KR101053058B1 - Rubber composition - Google Patents

Abstract

The present invention relates to a rubber composition, wherein the rubber composition comprises 60 to 95 parts by weight of non-petroleum raw materials, based on 100 parts by weight of the rubber composition, the non-petroleum raw materials include natural rubber, silica and palm oil, The rubber hardness is 35 to 95.

The rubber composition according to the present invention can improve tensile performance, braking performance on wet roads, improve fuel efficiency of automobiles due to reduction of tire rolling resistance, and reduce petroleum consumption by applying alternative raw materials due to exhaustion of petroleum resources. That has the advantage.

Rubber composition, non-petroleum type, inorganic filler, bio filler, vegetable oil

Description

Rubber composition {RUBBER COMPOSITION}

The present invention relates to a rubber composition, and more particularly, improves tensile performance, braking performance on wet roads, improves vehicle fuel economy due to reduced tire rolling resistance, and applies alternative raw materials due to exhaustion of petroleum resources. It relates to a rubber composition.

Recently, the tire industry is increasing the demand for environmentally friendly products. Recently, environmental issues such as climate change agreements and tightening environmental regulations are becoming more important. Petroleum raw materials are finite and supply is decreasing every year.

However, more than 60% of the tires on the market today are made using petroleum resources. For example, a radial tire for a passenger car contains 25% of the total weight of synthetic rubber, 20% of carbon black, and 15% of aromatic oils. .

Since the use of such petroleum resources is shown to be limited, there is an urgent need for a method for manufacturing tires using materials that can replace petroleum.

Accordingly, an object of the present invention is to improve the heat resistance and tensile performance, braking performance on wet roads, improved vehicle fuel economy due to reduced tire rolling resistance, and to apply a rubber composition to which alternative raw materials are applied due to exhaustion of petroleum resources. To provide.

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, and other technical problems will be clearly understood by the average technician from the following description.

In order to achieve the above object, the present invention comprises 60 to 95 parts by weight of non-petroleum-based raw materials, based on 100 parts by weight of the rubber composition, the non-petroleum-based raw materials include natural rubber, silica and palm oil, the rubber hardness after vulcanization is It provides a rubber composition of 35 to 95.

The rubber composition according to the present invention can improve tensile performance, braking performance on wet roads, improve fuel efficiency of automobiles due to reduction of tire rolling resistance, and reduce petroleum consumption by applying alternative raw materials due to exhaustion of petroleum resources. That has the advantage.

The present invention provides an environmentally friendly tire rubber composition in which part or all of the petroleum based raw materials currently used in tires are replaced with non-petroleum based raw materials.

That is, the present invention relates to a tire rubber composition in which at least 60% of the total weight is composed of non-petroleum raw materials. As the non-petroleum raw material, natural rubber, inorganic fillers, vegetable oils and the like can be used. By using natural rubber in place of synthetic rubber and inorganic filler in place of petroleum oil in place of carbon black, eco-friendly tires can be provided for future oil supply reduction.

Hereinafter, the present invention will be described in more detail.

The present invention provides a rubber composition comprising a non-petroleum raw material and a silane coupling agent.

Tires currently on the market use more than 60% of the total weight of petroleum-based raw materials. For example, synthetic rubbers such as styrene-butadiene rubber (SBR) and butyl rubber (IIR), which are used as rubber components, are obtained by monomers obtained by decomposing naphtha of crude oil. Extracted, polymerized and used. Aromatic, naphthene and paraffin oils used as process oils are components obtained by atmospheric distillation of crude oil. Waxes, anti-aging agents, resins, adhesives, vulcanization accelerators, and the like use petroleum-based raw materials.

The present invention is to replace the petroleum-based raw materials such as synthetic rubber, carbon black, petroleum-based oils with non-petroleum-based raw materials, it is included in the content of 60 to 95 parts by weight of non-petroleum raw materials based on 100 parts by weight of the rubber composition.

Natural rubber may be used when the non-petroleum raw material substitutes for synthetic rubber. The natural rubber is 50 parts by weight or more, preferably 70 parts by weight or more and less than 80 parts by weight based on 100 parts by weight of the raw material rubber.

When the content of the natural rubber is less than 50 parts by weight, the effect of suppressing the use of petroleum resources is small, and there is a problem that the rotational resistance is increased, and when more than 80 parts by weight, there is a problem that the workability is lowered.

When the non-petroleum raw material replaces carbon black, an inorganic filler, a bio filler, or the like may be used.

The inorganic fillers include silica, clay, aluminum oxide, magnesium oxide, titanium oxide, talc, sericite, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, and the like.

The biofiller includes plant polysaccharides such as starch and cellulose; Sea polyps, animal polysaccharides such as chitin and chitosan.

Among them, silica is preferable in order to secure reinforcement of rubber.

It is preferable that the silica has a BET surface area of 140 to 260 m ² / g. When the BET surface area of the silica is less than 140m ² / g, there is a problem of poor reinforcement, and when it exceeds 260m ² / g, there is a problem that the physical properties are lowered because the dispersibility is lowered and aggregated.

When the non-petroleum-based raw materials replace petroleum oils, vegetable oils, semi-dry oils having an oxo of 100 to 130, or less than 100 oxo, preferably 20 to 95 undrying oils may be used. In this case, the oxo value means the number of grams of iodine absorbed by 100 g of oil or fat.

The vegetable oils include sesame oil, sesame oil, sunflower oil, coconut oil, palm oil, palm kernel oil, soya bean oil, rice bran oil oil, olive oil, geranium oil, chamomile oil, tea tree oil, lemon oil, ylang ylang oil, jasmine oil ( jasmine oil, rose oil, lavender oil, camellia oil, castor oil, cotton seed oil, linseed oil, rape seed oil oil, arachis oil, rosin oil, pine oil, tall oil, corn oil, safflower oil, jojoba oil , Macadamia nut oil, tung oil and the like.

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The present invention has a rubber hardness having a range of 35 to 95 after vulcanization by including a vegetable fat in the content of the vegetable fat.

If the rubber hardness is less than 35, the required rigidity cannot be obtained, and if the rubber hardness is greater than 95, there is a problem that workability is lowered.

If the oxo value of the semi-dry oil is less than 100, there is a problem that the workability is lowered, and if it exceeds 130, the hardness is lowered, the rotational resistance is increased, and the steering stability is lowered.

When the oxo value of the said non-drying oil is less than 20, there exists a problem that workability falls.

It is preferable to use the said silane coupling agent with the said inorganic filler. As the silane coupling agent, 3,3'-bis (trimethoxysilylpropyl) disulfide,

3,3'-bis (triethoxysilylpropyl) disulfide,

3,3'-bis (triethoxysilylpropyl) tetrasulfide,

3,3'-bis (triethoxysilylpropyl) octasulfide,

3,3'-bis (trimethoxysilylpropyl) tetrasulfide,

2,2'-bis (triethoxysilylethyl) tetrasulfide,

3,3'-bis (trimethoxysilylpropyl) trisulfide,

3,3'-bis (tributoxysilylpropyl) disulfide,

3,3'-bis (trimethoxysilylpropyl) hexasulfide,

3,3'-bis (trimethoxysilylpropyl) octasulfide,

3,3'-bis (trioctoxysilylpropyl) tetrasulfide,

3,3'-bis (trihexoxysilylpropyl) disulfide,

3,3'-bis (tri-2 "-ethylhexoxylpropyl) tetrasulfide,

3,3'-bis (triisooctoxysilylpropyl) tetrasulfide,

3,3'-bis (tri-t-butoxysilylpropyl) disulfide,

2,2'-bis (methoxydiethoxysilylpropyl) tetrasulfide,

2,2'-bis (tripropoxysilylehtyl) pentasulfide,

3,3'-bis (tricylconeoxysilylpropyl) tetrasulfide,

3,3'-bis (tricylcopentoxysilylpropyl) tetrasulfide,

2,2'-bis (tri-2 "-methylcylcohexoxysilylethyl) tetrasulfide,

bis (trimethoxysilylmethyl) tetrasulfide,

3-methoxyethoxypropoxysilyl-3'-diethyxybutoxy-silylpropyltetrasulfide,

2,2'-bis (dimethylsecbutoxysilylethyl) trisulfide,

2,2'-bis (phenylmethylmethoxysilylpropyl) tetrasulfide,

3,3'-bis (di-tert-butylmethoxysilylethyl) trisulfide,

3,3'-bis (diphenylisopropoxysilylpropyl) tetrasulfide,

3,3'-bis (diphenylcyclohexoxysilylpropyl) disulfide,

3,3'-bis (dimethylethylmercaptosilylpropyl) tetrasulfide,

2,2'-bis (methylethoxypropylsilylethyl) tetrasulfide,

3,3'-bis (diethylmethoxysilylpropyl) tetrasulfide,

3,3'-bis (ethyldisec-butoxysilylpropyl) disulfide,

3,3'-bis (propyldiethoxysilylpropyl) disulfide,

3,3'-bis (butyldimethoxysilylpropyl) trisulfide,

3,3'-bis (phenyldimethoxysilylproryl) tetrasulfide,

3'-trimethoxysilylpropyltetrasulfide,

4,4'-bis (trimethoxysilylbytyl) tetrasulfide,

6,6'-vis (triethoxysilylhexyl) tetrasulfide,

12,12'-bis (triisopropoxysilyldodexyl) disulfide,

18,18'-bis (trimethoxysilylloctadexyl) tetrasulfide,

18,18'-bis (tripropoxysilyloctadecenyl) tetrasulfide,

4,4'-bis (trimethoxysilyl-buten-2-yl) tetrasulfide,

4,4'-bis (trimethoxysilylcyclohexylene) trisulfide,

5,5'-bis (dimethoxymethylsilylpentyl) trisulfide,

3,3'-bis (trimethoxysilyl-2-methylpropyl) tetrasulfide,

3,3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide, etc. are mentioned.

The silane coupling agent is included in 2 to 22 parts by weight based on 100 parts by weight of rubber. If the content of the silane coupling agent is less than 2 parts by weight, the effect of addition is not sufficiently obtained. If the content of the silane coupling agent is more than 22 parts by weight, the raw material cost increases and the effect according to the present invention cannot be obtained.

Meanwhile, the rubber composition according to the present invention may further include an additive. Examples of the additives include zinc oxide, a vulcanizing agent, and aromatic oil, stearic acid, a vulcanization accelerator, sulfur, and the like, which are usually added to a rubber composition.

The content of the additive can be easily adjusted arbitrarily according to the desired physical properties.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[Examples 1-3 and Comparative Example 1]

Comparative Example 1

60 parts by weight of carbon black, 25 parts by weight of aromatic oil, 3 parts by weight of zinc oxide, based on 100 parts by weight of raw rubber using 21 parts by weight of natural rubber and 79 parts by weight of styrene-butadiene rubber, using the composition shown in Table 1 below. A rubber composition was prepared by adding 1 part by weight of stearic acid, 1.8 parts by weight of a vulcanization accelerator and 2 parts by weight of sulfur, and blending in a half-barrier mixer.

Example 1

A rubber composition was prepared according to the same composition and method as in Comparative Example 1, except that 79 parts by weight of natural rubber and 21 parts by weight of styrene-butadiene rubber were used.

Example 2

A rubber composition was manufactured according to the same composition and method as in Example 1, except that 60 parts by weight of silica and 3 parts by weight of silane coupling agent were used instead of carbon black for 100 parts by weight of the raw material rubber.

Example 3

A rubber composition was manufactured according to the same composition and method as in Example 2, except that 5 parts by weight of aromatic oil and 20 parts by weight of natural oil were used instead of 25 parts by weight of raw material rubber.

Compounding agent Comparative Example 1 Example 1 Example 2 Example 3 Natural rubber ¹⁾ 21 79 79 79 Styrene-butadiene rubber ²⁾ 79 21 21 21 Carbon black ³⁾ 60 60 0 0 Silica ⁴⁾ 0 0 60 60 Silane coupling agent ⁵⁾ 0 0 3 3 Aromatic oil ⁶⁾ 25 25 25 5 Natural oils ⁷⁾ 0 0 0 20 Zinc oxide ⁸⁾ 3 3 3 3 Stearic acid ⁹⁾ One One One One Vulcanization Accelerator ¹⁰⁾ 1.8 1.8 1.8 1.8 Sulfur ¹¹⁾ 2 2 2 2

(Unit: parts by weight)

week)

1) RSS # 3 (Southland Rubber)

2) VSL5025 (Lanxess)

3) HAF (Dongyang Steel Chemical)

4) Ultrasil 7000Gr (Degussa)

5) Si75 (Degussa)

6) A # 2 (Michang Petroleum Industries)

7) Palm oil

8) Zinc Oxide (Hanil Chemical)

9) stearic acid (LG)

10) N-cyclohexyl-2-benzothiazylsulfenamide (Lanxess)

11) Ground sulfur (Miwon Corporation)

The physical property measurement method of the rubber specimens prepared in Comparative Example 1 and Examples 1 to 3 was in accordance with the following method. The results are shown in Table 2 below.

(1) Mooney Viscosity (ML1 + 4, 125 ° C): A Mooney MV2000 (Alpha Technology) instrument was used to obtain a large rotor, preheating 1 minute, rotor operation time 4 minutes, and temperature 125 ° C.

(2) Tensile Properties: Hardness was measured using a Shore A hardness tester, and tensile properties were measured using an Instron tester according to ASTM D412 test method.

(3) Viscoelastic properties: Using a DMTS (Dynamic Material Testing System) tester was measured by temperature sweep from -60 ℃ to 80 ℃ at 10Hz, static strain 5%, dynamic strain 0.5% conditions. At this time, the higher the 0 ° C tanδ value, the better the braking performance on the wet road surface, and the lower the 60 ° C tanδ value, the lower the rotation resistance performance.

Properties Comparative Example 1 Example 1 Example 2 Example 3 Uncured Property ML1 + 4 (125 ° C) 26 27 27 27 Hardness (Shore A) 48 49 49 50 Tensile Properties 100% modulus (kgf / cm ² ) 15 19 20 22 300% modulus (kgf / cm ² ) 62 64 65 68 % Elongation 530 515 502 489 Tensile strength (kgf / cm ² ) 133 136 138 143 Viscoelastic 0 ℃ tanδ 0.245 0.254 0.252 0.259 60 ℃ tanδ 0.132 0.121 0.124 0.122

As shown in Table 2, the specimens of Examples 1 to 3 using non-petroleum-based raw materials showed similar trends in unvulcanized physical properties and hardness compared to the specimens of Comparative Example 1, but the tensile properties were generally increased and tangent was 0 ° C. It can be seen that the δ value is also increased to improve the braking performance on the wet road surface. This is due to the hydrophilicity of the silica itself by silanol groups on the silica surface. In addition, the tan δ value of 60 ° C decreases, resulting in less fuel economy.

This resulted in improved overall tire performance, such as braking performance and rolling resistance, on wet roads compared to petroleum-based raw materials.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (12)

Per 100 parts by weight of the rubber composition, 60 to 95 parts by weight of non-petroleum raw materials, The non-petroleum raw materials include natural rubber, silica and palm oil The rubber composition after vulcanization is 35-95. According to claim 1, wherein the rubber composition comprises a raw material rubber, A rubber composition comprising at least 50 parts by weight of the natural rubber based on 100 parts by weight of the raw material rubber. delete delete The rubber composition of claim 1, wherein the silica has a BET surface area of 140 to 260 m ² / g. delete delete delete delete delete delete delete