and then mixing additives as needed can be used in the same way as the composite described above, and can also be made into a molded article.

The present application is specifically described through the following examples, but the scope of the present invention is not limited by the following examples.

<Examples and Comparative Examples>

Comparative Example 1

A 20 ㎛ thick polypropylene resin film (Polypropylene (PP): manufactured by LG Chemical) without an additive layer was prepared. The laminate was pulverized and mixed, and the mixture was melted to produce a melt. Thereafter, the film was extruded and formed into strands. At this time, the equipment used was a Twin Screw Extruder (manufactured by Bautek, BA11 extruder), and the process conditions were a temperature of 240°C and a rotation speed of 25 rpm.

The extruded extrudate was pelletized through a pelletizer to manufacture a resin composite.

Comparative Example 2

A composite preform was manufactured by depositing an indium (In) additive layer with a thickness of 20 nm on a 20 μm thick polypropylene resin film (Polypropylene (PP): manufactured by LG Chemical). At this time, the additive layer was formed using a sputtering method (driving power 1 kW, process pressure 2 mTorr, sputtering gas flow rate 50 sccm).

The above laminate was crushed and mixed, and the mixture was melted to produce a melt. Thereafter, the melt was extruded and formed into a strand. At this time, the equipment used was a Twin Screw Extruder (manufacturer: Bautek BA11 extruder), and the process conditions were a temperature of 240°C and a rotation speed of 25 rpm.

The extruded extrudate was pelletized through a pelletizer to manufacture a resin composite.

Comparative Example 3

A resin composite was manufactured using the same method as in Comparative Example 2, except that aluminum (Al) was deposited to a thickness of 100 nm instead of indium (In).

Example 1

A first composite preform was manufactured by depositing an indium (In) additive layer to a thickness of 20 nm on a 20 μm thick polypropylene resin film (Polypropylene (PP): manufactured by LG Chemical), and a second composite preform was manufactured by depositing aluminum (Al) to a thickness of 100 nm on another 20 μm thick polypropylene resin film.

The first and second composite preforms were pulverized and mixed, and the mixture was melted to produce a melt. Thereafter, the melt was extruded and formed into a strand. At this time, the equipment used was a Twin Screw Extruder (manufacturer: Bautek BA11 extruder), and the process conditions were a temperature of 240°C and a rotation speed of 25 rpm. At this time, the weight ratio of the first composite preform and the second composite preform was 1:1.

The extruded extrudate was pelletized through a pelletizer to manufacture a resin composite.

<Method of Measuring Physical Properties>

1. Complex viscosity measurement

The above-mentioned manufactured resin composite was melted at a temperature of 200°C using a hot press melter. As the resin film melts, the additive is dispersed on the melted resin film.

Thereafter, in order to analyze the rheological behavior of the molten composite resin, the composite viscosity was measured in the range of 0.1 to 1,000 rad/s and at 220°C using an Ares G2 Rheometer, and the results are shown in Fig. 1.

From these results, it was confirmed that the viscosity increased in Comparative Examples 2, 3, and Example 1, which included the additive layer, compared to Comparative Example 1, which did not include the additive layer. In addition, it was confirmed that the composite viscosity of Example 1 was located between Comparative Examples 2 and 3.

This indicates that the viscosity has increased due to the influence of additive particles dispersed in the molten thermoplastic resin. Even if the particles have the same shape, the increase in composite viscosity can be high.

2. Measurement of renal viscosity

A graph showing the change in elongational viscosity (unit: Pa*s) over time using an elongational viscosity device attached to the Ares G2 Rheometer is shown in Fig. 2. At Frequency 4 or higher, which is a stable measurement range, the elongational viscosity is shown in the order of Comparative Example 3, Example 1, Comparative Example 2, and Comparative Example 4. When comparing the elongational viscosity, which is indicated as resistance to stretching, the elongational viscosities of Comparative Examples 2, 3, and Example 1, which include the additive layer, are higher than those of Comparative Example 1, where the additive layer is not formed. This increase in elongational viscosity indicates that the bonding between the substrate and the additive layer is strengthened within the composite material. In addition, it was confirmed that the composite viscosity of Example 1 was located in the middle of Comparative Example 2 and Comparative Example 3.

3. Observation of the appearance

As shown in Fig. 3, the appearance of the resin composites manufactured in Comparative Examples 1 to 3 and Example 1 was measured using a digital camera.

It was confirmed that the color of Example 1 containing both indium and aluminum was different from Comparative Examples 2 and 3 containing only indium or aluminum. This confirms that the colors of indium and aluminum were not simply displayed, but rather that the colors of indium and aluminum were mixed.

Claims (12)

A method for manufacturing a thermoplastic resin composite containing an additive,
A step of manufacturing two or more composite preforms as laminates by forming additive layers each containing an additive on a thermoplastic resin film; and
A method for manufacturing a thermoplastic resin composite, comprising the step of supplying two or more composite preforms to an extruder and melt-extruding them,
The step of manufacturing the above composite preform comprises the step of manufacturing a first composite preform and a second composite preform, wherein the first composite preform and the second composite preform comprise different additive layers,
A method for producing a thermoplastic resin composite, wherein the ratio of the thickness of the thermoplastic resin film to the additive layer is 10,000 to 50:1. A method for manufacturing a thermoplastic resin composite according to claim 1, wherein the additive layer is formed by deposition or coating. A method for producing a thermoplastic resin composite according to claim 1, further comprising a step of pulverizing the composite preform before the step of melt-extruding the composite preform. A method for manufacturing a thermoplastic resin composite according to claim 1, wherein the step of melt-extruding the composite preform uses an extruder, and the rotation speed of a screw provided in the extruder is 50% or less of the maximum speed of the equipment. A method for manufacturing a thermoplastic resin composite according to claim 1, wherein the step of melt-extruding the composite preform uses an extruder, and the peripheral speed of a screw provided in the extruder is 10 m/sec or less. A method for producing a thermoplastic resin composite according to claim 1, wherein the step of melt-extruding the composite preform uses an extruder, the extruder includes a plurality of heating zones, and the plurality of heating zones have a temperature gradient. A method for producing a thermoplastic resin composite according to claim 1, wherein the step of melt-extruding the composite preform uses an extruder, and the extruder is a single-screw extruder or a twin-screw extruder. A method for manufacturing a thermoplastic resin composite according to claim 1, wherein the additive is a material selected from the group consisting of a metal of indium (In), titanium (Ti), tin (Sn), silicon (Si), germanium (Ge), aluminum (Al), copper (Cu), nickel (Ni), vanadium (V), tungsten (W), tantalum (Ta), molybdenum (Mo), neodymium (Nb), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) or silver (Ag), an oxide of the metal, a nitride of the metal, an oxynitride of the metal and carbon nanotubes. A method for manufacturing a thermoplastic resin composite according to claim 1, wherein the weight ratio of the additive layer to the entire composite preform is 30 wt% or less. A method for producing a thermoplastic resin composite according to claim 1, wherein the step of melt-extruding the composite preform further includes a step of supplying a second additive selected from the group consisting of a flame retardant, an impact modifier, a flame retardant, a flame retardant auxiliary agent, a lubricant, a plasticizer, a heat stabilizer, an anti-drip agent, an antioxidant, a compatibilizer, a light stabilizer, a pigment, a dye, an inorganic additive, and an anti-drip agent. A thermoplastic resin composite manufactured by a method for manufacturing a thermoplastic resin composite according to any one of claims 1 to 10. A molded article comprising a thermoplastic resin composite according to claim 11.