KR20150039320A - A method of Grommet rubber for automobile - Google Patents
A method of Grommet rubber for automobile Download PDFInfo
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- KR20150039320A KR20150039320A KR20130117742A KR20130117742A KR20150039320A KR 20150039320 A KR20150039320 A KR 20150039320A KR 20130117742 A KR20130117742 A KR 20130117742A KR 20130117742 A KR20130117742 A KR 20130117742A KR 20150039320 A KR20150039320 A KR 20150039320A
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- South Korea
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- grommet
- rubber
- vulcanization
- whitening
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R16/00—Electric or fluid circuits specially adapted for vehicles and not otherwise provided for; Arrangement of elements of electric or fluid circuits specially adapted for vehicles and not otherwise provided for
- B60R16/02—Electric or fluid circuits specially adapted for vehicles and not otherwise provided for; Arrangement of elements of electric or fluid circuits specially adapted for vehicles and not otherwise provided for electric constitutive elements
- B60R16/0207—Wire harnesses
- B60R16/0215—Protecting, fastening and routing means therefor
- B60R16/0222—Grommets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08K3/06—Sulfur
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives 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
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
More particularly, the present invention relates to a process for producing a grommet rubber composition for automobiles, which comprises processing a grommet rubber composition containing a rubber compound of ethylene-propylene-diene monomer (EPDM), a plasticizer and a vulcanization accelerator, To a method of manufacturing a grommet for automobiles capable of solving the problem of whitening of an automotive grommet.
Generally, a grommet for automobiles is made of a soft rubber material and has a corrugated shape for protecting the wire harness from breakage by external cracks or other external objects when the wire harness is connected to a predetermined portion Lt; / RTI >
A conventional grommet includes a corrugated pipe for protecting a wire harness moving from a vehicle body to a vehicle door, and a panel insertion groove provided in a through hole of a car panel along an outer circumferential surface at one end of a conical body having a penetrating portion inside And a protrusion formed in the other end portion of the hollow portion to be connected to the penetration portion of the body.
Automotive grommets are produced by blending base polymers, processing aids, crosslinking agents, fillers, vulcanization accelerators, etc., and pressing or injection molding the grommets. The grommet rubber thus manufactured is mounted on the vehicle, There is a problem that the commerciality of the vehicle is lowered due to the occurrence of whitening of the grommet rubber. Existing automotive grommet rubber is a major factor in the deterioration of the marketability due to the migration of the plasticizer and the vulcanization accelerator to the surface of the radiator hose after a certain period of time due to external environmental conditions, particularly, heat, humidity and ozone. The reason for this is that when the vulcanization accelerating agent which helps and accelerates the vulcanization is activated and the vulcanization time of the rubber product is not sufficient, the accelerator And the zinc oxide is transferred to the hose surface to cause whitening.
Therefore, in the present invention, the optimum blending conditions and vulcanization conditions of the grommet composition at the time of manufacturing the automotive grommet rubber were confirmed to complete the present invention.
DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a grommet rubber composition containing a specific combination of EPDM (ethylene-propylene-diene monomer) rubber, plasticizer and vulcanization accelerator, The present invention also provides a method of manufacturing a grommet for automobiles.
In addition, the present invention solves the problem of whitening of a grommet for a vehicle, which is problematic in the field, by finding the optimal blending condition and optimum vulcanizing condition of the grommet composition in manufacturing a grommet for automobile, The present invention also provides a method for manufacturing a grommet for automobiles.
However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.
In order to achieve the above object, a method of manufacturing a grommet for automobiles according to an embodiment of the present invention comprises the steps of: 100 phr of an EPDM rubber, 1 to 5 phr of a vulcanization accelerator, 65 to 75 phr of a plasticizer, 1 to 2 phr of a vulcanizing agent, 160 to 200 phr, and 1 to 10 phr of at least one additive selected from graphite, molybdenum disulfide and wax, to prepare a mixture; A second step of press molding the mixture at a vulcanization temperature of 190 to 195 DEG C and a vulcanization time of 140 seconds to 180 seconds to produce a molded article; And a third step of evaluating the whiteness of the molding by an immersion test method.
According to an additional feature of the present invention, the vulcanization accelerator is selected from the group consisting of tetramethylthiuram disulfide, zinc di-n-butyl dithiocarbamate, dipentamethylenethiuram tetrasulfide, 1,3-diphenyl guanidine, Thiazole disulfide, and thiazole disulfide.
According to an additional feature of the present invention, the plasticizer is characterized in that it is composed of at least one selected from paraffinic oil, aromatic oil and naphthenic oil.
According to an additional feature of the present invention, the additive further comprises at least one processing aid selected from zinc oxide, magnesium oxide, and potassium hydroxide.
The method for manufacturing a grommet for automobiles according to an embodiment of the present invention is characterized in that the automotive grommet rubber is excellent in whitening resistance and can cause a problem of whitening of an automotive grommet in a field, Thereby providing the effect of enhancing the merchantability of the automobile.
In addition, the manufacturing method of automotive grommet rubber according to another embodiment of the present invention provides an effect of increasing the wear resistance of the rubber member and maintaining frictional force or proper level, thereby prolonging the service life of the vehicle holding and grommet structure do.
1 is a perspective view showing a waterproof structure of an automotive grommet according to the present invention;
2 is a cross-sectional view showing the waterproof structure of the automotive grommet according to the present invention.
3 is a view showing a use state of a vehicle grommet according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a detailed description of preferred embodiments of the present invention will be given with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
As shown in FIGS. 1 to 3, the
A panel insertion groove is formed at one end of the
When the
The depth of the waterproofing
The composition of the automotive grommet rubber material is selected from the group consisting of 100 phr of EPDM rubber, 1 to 5 phr of vulcanization accelerator, 65 to 75 phr of plasticizer, 1 to 2 phr of vulcanization agent, 160 to 200 phr of inorganic filler and molybdenum disulfide and wax And 1 to 10 phr of at least one additive.
EPDM (ethylene-propylene-diene monomer) rubber is a raw material rubber and has good heat resistance and water resistance, and is suitable for use as a main material of grommet rubber.
The vulcanization accelerator promotes the vulcanization of the EPDM rubber. In the present invention, the vulcanization accelerator includes tetramethylthiuram disulfide (TMTD) (hereinafter referred to as "TT"), zinc di-n-butyldithiocarbamate (Zincdi-nbutyldithiocarbamate, hereinafter referred to as "BZ"), dipentamethylenethiuramtetrasulfied (hereinafter referred to as "TRA"), 1,3-diphenylguanidine , Hereinafter referred to as "D") and dibenzothiazole disulfide (hereinafter referred to as "DM "). The vulcanization accelerator is preferably used in an amount of 1 to 5 phr per 100 phr of EPDM. If less than 1 phr is used, mechanical properties of the grommet rubber itself may be deteriorated due to incomplete vulcanization at the time of product molding, , The unreacted vulcanization accelerator may migrate to the surface of the grommet rubber to cause whitening, so that it is preferable to use the rubber within the above range. The vulcanization accelerator is preferably used in combination with the vulcanization accelerator.
It is preferable to use at least one selected from the group consisting of paraffin oil, aromatic oil and naphthenic oil. The amount of the plasticizer is preferably 70 to 75 phr per 100 phr of EPDM. If the amount of the plasticizer used is less than 70 phr, there is a problem in workability, which may cause problems in flowability during molding. If the plasticizer is used in excess of 75 phr, whitening may occur.
As the vulcanizing agent, sulfur is used. As the precursor thereof, at least one selected from powdered sulfur, insolublesulfur and precipitated sulfur may be used. The use of 1 to 2 phr of vulcanizing agent per 100 phr of EPDM is advantageous to the mechanical properties of grommet rubber.
The inorganic filler is used to improve the mechanical properties of the goromet rubber, and at least one selected from carbon black, calcium carbonate (CaCO3), diatomaceous earth (ash: Si, Al, Ca), and clay .
The amount of the inorganic filler to be used is preferably 160 to 200 phr per 100 phr of EPDM. If it is outside this range, the mechanical properties required for automotive grommet rubber may not be satisfied. .
The additive may be at least one selected from graphite, molybdenum disulfide (MoS 2 ) and wax.
The amount of the additive to be used is preferably 1 to 10 phr per 100 phr of the main EPDM. When the amount of the additive is less than 1 phr, sufficient physical properties may not be obtained. If the additive is used in an amount exceeding 10 phr, Mechanical properties may be deteriorated. Therefore, it is preferable to use within the above range.
The processing aid may be further added to the additive, and the processing aid may be at least one selected from zinc oxide (ZnO), magnesium oxide (MgO), and potassium hydroxide (Hydrated lime).
As another embodiment of the present invention, there is provided a method of manufacturing a grommet for automobiles according to the present invention, comprising the steps of: providing a rubber composition comprising 100 phr of an EPDM rubber, 1 to 5 phr of a vulcanization accelerator, 65 to 75 phr of a plasticizer, A first step of mixing a rubber composition comprising 160 to 200 phr of a filler and 1 to 10 phr of at least one additive selected from graphite, molybdenum disulfide and wax to prepare a mixture; And a second step of press molding the mixture at a vulcanization temperature of 190 to 195 DEG C and a vulcanization time of 140 seconds to 180 seconds to produce a molded article.
In addition, the manufacturing method may further include a third step of evaluating the blooming of the molding by an immersion test method.
The characteristics of each composition of the grommet rubber composition in the first step are the same as those described above.
In the second step, if the vulcanization temperature is lower than 190 ° C, the vulcanization is insufficient and the mechanical properties of the grommet rubber are lowered. If the vulcanization temperature is higher than 195 ° C, the mechanical properties may deteriorate. . The vulcanization time is determined by the vulcanization temperature as the vulcanization time which can prevent the whitening of the grommet rubber and optimize the mechanical properties when the gum rubber composition is vulcanized at the vulcanization temperature.
The third step of the immersion test method is a method of visually confirming the occurrence of whitening on the surface after immersing at 75 to 85 ° C for 150 to 180 hours. As a result, the whitening phenomenon of the grommet rubber And it is possible to improve evaluation efficiency and reproducibility by shortening the evaluation period, which takes about 30 days, to one week.
In addition, a sample may be collected from the molding, and the cause of whitening may be confirmed through Fourier-Transform Infrared (FT-IR), Scanning Electron Microscope (SEM), and EDS (Energy Dispersive Spectroscopy) analysis.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.
Example
Examples 1 to 2 and Comparative Examples 1 to 3
The gum rubber composition for automobile as shown in Table 1 was mixed to prepare a mixture. Then, the grommet rubber for automobile was produced by press molding at the vulcanization temperature and vulcanization time shown in Table 1 below.
In addition, Example 2 and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1 to prepare grommet rubber as shown in Table 1 below.
(3) DM: dibenzothiazole disulfide (4) BZ: zinc di-n-butyl dithiocarbamate
(5) CZ: N-cyclohexylbenzothiazole sulfenamide
(6) TT: Tetramethylthioran disulfide
(7) TRA: dipentamethylene thiuram tetrasulfide
Experimental Example
Conditions and Results of Whitewash Evaluation
After taking a sample from the grommet rubber, it is immersed in a glass beaker together with tap water. After immersing at 80 ° C for 168 hours, visually check whether whitening of the surface occurred. The water is changed every 24 hours and the container is cleaned when water is exchanged. The whitening resistance evaluation results of Experimental Examples 1 to 4 and Comparative Experimental Example 1 are shown in Table 2 below.
From the results of the whitening resistance evaluation in Table 2, it can be confirmed that the whitening phenomenon occurs in the case of the grommet rubber produced out of the composition material, composition ratio, or vulcanizing condition presented by the present invention.
As described above, preferred embodiments of the present invention have been disclosed in the present specification and drawings, and although specific terms have been used, they have been used only in a general sense to easily describe the technical contents of the present invention and to facilitate understanding of the invention , And are not intended to limit the scope of the present invention. It is to be understood by those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.
100: Automotive grommet 110: Body
111: Inner waterproof chin 115: Waterproof chin seat
117: Waterproof barrier 119: Installation hole
120: panel 130:
140: Wrinkle portion 150: Wire harness
Claims (4)
A second step of press molding the mixture at a vulcanization temperature of 190 to 195 DEG C and a vulcanization time of 140 seconds to 180 seconds to produce a molded article; And
And a third step of evaluating the whiteness of the molding by an immersion test method.
Wherein the vulcanization accelerator is at least one selected from tetramethylthiuram disulfide, zinc di-n-butyl dithiocarbamate, dipentamethylenethiuram tetrasulfide, 1,3-diphenyl guanidine and dibenzothiazole disulfide Wherein the grommet is made of a rubber.
Wherein the plasticizer is at least one selected from paraffinic oils, aromatic oils and naphthenic oils.
Wherein the additive further comprises at least one processing aid selected from zinc oxide, magnesium oxide and potassium hydroxide.
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KR20130117742A KR20150039320A (en) | 2013-10-02 | 2013-10-02 | A method of Grommet rubber for automobile |
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KR20130117742A KR20150039320A (en) | 2013-10-02 | 2013-10-02 | A method of Grommet rubber for automobile |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019055964A1 (en) * | 2017-09-18 | 2019-03-21 | Bridgestone Americas Tire Operations, Llc | Rubber articles with improved fire properties |
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2013
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019055964A1 (en) * | 2017-09-18 | 2019-03-21 | Bridgestone Americas Tire Operations, Llc | Rubber articles with improved fire properties |
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