KR20140087910A - Long glassfiber reinforced resin composite and molded products including the same - Google Patents
Long glassfiber reinforced resin composite and molded products including the same Download PDFInfo
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- KR20140087910A KR20140087910A KR1020120158710A KR20120158710A KR20140087910A KR 20140087910 A KR20140087910 A KR 20140087910A KR 1020120158710 A KR1020120158710 A KR 1020120158710A KR 20120158710 A KR20120158710 A KR 20120158710A KR 20140087910 A KR20140087910 A KR 20140087910A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
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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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
Styrene-acrylonitrile (ASA) resin matrix, and 10 to 90 parts by weight of long glass fibers per 100 parts by weight of the ASA resin matrix .
Description
Long fiber reinforced resin composite and a molded article comprising the same.
BACKGROUND ART [0002] In recent years, a number of researches have been conducted to replace a metallic exterior material used in a vehicle with a lightweight plastic material in accordance with the tendency of a vehicle to be lightened. Plastics for vehicle exterior materials that replace metals are often subjected to post-treatments such as coating processes in order to improve weatherability and appearance characteristics. Such post-treatment processes lead to an increase in costs and may have a negative impact on the environment .
One embodiment of the present invention provides a composite material capable of producing a molded article having a high weather resistance and high appearance without a plating / coating process.
Another embodiment of the present invention provides an injection molded article produced from the composite material.
The long glass fiber reinforced resin composite provided in accordance with an embodiment of the present invention comprises an acrylate-styrene-acrylonitrile resin matrix (hereinafter referred to as ASA resin matrix) And a long glass fiber (LGF) in a weight part.
The ASA resin matrix comprises 40 to 90 parts by weight of a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, and a copolymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are grafted to an acrylate-based rubbery polymer (hereinafter referred to as a g-ASA copolymer 10 to 60 parts by weight).
In the long glass fiber reinforced resin composite, the glass fibers are arranged in parallel in the longitudinal direction of the composite (that is, the pulling direction of the glass fibers) in the composite, and the glass fibers continuous in the longitudinal direction of the resin composite The ratio may be at least 95% based on the total weight of the glass fibers.
An injection molded article provided according to another embodiment of the present invention is produced from the long glass fiber reinforced resin composite.
The proportion of the fiber that maintains the length in the long glass fiber reinforced resin composite among the long fibers in the injection molded product may be 10% or more.
A composite material which is lightweight compared to a metal material and excellent in mechanical strength as compared with a plastic material and capable of producing a molded article having a high weather resistance and high appearance without a plating / coating process is provided.
1 schematically shows an example of an apparatus used for manufacturing a long fiber reinforced resin composite according to an embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the appended claims.
In this specification, unless otherwise stated, the phrase "the glass fibers are arranged in parallel" includes the case where they are arranged substantially parallel, and the term "glass fibers are continuous in the longitudinal direction of the resin composite material" Quot; is meant that the glass fibers extend substantially over the entire length of the resin composite material, such as at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% of the length of the resin composite material do.
As used herein, unless otherwise defined, " copolymerization "means block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and" copolymer "means a block copolymer, random copolymer, graft copolymer or alternating copolymer .
The long glass fiber reinforced resin composite provided according to an embodiment of the present invention comprises an acrylate-styrene-acrylonitrile resin matrix (hereinafter, also referred to as an ASA resin matrix) and 10 to 90 wt% Includes long lasting fibers.
(A) ASA Resin matrix
The long glass fiber reinforced resin composite includes an acrylate-styrene-acrylonitrile (ASA) resin matrix, wherein the ASA resin matrix is a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer (hereinafter also referred to as a SAN copolymer) ) And 10 to 60 parts by weight of a copolymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are grafted to an acrylate-based rubbery polymer (hereinafter also referred to as a g-ASA copolymer). When the ASA resin matrix has such a composition, not only excellent weatherability can be exhibited, but also the mechanical properties of the resin composite produced are further improved.
Throughout this specification, in relation to the composition of the ASA resin matrix, it is understood that "can be made" or "done" substantially affects the weatherability and mechanical properties of the ASA resin matrix and the long glass fiber- But may include other additives which are insufficient, for example, various additives.
The SAN-based copolymer is prepared by copolymerizing 60 to 90 parts by weight of an aromatic vinyl monomer and 10 to 40 parts by weight of a vinyl cyanide monomer. As the aromatic vinyl monomer, styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene, or a combination thereof may be used. Specific examples of the alkyl-substituted styrene include o -ethylstyrene, m -ethylstyrene, p -ethylstyrene, and -methylstyrene. The vinyl cyanide monomer may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or a combination thereof.
The SAN-based copolymer can be produced by copolymerizing the aromatic vinyl monomer and the vinyl cyanide monomer by a conventional radical polymerization method, and the production method thereof is not particularly limited. Commercially available products such as AP-H of Cheil Industries, 82TR of LG Corp., and Luran of BASF may be used as the SAN-based copolymer.
The g-ASA graft copolymer is a copolymer of a core-shell structure prepared by graft-polymerizing a styrene-based monomer and a vinyl cyanide-based monomer to an acrylate-based rubbery polymer. There is no particular limitation on the kind of g-ASA copolymer that can be used, and the g-ASA copolymer can be appropriately selected and used if necessary. For example, as the g-ASA copolymer, commercially available products such as CHAT of Cheil Industries Co., Ltd. and A600N of UMG Co. can be used.
As a non-limiting example, the g-ASA copolymer may be prepared according to any method known to those of ordinary skill in the art. For example, a method of producing an acrylate-based rubbery polymer and graft copolymerizing styrene and acrylonitrile with one or more cores of the acrylate-based rubbery polymer through, for example, emulsion polymerization to form one or more shell layers . ≪ / RTI >
The acrylate-based rubbery polymer may be prepared by using an acrylate-based monomer as a main monomer. The acrylate monomer may be at least one selected from the group consisting of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and hexyl acrylate, but is not limited thereto. The acrylate-based monomer may be copolymerized with one or more other radically polymerizable monomers. When copolymerized, the amount of the at least one radically polymerizable other monomer may be 5 to 30% by weight, more preferably 10 to 20% by weight, based on the total weight of the acrylate rubber.
Specific examples of the aromatic vinyl monomer and the vinyl cyanide monomer contained in the shell layer are as described above.
In the total g-ASA copolymer, the amount of the acrylate-based rubbery polymer is 30 to 70% by weight, specifically 40 to 60% by weight, and the amount of the aromatic vinyl monomer and the vinyl cyanide monomer to be grafted is 30 To 70% by weight, and more specifically, from 40 to 60% by weight. In the shell layer made of the aromatic vinyl monomer and the vinyl cyanide monomer, the content of the aromatic vinyl monomer is not particularly limited. Based on the total weight of the shell layer, is 50 to 80% by weight, specifically 60 to 70% by weight based on the total weight of the shell layer, and the cyanide vinyl monomer is 20 to 50% by weight, 40% by weight.
The ASA resin matrix may have a melt flow index, measured based on ASTM 1238, of 5 to 20 g / 10 min.
The ASA resin matrix may further include at least one additive required to improve injection moldability and balance among properties, or depending on the end use of the resin composition. Specifically, examples of the additives include flame retardants, surfactants, nucleating agents, coupling agents. Lubricants, antistatic agents, pigments, dyes, flame retardants, and the like may be used alone or in combination of two or more kinds thereof. These additives may be used alone or in combination of two or more.
The amount of the additives is not particularly limited and can be appropriately adjusted according to the purpose of use. For example, in an amount of 0 to 10 parts by weight, specifically 0.1 to 10 parts by weight, based on 100 parts by weight of the ASA resin matrix.
The ASA resin is impregnated with long-glass fibers to be described later through a pultrusion process in a molten state, and is made into a long glass fiber reinforced composite.
ASA resin has excellent weather resistance, chemical resistance and thermal stability and is used for housing of electric and electronic parts intended for outdoor use, building materials, sporting goods and the like. Unlike other resins which require plating or coating process to enhance the weatherability and appearance of the product, ASA resin has excellent weatherability and can be applied to various products used outdoors. It is possible to provide an excellent appearance. However, the ASA resin has a problem that the mechanical properties such as the flexural modulus and the impact strength are extremely low for use as a metal replacement plastic sheathing for lightening the vehicle.
The long glass fiber reinforced resin composite comprising the ASA resin matrix and the long glass fibers according to an embodiment of the present invention is suitable for use as an exterior material of a vehicle because it has excellent mechanical properties while ensuring excellent weather resistance.
(B) long glass fiber
The long glass fiber included in the long glass fiber reinforced composite is a long glass fiber produced from a fiberizable glass. Specific examples of usable long fiber include fluorine and / or fluorine as well as "E-glass "," A-glass ", & Or a fiberizable glass composition commonly used as an E-glass derivative without boron. Most glass fibers used as reinforcing materials can be glass fibers formed from E-glass, and glass filaments can be prepared from the glass composition by an appropriate method.
The long fibers may have a nominal filament diameter of about 4 to about 35 micrometers, specifically about 9 to about 25 micrometers.
The long glass fiber may be surface-treated with a binder containing a coupling agent. As the coupling agent, silane coupling agents such as aminosilane, epoxy silane, amide silane, azidosilane and acryl silane, titanate coupling agents and mixtures thereof can be used.
The long glass fiber reinforced resin composite according to an embodiment of the present invention is manufactured by a draw-forming method in which a matrix resin composition is impregnated into a fiber while pulling long fiber. By way of non-limiting example, as shown in Fig. 1, continuous fibers are pulled from a glass fiber creel while passing through a fiber impregnation mechanism provided inside a melt pool, while ASA to form an ASA resin matrix The resin composition is melted in the melt pool and supplied to the fiber impregnation mechanism, the continuous fiber is impregnated with the ASA resin composition, the melted impregnated material is optionally heated, cooled, and then pelletized, Cut perpendicularly to the drawing direction of the glass fiber to obtain a long glass fiber reinforced resin composite. In addition to this method, a method in which a bundle of long fibers is passed through a resin impregnation bath to impregnate the bundle of long fibers, a method in which a resin powder is attached to long fibers, and then the resin is melted and impregnated can be used.
The long glass fiber reinforced resin composite obtained may contain about 10 to 90 parts by weight, specifically about 40 to 80 parts by weight, more specifically 40 to 70 parts by weight of long glass fibers per 100 parts by weight of the ASA resin matrix . When it is included in the above range, it is possible to provide a fiber-reinforced resin composite capable of producing a molded article exhibiting excellent weather resistance and remarkably improved mechanical properties. In the case of a resin composite prepared by supplying short-fiber type glass fibers to a fiber composition in a side feeding manner, incorporation of 40 parts by weight or more of glass fibers has a problem of causing remarkable deterioration in impact property and workability . However, when the long glass fiber composite is produced by using the drawing-forming method, the content of the long glass fiber in the fiber composite can be increased, and the mechanical properties of the molded product produced from the fiberglass composite can be greatly improved.
In the long glass fiber resin composite, glass fibers are arranged parallel to the length direction of the resin composite, and at least about 95%, specifically about 96% or more, about 97% or more, about 98% Or more and about 99% or more of the resin composite may be present continuously in the longitudinal direction of the resin composite. The length of the glass fiber can be adjusted as needed, and is not particularly limited. For example, the average length of the glass fibers in the resin composite may be 5 to 20 mm, specifically 8 to 15 mm.
According to another embodiment of the present invention, a molded article produced from the long glass fiber composite is provided. The molded article can be produced from the long glass fiber resin composite by any of various methods known in the art, such as injection molding.
The proportion of the fiber in the injection molded article that maintains the original length in the resin composite among the long fibers may be 5% or more, specifically 10% or more. In the case of the long glass fiber resin composite, it is easy to control the length of the glass fiber in the manufacturing process. When the composite thus produced, for example, pellets, is used as a raw material for a molding process such as injection molding, So that the aspect ratio of the glass fiber contained in the final product is high and the surface area is small, thereby contributing to improvement of the mechanical properties of the produced molded product.
The injection-molded product is excellent in weather resistance without being subjected to a coating step, can exhibit a high-grade appearance, and is excellent in mechanical properties such as bending strength, so that it can be effectively used as a substitute for a metal material used as a vehicle exterior material.
Example
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples and comparative examples are for illustrative purposes only and are not intended to limit the present invention.
[Ingredients Used]
(a) SAN (styrene-acrylonitrile) copolymer: manufactured by Cheil Industries, Ltd., AP-H
(b1) g-ASA: acrylate-styrene-acrylonitrile graft copolymer, trade name: CHT, manufactured by Cheil Industries,
(c) g-ABS: Acrylonitrile-butadiene-styrene graft copolymer, manufactured by Cheil Industries, Ltd., CHAK
(d) long fiber: Owens corning SE1200, glass fiber diameter = 16 占 퐉
(e) Short glass fiber: Nittobo CSF3PE-293, glass fiber diameter = 13 占 퐉, glass fiber length = 3 mm
[Production of glass fiber composite material]
Example One
Using a device as shown in Fig. 1, glass fibers were pulled from a fiber creel through a melt pool, and through a puller and a pelletizer, A mixture of (a) SAN copolymer and (b) g-ASA copolymer having the composition as described in 1 is supplied to and melt in the melt pool so that the glass fiber passing through the melt pool is impregnated with the resin melt Respectively. (a) a SAN copolymer and (b) a g-ASA copolymer as a strand, cutting the fiber bundle by cooling, cutting the bundle, cutting the fiber bundle into a pallet having a glass fiber content of 30% Lt; / RTI > fiber reinforced composite.
Example 2
A long glass fiber reinforced composite (glass fiber content: 40% by weight) was prepared in the same manner as in Example 1, except that the amounts of the ASA matrix component and the long fiber glass component used were changed as shown in Table 1 below.
Comparative Example 1 to 5
A glass fiber reinforced composite in the form of a resin pallet or pallet was produced in the same manner as in Example 1, except that the amounts of the ASA matrix component and the long glass fibers used were changed as shown in Table 1 below.
[% By weight]
[% By weight]
[Property test]
Specimen manufacturing
The pellets prepared in Examples 1 and 2 and Comparative Examples 1 to 5 were dried at 80 degrees Celsius for 4 hours, and then, specimens were prepared using an injection machine (model: JSW J75 II). The prepared specimens were aged for 1 hour and then measured for Izod impact strength, flexural strength, flexural modulus and weather resistance (color difference: dE) by the following method, and the results are shown in Table 2 .
(1) Izod impact strength (thickness 1/8 "): Measured according to ASTM D-256 standard (unit: kgf · cm / cm)
(2) Flexural strength: Measured according to ASTM D790 standard. (Unit: MPa)
(3) Flexural modulus: Measured according to ASTM D790 standard. (Unit: MPa)
(4) Wheather-O-meter (dE): Measured using the colorimeter Minolta 3200D according to SAE J 1960 standard.
The specimens prepared from the pallets of Example 1 and Example 2, which were prepared to have the above-mentioned long fiber glass content, were found to have not only a remarkably high flexural strength, flexural modulus and impact strength but also excellent weatherability.
On the other hand, Comparative Example 1 in which glass fiber was not used, Comparative Example 2 and Comparative Example 3 using short glass fibers were excellent in weatherability but mechanical properties such as flexural strength were not significantly better than Examples 1 and 2, The long glass fiber reinforced resin composites including the matrix (Comparative Example 4 and Comparative Example 5) were found not only to have poor weather resistance but also to have lower flexural strength and flexural modulus than Examples 1 and 2.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.
Claims (5)
Wherein the ASA resin matrix comprises 40 to 90 parts by weight of a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer and 10 to 60 parts by weight of a copolymer obtained by grafting an aromatic vinyl monomer and a vinyl cyanide monomer to an acrylate rubber- Resin complex.
In the long glass fiber reinforced resin composite, the glass fibers are arranged parallel to the longitudinal direction of the composite in the composite, and the ratio of the continuous glass fibers in the longitudinal direction of the composite resin is 95 % Of long fiber reinforced resin composite.
Wherein the proportion of the fibers that maintain the length in the long glass fiber reinforced resin composite among the long fibers present in the injection molded article is 5% or more.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020120158710A KR20140087910A (en) | 2012-12-31 | 2012-12-31 | Long glassfiber reinforced resin composite and molded products including the same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020120158710A KR20140087910A (en) | 2012-12-31 | 2012-12-31 | Long glassfiber reinforced resin composite and molded products including the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273308A (en) * | 2015-10-21 | 2016-01-27 | 惠州市昌亿科技股份有限公司 | Halogen-free flame retardant long glass fiber and PP (polypropylene) composite material and preparation method thereof |
| CN105273316A (en) * | 2015-10-21 | 2016-01-27 | 惠州市昌亿科技股份有限公司 | Long glass fibers with few revealed slight glass fibers and PP (polypropylene) composite material containing long glass fibers and having high impact resistance |
-
2012
- 2012-12-31 KR KR1020120158710A patent/KR20140087910A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273308A (en) * | 2015-10-21 | 2016-01-27 | 惠州市昌亿科技股份有限公司 | Halogen-free flame retardant long glass fiber and PP (polypropylene) composite material and preparation method thereof |
| CN105273316A (en) * | 2015-10-21 | 2016-01-27 | 惠州市昌亿科技股份有限公司 | Long glass fibers with few revealed slight glass fibers and PP (polypropylene) composite material containing long glass fibers and having high impact resistance |
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