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WO2008075809A1 - Composite of nylon polymer - Google Patents

Composite of nylon polymer Download PDF

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Publication number
WO2008075809A1
WO2008075809A1 PCT/KR2006/005622 KR2006005622W WO2008075809A1 WO 2008075809 A1 WO2008075809 A1 WO 2008075809A1 KR 2006005622 W KR2006005622 W KR 2006005622W WO 2008075809 A1 WO2008075809 A1 WO 2008075809A1
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WIPO (PCT)
Prior art keywords
nylon
based resin
resin composite
weight
composite according
Prior art date
Application number
PCT/KR2006/005622
Other languages
French (fr)
Inventor
Jung Hoon Park
Young Jun Lee
Tae Wook Kim
Bum Seok Youn
Original Assignee
Cheil Industries Inc.
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Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=38736804&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2008075809(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Cheil Industries Inc. filed Critical Cheil Industries Inc.
Priority to EP06835326.7A priority Critical patent/EP2125954B1/en
Priority to JP2009542619A priority patent/JP5295974B2/en
Publication of WO2008075809A1 publication Critical patent/WO2008075809A1/en
Priority to US12/486,862 priority patent/US9796845B2/en

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08L51/04—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 rubbers
    • 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
    • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • the present invention relates to a nylon-based resin composite, and more particularly to a nylon-based resin composite with low warpage and improved impact resistance as well as high mechanical strength.
  • nylons as engineering plastics has a history of almost four decades, but there is still a growing demand for nylons .
  • nylons There are many basic types of nylon, including nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, copolymers thereof, and blends thereof.
  • Nylons have respective inherent characteristics in terms of their usefulness and can exhibit various performance characteristics. Based on these characteristics, a great demand for nylon products is currently maintained.
  • composites of nylon resins and inorganic reinforcing materials exhibit high mechanical strength and markedly improved heat resistance, and thus they are used as structural materials and interior/exterior materials for automobiles.
  • nylon resins have a high moisture absorption rate in view of their molecular structures, they exhibit dimensional instability and high warpage. Further, the addition of inorganic material to nylon resins causes low impact resistance of the resulting composites.
  • the present invention has been made to solve the foregoing problems of the prior art, and it is an object of the present invention to provide a nylon-based resin composite that has a sufficiently low moisture absorption rate to substantially prevent the occurrence of deformation and can attain both low warpage and improved impact resistance.
  • a nylon-based resin composite comprising 100 parts by weight of a base resin and 1 to 30 parts by weight of an impact modifier wherein the base resin consists of 20 to 80% by weight of a modified nylon-based thermoplastic resin containing benzene rings in the main chain and 20 to 80% by weight of a reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more.
  • the nylon-based resin composite of the present invention has a sufficiently low moisture absorption rate to substantially prevent the occurrence of deformation and can attain both low warpage and improved impact resistance.
  • the present invention provides a nylon-based resin composite comprising 100 parts by weight of a base resin and 1 to 30 parts by weight of an impact modifier wherein the base resin consists of 20 to 80% by weight of a modified nylon- based thermoplastic resin containing benzene rings in the main chain and 20 to 80% by weight of a reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more.
  • the nylon-based resin composite according to the embodiment of the present invention comprises a base resin and an impact modifier.
  • the base resin includes a modified nylon-based thermoplastic resin and a reinforcing fiber.
  • the modified nylon-based resin contains benzene rings in the main chain, as represented by Formula 1 :
  • n is from 50 to 500.
  • the modified nylon represented by Formula 1 is prepared by polycondensation of hexamethylene diamine with terephthalic acid, and is referred to simply as ⁇ nylon 6T" .
  • the modified nylon-based thermoplastic resin has an intrinsic viscosity of 0.7 to 0.9 dl/g, an average molecular weight of 10,000 to 100,000, and a moisture absorption rate of 0.1% or less.
  • the reinforcing fiber is used to enhance the low warpage and heat resistance of the nylon-based resin composite.
  • the reinforcing fiber is selected from glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, silicon carbide fibers, and mixtures thereof.
  • a glass fiber is preferably used as the reinforcing fiber.
  • the reinforcing fiber is specially designed in the form of a plate whose cross-sectional aspect ratio is 1.5 or more and length is within the range of 2 mm to 13 mm.
  • the cross-sectional aspect ratio is defined as a ratio of the longest diameter (width, ⁇ a' ) to the shortest diameter (height, ⁇ b' ) in the cross section of the reinforcing fiber, as depicted in the following drawing.
  • Reinforcing fibers have been used to increase the strength of thermoplastic resins.
  • glass fibers that have a length of 3 mm to 6 mm, a cross-sectional aspect ratio of about 1 (i.e. a circular cross section) , and a cross-sectional diameter of 10 ⁇ m to 20 ⁇ m.
  • the reinforcing fiber used in the present invention has a cross-sectional aspect ratio of 1.5 or more and preferably from 2 to 8.
  • a surface coupling agent is preferably coated on the surface of the reinforcing fiber in order to increase the binding force between the surface of the reinforcing fiber and the surface of the modified nylon-based thermoplastic resin.
  • the surface coupling agent is selected from urethane resins, epoxy resins, and mixtures thereof.
  • the reinforcing fiber used in the present invention preferably has a moisture absorption rate of 0.05% or less.
  • the base resin is defined to include the modified nylon- based thermoplastic resin and the reinforcing fiber. Taking into consideration the mechanical strength and production processing of the final nylon-based resin composite, it is preferred that the base resin consist of 20 to 80% by weight of the modified nylon-based thermoplastic resin and 20 to 80% by weight of the reinforcing fiber.
  • a reactive olefinic copolymer or a core-shell copolymer may be used as the impact modifier.
  • the reactive olefinic copolymer may be an ethylene/propylene rubber, an isoprene rubber, an ethylene/octene rubber, an ethylene-propylene-diene terpolymer (EPDM), or the like.
  • the reactive olefinic copolymer may be a graft copolymer in which 0.1 to 5% by weight of one or more reactive functional groups selected from maleic anhydride, glycidyl methacrylate and oxazoline are grafted onto an olefinic copolymer.
  • the grafting of the reactive functional group onto the olefinic copolymer can be readily carried out by those skilled in the art to which the present invention pertains.
  • the core-shell copolymer is prepared by polymerizing at least one monomer selected from monomers of diene rubbers, acrylate rubbers and silicone rubbers to prepare a rubbery polymer, and grafting the rubbery polymer with at least one monomer selected from the group consisting of styrene, ⁇ - methylstyrene, halogenated styrenes, alkylated styrenes, acrylonitrile, methacrylonitrile, Ci-Ce alkyl methacrylates, Ci-Cs alkyl acrylates, maleic anhydride, N- (C 1 -C 4 ) alkyl- substituted maleimide and N-phenyl-substituted maleimide as graftable unsaturated compounds.
  • the content of the rubber in the core-shell copolymer is preferably from 30 to 90 parts by weight .
  • diene rubbers include butadiene rubbers, acrylic rubbers, ethylene/propylene rubbers, styrene/butadiene rubbers, acrylonitrile/butadiene rubbers, isoprene rubbers, and ethylene-propylene-diene terpolymers (EPDM) .
  • Suitable acrylate monomers of acrylate rubbers include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate.
  • Curing agents may be used for the polymerization of the acrylate monomers. Examples of such curing agents include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, allyl methacrylate, and triallyl cyanurate.
  • the silicone rubbers may be synthesized from cyclosiloxanes .
  • cyclosiloxanes there may be exemplified hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane .
  • At least one curing agent may be used for the preparation of the silicone rubbers.
  • curing agents include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, and tetraethoxysilane.
  • the Ci-C 8 alkyl methacrylates and the Ci-Cs alkyl acrylates are esters of methacrylic and acrylic acid, respectively, and are prepared from monohydric alcohols having one to eight carbon atoms. Specific examples of these esters include methyl methacrylate, ethyl methacrylate, and propyl methacrylate . Of these, most preferred is methyl methacrylate.
  • the preparation of the core-shell copolymer can be readily carried out by those skilled in the art to which the present invention pertains .
  • the impact modifier is preferably used in an amount of 1 to 30 parts by weight and more preferably 2 to 10 parts by weight, based on 100 parts by weight of the base resin.
  • the nylon-based resin composite of the present invention may further comprise at least one additive selected from antioxidants, heat stabilizers, light stabilizers, flow enhancers, lubricants, antibacterial agents, release agents, nucleating agents and other additives so long as the additive does not impair the basic physical properties of the nylon- based resin composite.
  • the additive may be added in an amount of 30 parts by weight or less, based on 100 parts by weight of the base resin.
  • the resin composition of the present invention may be prepared by any known process.
  • the resin composition of the present invention can be prepared by mixing the essential components with at least one optional additive, melt-extruding the mixture within an extruder, and pelletizing the molten mixture .
  • the resin composition of the present invention may be molded into a variety of products.
  • the resin composition of the present invention is suitable for the manufacture of interior/exterior materials for automobiles, highly heat- resistant materials for electronic components and exterior materials for electrical and electronic products, including computers, electric home appliances and cell phones.
  • the nylon-based resin composite according to the embodiment of the present invention will be explained with reference to the following specific examples and comparative examples. These examples are provided to illustrate that the nylon-based resin composite of the present invention exhibits high flexural strength, high flexural modulus, high impact strength and low warpage. Disclosures that are not included herein will be readily recognized and appreciated by those skilled in the art, and thus their description is omitted.
  • (A) Modified nylon-based resin A highly heat-resistant modified nylon (polyphthalamide: HTN-501, DuPont) containing benzene rings in the main chain was used.
  • Nylon-based resin composites having the compositions indicated in Table 1 were prepared.
  • the flexural strength of the nylon-based resin composites was measured in accordance with ASTM D-790 and the obtained values were expressed in kgf/cm 2 .
  • the flexural modulus of the nylon-based resin composites was measured in accordance with ASTM D-790 and the obtained values were expressed in kgf/cm 2 .
  • Notched specimens and unnotched specimens of the respective nylon-based resin composites were produced. These specimens had a thickness of 1/8".
  • the impact strength of the specimens was measured at room temperature (25°C) by Izod testing in accordance with ASTM D-256 and the obtained values were expressed in kgf- cm/cm.
  • Table 1 shows the test results for the flexural strength, flexural modulus, IZOD impact strength and warpage of the nylon-based resin composites of Examples 1 to 4 and Comparative Examples 1 and 2.
  • the results of Table 1 demonstrate that the nylon-based resin composites of Examples 1 to 4 showed high mechanical strength, improved impact resistance and low warpage with increasing content of the glass fiber.
  • the physical properties of the nylon-based resin composites of Examples 1 and 3 were compared with those of the nylon-based resin composites of Comparative Examples 1 and 2, which had the same content of glass fiber, respectively.
  • the nylon-based resin composites of Examples 1 and 3 showed higher mechanical strength and impact resistance than those of Comparative Examples 1 and 2, respectively.
  • the nylon-based resin composites of Examples 1 and 3 showed low warpage and markedly increased unnotched impact strength when compared to those of Comparative Examples 1 and 2, respectively.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Disclosed is a nylon-based resin composite that has a sufficiently low moisture absorption rate to substantially prevent the occurrence of deformation and can attain both low warpage and improved impact resistance. The nylon-based resin composite comprises 100 parts by weight of a base resin and 1 to 30 parts by weight of an impact modifier wherein the base resin consists of 20 to 80% by weight of a modified nylon-based thermoplastic resin containing benzene rings in the main chain and 20 to 80 % by weight of a flat reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more.

Description

[DESCRIPTION] [Invention Title]
COMPOSITE OF NYLON POLYMER
[Technical Field]
The present invention relates to a nylon-based resin composite, and more particularly to a nylon-based resin composite with low warpage and improved impact resistance as well as high mechanical strength.
[Background Art]
The development of nylons as engineering plastics has a history of almost four decades, but there is still a growing demand for nylons . There are many basic types of nylon, including nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, copolymers thereof, and blends thereof. Nylons have respective inherent characteristics in terms of their usefulness and can exhibit various performance characteristics. Based on these characteristics, a great demand for nylon products is currently maintained.
Particularly, composites of nylon resins and inorganic reinforcing materials (e.g., a glass fiber) exhibit high mechanical strength and markedly improved heat resistance, and thus they are used as structural materials and interior/exterior materials for automobiles.
However, since nylon resins have a high moisture absorption rate in view of their molecular structures, they exhibit dimensional instability and high warpage. Further, the addition of inorganic material to nylon resins causes low impact resistance of the resulting composites.
It is generally known that impact resistance of a composite of a nylon resin and an inorganic material is low because stress accumulates at the interfaces between the nylon molecules and the inorganic material due to low interfacial binding force between the nylon resin and the inorganic material when multiple impacts are applied to the composite, and as a result, cracks occur at the interfaces. Further, since weak C-C bonds present in the main chain of a nylon resin tend to be cleaved due to the inherent structural characteristics of the nylon resin, the nylon resin suffers from the problem that it is difficult to attain low warpage . This problem can be solved to some extent by the addition of an inorganic reinforcing material to a nylon resin, but an improvement in the warpage of the resulting composite provided by the inorganic reinforcing material is negligible. Although the warpage of the composite is slightly decreased by the addition of the inorganic reinforcing material, a low interfacial binding force between the inorganic reinforcing material and the nylon molecules results in poor mechanical properties [e.g., low impact resistance) of the composite.
[Disclosure] [Technical Problem] The present invention has been made to solve the foregoing problems of the prior art, and it is an object of the present invention to provide a nylon-based resin composite that has a sufficiently low moisture absorption rate to substantially prevent the occurrence of deformation and can attain both low warpage and improved impact resistance.
Objects to be accomplished by the present invention are not limited to the above-mentioned object of the present invention. Other objects not mentioned above will be understood clearly to those skilled in the art from the following description.
[Technical Solution]
According to an embodiment of the present invention for achieving the above object, there is provided a nylon-based resin composite comprising 100 parts by weight of a base resin and 1 to 30 parts by weight of an impact modifier wherein the base resin consists of 20 to 80% by weight of a modified nylon-based thermoplastic resin containing benzene rings in the main chain and 20 to 80% by weight of a reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more.
[Advantageous Effects]
The nylon-based resin composite of the present invention has a sufficiently low moisture absorption rate to substantially prevent the occurrence of deformation and can attain both low warpage and improved impact resistance.
[Mode for Invention] The present invention provides a nylon-based resin composite comprising 100 parts by weight of a base resin and 1 to 30 parts by weight of an impact modifier wherein the base resin consists of 20 to 80% by weight of a modified nylon- based thermoplastic resin containing benzene rings in the main chain and 20 to 80% by weight of a reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more.
Specific details of other embodiments are included in the following description. The advantages and features of the present invention and methods for achieving them will become more apparent from the following embodiments that are described in detail below. However, the present invention is not limited to the illustrated embodiments and may be embodied in various different forms. Rather, the disclosed embodiments are provided so that the disclosure of the present invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which the present invention pertains . The scope of the present invention is defined by the claims that follow. The nylon-based resin composite according to the embodiment of the present invention comprises a base resin and an impact modifier.
The base resin includes a modified nylon-based thermoplastic resin and a reinforcing fiber. The modified nylon-based resin contains benzene rings in the main chain, as represented by Formula 1 :
Figure imgf000006_0001
wherein n is from 50 to 500.
The modified nylon represented by Formula 1 is prepared by polycondensation of hexamethylene diamine with terephthalic acid, and is referred to simply as λnylon 6T" .
Preferably, the modified nylon-based thermoplastic resin has an intrinsic viscosity of 0.7 to 0.9 dl/g, an average molecular weight of 10,000 to 100,000, and a moisture absorption rate of 0.1% or less.
The reinforcing fiber is used to enhance the low warpage and heat resistance of the nylon-based resin composite. The reinforcing fiber is selected from glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, silicon carbide fibers, and mixtures thereof. As the reinforcing fiber, a glass fiber is preferably used. The reinforcing fiber is specially designed in the form of a plate whose cross-sectional aspect ratio is 1.5 or more and length is within the range of 2 mm to 13 mm.
The cross-sectional aspect ratio is defined as a ratio of the longest diameter (width, λa' ) to the shortest diameter (height, λb' ) in the cross section of the reinforcing fiber, as depicted in the following drawing.
Figure imgf000007_0001
* cross-sectional aspect ratio = a/b
Reinforcing fibers have been used to increase the strength of thermoplastic resins. For example, there have been used glass fibers that have a length of 3 mm to 6 mm, a cross-sectional aspect ratio of about 1 (i.e. a circular cross section) , and a cross-sectional diameter of 10 μm to 20 μm. In contrast, the reinforcing fiber used in the present invention has a cross-sectional aspect ratio of 1.5 or more and preferably from 2 to 8.
A surface coupling agent is preferably coated on the surface of the reinforcing fiber in order to increase the binding force between the surface of the reinforcing fiber and the surface of the modified nylon-based thermoplastic resin. The surface coupling agent is selected from urethane resins, epoxy resins, and mixtures thereof. The reinforcing fiber used in the present invention preferably has a moisture absorption rate of 0.05% or less.
The base resin is defined to include the modified nylon- based thermoplastic resin and the reinforcing fiber. Taking into consideration the mechanical strength and production processing of the final nylon-based resin composite, it is preferred that the base resin consist of 20 to 80% by weight of the modified nylon-based thermoplastic resin and 20 to 80% by weight of the reinforcing fiber.
A reactive olefinic copolymer or a core-shell copolymer may be used as the impact modifier.
The reactive olefinic copolymer may be an ethylene/propylene rubber, an isoprene rubber, an ethylene/octene rubber, an ethylene-propylene-diene terpolymer (EPDM), or the like. The reactive olefinic copolymer may be a graft copolymer in which 0.1 to 5% by weight of one or more reactive functional groups selected from maleic anhydride, glycidyl methacrylate and oxazoline are grafted onto an olefinic copolymer. The grafting of the reactive functional group onto the olefinic copolymer can be readily carried out by those skilled in the art to which the present invention pertains.
The core-shell copolymer is prepared by polymerizing at least one monomer selected from monomers of diene rubbers, acrylate rubbers and silicone rubbers to prepare a rubbery polymer, and grafting the rubbery polymer with at least one monomer selected from the group consisting of styrene, α- methylstyrene, halogenated styrenes, alkylated styrenes, acrylonitrile, methacrylonitrile, Ci-Ce alkyl methacrylates, Ci-Cs alkyl acrylates, maleic anhydride, N- (C1-C4) alkyl- substituted maleimide and N-phenyl-substituted maleimide as graftable unsaturated compounds. The content of the rubber in the core-shell copolymer is preferably from 30 to 90 parts by weight . Examples of the diene rubbers include butadiene rubbers, acrylic rubbers, ethylene/propylene rubbers, styrene/butadiene rubbers, acrylonitrile/butadiene rubbers, isoprene rubbers, and ethylene-propylene-diene terpolymers (EPDM) .
Examples of suitable acrylate monomers of acrylate rubbers include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate. Curing agents may be used for the polymerization of the acrylate monomers. Examples of such curing agents include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, allyl methacrylate, and triallyl cyanurate.
The silicone rubbers may be synthesized from cyclosiloxanes . As the cyclosiloxanes, there may be exemplified hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane .
At least one curing agent may be used for the preparation of the silicone rubbers. Examples of such curing agents include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, and tetraethoxysilane.
The Ci-C8 alkyl methacrylates and the Ci-Cs alkyl acrylates are esters of methacrylic and acrylic acid, respectively, and are prepared from monohydric alcohols having one to eight carbon atoms. Specific examples of these esters include methyl methacrylate, ethyl methacrylate, and propyl methacrylate . Of these, most preferred is methyl methacrylate.
The preparation of the core-shell copolymer can be readily carried out by those skilled in the art to which the present invention pertains .
Taking into account the impact modification, flowability and other mechanical properties of the final nylon-based resin composite, the impact modifier is preferably used in an amount of 1 to 30 parts by weight and more preferably 2 to 10 parts by weight, based on 100 parts by weight of the base resin.
The nylon-based resin composite of the present invention may further comprise at least one additive selected from antioxidants, heat stabilizers, light stabilizers, flow enhancers, lubricants, antibacterial agents, release agents, nucleating agents and other additives so long as the additive does not impair the basic physical properties of the nylon- based resin composite. The additive may be added in an amount of 30 parts by weight or less, based on 100 parts by weight of the base resin.
The resin composition of the present invention may be prepared by any known process. For example, the resin composition of the present invention can be prepared by mixing the essential components with at least one optional additive, melt-extruding the mixture within an extruder, and pelletizing the molten mixture .
The resin composition of the present invention may be molded into a variety of products. The resin composition of the present invention is suitable for the manufacture of interior/exterior materials for automobiles, highly heat- resistant materials for electronic components and exterior materials for electrical and electronic products, including computers, electric home appliances and cell phones. Hereinafter, the nylon-based resin composite according to the embodiment of the present invention will be explained with reference to the following specific examples and comparative examples. These examples are provided to illustrate that the nylon-based resin composite of the present invention exhibits high flexural strength, high flexural modulus, high impact strength and low warpage. Disclosures that are not included herein will be readily recognized and appreciated by those skilled in the art, and thus their description is omitted.
1. Examples and Comparative Examples
Specific specifications of (A) a modified nylon-based resin, (B) reinforcing fiber and (C) an impact modifier used in the following examples and comparative examples are as follows .
(A) Modified nylon-based resin: A highly heat-resistant modified nylon (polyphthalamide: HTN-501, DuPont) containing benzene rings in the main chain was used.
(B) Reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more: A glass fiber (CSG 3PA-820, Nitto Boseki, Japan) having a cross-sectional aspect ratio of 4 (width: 28 μm, height: 7 μm) was used.
(B' ) Glass fiber having a cross-sectional aspect ratio of about 1: A circular glass fiber (P952, Vetrotex) having a cross-sectional aspect ratio of about 1 (length: 3 mm, diameter: 10 μm) was used.
(C) Impact modifier: An olefinic impact modifier (Fusabond MN-493D, DuPont) was used.
Nylon-based resin composites having the compositions indicated in Table 1 were prepared.
2. Tests for physical properties of nylon-based resin composites (1) Flexural strength
The flexural strength of the nylon-based resin composites was measured in accordance with ASTM D-790 and the obtained values were expressed in kgf/cm2.
(2) Flexural modulus
The flexural modulus of the nylon-based resin composites was measured in accordance with ASTM D-790 and the obtained values were expressed in kgf/cm2.
(3) Izod impact strength
Notched specimens and unnotched specimens of the respective nylon-based resin composites were produced. These specimens had a thickness of 1/8". The impact strength of the specimens was measured at room temperature (25°C) by Izod testing in accordance with ASTM D-256 and the obtained values were expressed in kgf- cm/cm.
( 4 ) Warpage Thin film specimens (width: 6", height: 6", thickness:
1/16") of the respective nylon-based resin composites were produced by injection molding. After the three edges of each of the specimens were attached to the ground, the distance of the remaining edge of the specimen from the ground was measured and the obtained values were expressed in mm. TABLE 1
Figure imgf000015_0001
Note: l: Reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more 2: Reinforcing fiber having a cross-sectional aspect ratio of about 1
Table 1 shows the test results for the flexural strength, flexural modulus, IZOD impact strength and warpage of the nylon-based resin composites of Examples 1 to 4 and Comparative Examples 1 and 2.
The results of Table 1 demonstrate that the nylon-based resin composites of Examples 1 to 4 showed high mechanical strength, improved impact resistance and low warpage with increasing content of the glass fiber. The physical properties of the nylon-based resin composites of Examples 1 and 3 were compared with those of the nylon-based resin composites of Comparative Examples 1 and 2, which had the same content of glass fiber, respectively. As a result, the nylon-based resin composites of Examples 1 and 3 showed higher mechanical strength and impact resistance than those of Comparative Examples 1 and 2, respectively. Particularly, the nylon-based resin composites of Examples 1 and 3 showed low warpage and markedly increased unnotched impact strength when compared to those of Comparative Examples 1 and 2, respectively. Although the present invention has been described herein with reference to the foregoing embodiments, the present invention is not limited to the embodiments and may be embodied in various different forms. Those skilled in the art will appreciate that the present invention may be practiced otherwise than as specifically described without changing the technical spirit or essential features of the present
'invention. Therefore, it should be understood that the foregoing embodiments are merely illustrative in all aspects and are not to be construed as limiting the present invention.

Claims

[CLAIMS] [Claim 1]
A nylon-based resin composite comprising 100 parts by weight of a base resin and 1 to 30 parts by weight of an impact modifier wherein the base resin consists of 20 to 80% by weight of a modified nylon-based thermoplastic resin containing benzene rings in the main chain and 20 to 80% by weight of a reinforcing fiber having a cross-sectional aspect ratio of 1.5 or more.
[Claim 2]
The nylon-based resin composite ' according to claim 1, wherein the modified nylon-based thermoplastic resin has an intrinsic viscosity of 0.7 to 0.9 dl/g.
[Claim 3]
The nylon-based resin composite according to claim 1, wherein the modified nylon-based thermoplastic resin has an average molecular weight of 10,000 to 100,000.
[Claim 4]
The nylon-based resin composite according to claim 1, wherein the reinforcing fiber has a cross-sectional aspect ratio of 2 to 8.
[Claim 5 ]
The nylon-based resin composite according to claim 1, wherein the reinforcing fiber is selected from glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, silicon carbide fibers, and mixtures thereof.
[Claim 6]
The nylon-based resin composite according to claim 1, wherein the reinforcing fiber is a glass fiber.
[Claim 7]
The nylon-based resin composite according to claim 1, wherein the impact modifier is selected from a reactive olefinic copolymer and a core-shell copolymer and mixtures thereof.
[Claim 8]
The nylon-based resin composite according to claim 7, wherein the reactive olefinic copolymer is prepared by grafting one or more reactive functional groups selected from maleic anhydride, glycidyl methacrylate and oxazoline onto an olefinic copolymer selected from ethylene/propylene rubbers, isoprene rubbers, ethylene/octene rubbers and ethylene- propylene-diene terpolymers (EPDM) ; and the core-shell copolymer is prepared by polymerizing at least one monomer selected from monomers of diene rubbers, acrylate rubbers and silicone rubbers to prepare a rubbery polymer, and grafting the rubbery polymer with at least one monomer selected from the group consisting of styrene, α-methylstyrene, halogenated styrenes, alkylated styrenes, acrylonitrile, methacrylonitrile, Ci-Cs alkyl methacrylates, Ci-Cs alkyl acrylates, maleic anhydride, N- (C1-C4) alkyl-substituted maleimide and N-phenyl-substituted maleimide as graftable unsaturated compounds .
[Claim 9]
The nylon-based resin composite according to claim 1, further comprising at least one additive selected from antioxidants, heat stabilizers, light stabilizers, flow enhancers, lubricants, antibacterial agents, release agents, and nucleating agents.
[Claim 10]
A pellet produced by extruding the nylon-based resin composite according to any one of claims 1 to 9.
PCT/KR2006/005622 2006-12-18 2006-12-21 Composite of nylon polymer WO2008075809A1 (en)

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