KR102066167B1 - Benzoxazine Compound and Preparing Method Thereof - Google Patents

Abstract

The present invention relates to a benzoxazine compound and a method for manufacturing the same, and more particularly, to maximize compatibility with silica, which has been spotlighted as a tire reinforcing material, to improve processability when compounding with a silica compound, and to maximize vulcanization properties of rubber materials. The present invention relates to a benzoxazine compound which can greatly improve mechanical properties, which can be usefully used for manufacturing high quality tires, and a method of manufacturing the same.

Description

Benzoxazine Compound and Preparing Method Thereof}

The present invention relates to benzoxazine compounds and methods for their preparation.

Rubber for tires requires various characteristics depending on the required performance of the tire. For example, since the tread rubber is a part where the tire contacts the ground, the rubber wears out and the temperature increases due to friction with the ground. Among the various characteristics, abrasion resistance, heat generation characteristics, and braking force are particularly important. The rubber composition for tires uses various additives according to each rubber. That is, in addition to the rubber composition for tires that are commonly used, various additives are used to further improve specific physical properties.

Generally, the rubber composition for tires contains various additives based on natural rubber and synthetic rubber. For example, carbon black, which is used as a reinforcing filler such as heavy steel, oil resistance, heat resistance, etc., an anti-aging agent that stops a chain reaction that is automatically oxidized by oxygen, and softens rubber and gives plasticity to facilitate processing. A softening agent and a crosslinking agent for chemically bonding the molecules of the linear polymer compound to each other to take a network structure are added.

In the case of tire tread rubber composition, white inorganic fillers such as white carbon, calcium carbonate and clay are added in addition to carbon black and silica, which are commonly used to improve strength, elasticity, abrasion resistance, and ozone resistance of rubber. Doing.

Background Art In recent years, rubbers for tires have been increasingly used as a reinforcing filler, in which silica having excellent braking force and rolling resistance on wet roads is mixed with carbon black or silica alone. However, silica has a strong hydrophilic group and due to the interaction between the silica due to the high cohesiveness and low dispersibility may increase the viscosity due to poor dispersion when used in the rubber composition and rubber properties due to the gelation reaction when left for a long time. In order to solve this problem, dispersing aids, process oils and coupling agents are used to improve the dispersibility of silica.

However, in spite of this treatment, the dispersibility of silica is lowered, resulting in a problem of irregular wear phenomenon in the finished tire made of a rubber composition to which silica is applied. On the other hand, when carbon black is used as a reinforcing filler in a rubber composition, the wear resistance of the rubber is improved, but there is a problem in that braking force and rotational resistance characteristics on wet roads are lower than those of silica.

The main object of the present invention is to maximize the compatibility with silica, which has been spotlighted as a tire reinforcement material to improve the processability when compounding with a silica compound, and to maximize the vulcanization properties of rubber to greatly improve mechanical properties such as tensile properties, wear resistance, elongation, etc. It is to provide a benzoxazine compound and a method for producing the same.

The present invention also provides a rubber composition comprising the benzoxazine compound and a tire manufactured using the rubber composition.

In order to achieve the above object, one embodiment of the present invention provides a benzoxazine compound represented by the following formula (1).

[Formula 1]

In Formula 1, Z is-(S) n- or -R _1- (S) nR _2- , R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms, n is 1 to An integer of 4; R ₃ And R ₃ ′ are each independently an alkylene group having 3 to 10 carbon atoms; X ₁ to X ₃ are each independently a substituted or unsubstituted hydroxy, acetyl or epoxy group alkyl group having 1 to 5 carbon atoms, X ₁ 'to X ₃ ' are each independently substituted with a hydroxy group, acetyl group or epoxy group or It is an unsubstituted alkyl group having 1 to 5 carbon atoms.

In a preferred embodiment of the present invention, in Chemical Formula 1, Z is-(S) n-, and n is an integer of 1 to 3; R ₃ And R ₃ ′ is — (CH ₂ ) ₃ —; X ₁ to X ₃ may be each independently a methyl group or an ethyl group, and X ₁ ′ to X ₃ ′ may each independently be a methyl group or an ethyl group.

Another embodiment of the present invention provides a method for preparing a benzoxazine compound, comprising reacting a bisphenol compound, an aldehyde compound, and an amine compound containing sulfur to produce a benzoxazine compound represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, Z is-(S) n- or -R _1- (S) nR _2- , R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms, n is 1 to An integer of 4; R ₃ and R ₃ ′ each independently represent an alkylene group having 3 to 10 carbon atoms; X ₁ to X ₃ are each independently a substituted or unsubstituted hydroxy, acetyl or epoxy group alkyl group having 1 to 5 carbon atoms, X ₁ 'to X ₃ ' are each independently substituted with a hydroxy group, acetyl group or epoxy group or It is an unsubstituted alkyl group having 1 to 5 carbon atoms.

In another preferred embodiment of the present invention, in formula 1, Z is-(S) n-, n is an integer of 1 to 3; R ₃ and R ₃ ′ are — (CH ₂ ) ₃ —; X ₁ to X ₃ may be each independently a methyl group or an ethyl group, and X ₁ ′ to X ₃ ′ may each independently be a methyl group or an ethyl group.

In another preferred embodiment of the present invention, the reaction may be carried out at 60 to 100 ℃ in the presence of a solvent for 4 to 8 hours.

In another preferred embodiment of the present invention, the amine compound is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane ( 3-aminopropylMethylDiethoxysilane), 3-aminopropylmethyldimethoxysilane and 3-ureidopropyltriethoxysilane (3-ureidopropyltriethoxysilane) may be one or more selected from the group consisting of.

In another preferred embodiment of the present invention, the sulfur-containing bisphenol compound may be thiobisphenol.

In another preferred embodiment of the present invention, with respect to 1 mol of the sulfur-containing bisphenol compoundol, the amine compound may be 0.5-10 mol and the aldehyde compound 1.0-20 mol.

Yet another embodiment of the present invention provides a rubber composition comprising the benzoxazine compound and a tire manufactured using the rubber composition.

The benzoxazine compound according to the present invention can maximize the compatibility with silica, which has been spotlighted as a tire reinforcing material, improve the processability when compounding with a silica compound, and maximize the vulcanization properties to greatly improve the mechanical properties of the rubber material. It can be usefully used for tire production.

1 is an NMR spectrum of the benzoxazine compound prepared in Example 1 of the present invention.
2 is an infrared spectroscopic spectrum of the benzoxazine compound prepared in Example 1 of the present invention.
3 is a result of GPC analysis of the benzoxazine compound prepared in Example 1 of the present invention.
4 is an NMR spectrum of the benzoxazine compound prepared in Example 2 of the present invention.
5 is an infrared spectroscopic spectrum of the benzoxazine compound prepared in Example 2 of the present invention.
6 is a result of GPC analysis of the benzoxazine compound prepared in Example 2 of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

The present invention relates to a benzoxazine compound represented by the following general formula (1) in one aspect.

[Formula 1]

In Formula 1, Z is-(S) n- or -R _1- (S) nR _2- , R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms, n is 1 to An integer of 4; R ₃ And R ₃ ′ are each independently an alkylene group having 3 to 10 carbon atoms; X ₁ to X ₃ are each independently a substituted or unsubstituted hydroxy, acetyl or epoxy group alkyl group of 1 to 5 carbon atoms, X ₁ 'to X ₃ ' are each independently substituted with a hydroxy group, acetyl group or epoxy group or It is an unsubstituted alkyl group having 1 to 5 carbon atoms.

In particular, in Formula 1, Z is-(S) n-, n is an integer of 1 to 3; R ₃ and R ₃ ′ are — (CH ₂ ) ₃ —; X ₁ to X ₃ are each independently a methyl group or an ethyl group, and X ₁ 'to X ₃ ' is each independently a methyl group or an ethyl group is preferable in view of workability and cost.

The benzoxazine compound represented by the following Chemical Formula 1 according to the present invention contains a silane capable of reacting with silica, and a compound in which a sulfur group is introduced to induce efficient vulcanization with rubber. In addition to chemically bonding rubber and silica in the rubber composition, it also reacts with the coupling agent itself and cures, thereby maximizing the vulcanization properties of the rubber, thereby greatly improving mechanical properties such as tensile properties, abrasion resistance, and elongation. Can be.

In another aspect, the present invention relates to a method for producing a benzoxazine compound, comprising reacting a sulfur-containing bisphenol compound, an aldehyde compound, and an amine compound to produce a benzoxazine compound represented by the following formula (1).

[Formula 1]

In Formula 1, Z is-(S) n- or -R _1- (S) nR _2- , R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms, n is 1 to An integer of 4; R ₃ And R ₃ ′ are each independently an alkylene group having 3 to 10 carbon atoms; X ₁ to X ₃ are each independently a substituted or unsubstituted hydroxy, acetyl or epoxy group alkyl group having 1 to 5 carbon atoms, X ₁ 'to X ₃ ' are each independently substituted with a hydroxy group, acetyl group or epoxy group or It is an unsubstituted alkyl group having 1 to 5 carbon atoms.

In particular, in Formula 1, Z is-(S) n-, n is an integer of 1 to 3; R ₃ and R ₃ ′ are — (CH ₂ ) ₃ —; X ₁ to X ₃ are each independently a methyl group or an ethyl group, and X ₁ 'to X ₃ ' is each independently a methyl group or an ethyl group is preferable in view of workability and cost.

More specifically, the benzoxazine compound represented by Chemical Formula 1 according to the present invention is a bisphenol compound (A), an aldehyde compound (B) and an amine compound (C) containing sulfur in the presence of a solvent, as shown in Scheme 1 below. After the reflux reaction, the solvent may be removed by distillation under reduced pressure to prepare a benzoxazine compound of Chemical Formula 1 according to the present invention.

Scheme 1

In Scheme 1, Z, R ₃ , R ₃ ', X _{1 ,} X ₂ , X _{3 ,} X ₁ ', X ₂ ′ and X ₃ ′ are as described above.

The solvent used in the reaction of the sulfur-containing bisphenol compound, the aldehyde compound and the amine compound is an aromatic hydrocarbon solvent such as toluene, xylene, trimethylbenzene; Halogen solvents such as chloroform, dichloroform and dichloromethane; Ether solvents such as THF, dioxane and the like can be used. And the heating temperature may be carried out for 4 to 8 hours at 60 ~ 100 ℃. In this case, the content of the solvent is preferably 300 to 500 parts by weight based on 100 parts by weight of the bisphenol compound, aldehyde compound and amine compound containing sulfur.

If the reaction is carried out below the above-mentioned reaction temperature range, the unreacted compound may be present in excess, which may lower the hardenability due to volatiles during curing, and it may take several tens of hours to obtain a desired level of product. In the case where the reaction is performed in excess of the above-described temperature range, it is impossible to control the change over time and the molecular weight with increasing the cost of the manufacturing process, which may lead to product defects.

In addition, since the product produced in the reaction described above is hydrophobic, an appropriate kind and amount of solvent are required, and the most preferred solvent in the present invention is dioxane.

In the preparation of the benzoxazine, when the content of the solvent is too small, the viscosity of the reactant becomes high, the stirring stress increases, and the workability decreases. When the benzoxazine is excessively excessive, the cost of removing the solvent after the reaction becomes uneconomical. Can be. In addition, when the selection of the appropriate solvent and the mixing reaction is not made properly, the raw materials do not participate in the reaction, the yield may be lowered.

In the above reaction, the amine compound may contain 0.5 to 10 moles, preferably 1.5 to 3.5 moles per mole of bisphenol compound containing sulfur, and the aldehyde compound is 1 to 20 moles per mole of arylphenol. Moles, preferably 3 to 6 moles .

If less than 0.5 mole of amine compound is added to 1 mole of sulfur-containing bisphenol compound, the oxazine ring is not sufficiently formed and the curing property is lowered. Due to the presence of a large amount, there may be a problem that volatilization does not occur properly during curing, and when an aldehyde compound is added to less than 1 mole with respect to 1 mole of a bisphenol compound containing sulfur, it does not induce a sufficient reaction with an amine. As a result, the oxazine ring is not formed, and if it exceeds 20 mol, a large amount of unreacted bisphenol may be present, which may cause a problem that curing is not sufficiently performed.

The sulfur-containing bisphenol compound can be used without limitation as long as it is a bisphenol compound substituted with sulfur, and may be preferably thiobisphenol (thiobisphenol) in terms of workability and mechanical properties of rubber specimens.

In addition, the aldehyde compound is not particularly limited, but as a specific example, may be one or more selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde and butylaldehyde, the formaldehyde is p-formaldehyde as the polymer B, it can be used in the form of formalin which is a form of aqueous solution, and since the progress of reaction is moderate, it is preferable to use p-formaldehyde.

In addition, an amine silane may be used as the amine compound, preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyl May be one or more selected from the group consisting of 3-aminopropylMethylDiethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-ureidopropyltriethoxysilane, and more. Preferably 3-aminopropyltriethoxysilane (3-aminopropyltriethoxysilane) is good in terms of rubber properties after vulcanization.

In still another aspect, the present invention relates to a rubber composition comprising a benzoxazine compound represented by Chemical Formula 1.

The rubber composition of the present invention includes 2 to 20 parts by weight of the benzoxazine compound represented by Formula 1 and 30 to 80 parts by weight of silica based on 100 parts by weight of a rubber material such as natural rubber and synthetic rubber. When the benzoxazine compound is added at less than 2 parts by weight with respect to 100 parts by weight of the rubber material, the effect is insignificant compared to the addition of the benzoxazine compound, and when added in excess of 20 parts by weight, the silica contained in the composition is dispersed. This is not done smoothly, a problem may arise that the cost rises.

In addition, when the silica content is less than 30 parts by weight with respect to 100 parts by weight of the rubber material, the effect of the addition is insignificant, and when the content is added in excess of 80 parts by weight, the amount of silica added is too much relative to the composition so that the silica is dispersed. This may not occur smoothly.

In this case, the rubber material means a raw rubber such as natural rubber and synthetic rubber used to manufacture the rubber composition.

On the other hand, sulfur, vulcanization accelerators and other additives that are commonly added, and other rubber materials can be used in combination depending on the use of the rubber composition, its type and use will be apparent to those skilled in the art.

Since the rubber composition according to the present invention contains the benzoxazine compound represented by Chemical Formula 1, the mechanical properties of the rubber can be greatly improved by maximizing the vulcanization properties of the rubber without bringing down the overall physical properties required for the rubber for tires. have.

The rubber composition according to the present invention can be included in various rubber components constituting the tire. Such rubber components include treads (tread caps and tread bases), sidewalls, sidewall inserts, apex, chafers, wire coats or innerliners, and the like. Preferably it can be used as a rubber composition for tire tread.

In another aspect, the present invention relates to a tire manufactured using the rubber composition. The method of manufacturing a tire using the rubber composition may be applied to any method used in the related art, and thus detailed description thereof will be omitted.

The tire may be a passenger car tire, a racing tire, an airplane tire, a farm tire, an off-the-road tire, a truck tire or a bus tire. The tire may also be a radial tire or a bias tire .

Hereinafter, the content of the present invention will be described in detail through examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto.

< Example  1>

1-1: represented by Formula 1 Benzo Photo  Preparation of the compound

Into a 1,000 ml four-necked flask with 400 g of dioxane, 27.57 g (0.126 mol) of thiobisphenol, 16.49 g (0.505 mol) of para-formaldehyde, and 55.93 g (0.253 mol) of 3-aminopropyltriethoxysilane were added in this order. , The reaction was carried out for 6 hours under reflux reaction at 95 ℃, after completion of the reaction distillation under reduced pressure and dried to give a benzoxazine compound represented by the formula (1) (Z is -S-, R ₃ is-(CH ₂ ) _3- , X ₁ to X ₃ is -CH ₂ CH ₃ ) to 92 g. The yield of the benzoxazine compound obtained is 93.2% relative to the raw material solids.

The obtained benzoxazine was confirmed in structure by nuclear magnetic resonance analysis (NMR), and is shown in FIG. 1. The NMR instrument used in the NMR analysis is the Bruance Avance 500. The infrared spectrum used is shown in FIG. 2. The Infrared Spectrometer is a Spectrum 100 product from Perkin Elmer. In addition, the molecular weight distribution of the compound synthesized from the reaction raw material was confirmed using gel permeation chromatography (GPC) and is shown in FIG. 3. GPC used is Waters, and the device configuration is 515HPLC Pump, 717 Plus Autosampler, Column Oven, 2414 RI Detector.

1-2: Rubber Composition Preparation

65 parts by weight of silica, 4 parts by weight of the benzoxazine compound prepared in Example 1-1, and a blend with respect to 100 parts by weight of a rubber material having SBR (Styrene Butadiene Rubber, Dongjin) and BR (Butadiene Rubber) in a 4: 1 ratio. 3 parts by weight of zinc oxide and 2 parts by weight of stearic acid by the smooth dispersion of. Then, 1 part by weight of sulfur was blended using a mixer (BR 1600 BANBURY MIXER, FARREL) at a temperature of 30 ° C. at a rotational speed of 60 RPM.

1-3: Rubber Specimen Manufacturing

The rubber composition obtained in Example 1-2 was put into a mill (open mill surface temperature: 100 ° C., roll interval 0.8 mm) to prepare a sheet having a thickness of 2.5 mm. The rubber sheet thus prepared was filled in a vulcanized mold preheated to 160 ° C., vulcanized at 160 ° C. for 25 minutes at 50 kgf / cm ^2, and left at room temperature for 24 hours to prepare a rubber specimen.

<Example 2>

1-1: represented by Formula 1 Benzo Photo  Preparation of the compound

Into a 1,000 ml four-neck flask containing 400 g of dioxane, 27.57 g (0.126 mol) of thiobisphenol, 16.49 g (0.505 mol) of para-formaldehyde, and 42.25 g (0.253 mol) of 3-aminopropyltrimethoxysilane were added in this order. , The reaction was carried out for 6 hours under reflux reaction at 95 ℃, after completion of the reaction distillation under reduced pressure and dried to give the benzoxazine compound represented by the formula (Z) is -S-, R ₃ is-(CH ₂ ) _3- , X ₁ to X ₃ is -CH ₃ ) to yield 81 g. The yield of the benzoxazine compound obtained is 95.6% relative to the raw material solids.

The obtained benzoxazine was confirmed by structure using nuclear magnetic resonance analysis (NMR), and is shown in FIG. 4. The NMR instrument used in the NMR analysis is the Bruance Avance 500. The infrared spectrum used is shown in FIG. 5. The Infrared Spectrometer is a Spectrum 100 product from Perkin Elmer. In addition, the molecular weight distribution of the compound synthesized from the reaction raw material was confirmed using gel permeation chromatography (GPC) and is shown in FIG. 6. GPC used is Waters, and the device configuration is 515HPLC Pump, 717 Plus Autosampler, Column Oven, 2414 RI Detector.

2-2: rubber composition

Thereafter, a rubber composition was prepared in the same manner as in Example 1-2.

2-3: rubber composition

Thereafter, rubber specimens were prepared in the same manner as in Example 1-3.

< Comparative example  1>

A rubber specimen was prepared in the same manner as in Example 1, but a rubber specimen was prepared without adding the benzoxazine compound prepared in Example 1-1.

< Comparative example  2>

A rubber specimen was prepared in the same manner as in Example 1, except that the rubber specimen was prepared by adding TESPT [3- (triethoxysilyl) propyl] tetrasulfide (ILSIN Chemtech), a universal coupling agent, in place of the benzoxazine compound prepared in Example 1-1. Prepared.

< Comparative example  3>

Into a 1,000 ml four-necked flask containing 400 g of dioxane, 28.76 g (0.126 mol) of bisphenol A, 16.49 g (0.505 mol) of para-formaldehyde, and 55.93 g (0.253 mol) of 3-aminopropyltriethoxysilane were added in this order. The reaction was carried out under a reflux reaction at 95 ° C. for 6 hours, and after completion of the reaction, distillation under reduced pressure and drying resulted in no benzoxazine compound (Z is -C (CH ₃ ) _2- ) and R ₃ is-(CH ₂ ). ₃ −, X ₁ to X ₂ are —CH ₂ CH ₃ ) to give 89 g. The yield of the benzoxazine compound obtained is 89.1% relative to the raw material solids.

Thereafter, rubber specimens were prepared in the same manner as in Example 1.

The tensile strength and elongation of the rubber specimens prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below.

Tensile strength (kgf / cm ² ) and elongation (%)

Tensile strength was measured using a Umad-Shimadzu-AG-1S tensile tester of Shimadzu at a cross head speed of 500 mm / min. The elongation was measured until the film broke under the same conditions as the tensile strength. .

Instrument specifications and conditions

Model Name: U.T.M-Shimadzu AG-1S (Load cell: PFG-5kN)

Specimen Specification: Dumbbell No. 3

Test speed: 500mm / min

<Shore A>

After the rubber specimens were left for 24 hours, the thickness was normalized to 7 mm ± 0.5 mm in three layers, and the hardness of the rubber specimens was measured using the following equipment and conditions.

Instrument specifications and conditions

 Model Name: Shore Hardness Tester (Shore-A Type)

Specimen Size: Thickness 7mm ± 0.5mm

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 UTM
The tensile strength
(kgf / cm ² ) 186.2 184.4 144.5 158.5 153.2 % Elongation 872.6 1020.1 1181.8 560.7 980.2 Shore A 71 72 61 74 68

As shown in Table 1, Comparative Examples 1 and 3 increase the elongation due to the lack of vulcanization, while the tensile strength is weak, and in Comparative Example 2, the tensile strength and hardness increase relatively, while the elongation is 50% or less. It was found to decrease. That is, it was confirmed that the conventional rubber composition did not improve both the tensile strength and the elongation of the rubber specimen. However, in the rubber specimens of Examples 1 and 2, it was confirmed that the elongation also increased significantly compared to Comparative Example 2 containing a universal coupling agent, while the tensile strength was greatly improved.

Therefore, the benzoxazine compound according to the present invention can maximize the compatibility with silica, which has been spotlighted as a tire reinforcing material to improve the processability when compounding with a silica compound, and can maximize the vulcanization properties to greatly improve the mechanical properties of the rubber material. Could confirm.

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 (10)

delete delete A method for producing a benzoxazine compound represented by the following Chemical Formula 1 by reacting thiobisphenol, para-formaldehyde and 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane in the presence of a solvent,
[Formula 1]

(In Formula 1, Z is -S-, R ₃ and R ₃ 'is propylene; X ₁ to X ₃ is a methyl group or ethyl group, X ₁ ' to X ₃ 'is a methyl group or ethyl group)
The solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, chloroform, dichloroform, dichloromethane, THF and dioxane, the thiobisphenol, para-formaldehyde and 3-aminopropyltrimethoxysilane or 3- A method for producing a benzoxazine compound, characterized in that 300 to 500 parts by weight based on 100 parts by weight of aminopropyltriethoxysilane.
delete The method of claim 3, wherein the reaction is carried out at 60 to 100 ℃ for 4 to 8 hours in the presence of a solvent.
delete delete delete Rubber composition comprising 2 to 20 parts by weight of benzoxazine compound represented by the following formula (1) and 30 to 80 parts by weight of silica based on 100 parts by weight of the natural rubber or synthetic rubber material
[Formula 1]

(In Formula 1, Z is -S-, R ₃ and R ₃ 'is propylene; X ₁ to X ₃ is a methyl group or ethyl group, X ₁ ' to X ₃ 'is a methyl group or ethyl group)
A tire manufactured using the rubber composition of claim 9.

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