KR101038629B1 - Functional polypropylene resin composition with odor removal and surface damage resistance - Google Patents

Abstract

The present invention relates to a functional polypropylene resin composition with improved odor removal and surface damage resistance, comprising: (A) 40 to 92 parts by weight of a high crystalline polypropylene resin; (B) 3 to 20 parts by weight of the thermoplastic rubber; (C) 3 to 25 parts by weight of the plate-shaped inorganic filler is coated on the surface of calcium carbonate; (D) 2 to 10 parts by weight of the high density polyethylene polymer; And (E) provides a polypropylene resin composition consisting of 0.1 to 5 parts by weight of a polymer additive for the surface modifier, excellent in odor removal effect and surface damage resistance, and excellent physical properties such as impact resistance, rigidity and fluidity It is possible to reduce the weight.

Polypropylene resin, odor removal, surface damage resistance, impact resistance, rigidity, light weight

Description

FUNCTIONAL POLYPROPYLENE RESIN COMPOSITE WITH IMPROVED ODOR CONTROL PROPERTIES AND SCRATCH RESISTANCE}

The present invention relates to a functional polypropylene resin composition having improved odor removal and surface damage resistance. More particularly, the present invention relates to an inorganic filler modified with a porous material and added to a polypropylene resin to remove odor and increase odor using an expanded specific surface area. The present invention relates to a functional polypropylene resin composition having improved surface damage.

In general, the polypropylene resin composition is known to be superior in chemical resistance, moldability, and economics to other materials, and the mechanical properties can be freely changed by adding various modifiers of rubbers and inorganics. Its use is expanding to special parts such as home appliances.

Furthermore, in addition to the conventional advantages of the above polypropylene according to the intended use, emotional quality such as odor and appearance are also considered as important factors for evaluating the quality of the polypropylene product. Therefore, there is a need for a polypropylene resin composition that can meet the newly required emotional quality while maintaining the conventional quality level.

 Currently known methods for removing or controlling the odor of polypropylene resin compositions include adsorbing odor compounds using porous materials such as silica, zeolite, calcium oxide, and charcoal, and injecting water, nitrogen, carbon dioxide, etc. Release and removal are mainly used.

In general, the method of adsorbing odorous compounds is mainly used, which is 3 to 5% by weight of porous adsorbent, and the types and amount of adsorption that can adsorb according to the size and specific surface area of the cavity are limited. Subsequently, the odor removal effect is insignificant and the compatibility with polypropylene resin is low, so that mechanical strength such as stiffness and impact resistance is remarkably lowered, so that the amount of the porous adsorbent added must be limited to within 5%.

On the other hand, conventional techniques known to improve the degree of scratching, that is, the surface damage resistance of the polypropylene resin composition, a method of improving the surface hardness of the resin composition, a method of increasing the compatibility with the inorganic filler, the lubricity of the surface of the molded article Improvement methods are generally used.

The method of improving the surface hardness is performed by using a propylene polymer in which the Pentad Isotactic Index (Pentad II) is mixed with at least 96% of a high crystalline propylene homopolymer or a propylene ethylene copolymer. In order to improve compatibility with the inorganic filler, a method of improving compatibility with the inorganic filler is generally used by using a polymer containing a polar group which is a modified polypropylene alone or a polyolefin polyol alone or a mixture thereof. Increasing the lubrication of the surface of the molded product means that the friction between the polymer and the surface of the processing machine is brought about, the lubricant used in this case is a general chemical structure having both non-polar and polar groups, the polar group is compatible with the polymer Non-polar groups help to lubricate the surface of the processing machine, such as higher fatty acids, fatty acid amide compounds, waxes, silicones, and the like. However, the above methods have a slight effect of improving the surface damage resistance of the polypropylene resin composition, and by the method described above, there is a problem of weakening or reducing physical properties such as impact resistance or rigidity of the polypropylene resin composition. there was.

The present invention has been proposed to solve the problems of the prior art as described above, the problem to be solved by the present invention is to obtain a specific material and composition ratio of the polypropylene resin composition to provide a polypropylene resin composition is significantly improved odor removal effect It is.

Another object of the present invention is to provide a polypropylene resin composition with improved surface damage resistance.

Another problem to be solved by the present invention is to provide a polypropylene resin composition having the above-described improvement effect, but also further enhanced physical properties such as impact resistance or rigidity.

Another problem to be solved by the present invention is to provide a polypropylene resin composition that is lighter than a conventional polymer resin composition.

As a means for solving the above problem, the polypropylene resin composition according to the present invention has the following composition and composition ratio.

(A) propylene homopolymer or crystalline polypropylene with propylene, C ₂ -C ₁₀ monomers and binary copolymers with a C ₂ -C ₁₀ monomer content of 0.3-25 mol% and an isotactic index (II) of 98% or more; 40 to 92 parts by weight of resin;

(B) 3 to 20 parts by weight of the thermoplastic rubber;

(C) 3 to 25 parts by weight of a plate-shaped inorganic filler having an average particle size of 2 to 4 µm coated with calcium carbonate (CaCO ₃ ) having an average particle size of 0.1 to 0.5 µm on the surface;

(D) 2 to 10 parts by weight of the high density polyethylene polymer; And

(E) 0.1 to 5 parts by weight of a polymer additive for surface modifier

Wherein the polymer additive for surface modifier (E) is a siloxane polymer containing at least 50% by weight of a siloxane polymer having a viscosity of 10,000,000 mm 2 / s or more based on 100% by weight of the polymer additive for surface modifier. do. In addition, the component (B) is characterized in that selected from the group of ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), ethylene-butene copolymer (EBR,) ethylene-octene (EOR) . In addition, the plate-shaped inorganic filler is characterized in that at least one of talc, wollastonite and mica. In addition, the component (D) is characterized in that the specific gravity is a high-density polyethylene of 0.95 ~ 0.97 range and the melt index of 190 ℃ 0.2 ~ 10 g / 10min.

The functional polypropylene resin composition having improved odor removal and surface damage resistance according to the present invention having the above-mentioned problem solving means has an excellent effect on odor removal of a product.

In addition, the present invention has the effect of significantly improving the surface damage resistance of the polypropylene resin composition and the physical properties of the polypropylene resin composition is strengthened compared to the existing technology. In addition, the present invention has the effect of providing a lightweight product compared to the existing polymer resin products.

In order to achieve the above object, the present invention is a total of 100 parts by weight, (A) 40 to 92 parts by weight of a high crystalline polypropylene resin; (B) 3 to 20 parts by weight of the thermoplastic rubber; (C) 3 to 25 parts by weight of the plate-shaped inorganic filler is coated on the surface of calcium carbonate; (D) 2 to 10 parts by weight of the high density polyethylene polymer; And (E) 0.1 to 5 parts by weight of the polymer additive for the surface modifier. Hereinafter, each component which comprises this invention is demonstrated.

(A) highly crystalline polypropylene

The polypropylene polymer used as component (A) in the polypropylene resin composition of the present invention is a crystalline polymer composed of a propylene homopolymer having a propylene monomer as a main component and a propylene-ethylene block copolymer containing ethylene. Used in admixture with polymers or block copolymers.

Unlike conventional polypropylene, high crystallinity polypropylene (High Crystallinity PolyPropylene) is also called HIPP (High Isotacticity PolyPropylene), HSPP (High Stiffness PolyPropylene), and for the purpose of improving impact resistance, high hardness and scratch resistance It is a compound formulated in place of the existing polypropylene, and has 20 to 40% higher stiffness, excellent heat resistance and scratch resistance, but high crystallinity, compared to conventional isotactic of commercially available PP. This has similar strengths.

The Isotactic Index of stereoregularity of PP, which is widely used now, is 94 ~ 97%. However, the isotactic index of the high stereoregular PP is at least 96%. Preferably, when the isotactic index is increased to 98% or more, the crystallinity of PP is increased, so that the mechanical properties and heat resistance of PP are excellently improved. Highly crystalline polypropylene can be used in the overall parts of automobiles and exteriors. Among them, the stiffness and heat resistance are superior to those of existing polypropylene, so these properties are applied to parts that want to reduce the specific gravity by reducing the amount of required parts or inorganic fillers. have.

(B) Thermoplastic elastomer rubbers

In the polypropylene resin composition of the present invention, the α-olefin copolymer rubber used as component (B) is added to increase the impact resistance by imparting elasticity to the entire polypropylene resin composition. In particular, due to the high crystallinity of component (A), there is a disadvantage in that quality deterioration such as cracking and deformation of the molded product occurs due to residual stress caused by large volume change during cooling after molding, and is added to compensate for this. Component (B) uses an ethylene α-olefin copolymer rubber having 3 or more carbon atoms in the olefin.

When the content of component (B) is 3 parts by weight or less, the impact strength of the polypropylene resin composition is lowered. When the content of the component (B) is 20 parts by weight or more, the impact resistance is excellent, but the rigidity is lowered and there is no effect of improving the surface damage resistance. It is therefore preferred to add 3 to 20 parts by weight, in particular 5 to 15 parts by weight, of component (B). Further, a melt index of 190 ° C. of 0.3 to 15 g / 10 min, preferably 0.5 to 10 g / 10 min, is used. If the melt index is less than 0.3 g / 10 min, it causes a poor dispersion, not only appearance defects but also mechanical properties decreases, and when the melt index exceeds 15 g / 10 min, impact resistance and heat resistance are deteriorated.

Component (B) of the present invention uses a density of 0.85 to 0.88 g / cc. The lower the density, the better the impact resistance of the component (B), but the higher the tackiness, the more abnormal the surface of the product occurs, and the higher the density, the higher the surface damage resistance, but the lower the impact resistance, so the density is 0.85 to 0.88 g / cc. It is preferable to use the ethylene alpha-olefin copolymer rubber whose carbon number of a phosphorus olefin is three or more.

(C) inorganic filler

Inorganic filler used as component (C) in the polypropylene resin composition of the present invention is a component used for reinforcing the heat resistance and rigidity of the polypropylene resin composition, and the types that can be used are talc, calcium carbonate, calcium sulfate, and oxidation. Magnesium, calcium stearate, wollastonite, mica, silica, calcium silicate, clay, carbon black, and the like can be used. Preferably, wollastonite and talc, which are plate-shaped, are preferably used.

In the present invention, the component (C) used is a coating of calcium carbonate having an average particle size of 0.1 to 1.5 μm on talc particles having an average particle size of 2 to 6 μm. The average particle size of the inorganic filler is measured by laser diffraction method using the Mie scattering theory according to the ISO 13320-1 standard. Preferably, calcium carbonate having an average particle size of 0.1 to 0.5 µm is coated on a talc surface having an average particle size of 2 to 4 µm. It should also be coated with 20 to 60% by weight of calcium carbonate in the total content of component (C). Only when calcium carbonate is coated can the cavity be created in the inorganic filler, which can be used to adsorb and remove odorous substances. In component (C), physical properties such as stiffness, such as the stiffness of the plate-like talc plays a role, because when the talc particles are 2 ㎛ or less productivity is reduced due to polarization phenomenon, dispersibility and physical properties are poor when 4 ㎛ or more. In addition, if the calcium carbonate content of the component (C) is 20% by weight or less, the surface damage resistance, impact resistance and odor removal effect is insignificant, and when 60% by weight or more, the improvement of physical properties such as stiffness of talc is halved. Calcium carbonate coated talc must be used as component (C) because calcium carbonate is a simple mixed form because it does not improve impact resistance and odor removal, and damages surface resistance and function.

When the content of component (C) is 3 parts by weight or less, the effect of removing odor and improving physical properties is less, and when it is 25 parts by weight or more, the effect of improving impact resistance and surface damage resistance is small, so it is added within the range of 3 to 25 parts by weight.

(D) high density polyethylene polymer

The high-density polyethylene polymer used as component (D) in the polypropylene resin composition of the present invention is added to the entire polypropylene resin composition in order to increase slip resistance and low whitening properties and to improve surface damage resistance.

Specific gravity of the high-density polyethylene used in the present invention is 0.95 ~ 0.97, 190 ℃ melt index of 0.2 ~ 10 g / 10min is used. If the specific gravity of the high density polyethylene is lower than 0.95, the impact resistance is improved, but the surface damage resistance is not improved, and if it is higher than 0.97, the slip resistance is improved, but the crystallinity is high and the compatibility with the polypropylene resin composition is insufficient, resulting in poor quality such as phase separation. do.

(E) Polymer Additives for Surface Modifiers

In the polypropylene resin composition of the present invention, the polymer additive for the surface modifier used as component (E) is added to improve the surface damage resistance of the polypropylene resin composition. The role of the polymer additive for the surface modifier added as component (E) reduces the friction between the polymer and the surface of the processing machine. As a general chemical structure, both nonpolar and polar groups are used to help maintain the compatibility with the polymers.The polar groups are either lubricating or higher fatty acids, fatty acid amide compounds, waxes, silicones, etc. have.

Component (E) is an ultra high molecular weight siloxane polymer and should contain at least 50% siloxane with a viscosity of at least 10,000,000 mm ² / s. The addition amount of component (E) is within 0.1%-5%, More preferably, it adds in 1%-4% of range. If the added amount is less than 1%, the effect of improving the surface damage resistance is small. If it is more than 5%, the effect of improving the surface damage resistance is no longer increased.

The manufacturing method of the polypropylene resin composition of this invention is not specifically limited. That is, it is possible to manufacture (A), (B), (C), (D), and (E) component by a normal mechanical kneading method. Specifically, for example, a method using a general melt kneader such as a short-barrier mixer, a single screw extruder, or a multi screw extruder can be adopted. At this time, it is preferable to perform kneading temperature at 160-240 degreeC. In addition, the molding process for the composition of the present invention is not particularly limited to extrusion molding, blow molding, injection molding, sheet molding, etc., but injection molding is most suitable.

The polypropylene resin composition according to the present invention may optionally contain a nucleating agent, antioxidant, colorant, slip agent, antistatic agent, UV stabilizer and the like. The type and content of such additives may be selected so as not to adversely affect the desired properties of the composition.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

The physical property evaluation method of the various compositions adopted by the following example and the comparative example was performed by the following test method.

1) Melt index was measured by ASTM D-1238. Test conditions were measured at 230 ^° C, 2.16kgf.

2) Flexural modulus and flexural strength were measured by ASTM D-790 method. Specimen size was 12.7 × 127 × 6.4mm and the speed of crosshead was 28mm / min under the test conditions.

3) Izod impact strength was measured by ASTM D-256 method and the specimen size was 63.5 × 12.7 × 3mm.

4) Evaluation of surface damage resistance is measured by holding a sapphire pen at a right angle to the test specimen and carrying a load of 0.5 kgf, a moving distance of 100 mm, and a moving speed of 100 mm / sec. The evaluation method measures and compares the scratch width which generate | occur | produced 5 times. It was measured based on the surface damage resistance determination table of [Table 1], and the smaller the scratch width, the better the surface damage resistance.

Surface damage determination table Rating Scratch width (μm) Exterior Grade 5 <100 Surface damage not recognized Grade 4 100-250 Surface damage is weakly perceived Level 3 250-400 Surface damage is recognized but no whitening 2.5 class 400-475 Partial surface damage and whitening 2nd class 475-550 Obvious surface damage and whitening 1st grade > 550 Very severe surface damage

5) The evaluation of the odor is carried out by placing a specimen of 30 X 30 X 3 mm in a 1 l glass container, sealing it, heating it at 100 ° C. for 2 hours, and leaving it at room temperature for 1 hour or more, based on the odor determination table of [Table 2]. Conduct a sensory evaluation.

Odor Rating Degree of smell division Grade 1
Grade 2
Grade 3
Grade 4
Grade 5
Grade 6 No smell.
I don't know what it smells, but I feel it.
The smell is weakly detected and you can see what the smell is
Strong smell that can be easily detected
Very strong smell
Intense, intense odor that causes shortness of breath Odorless (NONE)
Odor Detection (THRESHOLD)
Moderate Smell (MODERATE)
Strong smell (STRONG)
VERY STRONG
Unbearable Smell (OVER STRONG)

Hereinafter, the compositions and contents of Examples and Comparative Examples are shown in the following [Table 3], and the physical property evaluation results measured by the evaluation method for the Examples and Comparative Examples are shown in [Table 4].

division (A) (B) (C) (D)  (E) PP1 PP2 Rubber T1 T2 T3 C C1 C2 HDPE S1 S2 Example 1 80 10 10 Comparative Example 1 80 10 10 Example 2 70 10 20 Comparative Example 2 70 10 20 Comparative Example 3 70 10 20 Example 3 74 14 12 Comparative Example 4 74 14 12 Comparative Example 5 74 14 12 Comparative Example 6 74 14 9 3 Comparative Example 7 69 14 12 5 Comparative Example 8 66 14 12 5 3 Comparative Example 9 66 14 12 5 3

* (A) component

division I.I MI FM Izod unit % g / 10min kgf / cm ² kgf cm / cm PP1 98 35 18,500 10 PP2 95 35 14,500 10

* (B) component: Rubber which is an ethylene-octene binary copolymer

* (C) component: Inorganic filler

division ingredient Average particle size (μm) Content (parts by weight) T1 TALC 11 100 T2 TALC 5.5 100 T3 TALC 3.5 100 C CaCO ₃ 0.2 100 C1 TALC / CaCO ₃ 3.5 / 0.2 75/25 C2 TALC / CaCO ₃ 3.5 / 1.4 75/25

* (D) Component: HDPE-MI 4g / 10min (at 190 ℃), Specific Gravity 0.963

* (E) Ingredient: S1: Silicone oil master batch (Silicone oil 50%, PP 50%)

S2: siloxane-based polymer, siloxane gum 65% of viscosity 10,000,000mm ² / s or more

division MI FM Izod Surface damage resistance Smell Example 1 28 20,500 16 Class 3 (281μm) Grade 4 Comparative Example 1 28 16,000 15  Class 3 (310 μm) Grade 4 Example 2 27 21,500 16 Class 3 (310 μm) Grade 4 Comparative Example 2 24 20,300 13 Class 3 (328 μm) Grade 4 Comparative Example 3 25 19,500 11 Class 3 (345 μm) Grade 4 Example 3 25 20,000 13 Class 3 (343μm) Grade 4 Comparative Example 4 27 19,000 17 Class 3 (308 μm) Grade 2 Comparative Example 5 26 18,000 19 Class 3 (315 μm) Grade 2 Comparative Example 6 28 17,500 14 Class 3 (335μm) Grade 3 Comparative Example 7 24 18,500 18 Class 3 (280μm) Grade 2 Comparative Example 8 26 18,700 16 Class 3 (256 μm) Grade 2 Comparative Example 9 25 18,000 19 4th grade (228μm) Grade 2

Example  1 and Comparative example  One

Experiment on the basis of polypropylene resin having the same level of fluidity and different ranges of isotactic indices in order to confirm the difference in physical properties and surface damage resistance according to the isotactic index of component (A) polypropylene It was. Example 1 is based on I.I 98% polypropylene resin according to the present invention, Comparative Example 1 is based on the most commonly used polypropylene resin in the range of 94 to 97% I.I. In addition, 10 parts by weight of rubber as (B) component and 10 parts by weight of general TALC as (C) component were added, mixed for 2 minutes using a Henschel mixer, and extruded at a temperature range of 170 to 220 ° C to obtain a resin composition in pellet form.

As a result, in the case of using a high crystalline polypropylene resin having a high I. like in Example 1, it was possible to obtain a polypropylene resin composition having a relatively high rigidity and surface damage resistance than Comparative Example 1 when using a general polypropylene resin.

Example  2 and Comparative example  2 ~ 3

In order to confirm the difference in physical properties and surface damage resistance according to the average particle size of the component (C) inorganic filler, the average particle size of talc was changed and tested. It can be seen that the smaller the average particle size, the better the physical properties and the surface damage resistance. When CaCO ₃ is coated on talc, since talc influences physical properties, the use of inorganic fillers coated with CaCO ₃ on the basis of fine talc having an average particle size of 2 to 4 μm greatly improves physical properties and scratch resistance.

Example  3 and Comparative example  4 to 6

Example 3 and Comparative Examples 4 to 5 were carried out to confirm the improvement effect when using a talc and general talc coated with CaCO ₃ . The smaller the average particle size of the CaCO ₃ coating is excellent in surface damage and strength, and the larger the average particle size of the CaCO ₃ coating is excellent in the impact resistance (Izod impact value). In particular, when the talc coated with CaCO ₃ is used, the odor improving effect is excellent. In Comparative Example 6, a polypropylene resin composition prepared by simply mixing CaCO ₃ with talc was prepared, and surface damage resistance and odor were improved compared to Example 3, but the improvement effect was less than that of Comparative Example 4, and physical properties were inferior. Therefore, in order to improve the surface damage resistance and odor removal effect while maintaining the properties expressed by general micro talc, it is preferable to use an inorganic filler coated with CaCO ₃ having an average particle size of 0.1 to 0.5 μm on a talc surface having an average particle size of 2 to 4 μm. .

Comparative example  7 to Comparative example  9

Comparative Example 7 was tested to confirm the effect of improving the surface damage resistance of the component (D). Compared with Comparative Example 4, it can be seen that the physical properties and the degree of smell are similar, but the surface damage resistance is improved.

In Comparative Example 8 and Comparative Example 9, an experiment was conducted to compare the effect of improving the surface damage resistance of the silicone-based oil component and the siloxane-based polymer component which are generally used to improve the surface damage resistance. In order to improve the surface damage resistance it was confirmed that it is more preferable to use a siloxane polymer than the silicone oil generally used. In addition, it is more preferable to use a siloxane-based polymer because silicone oil is discharged to the surface when a large amount is added to cause a surface defect.

Preferred embodiments of the present invention described above are disclosed to solve the technical problem, and those skilled in the art to which the present invention pertains (man skilled in the art) various modifications, changes, additions, etc. within the spirit and scope of the present invention. It will be appreciated that such modifications and variations are intended to be within the scope of the following claims.

Claims (6)

(A) propylene homopolymer or crystalline polypropylene with propylene, C ₂ -C ₁₀ monomers and binary copolymers with a C ₂ -C ₁₀ monomer content of 0.3-25 mol% and an isotactic index (II) of 98% or more; 40 to 92 parts by weight of resin; (B) 3 to 20 parts by weight of the thermoplastic rubber; (C) 3 to 25 parts by weight of a plate-shaped inorganic filler having an average particle size of 2 to 4 µm coated with calcium carbonate (CaCO ₃ ) having an average particle size of 0.1 to 0.5 µm on the surface; (D) 2 to 10 parts by weight of the high density polyethylene polymer; And (E) 0.1 to 5 parts by weight of a polymer additive for surface modifiers; Is composed of, The polymer additive for surface modifier (E) is a propylene polymer comprising a siloxane polymer having a viscosity of 10,000,000 mm 2 / s or more based on 100% by weight based on 100% by weight of the polymer additive for surface modifier. Composition. delete The method according to claim 1, wherein the component (B) is Ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), ethylene-butene copolymer (EBR) Polypropylene resin composition, characterized in that selected from the group of (EOR). The method of claim 1, wherein the plate-shaped inorganic filler, Polypropylene resin composition, characterized in that at least one of talc, wollastonite and mica. The method according to claim 1, wherein the component (D), Polypropylene resin composition characterized in that the specific gravity is a high density polyethylene in the range of 0.95 ~ 0.97 and the melt index of 190 ℃ 0.2 ~ 10 g / 10min. delete