KR20170069736A - Thermoplastic composite with low porosity and its manufacturing method - Google Patents
Thermoplastic composite with low porosity and its manufacturing method Download PDFInfo
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- KR20170069736A KR20170069736A KR1020150177321A KR20150177321A KR20170069736A KR 20170069736 A KR20170069736 A KR 20170069736A KR 1020150177321 A KR1020150177321 A KR 1020150177321A KR 20150177321 A KR20150177321 A KR 20150177321A KR 20170069736 A KR20170069736 A KR 20170069736A
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- resin
- epoxy resin
- thermoplastic
- composite material
- fiber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
Abstract
More particularly, the present invention relates to a thermoplastic composite material prepared by applying thermoplastic resin particles and an epoxy resin on a fiber-reinforced layer and impregnating and polymerizing the same by heat treatment, and a method for producing the same will be. The thermoplastic composite material according to the present invention is not a thermoplastic polymer having a high melt viscosity but is firstly impregnated into a fiber reinforced layer by melting monomers having a low viscosity, and then polymerized to form a highly processable material. The fiber reinforced layer and the thermosetting and thermoplastic polymer A good integrated thermoplastic composite material can be obtained.
Description
More particularly, the present invention relates to a thermoplastic composite material prepared by applying thermoplastic resin particles and an epoxy resin onto a fiber-reinforced layer and impregnating and polymerizing the same by heat treatment, and a method for producing the same will be.
Recently, research and development for replacing metal materials with plastic composite materials have been progressing steadily.
Metal materials are excellent materials in terms of heat resistance and mechanical strength, and they are used in many fields such as automobile, aircraft, and construction. However, the metal material has a disadvantage that it is heavy because it has a high specific gravity. On the other hand, since plastic has a low specific gravity, it is advantageous to produce products that are several times lighter than metal in the case of making same-sized products, and efforts to utilize them as substitutes for metal materials are continuing. In particular, due to high oil prices, the automobile and aircraft industries are putting great effort into these efforts.
Plastics known to date are very difficult to achieve metal-like performance. Thus, attempts to replace metals by combining plastics with other materials to form composite materials have continued. The most widely used composite materials are thermosetting plastic composites. The thermosetting plastic composite material is produced by dispersing carbon fiber or glass fiber in a thermosetting resin such as an epoxy resin and partially curing the prepreg to prepare a prepreg. After the prepreg is processed into a desired shape, the thermosetting is completed do. The advantage of such a thermosetting plastic composite is that it has excellent heat resistance and mechanical properties once cured. On the other hand, since it is manufactured using a sheet-form prepreg, there is a limit to the shape of the product, and since the product is subjected to a heat hardening process, productivity is low and the product is not recycled.
Other forms of polymer composites are thermoplastic polymer composites. Thermoplastic polymer composites are excellent in melt processability, which enables them to process various types of products and can be recycled.
Thermoplastic polymer composites are made by mixing short fibers made of glass fiber or carbon fiber with a thermoplastic polymer capable of injection or extrusion. The thermoplastic polymer composite material has a high melt viscosity because it uses a polymer having a high molecular weight. Therefore, when the short fibers are compounded, the melt viscosity is further increased and the workability is lowered. Therefore, the content of the short fibers can not be increased, so that there is a limitation in the mechanical properties and the shortened fibers are oriented randomly. But it can not be used for products that require it.
On the other hand, when a reinforcing material and a thermoplastic polymer on a fabric such as a fiber fabric, which can greatly improve mechanical properties, are combined with each other, the thermoplastic polymer has poor processability because it is difficult to impregnate the reinforcing material on the fabric due to high melt viscosity.
It is an object of the present invention to solve the above-mentioned problems, and it is an object of the present invention to solve the above-mentioned problems, and to provide a fiber reinforced layer capable of enhancing mechanical properties by impregnating a resin mixture of thermosetting and thermoplastic resin particles into a fiber reinforced layer, And to provide a method for producing a good thermoplastic composite material.
In a preferred embodiment of the present invention, there is provided a method for producing a thermoplastic resin composition, comprising the steps of: applying a thermoplastic resin particle and an epoxy resin to a fiber reinforcing layer; And thermally treating the applied fiber-reinforced layer at a temperature of 220 to 300 ° C for 2 minutes to 1 hour to prepare a thermoplastic composite material by impregnating and polymerizing resin particles and an epoxy resin, wherein the epoxy resin is bisphenol S type Epoxy resin and novolak resin, and the porosity of the thermoplastic composite material is 1% or less. The present invention also provides a method for producing the thermoplastic composite material. When the heat treatment temperature is less than 220 ° C or the heat treatment temperature is less than 2 minutes, the resin is not melted and is present in a solid powder state, which causes property deterioration. When the heat treatment is performed at 300 ° C or more or for 1 hour or more, There arises a problem that the physical properties are deteriorated by deterioration. Further, when the prepared composite material has a porosity of more than 1%, there is a problem that the strength is lowered and molding property is difficult.
In another preferred embodiment of the present invention, the thermoplastic resin particles have a diameter of 30 to 300 microns and a molecular weight of 10,000 to 90,000. If the diameter is less than 30 μm, the handling property is not good. If the diameter is more than 300 μm, the workability impregnation property at the time of production is insufficient. If the molecular weight is less than 10,000, the physical properties are lowered. do.
In still another preferred embodiment of the present invention, the weight ratio of the thermoplastic resin particles to the epoxy resin is 90:10 to 70:30, wherein the bisphenol S type and the novolac resin are used together, And the weight ratio is 85:15 to 70:30. When the weight ratio is less than the above range, the melt viscosity is not sufficiently lowered, resulting in poor compatibility. Thus, the fiber reinforcing layer may not be sufficiently impregnated and peeling problems may occur between the fiber reinforcing layers. Is significantly reduced.
Another preferred embodiment of the present invention provides a thermoplastic composite material formed according to the above-described production method.
The thermoplastic composite material according to the present invention is not a thermoplastic polymer having a high melt viscosity but is firstly impregnated into a fiber reinforced layer by melting monomers having a low viscosity, and then polymerized to form a highly processable material. The fiber reinforced layer and the thermosetting and thermoplastic polymer A good integrated thermoplastic composite material can be obtained.
Hereinafter, the present invention will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.
A method for producing the thermoplastic composite material according to the present invention will be described below.
First, the thermoplastic resin particles and the epoxy resin are applied to the fiber reinforcing layer. At this time, it is possible to apply a mixture of the thermoplastic resin particles and the epoxy resin, but it is also possible to separately coat the mixture. In the case where the thermoplastic resin particles and the epoxy resin are mixed and coated, the weight ratio of the thermoplastic resin particles and the epoxy resin is preferably 90:10 to 70:30. If the weight ratio of epoxy resin is less than 10, the possibility of mechanical property deterioration and pore generation increases. If the weight ratio is more than 30, phase separation of thermoplastic resin and epoxy resin may occur and moldability may be deteriorated.
As the epoxy resin, bisphenol S type epoxy resin and novolac resin are preferably used in combination, but not limited thereto, and it is possible to include bisphenol A type epoxy resin, bisphenol F type epoxy resin and the like. When the bisphenol S type epoxy resin and the novolac resin are mixed and used, the weight ratio thereof is preferably 85:15 to 70:30. When the mixing ratio of the novolak resin is less than 15, the effect of increasing the heat resistance and rigidity by the novolac resin is insufficient. When the mixing ratio is more than 30, the impregnating property of the resin may be poor.
As the thermoplastic resin particles, cyclic butylene terephthalate, lactam and polyamide are preferable, but the present invention is not limited thereto. Other resins having a low melt viscosity can also be used. Examples thereof include polyolefins, polyarylates And polyesters. Generally, when a composite material using a polymer material is manufactured, the reinforcing material is wrapped around the polymer material. In this case, the reinforcing material should be sufficiently impregnated into the polymer material, and the higher the degree of impregnation, the better the mechanical properties. However, polymeric materials having excellent thermal and mechanical strengths, such as heat resistance and impact strength, have viscoelastic properties and are very difficult to be impregnated between the fiber reinforced layers because of their high melt viscosity, so that the production of high strength composites having a high fiber content It is a difficult situation. In order to solve the above problems, a sheet molding compound (SMC) and a bulk molding compound (BMC) have been developed and applied to some products. However, the polymer resin applied to such a method is not thermoplastic The use of the curable resin not only consumes much time and cost for production, but also disadvantageous to recycling.
The resin mixture composition as described above was used to facilitate penetration of resin into fibers, to increase the impregnation rate, and ultimately to improve the physical properties. More specifically, initially, it has a monomolecular structure in the form of a powder, but when heated, the viscosity becomes extremely low at a temperature higher than the melting point, and a resin mixture in which the penetration easily occurs between the fibers in a low viscosity state is used Respectively.
In addition, the resin mixture used may further include a polymerization catalyst, a UV stabilizer, a color control additive, and the like. As the polymerization catalyst, 0.2 to 0.6 mol% of at least one catalyst selected from the group consisting of Butyltin Chloride dihydroxide, Titanate and Distannoxane is used The catalyst is included to induce the polymerization reaction of the resin particles, and the preferable amount is 0.2 to 0.6 mol%. When the amount of the catalyst is less than 0.2 mol%, the polymerization reaction does not sufficiently take place, and there is a restriction on the formation of polybutylene terephthalate (PBT) and polyimide (nylon resin) (PBT) and polyamide (nylon resin) having a low molecular weight are formed and the stiffness is deteriorated due to the fact that a rapid polymerization reaction occurs around the catalyst before the polymerization is started, Occurs.
In the present invention, the thermoplastic resin particles preferably have a molecular weight of 10,000 to 90,000, and the particle size of the thermoplastic resin particles is preferably in a range of 30 to 300 μm. If it is less than 30 mu m, the handling property is not good. If it is more than 300 mu m, the processibility impregnation property at the time of production becomes insufficient. The particles of the above-described constitution are in the form of powder. The powder can be easily prepared by adding it to a melt of a monomer of a thermopolymerization catalyst and a thermoplastic polymer and dispersing the powder. The powder is dispersed in the fiber- It should be interpreted to include all forms of granules, pellets, etc., as long as it can be dispersed on the surface. By uniformly dispersing the powder composed of particles on the fiber reinforcing agent, the surface of the fiber reinforcing material is covered with the powder, and the volume ratio with the fiber reinforcing layer can be controlled according to the scattering thickness of the powder.
Next, the thermoplastic resin particles and the epoxy resin-coated fiber reinforcing layer are thermally treated at a temperature of 220 to 300 ° C for 2 minutes to 1 hour to impregnate and polymerize the thermoplastic resin particles and the epoxy resin to prepare a thermoplastic composite material. The heat treatment may be suitably selected, for example, at a temperature at which melting and polymerization of the monomer can be performed, for example, at 220 to 300 DEG C, and the heat treatment temperature may be adjusted stepwise as needed. In the present invention, preferably, the resin-coated fiber reinforced layer is heat-treated at a temperature of 200 to 300 ° C for 2 minutes to 1 hour, and more preferably at a temperature of 240 to 290 ° C. If the heat treatment temperature is less than 220 캜, the resin does not melt and is present in a solid powder state to cause deterioration of the physical properties. If the heat treatment temperature exceeds 300 캜, the resin deteriorates to deteriorate physical properties.
The thermoplastic composite thus produced can be manufactured into a desired type of component by a well-known thermoforming process. That is, the thermoplastic polymer composite may be heated by a heater, inserted into a mold having a desired shape, and pressurized to produce a desired part. Such a thermoforming process is a process that can not be applied to existing thermosetting polymer composites, and thus can be mass-produced.
The thermoplastic composite material produced as described above has a porosity of 1% or less. When the porosity is 1% or less, it is possible to use as a structural material which requires reliability since the internal defect of the material is very small.
The composite material of the present invention can be molded into a molded article by a conventional molding method. For the molding, they may be laminated in one direction or may be stacked as in (+ 45 ° / 0 ° / -45 ° / 90 °) 4 S so as to have pseudo-isotropy.
Since the thermoplastic composite material produced through the above process has excellent mechanical properties, thermal properties, toughness, impact resistance, and the like, the molded article formed using the composite material has characteristics that it is difficult to propagate the generated cracks. It is suitably used for material structural materials, automobiles, aircraft structural materials, and space structural materials.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.
Example 1
Prepare fiberglass as a fiber-reinforced layer. Cyclic butyleneterephthalate particles having a molecular weight of 10,000 and a diameter of 30 占 퐉 and bisphenol S type epoxy resin are prepared as thermoplastic resin particles. Here, the weight ratio of the cyclic butylene terephthalate particles to the bisphenol S type epoxy resin is 90:10, and the mixture is applied to one surface of the glass fiber. This is heat-treated at a temperature of 250 캜 for 10 minutes so that the cyclic butylene terephthalate particles and the epoxy resin are impregnated in the glass fiber to prepare a thermoplastic composite material.
Example 2
Prepare fiberglass as a fiber-reinforced layer. Polyamide particles and bisphenol S type epoxy resin having a molecular weight of 90,000 and a diameter of 300 占 퐉 are prepared as thermoplastic resin particles. Here, the weight ratio of the polyamide particles to the bisphenol S type epoxy resin is 70:30, and the mixture is applied to one surface of the glass fiber. This is heat-treated at a temperature of 240 DEG C for 10 minutes to prepare a thermoplastic composite material by infiltrating the polyamide particles and the epoxy resin into the glass fiber.
Example 3
Prepare fiberglass as a fiber-reinforced layer. Bisphenol S type epoxy resin and novolak resin were prepared from thermoplastic resin particles with cyclic butylene terephthalate particles having a molecular weight of 10,000 and a diameter of 30 占 퐉 and an epoxy resin. Here, the weight ratio of the cyclic butylene terephthalate particles to the epoxy resin is 90:10, and the weight ratio of the bisphenol S type epoxy resin and the novolak resin in the epoxy resin is 85:15. And this is applied to one side of the glass fiber. This is thermally treated at a temperature of 250 캜 for 10 minutes to prepare a thermoplastic composite material by impregnating the glass fiber with a cyclic butylene terephthalate particle, a bisphenol S type epoxy resin and a novolac resin.
Example 4
Prepare fiberglass as a fiber-reinforced layer. Bisphenol S type epoxy resin and novolak resin were prepared from thermoplastic resin particles with cyclic butylene terephthalate particles having a molecular weight of 10,000 and a diameter of 30 占 퐉 and an epoxy resin. Here, the weight ratio of the cyclic butylene terephthalate particles to the epoxy resin is 70:30, and the weight ratio of the bisphenol S type epoxy resin and the novolac resin is adjusted to 70:30 in the epoxy resin. And this is applied to one side of the glass fiber. Treated at a temperature of 290 占 폚 for 10 minutes to prepare a thermoplastic composite material by impregnating the glass fiber with a cyclic butylene terephthalate particle, a bisphenol S type epoxy resin and a novolac resin.
- Porosity measurement
Porosimeter is used to calculate the porosity.
Claims (5)
Treating the applied fiber-reinforced layer at a temperature of 220 to 300 ° C for 2 minutes to 1 hour to impregnate and polymerize resin particles and an epoxy resin to prepare a thermoplastic composite material,
Wherein the epoxy resin is one or two kinds selected from the group consisting of a bisphenol S type epoxy resin and a novolac resin, and the porosity of the thermoplastic composite material is 1% or less.
Wherein the thermoplastic resin particles have a diameter of 30 to 300 microns and a molecular weight of 10,000 to 90,000.
Wherein the thermoplastic resin particles and the epoxy resin are in a weight ratio of 90:10 to 70:30.
Wherein the epoxy resin is a mixture of a bisphenol S type epoxy resin and a novolak resin, and the weight ratio of the bisphenol S type epoxy resin and the novolac resin is 85:15 to 70:30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150177321A KR20170069736A (en) | 2015-12-11 | 2015-12-11 | Thermoplastic composite with low porosity and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150177321A KR20170069736A (en) | 2015-12-11 | 2015-12-11 | Thermoplastic composite with low porosity and its manufacturing method |
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| Publication Number | Publication Date |
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| KR20170069736A true KR20170069736A (en) | 2017-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020150177321A KR20170069736A (en) | 2015-12-11 | 2015-12-11 | Thermoplastic composite with low porosity and its manufacturing method |
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| KR (1) | KR20170069736A (en) |
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2015
- 2015-12-11 KR KR1020150177321A patent/KR20170069736A/en not_active Application Discontinuation
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