BRPI1000136A2 - silica-containing rubber component tire and use of the combination of blocked and unblocked alkoxyorganomercaptosilane binding agents - Google Patents

Abstract

TIRE WITH RUBBER COMPONENT CONTAINING SILICA AND USE OF THE COMBINATION OF ALCOXIORGANOMERCAPTOSILAN BINDING AGENTS BLOCKED AND NOT BLOCKED The invention relates to a tire that has at least one component of a rubber composition that comprises at least one elastomer containing a compound based on elastomer. silica reinforcement together with the use of a combination of silica binding agents. The binding agent combination comprises blocked and unblocked alkoxyorganomercaptosilane binding agents. Such a tire component can be, for example, a tread.

Description

"RUBBER COMPONENT TIRE CONTAINING SILICONE AND USE OF ANACOMBINATION OF ALCOXYORGANOMERCAPTOSILANOBLOCKED CONNECTION AGENTS"

Field of the invention

The invention relates to a tire having at least one component of a rubber composition comprising at least one conjugated diene-based elastomer containing silica reinforcement together with the use of a combination of binding agents for silica. The combination of the binding agent comprises blocked and unblocked alkoxyorganomercaptosilane binding agents. Such a tire component may be, for example, a tread.

Background of the invention

Tires may have a component with a silica reinforced rubber composition containing a silica binding agent. Such a tire component may be, for example, a tread.

Significant challenges can be presented regarding the use of binding agents in a silica-containing pneumatic rubber composition, particularly in relation to providing adequate uncured rubber processing viscosities (Mooney viscosity), and to provide abrasion resistance to the compositions. rubberized.

Such challenges may particularly include, for example, the production of a suitable rubber at a relatively high processing temperature.

In practice, binders for silica, particularly precipitated silica, in a diene-based rubber composition, generally containing one half, for example, alkoxy, reactive with hydroxyl groups (eg silanol groups) on silica and another different half ( for example, a sulfur-providing half) interacting with diene-based e-lastomers of the rubber composition to promote binding of the silica to the elastomer.

Such individual binding agents may include, for example, debis (3-triethoxysilylalkyl) polysulphides, blocked alkoxyorganomercaptosylans, and reversibly blocked mercapto half (having their mercapto moiety reversibly blocked).

In practice, the alkoxy half of such binding agents generally readily react with hydroxyl groups on silica during mixing of the silica (e.g. precipitated silica) with a diene-based rubber in a rubber composition.

The sulfuric moiety of such binding agents generally interacts with, for example, carbon-carbon double bonds of a conjugated diene-based elastomer in the rubber composition to complete the silica-elastomer bonding effect.

For processing the rubber composition, a series of blending steps is typically employed including at least a relatively high temperature, high shear, preparatory blending step (sometimes called non-productive), followed by a final temperature blending step. relatively minor (sometimes referred to as a productive blending step) where dressings are added, which is performed at a significantly lower temperature than that of the aforementioned non-productive blends to prevent or delay any significant pre-curing of the rubber during its use. mixing in the productive mixing step.

The reaction of the aforesaid alkoxy moiety of such a silica-binding agent generally occurs without significantly increasing the viscosity of the uncured rubber composition.

However, the interaction with the sulfur moiety of such a diene-based bonding agent-diomers of a rubber composition can significantly increase the viscosity of the uncured rubber composition to a degree where a temperature of the mixture is reduced to lower than 160 ° C is required, which in turn may require a series of rubber blending steps to silanolize, and offer adequate abrasion resistance for a sulfur cured rubber composition.

For example, the use of a bonding agent comprising an silica-reinforced alkoxy-mercaptosilane (e.g. precipitated silica) in a rubber composition containing conjugated diene-based elastomer may promote abrasion resistance in the sulfur-cured rubber composition.

However, mixing such a binder with the rubber composition containing silica reinforcement at a relatively high temperature (e.g. at least about 160 ° C) can generally result in a significantly increased unwanted viscosity (viscosity of Increased Mooney) in a non-productive blend of an uncured rubber composition blend. To reduce the increase in unwanted viscosity of the rubber composition during such a mixture of the rubber composition, the bonding agent may be mixed, for example, with the significantly lower temperature rubber composition (e.g., below about 150 ° C), causing an undesirable increase in mixing time, and thus an undesirable reduction in the production mixing efficiency, for the rubber composition.

Although the mechanism may not be fully understood, it is believed that in the case of silane polysulphide bonding agents, the sulfur-sulfur bonding of the bonding agent tends to break during the high temperature mixing stage to thereby release sulfur in the silane polysulphide. mixing the rubber composition causing a premature cure level and an undesirable increase in the viscosity of the mixture.

The use of an alkoxyorganomercaptosilane binder significantly and undesirably increases the viscosity of the rubber composition by exposing its half-mercury sulfur to the diene-based elastomer of the rubber composition during a high temperature mixture of the rubber composition.

Accordingly, the use of alkoxiorganomercaptosilanes is generally observed in the present invention as rendering such silica binding agents impractical for use in mixing with diene-based elastomers at high temperatures of the rubber mixture (for example at least about 160 ° C). Thus, a significantly lower temperature of the mixture should be observed in the range, for example, from about 120 ° C to about 150 ° C to prevent or retard premature cross-linking of the rubber with an increase in the temperature. undesirable viscosity in the rubber mixer. Such lower temperature of the rubber blend can significantly reduce the effectiveness of the felt operation of increasing the rubber composition blend time.

It is also contemplated in the present invention that the use of such a low mixing temperature for the rubber produces reduced silanization of the silica precipitated by the alkoxy group on the silica bonding agent, thereby causing porosity in the extruded rubber to form a molded rubber article.

To overcome such difficulties with alkoxyorganomercaptosyl-binding agents, and to improve mixing productivity and effectiveness by resisting a significant increase in viscosity of the uncured rubber composition, U.S. No. 7,074,876 proposes the use of blocked silane binding agents in silica rubber compositions. It has been observed that the use of such blocked binding agent has facilitated the mixing of the rubber composition with silica at relatively high temperatures (e.g. 170 ° C to 180 ° C) without burning the rubber composition compound (e.g. pre-cure). sulfuric acid), with higher processability of the rubber without developing an excessive increase in its viscosity. However, unlike the use of an alkoxiorganomercaptosilane based deleting agent, it has been observed that the use of a blocked alkoxiorganomercaptosilane releasing agent has produced sulfur-cured sulfur-cured silica rubber compositions with reduced abrasion resistance.

Accordingly, it remains desirable to improve the abrasion resistance of a sulfur-cured rubber composition (e.g., tread reduction) that the blocked alkoxymercaptosilane binding agent be used for the uncured rubber composition without compromising. unnecessarily processability (e.g., unnecessarily increased viscosity) of the cured rubber composition.

Thus, the problems cited above remain with respect to the use of a bonding agent for a silica (e.g. precipitated silica) and rubber composition containing diene-based elastomers for a pneumatic component (e.g., a band). where it is desirable to mix the uncured rubber composition at a relatively high temperature.

With respect to this invention, it was considered unexpected that the use of a blocked alkoxymercaptosilane binding agent combination (exhibits its inversely blocked metapercap) with an unblocked alkoxiorganomercaptosilane could promote abrasion resistance of an elastomer-based rubber composition reinforced with precipitated silica, and make it possible to prepare an uncured rubber composition at high mixing temperatures without significantly compromising (e.g. without significant increase) the viscosity of the rubber composition during the mixing operation.

Although the use of two bis (3-triethoxysilylpropyl) polysulphides has been suggested (e.g., US Patent 6,384,127) or a combination of an suggested alkoxyorganometaptosylan with an alkyl alkoxysilane (eg US 6,433,065), this invention is a significant option. for such teachings.

For this invention, it has been found that a selective combination of blocked or unlocked alkoxiorganomercaptosilane binding agents can be suitably used in a high temperature mixing process for a rubber composition containing a silica-reinforced elastomer combination with diene base.

It is considered in the present invention that such a finding was not readily discernible with inconsistent results without experimentation.

For this invention, it has been found that abrasion resistance for the silica-rich diene-based elastomer-containing rubber composition is promoted by the innovative and optimal use of two different but unique characteristics of silane binding agents.

More specifically, it has been observed, in a silica-rich rubber composition, that a combination of the binding agent comprising a siloxiorganomercaptosilane-reactive dosilane binding agent (thus without having its mercoated half being inversely blocked) together with A siloxiorganomercaptosilane with its inversely blocked half market may offer good rubber processability and promote improved abrasion resistance and rebound property (for example, lower hysteresis to provide lower rolling resistance for such a composite tire) therefore, during processing (for example, in the mixture), the uncured silica-containing rubber composition at a temperature of at least 160 ° C in a non-productive mixing step, thus without compromising the advantage of rubber processing at higher temperatures using only a siloxior binding agent It is also considered that the aforementioned improvement of the cured rubber composition (for example, its sulfur-cured abrasion resistance) can be obtained without increasing the total charge (increasing the total combined amounts) of the binding agents. individual.

Thus, a significant new aspect of this invention being observed is that a binding agent comprising a siloxiorganomercaptosilane may be added to the blender together with an alkoxiorganomercaptosilane having its inversely blocked mercapto half where the composition of the rubber is mixed at a mixing temperature. relatively high (for example at least about 160 ° C) without causing significant premature cure of the rubber composition (sometimes referred to as "product burn") is without the formation of an excessive rubber viscosity, and therefore without difficulty in processing the associated uncured rubber, and also in processing (e.g. extruding) the composition of the mixed rubber after its removal from the rubber mixer.

It is considered a significant contrast to use the binding agent comprising only siloxiorganomercaptosilane with a higher temperature of the rubber mixture (e.g. at least 160 ° C). This is an aspect that is considered in the present invention as a discovery that a higher mixing temperature can be successively used, which is considered to be undeterminable without experimentation, particularly since it is not known if one or more Bonding agents may have an adverse dominant effect on the viscosity of the rubber composition during the mixing stage.

Another novel aspect of the invention is the discovery that the use of the relatively high rubber blend temperature (e.g. at least about 160 ° C) of the combination of the blocked alkoxiorganomercaptosilane binding agent together with the sorbent Siloxiorganomercaptosilane bonding composition resulted in a sulfur-cured silica rubber composition with increased abrasion resistance and improved hysteretic properties (eg reduced internal heat generation of the sulfur-cured rubber composition during dynamic use). In contrast, simply by increasing the siloxiorganomercaptosilane charge with its inversely blocked mercapto half during the high temperature mixing step, when used alone, silica-rich rubber compositions were observed without significant improvement, and perhaps even a deterioration or reduction in abrasion resistance of the sulfur-cured rubber composition.

Another novel aspect of the invention was that the improvement of the above-cited abrasion resistance of the sulfur-cured silica-rich rubber composition through a combination of the alkoximercaptosilane and the blocked alkoxiorg-nomercaptosilane binding agent was not due to processability. (e.g., without a significant increase in rubber viscosity) of the uncured rubber composition at high mixing temperature (e.g. at least about 160 ° C). This was an aspect considered in the present invention to be a discovery that a higher temperature mixture could be used successively, which was considered to be indefinable without experimentation, particularly since it is not known whether one or more of the binding agents could have a adverse dominant effect.

In describing this invention, the terms such as "compound rubber", "rubber compound" and "compound", when used, refer to rubber compositions composed of one or more elastomers mixed with various ingredients, including curatives, such as sulfur and accelerators give healing. The terms "elastomer" and "rubber" may be used interchangeably in the present invention. All of these termos are believed to be well known to those skilled in the art. The term "phr", when used, refers to parts by weight per 100 parts by weight of the rubber. The term phs, when used, refers to parts by weight per 100 parts by weight of silica filler.

Summary and practice of the invention

According to this invention a tire is provided having at least one component which is composed of a rubber composition based on parts by weight per 100 parts by weight of rubber (phr).

(A) elastomers comprising:

(1) at least one non-functionalized conjugated diene-based elastomer, or

(2) conjugated diene based elastomers comprising

(a) from 0 to about 55, alternately from about 15 to about 55, phr of at least one non-functionalized conjugated diene-based elastomer, and

(b) from about 45 to about 100, alternately from about 45 to about 85, phr of at least one functionalized butadiene / elastomeric styrene copolymer rubber (having a Tg, for example, in the range of about -10 ° C to about -70 ° C) composed of at least one of:

(i) styrene / butadiene copolymer (SBR) elastomers having a styrene bound in a range of about 20 to about 45% containing alkoxy silane groups (e.g., -Si- (OR) n) groups ; (with said alkoxy groups being reactive with hydroxyl groups contained in said precipitated silica reinforcement filler),

(ii) styrene / butadiene copolymer elastomers having a styrene content in a range of about 20 to about 45% and containing amino-alkoxy silane groups with the said amino-alkoxy silane groups attached to the elastomer through the atom silicon moiety (e.g., R "- (NHX-R ') m - Si (OR) n, where R' is an alkylene group of about 1 to 12 carbon atoms, R" is an alkyl group of about 0 to 10 carbon atoms and R is an alkyl group containing from 1 to 20 carbon atoms where at least one of said R groups is preferably an ethyl group, m is 1 or 2, η is 1 or 2, and χ is a value ranging from 0 to 2); (with said alkoxy silane groups being reactive with the hydroxy groups contained in the precipitated silica reinforcement filler),

(iii) styrene / butadiene copolymer elastomer containing a functionalamine group (functionalized amine SBR); (with said functional group being reactive with hydroxyl groups contained in the precipitated silica reinforcement filler);

(iv) styrene / butadiene copolymer elastomer having a bound styrene content in a range of about 20 to about 45% and containing desylane sulfide leaving groups with said silane sulfide groups attached to the elastomer via the silicon atom (for example, (RO) x.Ry-Si-R'-S), where χ ranges from 1, 2 and 3, and y ranges from 0, 1 and 2, R is the same or a different alkylene group having from 1 to 16 carbon atoms, and R 'is an alkyl, aryl or alkylaryl group of 1 to 15 carbon atoms);

(v) styrene / butadiene copolymer elastomer having hydroxyl functional groups (functionalized hydroxyl SBR); with said hydroxyl groups being reactive with hydroxyl groups on precipitated silica; and

(vi) styrene / butadiene elastomer having epoxy groups (functionalized epoxy SBR); (with said epoxy groups being reactive with hydroxyl groups on precipitated silica);

(B) about 30 to about 120 phr of booster filler comprising:

(1) amorphous synthetic silica (eg precipitated silica) which contains hydroxy groups (eg silanol groups) on its surface, or

(2) a combination of rubber-reinforced carbon black and said precipitated silica comprising from about 40 to about 110 phr of said precipitated silica (with the remainder of said reinforcing filler, therefore comprising said carbon black). rubber reinforced smoke);

(C) a combination of silica binding agents comprising:

(1) alkoxyorganomercaptosilane, and

(2) blocked alkoxiorganomercaptosilane (presenting its reversibly blocked mercapto half,

wherein the ratio (e.g., weight ratio) of said alkoxiorganomercaposylane to said blocked alkoxiorganomercaptosilane is in the range of about 0.1 / 1 to about 0.5 / 1, alternately from about 0.15 / 1 at about 0.45 / 1.

In one embodiment, said elastomer is at least one non-functionalized conjugated thiene-based elastomer comprising at least one polymer with at least one isoprene and 1,3-polybutadiene, and styrene terpolymer and at least one isoprene and 1,3 In one embodiment, said elastomer is a combination of the non-functionalized conjugated diene combase elastomer and said functionalized elastomer, wherein said non-functionalized conjugated diene-based elastomer comprises at least one isoprene and at least one polymer. , 3-polybutadiene and styrene terpolymer and is an isoprene and 1,3-butadiene.

In one embodiment, said elastomer is a combination of a non-functional conjugated diene-based elastomer and said functionalized elastomer, wherein said non-functionalized conjugated diene-based elastomer comprises:

(A) 1,4-polybutadiene rubber, or

(B) 1,4-polybutadiene useful rubber and 1,4-polyisoprene useful rubber.

The various preparation and use of blocked mercaptoalkoxysilanes has been found, for example, in patent publications PCT / US98 / 1739, US No. 3,692,812 as well as in various literature publications, such as, for example, in Gornowicz, G., "Preparation of Silylalkanethiols", J. Org. Chem. Volume 33, No. 7, July 1968; Vorkonov, MG et al., Trialkoxysilylalanethiols and Bis (trialkoxvsilvlalkvl) sulfides, Izvestiya Akademii NaukSSSR and Seriya Khimicheskyeya, No. 8, page 1849 to 1851, August 1977.

In practice, the blocked alkoxiorganomercaptosilane, the mercapto group, or half, is initially unreactive with the diene-based elastomer due to the blocking group. The blocking group substantially prevents the mercapto mercaptoalkoxy group from prematurely attaching to the diene-based elastomer during mixing of the rubber composition. Thus, in practice, substantial bonding of the silica to the diene-based elastomer is avoided until later in rubber processing and possibly even cure of the high temperature rubber composition, thereby minimizing premature curing. undesirable (burning), and the undesirable associated increase in viscosity of the rubber composition during the blending step, and possibly subsequent processing of the netap such as, for example, in processing the blended rubber composition to form rubber compositions, molded, uncured, such as tire treads and other pneumatic components.

It is therefore considered that an unblocking agent is used to unblock the alkoxiorganomercaptosilane as a material capable of unblocking the blocked mercaptoal-coxisilane to allow interaction of the mercapto group, or half of the mercapto-alkoxisilane with the diene-based elastomer. It should be considered that the choice of the unblocking agent will depend on the blocking group used to block the chemical activity of mercaptoalkoxysilane as interaction with the dithiene elastomer is considered, which can be readily understood by one of skill in the art.

When the reaction of the alkoxiorganomercaptosilane mercapto group is desired to bind the amorphous silica to the diene-based elastomer, the unlocking agent (unlocking agent) is added to the mixture to unlock the blocked mercaptosilane. The unlocking agent is added to facilitate reactivity of the mercapto group. An example amount of the unlocking agent may be about 0.1 to 5 phr; most preferably in the range 0.5 to 3 phr.

In practice, the unblocking agent may be a nucleophile containing a hydrogen atom, unstable enough that the hydrogen atom can be transferred to the site of the original blocking group to form the alkoxyiorganomercaptosilane. Thus, with a blocking group acceptor molecule, a nucleophilic hydrogen exchange can occur with the alkoxiorganomercaptosilane blocking group to form the unlocked alkoxyorganomaptaptosilane and the corresponding nucleophilic derivative containing the original blocking group. Such transfer of the alkoxyorganometercaphosilane blocking group to the nucleophile may be driven, for example, by greater thermodynamic stability of the products (alkoxyorganomaptaptosilane and nucleophile containing the blocking group) relative to the starting reagents (blocked alkoxiorganometercosilane and nucleophile). -ophile). For example, amine-unlocked carboxyl blocking groups can produce amides, amine-unlocked sulfonyl blocking groups can produce sulfonamides, amine-unlocked sulfinyl blocking groups can produce sulfenamides, amine-unlocked phosphonyl blocking groups, ammonium-blocking groups. Phosphonyl unblocked by amines can produce phosphonamides. Importantly, regardless of the blocking group initially present in blocked mercaptosilane and independent of the unblocking agent used, the initially inactive blocked mercaptoalcoxisilane (from the point of view of diene-based elastomer binding) is substantially converted to the desired point in the procedure for rubber for active mercaptoalkoxysilane.

The unlocking agent may be added to the rubber mixture, for example in the curing agent package (together with the sulfur curing agent) or alternately in any other mixing step in the rubber blending process. It is a single component, although it is practically subsequently added to the pre-reactive amorphous silica compound, and generally together with the curing agent in the mixing step with the addition of the final curing agent.

Several classes of materials that can act as unlocking agents, but which are not normally cure accelerators, allow the selection between the two, are several oxides, hydroxides, carbonates, bicarbonates, alkoxides, phenoxides, sulfenamide salts, acetyl acetonates, carbon anions derived from high acidity CN bonds, malonic acid esters, cyclopentadien, phenols, sulfonamides, nitrites, fluorenes, tetraalkyl ammonium salts and tetraalkyl phosphonium salts.

Representative examples of various unlocking agents are, for example, such nucleophiles as amines, imines and guanidines that contain at least one N-H bond. Some examples include: N, N'-diphenylguanidine, Ν, Ν'-di-ortho-tolylguanidine, hexamethylenetetraamine and 4,4'-diaminodiphenylmethane.

Thus, when it is desired to unblock the blocked alkoxiorganomercaptosilane to allow interaction of the mercapto group (half) with the elastomer to thereby bind the hydrophobic silica, pretreated to the elastomer, it is observed that several unblocking agents may be present. depending on the half or blocking agent used to block the chemical activity of the blocked alkoxiorganomercap-tosylan mercapto group.

Representative examples of various blocked & alkoxyorganomercaptosilane & are, for example, 2-triethoxysilyl-1-ethyl thioacetate; "2-trimethoxysilyl M-ethyl thioacetate; 2- (methyldimethoxysilyl) -1-ethyl thiocytate; ; trimetoxisililmetil thioacetate; triisopropoxisililmetil thioacetate; metildietoxisililmetiltioacetato; metildimetoxisililmetil thioacetate; metildiisopropoxisililmetil thioacetate; dimetiletoxisililmetil thioacetate; dimetilmetoxisililmetil thioacetate; dimetilisopropoxisililmetil thioacetate; metildimetoxisililmetil thioacetate; metildiisopropoxisililmetil thioacetate; dimetiletoxisililmetil thioacetate; dimetilmetoxisililmetil thioacetate; dimetilisopropoxisililmetil thioacetate; 2 - triisopropoxisilil- 1 ethyl thioacetate 2- (methyldiethoxy silyl) -1-ethyl thioacetate 2- (methyldiisopropoxy-silyl) -1-ethyl thioacetate 2- (dimethylethoxy-silyl) -1-ethyl thioacetate 2- (dimethylmethoxy-silyl) -1-ethyl ioa-ketate; 2-dimethylisopropoxy-silyl) -1-ethyl thioacetate; 3-triethoxysilyl-1-propyl thioacetate; 3-trisopropoxy silyl-1-propyl thioacetate; 3-methyldiethoxy silyl-1-propyl thioacetate; 3-methyldi-methoxysilyl-1-propyl thioacetate; 3-methyldiisopropoxy silyl-1-propyl thioacetate; 1- (2-triethoxysilyl-1-ethyl) -4-thioacetylcycloexane; 1- (2-triethoxysilyl-1-ethyl) -3-thioacetylcyclohexane; 2-triethoxysilyl-5-thioacetylnorbornene; 2-triethoxysilyl -A-thioacetylnorbornene; 2- (2-triethoxysilyl-1-ethyl) -5-thioacetylnorbornene; 2- (2-triethoxysilyl-1-ethyl) -4-thioacetylnorbornene; 1- (1-oxo-2-thia-5-triethoxylysylpenyl) benzoic acid; 6-triethoxysilyl-1-hexyl thioacetate; 1-thetoethoxysilyl-5-hexyl thioacetate; 8-triethoxysilyl-1-octyl thioacetate; 1-thetoethoxysilyl-7-octyl thioacetate; 6 - triethoxysilyl -1 - hexyl thioacetate; 1-triethoxysilyl-5-octylthioacetate; 8-trimethoxysilyl-1-octyl thioacetate; 1-trimethoxysilyl-7-octylthioacetate; 10-triethoxy silyl-1-decyl thioacetate; 1-triethoxysilyl-9-decyl thioacetate; 1-triethoxysilyl-2-butylthioacetate; 1-triethoxysilyl-3-butyl thioacetate; 1-triethoxysilyl-3-butyl thioacetate; 1-triethoxysilyl-3-methyl-2-butyl thioacetate; 1-triethoxysilyl-3-methyl-3-butyl thioacetate; 3-tri-methoxysilyl-1-propyl thiooctoate; 3-triethoxysilyl-1-propyl thiopalmitate; 3-triethoxysilyl-1-propyl thiooctoate; 3-triethoxysilyl-1-propyl thiobenzoate; 3-triethoxysilyl-1-propylthio-2-ethylexanoate; 3-methyldiacetooxy-silyl-1-propyl thioacetate; 3-triacetoxysilyl-1-propyl thioacetate; 2-methyldiacetoxysilyl -1-ethyl thioacetate; 2-triacetoxysilyl-1-ethyl thioacetate; 1-methyl diacetoxy silyl-1-ethyl thioacetate; 1-triacetoxysilyl-1-ethyl thioacetate; 3 - ethoxydodecyloxy-1-propyl thioacetate; 3-ethoxyditetradecyloxy-1-propyl thioacetate; 3-ethoxydidodecyloxy-1,1-propyl thiooctoate; 3-ethoxyditetradecyloxy-1-prop-H-thiocyteate; tris - (3-triethoxysilyl-1-propyl) trithiophosphate; bis - (3-triethoxysilyl-1-propyl) methyl dithiophosphonate; bis - (3-triethoxy-1 H -l-1-propyl) ethyl dithiophosphonate; 3-triethoxysilyl-1-propyldimethylthiophosphinate; 3-triethoxysilyl-1-propyl-diethylthiophosphinate; tris - (3 - triethoxysilyl -1 - propyl) tetrathiophosphate; bis - (3-triethoxysilyl-1-propyl) methyltrithiophosphonate; bis - (3-triethoxysilyl-1-propyl) ethyltrithiophosphonate; 3-triethoxysilyl-1-propyldimethyldithiophosphinate; 3 - triethoxysilyl - 1 - propyldiethyldithiophosphinate; tris - (3-methyldimethoxysilyl-1-propyl) trithiophosphate; bis-3-methyldimethoxysilyl-1-propyl) methyldiothiophosphonate; bis - (3-methyldimethoxysilyl-1-propyl) ethylditiophosphonate; 3 - methyldimethoxysilyl -1-propyldimethylthiophosphinate; 3 - methyldimethoxysilyl -1-propyldiethylthiophosphinate; 3-triethoxysilyl -1-propylmethylthiosulfate; 3-triethoxysilyl-1-propylmethanotphsulfonate; 3-triethoxysilyl-1-propylethanothiosulfonate; 3-triethoxysilyl-1-propylbenzenothiosulfonate; 3-triethoxysilyl-1-propyl toluenothiosulfonate; 3-triethoxysilyl-1-propylnaphthalenothiosulfonate; 3 - triethoxysilyl - 1

propylxylene thiosulfonate; triethoxysilylmethylmethyl thiosulfate; triethoxysilylmethyl methanethiosulfonate; triethoxysilylmethylbenzenethio sulfonate; triethoxysilylmethyltoluetiosulfonate; triethoxysilylmethylnaphthalenothiosulfonate; triethoxysilylmethylxylene thiosulfonate and 3-octanothio-1-propyltriethoxysilane.

In summary, a blocked alkoxiorganomercaptosilane may be, for example, mercaptopropil triethoxysilane, with its mercapto group blocked by such a moiety (organo-mercapto trialkylsilane, or mercaptopropyl triethoxysilane having a blocked mercapto half with a half capable of being unlocked at elevated temperature) It may be used such that its mercapto half is then unlocked during vulcanization of the associated rubber composition at elevated temperature, such as, for example, a temperature in a range of about 140 ° C to about 170 ° C. For example, see U.S. Nos. 6,127,468, 6,204,339, 6,414,061, 6,528,673 and 6,608,125 which are incorporated by the present invention in their entirety. In practice, an unlocking agent may comprise, for example, at least one N1N'-diphenylguanidine and N, N'-diortho-tolyl guanidine.

One representative of a blocked alkoxiorganomercaptosilane binding agent is, for example, Momentive NXT ™, which in the present invention comprises 3-octa-notio-1-propyltriethoxysilane.

In practice, various alkoxyorganomercaptosilanes may, for example, be represented by the general formula (I):

(I) (X) n (R 2 O) 3-n-Si-R 3 -SH

where X is a radical selected from halogen, particularly chlorine or bromine, preferably a chlorine radical and alkyl radicals having from 1 to 16, preferably from 1 to 4 carbon atoms, preferably selected from methyl, ethyl, n-propyl and n-butyl; where R2 is an alkyl radical having from 1 to 16, preferably from 1 to 4 carbon atoms, preferably selected from methyl and ethyl radicals, and R3 is an alkyl radical having from 1 to 16, preferably from 1 to 4 carbon atoms, preferably a radical propylene; η is a number from 0 to 3, preferably 0.

Representative alkoxiorganomercaptosilanes are, for example, triethoxy-mercapto-propylsilane, trimethoxy-mercaptopropylsilane, methyldimethoxy-mercaptopropylsilane, methyldiethoxy-mercaptopropyl silane, dimethylmethoxy mercaptopropylsilane, triethoxymetaptoethylsilane and tripropropylsilane.

Another representative example of the alkoxiorganomercaptosilane binding agent (unlocked binding agent) is an oligomeric organomercaptosilane comprising a reaction product of 2-methyl-1,3 "-propane and S - [3 - (triethoxysilyl) propyl] thiooctanol or alternatively with S - [3 - trichlorosilyl) propyl] thiooctanoate, particularly as mentioned in European Patent Publication EP1 958983. A representative of such an oligomeric organometercosilane may be, for example, Momentive NXT-Z100 ™.

According to this invention, a method of preparing a rubber composition comprises mixing, based on parts by weight per 100 parts by weight of diene-based elastomer (phr):

(A) elastomers comprising:

(1) at least one conjugated diene-based elastomer, or

(2) conjugated diene based elastomers comprising

(A) from 0 to about 55, alternately from about 15 to about 55, phr of at least one conjugated diene-based elastomer, and

(b) from about 45 to about 100, alternately from about 45 to about 85, phr of at least one functionalized butadiene / elastomeric styrene copolymer rubber (having a Tg, for example, in the range of about -10 ° C to about -70 ° C) composed of at least one of:

(i) styrene / butadiene copolymer (SBR) elastomers having a styrene bound in a range of about 20 to about 45% containing alkoxy silane groups (e.g., -Si- (OR) n) groups ; (with said alkoxy groups being reactive with hydroxyl groups contained in said precipitated silica reinforcement filler),

(ii) styrene / butadiene copolymer elastomers having a styrene content in a range of from about 20 to about 45% and containing amino-alkoxy silane groups with said amino alkoxy silane groups attached to the elastomer through the atom silicon moiety (e.g., R "- (NHX-R ') m - Si (OR) n where R' is an alkylene group of about 1 to 12 carbon atoms, R" is an alkyl group of about from 0 to 10 carbon atoms and R is an alkyl group containing from 1 to 20 carbon atoms where at least one of said R groups is preferably an ethyl group, m is 1 or 2, η is 1 or 2, and χ is a value that ranges from 0 to 2); (with said alkoxy silane groups being reactive with the hydroxy groups contained in the precipitated silica reinforcement filler),

(iii) styrene / butadiene copolymer elastomer containing a functionalamine group (functionalized amine SBR); (with said functional group being reactive with hydroxyl groups contained in the precipitated silica reinforcement filler);

(iv) styrene / butadiene copolymer elastomer having a bound styrene content in a range of about 20 to about 45% and containing desylane sulfide leaving groups with said silane sulfide groups attached to the elastomer via the silicon atom (for example, (RO) x.Ry-Si-R'-S), where χ ranges from 1, 2 and 3, and y ranges from 0, 1 and 2, R is the same or a different group of alkylene having from 1 to 16 carbon atoms, and R 'is an alkyl group; aryl (alkylaryl of 1 to 15 carbon atoms);

(v) styrene / butadiene copolymer elastomer having hydroxyl functional groups (functionalized hydroxyl SBR); (with said hydroxyl groups being reactive with hydroxyl groups on precipitated silica; and

(vi) styrene / butadiene elastomer having epoxy groups (functionalized epoxy SBR); (with said epoxy groups being reactive with hydroxyl groups on precipitated silica);

(B) about 30 to about 120, alternately from about 40 to about 110phr of reinforcing filler at a mixing temperature in a range of about 140 ° C to about 180 ° C, where said filler The reinforcing material comprises a combination of rubber-reinforced carbon black of from about 40 to about 110 phr of the precipitated silica containing hydroxyl groups (e.g. silanol groups) on its surface;

(C) a combination of silica binding agents comprising:

(1) alkoxyorganomercaptosilane, and

(2) blocked alkoxiorganomercaptosilane (having its mercapto half reversibly blocked;

(D) a mixture of an unlocking agent and the mixture of the resulting rubber (at a temperature such as, for example, in a range from about 100 ° C to about 125 ° C and simultaneously or

thereafter mixing a sulfur curing agent at a temperature in a range from about 100 ° C to about 125 ° C and thereafter

(E) curing the resulting mixture at an elevated temperature, for example at a range of from about 140 ° C to about 170 ° C.

In one embodiment, said conjugated diene-based elastomer comprises:

(A) polybutadiene rubber, particularly 1,4-polybutadiene rubber, or

(B) a combination of polybutadiene rubber, particularly eis1,4-polybutadiene rubber, and 1,4-polyisoprene rubber.

Preferably, the ratio (e.g., weight ratio) of said alkoxiorganomercaptosilane to said blocked alkoxiorganomercaptosilane is in the range of from about 0.1 / 1 to about 0.5 / 1.

According to this invention, a rubber composition is provided according to this invention (according to said method).

According to this invention, an article of production is provided having at least one component comprising said rubber composition.

According to this invention, a tire is provided having at least one component comprising said rubber composition.

Accordingly, the said component of the tire is a tread and particularly a tread for use with a tire surface.

In practice, various conjugated diene-based elastomers may be used for the composition of rubber, such as polymers comprising at least one 1,3-butadiene and isoprene and copolymers comprising at least one 1,3-styrene. -butadiene and isoprene. Such elastomers are therefore sulfur curable elastomers.

Representative examples of such conjugated diene based elastomers are, for example, 1,4-polyisoprene rubber (natural and / or synthetic), and preferably natural rubber, butadiene / styrene copolymer rubber prepared by emulsion polymerization. , butadiene / styrene rubber prepared by solution polymerization, 3,4-polyisoprene rubber, isoprene / butadiene rubber, butadiene / isoprene / styrene terpolymer rubber, lo 1,4-polybutadiene, polybutadiene rubber vinyl content (35 to 50% vinyl content), large amount of vinyl polybutadiene rubber (50 to 90% vinyl content, styrene / isoprene copolymers, deacrylonitrile / butadiene / styrene terpolymer rubber prepared by emulsion polymerization and acrylonitrile / butaeljene cup-polymer rubber.

Other additional conjugated diene-based elastomers include solution polymerization butadiene / styrene high polymer vinyl rubber (HV-S-SBR) having a bound styrene content in a range of about 5 to about 45 % and a 1,2-vinyl content based on its polybutadene moiety in a range of about 30 to about 90%, particularly that having (HV-S-SBR) a relatively high glass transition value ( Tg) in a range of about -20 ° C to about -40 ° C to provide adequate wet traction for the tread and also a relatively high hot rebound value (100 ° C) to promote rolling resistance. relatively low for the composition of the tire tread. Such highly specialized butadiene / vinyl styrene rubber (HV-S-SBR) may be prepared, for example, by polymerization in an organic solution of styrene and 1,3-butadiene monomers to include a chemical modification at the chain ends. polymers and to promote the formation of 1,2-vinyl groups in the debutadiene portion of the copolymer. A representative of the HV-S-SBR rubber may be, for example, Firestone / Bridgestone Duradene 738Tm.

Other conjugated diene-based elastomers are functionalized butadiene / styrene copolymer elastomers (functionalized SBR elastomers) containing amine and / or siloxy (e.g. alkoxy silane as Si (OR) 3 functional groups).

Representatives of functionalized amine SBR elastomers are, for example, DR Olefinverbund GmbH and T5560 ™ synthetic rubber "5E SLR-4630" and JSR chain functionalized elastomers, mentioned in US Patent No. 6,936,669 .

A representative of functionalized silicon SBR elastomers is, for example, SE SLR-4601 synthetic rubber from Dow Olefinverbund GmbH.

A representative of a combination of functionalized amino-siloxy SBR elastomers with one or more amino-siloxy groups attached to the elastomer is, for example, JSR HPR355 ™ and functionalized amino-siloxy SBR elastomers mentioned in US Patent Application 2007/0185267 .

Butadiene / styrene elastomers functionalized with a sulfonyl groups are mentioned in WO 2007/047943.

One representative of the functionalized hydroxy SBR elastomers is, for example, Asahi's Tufdene 3330 ™.

A representative of the functionalized epoxy SBR elastomers is, for example, Asuf's Tuf-dene E50 ™.

In practice, it is therefore contemplated that said sulfur vulcanizable conjugated diene-based elastomer may comprise, for example, minimal isoprene and 1,3-butadiene polymers; styrene copolymers and at least one isoprene and 1,3-butadiene; Large vinyl butadiene / styrene elastomers having a 1,2-vinyl content based on their polybutadiene in a range of about 30 to 90% and functionalized styrene and 1,3-butadiene ("SBR functionalized") copolymers ) selected from functionalized amine SBR, functionalized silicon SBR, a combination of amine and functionalized silicon SBR, functionalized epoxy SBR and functionalized hydroxy SBR.

Example 1

Rubber compositions were prepared to evaluate the effect of a combination of a blocked alkoxiorganomercaptosilane binding agent (having reversibly blocked mercaptoam) with an alkoxiorgano mercaptosilane binding agent with its unlocked mercapto moiety, which is sometimes called -in this example as a "reactive silane". Reactive silane was added to the rubber mixture in the second non-productive mixing step (NP2) to evaluate a better use for the invention.

Sample A is a comparative rubber containing what is considered in the present invention as an 8 phs loading level of blocked siloxiorganomer-captosilane binding agents (parts by weight per 100 parts by weight of reinforcing silica, ouphs) .

The BeC samples are comparative rubber samples containing higher loading levels of 9.5 and 11 phs, respectively, when compared to the 8 phs loading of the a-sample rubber, blocked siloxiorganomercaptosilane binding agent (group 1). mercapto Teversely blocked).

Sample D is a comparative rubber sample containing what is considered in the present invention as an 8 phs loading level of siloxiorga-nomercaptosilane binding agent.

Experimental EeF rubber samples contain a combination of an al-coxiorganomercaptosilane and a blocked alkoxymercaptosilane binding agent with the combined loading levels of two binding agents being 9.5 and 11 phs, respectively. Alkoxyiorganomercaptosilane was added to the rubber composition in the non-productive second stage mixture (NP2).

The rubber compositions were prepared by mixing the components in four steps of productive (PR) and non-productive (NP) sequential blends. The elimination temperature for NP1, NP2 was 170 ° C. The elimination temperature for NP3 and PR was 160 and 120 ° C, respectively.

The basic recipe for rubber samples is given in Table 1 below and is described in parts by weight unless otherwise indicated.

Table 1

Non-Productive Mixing Step (NP1) (mixed at Partescercar temperature 170 ° C

SBR1 Functionalized Solution 84

1,4-polybutadiene rubber 16

Silica3 60

Rubber & Resin Processing Oil4 28.5

Blocked alkoxiorganomercaptosilane binding agent5 variables

Variable Alkoxy-mercaptosilane 6 Binding Agent

Fatty acid7 3

Second Non-Productive Mixing Step (NP2) (mixed with temperature) <table> table see original document page 18 </column> </row> <table>

1 SBR prepared by polymerization of JSR's HPR355 ™ functionalized company solution, which can be described as a styrene / butadiene decopolymer elastomer functionalized SBR having aminosilane functional groups having a styrene content of about 27% and a content about 58% vinyl based on total elastomer.

2 Useful 1,4-polybutadiene rubber such as CB25 ™ from Lanxess Company.

3 Precipitated silica such as Rhodia's Zeosil Ζ1 165MP ™.

4 Naphthenic Rubber Processing Oil.

5 Blocked alkoxyorganomercaptosilane binding agent (displaying its reversively blocked mercapto moiety) from Momentive Company as NXT ™ may comprise a 3-octanothio-1-propyltriethoxysilane.

6Aluminum alkiorganomercaptosilane binding agent (without its mercapto moiety "being reversibly blocked) from Momentive Company as NXT®Z100 as an unlocked silo-xiorganomercaptosilane.

Table 2 describes the processing and physical properties of rubber compositions.

Table 2

<table> table see original document page 18 </column> </row> <table> Alkoxiorganomercaptosilane blo- 4.8 4.8 4.8 O 4.8 4.8qured (phr)

Alkoxyiorganomercaptosilane (phr) OO O 4.8 O O

NP2 (second stage of non-productive mixing):

Alkoxiorganomercaptosilane blo- 2.4 3.75 5.1 O 2.4 2.4quar

Alkoxiorganomercaptosilane (phr) OO O 2.4 1.35 2.7PR (productive mixing stage)

Diphenylguanidine Accelerator 2.1 2.1 2.1 0.8 1.8 1.4 (DPG) (phr)

Rheometer 1,160 ° C

Maximum torque (dNm) 17.26 17.42 17.27 18.93_ 17.51 17.48

Minimum torque (dNm) 2.20 2.14 2.03 6.38 2.60 2.83

T90 (minutes) 11.43 10.45 9.62 5.35 8 ~ 41 5.82

Moonev's Visibility. 100 ° C 67 67 64 110 76 74ML (1 + 4)

RPA (boracap process analysis). (100 ° C)

Storage module not 0.20 0.20 0.20 0.50 0.24 0.26 cured (G '), 15% strain, MPa

Storage Module (G '), 1.55 1.58 1.56 1.71 1.65 1.6210% strain, MPa

Tan delta cured at temperature 0.131 0.105 0.103 0.100 0.102 0.090 from 100 ° C, strain 10%

Moonev Scorch, 120 ° C

Burning time with elevation 54.07 51.7 47.27 14.88 34.57 21.63from 5 points min

Stress strain, ATS. 14 min

160 ° C2 <table> table see original document page 20 </column> </row> <table>

1Data according to Alpha Technologies RPA2000TM Instrument Rubber Process Analyzer, former Flexsys Company and Monsanto Company.

2Data according to InstronCorporation's automatic testing system equipment that incorporates six tests into one system. Such equipment may determine final tension, final stretch, modulus, etc. The data recorded in the table are produced by processing the ring tension test.

3D data obtained by spectrometric analytical instrument.

It can be seen from Table 2 that the comparative sample A of silica rubber containing a load of a total of 7.2 phr (8.0 phs of blocked alkoxygior-nomercaptosilane binding agent exhibited desirable processing characteristics as indicated by viscosity relatively low Mooney rate of 67 units.

It can also be observed that for comparative B and C rubber samples, the processing characteristic (Mooney viscosity) of the silica-containing rubber compositions is maintained or improved (when reduced) when the blocked alkoxiorganomercaptosilane deleting agent charge has been increased to 8.55 and 9.9 phr (9.5 and 11 phs).

However, the comparative sample of rubber D containing a 7.2 phr (8phs) charge of the alkoxymercaptosilane binding agent exhibited undesirable processing characteristics as indicated by the very high Mooney viscosity of 110 units.

Experimental EeF rubber samples exhibited slightly higher but still desirable Mooney viscosities when comparing the comparative BeC rubber samples with the same total charge levels as locked / unlocked alkoxygior-nomercaptosilane binding agents.

It can be seen from Table 2 that the comparative rubber sample. Having a 7.2 phr (8 phs) charge of the alkoxiorganomercaptosylanoblocked binding agent exhibited desirable processing characteristics as indicated by the relatively high storage / elastic modulus G ' low with 15% strain of 0.20 Mpa.

It can also be observed that for the comparative samples of rubber B and C, the processing characteristic (storage modulus G '/ uncured elastic with 15% strain) of the silica-containing rubber compositions were the same as the comparative rubber sample. The load of blocked alkoxiorganomer-captosilane binding agent was increased to 8.55 and 9.9 phr (9.5 and 11 phs).

However, the comparative sample of rubber D containing a 7.2 phr (8phs) load of alkoxymetercosphosyl binding agent exhibited undesirable processing characteristics as indicated by the G'storage / uncured elastic modulus with 15% strain of 0.50 MPA

Experimental EeF rubber samples exhibited slightly larger but still desirable 15% strain uncollected elastic / storage modulus G 'than the comparative BeC rubber samples with the same total charge levels as alkoxyiorganomercaptosilane binding agents. locked / unlocked.

It can therefore be observed that the processing characteristics of the composition of the rubber containing a combination of two different alkoxygior mercaptosilane binding agents were essentially maintained compared to the comparative sample of rubber A.

This is considered in the present invention to be significant (as will be discussed later) in the sense that the physical properties of the resulting silica-containing rubber composition can be improved by using the combination of Binding Agents without significantly affecting the processing characteristics of the rubber (Mooney viscosity and storage modulus G '/ uncured rubber of the rubber composition). In Table 2, it can be seen that the minimum torque value during curing of the silica-containing rubber composition by rubber process analyzer as equipment RPA 2000TM was substantially maintained by the use of the locked and unlocked alkoxiorganomercaptosilane coupling binders when compared to the minimum torque of the comparative rubber A sample.

In contrast, the use of the alloxiorganomercaptosilane binding agent alone provides a rubber composition having a higher, normally undesirable minimum torque.

This is considered to be significant in the present invention, as will be discussed later, that the improvement in the properties of the rubber composition obtained by the use of the binding agent combination was not due to the processability (minimum torque) of the rubber composition.

It can also be seen from Table 2 that a large desirable elongation at break property (significantly greater than 300% elongation) for the comparative show of rubber A was substantially maintained by the use of the locked and unlocked alkoxiorganomercaptosilane combined deleting agents, while Use of the unblocked alkoxiorganomercaptosilane alone could cause the rubber composition to elongate less than 300%.

It can also be seen from table 2 that rebound values at 23 ° C and high temperatures were improved by the use of locked and unlocked alkoxiorganomercaptosilane combined binders when compared to comparative samples of rubber A and D. rebound of the EeF rubber test samples were equal to or greater than the comparative values of the BeC samples where an equal amount of the total binding agents were used. This is also considered significant in the sense that the composition of the high-value rubber is indicative of a low rubber composition hysteresis that promotes low internal heat formation and low tire rolling resistance which has a tread of such composition. rubber with resulting improved fuel economy for an associated vehicle.

It can also be seen from Table 2 that although the increase in the blocked alkoxiorganomercaptosilane binding agent in the rubber composition provides a slight improvement in DIN and Grosch abrasion resistance in comparative samples of rubber B and C, the use of of the locked and unblocked alkoxiorga-nomercaptosilane combined binder (EeF rubber test samples) resulted in significantly increased abrasion resistance silica-reinforced rubber compositions when compared with comparative rubber samples A and D, and by the use of binding agents only. This is considered to be significant in the sense that the use of alkoxiorganomercaptosilane in combination with blocked alkoxiorganomercaptosilane leads to a synergistic increase in the indicated properties of the rubber composition.

This example demonstrates the desire and benefit of using the al-coxiorganomercaptosilane binding agent combined with the blocked alkoxiorganomercaptosylan binding agent to improve the performance of rubber composition without significantly compromising processing characteristics (Mooney viscosity and torque). of the rubber composition containing only alkoxygior-nomercaptosilane binding agent. The desirable properties of the rubber composition (rubber cured or non-cured rubber properties) were obtained even when the alkoxy-nomercaptosilane (unblocked) binding agent is added at the NP2 mixing step or stage at a relatively high mixing temperature of about 170 ° C. ° C.

Example Il

Rubber compositions have been prepared to evaluate the effect of a combination of a blocked alkoxiorganomercaptosilane binding agent (having its reverse blockade of mercapto) and an alkoxiorganomercaptosilane without its blockade of blockade (which is sometimes referred to herein). -example as "reactive silane").

This example II differs from example 1 in the addition sequence of the reactive silane binding agent. For this example II, instead of adding the silanoreactive binding agent in the second non-productive mixing stage (NP2) as was performed in example I, the reactive silane binding agent was added in the third nonreactive mixing stage. (NP3) to evaluate the desirable practices for this invention.

Sample A is a comparative sample containing what is considered to be an appropriate 8 phs loading level of the blocked alkoxyorganomercaptosilane binding agent.

BeC rubber samples are comparative samples containing higher loading levels of 9.5 and 11 phs, respectively, when compared to the 8phs loading level for the comparative locked-alkoxiorganomer-captosilane binding agent rubber A sample.

Comparative sample D contained what is considered in the present invention with a suitable loading level of 8 phs of the unlocked alkoxiorganomercaptosilan binding agent having a tread of such rubber composition.

Experimental samples of GeH rubber contained a combination of blocked and unblocked alkoxiorganomercaptosilane agents with combined loading levels of 9.5 and 11 phs, respectively. For preparation of these experimental rubber samples, the unlocked alkoxiorganomercaptosilane binding agent was added to the rubber composition in the third non-productive mixing step (NP3).

The rubber compositions were prepared by mixing the components into three non-productive sequential mixing stages (NP1, NP2 and NP3) followed by the productive mixing stage (PR) in internal rubber mixers. Elimination mixing temperatures for the mixing stages were about 170 ° C for NP1 and NP2, about 160 ° C for NP3 and about 120 ° C for PR.

The basic recipe for rubber samples is given in the following table 3e described in parts by weight unless otherwise indicated.

Table 3

<table> table see original document page 24 </column> </row> <table> (DPG)

The components described are those used in example 1 unless otherwise specified.

Table 4 below illustrates the processing characteristics and various physical properties of the basic recipe rubber compositions of Table 3.

Table 4

<table> table see original document page 25 </column> </row> <table> <table> table see original document page 26 </column> </row> <table> Abrasion loss rate Gros-43,5 40.7 40.5 36.6 34 32.9ch, 23 ° C, mg / km

It can be seen from Table 4 that the comparative rubber sample G exhibited slightly higher but still very desirable Mooney viscosity than the comparative samples A1 B and C, although the experimental sample H had a much higher but still acceptable Mooney viscosity than comparative samples A, B and C.

It can be seen from table 4 that the Gexibiu rubber specimen G 'storage / elastic modulus very desirable, with 15% ce-pa, while experimental sample H exhibited uncured storage / elastic modulus G'. slightly larger but still acceptable than comparative samples A, B and C.

Comparing the experimental rubber sample F (from example I) with the experimental sample H (from example II), it can be seen that the addition of a reactive silane binding agent in the second non-productive mixing step (NP2) is more desirable than -view of Mooney's stickiness.

Therefore, it can be observed that the processing characteristic of the rubber composition containing a combination of unblocked alkoxiorganomercap-tosylan binding agents (GeH experimental samples) was essentially maintained compared to comparative sample A which used only one compounding agent. blocked alkoxy-ganomercaptosilane binding.

This is considered herein to be significant (as will be discussed later) in that the physical properties of the resulting composition of silica-containing rubber can be improved by using the combination of binding agents without significantly affecting rubber processing characteristics (Mooney viscosity and storage modulus G '/ uncured rubber of rubber composition).

Table 4 shows that the minimum torque value during curing of the silica-containing rubber composition by the rubber process analyzer was substantially maintained by the use of locked and unlocked alkoxiorganomercap-tosylan combined binding agents as compared to the torque. comparative sample of rubber A.

It is considered in the present invention to be significant that the improved properties of the rubber composition obtained by the use of the combination of binding agents was not due to the processability of the minimum torque mentioned above of the rubber composition.

It can also be seen from Table 4 that a large elongation at break property (significantly greater than 300% elongation) for the comparative sample of rubber A was substantially maintained by the use of the locked and unlocked alkoxiorganomercaptosilane binding agents while The use of the unblocked alkoxiorganomercaptosilane alone could cause the rubber composition to elongate less than 300%.

It can also be seen from table 4 that rebound values at 23 ° C and high temperatures were improved by the use of locked and unlocked alkoxiorganomercaptosilane combined binders when compared to the comparative sample of rubber A. GeH rubber experimental samples were equal to or greater than the comparative values of the BeC samples where an equal amount of total binding agents were used. This is also considered significant in the sense that the high rebound rubber composition is indicative of a low hysteresis of the rubber composition that promotes low internal heat formation and promotes low rolling resistance of a tire having a tread. of such a rubber composition with the resulting expected improved fuel economy for an associated vehicle.

It can also be seen from Table 4 that while the increase in the blocked alkoxiorganomercaptosilane binding agent in the rubber composition provides little improvement in DIN and Grosch abrasion resistance in comparative samples of rubber B and C, the use of of the locked and unlocked alkoxiorga-nomercaptosilane combined binder (experimental GeH rubber samples) resulted in significantly increased abrasion resistance silica-reinforced rubber compositions when compared with comparative rubber samples A and D, and by the use of binding agents only. This is considered to be significant in the sense that the use of alkoxiorganomercaptosilane combined with the blocked alkoxiorganomercaptosilane leads to a synergistic increase in the indicated properties of the rubber composition.

This example demonstrates the desire and benefit of using the al-coxiorganomercaptosilane binding agent combined with the blocked alkoxiorganomercaptosylan binding agent to improve the performance of rubber composition without significantly compromising processing characteristics (Mooney viscosity and torque). of the rubber composition containing only alkoxygior-nomercaptosilane binding agent. The desirable properties of the rubber composition (rubber properties cured or not) were obtained even when the alkoxy-nomercaptosilane (unblocked) binding agent is added at the NP3 mixing step or stage at a relatively high mixing temperature of about 160 ° C. ° C.

Example III

Rubber compositions were prepared to evaluate the effect of a combination of a blocked silane binding agent and a more reactive (unlocked) silane binding agent. Reactive silane binding agent was added at different mixing stages in order to evaluate a best practice of this invention.

This example III differs from examples I and II in that the total charge of the combination of blocked and unblocked silane binding agents is reduced to 8 phs in the rubber composition with the intention of reducing the cost of the rubber composition.

Experimental samples of rubber I, J, K, and L contained a combination of blocked and unblocked alkoxygiorganomercaptosilane binding agents. The most reactive unblocked binding agent was added in the second nonproductive mixing step (NP2) for the experimental samples I and J, and in the third nonproductive mixing step (NP3) for the K eTL experimental samples.

Rubber samples were prepared by mixing the components in three non-productive sequential mixing stages (NP1, NP2 and NP3) followed by the productive blending stage (PR) in the same manner as in Example I.

The basic recipe for rubber samples is given in the following table 5e described in parts by weight unless otherwise indicated.

Table 5

<table> table see original document page 29 </column> </row> <table> Variable Alkoxy-mercaptosilane Binding Agent6

Productive Mixing Step (PR) (mixed at a temperature of about 120 ° C

<table> table see original document page 30 </column> </row> <table>

The described components are those used in example 1 unless otherwise specified.

Table 6 below illustrates the processing characteristics and various physical properties of the basic recipe rubber compositions of Table 5.

Table 6

Binding Agent / Mixing Step Comparative

<table> table see original document page 30 </column> </row> <table> <table> table see original document page 31 </column> </row> <table> <table> table see original document page 32 < / column> </row> <table>

A. With respect to rubber processing, called Moo-nev viscosity and Storage Module G '/ uncured rubber for uncured rubber

It can be seen from table 6 that the experimental rubber samples I, J, K and L exhibited slightly higher Mooney viscosity, but still much more desirable than comparative sample A. The processability (Mooney viscosity) of comparative sample A was therefore substantially maintained when the silanodlocked binding agent was used to partially replace the blocked silane binding agent.

It can also be seen from Table 6 that the rubber I, J, K and L experimental samples demonstrated uncured storage / elastic modulus G 'with slightly larger but still much more desirable 15% strains than the comparative sample. The processability of the comparative sample of rubber A was therefore substantially maintained when the unlocked silane binding agent was used to partially replace the blocked silane binding agent.

B. Regarding hysteresis, in the sense of rebound physical property, and property of the Tan Delta test of sulfur-cured rubber composition

It can be seen from Table 6 that the rebound physical property (100 ° C) was improved when the unlocked silane binding agent was used to partially replace the blocked binding agent in the I, J, K and L.

This has been considered in the present invention to be significant in that the high temperature (100 °) high rebound rubber compositions have low hysteresis of the rubber composition, promoting low internal heat formation and low rolling resistance formation for a tire which has a tread of the rubber composition, thus promoting better fuel economy for an associated vehicle. It can also be seen from table 6 that the physical property of the Tan delta test was improved when the binder of the Unblocked silane was used to partially replace the blocked silane binding agent as observed in experimental rubber samples I, J, K and L.

The reduction in Tan delta value is considered to be beneficial in the sense of reduced hysteresis, thus indicating a beneficial impact on reducing internal heat production and forming and promoting reduction in rolling resistance of a tire which has a tread of the composition of the tire. rubber, thereby promoting better fuel economy for an associated vehicle.

In summary, a rubber composition with a relatively high and low Tan delta hotbull property combination exhibits low hysteresis with relatively lower resulting internal heat formation with formation of a corresponding lower temperature during the dynamic work of the rubber composition, providing foreseeable lower resistance to a tire with a tread of such a rubber composition, with a corresponding increase in fuel economy for an associated vehicle.

C. Regarding the abrasion resistance of sulfur-cured rubber composition

It can be seen from Table 6 that the abrasion resistance property of Grosch and DIN was significantly improved when the silaneblocked binder was used to partially replace the blocked silane binder in the I, J experimental samples. , K and L.

It is considered in the present invention to be significant that such increased abrasion resistance of the rubber composition can predictably reduce tread wear, and thereby promote a longer wearing time for such a tread.

In summary, a rubber composition with improved abrasion resistance was obtained without a significant increase in rubber processing difficulties (Mooney viscosity and minimum torque considerations) of uncured rubber.

That example III, therefore, demonstrates a significant benefit from the use of a locked-and-unlocked alkoxiorganomercaptosilane binding agent combination where the unlocked alkoxiorganomercaptosilane binding agent is used to replace a portion of the locked alkoxiorganomercaaptosilane binding agent with a rubber composition. silica reinforcement, where various physical properties are improved without significantly compromising the characteristics of Mooney's viscosity processing and minimum torque) of the rubber composition.

While certain representative embodiments and details have been demonstrated for the purpose of illustrating the invention, it will be clear to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. Tire having at least one component CHARACTERIZED by the fact that it is based on parts by weight per 100 parts by weight of rubber (phr), (A) elastomers comprising: (1) at least one non-functionalized conjugated diene-based elastomer, or (2) conjugated diene-based elastomers comprising (a) from 0 to about 55, alternately from about 15 to about 55, phr of at least one non-functionalized conjugated diene-based elastomer, and (b) from about 45 to about 100, alternately from about 45 to about 85, at least one functionalized butadiene / elastomeric styrene copolymer rubber (having a Tg1 in the range of about - 10 ° C to about -70 ° C) composed of at least one of: (i) styrene / butadiene copolymer (SBR) elastomers having a styrene bound in a range of about 20 to about 45% containing alkoxy silane groups (for example, -Si- (OR) n groups); (with said alkoxy groups being reactive with hydroxyl groups contained in said precipitated silica reinforcing filler), (ii) styrene / butadiene copolymer elastomers having a styrene content in a range of from about 20 to about 45% and containing amino-alkoxy silane groups with said amino alkoxy silane groups attached to the elastomer via the silicon atom (e.g. R "- (NHX-R ') m - Si - (OR) n groups). where R 'is an alkylene group of from 1 to 12 carbon atoms, R' is an alkyl group of about 0 to 10 carbon atoms and R is an alkyl group containing from 1 to 20 carbon atoms where at least one of said groups R is preferably an ethyl group, m is 1 or 2, η is 1 or 2, and χ is a value ranging from 0 to 2); (with said alkoxy silane groups being reactive with the hydroxy groups contained in the precipitated silica reinforcement filler), (iii) styrene / butadiene copolymer elastomer containing a functionalamine group (functionalized amine SBR); (with said functional group being reactive with hydroxyl groups contained in the precipitated silica reinforcing filler); (iv) styrene / butadiene copolymer elastomer having a bound styrene content in a range of about 20 to about 45% and containing groups desilane sulfide with the said silane sulfide groups connected to the elastomer via the silicon atom (eg (RO) x.Ry-Si-R'-S), where χ ranges from 1, 2 and 3, y ranges from -0, 1 and 2, R is the same or a different alkylene group having from 1 to 16 carbon atoms, and Re is an alkyl, aryl or alkylaryl group of 1 to 15 carbon atoms); styrene / butadiene copolymer having hydroxylfunctional groups (functionalized hydroxyl SBR); with said hydroxyl groups being reactive with hydroxyl groups on precipitated silica; and (vi) styrene / butadiene elastomer having epoxy groups (functionalized epoxy SBR); (with said epoxy groups being reactive with hydroxyl groups on the precipitated silica); (B) about 30 to about 120 phr of reinforcing filler comprising: (1) amorphous synthetic silica (eg precipitated silica) containing hydroxyl groups. -droxyl (eg silanol groups) on its surface, or (2) a combination of rubber-reinforced carbon black and said precipitated silica comprising from about 40 to about 110 phr of said precipitated silica (with the the remainder of said reinforcing filler, therefore, comprising said rubber-reinforced carbon black), (C) a combination of silica binding agents comprising: (1) alkoxiorganomercaptosilane, and (2) blocked alkoxiorganomercaptosilane (exhibiting its reversibly blocked mercapto, wherein the ratio (e.g., weight ratio) of said alkoxymercaptosilane to said blocked alkoxygiorcaptosilane is in the range of about 0.1 / 1 to about 0.5 / 1. Tire according to Claim 1, characterized in that the non-functionalized conjugated diene-based cytostelastomer comprises: (A) 1,4-polybutadiene rubber, or (B) 1,4-polybutadiene rubber; and useful 1,4-polyisoprene rubber. Tire according to claim 1, characterized in that said elastomers are a combination of: (A) 15 to 55 phr of at least one non-functionalized conjugated diene-based elastomer, and (B) 45 to 85 of at least one of said functionalised butadien / styrene elastomers. Tire according to claim 1, characterized in that said functionalized butadiene / styrene copolymer rubber comprises a butadiene / styrene copolymer (SBR) elastomer having a bound styrene in the range of 20 to 45% containing reactive alkane silane groups having hydroxyl groups contained in said precipitated silica reinforced pre-filler. Tire according to Claim 1, characterized in that the elastomeric functionalized styrene / butadiene rubber comprises a styrene / butadiene decopolymer elastomer having a bound styrene content in the range of 20 to 45% and containing amino and alkoxy groups. silane, wherein said alkoxy silanes groups are reactive with hydroxyl groups contained in the precipitated silica reinforced filler. Tire according to Claim 1, characterized in that the elastomeric butadiene / functionalized styrene rubber comprises a butadiene / styrene decopolymer elastomer containing an amine functional group. Tire according to Claim 1, characterized in that the functionalized butadiene / styrene rubber comprises a styrene / butadiene copolymer elastomer having a bound styrene content in a range of 20 to 45% and containing silane leaving groups. -sulfide with said silane sulfide groups connected to the elastomer through the silicon atom. Tire according to claim 1, characterized in that the elastomeric functionalized styrene / butadiene rubber comprises a styrene / butadiene elastomer having hydroxyl functional groups. A tire according to claim 1, characterized in that said elastomeric functionalized styrene / butadiene rubber comprises a styrene / butadiene elastomer having epoxy groups. A method of preparing a rubber composition characterized in that it comprises mixing, based on parts by weight per 100 parts by weight of the diene-based elastomer (phr) :( A) Elastomers comprising: (1) No a conjugated diene-based elastomer, or (2) conjugated diene-based elastomers comprising (a) from 0 to about 55 phr of at least one conjugated diene-based elastomer, and (b) about 45 at about 100 phr of at least one functionalized elastomeric debutadiene / styrene copolymer rubber composed of at least one of: (i) styrene / butadiene copolymer (SBR) elastomers having a bound styrene in a range of about 20 to about 45% containing alkoxy silane groups, (ii) styrene / butadiene copolymer elastomers having a styrene content in the range of about 20 to about 45% and containing amino-alkoxy silane groups with said groups amino alkoxy silane connected to the asomer through the silicon atom, (iii) styrene / butadiene copolymer elastomer containing a functionalamine group, (iv) styrene / butadiene copolymer elastomer having a bound styrene content in a range of from about 20 to about 45 % and containing desylane sulfide leaving groups with said silane sulfide groups connected to the elastomer through the silicon atom (v) styrene / butadiene copolymer elastomer having hydroxylfunctional groups; and (vi) styrene / butadiene elastomer having epoxy groups; (B) about 30 to about 120 ° C of the reinforcing filler at a demix temperature in a range of about 140 ° C to about 180 ° C, where said The reinforcing filler comprises a combination of rubber-reinforced carbon black from about 40 to about 110 phr of the precipitated silica containing hydroxyl groups on its surface; and (C) a silica linker comprising: (1) alkoxiorganomercaptosilane, and (2) blocked alkoxiorganomercaptosilane (having its reversibly blocked mercapto moiety; (D) a mixture of an unlocking agent with the resulting rubber mixture, and simultaneously or subsequently mixing a sulfur curing agent and subsequently (E) curing the resulting mixture at an elevated temperature.