KR101180874B1 - Thermoplastic vulcanizates composition having improved foaming formability, and molded article manufactured therefrom - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to thermoplastic vulcanizate compositions. More specifically, ethylene-propylene-diene rubber, paraffin oil, high-elasticity polypropylene having an elongational viscosity of 1.0 × 10 ⁶ to 1.0 × 10 ⁷ poise, an olefin block copolymer, an inorganic filler, a compatibilizer, a crosslinking agent, and a stabilizer It relates to a thermoplastic crosslinked elastomer composition comprising.
Thermoplastic crosslinked elastomer composition of the present invention has a low specific gravity and excellent mechanical properties, it is possible not only to foam at a high magnification, but also has the advantage of less destruction of the foam cell (cell). Accordingly, it is expected to be able to manufacture a molded article with excellent mechanical properties and lighter weight, and can be applied to various material fields such as automotive weather strip and window gasket of a building.

Description

Thermoplastic crosslinked elastomer composition having improved foam moldability, and a molded article formed by the composition {THERMOPLASTIC VULCANIZATES COMPOSITION HAVING IMPROVED FOAMING FORMABILITY, AND MOLDED ARTICLE MANUFACTURED THEREFROM}

The present invention relates to a thermoplastic crosslinked elastomer composition and a molded article formed by the composition.

Thermoplastic vulcanizates (TPVs) are resins having both thermoplastic and rubber elasticity, and refer to a composition mainly composed of crosslinked ethylene-propylene-diene rubber (hereinafter referred to as 'EPDM') and polypropylene.

Crosslinked EPDM is molded in the form of foam and is used as a weather seal in the automotive industry. This is because the crosslinked EPDM can maintain the required shape as it has elastic properties, and can effectively prevent noise, dust, moisture, etc. flowing from the outside of the vehicle.

However, EPDM requires a lot of equipment, time, and attention to foam profile forming process and vulcanization process, so that there is a problem of low productivity.

Thus, many studies have been made to further supplement the above problems and the properties of EPDM. For example, U.S. Patent No. 7,319,121 foams a composition containing EPDM, styrene-ethylene-propylene-styrene copolymer (SEPS), acrylic-modified polytetrafluoroethylene, long-chain branched polyolefin, and the like to make the surface soft and low moisture. Foams with water absorption, improved mechanical properties are disclosed.

However, the composition has a high specific gravity and a foaming ratio of about 2 times, which is not only limited to reducing the density of the molded article, but also rapidly decreases mechanical properties such as permanent compression rate, tensile strength, and tear strength during foaming. There is a problem that (cell) is easily broken, there is an urgent need to develop a thermoplastic crosslinked elastomer composition that satisfies excellent foam moldability and mechanical properties.

The present invention provides a thermoplastic crosslinked elastomer composition having low specific gravity and excellent mechanical properties.

Moreover, this invention provides the method of foaming the said thermoplastic crosslinked elastomer resin composition.

Moreover, this invention provides the molded article manufactured from the said thermoplastic crosslinked elastomer resin composition.

Thermoplastic crosslinked elastomer composition according to one embodiment of the present invention

10 to 60 weight percent of ethylene-propylene-diene rubber;

10 to 60 weight percent of paraffin oil;

5-40% by weight of high melt strength polypropylene having a draw viscosity of 1.0 × 10 ⁶ to 1.0 × 10 ⁷ poise;

5 to 40 weight percent of olefin block copolymers;

1 to 30% by weight of organic modified inorganic fillers;

0.5 to 10 weight percent of a compatibilizer;

0.05 to 5% by weight of crosslinking agent; And

And 0.05 to 3 weight percent of a stabilizer.

The ethylene-propylene-diene rubber is ENB (ethylidene norbornene) content of 4.5 to 12% by weight, ethylene (ethylene) content of 50 to 80% by weight, Mooney viscosity (Money viscosity, ML1 + 8, 125 ℃) Is preferably from 45 to 70.

The paraffin oil preferably has a kinematic viscosity of 90 to 180 cSt at 40 ℃.

The high melt strength polypropylene preferably has a weight average molecular weight of 200,000 to 500,000.

Preferably, the olefin block copolymer has a Melt Index of 0.3 to 3.0 g / 10 min at 190 ° C. and 2.16 kg.

The inorganic filler is preferably quaternary ammonium salt modified montmorillonite.

The inorganic filler is preferably an average particle diameter of 1 to 30 ㎛.

The compatibilizer may be maleic anhydride grafted polypropylene; In particular, the maleic anhydride is preferably grafted to 3 to 10% by weight.

On the other hand, according to another embodiment of the present invention, the thermoplastic crosslinked elastomer composition using an extruder having a length (L) / outer diameter (D) ratio of 28 or more, process temperature 140 to 210 ℃, and supply gas 0.40 to 0.80 ml Provided is a method of foaming under the condition of / min.

On the other hand, according to another embodiment of the present invention, the thermoplastic crosslinked elastomer composition using an extruder having a length (L) / outer diameter (D) ratio of 28 or more, the process temperature 140 to 210 ℃, and the foaming gas supply amount 0.40 to 0.80 A method of foaming under the condition of ml / min is provided.

On the other hand, the present invention provides a molded article prepared from the thermoplastic crosslinked elastomer composition according to another embodiment.

The molded article can be used as a weather strip for automobiles, window gaskets of buildings and the like.

Thermoplastic crosslinked elastomer composition of the present invention has a low specific gravity and excellent mechanical properties, it is possible not only to foam at a high magnification, but also has the advantage of less destruction of the foam cell (cell). Accordingly, it is expected to be able to manufacture a molded article with excellent mechanical properties and lighter weight, and can be applied to various material fields such as automotive weather strip and window gasket of a building.

Hereinafter, a thermoplastic crosslinked elastomer composition according to the present invention, a method of foaming the composition, and a molded article made of the composition will be described.

In the course of studying the thermoplastic vulcanizate composition, the inventors have mixed ethylene-propylene-diene rubber with high-elasticity polypropylene, olefin block copolymer, organic modified inorganic filler, compatibilizer, and the like. In this case, it is possible to reduce the specific gravity of the composition and foam molding with high magnification, which makes it possible to reduce the weight of the molded article (low density), and at the same time, it is confirmed that there is little destruction of the foam cell due to excellent mechanical properties. Completed.

Thermoplastic crosslinked elastomer composition according to one embodiment of the present invention

10 to 60 weight percent of ethylene-propylene-diene rubber;

10 to 60 weight percent of paraffin oil;

5-40% by weight of high melt strength polypropylene having a draw viscosity of 1.0 × 10 ⁶ to 1.0 × 10 ⁷ poise;

5 to 40 weight percent of olefin block copolymers;

1 to 30% by weight of organic modified inorganic fillers;

0.5 to 10 weight percent of a compatibilizer;

0.05 to 5% by weight of crosslinking agent; And

Stabilizer 0.05-3 wt%

.

First, the ethylene-propylene-diene rubber (hereinafter referred to as 'EPDM') includes at least two or more monoolefin monomers (2 to 10 carbon atoms, preferably 2 to 4 carbon atoms), and at least one poly-unsaturated olefin ( Terpolymer derived from 5 to 20 carbon atoms.

The monoolefin monomer may be each CH ₂ = CH-R (R is H or an alkyl group having 1 to 12 carbon atoms), preferably ethylene and propylene. Preferred repeating units by at least two monoolefin monomers may comprise 90 to 99.6% by weight, based on the total weight of EPDM.

The poly-unsaturated olefin may be straight chained, branched, cyclic, bicyclic, bridged ring, or the like, preferably a nonconjugated diene. Can be. The poly-unsaturated olefin may be included in an amount of 0.4 to 10% by weight based on the total weight of EPDM.

In addition, the EPDM has a content of ethylidene norbornene (ENB) of 4.5% by weight or more, preferably 4.5 to 12% by weight, more preferably 4.5 to 9% by weight; The content of ethylene is at least 50% by weight, preferably 50 to 80% by weight, more preferably 60 to 75% by weight; It is preferable that the Mooney viscosity (ML1 + 8, 125 ° C) is 45 or more, preferably 45 to 70, more preferably 45 to 60.

In the thermoplastic crosslinked elastomer composition according to the present invention, the EPDM may be included in an amount of 10 to 60% by weight, preferably 15 to 50% by weight, and more preferably 15 to 40% by weight, based on the total weight of the composition.

That is, in order to impart the minimum elasticity required for the thermoplastic crosslinked elastomer composition, the EPDM is preferably included in more than 10% by weight of the total weight of the composition, flowability and molding by the rapid increase in viscosity when the excessive addition of the EPDM In order to prevent deterioration of the property, it is preferably included in 60 wt% or less.

At this time, the EPDM has a higher viscosity, the rubber properties such as elasticity is improved, while the flowability is reduced, resulting in difficulties in the elastic body manufacturing process. The composition according to the invention thus comprises paraffin oil as process oil. The paraffin oil serves to appropriately reduce the hardness of the thermoplastic crosslinked elastomer according to the present invention and to increase moldability.

The paraffin oil may have a kinematic viscosity at 40 ° C. of 90 cSt or more, preferably 90 to 180 cSt, more preferably 100 to 150 cSt in order to exhibit the effect in the process conditions according to the present invention.

In addition, the paraffin oil may be included to 10 to 60% by weight, preferably 20 to 55% by weight, more preferably 20 to 50% by weight relative to the total weight of the composition.

That is, in order to be able to express the effect of the minimum limit according to the addition of the paraffin oil, the paraffin oil is preferably included to be at least 10% by weight based on the total weight of the composition, absorbed when the excessive addition of the paraffin oil In order to prevent the oil from falling out or deteriorating mechanical properties, it is preferably included in 60 wt% or less.

When using the paraffin oil containing the paraffin oil as the EPDM, in consideration of the content of the paraffin oil contained in the EPDM commodity, the content of the entire paraffin oil may be adjusted to be within the above range.

In addition, the composition according to the present invention comprises a high melt strength polypropylene (hereinafter referred to as "HMS-PP").

The HMS-PP is a kind of long-chain branched polyolefin, and has excellent moldability, chemical resistance, heat resistance, and the like. In the thermoplastic crosslinked elastomer composition of the present invention, the HMS-PP is used as a component for imparting the physical properties together with basic thermoplasticity.

In general, polypropylene has a weak melt tension due to the linear structure of the polymer chain.To solve this problem, polypropylene has a low melt index (MI) or a molecular weight distribution (MWD) method. Can be prepared. The most effective method is to increase the melt tension by introducing a long chain branch structure in the polypropylene back bone, and then secondly re-arrangement after breaking the polypropylene chain. It is common to create branch structures.

Therefore, in the case of HMS-PP, unlike the general polypropylene, the melt tension is increased due to the long chain structure, thereby improving tensile strength, flexural strength, flexural modulus, and scratchability. In particular, in the case of general polypropylene, the stretching viscosity increases to some extent and then saturates. However, in the case of HMS-PP having a long chain structure, the stretching viscosity is increased even at the point where the stretching viscosity of the general polypropylene is saturated. Shows a growing aspect.

HMS-PP included in the composition of the present invention has a stretching viscosity of 1.0 × 10 ⁶ to 1.0 × 10 ⁷ poise, for the purpose of enabling high magnification foam molding by excellent viscosity properties of the composition according to the invention 5 to 40% by weight, preferably 5 to 30% by weight, and more preferably 5 to 20% by weight, based on the total weight of the composition. That is, the synergistic effect of improving the foaming moldability and mechanical properties of the resin composition with EDPM within the weight range is excellent.

In addition, the HMP-PP may use a weight average molecular weight of 200,000 or more, preferably 200,000 to 500,000, more preferably 200,000 to 350,000 to express the above effects.

In addition, the HMS-PP preferably has a draw viscosity of 1.0 × 10 ⁶ to 1.0 × 10 ⁷ poise, and more preferably, high melt strength polypropylene produced by Honam Petrochemical Co., Ltd. may be used.

In addition, the composition according to the present invention comprises an olefin block copolymer (hereinafter referred to as 'OBC').

The OBC is a component added together with the above-described EPDM and HMS-PP to impart synergistic effect to improve the foam moldability and mechanical properties of the resin composition. That is, the addition of the OBC increases the viscoelasticity of the portion between the foam cells (cell) can be obtained the effect of maintaining the foam cell and increase the mechanical properties.

The OBC included in the composition of the present invention refers to a block polymer in which heterologous polyolefin polymers such as ethylene, propylene, butene, isoprene, hexene, octene, etc. are covalently bonded to each other. Various combinations are possible, such as a block copolymer which consists of polyolefin blocks which form a rubbery phase.

In particular, the OBC is copolymerized using a chain shuttling technology that alternately generates heterogeneous polymer chain blocks using a dual-catalyst in tandem in one or more reactors. It is preferable to chain.

In other words, in the conventional random polyolefin copolymer, side chains such as octene are grafted on the polyethylene main chain, and as the comonomer content increases, the Tm and heat resistance are lowered, and the crystallization time is decreased. There is a problem that becomes longer. In contrast, the OBC made of the chain shuttling technology has flexibility, processability, elastic resilience, and permanent compressive stiffness without a decrease in Tm and heat resistance even when the comonomer content is increased. This is preferable because it can improve the mechanical properties reduced by foaming at the time of foam cell formation.

The OBC has a melt index of at least 0.3 g / 10 minutes, preferably 0.3 to 3.0 g / 10 minutes, more preferably 0.3 to 1.5 g / 10 minutes at 190 ° C. and 2.16 kg. Preferred for expression.

In addition, the OBC may have a specific gravity of 0.860 or more, preferably 0.860 to 0.880, more preferably 0.860 to 0.870. In addition, Tm (melting temperature) may be used at 115 ℃ or more, preferably 115 to 125 ℃, more preferably 115 to 120 ℃.

In addition, the OBC may be included in 5 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight based on the total weight of the composition. That is, within the weight range, the synergistic effect of improving the foaming moldability and mechanical properties of the resin composition together with the EDPM and HMS-PP described above is excellent.

In addition, the composition according to the present invention comprises an organically modified mineral filler.

The organically modified inorganic filler is excellent in compatibility and dispersibility in the composition, even if a small amount is added compared to the general inorganic filler kaolin (talc), etc. can express the same or more addition effect, the composition There is an advantage that can lower the specific gravity of.

In particular, the organically modified inorganic filler is preferably ternary ammonium salt modified montmorillonite (quaternary ammonium salt modified montmorillonite), more preferably may be montmorillonite modified with dimethyl dihydrogenated tallow quaternary ammonium.

In addition, the inorganic filler may be used having an average particle diameter of 1 to 30 ㎛, preferably 1 to 20 ㎛, more preferably 1 to 10 ㎛. That is, in order to sufficiently express the heat resistance and rigidity reinforcement effect according to the addition of the inorganic filler, the average particle diameter is preferably 1 μm or more, and in order to prevent workability during extrusion molding due to excessive average particle diameter, It is preferable that an average particle diameter is 30 micrometers or less.

In addition, in consideration of the above-described physical properties improving effect, specific gravity of the composition and molding workability, the content of the inorganic filler is 1 to 30% by weight, preferably 1 to 20% by weight, more preferably based on the total weight of the composition. It may be 1 to 10% by weight.

In addition, the composition according to the invention comprises a compatibilizer.

The compatibilizer is a component added to further improve the compatibility and dispersibility of the aforementioned EPDM, HMS-PP, OBC and the inorganic filler. If the inorganic filler is unevenly dispersed in the composition, this can easily destroy the foaming cells, so it is preferable to add the compatibilizer to minimize this.

In particular, in the present invention, the compatibilizer is preferably maleic anhydride grafted polypropylene (hereinafter referred to as 'PP-g-MAH'), wherein maleic anhydride is 3% by weight. As mentioned above, it is more preferable to be grafted at 3 to 10 weight%, More preferably, to 3 to 7 weight%.

That is, the composition according to the present invention uses ternary ammonium salt modified montmorillonite modified with quaternary ammonium salt as the inorganic filler, and at the same time, maleic anhydride grafted polypropylene is used as a compatibilizer. By using to improve the dispersibility of the inorganic filler, it is possible to exert a synergistic effect that the mechanical properties of the foaming cell is further improved.

In addition, the compatibilizer may be included in 0.5 to 10% by weight, preferably 1 to 7% by weight based on the total weight of the composition. That is, it is preferable to include 0.5% by weight or more in order to impart a dispersibility improving effect of the inorganic filler, it is preferably included in 10% by weight or less in order to prevent the physical properties of the composition from deteriorating when an excessive amount of the compatibilizer is added. .

The composition according to the invention also comprises a crosslinking agent.

The thermoplastic crosslinked elastomer is prepared to add a crosslinking agent for crosslinking the rubber part, which is basically a soft segment, and to be dynamically crosslinked using an extruder to express a viscosity and elasticity such as rubber.

Usable as the crosslinking agent may be selected from those conventional in the art to which the present invention pertains, and preferably, a phenol resin crosslinking agent, a peroxide crosslinking agent, a silane crosslinking agent, or the like may be used.

The crosslinking agent may be included in 0.05 to 5% by weight, preferably 0.05 to 3% by weight, based on the total weight of the composition. That is, the crosslinking agent is preferably contained in an amount of 0.05% by weight or more based on the total weight of the composition in order to prevent the crosslinking is not sufficiently made to decrease the physical properties of the molded article, foreign matter such as black spots on the surface of the molded article when the crosslinking agent is added in excess It is preferable that it can be observed and 5 wt% or less in order to prevent the moldability from deteriorating.

At this time, if necessary, the composition according to the present invention may further include a crosslinking aid. The crosslinking aid may also be used in the art to which the present invention belongs, preferably a metal oxide (metal oxide), a metal halide (metal halide), or a mixture thereof may be used, more preferably ZnO and SnCl ₂ may be mixed and used. The crosslinking assistant may be further included in an amount of 0.05 to 5% by weight based on the total weight of the composition for the same reason as the crosslinking agent.

In addition, the composition according to the invention comprises a stabilizer.

The stabilizer is added to prevent the resin from deteriorating during molding of the composition, and to prevent the physical properties from deteriorating when the molded article is used for a long time, and is preferably used in the art to which the present invention belongs. Heat stabilizers, light stabilizers, halogen scavengers and the like may be added.

In this case, the stabilizer may be included in 0.05 to 3% by weight, preferably 0.05 to 1% by weight based on the total weight of the composition. That is, it is preferable to include 0.05% by weight or more in order to express the minimum effect by the addition of the stabilizer, 3% by weight or less in order to prevent the blooming phenomenon on the surface of the molded article during the excessive addition It is preferable to be included as.

On the other hand, according to another embodiment of the present invention, there is provided a method for producing a resin with the thermoplastic crosslinked elastomer composition and a method for foaming the resin.

First, a method of preparing a resin with the composition according to the present invention may use a conventional method in the art, preferably a reactive extrusion process.

Equipment for performing the reaction extrusion method includes an internal mixer (external mixer) and an extruder (extruder); The internal mixer may be a banbury mixer or kneader mixer; In the case of the extruder, a twin screw extruder having a length (L) / outer diameter (D) ratio of 32 or more is preferable, and at least one side feeder is preferably provided. At this time, the reaction temperature in the manufacturing process is preferably performed to be 160 to 220 ℃.

In addition, the method of foaming the resin may use a conventional method in the art, preferably a gas foaming method.

It is preferable to use an extruder equipped with a gear pump and a static mixer as a facility for performing the gas foaming method. In this case, the extruder is preferably a single screw extruder having a length (L) / outer diameter (D) ratio of 28 or more, and the nucleating agent and foaming gas (CO ₂ , N _2, etc.), and at least one side feeder capable of introducing the foaming gas or the like is preferably provided.

In addition, the foaming process is preferably carried out at a process temperature of 140 to 210 ℃, and the conditions of the foaming gas supply amount 0.40 to 0.80 ml / min.

In particular, the thermoplastic crosslinked elastomer composition according to the present invention can increase the foaming ratio in the foaming process by 2.5 to 3.5 times, preferably 2.8 to 3.3 times by synergistic effects, as described above including EPDM, HMS-PP, OBC, etc. It is possible to reduce the weight (lower density) of the molded article, but also has the advantage of excellent mechanical properties.

On the other hand, the present invention provides a molded article prepared from the thermoplastic crosslinked elastomer composition according to another embodiment.

As described above, the molded article is lightweight (low density) in the foam molding using the thermoplastic crosslinked elastomer composition according to the present invention, while having excellent mechanical properties, and thus, has little advantage of breaking the foam cell.

Accordingly, the molded article according to the present invention is expected to be applicable to various material fields, such as automotive weather strips and window gaskets for buildings.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

[Manufacture of Resin]

Each component was mixed by the composition ratio shown in following Table 1, and the resin of Examples 1-2 and Comparative Examples 1-8 was manufactured. In this case, a twin screw extruder having an internal mixer and an extruder, a length (L) / outer diameter (D) ratio of 52, was used as a manufacturing facility, and the reaction temperature was 160. To 220 ° C.

Example  One

EPDM (manufacturer: Kumho Polychem, product name: KEP-960NF, ENB content: 5.7% by weight, ethylene content: 70% by weight, Mooney viscosity (ML1 + 8, 125 ° C): 49) was added to the whole composition It was added to 25.80% by weight. That is, the EPDM product (KEP-960NF) is a product having a paraffin oil content of 50 PHR (Part per Hundred Resin), and the product is added so that the content of pure EPDM is 25.80% by weight based on the total composition. In consideration of the content of the paraffin oil contained basically, the content of the paraffin oil contained in the total composition was adjusted to 33.55% by weight. At this time, the additional paraffin oil was used as a product of Michang Petrochemical Co., Ltd. (product name: W-1900, kinematic viscosity (40 ℃): 137 cSt).

In addition, HMS-PP (manufacturer: Honam Petrochemical Co., Ltd., product name: SMS-513, weight average molecular weight: 300000, stretching viscosity: 1.0 × 10 ⁶ to 1.0 × 10 ⁷ poise) was 15% by weight based on the total composition;

OBC (manufacturer: DOW, product name: D9007, melt index (190 ° C., 2.16 kg): 0.5 g / 10 min, specific gravity: 0.866, Tm: 119 ° C.) was 10% by weight based on the total composition;

Montmorillonite modified with dimethyl dihydrogenated tallow quaternary ammonium as an inorganic filler (manufacturer: Southern Clay Products, product name: Cloisite 15A (57 wt% pure mineral content), average particle diameter: 6 μm) was 8.77 wt% (pure inorganic content) About 5% by weight);

As a compatibilizer, PP-g-MAH (manufacturer: Honam Petrochemical Co., Ltd., product name: PH-200, MAH graft ratio: 4 wt%) was 5 wt% based on the total composition;

Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer (Manufacturer: Ciba, product name: IRGANOX 1010), bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (manufacturer : Ciba, product name: MAGNAFLOC 6260), and a hydrotalcite-like compound (manufactured by Kyowa Chemical Industry, product name: DHT-4A) were mixed to 0.15% by weight of the total composition;

Dimethylol phenolic resin (manufacturer: SI Group, product name: SP-1045) as a crosslinking agent was 0.87% by weight based on the total composition; And

As a crosslinking aid, ZnO was added in an amount of 0.52% by weight based on the total composition and 0.35% by weight of SnCl ₂ in the total composition.

Example  2

Except for mixing each component in the content of Table 1, the same components as in Example 1 were used, in which the remaining components except the inorganic filler and PP-g-MAH was first mixed to crosslink the EPDM, and then inorganic Resin was prepared by separately mixing the filler and PP-g-MAH.

Comparative example  One

Instead of HMS-PP, a general polypropylene (manufacturer: Honam Petrochemical Co., Ltd., product name: Y-120, weight average molecular weight: 200,000) was added, no OBC was added, and an organically modified organic kaolin (inorganic filler) ( Manufacturer: BASF, product name: Satintone Whitetex Clay), except for using the same components as in Example 1 in the content of Table 1 to prepare a resin.

Comparative example  2

Instead of HMS-PP, a general polypropylene (manufacturer: Honam Petrochemical Co., Ltd., product name: Y-120, weight average molecular weight: 200,000) was added, and the same components as in Example 1 were added except that OBC was not added. Resin was prepared by mixing to the content of Table 1.

Comparative example  3

The same ingredients as in Example 1 were mixed in the contents of Table 1, except that OBC was not added and organic kaolin (manufacturer: BASF, product name: Satintone Whitetex Clay), which was not organically modified, was used as an inorganic filler. Prepared.

Comparative example  4

5.38% by weight of pure sodium montmorillonite (manufacturer: Southern Clay Products, product name: Cloisite Na + (93 wt% pure mineral content), average particle diameter: 6 μm) without OBC added and not organically modified with inorganic filler Except that the content of about 5% by weight), the same components as in Example 1 were mixed in the content of Table 1 to prepare a resin.

Comparative example  5 ~ 7

Except that OBC was not added, the same components as in Example 1 were mixed in the content of Table 1 to prepare a resin.

Comparative example  8

8.06% by weight of montmorillonite modified by dimethyl dihydrogenated tallow quaternary ammonium (manufacturer: Southern Clay Products, product name: Cloisite 20A (62 wt% pure mineral content), average particle size: 6 μm) without OBC added Except that it is added to the pure inorganic content of about 5% by weight), the same components as in Example 1 were mixed in the content of Table 1 to prepare a resin.

Content (% by weight) Example Comparative example One 2 One 2 3 4 5 6 7 8 EPDM 25.80 28.56 29.95 30.90 29.95 32.34 33.45 32.34 30.91 31.21 Paraffin oil 33.55 37.10 38.90 40.11 38.90 42.00 43.45 42.05 40.10 40.51 PP HMS-PP 15 12 - - 12 13 14 13 13 13 PP - - 12 13 - - - - - - OBC 10 10 - - - - - - - - radish
group
insect
camp
My Cloisite
15A 8.77
(5) ^* 5.26
(3) ^* - 8.77
(5) ^* - - 1.75
(1) ^* 5.26
(3) ^* 8.77
(5) ^* - Cloisite
20A - - - - - - - - - 8.06
(5) ^* Cloisite
Na + - - - - - 5.38
(5) ^* - - - - kaoline - - 12 - 12 - - - - - PP-g-MAH 5 5 5 5 5 5 5 5 5 5 stabilizator 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Cross-linking agent 0.87 0.97 1.00 1.03 1.00 1.07 1.10 1.10 1.03 1.03 Bridge
pharmacy ZnO 0.52 0.58 0.60 0.62 0.60 0.64 0.66 0.66 0.62 0.62 SnCl ₂ 0.35 0.39 0.40 0.41 0.40 0.43 0.44 0.44 0.41 0.41

(() ^{* In} Table 1 is the content of pure inorganic matter in inorganic filler)

[Measurement of Physical Properties of Resin]

The physical properties of the resins prepared in Examples 1 to 2 and Comparative Examples 1 to 8 were measured by the following method, and the results are shown in Table 2.

① Specific Gravity: Measuring Method ISO 1183 / Equipment Electronic Densimeter

② Shore Hardness: Measuring Method ISO 868 / Equipment: Analogue Shore Hardness Tester

③ Tensile Strength: Measuring Method ISO 37 (II) / Equipment: Universal Materials Testing Machine

division Example Comparative example One 2 One 2 3 4 5 6 7 8 importance 0.919 0.909 0.972 0.920 0.970 0.919 0.893 0.904 0.917 0.913 Shore hardness 68A 67A 68 65 70 67 63 66 67 66A Tensile Strength (MPa) 7.20 7.50 6.30 5.30 6.50 4.60 4.30 5.90 6.20 4.80

As shown in Table 2, the resins according to Examples 1 to 2 were confirmed to have the same or more Shore hardness and tensile strength while having a lower specific gravity than the resins of Comparative Examples 1 to 8.

In particular, Examples 1 and 2 include EPDM, HMS-PP, OBC, and PP-g-MAH, despite the fact that the inorganic filler content is less than half compared to Comparative Examples 1 and 3, Low specific gravity and excellent mechanical properties.

[Resin firing]

As shown in Table 3, each of the resins of Examples and Comparative Examples prepared above were foam molded in the following manner.

Foam example  1-4

The resin prepared in Example 2 was used. The foaming equipment was equipped with a gear pump and a static mixer, a single screw extruder having a length (L) / outer diameter (D) ratio of 33, and a foaming gas (CO ₂ ) and a nucleating agent. It was used, and the conditions of the process temperature 140-160 degreeC and foaming gas supply amount 0.50-0.75 mL / min were made.

Foam example  5 ~ 7

Except for using the resin prepared in Comparative Example 6, it was foamed under the conditions of Table 3 using the same equipment as Foam Examples 1-4.

division Foaming example 1 Foaming example 2 Foaming example 3 Foaming example 4 Foaming example 5 Foaming example 6 Foaming example 7 Resin type Example 2 Example 2 Example 2 Example 2 Comparative Example 6 Comparative Example 6 Comparative Example 6 Die temperature (℃) 140 150 150 160 140 150 160 Gas supply
(Ml / min) 0.75 0.50 0.75 0.50 0.75 0.75 0.50 Nucleating agent (%) - One One One - One One

[ Foam  Property measurement]

The physical properties of the foams prepared through the foaming examples 1 to 7 were measured by the following method, and the results are shown in Table 4 below.

① Specific Gravity: Measuring Method ISO 1183 / Equipment Electronic Densimeter

② Foam magnification: Measuring method ISO 1183 / Equipment Electronic Densimeter

division Foaming example 1 Foaming example 2 Foaming example 3 Foaming example 4 Foaming example 5 Foaming example 6 Foaming example 7 importance 0.331 0.289 0.290 0.273 0.434 0.379 0.362 Foam magnification (times) 2.8 3.2 3.1 3.3 2.1 2.4 2.5

As shown in Table 4 above, the foams according to Foaming Examples 1 to 4 were able to be foamed at a higher magnification compared to Foaming Examples 5 to 7 using the resin of Comparative Example 6 by using the resin of Example 2. In addition, the foaming example 5 increased the foaming ratio to 2.1 times using the resin of Comparative Example 6, but the specific gravity is high and the foaming cells (cells) are easily destroyed, resulting in poor mechanical properties.

Claims (13)

10 to 60 weight percent of ethylene-propylene-diene rubber;
10 to 60 weight percent of paraffin oil;
5-40% by weight of high melt strength polypropylene having a draw viscosity of 1.0 × 10 ⁶ to 1.0 × 10 ⁷ poise;
5 to 40 weight percent of olefin block copolymers;
1 to 30% by weight of organic modified inorganic fillers;
0.5 to 10 weight percent of a compatibilizer;
0.05 to 5% by weight of crosslinking agent; And
Stabilizer 0.05-3 wt%
Thermoplastic crosslinked elastomer composition comprising a. The method of claim 1,
The ethylene-propylene-diene rubber is ENB (ethylidene norbornene) content of 4.5 to 12% by weight, ethylene (ethylene) content of 50 to 80% by weight, Mooney viscosity (Money viscosity, ML1 + 8, 125 ℃) Thermoplastic crosslinked elastomer composition having a value of 45 to 70. The method of claim 1,
The paraffin oil is a thermoplastic crosslinked elastomer composition having a kinematic viscosity of 90 to 180 cSt at 40 ℃. The method of claim 1,
The high melt strength polypropylene has a weight average molecular weight of 200,000 to 500,000 thermoplastic crosslinked elastomer composition. The method of claim 1,
The olefin block copolymer is a thermoplastic crosslinked elastomer composition having a melt index of 0.3 to 3.0 g / 10 min at 190 ° C. and 2.16 kg. The method of claim 1,
The inorganic filler is a thermoplastic crosslinked elastomer composition of quaternary ammonium salt modified montmorillonite. The method of claim 1,
The inorganic filler is a thermoplastic crosslinked elastomer composition having an average particle diameter of 1 to 30 ㎛. The method of claim 1,
The compatibilizer is a thermoplastic crosslinked elastomer composition of maleic anhydride grafted polypropylene. The method of claim 8,
The compatibilizer is a thermoplastic crosslinked elastomer composition wherein the maleic anhydride is polypropylene grafted to 3 to 10% by weight. The method of claim 1,
Thermoplastic crosslinked elastomer composition further comprising 0.05 to 5% by weight of the crosslinking aid. The composition according to any one of claims 1 to 10, using an extruder having a length (L) / outer diameter (D) ratio of 28 or more, process temperature 140 to 210 ℃, and blowing gas supply amount 0.40 to 0.80 ml / min How to foam on condition of. Molded article made from the composition according to any one of claims 1 to 10. The method of claim 12,
Molded parts for use as automotive weather strips or as window gaskets for buildings.