WO2002051930A1 - Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties - Google Patents

Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties Download PDF

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Publication number
WO2002051930A1
WO2002051930A1 PCT/KR2000/001520 KR0001520W WO02051930A1 WO 2002051930 A1 WO2002051930 A1 WO 2002051930A1 KR 0001520 W KR0001520 W KR 0001520W WO 02051930 A1 WO02051930 A1 WO 02051930A1
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Prior art keywords
polypropylene
resin composition
polypropylene resin
weight
mica
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PCT/KR2000/001520
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French (fr)
Inventor
Yoon-Hwan Lee
Man-Seang Her
Jong-Soo Hong
Original Assignee
Samsung General Chemicals Co., Ltd.
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Publication date
Application filed by Samsung General Chemicals Co., Ltd. filed Critical Samsung General Chemicals Co., Ltd.
Priority to CN00820094.7A priority Critical patent/CN1225498C/en
Priority to PCT/KR2000/001520 priority patent/WO2002051930A1/en
Publication of WO2002051930A1 publication Critical patent/WO2002051930A1/en

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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

Definitions

  • the present invention relates to a polypropylene resin composition having better rigidity and thermal resistance and more improved low warpage properties than prior art polypropylene resins, and more particularly, to a polypropylene resin composition which comprises a polypropylene resin, an organic silane compound, an acid-modified polypropylene polymer, and a mica and glass fiber as an inorganic filler.
  • Polypropylene resins have wide range of industrial use in automotive interior members, home electronic appliances and industrial materials since the resins exhibit excellent physical property, chemical resistance and moldability.
  • the polypropylene resin is inferior in secondary processability, especially in coating property at solid state and adhesiveness with other materials, due to the nonpolarity in the chemical structure of molecule.
  • the polypropylene resin lacks dimensional stability due to the crystalline structure and heat resistance and rigidity are inferior to other resin such as polystyrene and styrene-acrylonitrile copolymer which are competitively applied in home electronic appliances. Therefore, methods for developing polypropylene resin for use in parts of automobile or electric/electronic products by adding inorganic filler or other resins to the polypropylene resin are being proposed.
  • 174550 disclose resin composition having improves mechanical rigidity, heat resistance and coating property by blending styrene polymer and commercially used styrene butadiene block copolymer with polypropylene. These compositions, however, have improvement of mechanical properties and is not proper to use as a general purpose material because of the use of relatively expensive commercial additives.
  • Japanese Patent Publication Hei 3-126140 discloses resin composition prepared by blending nylon resin having excellent thermal resistance and glass fiber having great influence on improving rigidity and heat resistance as inorganic filler and acid-modified polypropylene with polypropylene resin.
  • Above composition uses nylon resin having lower viscosity than that of polypropylene so the matrix of the prepared resin composition is nylon resin enabling the use of the composition at the high temperature of 150-170 ° C.
  • This resin has limit in using for general purpose because of the high price of nylon resin in spite of excellent rigidity, coating property, chemical resistance and heat resistance.
  • needle type filler such as glass fiber, carbon fiber and whisker, plate type filler such as mica and talc, or globular type filler such as calcium carbonate and alumina are used as an inorganic filler to polypropylene resin in order to enhance rigidity, heat resistance and other mechanical properties.
  • the polypropylene resin filled with glass fiber are used for products requiring high rigidity and heat resistance.
  • Glass fiber has great effect on enhancing mechanical properties due to the fiber structure of higher aspect ratio than that of other inorganic filler such as globular or plate type filler.
  • the mica of plate type can be used as a filler. Since mica is relatively low in cost and has various material colors (gray, white, yellow and dark brown), it can be usefully applied to electric or electronic parts, and to automobile components without coloring.
  • the mica however, is inferior to the needle type filler in tensile impact strength, flexural modulus, Izod impact strength and heat resistance, and has low bulk density of the filler. Therefore, feeding of materials becomes difficult when producing composition with high content of fHler (for example, more than 40wt%), reducing productivity and processability.
  • the object of the invention is to solve the problems of prior art compositions as mentioned above by providing a polypropylene resin composition having excellent rigidity and heat resistance that can be applied to automobile parts and electric/electronic elements, and also filled with glass fiber and mica having low warpage(deformation) properties.
  • the polypropylene resin composition of the present invention comprises 100 parts by weight of polypropylene base composition(hereinafter referred to as a base resin composition) and 0.01-2.0 parts by weight of organic silane compounds, said base resin composition comprising 20-69% by weight of polypropylene, 1.0-30% by weight of modified polypropylene modified with unsaturated carboxylic acid or derivative thereof, 30-50% by weight of total amount of glass fiber and mica as inorganic fillers.
  • a base resin composition polypropylene base composition
  • organic silane compounds organic silane compounds
  • the polypropylene in the polypropylene resin composition of the present invention is preferably an isotactic crystalline polypropylene polymer having 5 ⁇ 70g/10 minutes(ASTM D1238, 230 ° C) of melt index(MI). hen the melt index is below 5g/10min, productivity is reduced because the moldability of parts becomes bad, and when the melt index is above 70g/10rnin, impact strength greatly decreases.
  • the modified polypropylene in the polypropylene resin composition of the present invention is the one modified with unsaturated carboxylic acid or its derivative.
  • the examples of the polypropylene are polypropylene homo-polymer, ethylene/propylene co-polymer or propylene/ ⁇ - olefin unconjugated diene compound co-polymer (for example EPDM).
  • the ⁇ -olefin may be ethylene, 1-butene, 1-heptene, 1-hexene, 4-methylpentene, or a mixture thereof.
  • the unsaturated carboxylic acid for modifying the polypropylene such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic.acid, ditraconic acid, sorbic acid or phosphorus grica acid.
  • the derivatives of unsaturated carboxylic acid may be acid anhydride, ester, amide, imide or metallic salt, and the examples are maleic acid anhydride, itaconic acid anhydride, ditraconic acid anhydride, methylacrylic acid, methylmethacrylic acid, ethylacrylic acid, butylacrylic acid, maleic acid mono ether/ester, acryl amide, maleic acid mono amide, N-butyl maleimide, sodium acrylate and sodium methacrylate, which can be used as a single compound or a mixture of two or more of compounds.
  • One method for modifying polypropylene is to dissolve polypropylene in appropriate organic solvent, and then mix with unsaturated carboxylic acid or its derivative and radical generator. Another method is to graft copolymerize the above components by using extruder.
  • the amount of unsaturated carboxylic acid or its derivative, which is used as modifying agent, in the modified polypropylene resin is preferably 0.1-10% by weight. When the amount is less than 0.1% by weight, the effect of the modified polypropylene as a compatibilizer is very little. When the amount is more than 10% by weight, lots of modifying agents remain unreacted in polypropylene and these unreacted modifying agents sublimate and remain in the air and generate a strong smell during the production of polypropylene resin composition by melt mixing with mica or glass fiber. In addition, the polypropylene resin composition obtained is colored yellowish brown dropping the value of the products.
  • the quantity of the modified polypropylene is preferably 1.0-30% by weight in the entire base resin composition.
  • the filler and polypropylene resin cannot maintain the surface adhesive strength, and cannot contribute to the improvement of physical properties of the resin composition.
  • the quantity of the modified polypropylene is more than 30% by weight, there is no more effect of improving physical properties occurred as the quantity increases.
  • the glass fiber and mica are used as an inorganic filler of the polypropylene resin composition of the present invention.
  • the average diameter may be 5-15 micrometers or preferably 9-13 micrometers, and the length is l ⁇ 16mm.
  • the average diameter of glass fiber is smaller than 5 micrometers, it is easily broken during mixing so rigidity is weakened.
  • the average diameter of glass fiber is larger than 15 micrometers, mechanical rigidity cannot be obtained and appearance becomes bad due to deteriorated deformation.
  • the length of the glass fiber is not limited to fixed length and any glass fiber which is commercially available may be used, but using chopped strand with length of l ⁇ 8mm is preferable considering the working environment of mixing process.
  • the mica of the polypropylene resin composition of the present invention is aluminosilicate containing alkali metal such as potassium, magnesium, aluminum or iron, which is generally used as filler and reinforcing agent.
  • Usable mica is white mica (muscovite), gold-color mica (phlogopite), black mica (biotite), sodium carbonate mica, silk mica, iron mica, vanagine mica or so. Any kind of mica which is commercially available can be used and the average diameter is 10 ⁇ 500micrometers, or more preferably 5O ⁇ 250rriicrometers. When the average diameter is smaller than lQmicrometers, desirable heat resistance and rigidity can not be obtained, and when the average diameter is larger than 500micrometers, the particles of mica can be seen visually, making appearance somewhat bad.
  • the appropriate quantity of inorganic filler, summing up the quantity of glass fiber and mica, is preferably 30-50% by weight in the entire base resin composition.
  • the quantity is less than 30% by weight, desired effect cannot be fully obtained.
  • the quantity is more than 50% by weight, the composition is disadvantageous in dispersability with resin and appearance.
  • the quantity of glass fiber in the entire inorganic filler is preferably not more than 45% by weight. When the content is more than 45% by weight, the appearance of molded product becomes bad and the working environment deteriorates during mixing extrusion of the materials.
  • Preferable weight ratio of glass fiber and mica is 1: 0.5 - 8 (glass fiber: mica).
  • the ratio of mica is less than 0.5, the effect of preventing warpage of the product produced from the resin composition is not obtained, and when the ratio is more than 8, desired rigidity cannot be realized due to the relatively low quantity of glass fiber.
  • the organic silane compound of the polypropylene resin composition of the present invention is not limited to the specific kind.
  • the examples are gamma- aminopropyltriethoxysilane, alpha-glycidoxypropyltrimethoxysilane, beta-(3 ,4- epoxycyclohexyl)ethyltrimethoxysilane, beta-methacryloxypropyltrimethoxysilane, alpha-aminopropyltriethoxysilane, N-beta-(aminoethyl)-alpha- aminopropyltrimethoxysilane, and N-beta-(aminoethyl)-alpha- aminopropylmethyldiethoxysilane.
  • the aminosilane compound containing 1 or 2 of amino groups is preferable.
  • the appropriate quantity of organic silane compound for improving physical properties is 0.01-2.0 parts by weight per 100 parts by weight of base resin composition, or more preferably 0.05-1.0 parts by weight.
  • Narious common additives such as reinforcing agent, filler, heat resistance stabilizer, weather resistance stabilizer, electrification protector, lubricant, slip agent, nucleating additive, flame retardant additive, pigment and dyes can be added to the polypropylene resin composition of the present invention, as long as the addition does not exhibit adverse effects to the resin composition of the present invention.
  • Specific examples are talc, carbon fiber, calcium carbonate, clay, silica, alumina, carbon black, magnesium hydride, zeolite and barium sulfate.
  • the resin composition of the present invention it is preferable to use single or two axis extruder for mixing.
  • Generally known processing conditions for producing polypropylene resin composition can be used and the components can be mixed at above melting point of polypropylene.
  • Polypropylene polypropylene homo-polymer having lOg/lOmin (230°C) of melt index
  • Inorganic filler - Glass fiber: fiber whose surface is treated with aminosilane having average diameter 1 lmicrometers and 3mm of length - Mica: brown color suzorite mica with 250 micrometers of average diameter (not surface treated, mica(l)), brown color suzorite mica of 60 micrometers of average diameter (not surface treated, mica (2))
  • Modified polypropylene polypropylene homo polymer containing more than 0.2% by weight of maleic acid anhydride and having melt index of 11 Og/1 Omin
  • Organic silane compound aminosilane compound containing one or two of amino groups
  • Polypropylene, modified polypropylene, organic silane compound and additives are dry blended with Hensel mixer at JSW TEX44 ALPHA 2-axis mixing extruder according to the components and quantities of table 1, and are introduced into a main hopper simultaneously. Mica and glass fiber are introduced by using weight type feeder during extrusion, and the resin composition is prepared. The resin composition is then blow molded by using Samsung Kloekner FCM-110 (forming capacity 1 lOtons) to produce test samples as prescribed in ASTM standard, and thermal transforming temperature, Izod impact strength, tensile strength, elongation, flexural modulus, shrinking rate and dimensional stability is measured.
  • test conditions of each samples are as follows.
  • a sheet with 2mm of thickness and 100mm of width and length are blow molded and after maintaining at room temperature and 50% of moisture for some time, the sizes in the direction of flow and in the perpendicular direction of flow are measured.
  • Example, CE Comparative Example organic silane compound (1): alpha-aminopropyltrimethoxysilane organic silane compound (2): beta-methocryloxypropyltrimethoxysilane organic silane compound (3): gamma-aminopropyltriethoxysilane
  • the compositions of examples 1 to 3 have high thermal transforming temperature, large tensile strength, curvature strength and impact strength, small shrinking rate, and good dimensional stability compared with the compositions of comparative examples 1 to 3.
  • the composition of comparative example 4 is inferior to other example in dimensional stability.
  • the polypropylene resin composition prepared according to the present invention has favorable mechanical properties such as good rigidity and heat resistance and also exhibits low warpage and deformation. Therefore the polypropylene resin composition of the present invention is appropriate to use in rotating members such as fan which induces warpage in the final molded product and require high dimensional stability.

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Abstract

The present invention provides a low flexible polypropylene resin composition, which comprises a polypropylene resin composition comprising 20∩69 percent by weight of a polypropylene, 1.0∩30 percent by weight of a modified polypropylene modified by grafting unsaturated carboxylic acid or derivatives thereof and 30∩50 percent by weight of a glass fiber and mica as an inorganic fillers and 0.01∩2.0 percent by weight of a organicsilane compounds. The low flexible polypropylene resin composition of this invention has excellent heat resistance and stiffness.

Description

POLYPROPYLENE RESIN COMPOSITION HAVING THERMAL RESISTANCE, HIGH RIGIDITY AND LOW WARPAGE PROPERTIES
TECHNICAL FIELD
The present invention relates to a polypropylene resin composition having better rigidity and thermal resistance and more improved low warpage properties than prior art polypropylene resins, and more particularly, to a polypropylene resin composition which comprises a polypropylene resin, an organic silane compound, an acid-modified polypropylene polymer, and a mica and glass fiber as an inorganic filler.
BACKGROUND ART
Polypropylene resins have wide range of industrial use in automotive interior members, home electronic appliances and industrial materials since the resins exhibit excellent physical property, chemical resistance and moldability. The polypropylene resin, however, is inferior in secondary processability, especially in coating property at solid state and adhesiveness with other materials, due to the nonpolarity in the chemical structure of molecule. Also, the polypropylene resin lacks dimensional stability due to the crystalline structure and heat resistance and rigidity are inferior to other resin such as polystyrene and styrene-acrylonitrile copolymer which are competitively applied in home electronic appliances. Therefore, methods for developing polypropylene resin for use in parts of automobile or electric/electronic products by adding inorganic filler or other resins to the polypropylene resin are being proposed.
Regarding these resins, Japanese laid open patent publication Sho 64-87645 and Sho 1-
174550 disclose resin composition having improves mechanical rigidity, heat resistance and coating property by blending styrene polymer and commercially used styrene butadiene block copolymer with polypropylene. These compositions, however, have improvement of mechanical properties and is not proper to use as a general purpose material because of the use of relatively expensive commercial additives.
Japanese Patent Publication Hei 3-126140 discloses resin composition prepared by blending nylon resin having excellent thermal resistance and glass fiber having great influence on improving rigidity and heat resistance as inorganic filler and acid-modified polypropylene with polypropylene resin. Above composition uses nylon resin having lower viscosity than that of polypropylene so the matrix of the prepared resin composition is nylon resin enabling the use of the composition at the high temperature of 150-170 °C. This resin, however, has limit in using for general purpose because of the high price of nylon resin in spite of excellent rigidity, coating property, chemical resistance and heat resistance.
On the other hand, needle type filler such as glass fiber, carbon fiber and whisker, plate type filler such as mica and talc, or globular type filler such as calcium carbonate and alumina are used as an inorganic filler to polypropylene resin in order to enhance rigidity, heat resistance and other mechanical properties. Especially, the polypropylene resin filled with glass fiber are used for products requiring high rigidity and heat resistance.
Glass fiber has great effect on enhancing mechanical properties due to the fiber structure of higher aspect ratio than that of other inorganic filler such as globular or plate type filler.
Generally, as the amount of filling glass fiber in polypropylene resin increases, rigidity and heat resistance improves, but the high degree of orientation causes lots of difference between shrinking rates of the molded product in the direction of flow and in the perpendicular direction of flow. This difference cause warpage in the final product, makes it difficult to use the resin in rotating members such as a fan which require high dimensional stability, and makes the appearance bad. Moreover, large warpage and deformation can occur in large scale products.
In order to minimize warpage and make products with excellent rigidity and good appearance, the mica of plate type can be used as a filler. Since mica is relatively low in cost and has various material colors (gray, white, yellow and dark brown), it can be usefully applied to electric or electronic parts, and to automobile components without coloring. The mica, however, is inferior to the needle type filler in tensile impact strength, flexural modulus, Izod impact strength and heat resistance, and has low bulk density of the filler. Therefore, feeding of materials becomes difficult when producing composition with high content of fHler (for example, more than 40wt%), reducing productivity and processability.
DISCLOSURE OF INVENTION
The object of the invention is to solve the problems of prior art compositions as mentioned above by providing a polypropylene resin composition having excellent rigidity and heat resistance that can be applied to automobile parts and electric/electronic elements, and also filled with glass fiber and mica having low warpage(deformation) properties.
The polypropylene resin composition of the present invention comprises 100 parts by weight of polypropylene base composition(hereinafter referred to as a base resin composition) and 0.01-2.0 parts by weight of organic silane compounds, said base resin composition comprising 20-69% by weight of polypropylene, 1.0-30% by weight of modified polypropylene modified with unsaturated carboxylic acid or derivative thereof, 30-50% by weight of total amount of glass fiber and mica as inorganic fillers.
The polypropylene in the polypropylene resin composition of the present invention is preferably an isotactic crystalline polypropylene polymer having 5~70g/10 minutes(ASTM D1238, 230 °C) of melt index(MI). hen the melt index is below 5g/10min, productivity is reduced because the moldability of parts becomes bad, and when the melt index is above 70g/10rnin, impact strength greatly decreases.
The modified polypropylene in the polypropylene resin composition of the present invention is the one modified with unsaturated carboxylic acid or its derivative. The examples of the polypropylene are polypropylene homo-polymer, ethylene/propylene co-polymer or propylene/α- olefin unconjugated diene compound co-polymer (for example EPDM). The α-olefin may be ethylene, 1-butene, 1-heptene, 1-hexene, 4-methylpentene, or a mixture thereof.
The unsaturated carboxylic acid for modifying the polypropylene, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic.acid, ditraconic acid, sorbic acid or phosphorus grica acid. And the derivatives of unsaturated carboxylic acid may be acid anhydride, ester, amide, imide or metallic salt, and the examples are maleic acid anhydride, itaconic acid anhydride, ditraconic acid anhydride, methylacrylic acid, methylmethacrylic acid, ethylacrylic acid, butylacrylic acid, maleic acid mono ether/ester, acryl amide, maleic acid mono amide, N-butyl maleimide, sodium acrylate and sodium methacrylate, which can be used as a single compound or a mixture of two or more of compounds.
One method for modifying polypropylene is to dissolve polypropylene in appropriate organic solvent, and then mix with unsaturated carboxylic acid or its derivative and radical generator. Another method is to graft copolymerize the above components by using extruder.
The amount of unsaturated carboxylic acid or its derivative, which is used as modifying agent, in the modified polypropylene resin is preferably 0.1-10% by weight. When the amount is less than 0.1% by weight, the effect of the modified polypropylene as a compatibilizer is very little. When the amount is more than 10% by weight, lots of modifying agents remain unreacted in polypropylene and these unreacted modifying agents sublimate and remain in the air and generate a strong smell during the production of polypropylene resin composition by melt mixing with mica or glass fiber. In addition, the polypropylene resin composition obtained is colored yellowish brown dropping the value of the products.
The quantity of the modified polypropylene is preferably 1.0-30% by weight in the entire base resin composition. When the quantity of the modified polypropylene is less than 1.0% by weight, the filler and polypropylene resin cannot maintain the surface adhesive strength, and cannot contribute to the improvement of physical properties of the resin composition. When the quantity of the modified polypropylene is more than 30% by weight, there is no more effect of improving physical properties occurred as the quantity increases.
The glass fiber and mica are used as an inorganic filler of the polypropylene resin composition of the present invention. In the case of glass fiber, the average diameter may be 5-15 micrometers or preferably 9-13 micrometers, and the length is l~16mm. When the average diameter of glass fiber is smaller than 5 micrometers, it is easily broken during mixing so rigidity is weakened. When the average diameter of glass fiber is larger than 15 micrometers, mechanical rigidity cannot be obtained and appearance becomes bad due to deteriorated deformation. In the present invention, the length of the glass fiber is not limited to fixed length and any glass fiber which is commercially available may be used, but using chopped strand with length of l~8mm is preferable considering the working environment of mixing process.
The mica of the polypropylene resin composition of the present invention is aluminosilicate containing alkali metal such as potassium, magnesium, aluminum or iron, which is generally used as filler and reinforcing agent. Usable mica is white mica (muscovite), gold-color mica (phlogopite), black mica (biotite), sodium carbonate mica, silk mica, iron mica, vanagine mica or so. Any kind of mica which is commercially available can be used and the average diameter is 10~500micrometers, or more preferably 5O~250rriicrometers. When the average diameter is smaller than lQmicrometers, desirable heat resistance and rigidity can not be obtained, and when the average diameter is larger than 500micrometers, the particles of mica can be seen visually, making appearance somewhat bad.
The appropriate quantity of inorganic filler, summing up the quantity of glass fiber and mica, is preferably 30-50% by weight in the entire base resin composition. When the quantity is less than 30% by weight, desired effect cannot be fully obtained. When the quantity is more than 50% by weight, the composition is disadvantageous in dispersability with resin and appearance. And the quantity of glass fiber in the entire inorganic filler is preferably not more than 45% by weight. When the content is more than 45% by weight, the appearance of molded product becomes bad and the working environment deteriorates during mixing extrusion of the materials.
Preferable weight ratio of glass fiber and mica is 1: 0.5 - 8 (glass fiber: mica). When the ratio of mica is less than 0.5, the effect of preventing warpage of the product produced from the resin composition is not obtained, and when the ratio is more than 8, desired rigidity cannot be realized due to the relatively low quantity of glass fiber.
The organic silane compound of the polypropylene resin composition of the present invention is not limited to the specific kind. The examples are gamma- aminopropyltriethoxysilane, alpha-glycidoxypropyltrimethoxysilane, beta-(3 ,4- epoxycyclohexyl)ethyltrimethoxysilane, beta-methacryloxypropyltrimethoxysilane, alpha-aminopropyltriethoxysilane, N-beta-(aminoethyl)-alpha- aminopropyltrimethoxysilane, and N-beta-(aminoethyl)-alpha- aminopropylmethyldiethoxysilane. Especially, in the present invention, the aminosilane compound containing 1 or 2 of amino groups is preferable.
The appropriate quantity of organic silane compound for improving physical properties is 0.01-2.0 parts by weight per 100 parts by weight of base resin composition, or more preferably 0.05-1.0 parts by weight. Narious common additives such as reinforcing agent, filler, heat resistance stabilizer, weather resistance stabilizer, electrification protector, lubricant, slip agent, nucleating additive, flame retardant additive, pigment and dyes can be added to the polypropylene resin composition of the present invention, as long as the addition does not exhibit adverse effects to the resin composition of the present invention. Specific examples are talc, carbon fiber, calcium carbonate, clay, silica, alumina, carbon black, magnesium hydride, zeolite and barium sulfate.
In producing the resin composition of the present invention, it is preferable to use single or two axis extruder for mixing. Generally known processing conditions for producing polypropylene resin composition can be used and the components can be mixed at above melting point of polypropylene. However, it is essential to insert glass fiber and mica simultaneously or separately during extrusion in order to sufficiently maintain the shape of filler.
The present invention will now be described in more detail with reference to the examples and comparative examples. The examples, however, are for the purpose of illustration only and are not intended to limit the scope of protection of the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
The quantity of each component and physical properties of compositions in examples 1 to 3 are shown in table 1.
The components used in examples 1 to 3 and comparative examples 1 to 4 are as follows:
1) Polypropylene: polypropylene homo-polymer having lOg/lOmin (230°C) of melt index
2) Inorganic filler: - Glass fiber: fiber whose surface is treated with aminosilane having average diameter 1 lmicrometers and 3mm of length - Mica: brown color suzorite mica with 250 micrometers of average diameter (not surface treated, mica(l)), brown color suzorite mica of 60 micrometers of average diameter (not surface treated, mica (2))
3) Modified polypropylene: polypropylene homo polymer containing more than 0.2% by weight of maleic acid anhydride and having melt index of 11 Og/1 Omin
4) Organic silane compound: aminosilane compound containing one or two of amino groups
Polypropylene, modified polypropylene, organic silane compound and additives are dry blended with Hensel mixer at JSW TEX44 ALPHA 2-axis mixing extruder according to the components and quantities of table 1, and are introduced into a main hopper simultaneously. Mica and glass fiber are introduced by using weight type feeder during extrusion, and the resin composition is prepared. The resin composition is then blow molded by using Samsung Kloekner FCM-110 (forming capacity 1 lOtons) to produce test samples as prescribed in ASTM standard, and thermal transforming temperature, Izod impact strength, tensile strength, elongation, flexural modulus, shrinking rate and dimensional stability is measured.
The test conditions of each samples are as follows.
1) Thermal transformation temperature Measured at low load(4.6kg) based on D648.
2) Izod impact strength
Measured by N notched specimen at room temperature based on D256
3) Tensile strength and elongation
Measured at room temperature based on D638 4) Flexural modulus
Measured at room temperature based on D790
5) Shrinking rate (warpage/degree of deformation) A sheet with 2mm of thickness and 100mm of width and length are blow molded and after maintaining at room temperature and 50% of moisture for some time, the sizes in the direction of flow and in the perpendicular direction of flow are measured.
Table 1
Figure imgf000010_0001
Note:
E: Example, CE: Comparative Example organic silane compound (1): alpha-aminopropyltrimethoxysilane organic silane compound (2): beta-methocryloxypropyltrimethoxysilane organic silane compound (3): gamma-aminopropyltriethoxysilane
(©: no warpage, O: little warpage, : large warpage due to big difference of shrinking rate in the longitudinal and transverse direction)
As can be seen from table 1, the compositions of examples 1 to 3 have high thermal transforming temperature, large tensile strength, curvature strength and impact strength, small shrinking rate, and good dimensional stability compared with the compositions of comparative examples 1 to 3. The composition of comparative example 4 is inferior to other example in dimensional stability.
The polypropylene resin composition prepared according to the present invention has favorable mechanical properties such as good rigidity and heat resistance and also exhibits low warpage and deformation. Therefore the polypropylene resin composition of the present invention is appropriate to use in rotating members such as fan which induces warpage in the final molded product and require high dimensional stability.

Claims

CLAIMSWhat is claimed is:
1. A polypropylene resin composition which comprises 100 parts by weight of polypropylene base composition and 0.01-2.0 parts by weight of organic silane compound, said polypropylene base composition comprising 20-69% by weight of polypropylene, 1.0-30% by weight of modified polypropylene modified with unsaturated carboxylic acid or derivative thereof, 30-50% by weight of glass fiber and mica as inorganic fillers.
2. The polypropylene resin composition according to claim 1, wherein said polypropylene is isotatic crystalline propylene homo polymer having 5-70g/10min (230 °C) of melt index.
3. The polypropylene resin composition according to claim 1, wherein said modified polypropylene is a polypropylene homo polymer, ethylene/propylene copolymer or propylene/alpha-olefin unconjugated diene compound copolymer modified with unsaturated carboxylic acid or derivative thereof.
4. The polypropylene resin composition according to claim 3, wherein said unsaturated carboxylic acid is two or more selected from the group consisting of maleic acid anhydride, itaconic acid anhydride, ditraconic acid anhydride, methylacrylic acid, methylmethacrylic acid, ethylacrylic acid, butylacrylic acid, maleic acid monoester, acryl amide, maleic acid mono amide, N-butyl maleimide, sodium acrylate and sodium methacrylate.
5. The polypropylene resin composition according to claim 3, wherein the quantity of said unsaturated carboxylic acid or derivative thereof added to modified polypropylene is 0.1-10 % by weight.
6. The polypropylene resin composition according to claim 1, wherein said organic silane compound is amino silane compound containing one or two of amino groups.
7. The polypropylene resin composition according to claim 1, wherein the weight ratio of said glass fiber and mica is 1: 0.5 ~ 8(glass fiber: mica).
8. The polypropylene resin composition according to claim 1, wherein said glass fiber has average diameter of 5~15micrometers and length of 1-16mm, and the mica has average diameter of 10~500micrometers.
PCT/KR2000/001520 2000-12-22 2000-12-22 Polypropylene resin composition having thermal resistance, high rigidity and low warpage properties WO2002051930A1 (en)

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US20150218353A1 (en) * 2012-05-22 2015-08-06 Borouge Compounding Shanghai Co., Ltd. a corporation Moulded article with low warpage
JP2016503089A (en) * 2012-12-24 2016-02-01 エルジー・ケム・リミテッド Olefin resin composition
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US20150218353A1 (en) * 2012-05-22 2015-08-06 Borouge Compounding Shanghai Co., Ltd. a corporation Moulded article with low warpage
JP2016503089A (en) * 2012-12-24 2016-02-01 エルジー・ケム・リミテッド Olefin resin composition
WO2018056136A1 (en) * 2016-09-20 2018-03-29 株式会社Ｔｂｍ Sheet and packaging container
CN110483889A (en) * 2019-08-16 2019-11-22 上海交通大学 A kind of rotation molding polypropylene alloy material and preparation method thereof
CN111978631A (en) * 2020-07-27 2020-11-24 青岛中新华美塑料有限公司 Polypropylene warm edge spacing strip and preparation method thereof
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CN114213748A (en) * 2021-11-16 2022-03-22 上海金发科技发展有限公司 Mica filled polypropylene composite material and preparation method and application thereof
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