Rubber mixture and tyre with thereof application

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture, and to a tyre, and to the rubber mixture, suitable for the application as a component of the tyre framework, especially as rubber for the tyre bead filler and to the tyre, in which the said rubber mixture is applied. The rubber mixture contain a caoutchouc component, selected from, at least, one of natural caoutchouc and synthetic caoutchouc, and a resin composition, containing resorcinol resin of a novolac type and phenol resin of a resol type, in an amount from 1 to 30 wt.p. calculated per 100 wt.p. of the caoutchouc component. The content of dimethylene ether groups in phenolic resin of the resol type constitutes from 20 mol. % to 100 mol. % relative to the total content of binding groups, obtained from aldehydes, binding aromatic rings, obtained from phenol, to each other. The absence of application of hexamethylenetetraine or hexamethoxymethylmelamine as a hardening agent results in an increase of the hardening ability and thermal stability of the resin composition, with the rubber mixture possessing characteristics of high elasticity, large rupture elongation and low heat release.

EFFECT: tyre, containing the said rubber mixture in the bead part of the tyre, possesses an increased service term when applied.

10 cl, 1 dwg, 3 tbl, 11 ex

 

The technical field to which the invention relates.

The present invention relates to rubber mixtures and to the bus, and refers to the rubber compound suitable for use as parts of the carcass of the tyre, especially as rubber for side filler bus and to the bus that uses a specified rubber compound having excellent durability.

The level of technology

Still for details of the tire carcass and the like used highly elastic rubber. As a means of enhancing the elasticity of the rubber, the literature describes a way to increase the amount of filler, such as carbon black or the like, for example, in patent reference 1, and, in addition, there is a method of increasing the amount of sulfur vulcanizing the material, in order to increase the points of the staple, and others; however, in the case of increasing the amount of filler, such as carbon black or the like, a problem arises because the processability of the rubber composition in the enterprise, as well as its resistance to degradation, such as elongation or the like, may deteriorate, and may increase the heat dissipation rubber compound. In addition, in the case of increasing the amount of sulfur vulcanizing ingredient, also has a problem that may decrease the elongation at break and can vozrastjushchaja changes associated with thermal decomposition.

In this regard, as a means of increasing the elasticity of the rubber composition with suppression of the decrease in elongation at break, the described method of adding unmodified phenolic resins, Novolac type, which can be obtained by condensation of phenol and aldehyde in the presence of an acid catalyst, or a modified phenol resin, Novolac type, which was modified unsaturated oil such as tall oil, cashew butter, or the like, or aromatic hydrocarbons, such as xylene, mesitylene or the like, and hexamethylenetetramine as a curing agent capable of cured resin, for example, in patent references 2 and 3.

In patent reference 4, a method in which phenol resin rezol type is used instead of the above hexamethylenetetramine as a curing agent for phenolic resins, Novolac type, which can be added to rubber to improve the resistance of podocarpaceae rubber mixture during processing.

Patent reference 1: JP-A 9-272307.

Patent reference 2: JP-A 5-98081.

Patent reference 3: JP-A 2001-226528.

Patent reference 4: JP-A 57-57734.

Disclosure of inventions

Problems to be solved in the present invention

However, in the method described in the patent is the links 2 and 3, hexamethylenetetramine and hexamethoxymelamine commonly used as curing agents emit volatile gases, such as ammonia, formaldehyde or the like, when heated to the decomposition temperature or higher during the stages of mixing or vulcanization. In the case of such products from rubber as the tyres that contain steel cords or organic fiber cord, gaseous ammonia causes a decrease in the adhesion between rubber and cord. In addition, since the hexamethylenetetramine also serves as a vulcanization promoter for rubber, the disadvantage is the fact that adding a large number of hexamethylenetetramine, the rubber can easily be podocarpaceae.

With regard to formaldehyde, then its concentration in the air inside the premises must not exceed the specified level at the production site from the point of view of environmental safety, and any work must be carried out so that the concentration does not exceed the specified level.

For this reason, when hexamethylenetetramine or hexamethoxymelamine are used as curing agents, there are limitations on the quantity of such added agents and components where they can be added.

In addition, in the method described in patent reference 4, as the CTE is the approving agent is used phenolic resin rezol type; however, since the phenolic resin rezol type in accordance with the standard method is obtained by polymerization of phenol and formaldehyde in the presence of an alkaline catalyst, phenol group in the resin is almost completely associated with the methylene groups (which contain up to 10 mol.% dimethylanisole ether). Therefore, in this way can be solved the above problems; however, when the rubber compound used in the tire, its tensile strength is insufficient, and when the rubber compound is used for the tire bead, the specified composition does not correspond to the life of the tire, as its adhesiveness relative to the cord is insufficient.

The present invention is made considering the above situation, and one object of the invention to provide rubber mixtures, which are able to enhance the curing ability of the resin composition in the above-mentioned mixture without the use of hexamethylenetetramine or hexamethoxymelamine as curing agents, which can increase thermal stability of the composition, and has the characteristics of elasticity, a significant elongation at break and a small dissipation. Another object of the invention is to develop tyres, Kotor, which contains the rubber mixture in the on-Board bus parts, and therefore has an increased service life when using it, as well as improved environmental safety.

Resolving problems

The above problems can be solved by the present invention are described below.

Specifically, paragraph 1, of the formula the present invention relates to a rubber mixture which contains a rubber component selected from at least one of natural rubber and synthetic rubber, and a resin composition containing resorcinol resin Novolac type phenolic resin rezol type, in which the content of the groups dimethylanisole ether phenolic resin rezol type is from 20 mol.% to 100 mol.%, relative to the total content of the linking groups derived from aldehydes that connect to the aromatic ring derived from phenol.

Paragraph 2 of the formula of the invention relates to a rubber mixture according to item 1, in which resorcinol resin Novolac type obtained by reacting the resorcinol and the aldehyde in a molar ratio of aldehyde/resorcinol) from 0.4 to 0.8.

Paragraph 3 of the formula of the invention relates to a rubber mixture according to item 1 or 2, in which the content resorcinol resin, Novolac-type resin composition ranges from 18% by weight to 50% by mass.

Paragraph 4 of the formula of the invention relates to a rubber mixture according to any one of the of unstow 1-3, in which the content of the resin composition is from 1 to 30 parts by weight per 100 parts by mass of the rubber component.

Paragraph 5 of the formula of the invention relates to a rubber mixture according to any one of items 1-4, in which the resin composition further comprises a filler.

Paragraph 6 of the formula of the invention relates to a rubber mixture according to paragraph 5, in which the content of the filler is from 1 to 100 parts by weight per 100 parts by weight of the resin composition.

Paragraph 7 of the formula of the invention relates to a rubber mixture according to item 5 or 6, in which the filler is a fumed silicon dioxide.

Paragraph 8 of the formula of the invention relates to a rubber mixture according to any one of items 1-7, in which the rubber component is a diene rubber.

Paragraph 9 of the claims refers to the tire, in which at least part of the side part of the tire includes a rubber mixture according to any one of items 1-8.

Paragraph 10 of the claims refers to the bus on paragraph 9, in which the side part of the tire containing the rubber compound is a side filler.

Paragraph 11 of the claims refers to the bus according to item 9 or 10, in which the rubber mixture further comprises carbon black, and the content of carbon black is from 30 parts by weight to 100 parts by weight of the E. per 100 parts by mass of the rubber component.

Advantages of the invention

According to paragraph 1 of the present invention, hardening ability and thermal stability of the resin composition can be improved without the use of hexamethylenetetramine or hexamethoxymelamine as the curing agent, there can be obtained a rubber compound, which has the characteristics of high elasticity and high elongation at break.

According to paragraph 2 of the invention, provides easy adjustment of interaction during curing of the resin composition, there can be obtained a rubber compound with excellent mechanical properties and machinability.

According to the point of invention 3, the curing ability of the resin composition can be improved, and can be obtained rubber compound, which has the characteristics of high elasticity and low heat production.

Pursuant to paragraph 4 of the invention may be obtained rubber compound, which has the characteristics of high elasticity and high elongation at break.

According to the point of invention 5, the resistance of the rubber to stick together, which can occur when the resin composition for some time remains, in itself, can be improved without reducing the modulus of elasticity and relative elongation at break of the rubber.

According to the paragraph which the invention 6, the resistance of the rubber to stick together, which can occur when the resin composition for a time remains in itself, can be improved without reducing the modulus of elasticity and relative elongation at break of the rubber.

Under paragraph invention 7, the resistance of the rubber to stick together, which can occur when the resin composition for some time remains, in itself, can be improved without reducing the modulus of elasticity and relative elongation at break of the rubber.

According to the point of invention 8, can be obtained rubber compound, which has the characteristics of high elasticity and greater elongation at break.

According to the point of invention 9, the rubber mixture that can be obtained without the use of hexamethylenetetramine or hexamethoxymelamine as a curing agent and which has the characteristics of high elasticity, the larger the elongation at break and low heat production, is used as the side part of the tire, so the tire has an increased service life when operating, taking into account environmental safety.

According to the paragraph of the invention 10, the rubber mixture can be effective adhesiveness against Korda and high elasticity, thus effectivelevitra the life of the tires.

According to the point of invention 11, the modulus of elasticity can be effectively improved without reducing the adhesion relative to the cord.

Brief description of drawing

The figure 1 shows the left half of the cross-section of one example of the tire of the present invention.

The best way of carrying out the invention

The present invention is described below with reference to his ways of implementation.

The rubber mixture

The rubber mixture of this variant implementation contains a rubber component selected from at least one of natural rubber and synthetic rubber, and a resin composition, which contains as integral parts resorcinol resin Novolac type phenolic resin rezol type, and content groups dimethylanisole ether phenolic resin rezol type is from 20 mol.% to 100 mol.% based on the content of the linking groups derived from aldehydes that connect to the aromatic ring derived from phenol.

The rubber component

The rubber component used in the rubber compound of this variant implementation, represents at least one selected from natural rubber (NR) and various types of synthetic rubbers. Specific examples of synthetic rubbers include all the I branch, Rubezhnoe, Ukraine rubber (IR), the styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butyl rubber (HR), halogenated butyl rubber (Br-IIR, Cl-IIR), ethylene-propylene-diene rubber (EPDM), cross-linked polyethylene rubber, chloroprene rubber, nitrile rubber, etc. the only One, or two or more of these rubber components may be used individually or in combination. The use of any of these components can lead to advantages, characteristic of the option exercise, in that the rubber mixture may have a high elasticity and a large elongation at break, due to the curing of the composition specified below phenolic resin according to the invention.

From rubbers are preferably used natural rubber (NR) and diene rubbers such as styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR) and the like, which give the rubber the characteristics of high elasticity and greater elongation at break.

The resin composition

The rubber mixture of the specified variant implementation contains a resin composition, which comprises as essential components, resorcinol resin Novolac type phenolic resin rezol type. Introduction the composition of phenolic resin which is a thermoplastic resin capable of stand is to enhance the modulus of elasticity of the rubber, is an effective method; however, one resorcinol resin Novolac type has no hardening ability in the absence of a curing agent, as specified in the resin no methylol group at the end of the molecule. On the other hand, since the phenolic resin rezol type has a methyl group at the end of the molecule, it has a hardening ability in the absence of a curing agent. However, when using the same phenolic resin rezol type curing ability is low, and the resin may not cause sufficient curing during vulcanization of rubber.

Therefore, in this embodiment, the inventors have found that when a resin composition is injected resorcinol resin Novolac type phenolic resin rezol type, the modulus of elasticity of the rubber compound can be increased without using a curing agent, and may also be increased elongation at break of the composition. Specifically, it is assumed that the combined use of resorcinol resin Novolac type phenolic resin rezol type results in a very bulky composition of the resin in which the phenolic resin rezol type and resorcinol resin Novolac type interact with each other and bulky resin composition may be effective is about to act as pseudolite structure in the rubber component, and thus increases the elasticity and elongation at break of the rubber.

In this embodiment, as mentioned above, the term "phenolic resin" is used to denote phenolic resins in a wide range, which includes not only the polycondensation products obtained from one of phenol, but also the polycondensation products obtained from any other phenols, such as cresol, Xylenol and other

Phenolic resin rezol type used in this embodiment, is obtained as a result of the interaction of phenol and aldehyde. In fact, phenolic resin rezol type known as a precursor of the resin before curing, however, when this reaction is used alkaline catalyst, then the reaction of the merger proceeds with the formation of mainly phenolic resin rezol type having a low degree of polymerization.

The phenol used in the phenolic resin rezol type in this embodiment includes, for example, phenol; Cresols, such as o-cresol, m-cresol, p-cresol, and others; Xylenol, such as 2,3-Xylenol, 2,4-Xylenol, 2.5-Xylenol, 2,6-Xylenol, 3,4-Xylenol, 3,5-Xylenol and others; ethylphenol, such as o-ethylphenol, m-ethylphenol, p-ethylphenol and others; isopropylphenol; butylphenol, such as butylphenol, p-tert-butylphenol and other; ALKYLPHENOLS such as p-tert-amylphenol, p-OCTI the phenol, p-Nonylphenol, p-cumylphenol, and others; halogenated phenols such as terfenol, chlorophenol, bromophenol, itfinal and others; substituted monophenol, such as p-phenylphenol, aminophenol, NITROPHENOL, dinitrophenol, trinitrophenol, and others; and monophenol, such as 1-naphthol, 2-naphthol, and others; and polyphenols such as resorcinol, alkylresorcinol, pyragollole, pyrocatechin, allylpyrocatechol, hydroquinone, alkyl hydroquinone, phloroglucinol, bisphenol a, bisphenol F, bisphenol S, dihydroxynaphthalene and other Single phenol or two or more phenols may be used individually or in combination.

Of these preferred phenols are selected from phenol, Cresols and phenols, which are economically attractive.

The aldehyde used in the phenolic resin rezol type, and resorcinol resin Novolac type in this embodiment includes, for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionic aldehyde, Polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butylaldehyde, Caproic aldehyde, allyl aldehyde, benzaldehyde, CROTONALDEHYDE, acrolein, tetraoxalate, phenylacetaldehyde, Truelove aldehyde, salicylic aldehyde, etc. the Only aldehyde, or two or more may be used individually or in combination.

Of these the aldehyde is preferred aldehyde, selected from formaldehyde and paraformaldehyde, which have excellent reactivity and cheap.

Phenolic resin rezol type can be obtained by reacting the above phenol and aldehyde in the presence of a catalyst, such as alkali metals, amines, salts of divalent metals and other

As the catalyst used in the specified interaction, for example, you can use the hydroxides of alkali metals such as sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.; oxides and hydroxides of alkaline earth metals such as calcium, magnesium, barium and others; sodium carbonate; aqueous ammonia; amines, such as triethylamine, hexamethylenetetramine, and others; salts of divalent metals such as magnesium acetate, zinc acetate, etc. In the present invention can be used single, or two or more of these catalysts, individually or in combination.

Upon receipt of phenolic resin rezol type, the molar ratio in the interaction of phenol and aldehyde is preferably such that the content of the aldehyde was from 0.80 to 2.50 mol, more preferably from 1.00 to 2.30 mol per 1 mol of phenol. When the molar ratio is within the specified range, then the interaction is easily adjustable, and can be obtained phenol with the Olu rezol type with a good yield.

Group content dimethylanisole ether phenolic resin rezol type used in this embodiment is from 20 mol.% to 100 mol.% in the calculation of the total content of the linking groups derived from aldehydes that connect to the aromatic ring derived from phenol, preferably from 20 mol.% up to 80 mol.%, more preferably from 25 mol.% up to 75 mol.%, even more preferably 35 mol.% up to 60 mol.%. When the content of the groups dimethylanisole ether is within the specified range can be obtained, the composition of the phenolic resin with good hardening ability, excellent thermal stability and absence of variations in quality.

The share of the linking groups in the phenol resin rezol type is determined using 1H-NMR. Specifically, phenolic resin rezol type is treated with acetic anhydride in pyridine as the catalyst to azetilirovanie methylol groups of the resin, and acetylated resin was analyzed by 1H-NMR.

The content of the linking groups of each type is determined based on the peak (2,04 ppm) acetone registered in the spectrum, in the form of methylene groups (around 3.8 ppm), groups dimethylanisole ether (about 4.5 ppm)and methyl groups (approximately 5,0 ppm). The ratio of the integral intensity of the peak is split in half (decreases in 2 times) for me is yanovych groups and methyl groups, while the ratio of the integrated intensity for dimethylanisole ether is reduced 4 times; and the relationship of these values are calculated with respect to the content (mol.%) groups dimethylanisole ether to the content of all linking groups derived from aldehydes (total content of methylene groups, groups dimethylanisole ether and methyl groups).

As device in the present invention is applied NMR analyzer "JNM-AL300 (300 MHz) and JEOL. In the above-mentioned measurement method, as the source material for phenolic resins rezol type are used, the phenol and formaldehyde; however, in other cases, where the phenols and the aldehydes differ from those specified ratio can be determined based on the same basic principle.

On the other hand, resorcine used for resorcinol resin Novolac type include, for example, resorcinol; methylresorcinol, such as 2-methylresorcinol, 5-methylresorcinol, 2.5-demetallization and others; 4-ethylresorcinol, 4-chlororesorcinol, 2-nitroresorcinol, 4-bromoresorcinol, 4-n-hexylresorcinol and others Can be used only resorcinol, or two or more of these resorcinol, or individually, or in combination.

Of these resorcinol, preferred is one selected from resorcinol and methylresorcinol that are cost benefits of the low.

Resorcinol resin Novolac type can be obtained by reacting the resorcinol and the above aldehyde in the presence of an acid catalyst with subsequent removal of water at the stage of removal of water. As the catalyst used in the preparation resorcinol Novolac resin of the type mentioned acids such as oxalic acid, hydrochloric acid, sulfuric acid, diethylsulfate, paratoluenesulfonyl acid or the like; and the only one, or two or more acids can be used individually or in combination. Because the resorcinol is an acid, the resin can be obtained in the absence of a catalyst.

Upon receipt resorcinol resin Novolac type the molar ratio of resorcinol and aldehyde (aldehyde compound/resorcinol) in the reaction mixture is preferably such that the amount of aldehyde is from 0.40 to 0.80 mol mol per mol of resorcinol, more preferably the amount of aldehyde is from 0.45 to 0.75 mol mol. When the molar ratio is within the specified range, then the interaction is easily adjustable and easier operation with resin.

Content resorcinol resin, Novolac-type resin composition is preferably between 18% by weight to 50% by weight, based on the entire resin composition, b is more preferably from 20 mass% to 45 mass%.

When the content resorcinol resin Novolac type is within the specified range, the curing ability of the component resin in this embodiment can be enhanced, and can be obtained a rubber mixture having the characteristics of high elasticity and low heat dissipation.

Preferably, the resin composition of this option may not have been previously added filler to strengthen the resilience of the resin to stick together, which can occur when the resin composition for a time remains by itself. In the invention can be used fillers of various types. For example, there may be mentioned calcium carbonate, calcium stearate, silicon dioxide, barium sulfate, talc, clay, graphite, and others; and the only one, or two or more fillers may be used individually or in combination. Of them it is preferable to use silicon oxide, and more preferably fumed silica, without deterioration of the physical characteristics of the rubber compound.

With regard to the amount of filler that can be added, preferably the filler is added in an amount of from 1 part by weight to 100 parts by weight per 100 parts by weight of the resin composition. When the content of the filler is within the specified range, the stability of the adhesion rubber compound, which can occur when the resin composition for some time remains, in itself, can be improved without reducing the modulus of elasticity and elongation at break of the rubber. More preferably, the specified content is 5 parts by mass to 90 parts by weight, even more preferably from 30 parts by weight to 80 parts by weight, even more preferably 8 parts by mass to 35 parts by mass.

Without a specific definition, in this embodiment, a method of mixing a phenolic resin rezol type and resorcinol resin Novolac type with the formation of the resin composition can be any, in which these two components can uniformly mixing and dispersing. For example, there may be mentioned a method of adding a phenolic Novolac resin to the phenolic type resin rezol type during the interaction, and their mixing, a method of adding a phenolic resin rezol type to the phenol Novolac resin type during the interaction, and their mixing, or how simple grinding and mixing of phenolic resin rezol type phenolic resins, Novolac type, as well as the method of mixing the resin in a twin-screw extruder, an open roll mill or in a kneading machine and other

Preferably, in this embodiment, the composition of phenolic resin which is a powder or solid. When the resin composition is not a powder or a solid, semi-solid or liquid substance, it is undesirable because it leads to the problem of manipulation with resin when injected into a molded product.

The content of the composition of phenolic resin in the rubber compound of this variant implementation is preferably from 1 to 30 parts by weight per 100 parts by mass of the rubber component, more preferably from 5 parts by mass to 20 parts by weight. When the resin content is within the specified range can be obtained a rubber mixture having the characteristics of high elasticity and high elongation at break.

Other components

In the rubber compound of this variant implementation, in addition to the rubber component and the resin composition mentioned above, if necessary, can be introduced various additives that are commonly used in the prior art rubber, such as fillers, vulcanizing agents, vulcanization promoter, zinc oxide, stearic acid, antioxidant, plasticizer and the like, which are expediently chosen in range, without deviating from the purpose of this variant implementation.

For example, the filler includes carbon black, silica, alumina, talc, calcium carbonate, aluminum hydroxide is INIA and other The type of filler is not specifically discussed; and in the invention can be used any filler total use for rubber, which is advisable pick. From the point of view of providing even higher elongation at break and tensile strength, preferably as a filler is used, at least one of carbon black and silica. When used inorganic filler such as silicon dioxide or the like, also can be used combining silane reagent.

In particular, when the rubber compound is used as the side part of the tire, it is preferable to use carbon black as filler, from the point of view of increasing the modulus of elasticity of the mixture, without reducing the adhesion of the mixture in relation to the cord.

The amount of filler that can be injected into the rubber mixture of this variant implementation, is preferably from 20 parts by mass to 150 parts by weight per 100 parts by mass of the rubber component. When the amount of filler is in the specified range, the rubber mixture can be completely reinforced, and prevents the dissipation, the mixture may be such physical characteristics as the resistance is a group of abrasion, the processability and the like. From the point of view of satisfaction of the requirements for gain and the characteristics of rubber, more preferably the amount of filler is from 30 parts by weight to 80 parts by mass.

In particular, when a filler is used, carbon black, preferably it ranges from 30 parts by weight to 100 parts by weight, per 100 parts by mass of the rubber component, more preferably from 40 parts by weight to 80 parts by weight. When the amount of carbon black is within the specified range, the modulus of elasticity of the rubber compound can be effectively increased without reducing the adhesion relative to the cord.

Without a specific definition, the vulcanization promoter includes, for example, promoters vulcanization type, thiazole, such as M (2-mercaptobenzothiazoles), DM (dibenzothiazyl), and others; the vulcanization promoters sulfenamide type, such as CZ (N-cyclohexyl-2-benzothiazolesulfenamide), and others; promoters vulcanization type guanidine, such as DPG (diphenylguanidine), and others; and their number, which can be used is preferably from 0.1 parts by mass to 5.0 parts by weight, per 100 parts by weight of the rubber, more preferably from 0.2 parts by mass to 3.0 parts by mass.

At asany antioxidant includes, for example, 3C (N-isopropyl-N'-phenyl-p-phenylenediamine), 6C [N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine], AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), product of high-temperature condensation of diphenylamine and acetone, etc. Preferably the amount of antioxidants is from 0.1 parts by mass to 6.0 parts by weight, per 100 parts by mass of the rubber component, more preferably from 0.3 part by weight to 5.0 parts by weight.

The rubber mixture of this variant implementation can be obtained, for example, by mixing the above components in a kneading machine or the like, for example, in the mill, Banbury mixer, honomale, internal mixer, etc.

Thus obtained compound containing at least one rubber component selected from natural rubber, synthetic isoprene rubber and synthetic diene rubber, and contains a special composition of the phenolic resin, is added to the mixture of this variant implementation, has excellent processability and is good for the environment, and the modulus of elasticity and elongation at break of the rubber is much greater than for conventional mixtures.

After stirring using the above mixing machine, rubber compound of this option is done by the means may be subjected to molding and vulcanization, and can usually be used tyres as an essential part of the tyre, such as rubber tread, podproducer, frame, side wall, the side of the tires, and others; as well as in other industrial products, such as anti-vibration rubber, belts, sleeves, and other

Bus

Bus this option, the implementation contains the above-mentioned rubber compound. Specifically, in the tire of this variant implementation of the above rubber compound is used, at least in the side part of the tire. Rubber side part of the tire, which uses rubber compound includes, for example, rubber side filler, the rubber covering Board the bus and other

In the case when the bus this option, the implementation is made, for example, a pneumatic tire can be used a method that includes receiving part of the onboard filler or reinforced rubber side bus operating with a lowered pressure (run flat tire) using the extruder and calender, then prilepljeni it to another part of the bus on the molded drum with the formation of the assembled uncured tire, the installation is not vulcanized tire in the mold, and cured under the action of compression on the inner side of the tire. Bus this option may not be filled in a nitrogen or inert gas, in addition to in the spirit.

In one preferred example, a pneumatic tire includes a pair of bead portions of the tire carcass, which toroidal associated with side part of the tire, a belt gripping the upper part of the casing and tread. In this embodiment, the pneumatic tire may have a radial structure, or diagonal structure.

Below is described a variant embodiment of the invention with reference to the drawing. The figure 1 shows the left half of the cross-section of one example of the tire (pneumatic tire) this option implementation.

In figure 1, the pneumatic radial tire 1R includes a pair of side parts 2 tires (shown only half), a pair of side walls 3 (shown only half)associated with the side parts 2 tires, and the tread 4, a toroidal associated with both side walls 3, in which the radial frame 8 has a rubber coating at least two layers, for example six-plane in the shown embodiment, radially situated cord passing between cores 7 side of the ring bus, each of which is embedded in each side portion 2 of the tire increases side part 2 tires, side walls 3 and part of the tread 4. Cords of organic fibers, such as a cord of 6,6-nylon, is suitable for multi-layered cord radial carcass 8.

Radial frame 8 teleshop the EIT designed that contains the wrapped layer of the end face 8Uhaving a coiled portion covering the periphery of the core 7 on-Board ring bus inside the bus in the direction of its outer part, and the bottom layer 8Dthat's outside covers wrapped layer of the end face 8Uthat includes a coiled portion; and in this case, the radial frame 8 has a construction containing the 4-layer wrapped layer of the end face 8Uand 2-layer bottom layer 8D. The end part of the lower layer 8Dlocated inside the core 7 of the side rings of the tire in the radial direction of the tire. Side filler 6, formed of hard rubber, is located between the wrapped layer of the end face 8U, ulibaetsa its end part and is located on the outer part of the core 7 of the side rings of the tire in the radial direction of the tire.

In figure 1, the tape 9 is located around the outer radial periphery of the frame 8, the tread rubber 10 is relatively small scale provided around the outer periphery of the tire 1R, and the tread rubber 10 and rubber 11 of the side wall are connected to each other on the outer connecting surface R. In the rubber of the tread 10 has a linear grooves 12, 13.

In the tire of this variant implementation of the above rubber compound is used in at least part of the side part 2 tires, and osobennostyami, to the side portion 2 of the tire containing the rubber compound represented side filler 6. When using the on-Board filler 6 can effectively manifest such characteristics of the rubber, as a high adhesiveness with respect to Corda was and high elasticity, and therefore effectively extended the life of the tires.

Thus obtained tire of this option exercise, in addition, has excellent reinforcement, abrasion resistance, etc. and corresponds to the solution lightweight design.

The present invention described above with reference to the examples of its embodiments; however, it is not limited to these options for implementation. The present invention can be modified or changed in any desired way within, not beyond the scope and intent of the present invention.

Examples

This alternative implementation is described in more detail with reference to the following examples; however the present invention is not limited to these examples.

Getting phenolic resin

Phenolic resin And rezol type

Phenol (1000 parts by weight) and 1294 parts by weight of aqueous 37%solution of formaldehyde (molar ratio (formaldehyde/phenol)=1,50) served in a reactor equipped with a stirrer, reflux condenser and thermometer and there is added 5 parts by weight of zinc acetate. After boiling for 1 hour, the resulting reaction water is removed in vacuum, and in this period the temperature is 90°C, then the reaction mixture is additionally interacts within 1 hour to get 1145 parts by weight of phenolic resin And rezol type - solids at room temperature (25°C).

Phenolic resin And rezol type analyzed by the method of 1H-NMR of the above conditions, and the content of the groups dimethylanisole ether based on the total content of the linking group formed from the aldehyde is 45 mol.%.

Phenolic resin In rezol type

Phenolic resin In rezol type (1115 parts by weight), a solid at room temperature are in accordance with the same reaction as in the case of phenolic resin And rezol type, with the exception that used to obtain the phenolic resin And rezol type number water 37%solution of formaldehyde replace 1121 parts by weight (molar ratio = 1,30).

Phenolic resin In rezol type analyzed by the method of 1H-NMR of the above conditions, and the content of the groups dimethylanisole ether is 35 mol.%.

Phenolic resin With rezol type

Phenolic resin With rezol type (1180 parts by weight), a solid at room temperature are in accordance with that the Oh reaction, as in the case of phenolic resin And rezol type, with the exception that used to obtain the phenolic resin And rezol type number water 37%solution of formaldehyde replace 1553 parts by weight (molar ratio = 1,80).

Phenolic resin With rezol type analyzed by the method of 1H-NMR of the above conditions, and the content of the groups dimethylanisole ether is 60 mol.%.

Phenolic resin D rezol type

Phenolic resin D rezol type (1180 parts by weight), a solid at room temperature are in accordance with the same reaction as in the case of phenolic resin And rezol type, with the exception that used to obtain the phenolic resin And rezol type number water 37%solution of formaldehyde replace 1121 parts by weight (molar ratio = 1,30) and 5 parts by weight of zinc acetate replaced with 70 parts by weight of aqueous 25%solution of sodium hydroxide. However, when removing part of the resin turns into a gel.

Phenolic resin D rezol type analyzed by the method of 1H-NMR of the above conditions, and the content of the groups dimethylanisole ether is 10 mol.%.

Resorcinol resin Novolac type

Resorcinol (1000 parts by weight) and 3 parts by weight of oxalic acid is served in a reactor equipped with a stirrer, a reverse holo is rinicom and thermometer. The reaction mixture is heated to the temperature of the mixture To 100°C, and after reaching this temperature, gradually add 369 parts of aqueous 37%solution of formaldehyde for 30 minutes in the reaction mixture (molar ratio (formaldehyde/phenol)=0,50). The mixture is then boiled for 1 hour, and the formed reaction water is removed at atmospheric pressure and in vacuum until the temperature of the mixture reaches 170°C; thus, receive 1040 parts by weight resorcinol resin Novolac type, a solid substance at room temperature.

Obtaining a resin composition

Obtained above resorcinol resin Novolac type phenolic resin rezol type mix in combination, receiving the compositions listed in table 1, and pulverized in an impact mill to obtain a powder compositions compositions (1)to(3) and (5)to(7). Add 5.0 parts by weight of fumed silica (trade mark of Nippon Aerosil, "AEROSIL R972") to 100 parts by weight of the composition (1) resin to obtain a composition (4) resin.

Table 1
ResinNovolac typeRezol typeThe ratio of resin by weight (Novolac type/rezol type)
The resin composition (1)Resorcinol resin Novolac typePhenolic resin And rezol type30/70
The resin composition (2)Resorcinol resin Novolac typePhenolic resin And rezol type40/60
The composition of resin (3)Resorcinol resin Novolac typePhenolic resin And rezol type20/80
The resin composition (5)Resorcinol resin Novolac typePhenolic resin In rezol type30/70
The resin composition (6)Resorcinol resin Novolac typePhenolic resin With rezol type30/70
The resin composition (7)Resorcinol resin Novolac typePhenolic resin D rezol type30/70

Evaluation of various properties

Features rubber

(1) the tensile Elongation of the tensile strength:

From the obtained vulcanized rubber do the harvesting, receiving standard samples JIS panteleimonas form No. 3; and according to the Japan standard JIS-K6251 samples are subjected to a tensile test at 25°C to determine their elongation at break and tensile strength. The results are shown in table 2.

(2) the dynamic Module of elasticity E':

The obtained vulcanized rubber analyzed with a spectrometer Toyo Seiki to determine the dynamic module of elasticity E' and loss tangent tgδ at an initial load of 100 g, and at strain of 2%, the frequency of tests 50 Hz and the test temperature 25°C and 60°C. the Results are shown in table 2.

Performance tires

(1) Confirmation of allocation gaseous formaldehyde

The presence or absence of allocation of gaseous formaldehyde by vulcanization, in the course of obtaining samples of the tires of examples and comparative examples, confirmed using a gas detector (Gastec's No. 91 and No. 91LL).

(2) Resistance to peeling:

Tires obtained in the examples and comparative examples, test in test exfoliation T-type according to the standard JIS-K6854 to determine the resistance to exfoliation of the bus between the layer of fabric and a layer covering rubber. The results are presented as indices, on the basis of the resistance is of the delamination index 100 tire of comparative example 1 taken as 100.

(3) the Life of a tyre with a lowered pressure

The following test tire put on the rim and experience in running the dryer under the conditions listed below.

The test tire: tire size 285/50R20

Rim: 6JJ×20

Internal pressure: 0 kPa

Load: 9,8 kN

Speed: 90 km/h

The above life testing on the drum, the durability is measured by the distance of the run to failure, and the results are shown in the form of indexes, according to the formula below. Tires with a higher index have an increased service life.

The service life of tires with low pressure (index)=(distance mileage test tire/distance mileage tire of comparative example 1)×100

(4) the Presence or absence of interfacial peeling

After the above test tyres with run-flat pressure on Jogging the drum, the tire is subjected to visual inspection for the presence or absence of interfacial peeling in parts tires with puff rubber coating.

Examples 1 to 11, comparative examples 1-8

A mixture having the composition specified in the following table 2 and table 3, are mixed in the Banbury mixer to prepare uncured rubber compound, which is formed in the form of a sheet having a thickness of 2 mm, and vulcanizer at 145°C for 30 minutes. Test characteristics obtained is of vulcanized rubber in accordance with the methods above.

Then radial tires (tire size: 255/55R18)containing as a side filler any of the 19 types of rubber compound, prepared as described above according to the standard method, and the tests for operational properties of the tire. The summarized results are presented in table 2 and table 3.

As is evident from the results given in table 2 and table 3, each compound of examples containing a specific resin composition has an increased dynamic module of elasticity E' and low heat generation, compared to comparative examples 1-4, where the mixture has the same composition as in examples of the invention, except that they contain no phenolic resin; and, moreover, because they have a large elongation for rubber compounds is confirmed by the increase of the service life of tires with low pressure, which contains the rubber mixture of the invention.

On the other hand, in comparative example 5, where as normally introduced phenolic Novolac resin type and hexamethylenetetramine, the value of the dynamic module of elasticity E' increases, but the elongation at break decreases. It was found that such a composition has a lower adhesive ability (resistance to peeling) between the rubber in the cord when the vulcanization of the tire, moreover, the service life of tires with low pressure drops. In comparative example 6, where we introduce a phenolic Novolac resin type and hexamethoxymelamine, increase the value of the dynamic module of elasticity E' and elongation at break, and the life of a tyre with a lowered pressure is improving; however, when mixing a rubber mixture is allocated gaseous formaldehyde. In addition, in comparative example 7, where we introduce only phenolic resin rezol type, modulus of elasticity and elongation at break are high; however, especially at high temperatures, increases the value of tgδ due to insufficient curing of the resin, and it is impossible to obtain a rubber compound that meet all the requirements.

1. The rubber mixture, which contains a rubber component selected from at least one of natural rubber and synthetic rubber, and a resin composition containing resorcinol resin Novolac type phenolic resin rezol type in the number from 1 to 30 parts by weight per 100 parts by mass of the rubber component,
in which the content of the groups dimethylanisole ether phenolic resin rezol type is from 20 mol.% to 100 mol.%, relative to the total content of the linking groups derived from aldehydes, which connect with the battle of the aromatic ring, derived from phenol.

2. Rubber mixture according to claim 1, in which resorcinol resin Novolac type obtained by reacting the resorcinol and the aldehyde in a molar ratio of aldehyde/resorcinol) from 0.4 to 0.8.

3. Rubber mixture according to p. 1, in which the content resorcinol resin, Novolac-type resin composition ranges from 18% by weight to 50% by mass.

4. Rubber mixture according to claim 1, in which the resin composition further comprises a filler.

5. Rubber mixture according to claim 4, in which the content of the filler is from 1 part by weight to 100 parts by weight, per 100 parts by weight of the resin composition.

6. Rubber mixture according to claim 4, in which the filler is a fumed silicon dioxide.

7. Rubber mixture according to any one of claims 1 to 6, in which the rubber component is a diene rubber.

8. The tire, in which at least part of the side part of the tire includes a rubber mixture according to any one of claims 1-7.

9. The tire of claim 8, in which the side part of the tire containing the rubber compound is a side filler.

10. The tire of claim 8 or 9, in which the rubber mixture further comprises carbon black, the content of which ranges from 30 parts by weight to 100 parts by weight per 100 parts by mass of the rubber component.



 

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2 tbl, 2 ex

Rubber filler // 2530130

FIELD: chemistry.

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