KR20240098289A - Anti vibration rubber composition for vessel mount with high durability - Google Patents

Abstract

The present invention relates to a highly durable anti-vibration rubber composition for ship mounts. The first subject is made of natural rubber or styrene butadiene rubber (SBR); The second subject is prepared with chlorinated isobutylene-isoprene rubber (CIIR); Carbon black for fast extruding furnace (FEF) rubber prepared with a particle size of 40 nm to 48 nm; A softener prepared from paraffin-based process oil; A material binder prepared from at least one of clay, silicate, phosphate, lime milk, and resin; Tear and anti-vibration reinforcement; Activator prepared from zinc oxide (ZnO, Zinc Oxide); Mold release agent prepared from stearic acid; Anti-aging agents including paraffin wax, acetone diphenylamine, and TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline); and accelerators including CZ (CBS, N-cyclohexyl-2-benzothiazole Sulfenamide), BZ (ZDBC, Zinc Dibutyl Dithiocarbamate), M (Mercaptobenzothiazole), TT (Thiram), and S (Sulfur).

Description

Anti-vibration rubber composition for ship mount with high durability {ANTI VIBRATION RUBBER COMPOSITION FOR VESSEL MOUNT WITH HIGH DURABILITY}

The present invention relates to a highly durable anti-vibration rubber composition for ship mounts.

The anti-vibration mount for ships mainly attenuates and protects the shock and vibration of important equipment within a submarine against collisions and shocks such as accidents caused by indirect or direct shock underwater during wartime.

Anti-vibration mounts for submarines applied to actual naval vessels must meet the specifications presented by the Navy, and there is a greater need for local development.

The elastic material used in the manufacture of existing anti-vibration mounts for ships is made based on a combination of natural rubber and chloroprene rubber due to the need for high shock absorption and durability.

However, chloroprene rubber, which is used in the manufacture of existing anti-vibration mounts for ships, is highly volatile and toxic, raising concerns about lung cancer and skin irritation when workers are exposed to it for a long time. The use of these substances is strictly regulated by classifying them as hazardous substances and establishing exposure standards in the work environment.

For example, prior art documents for further improving the dustproof properties in low-temperature environments without impairing the mechanical properties, compression set, or elongation fatigue of chloroprene rubber include Korean Patent Publication No. 10-2014-0016323. There are “chloroprene rubber compositions and vulcanized rubbers thereof, and rubber-like articles, anti-vibration rubber members, engine mounts and hoses” (hereinafter referred to as ‘prior art’) using the vulcanized rubber.

However, in the case of technologies related to existing anti-vibration rubber compositions for water trap mounts, including the prior art, no technology has been proposed that can provide sufficient durability by replacing the use of chloroprene rubber (chloroprene rubber). Even if the use of Chloroprene Rubber was replaced, there was a problem in that it could not provide high durability properties suitable for use in ships.

The present invention was created to solve the above problems, and the purpose of the present invention is to provide a rubber composition that does not use chloroprene rubber as the main material, but is capable of exhibiting high durability and is suitable for manufacturing anti-vibration mounts for ships. there is.

In order to achieve the above object, the highly durable anti-vibration rubber composition for ship mounting of the present invention includes a first main material made of natural rubber or styrene butadiene rubber (SBR); The second subject is prepared with chlorinated isobutylene-isoprene rubber (CIIR); and carbon black for fast extruding furnace (FEF) rubber prepared with a particle size of 40 nm to 48 nm; Includes.

In addition, the styrene butadiene rubber has a styrene content of 23.5% by weight.

In addition, the highly durable anti-vibration rubber composition for ship mounts includes 65 to 75 parts by weight of the first main ingredient; 25 to 35 parts by weight of the second main ingredient; and 55 to 65 parts by weight of the carbon black for positive extrusion rubber.

Specifically, the highly durable anti-vibration rubber composition for a ship mount includes 70 parts by weight of the first main ingredient and 30 parts by weight of the second main ingredient; and 60 parts by weight of the carbon black for positive extrusion rubber.

In addition, the highly durable anti-vibration rubber composition for ship mounting includes a softener prepared from paraffin-based process oil; A material binder prepared from at least one of clay, silicate, phosphate, lime milk, and resin; Tear and dust-proof reinforcement made of silica aerogel; Activator prepared from zinc oxide (ZnO, Zinc Oxide); and a mold release agent prepared from stearic acid.

In addition, the highly durable anti-vibration rubber composition for ship mounts includes 15 to 25 parts by weight of the softener; 8 to 12 parts by weight of the material binder; 8 to 12 parts by weight of the tear and dust-proof reinforcing agent; 4 to 5 parts by weight of the activator; and 1 to 2 parts by weight of the release agent.

In addition, the highly durable anti-vibration rubber composition for vessel mounting includes paraffin wax, acetone diphenylamine, and TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline). Anti-aging agents; and accelerators including CZ (CBS, N-cyclohexyl-2-benzothiazole Sulfenamide), BZ (ZDBC, Zinc Dibutyl Dithiocarbamate), M (Mercaptobenzothiazole), TT (Thiram), and S (Sulfur).

In addition, the highly durable anti-vibration rubber composition for vessel mounting includes 1 to 3 parts by weight of paraffin wax, 1 to 2 parts by weight of acetone diphenylamine, and TMDQ (Polymerized 2,2). ,4-trimethyl-1,2-dihydroquinoline) an anti-aging agent containing 1 to 2 parts by weight; and 0.5 to 1.5 parts by weight of CZ (CBS, N-cyclohexyl-2-benzothiazole Sulfenamide), 0.5 to 1.5 parts by weight of BZ (ZDBC, Zinc Dibutyl Dithiocarbamate), 0.5 to 1 part by weight of M (Mercaptobenzothiazole), and TT ( It further includes an accelerator comprising 0.5 to 1 part by weight of Thiram) and 0.5 to 1.5 parts by weight of S (Sulfur).

According to the present invention, it is possible to provide a rubber composition capable of exhibiting high durability suitable for manufacturing an anti-vibration mount for ships using rubber that can replace chloroprene rubber as the main material.

Preferred embodiments of the present invention will be described in more detail with reference to the attached drawings, but already well-known technical parts will be omitted or compressed for brevity of explanation.

1. Description of anti-vibration rubber composition for ship mount with high durability

The highly durable anti-vibration rubber composition for ship mounts of the present invention will be described in detail below.

Specifically, the highly durable anti-vibration rubber composition for ship mounting of the present invention includes a first main ingredient made of natural rubber or styrene butadiene rubber (SBR); The second subject is prepared with chlorinated isobutylene-isoprene rubber (CIIR); Carbon black for fast extruding furnace (FEF) rubber; softener; material binder; Tear and anti-vibration reinforcement; activator; Hyeong-Je Lee; Anti-aging agents; and an accelerator.

Here, the first subject is made of either natural rubber or styrene butadiene rubber (SBR), and considering the properties of wear resistance, aging resistance, and heat resistance, it is necessary to expect further improvement in physical properties. It is more preferable to apply styrene butadiene rubber (SBR).

Such styrene butadiene rubber (SBR) is prepared as a polymerized emulsion type with a styrene content of 23.5% by weight, and is preferably SBR 1502 (a product of Astlett Rubber).

Specifically, styrene butadiene rubber (SBR) has a styrene content of 23.5% by weight, which is 23.5% by weight for 100 parts by weight of the total styrene butadiene rubber (SBR). It corresponds to an ingredient that has been polymerized to have the same amount of ingredients.

Moreover, styrene butadiene rubber exhibits a Mooney viscosity (based on MML 1+4 (100°C), when tested with ASTM D1646) of 52 MU, and the volatile matter content (when tested with ASTM D5668) is 0.3 wt%. It has the characteristics of

In addition, styrene butadiene rubber has a tensile stress at 300 % elongation is 185 kg/cm ² , tensile strength is 300 kg/cm ² , and ultimate elongation is 470%.

It is desirable to have an appropriate content of 65 to 75 parts by weight of the first base material. However, if the first base material is provided in less than 65 parts by weight, there is a problem in that the level of wear resistance and heat resistance decreases, and if it exceeds 75 parts by weight, it will be explained later. There was a problem of lowering the rate of change due to impact, which had a negative impact on the improvement of the balanced physical properties with the second subject.

Most preferably, the first base material has an amount of 70 parts by weight.

Next, the second subject is chlorinated isobutylene-isoprene rubber (CIIR), which is ionically polymerized isobutylene and a small amount of isoprene in a liquid state at low temperature, CIIR 1066 (EXXON) It is desirable to use product).

This second subject corresponds to ingredients that provide improved physical properties to the overall composition, such as being able to withstand changes in climate, have excellent electrical insulation, and absorb shock well.

In addition, it is desirable for the second main ingredient to have an appropriate content level of 25 to 35 parts by weight. However, if the second main agent is provided at less than 25 parts by weight, there is a problem in that the level of change in tensile strength and elongation rate according to aging conditions increases. If the weight part was exceeded, there was a problem of lowering the level of wear resistance by adversely affecting the improvement of the balanced physical properties with the first main ingredient.

Most preferably, the secondary agent has an amount of 30 parts by weight.

Next, carbon black for fast extruding furnace (FEF) rubber is a component used as a material hardness enhancer. It is light in weight, has strong elasticity, and is resistant to corrosion, so it can be manufactured in a variety of shapes. It allows the realization of weight and torque or strength.

For this purpose, the positive extrudable carbon black for rubber added in the highly durable anti-vibration rubber composition for ship mount according to the present invention is N550 (product of Corax), which is a positive extrudable carbon black for rubber prepared with a particle size of 40 nm to 48 nm. It is desirable to use it.

Specifically, carbon black for positive extrusion rubber, which has small shrinkage strain and a smooth surface during extrusion, low heat generation and good heat conduction, has an iodine adsorption amount of 42 mg/g, a nitrogen adsorption surface area of 42 ㎡/g, and 122 cc/ It has the characteristics of 100g DBP oil absorption, up to 0.75% ash content, and up to 1.0% heating loss.

It is desirable that the carbon black for positive extrudable rubber has an appropriate content of 55 to 65 parts by weight, which is a specified value to maintain the physical properties related to the durability improvement expressed by the subjects described above. This is because if the content level of carbon black is outside the appropriate range, it not only lowers the level of tensile strength and elongation, but also lowers the specific gravity and adversely affects processability.

Most preferably, the carbon black for positive extrudable rubber has an amount of 60 parts by weight.

In addition, the softener is an ingredient used to increase durability and is prepared from paraffin-based process oil. It imparts plasticity to the rubber in the mixing process of each component that makes up the entire composition to facilitate processability. As an ingredient, Michang's P-4 product can be used as a product example.

This softener has the characteristics of a flash point of 240°C, a pour point of -12.5°C, a kinematic viscosity of 103.0 cSt (40°C), and an aniline point of 113.0°C, and is preferably prepared in an amount of 15 to 25 parts by weight (most preferably, 20 parts by weight). do.

This is because if the softener is provided in less than 15 parts by weight, lubricity and solubility are impaired, and if the softener exceeds 25 parts by weight, it not only causes problems with processability but also causes a decrease in physical properties related to durability related to hardness.

Next, the cleaning binder is an inorganic or organic material used to combine and integrate two other raw materials, and is implemented as one of clay, silicate, phosphate, lime milk, or resin.

It is desirable that the cleaning binder has an appropriate content of 8 to 12 parts by weight (most preferably, 10 parts by weight).

In addition, the tear and dust-proof reinforcing agent is a component prepared from silica airgel, and is preferably contained in an appropriate amount of 8 to 12 parts by weight (most preferably, 10 parts by weight).

Next, the activator is made of zinc oxide (ZnO, Zinc Oxide) and is added to disperse the first main agent. It is desirable to have an appropriate content of 4 to 6 parts by weight (most preferably, 5 parts by weight).

Next, the mold release agent is made of stearic acid and is an ingredient that helps the product using the entire composition to be easily separated from the mold. It is desirable to have an appropriate content of 1 to 2 parts by weight (most preferably, 1.5 parts by weight). .

In this regard, the activator and release agent must not exceed the appropriate content level. If the content is below the appropriate content level, the cross-linking density will decrease, and if the content exceeds the appropriate content level, the specific gravity will be excessively high and the level of promoting activity will be unnecessary. This is because there is a problem of excessiveness.

In addition, the anti-aging agent is a mixture of three ingredients: paraffin wax, acetone diphenylamine, and TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline).

Here, paraffin wax (CAS: 8002-74-2) is a non-coloring, non-discoloring, non-polluting ingredient that prevents sunlight cracking and ozone cracking, and has an ash content of 0.3% or less, a solidification point of 65°C or higher, SONNOC (a Seojin Chems product) can be used, which has a heating loss of less than 0.3% and a specific gravity of 0.93.

In addition, acetone diphenylamine is an anti-aging agent with excellent non-staining and non-staining properties, has the three-dimensional structure of alkylate bisphenol, and is most efficient for vulcanization and hardening products.

Acetone diphenylamine is an anti-aging agent that is particularly excellent in heat resistance and bending resistance. It is almost unaffected by vulcanization accelerators and is mainly used in areas that undergo aging by cracking due to a lot of physical force. BLE-N (from Kumanox) is available with specifications of viscosity (at 25 ± 0.2 °C), ash content of 28.0 - 34.0%, and heat loss of less than 0.5% (when heated for 2 hours at 105 ± 5 °C). there is.

In addition, TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline) has an antioxidant-like effect and is an ingredient that stops the chain reaction of auto-oxidation caused by oxygen, which is a major factor in the aging phenomenon. .

This TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline) can use 184-RD (product of RUBATAN), which has the characteristics of specific gravity of 1.095, melting point of at least 77 ℃, and monomer content of 3% by weight. You can.

Specifically, the anti-aging agent is 1 to 3 parts by weight of paraffin wax, 1 to 2 parts by weight of acetone diphenylamine, and 1 to 2 parts by weight of TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline). It is desirable to have a content level of 2 to 2 parts by weight, which means that if each of the three types of anti-aging agents is prepared below the appropriate content level, sufficient anti-aging function is not achieved, cracks easily occur under aging conditions, and the content level may be exceeded. This is because there is a problem that the proportion is excessively high and the level of accelerator-based accelerator activity, which will be explained later, is unnecessarily excessive.

Lastly, the accelerator is a mixture of five ingredients: CZ (CBS, N-cyclohexyl-2-benzothiazole Sulfenamide), BZ (ZDBC, Zinc Dibutyl Dithiocarbamate), M (Mercaptobenzothiazole), TT (Thiram), and S (Sulfur).

These accelerators are substances added to shorten the time of chemical reaction. For SULFENAMIDE-based CZ, ORICEL-CZ (product of Kumho Monsanto) can be used as a sustained-acting accelerator for NR, SBR, BR, IR, EPDM, and NBR. BZ of the THIOCARBA-MATE series can be used as a low-temperature vulcanizing agent for NR, IR, BR, SBR, NBR, and LATEX. ORICEL-BZ (a product of Kumho Monsanto) can be used.

In addition, M of the THIAZOL series is an accelerator for NR, SBR, NBR, and IIR, and ORICEL-M (a product of Kumho Monsanto) can be used as an ingredient that acts as a retardant in sulfur-modified CR, and TT of the THIURAM series. is a secondary accelerator for NB, SBR, and BR, enables sulfur-free vulcanization, and ORICEL-TT (product of Kumho Monsanto) can be used as the main accelerator for IIR (isobutylene-isoprene rubber).

Lastly, sulfur (S) is an ingredient that acts as a bridge by interconnecting with the accelerators of CZ, BZ, M, and TT. Miwon Chemical Co., Ltd.'s MIDAS SP product can be used.

Specifically, the accelerator is 0.5 to 1.5 parts by weight of CZ (CBS, N-cyclohexyl-2-benzothiazole Sulfenamide), 0.5 to 1.5 parts by weight of BZ (ZDBC, Zinc Dibutyl Dithiocarbamate), 0.5 to 1 part by weight of M (Mercaptobenzothiazole), and TT ( It is desirable to have an appropriate amount of each accelerator of 0.5 to 1 part by weight of Thiram) and 0.5 to 1.5 parts by weight of S (Sulfur).

This means that if each accelerator is below the appropriate content level, its role as an accelerator may not be sufficiently performed and the crosslinking density may be lowered, which may affect the tensile strength.

2. Description of the physical property test results of a highly durable anti-vibration rubber composition for ship mounts

Regarding the anti-vibration rubber composition for ship mounts with high durability according to the present invention, the levels of various physical properties related to durability were measured through various experimental methods as follows, and the properties were defined by means obvious to those skilled in the art. For this purpose, the following experimental methods were used.

(1) Example preparation

As the most preferable example of the highly durable anti-vibration rubber composition for ship mounting according to the present invention, it was prepared under the mixing conditions shown in Table 1 below for the examples and used to compare the results of various physical property evaluations to be conducted below.

Example Topic 1 70g Topic 2 30g Carbon black for positive extrusion rubber 60g softener 20g material binder 10g Tear and dust proof reinforcement 10g activator 5g Brother Lee 1.5g Aging
preventer paraffin wax 2.0g Acetone diphenylamine 1.5g TMDQ 1.5g accelerant C.Z. 1.0g B.Z. 1.0g M 0.8g TT 0.5g S 1.0g

(2) Tensile strength, elongation and aging test evaluation

After measuring the tensile strength and elongation using the anti-vibration rubber for ship mount made using Example 1 mixed according to Table 1, the tensile strength and the rate of change were measured through an additional aging test, and the test method was 'KS M 6518'. It was conducted based on the standards of ':2021', and the results are shown in Table 2 below.

tensile strength 19.2MPa elongation rate 660% aging test
(70℃±1℃, 96h) Tensile strength change rate -3.2% Rate of change in elongation -6.2%

As shown in Table 2, the embodiment prepared as a highly durable anti-vibration rubber composition for ship mount according to the present invention not only has sufficient tensile strength and elongation to be used for ship mount, but also has tensile strength and elongation through aging tests. It can be seen that the rate of change in elongation is not high.

(3) Evaluation of permanent compression set rate and volume change rate due to immersion

After measuring the permanent extrusion shrinkage rate using the anti-vibration rubber for ship mount made using Example 1 mixed according to Table 1, the volume change rate was additionally measured through an immersion test, and the test method was in accordance with 'KS M 6518:2021'. It was conducted in accordance with the standards, and the results are shown in Table 3 below.

Permanent compression loss rate (70℃±1℃, 22h) 8% Immersion test (No.3oil, 100℃±1℃, 24h) rate of change of volume 0.1%

As shown in Table 3, the example prepared as a highly durable anti-vibration rubber composition for ship mount according to the present invention has a permanent extrusion shrinkage rate sufficient for use for ship mount, and the volume change rate according to the immersion test is also not large. It shows significant results at this level.

(4) Peel strength and neutral salt spray test evaluation

The peeling strength was measured using anti-vibration rubber for ship mounts made using Example 1 mixed according to Table 1. The test method was conducted based on the standards of 'KS M 6518:2021', and the results are shown in Table 4 below. .

In addition, a neutral salt spray test was performed using anti-vibration rubber for ship mounting made using Example 1 mixed according to Table 1. The test method was conducted in accordance with the standards of 'KS D 8834:2015', and the results are as follows. Same as Table 4.

Peel strength 13.7kN/m Neutral salt spray test (48h, presence or absence of red rust) clear

As shown in Table 4, the examples prepared as highly durable anti-vibration rubber compositions for ship mounts according to the present invention have sufficient peel strength to be used for ship mounts, and the results of the neutral salt spray test also showed no abnormalities.

The embodiments disclosed in the present invention are not intended to limit but illustrate the technical idea of the present invention, and the scope of the technical idea of the present invention is not limited by these examples. The scope of protection should be interpreted in accordance with the claims below, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

Claims (8)

The first subject is made of natural rubber or styrene butadiene rubber (SBR);
The second subject is prepared with chlorinated isobutylene-isoprene rubber (CIIR); and
Carbon black for fast extruding furnace (FEF) rubber prepared with a particle size of 40 nm to 48 nm; Characterized by including
A highly durable anti-vibration rubber composition for ship mounts.
According to paragraph 1,
The styrene butadiene rubber is characterized in that the styrene content is 23.5% by weight.
A highly durable anti-vibration rubber composition for ship mounts.
According to paragraph 1,
The highly durable anti-vibration rubber composition for ship mounts includes,
65 to 75 parts by weight of the first main ingredient;
25 to 35 parts by weight of the second main ingredient; and
Characterized in that it contains 55 to 65 parts by weight of carbon black for positive extrusion rubber.
A highly durable anti-vibration rubber composition for ship mounts.
According to paragraph 3,
The highly durable anti-vibration rubber composition for ship mounts includes,
70 parts by weight of the first main ingredient;
30 parts by weight of the second main agent; and
Characterized in that it contains 60 parts by weight of carbon black for positive extrusion rubber.
A highly durable anti-vibration rubber composition for ship mounts.
According to paragraph 3,
The highly durable anti-vibration rubber composition for ship mounts includes,
A softener prepared from paraffin-based process oil;
A material binder prepared from at least one of clay, silicate, phosphate, lime milk, and resin;
Tear and dust-proof reinforcement made of silica aerogel;
Activator prepared from zinc oxide (ZnO, Zinc Oxide); and
Characterized in that it further comprises a mold release agent prepared from stearic acid.
A highly durable anti-vibration rubber composition for ship mounts.
According to clause 5,
The highly durable anti-vibration rubber composition for ship mounts includes,
15 to 25 parts by weight of the softener;
8 to 12 parts by weight of the material binder;
8 to 12 parts by weight of the tear and dust-proof reinforcing agent;
4 to 6 parts by weight of the activator; and
Characterized in that it contains 1 to 2 parts by weight of the release agent.
A highly durable anti-vibration rubber composition for ship mounts.
According to clause 5,
The highly durable anti-vibration rubber composition for ship mounts includes,
Anti-aging agents including paraffin wax, acetone diphenylamine, and TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline); and
An accelerator including CZ (CBS, N-cyclohexyl-2-benzothiazole Sulfenamide), BZ (ZDBC, Zinc Dibutyl Dithiocarbamate), M (Mercaptobenzothiazole), TT (Thiram) and S (Sulfur);
A highly durable anti-vibration rubber composition for ship mounts.
In clause 7,
The highly durable anti-vibration rubber composition for ship mounts includes,
1 to 3 parts by weight of the paraffin wax, 1 to 2 parts by weight of the acetone diphenylamine, and 1 to 2 parts by weight of the TMDQ (Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline) Anti-aging agents, including boo; and
0.5 to 1.5 parts by weight of CZ (CBS, N-cyclohexyl-2-benzothiazole Sulfenamide), 0.5 to 1.5 parts by weight of BZ (ZDBC, Zinc Dibutyl Dithiocarbamate), 0.5 to 1 part by weight of M (Mercaptobenzothiazole), and TT (Thiram) ) 0.5 to 1 part by weight of an accelerator containing 0.5 to 1.5 parts by weight of S (Sulfur);
A highly durable anti-vibration rubber composition for ship mounts.