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    • 专利摘要:
    The present invention relates to a polyolefin composite resin composition containing various kinds of ethylene-α-olefin copolymers, calcium-methilicate-silicate inorganic reinforcing materials, modified resins, and various additives in crystalline ethylene-propylene copolymers as basic materials. In addition, the composition of the present invention has not only improved impact resistance, heat resistance, and paintability, but also has excellent injection moldability, so that the thickness of the molded product can be reduced, thereby reducing the production cost of parts and reducing the weight of the molded product. (sink mark and flow mark) are improved to improve the appearance of the molded product after injection, and in particular, the shrinkage ratio, heat sag and coefficient of linear expansion, etc. are reduced to reduce the dimensional stability of the molded product. As the resin composition, it can be usefully used as a material for various automobile parts.
    公开号:KR19990039954A
    申请号:KR1019970060219
    申请日:1997-11-15
    公开日:1999-06-05
    发明作者:박봉현
    申请人:정몽규；현대자동차 주식회사；
    IPC主号:
    专利说明:

    Polyolefin Composite Resin Composition for Automotive Parts
    The present invention relates to a polyolefin-based composite resin composition for automobile parts, and more particularly, to various types of ethylene-propylene copolymers, wherein two or more kinds of ethylene-α-olefin copolymer rubbers The present invention relates to a polyolefin composite resin composition for automobile parts containing calcium-methilicate-silicate inorganic reinforcing materials, modified resins and various additives.
    Alloys of acrylonitrile-butadiene-styrene (ABS) copolymers, polycarbonate / acrylonitrile-butadiene-styrene (PC / ABS) copolymer resins, and poly for conventional automotive interior and exterior components and electronic components Alloys of carbonate / polybutyrene terephthalate (PC / PBT) copolymer resins, such as polyamides and polyurethane resins, have been widely used due to their excellent physical properties. However, among the above-mentioned synthetic resins, except for polyamides, which are difficult to be replaced by polyolefin-based composite resins due to the large difference in mechanical and thermal properties, many of the parts of the automobile parts and electronic parts are polyolefin-based resins for light weight, cost reduction, and recycling. It is replaced by a composite resin.
    In general, polyolefin resins (PE) and polypropylene (PP), which are widely used, have a small specific gravity and have advantages in terms of formability, mechanical rigidity, and price compared to other resins. It is a resin widely used for industrially manufacturing parts used in the fields of automobiles, aviation, and electronics. However, polyolefin-based resins are limited in the physical properties that can be represented by the homopolymers, and thus are limited in the application range, and thus, it is difficult to apply them to industrial fields requiring special physical properties.
    In order to overcome the limitations of the olefin resin, a polyolefin composite resin has been developed in which a polyolefin resin is blended with another resin or a mineral filler is added to give a new function. It is used in various fields that were difficult to apply. In particular, polyolefin composite resins in which impact reinforcing materials such as copolymers or elastomers and inorganic reinforcing materials are added to polyolefin resins are widely used as materials for automobiles and electronic parts.
    Polyolefin composite resin is basically a polyolefin-based copolymer as a base material (additional impact reinforcing material ethylene-α-olefin copolymer or elastomer (elastomer), or as a rigid reinforcing material such as inorganic filler and other additives Melt kneading using a kneader or an extruder to express new physical properties and functions that cannot be realized by the polymer itself, and changes the type of polyolefin copolymer, various kinds of impact reinforcing materials or rigid reinforcing materials. Various methods for improving various physical properties have been proposed and put into practical use. The polyolefin-based composite resin should be selected in the type, properties, size and content of the resin and filler in accordance with the application characteristics in the field of solidification. In particular, since the physical properties and formability can be greatly affected by the change in processing conditions, it is necessary to select the processing equipment and processing conditions appropriately to maintain the processability and reproducibility of the resin itself and to improve the characteristic properties by the filler. It is important. In addition, the addition of additives to prevent deformation and aging of the resin due to high temperature and high pressure during processing is also an important factor in determining the properties of the composite resin. In addition, there is an interface between two components of the polymer base material and the filler material, and the physical properties of the material depend on the adhesion of the interface.
    In order to use polyolefin composite resin in various fields, it has to be excellent in high rigidity, high impact resistance, high heat resistance, dimensional stability and scratch resistance, and according to the light weight trend of parts The performance should be extremely excellent and the molding time of parts should be short in terms of cost reduction and production volume. In addition, it should be excellent in paintability and appearance after molding depending on whether the part is paint type or unpainted type. However, polyolefin-based composite resins have not yet been developed to meet these requirements as a whole.
    As a synthetic resin used for molding large parts such as bumper fascia and instrument panel among automobile parts, researches are being actively conducted to develop polyolefin composite resins with small shrinkage and linear expansion coefficient. Bumper fascia and panel are parts having a relatively thin thickness compared to a large surface area, and there is a fear that the molded article may bend or sag if the source material does not have sufficient rigidity. In addition, in recent years, there is a tendency to reduce the thickness of the parts used in terms of weight reduction and cost reduction of the vehicle, so that the flexural modulus is large, the linear expansion coefficient and the sag due to heat are small, and the development of raw materials having excellent dimensional stability is required.
    Crystalline ethylene-propylene copolymer (melt index) of about 20 to 45 g / 10 minutes and containing about 7 to 12% by weight of propylene-propylene rubber (propylene: 92 to 95% by weight, ethylene: 5 to 8 wt%) of ethylene-propylene copolymer rubber (propylene: 25-45 wt%) and a mixture of fine talc (talc) having an average particle size of 2-4 μm to increase rigidity were mechanically mixed using a kneader or an extruder. It is well known to melt-knead and obtain a polyolefin composite resin. However, this composition has problems such as the use of a large amount of expensive olefin rubber in order to increase the impact strength and the deterioration in formability by using a large amount of talc to increase the rigidity.
    European Patent EP 0557124 A1 relates to a very hard polyolefin composite resin, which is composed of 55 to 75% by weight of a high crystalline ethylene-propylene copolymer having a high melt index to improve moldability, Ultra-high polyolefin composite resins were prepared by mixing 25 to 45 wt% of the crystalline ethylene-propylene copolymer having a melting temperature and 1 to 25 wt% of the fine talcum having an average particle size of 5 μm or less. However, a high crystalline ethylene-propylene copolymer is used to increase the rigidity, which increases the production cost of the composition, making it difficult to apply to automotive parts. In addition, excessively increased stiffness makes the impact strength at a low temperature vulnerable, and the crystallinity of the composition is increased to reduce paintability (EP 0531154 A2, EP 059662 A1, EP 0496625 A2). In addition, when a large amount of the olefinic rubber component is kneaded into the ethylene-propylene copolymer, the fluidity of the composition is poor, the weld line is weak, and the moldability of the large injection molding is poor, and the appearance of the injection molding is poor. In addition, the ethylene-propylene copolymer and the olefinic rubber, which are the main raw materials of the composition, are nonpolar resins, and thus have disadvantages in poor paintability.
    Accordingly, the present inventors have been developing polyolefin-based composite resins that can replace the alloy of polycarbonate / acrylonitrile-butadiene-styrene copolymers widely used as automobile parts, and based on ethylene-propylene copolymers, The present invention was completed by developing a polyolefin composite resin composition having excellent impact resistance, heat resistance, flowability, dimensional stability, paintability, and moldability, containing an ethylene-α-olefin copolymer and various additives.
    An object of the present invention is a polyolefin composite resin composition comprising an ethylene-α-olefin copolymer and various additives which can improve rigidity, impact resistance, flowability, dimensional stability and formability based on an ethylene-propylene copolymer. To provide.
    In order to achieve the above object, the present invention contains a crystalline ethylene-propylene copolymer and at least one kind of ethylene-α-olefin copolymer, calcium-meth-silicate-based ulastonite, modified resin, and various additives. It provides a polyolefin resin composition.
    Hereinafter, the present invention will be described in detail.
    The composition of the present invention is 1) a crystalline ethylene-propylene copolymer (ethylene: 1 to 10% by weight) having a melt index of 20 to 60 g / 10 minutes (230 ° C) and containing 0.5 to 15% by weight of ethylene-propylene rubber. , Propylene: 90 to 99% by weight), 50 to 95% by weight, 2) ethylene-propylene copolymer rubber (propylene) having a melt index of 0.1 to 5 g / 10 min (230 ° C., 2.16 kg) as an ethylene-α-olefin copolymer : 20 to 50% by weight), respectively, 5 to 25% by weight, and 3) ethylene-α-olefin copolymers having an melt index of 0.1 to 15 g / 10 minutes (230 ° C., 2.16 kg) (octene: 20 to 30% by weight), 5 to 30% by weight, 4) 5 to 20% by weight of urastonite, a needle-like calcium-meth-silicate-based inorganic reinforcing material having an aspect ratio of 10 to 19 and an average particle size of 5 to 25 μm. %, 5) Ethylene-propylene rubber or ethylene-2-hydroxyethylene methacrylate copolymer grafted with maleic anhydride as modified resin (ethyl 1 to 10 wt% of ene-2-hydroxy ethylene methacrylate copolymer) and 6) to phenol based to 0.05 to 3 wt% of an amino silane or amino titanium compound as a coupling agent as an additive and an antioxidant 0.05 to 0.5% by weight of the compound and phosphorus or amine compound, 0.05 to 0.5% by weight of UV stabilizer, Hals-based compound to 0.05 to 0.5% by weight, antistatic agent, and 0.05 to 0.1% by weight of alkylamine compound, and processing lubricant Calcium stearate compound and the like are polyolefin-based composite resin compositions composed of 0.05 to 0.5% by weight of composition.
    The ethylene-propylene copolymer, component 1) of the polyolefin-based composite resin composition of the present invention, under a mixed catalyst of titanium trichloride (TiCl 3 ) and an alkyl aluminum compound, generally called a Ziegler-Natta type catalyst, Or a mixed catalyst of a titanium compound and a magnesium compound.
    In the present invention, the crystalline ethylene-propylene copolymer (ethylene: 1 to 10% by weight) having a melt index of 20 to 60 g / 10 minutes (230 ° C., 2.16 kg) and a content of ethylene-propylene rubber of 0.5 to 15% by weight. Is used in an amount of 50 to 95% by weight, and ethylene-propylene copolymer rubber (hereinafter, abbreviated as "EPR") is prepared by injecting an excessive amount of gaseous ethylene into a reactor for preparing an ethylene-propylene copolymer. In this method, since the ethylene-propylene copolymer and a large amount of EPR are produced directly in the reactor, the EPR is uniformly distributed in the crystalline polypropylene matrix, and the propylene component and the crystalline poly are present in excess in the EPR. Compatibility with the propylene matrix results in improved interfacial adhesion resulting in an improved impact strength of the ethylene-propylene copolymer. The composite resin produced through this method can reduce the cost by reducing the amount of ethylene-α-olefin copolymer rubber added to reinforce the impact resistance compared to the conventional method, that is, blended through melting and kneading. It is evenly distributed in the ethylene-propylene copolymer to produce a product having uniform physical properties and performance.
    When the ethylene-propylene copolymer of the present invention was measured with a differential scanning calorimeter (DSC), the melting point of polypropylene was 165 ° C, the melting point of polyethylene was 120 ° C, the crystallinity was 20 to 30%, and gel permeation chromatography. When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight () Is 170,000-245,000 and the number average molecular weight () Is a resin having 37,000 to 48,000.
    In the ethylene-propylene copolymer of the present invention, it is preferable to use a crystalline ethylene-propylene copolymer having a melt index of 20 to 60 g / 10 minutes (230 ° C., 2.16 kg), wherein the air having a melt index of less than 20 g / 10 minutes is used. The use of coalesce reduces the formability of the material, and the use of copolymers in excess of 60 g / 10 min reduces the impact resistance of the material.
    Among the components of the composition of the present invention, the ethylene-α-olefin copolymer rubber is added to improve the impact resistance of the polyolefin-based copolymer which is a base material, and as the α-olefin, 1-propylene, 1-butene and 1-octene are used. Can optionally be used. Ethylene-α-olefin copolymer rubbers are mainly polymerized using Ziegler-Natta type catalysts, in particular using vanadium-based or chromium-based catalysts. Ethylene-α-olefin copolymer rubber of 2) of the composition of the present invention is an ethylene-propylene copolymer rubber (content of propylene: 20-50% by weight) with a melt index of 0.1-5 g / 10 minutes (230 ° C., 16 kg). It is preferable to add 5-25 weight% of ethylene-propylene copolymer rubber which is 19-85ML1 + 4 (100 degreeC), specific gravity 0.86g / cm <3>, respectively.
    In addition, the ethylene-α-olefin copolymer rubber, which is component 3) added to the composition of the present invention, is an ethylene-octene copolymer rubber (content of octene: 20 to 30% by weight) and has a melt index of 0.1 to 15 g / 10 minutes (230 ° C). , 2.16 kg), and an ethylene-octene copolymer rubber (hereinafter abbreviated as "EOR") having a pattern viscosity of 19 to 50 ML 1 + 4 (121 ° C) is preferably added in a composition of 5 to 30% by weight.
    In the present invention, in order to increase the rigidity of the polyolefin composite resin composition, a compound of component 4) calcium-meth-stearate-based compound is added, and the needle-like calcium having an average particle size of 5 to 25 µm and an aspect ratio of 10 to 19 is added. It is preferable to add meta-stearate-based ulastonite in a composition of 5 to 20% by weight.
    In the present invention, in order to improve the paintability of the composition by adjusting the viscosity of the ethylene-α-olefin copolymer rubber is a method of protruding a lot of rubber to the surface during injection of the composition and a method of changing the viscosity using a modified resin , The modified resin of component 5) used in the present invention is ethylene-propylene rubber (hereinafter abbreviated as "GM-EPR") and ethylene-2- grafted maleic anhydride (maleic anhydride) A hydroxyethylene methacrylate copolymer (hereinafter abbreviated as "EHEMA") may be optionally used, but the modified resin is preferably added by 1 to 10% by weight. If the content of the modified resin is less than 1% by weight, the paintability of the composition becomes very poor, and if it exceeds 10% by weight, the paintability is excellent, but the moldability and physical properties of the composition are lowered.
    Additives used in the compositions of the present invention include coupling agents, primary and secondary antioxidants, ultraviolet stabilizers, processing lubricants, carbon black and antistatic agents.
    First, an inorganic reinforcing material, an ethylene-propylene copolymer, which is a basic material, and a coupling agent are added to increase the adhesive strength. The composition is 0.05 to 3% by weight, and is primarily used to prevent thermal decomposition generated when processing the resin. Phenolic compounds such as tetrakis [methylene (3,5-di-tetra-butyl-4-hydroxy-hydrocinnamate)] methane as an antioxidant and tris (2,4-di-t- as a secondary antioxidant Phosphorus or amine compounds such as butylphenyl) phosphite are added, and the content thereof is appropriately 0.05 to 0.5% by weight. In addition, UV stabilizers are used to prevent the decomposition of the resin due to weather resistance and ultraviolet light when exposed to the outdoors, poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1, 3,5-triazine-2,4-diyl]-[2- (2,2,6,6-tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6, 6-tetramethyl-piperidyl) -imino]} and the like are preferably added in a composition of 0.05 to 0.5% by weight. When the resin is melted and molded, a processing lubricant is added to lower the viscosity of the resin to improve processability. Compounds such as calcium stearate are added in a composition of 0.05 to 0.5% by weight, and carbon black is 0.5 to 2.0% by weight. The alkylamine compound is added in an amount of 0.05 to 0.1% by weight as an antistatic agent. In addition, a pigment, a dispersant, a moldability improving agent, a long-term heat stabilizer, a nucleating agent and a mold release improving agent may be added to the composition of the present invention in order to improve the physical properties of the composition.
    In order to obtain the polyolefin resin composition of the present invention, a raw material may be mixed using a Henschel mixer, a ribbon blender, or a V-blender, or a predetermined ratio of raw materials may be provided using different raw material feeders. Can be supplied and used. The processing equipment used is a single screw extruder, a twin screw extruder, a Kneader mixer or a Banbury mixer, etc., depending on the processing conditions. type). At this time, since the physical properties of the resin composition change depending on the processing conditions, mainly by using a twin screw extruder that can use a part of the extruder as a supply port in addition to one supply port, the conditions such as the screw rotation speed, the supply amount and the processing temperature are changed. It is desirable to optimize.
    Hereinafter, the polyolefin resin composition of this invention is demonstrated in detail by an Example. However, these Examples are only for illustrating the present invention and the present invention is not limited by the Examples.
    <Example 1>
    20% by weight of crystalline ethylene-propylene copolymer 2 (weight average molecular weight: 180,000, melt index: 20 g / 10 min, ethylene content: 48.8% by weight) and crystalline ethylene-propylene copolymer 3 (weight average molecular weight: 175,000, melt index: 22 g / 10 min, ethylene content: 47 wt%) EPR 1 (melt index: 3.2 g / 10 min, propylene content: 27 wt%) as ethylene-α-olefin copolymer rubber at 43 wt% This 16% by weight and EOR 1 (melt index: 0.7g / 10 minutes, octene content: 28% by weight) of 10% by weight, needle-like urastonite (average particle size: 8㎛, aspect ratio: 17% by weight, 2% by weight of EPR (GM-EPR) or ethylene-2-hydroxyethylene methacrylate (EHEMA) grafted maleic anhydride with modified resin, and 2.0% by weight of additive Polyolefin composite resin composition was prepared. The additive is calcium stearate as a processing lubricant, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate)] methane as the primary antioxidant, tris (2) as the secondary antioxidant. , 4-di-t-butylphenyl) phosphate is a poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine- 2,4-diyl]-[2, (2,2,6,6, -tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6,6-tetramethyl-pi Ferridyl) -imino]}, an amino silane-based or amino titanium-based compound as a coupling agent, an alkylamine-based compound as an antistatic agent, and carbon black were selected and added within the above-mentioned contents. The total amount of was added to 2.0% by weight. The composition composed of the above content was prepared in a pellet form after melt mixing using a mixer, an extruder or a blender. (See Table 1)
    <Example 2>
    Crystalline ethylene-propylene copolymer 3 (weight average molecular weight: 175,000, melt index: 22 g / 10 minutes, content of ethylene: 47 wt%) as base material, EOR 1 (melt index) as ethylene-α-olefin copolymer rubber at 61 wt% : 0.7g / 10min, octene content: 28% by weight) and 7% by weight of EOR 2 (melt index: 13g / 10min, octene content: 28% by weight) of 16% by weight. 10% by weight of ulastonite (average particle size: 8 µm, aspect ratio: 17), EPR (GM-EPR) or ethylene-2-hydroxyethylene methacrylate (EHEMA) grafted maleic anhydride with a modified resin The polyolefin-based composite resin composition was added with 2% by weight and 2.0% by weight of an additive. The additive is calcium stearate as a processing lubricant, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate)] methane as the primary antioxidant, tris (2) as the secondary antioxidant. , 4-di-t-butylphenyl) phosphate is a poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine- 2,4-diyl]-[2, (2,2,6,6, -tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6,6-tetramethyl-pi Ferridyl) -imino]}, an amino silane-based or amino titanium-based compound as a coupling agent, an alkylamine-based compound as an antistatic agent, and carbon black were selected and added within the above-mentioned contents. The total amount of was added to 2.0% by weight. The composition composed of the above content was prepared in a pellet form after melt mixing using a mixer, an extruder or a blender. (See Table 1)
    <Example 3>
    Crystalline ethylene-propylene copolymer 3 (weight average molecular weight: 175,000, melt index: 22 g / 10 minutes, content of ethylene: 47 wt%) as the base material, and EPR 1 (melt index) as ethylene-α-olefin copolymer rubber at 61 wt% : 3.2 g / 10 min, propylene content: 27 wt%) 8 wt% and EOR 1 (melt index: 0.7 g / 10 min, octene content: 28 wt%) 7 wt% and EOR 2 (melt index: 13g / 10min, octene content: 28% by weight) 10% by weight, 10% by weight of needle-like ulastonite (average particle size: 7㎛, aspect ratio: 17) as inorganic reinforcing material, maleic anhydride as a modified resin A polyolefin composite resin composition was prepared in which grafted EPR (GM-EPR) or ethylene-2-hydroxyethylene methacrylate (EHEMA) was added at 2% by weight and additives at 2.0% by weight. The additive is calcium stearate as a processing lubricant, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate)] methane as the primary antioxidant, tris (2) as the secondary antioxidant. , 4-di-t-butylphenyl) phosphate is a poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine- 2,4-diyl]-[2, (2,2,6,6, -tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6,6-tetramethyl-pi Ferridyl) -imino]}, an amino silane-based or amino titanium-based compound as a coupling agent, an alkylamine-based compound as an antistatic agent, and carbon black were selected and added within the above-mentioned contents. The total amount of was added to 2.0% by weight. The composition composed of the above content was prepared in a pellet form after melt mixing using a mixer, an extruder or a blender. (See Table 1)
    <Example 4>
    Crystalline ethylene-propylene copolymer 3 (weight average molecular weight: 175,000, melt index: 22 g / 10 minutes, content of ethylene: 47 wt%) as base material, EPR 1 (melt index) as ethylene-α-olefin copolymer rubber at 55 wt% : 3.2 g / 10 min, propylene content: 27 wt%), 10 wt%, EPR 2 (melt index: 0.6 g / 10 min, propylene content: 43 wt%), 10 wt% and EOR 1 (melt index) : 0.7g / 10min, octene content: 28% by weight), 7% by weight, needle-like urastonite (average particle size: 8㎛, aspect ratio: 17) as 13% by weight, modified resin Polyolefin-based composite with 2% by weight of ethylene-propylene copolymer rubber (GM-EPR) or ethylene-2-hydroxyethylene methacrylate copolymer (EHEMA) grafted with maleic anhydride, and 2.0% by weight of an additive A resin composition was prepared. The additive is calcium stearate as a processing lubricant, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate)] methane as the primary antioxidant, tris (2) as the secondary antioxidant. , 4-di-t-butylphenyl) phosphate is a poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine- 2,4-diyl]-[2, (2,2,6,6, -tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6,6-tetramethyl-pi Ferridyl) -imino]}, an amino silane-based or amino titanium-based compound as a coupling agent, an alkylamine-based compound as an antistatic agent, and carbon black were selected and added within the above-mentioned contents. The total amount of was added to 2.0% by weight. The composition composed of the above content was prepared in a pellet form after melt mixing using a mixer, an extruder or a blender. (See Table 1)
    In order to compare with the polyolefin composite resin composition of the present invention having the composition of the above-described embodiment, a polyolefin composite resin composition having a composition of the following Comparative Example was prepared.
    <Comparative Example 1>
    30% by weight of crystalline ethylene-propylene copolymer 1 (weight average molecular weight: 200,000, melt index: 15.6 g / 10 minutes, ethylene content: 49.3% by weight) and crystalline ethylene-propylene copolymer 2 (weight average molecular weight) : 180,000, melt index: 20 g / 10 min, ethylene content: 48.8 wt%) EPR 1 (melt index: 3.2 g / 10 min, propylene content: 27 wt%) as ethylene-α-olefin copolymer rubber at 32 wt% ) 8% by weight, EPR 2 (melt index: 0.6g / 10min, propylene content: 43% by weight), 9% by weight and EOR 1 (melt index: 0.7g / 10min, octene content: 28% by weight 7% by weight), a polyolefin-based composite resin composition was added to the talc (talc) 10% by weight as an inorganic reinforcing material, and 2.0% by weight additives. The additive is calcium stearate as a processing lubricant, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate)] methane as the primary antioxidant, tris (2) as the secondary antioxidant. , 4-di-t-butylphenyl) phosphate is a poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine- 2,4-diyl]-[2, (2,2,6,6, -tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6,6-tetramethyl-pi Ferridyl) -imino]}, an amino silane-based or amino titanium-based compound as a coupling agent, an alkylamine-based compound as an antistatic agent, and carbon black were selected and added within the above-mentioned contents. The total amount of was added to 2.0% by weight. The composition composed of the above content was prepared in a pellet form after melt mixing using a mixer, an extruder or a blender. (See Table 1)
    <Comparative Example 2>
    35 wt% crystalline ethylene-propylene copolymer 1 (weight average molecular weight: 200,000, melt index: 15.6 g / 10 min, ethylene content: 49.3 wt%) and crystalline ethylene-propylene copolymer 3 (weight average molecular weight) : 175,000, melt index: 22 g / 10 min, ethylene content: 47 wt%) EPR 1 (melt index: 3.2 g / 10 min, propylene content: 27 wt%) as ethylene-α-olefin copolymer rubber at 25 wt% ) 10% by weight and EOR 1 (melt index: 0.7g / 10min, octene content: 28% by weight) 10% by weight and EOR 2 (melt index: 13g / 10min, octene content: 28% by weight) 8 By weight, 10% by weight of acicular urastonite (average particle size: 8 µm, aspect ratio: 17) as inorganic reinforcing material, 2% by weight of GM-EPR or EHEMA as modified resin, and 2.0% by weight of additive A polyolefin composite resin composition added in% was prepared. The additive is calcium stearate as a processing lubricant, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate)] methane as the primary antioxidant, tris (2) as the secondary antioxidant. , 4-di-t-butylphenyl) phosphate is a poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine- 2,4-diyl]-[2, (2,2,6,6, -tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6,6-tetramethyl-pi Ferridyl) -imino]}, an amino silane-based or amino titanium-based compound as a coupling agent, an alkylamine-based compound as an antistatic agent, and carbon black were selected and added within the above-mentioned contents. The total amount of was added to 2.0% by weight. The composition composed of the above content was prepared in a pellet form after melt mixing using a mixer, an extruder or a blender. (See Table 1)
    Table 1 shows the compositions of the polyolefin composite resin compositions of Examples and Comparative Examples described above.
    ComponentExample 1Example 2Example 3Example 4Comparative Example 1Comparative Example 2 Ethylene-propylene copolymer 1 (A1)----3035 Ethylene-propylene copolymer 2 (A2)20---32- Ethylene-propylene copolymer 3 (A3)43616155-25 EPR 1 (B1)16-810810 EPR 2 (B2)---109- EOR 1 (C1)10978710 EOR 2 (C2)-1610--8 Filling material (F1)----10- Filling material (F2)7101013-10
    Modified resin (GM-EPR # or EHEMA-1 * )22222- additive222222 Unit: Weight% # GM-EPR: EPR * grafted maleic anhydride EHEMA: Ethylene-2-hydroxyethylene methacrylate (EMMA-1)
    <Experimental example> Various physical property test of polyolefin composite resin composition
    Composite resin composition prepared in the composition of the above Examples and Comparative Examples after the addition of a constant water removal process to prepare an injection or compression specimen. Specimens were mainly manufactured using an injection machine. Using a Korean Venus injection machine (model name: IDE90EN) at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C., injection pressure and holding pressure were fixed and used in an area where physical properties can be expressed well. . As described above, the injection molded specimens were measured for 48 hours at 23 ° C. and 50% of relative humidity (RH) after injection to measure the physical properties listed below. (See Table 2)
    (1) Melt Index (MI)
    It measured by the method of ASTM D1238 (230 degreeC, 2.16 kg), and used the automatic measuring device and the manual measuring device in parallel.
    (2) tensile strength and elongation
    It was measured by the method specified in ASTM D638 (Type I, cross-head speed: 50 mm / min).
    (3) flexual strength
    It was measured by the method specified in ASTM D790 (cross-head speed: 30 mm / min).
    (4) Notch / IZOD impact strength
    It was measured at room temperature (23 ° C) and low temperature (-30 ° C) by the method specified in ASTM D256 (weight of the rotary weight = 5 lb).
    (5) heat deflection temperature
    It was measured by the method specified in ASTM D648 (load = 4.16 kg).
    (6) mold shrinkage
    It measured by the method of ASTM D955.
    (7) coefficient of linear thermal expansion (CLTE)
    The dimensional change at that time was measured by changing the temperature in the range of -30 to 80 ° C by the method specified in ASTM D696.
    (8) Heat sag
    The specimens of 110 × 20 × 3 mm were fixed in parallel to the bottom in the longitudinal direction, and then maintained in an oven at 120 ° C. for 1 hour, and then the strain values were measured.
    (9) paintability
    Comparison of paint adhesiveness was performed by coating chlorinated polypropylene primer with 5 ~ 7㎛ on 50 × 100 × 2mm specimens, and coating polyurethane-based paint with 20 ~ 30㎛ on it, and then using 85 ℃ oven After curing for 30 minutes at room temperature and left for 24 hours at room temperature, 100 grids of 2 mm were made and the coating adhesiveness was tested with a tape. Table 2 shows the test results.
    examExample 1Example 2Example 3Example 4Comparative Example 1Comparative Example 2 Melt Index (g / 10min, 230 ℃)353227251519 Tensile Strength (㎏ / ㎠)170172172175170172 % Elongation500500500500500500 Flexural modulus (㎏ / ㎠)125001300013500150001100012000 Izod impact strength (23 ℃, ㎏㎝ / ㎝)NB * NBNBNBNBNB Izod impact strength (-30 ℃, ㎏㎝ / ㎝)8.58.37.97.97.57.7 Heat deflection temperature (℃)108110110115105105 Coefficient of linear expansion (10 -5 mm / min)4.84.64.54.35.14.8 Mold Shrinkage (10 -1 %)4.54.24.34.47.45.2 Heat deflection phenomenon (mm)3.93.73.74.15.44.8 Paint adhesion100/100100/100100/100100/100100/10095/100 * NB: non-break
    As described above, the polyolefin-based composite resin composition of the present invention not only has improved impact resistance, heat resistance, dimensional stability, and paintability, but also has excellent appearance after injection and is excellent in injection molding. By reducing the thickness, it is possible to reduce the production cost of parts and to reduce the weight of molded products, and to improve the sink mark and flow mark, so that the appearance of molded products after injection is excellent. The sagging phenomenon (heat sag) and the coefficient of linear expansion due to reduced polyolefin resin composition with improved dimensional stability of the molded article can be usefully used as a material of various automotive parts.
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] A polyolefin-based composite resin composition comprising a crystalline ethylene-propylene copolymer, at least one ethylene-α-olefin copolymer, calcium-methilicate-silicate ulastonite, a modified resin, and various additives.
    [2" claim-type="Currently amended] The ethylene-propylene copolymer according to claim 1, which contains 0.5 to 15% by weight of ethylene-propylene rubber (EPR) and has a melt index of 20 to 60 g / 10 min (230 ° C., 2.16 kg). 99 wt%) Polyolefin-based composite resin composition characterized in that it contains at least one kind at 50-95 wt%.
    [3" claim-type="Currently amended] The ethylene-propylene copolymer rubber (propylene: 20-50 wt%) having a melt index of 0.1 to 5 g / 10 minutes (230 ° C.) in each of the ethylene-α-olefin copolymers used is 5 or more. A polyolefin-based composite resin composition, characterized in that contained at 25% by weight.
    [4" claim-type="Currently amended] The ethylene-octene copolymer rubber (octene content: 5 to 30% by weight) having a melt index of 0.1 to 15 g / 10 minutes (230 ° C.) in the ethylene-α-olefin copolymer according to claim 1 A polyolefin composite resin composition, characterized in that it contains 30% by weight.
    [5" claim-type="Currently amended] The polyolefin according to claim 1, which contains 5 to 20% by weight of acicular calcium-meta-silicate based ulastonite, which is an inorganic reinforcing material having an average particle size of 5 to 25 µm and an aspect ratio of 10 to 19. System composite resin composition.
    [6" claim-type="Currently amended] The method of claim 1 wherein the modified resin is selected from ethylene-propylene rubber (EPR) or ethylene-2-hydroxyethylene methacrylate copolymer grafted with maleic anhydride (maleic anhydride) It contains 1 to 10% by weight of polyolefin composite resin composition.
    [7" claim-type="Currently amended] The process according to claim 1, wherein the processing lubricant is 0.05 to 0.5% by weight, the phenolic primary antioxidant is 0.05 to 0.5% by weight, the phosphorus or amine secondary antioxidant is 0.05 to 0.5% by weight, and the carbon black is 0.5 to 2.0% by weight. %, 0.05 to 0.5% by weight of a Halz-based UV stabilizer, 0.05 to 3% by weight of an amino silane or amino titanium coupling agent, and 0.05 to 0.1% by weight of an alkylamine antistatic agent. Composite resin composition.
    [8" claim-type="Currently amended] The method according to claim 1, wherein the viscosity of the ethylene-α-olefin copolymer rubber is adjusted to improve the paintability of the polyolefin resin composition, and thus the viscosity of the composition is changed to a modified resin and a method of protruding the rubber to the surface when the composition is injected Polyolefin resin composition characterized in that it is produced by a method.
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    同族专利:
    公开号 | 公开日
    KR100262887B1|2000-10-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-11-15|Application filed by 정몽규, 현대자동차 주식회사
    1997-11-15|Priority to KR1019970060219A
    1999-06-05|Publication of KR19990039954A
    2000-10-02|Application granted
    2000-10-02|Publication of KR100262887B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR1019970060219A|KR100262887B1|1997-11-15|1997-11-15|Composition of polyolefins polymer blend|
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