KR101447352B1

KR101447352B1 - Polypropylene Resin Composition

Info

Publication number: KR101447352B1
Application number: KR20130008860A
Authority: KR
Inventors: 김성세; 이윤환; 임재곤; 홍종수; 최창현
Original assignee: 삼성토탈 주식회사
Priority date: 2013-01-25
Filing date: 2013-01-25
Publication date: 2014-10-06
Also published as: KR20140111058A

Abstract

The present invention relates to high crystalline polypropylene; Inorganic filler; And a compatibilizer, wherein the inorganic filler comprises glass fiber and a plate-like mica, a plate-like talc or a mixture thereof, and the compatibilizer comprises a modified polypropylene and an organosilane compound.

Description

Polypropylene Resin Composition < RTI ID = 0.0 >

The present invention relates to a polypropylene resin composition, and more particularly, to a polypropylene resin composition improved in physical properties such as rigidity and high temperature low warpability by adding an inorganic filler such as glass fiber and mica to a polypropylene resin, It is about.

The polypropylene resin is excellent in mechanical properties, chemical resistance and moldability, and is widely used for automobile interior parts, home appliance parts, and industrial materials. However, since polypropylene exhibits non-polarity in terms of chemical structure, secondary workability, in particular, paintability and adhesiveness to other materials are poor, and the dimensional stability is insufficient due to the crystalline structure, and stiffness and heat resistance are also applied competitively Polystyrene, styrene-acrylonitrile copolymer and the like. For this reason, development of a material in which an inorganic filler or another resin is blended in a polypropylene resin is proposed as a component for automobiles and electric and electronic products.

In this connection, Japanese Patent Publication No. 64-87645 and Japanese Patent Publication No. 1-174550 disclose a composition in which a styrene polymer and a styrene butadiene block copolymer as a compatibilizer are blended in polypropylene to improve mechanical strength, heat resistance and paintability However, the degree of improvement of mechanical properties is very low, and a comparatively expensive compatibilizer is not suitable for application as a general purpose material.

Japanese Patent Laid-Open Publication No. 3-126740 discloses a resin composition blended with a polypropylene resin, a modified polypropylene resin, a nylon resin, an inorganic filler and / or a fibrous reinforcement. However, since the matrix of the resin composition is made into a nylon resin Which has limitations as a general-purpose material in terms of cost.

Korean Patent Laid-Open Publication No. 10-2003-002747 discloses a resin composition blended with a polypropylene resin, a high-shear-strength inorganic filler, wollastonite, and a compatibilizer. However, when the content of the filler is increased, .

SUMMARY OF THE INVENTION An object of the present invention is to provide a polypropylene resin composition which is improved in mechanical / thermal properties and which can obtain a good product that minimizes occurrence of warpage at room temperature as well as at high temperature.

In order to achieve the above-mentioned object, the present invention provides a method for producing an inorganic filler comprising a high crystalline polypropylene, an inorganic filler and a compatibilizer, wherein the inorganic filler comprises glass fiber and a plate-like mica, a plate-shaped talc or a mixture thereof, There is provided a polypropylene resin composition comprising a modified polypropylene and an organosilane compound.

According to the present invention, inorganic fillers and compatibilizers can be added to the polypropylene resin to improve physical properties. In particular, mechanical / thermal properties can be improved by applying glass fibers, which are high-shear-strength inorganic fillers, to polypropylene resins as inorganic fillers. In addition, the warpage phenomenon occurs in the final molded product due to the difference of the flow direction caused by the high orientation of the glass fiber and the shrinkage ratio in the direction perpendicular to the flow direction. The mica, talc, It is possible to provide a polypropylene resin composition capable of obtaining a good product with minimal occurrence of warpage.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a polypropylene resin composition comprising a highly crystalline polypropylene resin, an inorganic filler and a compatibilizer, wherein the inorganic filler comprises glass fiber and a plate-like mica, a plate-shaped talc or a mixture thereof, wherein the compatibilizer comprises a modified polypropylene and an organosilane compound To a polypropylene resin composition.

The highly crystalline polypropylene resin of the present invention is preferably an isotactic polypropylene polymer having a melt index (MI) of 1 to 70 g / 10 min (measured by ASTM D 1238 at 230 캜) and a crystallinity. When the melt index is less than 1 g / 10 min, the moldability of the component is not good and the productivity is lowered. On the other hand, when the melt index exceeds 70 g / 10 min, the impact strength sharply drops. The highly crystalline polypropylene is preferably used in an amount of 10.0 to 57.0 parts by weight based on 100 parts by weight of the polypropylene resin composition.

The inorganic filler of the present invention includes glass fiber and a plate-like mica, a plate-shaped talc, or a mixture thereof.

The glass fibers are preferably chopped strands having an average particle diameter of 5 to 15 mu m and a length of 1 to 16 mm in consideration of the kneading operation. When the average particle diameter is less than 5 탆, most of the particles are broken during mixing, and the stiffness developing effect becomes insufficient. When the average particle diameter is more than 15 탆, the molded article is deteriorated and the appearance is poor.

The glass fiber is preferably used in an amount of 10.0 to 30.0 parts by weight based on 100 parts by weight of the entire polypropylene resin composition. When the glass fiber content is less than 10.0 parts by weight, the effect of stiffness is insufficient. When the glass fiber content is more than 30.0 parts by weight, a warp phenomenon is caused and the appearance is not good.

It is preferable that the plate-like mica has an average particle diameter of 10 to 50 mu m and a maximum particle diameter of 100 mu m. If it is larger than the maximum value, the mica particles are observed with the naked eye, resulting in poor appearance and deterioration of physical properties. The mica is preferably used in an amount of 40.0 to 800.0 parts by weight with respect to 100 parts by weight of the glass fiber in order to suitably prevent warpage caused by the glass fiber. When the mica content is less than 40.0 parts by weight, If it exceeds 800.0 parts by weight, the relative content of the glass fiber becomes low, and the stiffness to be obtained by the resin composition becomes impossible, and the impact strength also sharply decreases.

The plate-like talc preferably has an average particle diameter of 3 to 6 mu m and a maximum particle diameter of 100 mu m. If it is larger than the maximum value, the talc particles are observed with the naked eye and the appearance is poor, and the kneading property and physical properties are deteriorated. The talc is preferably used in an amount of 40.0 to 800.0 parts by weight based on 100 parts by weight of the glass fiber in order to suitably prevent warpage caused by the glass fiber like the mica. When the talc content is less than 40.0 parts by weight, If it exceeds 800.0 parts by weight, the relative content of the glass fiber becomes low, and the stiffness to be obtained by the resin composition becomes impossible, and the impact strength also sharply decreases.

The present invention includes a compatibilizer for improving the kneadability of a polypropylene resin and an inorganic filler, and more specifically, a modified polypropylene and an organosilane compound are used. The compatibilizing agent is preferably used in an amount of 1.0 to 32.0 parts by weight based on 100 parts by weight of the total polypropylene resin composition, and 1.0 to 30.0 parts by weight of the modified polypropylene and 0.01 to 2.0 parts by weight of the organosilane compound are particularly preferably used Do. The modified polypropylene is obtained by modifying polypropylene with an unsaturated carboxylic acid or a derivative thereof, and its content is preferably 1.0 to 30.0 parts by weight. When the content of the modified polypropylene is less than 1.0 part by weight, the interfacial adhesion strength between the inorganic filler and the polypropylene resin can not be sufficiently maintained, and the physical properties are not improved. When the amount exceeds 30.0 parts by weight,

Examples of the unsaturated carboxylic acid for modifying the polypropylene include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, ditralic acid, sorbic acid and diglycidyl acid. Examples of the unsaturated carboxylic acid include acid anhydrides, esters, Amides, imides, metal salts and the like, and examples thereof include maleic anhydride, itaconic anhydride, anhydrodithioconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, maleic monoether / ester, Maleic acid monoamide, N-butyl maleimide, sodium acrylate, sodium methacrylate and the like. When the polypropylene is modified, the above-mentioned materials may be used alone or in admixture of two or more. The addition amount thereof is preferably 0.01 to 10 parts by weight based on the weight of the modified polypropylene. When the amount is less than 0.01 part by weight, the rigidity and heat resistance are poor. When the amount is more than 10 parts by weight, the impact strength is decreased and the cost is increased. In addition, the method of denaturation is not particularly limited, and a person skilled in the art can easily carry out the method using a conventional method known in the art.

The organosilane compound is not particularly limited and includes, for example, gamma-aminopropyltriethoxysilane, alpha-glycidoxypropyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxy (Aminoethyl) -alpha-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -alpha-alpha-aminopropyltrimethoxysilane, -Aminopropylmethyldiethoxysilane, and the like. Particularly, in the present invention, an aminosilane-based compound containing one or two amino groups is preferable. The content of the organosilane compound is 0.01 to 2.0 parts by weight, more preferably 0.05 to 1.0 part by weight. If it is out of the above range, the effect of increasing the physical properties can not be expected.

The present invention preferably further comprises a polyamide copolymer. The polyamide copolymer is preferably a polymer comprising an aromatic system, caprolactam system, and aliphatic monomer, and more preferably, a polyamide polymer comprising a caprolactam monomer having a low viscosity. When the viscosity is not sufficiently low, the dispersion of the polyamide copolymer in the polypropylene matrix is not uniform and the wetting phenomenon on the interface is not good and the physical properties are deteriorated. In addition, the polyamide copolymer containing monomers other than caprolactam- It is difficult to adjust the processing temperature during production, resulting in deterioration of productivity or decomposition of the constituents of the resin composition. The polyamide copolymer is preferably used in an amount of 1.0 to 49.0 parts by weight based on 100 parts by weight of the entire polypropylene resin composition. When the polyamide content exceeds 49.0 parts by weight, the matrix of the resin composition becomes polyamide, which has a cost limit.

The polypropylene resin composition of the present invention may contain various conventional additives such as a reinforcing material, a filler, a heat stabilizer, a weather stabilizer, an antistatic agent, a lubricant, a slip agent, a nucleating agent, a flame retardant, a pigment, a dye, Specific examples thereof include talc, carbon fiber, calcium carbonate, clay, silica, alumina, carbon black, magnesium hydroxide, zeolite, barium sulfate and the like.

As a method for producing the polypropylene resin composition of the present invention, kneading using a twin-screw extruder is preferred, and blending at a polypropylene melting point or higher can be performed using processing conditions for producing a commonly known polypropylene resin composition. However, in order to maintain a sufficient shape of the glass fiber in the inorganic filler, it is necessary to insert the side face of the glass fiber in the middle of the extruder.

The present invention can be more specifically understood by the following examples, and the following examples are only illustrative of the present invention and are not intended to limit the scope of protection of the present invention.

Example 1 to 4 and Comparative Example 1-3

The polypropylene, the polyamide, the mica, the talc, the modified polypropylene, the organosilane compound and the additive were dry-blended in a Henschel mixer at the components and compounding ratios shown in Table 1, And the glass fibers were fed by side feeding in the extruder and melt kneaded together in the extruder to prepare a resin composition.

Property measurement

The polypropylene resin compositions obtained in the above Examples and Comparative Examples were extruded with a TOYO-180T TOYO-180T (mold clamping force 180 ton) to prepare specimens determined in accordance with ASTM standards, and tensile strength, elongation, flexural modulus, impact strength, And dimensional stability were measured.

Test conditions for each test property are as follows.

1) Tensile strength and elongation: Measured at room temperature by the method of ASTM D 638.

2) Flexural modulus: Measured at room temperature by the method of ASTM D 790.

3) Impact strength: measured at room temperature by the method of ASTM D 256.

4) Heat distortion temperature: Measured at room temperature by the method of ASTM D 648.

5) Shrinkage: Measured at room temperature by the method of ASTM D 955.

6) Dimensional stability: It was measured as the sum of distortion after standing at room temperature for 48 hours.

7) High-temperature dimensional stability: The strain was measured by the sum of deformation after standing at 140 ° C for 1 hour.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polypropylene 56.5 46.5 36.5 56.5 56.5 59.5 57 Polyamide - 10 10 - - - - Glass fiber 25 25 25 25 40 25 25 Mica 10 - 10 - - - - Talc (Talc) 5 15 15 15 - 15 15 Modified polypropylene 3 3 3 3 3 - 3 Organosilane compound 0.5 0.5 0.5 0.5 0.5 0.5 - Measure
result The tensile strength
(Yield, kg / cm2) 600 710 650 670 1,100 600 580 Elongation (%) <10 <10 <10 <10 <10 <10 <10 Flexural modulus
(kg / cm2) 63,600 61,000 62,300 65,000 62,000 61,000 59,000 Impact strength
(kg.cm/cm) 10.6 8.2 9.0 8.7 15.0 7.4 6.0 Heat deformation temperature (캜) 160 160 160 160 163 160 160 Shrinkage (MD / TD, 1 / 1,000mm) 4.7 / 3.9 4.3 / 4.2 4.6 / 4.0 4.6 / 3.8 4.8 / 4.0 4.7 / 3.9 5.4 / 3.5 Dimensional stability
(Low bending property) ◎ ○ ◎ ○ × ○ × High temperature stability ◎ ○ ◎ ○ × ○ ×

(Dimensional stability:?: No warping,?: Almost no warping, X: large difference in shrinkage ratio in the direction of flow and perpendicular to the flow,

The components used in Examples 1 to 4 and Comparative Examples 1 to 3 in Table 1 are as follows.

1) Polypropylene: Highly crystalline polypropylene, Samsung Total, Melt Index (MI): 1 to 70 g / 10 min

2) Polyamide: Caprolactam-based polyamide, Kolon

3) inorganic filler

- Glass fiber: Aminosilane surface treated glass fiber, NEG INC. Product, particle size 9-13 탆, length 3.0-4.5 mm

- Mica: Pale brown Muscovite mica, manufactured by Amitech, particle size 10 to 50 탆

- talc: plate-shaped talc, manufactured by Kotetsa, particle size 3 to 5 탆

4) Modified polypropylene: A polypropylene homopolymer containing reacted maleic anhydride in an amount of at least 0.2 wt% based on the weight of the polypropylene and having a melt index of 120 g / 10 min,

5) Organic silane compound: Liquid gamma-aminopropyltriethoxysilane, OSI SPECIALTIES, INC. product

Claims

Wherein the inorganic filler comprises a glass fiber and a sheet-like mica, a plate-shaped talc or a mixture thereof, wherein the compatibilizer is a modified polypropylene and an organic silane Wherein the polypropylene resin composition is a polypropylene resin composition.

The high crystalline polypropylene resin according to claim 1, wherein the highly crystalline polypropylene resin is an isotactic polypropylene polymer having a melt index (MI) of 1 to 70 g / 10 min (ASTM D 1238, measured at 230 캜) By weight of the polypropylene resin composition.

2. The polypropylene resin composition according to claim 1, wherein the glass fiber is a chopped strand having an average particle diameter of 5 to 15 mu m and a length of 1 to 16 mm and a content of 10 to 30 weight% Lt; RTI ID = 0.0 > polypropylene < / RTI >

The polypropylene resin composition according to claim 1, wherein the plate-like mica has an average particle diameter of 10 to 50 μm and a maximum particle diameter of 100 μm, and the content thereof is 40 to 800 parts by weight per 100 parts by weight of the glass fiber.

The polypropylene resin composition according to claim 1, wherein the tabular talc has an average particle size of 3 to 6 탆 and a maximum particle size of 100 탆, and the content thereof is 40 to 800 parts by weight per 100 parts by weight of the glass fiber.

The polypropylene resin composition according to claim 1, wherein the compatibilizer contains 1.0 to 30.0 parts by weight of modified polypropylene and 0.01 to 2.0 parts by weight of an organosilane compound based on 100 parts by weight of the polypropylene resin composition.

The polypropylene resin composition according to claim 1, wherein the modified polypropylene is obtained by modifying polypropylene with an unsaturated carboxylic acid or a derivative thereof.

The composition according to claim 7, wherein the unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, Wherein the polypropylene resin composition is selected from the group consisting of an ester, an amide, an imide, and a metal salt.

The method of claim 1, wherein the organosilane compound is selected from the group consisting of gamma-aminopropyltriethoxysilane, alpha-glycidoxypropyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Alpha -aminopropyltrimethoxysilane, alpha-aminopropyltriethoxysilane, N-beta- (aminoethyl) -alpha-aminopropyltrimethoxysilane, and N-beta- (aminoethyl) Methyldiethoxysilane, and polypropylene resin composition.

delete

The polypropylene resin composition according to claim 1, wherein the polyamide copolymer is a polyamide polymer comprising a low viscosity caprolactam monomer.

The polypropylene resin composition according to claim 1, wherein the content of the polyamide copolymer is 1.0 to 49.0 parts by weight based on 100 parts by weight of the polypropylene resin composition.

The polypropylene resin composition according to claim 1, further comprising at least one member selected from the group consisting of a reinforcing material, a filler, a heat stabilizer, a weather stabilizer, an antistatic agent, a lubricant, a slip agent, a nucleating agent, a flame retardant, Resin composition.