KR102465088B1 - Wet Master Batch manufacturing method for damping vibration and rubber compound using it - Google Patents

Abstract

It relates to a method for producing a master batch of a rubber composition and a vibration damping rubber composition using the same.
To this end, (a) adding carbon black to distilled water, wet milling, and stirring in a mechanical dispersion process to prepare a filler slurry; (b) preparing a first wet masterbatch (WMB) by mixing and stirring a part of the latex and the filler slurry prepared in step (a) with oil; (c) preparing a second wet masterbatch (WMB) by mixing and stirring the first wet masterbatch with the remaining filler slurry and repeating until the adhesion test passes; (d) a coagulation step of preparing a compound mass by adding brine and dilute sulfuric acid to the second wet masterbatch (WMB); and (e) washing the coagulated WMB in distilled water multiple times to wash it enough to prevent salt from coming out and drying it to prepare a final WMB; A vibration damping rubber composition is provided.

Description

Wet Master Batch manufacturing method for damping vibration and rubber compound using it}

The present invention relates to a vibration damping elastic material, and more particularly, by dispersing carbon black in rubber-based latex and then solidifying it, which can maximize dispersion of carbon black in an aqueous solution to improve vibration damping properties. It relates to elastic materials.

Recently, consumer complaints regarding vibration and noise in various products such as home appliances and automobiles are increasing, and the demand for vibration and noise reduction is increasing accordingly.

The high vibration damping elastic material developed for this purpose is important to generate a lot of energy consumption. It is necessary to use a large amount of

In addition, since the high vibration damping type elastic material is exposed to ozone, ultraviolet rays, heat, moisture and, in some cases, basic components (for ports) in the atmosphere, durable rubber materials are used in this environment.

Conventionally, natural rubber (NR), whose main component is isoprene, has been mainly used for vibration insulation formulation. Natural rubber has excellent elasticity, abrasion resistance and low temperature resistance, but is durable as a rubber material with poor oil resistance, heat resistance, weather resistance and ozone resistance. This is a low characteristic.

Therefore, it is necessary to develop a highly durable and high vibration damping type elastic material that can improve the physical properties of natural rubber and synthetic rubber products by utilizing WMB (Wet Master Batch) technology capable of high dispersion of filler.

Korean Patent Publication No. 10-2014-0073003 (published on Jun. 16, 2014)

The present invention reflects the above needs, and a method for manufacturing a high vibration damping type wet masterbatch providing vibration damping and vibration isolation by dispersing carbon black in a rubber substrate and a rubber composition using the same intended to provide

To this end, the present invention provides a method for producing a masterbatch of a rubber composition, comprising the steps of: (a) adding carbon black to distilled water, wet milling, and stirring in a mechanical dispersion process to prepare a filler slurry; (b) preparing a first wet masterbatch (WMB) by mixing and stirring a part of the latex and the filler slurry prepared in step (a) with oil; (c) preparing a second wet masterbatch (WMB) by mixing and stirring the first wet masterbatch with the remaining filler slurry and repeating until the adhesion test passes; (d) a coagulation step of preparing a compound mass by adding brine and dilute sulfuric acid to the second wet masterbatch (WMB); and (e) washing the coagulated WMB in distilled water a plurality of times to wash it so that no salt comes out, and drying it to prepare a final WMB; provides a vibration damping type wet masterbatch manufacturing method comprising.

In addition, as the latex, any one of natural rubber (NR), SBR, and NBR may be used.

In addition, as the oil, any one of paraffin-based oil, naphthenic oil, and aromatic oil may be used.

In addition, 10% by weight of the filler slurry is added in the first wet masterbatch production step of step (b), and the remaining 90% weight range is added in the second wet masterbatch production step of step (c). characterized in that

In addition, the stirring process in step (b) is stirred at 24,000 rpm for 5 to 15 minutes, the stirring process in step (c) is stirred at 12,00 rpm for 5 to 15 minutes, and repeating until the adhesion test is passed. characterized.

In addition, in step (d), the volume ratio of brine and dilute sulfuric acid is added and mixed in a range of 0.1 to 1% of dilute sulfuric acid compared to 60 to 70% of brine.

According to another aspect of the present invention, in the rubber composition, there is provided a vibrating chain rubber composition comprising a rubber base, wet masterbatch (WMB), positively extrudable carbon black (FEF) and medium reinforcing carbon black (SRF).

In addition, the rubber substrate is CIIR, and the wet masterbatch is formed by dispersing carbon black, and 10 to 40 parts by weight of the wet masterbatch is added with respect to 100 parts by weight of the total including the rubber substrate and the wet masterbatch. characterized by being

In addition, with respect to 100 parts by weight of the rubber base to which the WMB is added, 57 to 63 parts by weight of the positive extrudable carbon black, and 19 to 21 parts by weight of the medium reinforcing carbon black are added.

In addition, zinc oxide (ZnO), S/A, and PEG are further added as a crosslinking activator, 5 parts by weight of ZnO is added with respect to 100 parts by weight of the rubber base to which WMB is added, and 1 part by weight of S/A is added. , PEG is characterized in that 0.5 parts by weight is added.

In addition, with respect to 100 parts by weight of the rubber base to which the WMB is added, it is characterized in that it is added as an accelerator for elasticity strengthening in any one of DM, TT, MB, or a combination of two or more.

In addition, with respect to 100 parts by weight of the rubber base to which the WMB is added, 1.5 parts by weight of DM, 1.0 parts by weight of TT, and 0.5 parts by weight of MB are added.

The high vibration damping type elastic material according to the present invention realizes vibration reduction and vibration damping by dispersing carbon black in a rubber substrate, and it utilizes WMB (Wet Master Batch) technology capable of high dispersion of fillers to produce natural and synthetic rubber products. to improve physical properties.

1 and 2 are views showing a vibration damping type WMB manufacturing process diagram and an actual WMB manufacturing process according to a preferred embodiment of the present invention;
3 is a view showing a viscoelasticity tester for analyzing the vibration insulation effect of the rubber composition to which WMB is added according to the present invention;
4 is a view showing the DMTA evaluation results in the viscoelasticity tester of FIG. 3 to analyze the vibration insulation effect of the rubber composition to which WMB is added according to the present invention.

The high vibration damping type elastic material according to the present invention realizes vibration reduction and vibration damping by dispersing carbon black in a rubber substrate, and it utilizes WMB (Wet Master Batch) technology capable of high dispersion of fillers to produce natural and synthetic rubber products. to improve physical properties.

Hereinafter, a method for manufacturing a high vibration damping type elastic material according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 and 2 are views showing a vibration damping type Wet Master Batch (WMB) manufacturing process diagram and an actual WMB manufacturing process according to a preferred embodiment of the present invention.

Here, the masterbatch makes it possible to make a high vibration damping type elastic material product by injecting a filler and an additive of carbon black into a rubber base in order to provide vibration reduction and vibration damping functions.

Referring to FIG. 1, 50 g of carbon black as a filler is added to 500 ml of distilled water, wet-milled (Wetting & Milling), and stirred in a Mechanical Dispersion process at 28,000 rpm for 20 to 30 minutes to form a filler slurry. manufactured (S110). At this time, the weight of carbon black added to distilled water is added in the range of 1 to 3 wt% based on the total weight.

Then, 277 g of latex and 27 g of the filler slurry are mixed with oil and stirred at 24,000 rpm for 5 to 15 minutes (Liquid mixing) to obtain a first wet masterbatch (WMB) (S120). In this case, the latex as a rubber base material is natural rubber, SBR (Styrene Butadiene Rubber) based on styrene and butadiene, NBR (Nitrile Butadiene Rubber) based on acrylonitrile and butadiene, etc. may be used. In addition, the oil is a process oil that makes the rubber flexible to facilitate dispersion, and may be used in accordance with the characteristics of the above-described rubber base material, such as paraffinic oil, naphthenic oil, aromatic oil, and the like. For example, rubber-based NR and SBR are suitable for all three types of oils, but aromatic oil is better, and rubber-based NBR, except for aromatic oil, is somewhat lacking in compatibility, so aromatic oil is preferable. In addition, it is preferable to add the filler thruly in the range of about 10 wt% based on the weight of the rubber-based latex.

Then, 304 g of the first wet masterbatch and 248 g of the filler slurry are mixed, stirred at 12,000 rpm for 5 to 15 minutes, and repeated until the adhesion test is passed to obtain a second wet masterbatch (WMB) (S130). At this time, about 10% of the filler slurry prepared in step 110 is added when obtaining the first wet masterbatch and the remaining 90% is added when obtaining the second wet masterbatch. For example, if an excessive amount of carbon black is applied to realize high vibration damping performance, a filler with a large surface area and a well-developed structure should be used. . Therefore, the present invention can solve the problem of heat generation by dispersing carbon black in rubber-based latex, and carbon black is powdered by stirring multiple times of the first wet masterbatch and the second wet masterbatch on the latex and strong stirring at high rpm. By maximizing acidity, the vibration damping characteristics of elastic materials can be improved.

Then, as a coagulation step, 1100 ml of brine and diluted sulfuric acid are added to the secondary wet master batch (WMB) to prepare a compound mass (Coagalation) (S140). At this time, the volume ratio of brine and dilute sulfuric acid is added and mixed in a range of 0.1 to 1% of dilute sulfuric acid compared to 60 to 70% of brine.

Next, the coagulated WMB is filtered through a sieve, washed 5-6 times in distilled water, washed enough to prevent salt from coming out (dewatering), and dried in an oven at 55-59° C. for 24-48 hours (Drying) to produce the final WMB. (S150).

As such, the masterbatch (WMB) according to the present invention is obtained by dispersing carbon black in a rubber-based latex and then solidifying it, thereby maximizing the dispersion of carbon black in an aqueous solution state to improve vibration damping properties.

Hereinafter, the vibration damping effect of the rubber composition to which the masterbatch according to the present invention is added will be described in preparation for the case where the masterbatch (WMB) according to the present invention is added to the rubber substrate and the case where the masterbatch (WMB) according to the present invention is not added.

Table 1 shows the LAB formulation table in the rubber composition (T-1) to which WMB according to the present invention is added and the general rubber composition (T-2) as a control.

material name T-1 T-2 note


CMB CIIR(1240) 70 100 WMB 30 - FEF 60 60 SRF 20 20 ZnO 5 5 S/A One One PEG4000 0.5 0.5 CMB total 186.5 186.5
FMB DM 1.5 1.5 TT 1.0 1.0 MB 0.5 0.5 TOTAL 189.3 189.3

In general, the rubber composition (T-1, T-2) forms CMB (Carbon Master Batch) and FMB (Final Master Batch). For example, CMB refers to a semi-finished rubber that is mixed with natural or synthetic rubber by mixing carbon, oil, reinforcing agent, and activator. say

In addition, FMB is a rubber that provides vibration damping properties by adding sulfur or accelerator for elasticity reinforcement to a compound in CMB state, and refers to a state in which it can be processed by completing the process as rubber.

Referring to Table 1, the general rubber composition (T-2) is CMB, in which carbon black, oil reinforcing agent, activator, etc. are blended in 100 parts by weight of the rubber base CIIR, and a small amount of DM, TT, MB as an accelerator is blended in FMB. to be.

The rubber composition (T-2) to which WMB is added according to the present invention is 100 weight parts by adding 30 parts by weight of WMB (wet masterbatch) prepared before 70 parts by weight of the rubber base CIIR compared to the T-1 rubber composition as a control. There is a difference in what constitutes wealth.

Here, CIIR (Chloro Isobutylene Isoprene Rubbers, chloro isobutylene isoprene rubber) is used as a rubber base for composing CMB. At this time, the rubber base is composed of 70 parts by weight of CIIR and 30 parts by weight of added WMB, and the WMB is preferably added in the range of 10 to 40 parts by weight.

In addition, positive extrudable carbon black (FEF) and medium reinforcing carbon black (SRF) are added as reinforcing materials. At this time, FEF (Fast Extruding Furnace) with a particle diameter of 40 to 48 nm and SRF (Semi Reinforcing Furnace) with a particle diameter of 61 to 100 nm are used as carbon black. Parts and 20 parts by weight of SRF are added, and it is possible within the range of 57 to 63 parts by weight of FEF and 19 to 21 parts by weight of SRF as 5% by weight of the control range of the addition ratio.

In addition, zinc oxide (ZnO) is added as an oxidizing agent or crosslinking activator to activate the crosslinking of rubber, which is vulnerable to deterioration and abrasion. At this time, 5 parts by weight of ZnO is added relative to the CIIR rubber base (100 parts by weight) to which WMB is added, and the range of addition ratio adjustment is possible in the range of 5% by weight.

In addition, as S/A (Stearic Acid) blending oil, 1 part by weight is added compared to the CIIR rubber base (100 parts by weight) added with WMB, and the adjustment range of the addition ratio is possible in the range of 5%.

In addition, PEG4000 (PolyEthylene Glycol) is an additive or lubricant, and 0.5 parts by weight of PEG4000 is added compared to the CIIR rubber base (100 parts by weight) to which WMB is added.

DM (Dibenzothiazyl Disulfide), TT (Tetramethyl Thiuram Disulfide), MB (2-Mercaptobenzoimidazole) can be used as a vulcanization accelerator for FMB to promote elasticity in a compound in CMB state. Here, DM is a Thiazol-based accelerator, and TT is a Thiuram-based accelerator. In addition, 1.5 parts by weight of DM, 1.0 parts by weight of TT, and 0.5 parts by weight of MB are added relative to the CIIR rubber base (100 parts by weight) to which WMB is added, and the addition ratio control range is possible in the range of 5% by weight.

Table 2 shows the comparison results of the physical properties of the unvulcanized state in the rubber composition (T-1) to which WMB is added according to the present invention of Table 1 and the rubber composition (T-2) not added as a control.

Item unit T-1 T-2 note MDR
160°× 30min ts2 min 02:17 02:39 - T10 min 02:01 02:43 - T50 min 03:45 05:08 T90 min 07:59 21:28 - ML dNm 9.8 11.2 - MH dNm 25.1 31.3 - basic physical properties HD IRHD 77 76 ts kgf/cm2 110.75 69.05 EB % 365.19 214.2 M100 kgf/cm2 32.64 46.72 M200 kgf/cm2 75.24 72.21 M300 kgf/cm2 103.04 - importance - - 1.204 1.205

Referring to Table 2, the MDR process is performed to measure the red-sulfur vulcanization temperature of rubber, and the basic physical properties are measured after a heat treatment process at 160° C. for 10 to 30 minutes during vulcanization. In T-1), high tensile strength and elongation can be confirmed, and improvement of basic physical properties can be predicted through this.

3 is a schematic diagram of a viscoelasticity tester, and the vibration insulation effect of the WMB-added rubber composition (T-1) according to the present invention is analyzed using the viscoelasticity tester.

Here, the viscosity of a material refers to the ability of the material to store energy, and the viscosity of the material refers to the ability to dissipate energy. In addition, viscoelasticity expresses the bonding between materials and corresponds to the actual behavior of most materials.

The viscoelasticity tester shown in FIG. 3 applies periodic strain or stress to the sample located in the chamber according to temperature, time, and frequency to show the sample's rheology as a mechanical response. It is an analytical instrument that measures rheological properties, especially viscoelasticity behavior.

4 is a view showing the DMTA evaluation results in the viscoelasticity tester of FIG. 3 to analyze the vibration insulation effect of the rubber composition to which WMB is added according to the present invention, and FIG. 4a is the rubber composition to which WMB is added according to the present invention. DMTA evaluation results for (T-1), Figure 4b is the DMTA evaluation results for the rubber composition (T-2) not added as a control.

Table 3 summarizes the vibration insulation evaluation results in the viscoelasticity tester.

Item unit T-1 T-2 note
DMTA E' MPa 18.25~23.75 17.63~23.60 E" Mpa 6.54~13.52 4.89~9.31 Tanδ - 0.35 to 0.63 0.27~0.44

4 and Table 3, the loss coefficient tanδ is the data that shows the results of vibration insulation, and the rubber composition (T-1) to which WMB is added has a higher loss coefficient tanδ than the general rubber composition (T-2). It can be seen that the vibration insulation effect of the compound was improved as WMB was added to the rubber composition.

As described above, the technical ideas described in the embodiments of the present invention may be implemented independently, or may be implemented in combination with each other. In addition, although the present invention has been described through the embodiments described in the drawings and detailed description of the invention, these are merely exemplary, and those of ordinary skill in the art to which the present invention pertains may make various modifications and equivalent other embodiments therefrom. It is possible. Accordingly, the technical protection scope of the present invention should be defined by the appended claims.

Claims (15)

delete delete delete delete delete delete delete delete In the method for producing a masterbatch of a rubber composition,
(a) preparing a filler slurry by adding carbon black to distilled water, wet milling, and stirring in a mechanical dispersion process;
(b) preparing a first wet masterbatch (WMB) by mixing and stirring a part of the latex and the filler slurry prepared in step (a) with oil;
(c) preparing a second wet masterbatch (WMB) by mixing and stirring the first wet masterbatch with the remaining filler slurry and repeating until the adhesion test passes;
(d) a coagulation step of preparing a compound mass by adding brine and dilute sulfuric acid to the second wet masterbatch (WMB); and
(e) washing the coagulated WMB in distilled water a plurality of times, washing enough to prevent salt from coming out, and drying it to prepare a final WMB; 10. The method of claim 9,
The latex is a vibration damping type wet masterbatch manufacturing method, characterized in that any one of natural rubber (NR), SBR (Styrene Butadiene Rubber), NBR (Nitrile Butadiene Rubber) is used. 10. The method of claim 9,
The oil is a vibration damping type wet masterbatch manufacturing method, characterized in that any one of paraffinic oil, naphthenic oil, and aromatic oil is used. 10. The method of claim 9,
10% weight range of the filler slurry is added in the first wet masterbatch production step of step (b), and the remaining 90% weight range is added in the second wet masterbatch production step of step (c). Vibration damping type wet master batch manufacturing method. 10. The method of claim 9,
The stirring process in step (b) is 24,000 rpm stirring for 5 to 15 minutes,
The stirring process in step (c) is stirred at 12,000 rpm for 5 to 15 minutes, and is repeated until the adhesion test is passed. 10. The method of claim 9,
In step (d), the volume ratio of brine and dilute sulfuric acid is in the range of 0.1 to 1% of dilute sulfuric acid compared to 60 to 70% of brine, and mixing is performed. rubber base,
15. A vibration damping type wet masterbatch composition comprising adding the vibration damping wet masterbatch prepared by the method of any one of claims 9 to 14 to the rubber substrate.

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