WO2024075857A1 - Composition de caoutchouc epdm ayant un effet de gaufrage de surface sur un moulage de coin de glissière de vitre à l'aide d'un uhmwpp, et produit de glissière de vitre pour véhicule l'utilisant - Google Patents

Composition de caoutchouc epdm ayant un effet de gaufrage de surface sur un moulage de coin de glissière de vitre à l'aide d'un uhmwpp, et produit de glissière de vitre pour véhicule l'utilisant Download PDF

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WO2024075857A1
WO2024075857A1 PCT/KR2022/014875 KR2022014875W WO2024075857A1 WO 2024075857 A1 WO2024075857 A1 WO 2024075857A1 KR 2022014875 W KR2022014875 W KR 2022014875W WO 2024075857 A1 WO2024075857 A1 WO 2024075857A1
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glass run
uhmwpp
weight
rubber composition
epdm
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PCT/KR2022/014875
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Korean (ko)
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남영
박준일
김성수
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유일고무 주식회사
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/435—Sulfonamides
    • 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
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • EPDM rubber composition that has an embossing effect on the surface of a glass run corner molded part using UHMWPP, and more specifically, is used in a corner molded part of a glass run channel product, which is a sealing part for automobiles. It relates to a rubber composition.
  • the Glass Run Channel is mounted on the edge of the window of a car door and serves as a guide (prevention of separation) when raising/lowering the window and blocks wind, rainwater, noise, and dust that may enter the interior from the outside. It is a sealing part that blocks. Therefore, considering the installation location of the product, it is a part that must satisfy the characteristics of the exterior material and the interior material at the same time because it is installed on the borderline between the automobile interior and exterior materials.
  • the glass run product includes an extruded rubber profile formed by an extrusion method and a corner molding part where the extruded cross section is molded to fit the corner of the car window. At this time, a unique feeling is created due to the difference in the molding method. do.
  • UHMWPP in order to improve the appearance quality of the corner molding part of the glass run channel (hereinafter referred to as glass run) product, which is an automobile part, UHMWPP was used to minimize the discoloration of the extruded cross section and corner molding part constituting the glass run part.
  • the purpose of this study is to provide an EPDM rubber composition that has an embossing effect on the surface of a glass run corner molding area and a glass run product for automobiles using the same.
  • An EPDM rubber composition having an effect of embossing the surface of a glass run corner molded part using UHMWPP includes ethylene propylene diene monomer (EPDM), reinforcing agent, softener, high-performance olefin resin, vulcanization activator, anti-foaming agent, vulcanizing agent, and a vulcanization accelerator, and the high-functional olefin resin may have a weight average molecular weight (Mw) in the range of 500,000 to 2,500,000, as measured by gel permeation chromatography (GPC).
  • Mw weight average molecular weight
  • the high-functional olefin resin may have a melting point in the range of 110°C to 200°C, as measured by differential scanning calorimetry (DSC).
  • the high-functional olefin resin may have a melt index (MI) of 0.05 to 20 g/10 min as measured by ASTM D1238.
  • the high-performance olefin-based resin may include ultra high molecular weight polypropylene (UHMWPP).
  • UHMWPP ultra high molecular weight polypropylene
  • the content of the high-functional olepine resin may range from 6 parts by weight to 24 parts by weight based on the weight parts of the ethylene propylene diene monomer (EPDM).
  • EPDM ethylene propylene diene monomer
  • the ethylene propylene diene monomer may have a pattern viscosity (ML1+4, 125°C) of 60 mu or less.
  • the ethylene propylene diene monomer may have an ethylidene norbornene (ENB) content of 7% by weight or more and an ethylene (Ethylene) content of 60.0% by weight or less.
  • the rubber composition includes 75 to 100 parts by weight of the reinforcing agent, 35 to 45 parts by weight of the softener, and 5 to 10 parts by weight of the vulcanization activator, based on 100 parts by weight of the ethylene propylene diene monomer (EPDM). It may include 2 to 5 parts by weight of the processing aid, 3 to 5 parts by weight of the anti-foaming agent, 1 to 2 parts by weight of the vulcanizing agent, and 2 to 5 parts by weight of the vulcanization accelerator.
  • EPDM ethylene propylene diene monomer
  • the reinforcing agent may include at least one of carbon black and silica.
  • the reinforcing agent may have an average particle diameter ranging from 40 to 48 nm.
  • the vulcanization activator may include zinc oxide and stearic acid.
  • the vulcanizing aid may include polyethylene glycol (PEG#4000: molecular weight 4,000) and a metal salt.
  • the vulcanization accelerator is at least one of 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), zinc di-n-butyl dithiocarbamate (ZnBDC), tetramethylthiuram disulfide (TMTD), and N-cyclohexyl-2-benzothiazyl sulfonamide (CBS).
  • MBT 2-mercaptobenzothiazole
  • MBTS dibenzothiazyl disulfide
  • ZnBDC zinc di-n-butyl dithiocarbamate
  • TMTD tetramethylthiuram disulfide
  • CBS N-cyclohexyl-2-benzothiazyl sulfonamide
  • a glass run product for automobiles according to another embodiment may be manufactured using an EPDM rubber composition that has an embossing effect on the surface of the glass run corner molded part using the UHMWPP.
  • the surface roughness of the corner molded portion of the glass run product may be 1.0 Ra or more.
  • the corner molding parts of glass run products are generally manufactured using the surface corrosion method of a transfer mold.
  • this surface corrosion method has the problem of deteriorating the exterior quality of the product due to wear of the corroded surface and adsorption of rubber oil vapor on the surface during the product manufacturing process.
  • Figure 1 is a schematic diagram of an apparatus for illustrating a transfer type molding method.
  • Figure 2 shows a surface photograph of a specimen manufactured using the rubber composition prepared according to Example 1 and Comparative Examples 1 to 2.
  • Figure 3 shows the equipment used to measure surface roughness in this example.
  • Figures 4a and 4b show poor dispersion of the rubber composition of Reference Example 2.
  • Figure 5 shows surface photographs of specimens manufactured using the rubber compositions prepared according to Reference Example 1, Example 2, and Example 3.
  • Figure 6a shows a sample using the existing glass run corner joint rubber.
  • Figure 6b shows a sample using the glass run corner joint rubber prepared using the rubber composition prepared according to Example 3.
  • first, second, and third are used to describe, but are not limited to, various parts, components, regions, layers, and/or sections. These terms are used only to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, the first part, component, region, layer or section described below may be referred to as the second part, component, region, layer or section without departing from the scope of the present invention.
  • An EPDM rubber composition having an effect of embossing the surface of a glass run corner molded part using UHMWPP includes ethylene propylene diene monomer (EPDM), reinforcing agent, softener, high-performance olefin resin, vulcanization activator, anti-foaming agent, vulcanizing agent, and a vulcanization accelerator.
  • EPDM ethylene propylene diene monomer
  • the high-functional olefin resin is used to ensure the surface corrosion effect.
  • the high-functional olefin resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 500,000 to 2,500,000, more specifically, in the range of 2,500,000. If the weight average molecular weight of the high-functional olefin resin satisfies the above range, a glass run product with excellent tensile strength and wear resistance can be produced.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the high-functional olefin resin may have a melting point measured by differential scanning calorimetry (DSC) in the range of 110°C to 200°C, more specifically 130°C to 180°C or 150°C to 175°C. .
  • DSC differential scanning calorimetry
  • the high-functional olefin resin may have a melt index (MI; melt index) of 0.05 to 20 g/10 min, more specifically 0.05 to 5 g/10 min, or 0.5 to 5 g/10 min, as measured by ASTM D1238. there is.
  • MI melt index
  • the melting point and melt index satisfy the above range, a glass run product with excellent tensile strength and wear resistance can be produced.
  • the high-functional olefin resin may include, for example, ultra high molecular weight polypropylene (UHMWPP).
  • UHMWPP ultra high molecular weight polypropylene
  • the content of the high-functional olefin resin may range from 6 parts by weight to 24 parts by weight, more specifically, from 10 parts by weight to 20 parts by weight, based on the weight parts of the ethylene propylene diene monomer (EPDM). If the content of the high-functional olefin-based resin is less than 6 parts by weight, there is a problem of insufficient embossing effect, and if the content of the high-functional olefin-based resin exceeds 24 parts by weight, dispersion failure may occur during the kneading process for manufacturing the high-performance composition. .
  • LDPE is sometimes used to reinforce rigidity. This is to incorporate the high hardness and physical properties of poly-olefin elastomer (POE: Poly Olefin Elastomer) into rubber compounding.
  • POE Poly Olefin Elastomer
  • UHMWPP material is difficult to process using the existing P.P polymer material processing method due to maximization of molecular weight and high viscosity, so a new method is needed in rubber compounding. .
  • the above-mentioned LDPE achieves plasticization through sufficient softening in the rubber mixture, but UHMWPP exists in a state in which the shape of UHMWPP itself is maintained in the rubber mixture.
  • This UHMWPP maintains its particle shape at high molding temperatures and can maintain its shape even after vulcanization of the corner molding part of the glass run product, thereby producing a surface embossing effect.
  • EPDM Ethylene propylene diene monomer
  • EPDM which has excellent weather resistance performance among synthetic rubbers, is used, and this is a common issue among not only domestic but also global weather strip manufacturers.
  • EPDM was also used as the base polymer in the present invention.
  • corner molding part of glass run products is done by transfer molding, and transfer molding requires excellent flow of rubber. Therefore, products with relatively low pattern viscosity are preferred.
  • EPDM ethylene/propylene content ratio
  • the ethylene propylene diene monomer (EPDM) used in this example preferably has a fringe viscosity (ML1+4, 125°C) of 60 mu or less, more specifically 20 mu or more and 30 mu or less. If the pattern viscosity of EPDM satisfies the above range, a low pattern viscosity of the EPDM rubber composition with an embossing effect on the surface of the glass run corner molded part using UHMWPP according to an embodiment can be secured, and thus excellent rubber flow is achieved. ), the molding workability of glass run products is excellent, which can improve productivity and ensure uniform product quality.
  • ML1+4, 125°C fringe viscosity
  • ENB 1, 4-Hexadiene
  • DCPD Dicyclopentadiene
  • EPDM containing ethylidene norbornene (ENB) was used. This is advantageous not only in terms of crosslinking properties, but also in securing productivity and high product properties due to fast crosslinking performance.
  • the ethylene propylene diene monomer has an ethylidene norbornene (ENB) content of 7% by weight or more, more specifically 7.5 to 9.0% by weight, based on the EPDM. It is desirable. When the ENB content included in EPDM satisfies the above range, the vulcanization reaction is activated and the productivity of glass run products can be improved.
  • the ethylene propylene diene monomer preferably has an ethylene content of 60.0% by weight or less, more specifically 55 to 60% by weight, based on EPDM.
  • the ethylene content included in EPDM satisfies the above range, crystallinity is excellent, so when a product is manufactured using the rubber composition of this example, automobile assembly workability is excellent.
  • the reinforcing agent may include at least one of carbon black and silica.
  • the carbon black is classified into N100 to N900 according to ASTM standards according to particle size.
  • N200 ⁇ N300 products with small particle sizes are generally used for tire products that require high durability
  • N700 ⁇ N900 products are generally used for products that require high dynamic characteristics.
  • N550 that is, FEF (Fast Extrusion Furnace) carbon black
  • FEF Fast Extrusion Furnace
  • the reinforcing agent may be included in the range of 75 parts by weight to 100 parts by weight based on 100 parts by weight of ethylene propylene diene monomer (EPDM). If the content of reinforcing agent is less than 75 parts by weight, mechanical properties may be significantly reduced.
  • EPDM ethylene propylene diene monomer
  • glass run products are functional parts, they also require high emotional quality, that is, appearance quality. Therefore, since the softener used in this embodiment may cause emotional quality issues such as discoloration and discoloration, paraffin oil, for example, rubber compounding oil (process oil), which is relatively excellent in discoloration, discoloration, and heat aging, can be used.
  • paraffin oil for example, rubber compounding oil (process oil), which is relatively excellent in discoloration, discoloration, and heat aging, can be used.
  • the softener may be included in the range of 35 parts by weight to 45 parts by weight based on 100 parts by weight of the ethylene propylene diene monomer (EPDM).
  • EPDM ethylene propylene diene monomer
  • the content of the softener is less than 35 parts by weight, dispersibility and processability are poor when manufacturing the rubber composition, and hardness increases, making molding difficult.
  • the softener content exceeds 45 parts by weight, dispersibility is poor, and physical properties are reduced due to a decrease in hardness, which may lead to a decrease in sealing performance.
  • calcium carbonate can be used as needed to improve appearance quality and secure cost competitiveness, and can be used in the range of 0 to 20 parts by weight based on 100 parts by weight of ethylene propylene diene monomer (EPDM). If the content of calcium carbonate exceeds 20 parts by weight, poor dispersion and deterioration of physical properties may occur.
  • EPDM ethylene propylene diene monomer
  • Vulcanization activator is a rubber raw material to improve the acceleration ability of vulcanization accelerator.
  • zinc oxide ZinC Oxide
  • metal oxide ZinC Oxide
  • stearic acid fatty acid
  • Processing aids are added in a small amount to the rubber mixture to improve processability such as mixing and dispersion of rubber raw materials, and polyethylene glycol (PEG#4000: molecular weight 4,000) and metal salt are added to ensure smooth molding process through lubricating effect. ) is used.
  • the vulcanization activator may include 5 to 10 parts by weight based on 100 parts by weight of the ethylene propylene diene monomer (EPDM).
  • EPDM ethylene propylene diene monomer
  • the steel processing aid may include 2 to 5 parts by weight based on 100 parts by weight of the ethylene propylene diene monomer (EPDM).
  • EPDM ethylene propylene diene monomer
  • Moisture that may exist inside the rubber is evaporated during the molding process, forming pores inside. Pores formed inside the product may affect the outside in the form of protrusions, and durability may be reduced in some cases.
  • CaO is used as an anti-foaming agent to remove moisture in advance, which is the cause of pore formation. In particular, it must be used in the extrusion process.
  • Moisture and calcium oxide react to produce calcium hydroxide, which has the same effect as the inorganic filler dispersed inside the rubber, so it can suppress the creation of pores.
  • the anti-foaming agent may be used in an amount of 3 to 5 parts by weight based on 100 parts by weight of the ethylene propylene diene monomer (EPDM).
  • EPDM ethylene propylene diene monomer
  • the crosslinking method for the rubber composition includes, for example, sulfur crosslinking, peroxide crosslinking, and resin crosslinking, but in this embodiment, it can be manufactured by the sulfur crosslinking method.
  • Sulfur crosslinks are formed when sulfur is combined in the double bond structure of the base polymer, and sulfur must be used to provide elasticity to the rubber compound.
  • the vulcanizing agent used sulfur
  • vulcanization accelerator can increase the vulcanization speed and enable efficient vulcanization at a relatively low temperature.
  • the vulcanizing agent may be included in an amount of 1 to 2 parts by weight based on 100 parts by weight of the ethylene propylene diene monomer (EPDM).
  • EPDM ethylene propylene diene monomer
  • a vulcanization accelerator may be used to accelerate the vulcanization reaction.
  • the vulcanization accelerator is at least one of 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), zinc di-n-butyl dithiocarbamate (ZnBDC), tetramethylthiuram disulfide (TMTD), and N-cyclohexyl-2-benzothiazyl sulfonamide (CBS).
  • MBT 2-mercaptobenzothiazole
  • MBTS dibenzothiazyl disulfide
  • ZnBDC zinc di-n-butyl dithiocarbamate
  • TMTD tetramethylthiuram disulfide
  • CBS N-cyclohexyl-2-benzothiazyl sulfonamide
  • the MBT (2-mercaptobenzothiazole) is generally less prone to contamination, exhibits smooth vulcanization, and has excellent aging resistance and physical properties. Facilitative ability has quasi-facilitative ability.
  • MBTS dibenzothiazyl disulfide
  • ZnBDC zinc di-n-butyl dithiocarbamate
  • TMTD tetramethylthiuram disulfide
  • super accelerator because it has a very strong vulcanization accelerator, is non-contaminating, and can secure high tensile strength and modulus.
  • CBS N-cyclohexyl-2-benzothiazyl sulfonamide
  • CBS is a sustained-acting accelerator, which is advantageous in securing the initial flowability of transfer molding by slowing down the initial vulcanization speed.
  • the vulcanization accelerator may include 2 to 5 parts by weight based on 100 parts by weight of the ethylene propylene diene monomer (EPDM).
  • EPDM ethylene propylene diene monomer
  • the EPDM rubber composition that has an effect of embossing the surface of the glass run corner molded part using UHMWPP contains 75 to 100 parts by weight of the reinforcing agent and the softener, based on 100 parts by weight of the ethylene propylene diene monomer (EPDM). 35 to 45 parts by weight, 5 to 10 parts by weight of the vulcanization activator, 2 to 5 parts by weight of the processing aid, 3 to 5 parts by weight of the anti-foaming agent, 1 to 2 parts by weight of the vulcanizing agent. parts, and may include 2 to 5 parts by weight of the vulcanization accelerator.
  • EPDM ethylene propylene diene monomer
  • the EPDM rubber composition which has an embossing effect on the surface of a glass run corner molded part using UHMWPP according to an embodiment, can secure excellent tensile strength and abrasion resistance because it contains the above-mentioned high-performance olefin resin.
  • an embossing effect can be implemented on glass run products, thereby ensuring excellent exterior quality and uniformity of exterior quality by minimizing discoloration between the extruded cross section and corner molding section.
  • a glass run product for automobiles manufactured using an EPDM rubber composition having a surface embossing effect on a glass run corner molded portion using the above-described UHMWPP can be provided.
  • the surface roughness of the corner molded part of the glass run product is 1.0Ra or more. If the surface roughness is 1.0 Ra or more, the discoloration of the extruded cross section can be minimized, and excellent external quality of the product can be secured.
  • corner molding of glass run products is generally produced by transfer molding.
  • Transfer molding is a compression mold that is applied when it is difficult to manufacture with an injection mold. Rubber is injected into the pot at the top of the upper mold and the glass run corners are formed with the force of closing the upper and lower molds.
  • This method is widely used because it is suitable for glass run corner molding, which is an automobile part where dimensional stability is most important. Therefore, it is most important that the weight of the input rubber is kept constant. If the weight of the rubber is large, the weight overflows from inside the molding space to the outside, causing the contact area with the extruded surface to be pushed, and if the input weight is small, the weight overflows from inside the molding space to the outside. , short shots occur.
  • Figure 1 is a schematic diagram of an apparatus for illustrating a transfer type molding method.
  • the transfer molding method is the most commonly used method for manufacturing glass run corner molding parts, and almost all glass runs are manufactured using the transfer molding method.
  • a certain weight of rubber is injected into a hole at the top of the mold called a POT, and as the prize mold mounted on the press descends, the injection rod is pressed into the hole, and the injected rubber is released into the glass run space. Molding takes place by injecting it into the body.
  • the mold temperature is set in the range of 180-200°C, and the vulcanization time is maintained at around 2 minutes (120 seconds) to 3 minutes (180 seconds) depending on the vulcanization characteristics of the rubber material in the injected state.
  • a vulcanization time of 4 to 5 minutes may be necessary.
  • Rubber compositions according to Examples 1 to 2 and Comparative Examples 1 to 2 were prepared by mixing at the composition ratio shown in Table 1 below.
  • the kneading process for each rubber composition was performed in a Banbury Mixer for CMB rubber and in a Kneader for FMB rubber.
  • the EPDM polymer used to manufacture CMB was KEP-330 (Kumho Polychem), and the carbon black was HS-45 from Orion Engineering Carbons. Additionally, ZnO (Zinc Oxide), Stearic Acid, and ZnO were used as vulcanization activators and processing aids. PEG#4000 (Poly Ethylene Glycol MW 4000) was used. Specific information on the EPDM polymer used in this example is shown in Table 2 below.
  • the softener used was a paraffin-based rubber compounding oil.
  • CaO Calcium Oxide
  • processing aid was used to ensure the stability of the glass run corner molding.
  • the processing aid is a blend of fatty acid derivatives (Mainly zinc soaps), and is used because it is efficient in filling every corner of the molded part with high flowability when the rubber composition is filled into the mold.
  • MBTS Mercaptobenzothiazole disulfide (C 14 H 8 N 2 S 4 )
  • ZnBDC Zinc dibutyl dithiocarbamate ([(C 4 H 9 ) 2 NCS 2 ] 2 Zn)
  • TMTD Tetramethyl thiuram disulfide ([(CH 3 ) 2 NCS 2 -] 2 )
  • the manufacturing process of the EPDM rubber composition with the surface embossing effect of the glass run corner molding part using UHMWPP in this embodiment can be largely divided into CMB (Carbon Master Batch) and FMB (Final Master Batch) processes.
  • the manufacturing process of CMB rubber is a process in which the pulverized base polymer and raw materials are mixed by adding reinforcing agents, softeners, high-functional olefin resins, vulcanizing activators, processing aids, and anti-foaming agents after first pulverizing the base polymer. am.
  • CMB rubber produced through this process is a material that does not undergo a vulcanization reaction even when heat is applied, so it cannot be molded into a product and can be stored for a long time.
  • CMB rubber can be subjected to a process called aging for a certain period of time to stabilize the base polymer against the high mechanical stress experienced during the manufacturing process.
  • the FMB process is a process of mixing CMB rubber with a fixed amount of vulcanizing agent (sulfur) and vulcanization accelerator. These raw materials must be mixed to create a finished rubber composition.
  • the rubber composition according to this example was designed with a focus on hardness (Shore) 70A, which is a general required property for glass run corner molded parts.
  • the rubber composition according to Example 1 has tensile strength and abrasion resistance compared to the rubber composition prepared according to Comparative Example 1 in which high-performance olefin resin was not used and Comparative Example 2 in which LDPE resin was used. You can confirm this excellence.
  • Table 5 and Figure 2 show surface roughness measurement results and surface photographs of specimens manufactured using the rubber compositions prepared according to Example 1 and Comparative Examples 1 to 3. That is, the surface embossing effect of the rubber compositions according to Example 1 and Comparative Examples 1 to 2 was compared and evaluated by measuring surface roughness.
  • Figure 3 shows the equipment used to measure surface roughness in this example. Specifically, the tip of the illuminance needle, indicated by a yellow circle in Figure 3, moves to measure surface roughness.
  • Example 1 the surface embossing effect could be confirmed with the naked eye.
  • Comparative Example 2 using LDPE resin a POE product
  • the surface roughness is lower than in the case of Comparative Example 1 without adding POE. It is believed that sufficient melting occurred during the specimen molding process, and this plasticization resulted in relatively good surface smoothness and low surface roughness.
  • the discoloration with the extruded cross section can be minimized.
  • Rubber compositions were prepared according to Examples 2 to 3 and Reference Examples 1 to 2 for each high-functional olefin resin (UHMWPP) content by mixing at the composition ratio shown in Table 6 below.
  • UHMWPP high-functional olefin resin
  • the rubber kneading method was the same as that in Experimental Example 1. That is, CMB rubber was kneaded in a Banbury Mixer, and FMB rubber was kneaded in a Kneader.
  • EPDM polymer was KEP-330 (Kumho Polychem), and carbon black was Orion Engineering Carbons' HS-45.
  • ZnO Zinc Oxide
  • Stearic Acid Stearic Acid
  • PEG#4000 Poly Ethylene Glycol MW 4000
  • the softener used was a paraffin-based rubber compounding oil.
  • Example 2 Example 3 Reference example 2 CMB polymer EPDM 100 100 100 100 adjuvant Carbon Black 85 85 80 80 softener Process Oil 40 40 40 40 High functionality Olefin type profit UHMWPP 5 10 20 25 Vulcanizing activator & Processing aid Zinc Oxide 8 8 8 8 Stearic Acid 1.5 1.5 1.5 1.5 PEG#4000 2 2 2 2 Process Aid 2 2 2 anti-foam agent Calcium Oxide 5 5 5 5 CMB Subtotal 248.5 253.5 258.5 263.5 FMB vulcanizing agent Sulfur 1.5 1.5 1.5 1.5 1.5 Vulcanization accelerator Accelerator MBT 0.7 0.7 0.7 0.7 Accelerator MBTS 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Accelerator ZnBDC One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One Accelerator TMTD 0.5 0.5 0.5 0.5 0.5 AcceleratorCBS 1.2 1.2 1.2 1.2 Total (CMB + FMB)
  • Example 2 Example 3 Unvulcanized rubber Basic physical properties scorch (Scorch at 125°C) VMs 24.3 25.5 26.8 T5 10’03 9'41 9’12 rheometer (180°C ⁇ 6 minutes) Tmax 39.2 40.5 41.8 Tmin 4.7 4.9 4.8 ts1 0’47 0'46 0’45 ts5 1’03 0'59 0’57 T10 0’57 0'56 0’55 T90 3’28 3'03 2’57
  • Example 2 Example 3 vulcanized rubber basic properties Basic physical properties Hardness KS M 6518 71 72 73 tensile strength 131.3 149.3 135.6 elongation rate 273.2 265.5 255.1 Aging properties (70°C ⁇ 72Hrs) Hardness change +1 +1 +1 Tensile strength change +1 0 +1 Elongation rate change -3 -2 -2 Compression permanent shrinkage rate (%) (70°C ⁇ 22Hrs) C/Set JIS K 6301 13.3 10.5 13.1
  • Figures 4a and 4b show the poor dispersion state of the rubber composition of Reference Example 2.
  • UHMWPP particles were visually confirmed on the surface ( Figure 4a). In severe cases, white UHMWPP particles separated and fell off ( Figure 4b). This is believed to be a phenomenon that occurs because excessively added UHMWPP was not sufficiently dispersed in the rubber compound.
  • Table 9 and Figure 5 show surface roughness measurement results and surface photos of specimens manufactured using the rubber compositions prepared according to Reference Example 1, Example 2, and Example 3.
  • Example 2 Example 3 surface roughness 0.125Ra 1.109 Ra 1.313Ra
  • Figure 6a is a sample using the glass run corner joint rubber manufactured using the rubber composition prepared according to Comparative Example 1 of Experimental Example 1
  • Figure 6b is a glass run manufactured using the rubber composition prepared according to Example 2. This shows a sample using corner joint rubber.
  • the present invention is not limited to the above-mentioned embodiments, but can be manufactured in various different forms, and those skilled in the art will be able to form other specific forms without changing the technical idea or essential features of the present invention. You will be able to understand that this can be implemented. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

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Abstract

Les présents modes de réalisation concernent une composition de caoutchouc EPDM utilisant un UHMWPP et ayant un effet de gaufrage de surface sur un moulage de coin de glissière de vitre, et un produit de glissière de vitre pour un véhicule l'utilisant. Spécifiquement, la composition de caoutchouc EPDM utilisant un UHMWPP et ayant un effet de gaufrage de surface sur un moulage de coin de glissière de vitre, selon un mode de réalisation, comprend un monomère d'éthylène propylène diène (EPDM), un agent de renforcement, un plastifiant, une résine oléfinique hautement fonctionnelle, un activateur de vulcanisation, un auxiliaire de traitement, un agent antimousse, un agent de vulcanisation et un accélérateur de vulcanisation, et la résine oléfinique hautement fonctionnelle peut avoir un poids moléculaire moyen en poids (Mw) dans la plage allant de 500 000 à 2 500 000 tel que mesuré par chromatographie par perméation de gel (GPC).
PCT/KR2022/014875 2022-10-04 2022-10-04 Composition de caoutchouc epdm ayant un effet de gaufrage de surface sur un moulage de coin de glissière de vitre à l'aide d'un uhmwpp, et produit de glissière de vitre pour véhicule l'utilisant WO2024075857A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960000745A (ko) * 1994-06-22 1996-01-25 배순훈 엘리베이터 운용 장치 및 방법
US20030087060A1 (en) * 2000-05-10 2003-05-08 Coran Aubert Y. Method of coating rubber with solventless crystalline polyolefin coatings
KR20160068340A (ko) * 2014-12-05 2016-06-15 현대자동차주식회사 웨더스트립 글래스 런 채널용 고무 조성물
KR20220039896A (ko) * 2020-09-21 2022-03-30 현대자동차주식회사 자동차 글라스 런 슬립코팅 조성물

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Publication number Priority date Publication date Assignee Title
KR960000745A (ko) * 1994-06-22 1996-01-25 배순훈 엘리베이터 운용 장치 및 방법
US20030087060A1 (en) * 2000-05-10 2003-05-08 Coran Aubert Y. Method of coating rubber with solventless crystalline polyolefin coatings
KR20160068340A (ko) * 2014-12-05 2016-06-15 현대자동차주식회사 웨더스트립 글래스 런 채널용 고무 조성물
KR20220039896A (ko) * 2020-09-21 2022-03-30 현대자동차주식회사 자동차 글라스 런 슬립코팅 조성물

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Title
KIM, SEONG SU ET AL.: "Development of EPDM Composite Materials and Glass Run Products with Excellent Durability by Utilizing UHMWPP", KWAHAK KONGHAK UI IRON KWA UNGYONG = THEORIES AND APPLICATIONS OF CHEMICAL ENGINEERING: PROCEEDINGS, KOREAN INSTITUTE OF CHEMICAL ENGINEERING, KOREA, vol. 27, no. 2, 1 October 2021 (2021-10-01) - 29 October 2021 (2021-10-29), KOREA , pages 2030, XP009554363, ISSN: 1225-9004 *

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