WO2007019561A1

WO2007019561A1 - Rubber compositions containing improved tackifiers

Info

Publication number: WO2007019561A1
Application number: PCT/US2006/031207
Authority: WO
Inventors: Wolfgang Pille-Wolf
Original assignee: Arizona Chemical Company
Priority date: 2005-08-09
Filing date: 2006-08-09
Publication date: 2007-02-15
Also published as: EP2940072B1; PL1913075T3; US20070037908A1; EP2940072A1; EP1913075A1; ES2531622T3; EP1913075B1

Abstract

The invention relates to compositions containing improved tackifiers, as weil as methods making and using the same.

Description

RUBBER COMPOSITIONS CONTAINING IMPROVED TACKIFIERS

The present invention is related to, and claims the benefit of 119(e) priority to U.S. provisional patent application Ser. No. 60/706,861 ; entitled "RUBBER COMPOSITIONS CONTAINING IMPROVED TACKIFIERS", which was filed on August 9, 2005, and is hereby incorporated, in its entirety, herein by reference.

Field of the Invention

The invention relates to compositions containing improved tackifiers, as well as methods making and using the same.

Background of the Invention

In rubber technology, particular importance is attached to the assembly of unvulcanized blanks from prefabricated semi-finished products. The

adhesion of the semi-finished product determines the cohesion and, above all, the dimensional stability of the "unvulcanized blank". The desired dimensional stability of the material is not guaranteed if the tackiness of the superimposed layers is insufficient. Air pockets are likely to form, on the other hand, if the layers adhere too tightly to one another- when the blank is assembled- resulting in poor fusion of the layers in the vulcanization process. The defects due to deficient autohesion are often not recognized until after vulcanization, and in some cases not until the finished product is in use, with all the economic disadvantages that then entails, like economic loss.

There is little understanding of the workings of the methods applied by those involved in production processes to improve the tackiness of compounds. These methods, which are based for the most part on empirical experience, treat the surface by covering the compound slabs with interleaving film of fabric materials and use resins as so-called tackifier in compounds.

A particular use, among many, of such rubber compositions is for the creation of tires, such as those used in transportation, preferably automobiles.

Among the many desirable attributes for tire tread compositions, a great

resistance to abrasion is preferred. That is, rubber compositions that easily break down under frictional forces is not desirable because such compositions

when used in a tire easily wear resulting in a short life. In addition, it is

preferable that tires have very good web and/or dry grip. While dry grip is usually maintained by many rubber compositions, wet grip is not. Rubber compositions having good wet grip, thus improved wet skid resistance, is highly desirable for use in tires. Finally, it is highly desired to create a tire that helps increase the fuel economy in the transportation industry, for example in the automobile industry. One manner in which to increase fuel efficiency into a tire is to create the tire from a rubber composition that "likes" to roll. A rubber composition that "likes" to roll, in other words, has a reduced tendency to resist rolling. If a rubber composition has a reduced tendency to resist rolling, less energy is required to roll the tire. For example, less energy would be required out of the engine of an automobile if the automobile included tires made from, at least in part, rubber compositions that had a reduced tendency to resist rolling. While rubber compositions capable of being useful in tires and/or tire tread compositions are known, no such rubber composition having maximized abrasion resistance, maximized wet grip (e.g. wet skid resistance), and minimized resistance to roiling (e.g. maximizing fuel economy) is known to date.

SUMMARY OF THE INVENTION

An object of the invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin wherein the at least one resin is selected from the group consisting of a rosin ester, terpene phenolic resin, terpene phenol, pentaerythritol rosin ester, a modified terpene resin, terpene resin, a polyterpene, and a phenol modified copolymer of styrene and alpha methyl styrene.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin having a softening point as determined by Ring & Ball of from 75 to 150⁰C.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 13O⁰C.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 13O⁰C and the resin has an OH value of from 5 to 150.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 13O⁰C and the resin has an OH value of from 30 to 50.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 5 to 150. Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50 and having a softening point as determined by Ring & Ball of from 75 to 15O⁰C.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; a filler; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; a filler selected from the group consisting of silica, alumina, and carbon black; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; a coupling agent; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; a coupling agent containing silane; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50 and the composition has an abrasion resistance as measured the DIN Abrasion method ISO37 of from 80 to 100 mm³.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50 and the composition has an abrasion resistance as measured the DIN Abrasion method ISO37 of from 80 to 100 mm³, a tanδ at 7O⁰C of about 0.129 or less, and a tanδ at 2O⁰C of about 0.205 or more.

Another object of the present invention relates to a composition containing at least one polymer selected from the group consisting of a rubber polymer or copolymer; and an effective amount of at least one resin, wherein the resin is a terpene phenol resin having an OH value of from 30 to 50 and the composition has an abrasion resistance as measured the DIN Abrasion method ISO37 of from 80 to 100 mm³; a tanδ at 7O⁰C that is at least at least 5%less than the tanδ at 7O⁰C of a composition not containing any resin; and has a tanδ at 2O⁰C that is at least 5% greater than the tanδ at 2O⁰C of a composition not containing any resin.

Another object of the present invention relates to a tire containing any one or more of the objects mentioned above.

Another object of the present invention relates to a tire containing a tread composition wherein the tread composition contains at least one rubber polyer, at least one rubber copolymer, or mixtures thereof, and an effective amount of at least one terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 13O⁰C and having a OH value of from 30 to 50; the

tread composition having an abrasion resistance as measured by the DIN Abrasion method ISO37 of from 80 to 100 mm³, a tanδ at 70⁰C of about 0.129 or less, and a tanδ at 2O⁰C of about 0.205 or more, wherein the tire has a reduced resistance to rolling and an increased wet skid

resistance.

Another object of the present invention relates to a tire containing a tread composition wherein the tread composition contains at least one rubber polyer, at least one rubber copolymer, or mixtures thereof, and an effective amount of at least one terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 130⁰C and having a OH value of from 30 to 50; the tread composition having an abrasion resistance as measured the DIN Abrasion method ISO37 of from 80 to 100 mm³; a tanδ at 7O⁰C that is at least at least 5%less than the tanδ at 7O⁰C of a composition not containing any resin; and has a tanδ at 2O⁰C that is at least 5% greater than the tanδ at 2O⁰C of a composition not containing any resin, wherein the tire has a reduced resistance to rolling and an increased wet skid resistance.

The above objects and further objects such as methods of making and using the above objects are described hereinbelow. While the detailed description discussed below is meant to represent the specific objects and embodiments of the invention, they are meant to me non-limiting in so far as to exemplify the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 : A graph of the tanδ as a function of temperature for various

compositions of the present invention containing resins as compared to a

composition according to the prior art containing Koresin.

Figure 2: A graph of tan δ as a function of temperature of compositions

of the present invention containing no resin (reference), terpene phenol resin TP115 and TP300.

Figure 3: A graph of tan δ as a function of temperature of tread compounds containing no resin (reference), a terpene phenolic resin TP2019 and a terpene phenolic resin TP2040HME.

DETAILED DESCRIPTION OF THE INVENTION

This application is related to the fields of chemistry and rubber sciences which is described, for example, Harry Barron's "Modern rubber chemistry" (1948), Chemical Pub. Co, and Edward William Duck's "Plastics and rubbers, (Chemistry in modern industry series)", (1971), Butterworths, and J. A Brydson's "Rubber chemistry", (1978), Applied Science Publishers, which are hereby incorporated, in their entirety, herein by reference.

The inventor has surprisingly discovered a tackifier that, when applied to rubber containing compositions, improves the mechanical strength, tear resistance, and vulcanization thereof, without significantly diminishing other important physical characteristics important for end-use applications of rubber compositions. Further, the inventors have discovered a rubber composition containing a tackifier at effective amounts that maximize abrasion resistance, maximize wet grip (e.g. wet skid resistance), and minimize resistance to rolling (e.g. maximizing fuel economy), as well as tires and tire tread compositions containing the same.

The present invention relates to a composition, method of making the composition, and methods of using the composition. The composition is preferably a rubber containing composition. The rubber containing

composition is preferably useful in tire production. Examples of rubber

compositions useful in tire production can be found in United States Patent

Nos. 4,487,892; 5,877, 249; 6,790,889; 6,525,118; 6,384,118; 6,384,117; 6,369,138; 6,348,531 ; 6,342,552; 6,228,908; 6,221 ,943; 6,180,710; and 5,994,448, as well as PCT published application WO2004013220 and

WO2004013221 and United States Published Patent Application Number 2006/0167160, which are all hereby incorporated, in their entirety, herein by reference.

Although the rubber composition may be utilized for any article, preferably that article is a tire. Examples of such tires include, but are not limited to, tires useful in the transportation industry. Examples of such tires include those useful in the automobile industry. Further examples include tires such as pneumatic tires.

The composition of the present invention, when used to create the tire of the present invention, may be used to create the entire tire and/or just a portion thereof. For example, the rubber composition may be used to create the tire tread composition. Accordingly, the present invention further relates to a tire containing the rubber composition of the present invention. Any one or more parts of the tire may contain the rubber composition, including the tire tread.

The compositions according to the present invention contains a resin.

The resin preferably provides tackiness to the composition. Thus the resin

may function as a tackifier and/or a tackifying agent. The resin may be any resin, but is not limited to a rosin ester, abietic

acid, abietic acid ester, terpene resin, terpene-phenol resin, terpene phenol,

pentaerythritol rosin ester, a modified terpene resin, a polyterpene, and a phenol modified copolymer of styrene and alpha methyl styrene or

hydrocarbon resins.

Examples of polyterpenes, terpene phenol resins and hydrocarbon based resins can be found in USP Nos. 6,900,274; 6,562,888; 6,274,657; 5,504,152; 4,380,513; 6,160,083; 5,723,709; 6,121 ,392; 5,959,010; 5,854,367; 5,789,474; 5,723,709; 4,879,351 ; 4,052,549; 5,051 ,485; 4,879,351 ; 4,797,460 and 5,457,175; as well as United Stated Published Patent Application Numbers 20050054801 and 20030229178, which are all hereby incorporated, in their entirety, herein by reference. Commercial product include those terpene-phenolic resins, rosin esters, modified terpene resins, polyterpene resins, and phenol modified copolymer of styrene and alpha methyl styrene or hydrocarbon resins, but are not limited to, sold by Arizona Chemical Company such as: SYLVARES TP105; SYLVARES TP95; SYLVARES TP115; SYLVARES TP300; SYLVARES TP2019; SYLVARES TP2040HME; SYLVARES TP; SYLVARES 525; SYLVARES TR 5147; and SYLVARES RE104. The composition may contain any amount of resin. The amount of the

resin may be up to 50 phr, preferably up to 30 phr, more preferably up to 15

phr, and most preferably up to 10 phr. Also, the amount of the tackifier may be at least 0.1 phr, preferably at least 0.5 phr, more preferably at least 1 phr, most preferably at least 2 phr. The amount of tackifier may be 0.1 , 0.2, 0.5, 1, 1.5,

2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 15, 20, 25, 30, 40, and 50 phr, including any and all ranges and subranges therein.

If the resin is a phenol modified copolymer of styrene and alpha methyl styrene, the molar ratio of styrene to alpha methyl styrene is from 0.1 to 5, more preferably from a 0.2 to 2..0. The molar ratio of styrene to alpha methyl styrene may be 0.1 , 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 1.2, 1.4, 1.6, 1.8, 2, 2.5,

3, 3.5, 4, 4.5, and 5, including any and all ranges and subranges therein.

If the resin is a rosin ester, preferably the rosin portion of the ester is at least one rosin acid compound. The rosin acid compound may be selected from those natural resin-based acids, such as those obtained from residues of distillation of natural oils. The rosin acid compound may be also be derived. Since the rosin compound is an acid, the derivative may be any commonly known derivative of a carbonyl-containing compound known in general

Organic Chemistry Textbooks, such as Organic Chemistry", 5th Edition, by Leroy G. Wade. Examples of such derivatives include, but is not limited to

esters, amine carboxylates, and nitrile derivative of the rosin acid compound. The rosin acids may include those that may be isolated from black liquor

skimmings, crude tall oil, tall oil pitch, and distilled tall oil. In addition rosin

acids may be those found in tall oil rosin, gum rosin and wood rosin. These

naturally occurring rosins may be suitably mixtures and/or isomers of monocarboxylic tricyclic rosin acids usually containing 20 carbon atoms. The tricyclic rosin acids differ mainly in the position of the double bonds. The rosin acid may be at least one of levopimaric acid, neoabietic acid, palustric acid, abietic acid, dehydroabietic acid, seco-dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, pimaric acid, paulstric acid, and isopimaric acid, or mixtures, isomers, and/or derivatives thereof. The rosins derived from natural sources also include rosins, i.e. rosin mixtures, modified notably by

polymerisation, isomerisation, disproportionation and hydrogenation. The

rosin acids may include those mentioned in United States Patents 6,875,842; 6,846,941 ; 6,344,573; 6,414,111 ; 4,519,952; and 6,623,554, which are hereby incorporated, in their entirety, herein by reference.

The composition may contain a rosin ester that is any ester of the above-mentioned rosin acids.

The resin may have a softening point, as determined by Ring & Ball, of from 75 to 15O⁰C, preferably from 85 to 135⁰C, most preferably from 90 to 130

⁰C. Therefore, the softening point is preferable less than 15O⁰C and greater

than 75⁰C. The softening point may be 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, and 15O ⁰C, including any and all ranges and

subranges therein.

In a preferred embodiment, the resin is a terpene-phenol resin. Examples of the terpene-phenol resin include commercial products (shown by the trade names) such as YS POLYSTAR T115, T145, S145, G150 and N125 of the YS POLYSTAR series manufactured by YASUHARA CHEMICAL Co., Ltd. Further examples include SYLVARES TP105; SYLVARES TP95; SYLVARES TP115; SYLVARES TP300; SYLVARES TP2019; SYLVARES TP2040HME; SYLVARES TP manufactured by Arizona Chemical Company.

When the resin is a terpene-phenol resin, the terpene-phenol resin may have any softening point mentioned above as determined by Ring & Ball. However, when the resin is a terpene-phenol resin, it may have a softening point less than 15O ⁰C, preferably less than 14O⁰C, more preferably less than 130⁰C, and most preferably less than 12O ⁰C. Further, when the resin is a terpene-phenol resin, it may have a softening point greater than 75⁰C, preferably greater than 80⁰C, more preferably greater than 90⁰C, most preferably greater than 95⁰C. When the resin is a terpene-phenol resin, the

softening point may be 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, and 15O ⁰C, including any and all ranges and subranges therein. When the resin is a terpene-phenol resin, the terpene-phenoi resin may

have any OH value. The terpene-phenol resin has a OH value that is less

than 150, preferably less than 100, more preferably less than 85, most

preferably less than 50. The terpene-phenol resin has a OH value that is greater than 5, preferably greater than 10, more preferably greater than 20, most preferably greater than 30. The terpene-phenol resin has a OH value that is 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140 and 150, including any and all ranges and subranges therein.

The composition of the present invention may contain a rubber polymer or copolymer. The rubber or elastomer may be present in the composition at any amount. The amount of rubber or elastomer may be not more than 99wt% and not less than 30wt%, preferably not more than 90wt% and not less than 40wt%, more preferably not more than 85wt% and not more than 45wt%, most preferably not more than 80wt% and not less than 50wt%, based upon the total weight of the composition. The composition may contain 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 and 99wt% of rubber or elastomer based upon the total weight of the composition, including any and all ranges and subranges therein.

The rubber polymer or copolymer may be any rubber polymer or

copolymer, including compounding combinations thereof. The rubber polymer or copolymer may be any rubber, especially those used in compositions

generally known to make tires for the transportation industry, more especially the automobile industry. Examples of the rubber polymer or copolymer, while

being non-limiting, are styrene butadiene rubber, polybutadiene rubber, natural rubber, halogenated butyl rubber, butyl rubber, polyisoprene rubber, and styrene/isoprene/butadiene terpolymer rubbers.

Examples of a styrene butadiene rubber are those copolymers containing any amount of styrene. For example the styrene butadiene rubber may. contain greater or less than 50% by weight of styrene. When the composition contains a styrene butadiene copolymer, the styrene butadiene rubber may contain 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, and 95% by weight of styrene, including any and all ranges and subranges therein.

Examples of polybutadiene rubbers may be any and may include those having a 1 ,4 configuration, 1 ,2 configuration, etc. Further the polybutadiene rubbers may contain any amount of those having 1 ,4 configuration and/or 1 ,2 configuration, etc .

Examples of polyisoprene rubber may be any and may include those having 1 ,4 configuration and/or cis-1,4 configuration, and/or 3,4 configuration,

etc. The polyisoprene rubber may contain any amount of those havingl ,4

configuration and/or cis-1 ,4 configuration, and/or 3,4 configuration, etc. Further the rubber polymer or copolymer may be hydrogenated or

partially hydrogenated. For example, a styrene butadiene copolymer may be fully hydrogenated or partially hydrogenated. When at least partially hydrogenated, the double bonds of the rubber polymer or copolymer may be

more or less than 50% hydrogenated. For example, a styrene butadiene copolymer may contain double bonds that are more or less than 50% hydrogenated, for example, in the butadiene portion of the copolymer. The rubber polymer or copolymer may such that the double bonds are 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 and 100% hydrogenated, including any and all ranges and subranges therein.

The composition of the present invention may also contain pigments and fillers, preferably reinforcing fillers. Examples of such pigments and fillers include inorganic and organic fillers. Examples of fillers include silicon- containing compounds and/or aluminum containing compounds and/or carbon black and/or clay. Examples of silicon containing compounds include silaceous compounds, such as silaceous pigments. Further examples include fumed and/or pyrogenic and/or precipitated silaceous compounds (silica). Further examples of silica include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate and aluminum silicate. Among these

types of silica, wet silica which most remarkably exhibits the effect of improving the fracture resistance and simultaneously improving the road gripping

property on wet roads and the low rolling resistance is more preferable.

Examples of aluminum containing compounds include alumina. Examples of alumina may include fumed and/or precipitated alumina. The above alumina can be any alumina. Examples of alumina include those represented by the following general formula: AI₂O₃.nH₂O; where n represents a number preferably ranging fromf 0 to 3.

The fillers may have any size and shape. The fillers may have any BET surface area, as measure using nitrogen gas. The inorganic filler may have a BET surface area of 50 to 500, for example. The BET surface area of the inorganic filler may be 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, and 500 square meters per gram. The BET method of measuring surface area is described in the Journal of the

American Chemical Society, Volume 60, page 304 (1930).

When the filler includes silica, the silica may have any specific surface area. It is preferable that the silica has a specific surface area in the range of

80 to 300 m.²/g and more preferably in the range of 10 to 220 m²/g as measured in accordance with the nitrogen adsorption method. When the

specific surface area is 80 m²/g or greater, the sufficient reinforcing effect is

exhibited. When the surface area is 300 m.²/g or smaller, no adverse effects on the processability are exhibited. In general, anhydrous silicic acid or

hydrated silicic acid in the form of fine powder which is used as the white reinforcing filler of rubber is used. Examples of the silica include commercial

products such as "NIPSIL" (manufactured by NIPPON SILICA KOGYO Co., Ltd.) having a specific surface area of about 200 m.sup.2/g and "ZEOSIL 1115MP" (manufactured by RHODIA Company) having a specific surface area of 117 m²/g.

When the inorganic filler is silica, various commercially available silicas may be considered for use in this invention such as, for example, only and without limitation, silicas commercially available from PPG Industries under the Hi-SiI trademark such as, for example, those with designations 210, 243, etc; silicas available from Rhone-Poulenc, with designations such as Zeosil 1165MP and silicas available from Degussa AG with designations such as VN2 and VN3, etc. The Rhone-Poulenc Zeosil 1165MP silica is reportedly characterized by having a BET surface area of about 160-170 and by a DBP value of about 250-290 and by having a substantially spherical shape.

The fillers may also contain metals. Examples of such metals include potassium, sodium, iron, aluminum, calcium, titanium, zirconium, and magnesium. Further, the fillers may halogen elements such as fluorine and/or

groups such as NH₄. Specific examples of the fillers include alumina hydrate (AL₂O₃H₂O),

aluminum hydroxide [AI(OH)₃] such as gibbsite and bayerite, aluminum

carbonate [AI₂(CO₃)₂], magnesium hydroxide (Mg(OH)₂), magnesium oxide (MgO), magnesium carbonate [MgCO₃], talc (3MgO.4SiO₂.H₂O), attapulgite (5MgO.8SiO₂.9H₂O), titanium white (TiO₂), titanium black (TiO_2n-1), calcium oxide (CaO), calcium hydroxide [Ca(OH)₂], aluminum magnesium oxide (MgO-AI₂O₃), clay (AI₂O₃.2SiO₂), kaolin (AI₂O₃.2SiO₂.2H₂O), pyrophillite (AI₂O₃.4SiO₂.H₂O), (AI₂O₃.4SiO₂.2H₂O), aluminum silicate (AI₂SiO₅, AI₄.3SiO₄.5H₂O and the like), magnesium silicate (Mg₂SiO₄, MgSiO₃ and the like), calcium silicate (Ca₂SiO.₄ and the like), aluminum calcium silicate (AI₂O₃. CaO.2SiO₂ and the like), magnesium calcium silicate (CaMgSiO₄), calcium carbonate (CaCO₃), zirconium oxide (ZrO₂), zirconium hydroxide [ZrO(OH)₂.nH₂O], zirconium carbonate [Zr(CO.₃).₂], various types of zeolite, feldspar, mica and montmorillonite.

Among the above inorganic fillers, at least one filler selected from carbon black, silica, various types of alumina and various types of clay is preferable as the filler used in the present invention.

Carbon black is not particularly limited. For example, SRF, GPF, FEF, HAF, ISAF and SAF can be used. Carbon black having an iodine adsorption [IA) of 60 mg/g or greater and a dibutyl phthalate absorption (DBP) of 80

nl/100 g or greater is preferable. The effect of improving the road gripping property and the fracture resistance is increased by using carbon black. HAF,

ISAF and SAF providing excellent abrasion resistance are more preferable.

The carbon black may have any outer surface area. The carbon black may have an outer surface area in the range of 130 to 200 m²/g as measured in accordance with the CTAB adsorption method is preferable.

The filler may have any diameter. The filler may have a diameter of 50 μm or smaller, preferably 25 μm or smaller, more preferably 10μm or smaller, most preferably 3 μm or smaller. When the diameter of the inorganic filler is 10μm or smaller, the fracture resistance and the abrasion resistance of the vulcanized rubber composition may be kept improved. The diameter of the filler may be 0.001 , 0.01 , 0.1 , 0.5, 1 , 2, 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 μm, including any and all ranges and subranges therein.

The composition may contain the filler at any amount. The composition contains from 5 to 250 phr, preferably from 10 to 150 phr, more preferably from 40 to 120 phr, most preferably from 60 to 120 phr of the inorganic filler. The composition may contain 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240

and 250 phr, including any and all ranges and subranges therein. In the present invention, the filler, such as those exemplified above, may

be used singly or in combination of two or more.

The composition of the present invention may contain a coupler or coupling agent. In many cases there tends to be a lack of, or at least an insufficient degree of, physical and/or chemical bonding and/or interaction between the filler and the rubber polymer or copolymer mentioned above so as to enable the filler to become a reinforcing filler for the rubber polymer and/or copolymer. While various solutions, treatments and procedures have been devised to overcome such deficiencies, compounds capable of enhancing the degree of physical and/or chemical bonding and/or interaction between the filler and the rubber polymer or copolymer are generally known as coupling agents, or couplers.

Examples of couplers include any coupler that is generally known in the art to the skilled artisan to enhance the degree of physical and/or chemical bonding and/or interaction between the filler and the rubber polymer or copolymer. In the case of a when silica is used as a filler, such coupling agents may generally be composed of a silane which has a constituent component, or moiety, (the silane portion) capable of reacting with the silica surface and, also, a constituent component, or moiety, capable of interacting

with the rubber, particularly a sulfur vulcanizable rubber which contains

Darbon-to-carbon double bonds, or unsaturation. In this manner, then the coupler may act as a connecting bridge between the silica and the rubber and

thereby enhances the rubber reinforcement aspect of the silica.

This ideal can be used by the skilled artisan so as to be applied to any filler although the specific chemical groups and chemistry may change according to the selection of the filler.

In one aspect, the silane of the coupling agent apparently forms a bond to the silica surface, possibly through interaction with silanol groups on the silica surface, and the rubber interactive component of the coupling agent apparently interacts with the rubber. Usually the rubber interactive component of the coupler is temperature sensitive and may tend to combine with the rubber during the higher temperature sulfur vulcanization of the rubber composition and after the silane group of the coupler has reacted with the silica. However, partly because of typical temperature sensitivity of the coupler, some degree of interaction may occur between the rubber-interaction component of the coupler and the rubber during initial rubber/silica/coupler mixing stage(s) and, thus, prior to the subsequent vulcanization of the rubber composition.

The rubber-interactive reactive group component of the coupler may be, for example, one or more of groups such as mercapto, amino, vinyl, epoxy,

and sulfur groups, preferably a sulfur or mercapto moiety and more preferably sulfur.

Numerous coupling agents may be used to combine silica and rubber

polymer or copolymer, such as, for example, silane coupling agents containing a polysulfide component, or structure such as, for example, bis- (trialkoxysilyalkyl) organosilane polysulfides containing from 2 to about 8 sulfur atoms in a polysulfide bridge such as, for example, bis-(3- triethoxysilylpropyl)tetrasulfide, trisulfide or disulfide. In the case of the disulfide, if in a high purity form, some free sulfur, or sulfur donor, may desirably be added with the coupler in a rubber mixing step to enhance an overall effect of interaction with the elastomer, or rubber.

The composition of the present invention may also contain other synthetic rubbers, and may further contain various chemicals conventionally used in the rubber industry such as process oils, antioxidants, vulcanizing agents, vulcanization auxiliary agents, vulcanization accelerators and scorch inhibitors.

The composition of the present invention may also contain at least one antioxidant. Representative antioxidants may be, for example, diphenyl-p-

phenylenediamine and others, such as, for example, those disclosed in the \/anderbilt Rubber Handbook (1978), pages 344-346. The composition of the present invention may also contain a wax,

preferably a paraffinic wax.

The composition of the present invention may also contain a fatty acid. An example of a fatty acid is a stearic acid.

The composition of the present invention may also contain other additives that traditionally and optionally may be present in rubber containing compositions, including those compositions specifically intended for use in tires. An example of these other additives include sulfur and inorganic oxides, such as zinc oxides.

The composition of the present invention has a Hardness Shore A as measured by DIN 53505 ranging from 50 to 100, preferably from 60 to 85, most preferably from 65 to 80. The Hardness Shore A may be 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100, including any and all ranges and subranges therein.

The composition of the present invention has a DIN Abrasion as measured by ISO 37 method of less than 110mm³, preferably less than

100mm³. The DIN abrasion of the composition may be greater than 50 mm³.

The composition may have a DIN abrasion of 50, 60, 70, 80, 85, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 , 102, 105, and 110 mm³, including any and

all ranges and subranges therein.

The composition of the present invention has a tensile strength as measured by DIN 53504 of from 10 to 30, preferably from 15 to 25, most preferably from 17 to 21 Mpa. The tensile strength of the composition may be 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, and 30 Mpa, including any and all ranges and subranges therein.

The composition of the present invention has an elongation at break as measured by DIN 53504 of from 200 to 450, preferably from 250 to 425%, most preferably from 300 to 400%. The elongation at break may be 200, 250, 300, 325, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 410, 425, and 450%, including any and all ranges and subranges therein.

The composition of the present invention has a Tension at 300% elongation as measured by DIN 53504 of from 10 to 30, preferably from 12 to 20 Mpa. The Tension at 300% elongation may be 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, and 30 Mpa, including any and all ranges and subranges therein.

The composition of the present invention has a tear resistance as

neasured by DIN 53507 of greater than 5, preferably greater than 10, most preferably greater than or equal to about 15 N/mm. The tear resistance of the

composition may be less than 50. Preferably the tear resistance is in the range of from about 15 to about less than 25 N/mm. The tear resistance may

be 5, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, and 25 N/mm, including any and all ranges and subranges therein.

The composition of the present invention has a tear resistance that is preferably about equal or at least 5% greater than that of a composition that does contain the above-mentioned resin or when compared to compositions containing equivalent amounts of Koresin, for example.

The composition of the present invention has any T₉. The composition of the present invention has a T₉ less than O⁰C, preferably less than 1O⁰C, most preferably less than 20⁰C, and most preferably from -50⁰C to -25⁰C. The T₉ may be -50, -45, -40, -35, -30, -25, -20, -15, -10, -5 and -1⁰C, including any and all ranges and subranges therein.

The composition of the present invention has preferably and/or improved vulcanization when containing the above-mentioned tackifier as

compared to those compositions that do not contain the resin of the present invention and/or that of those compositions containing Koresin. When the composition of the present invention has or improved

vulcanization as measure by tanδ described below and in the attached report, the improvement is at least 5% that of those compositions that do not contain

the resin of the present invention and/or that of those compositions containing Koresin

The presence of the resin with a rubber polymer and/or copolymer in the composition of the present invention is considered herein to be beneficial because of observed viscoelastic properties of the composition such as complex and storage modulus, loss modulus tanδ and loss compliance at different temperature/frequency/strain as hereinafter generally described.

The properties of complex and storage modulus, loss modulus, tanδ and loss compliance are understood to be generally well known to those having skill in such art. They are hereinafter generally described.

The viscoelastic properties of the present invention when used for a compounded rubber blend, such as for a tire tread application, are considered herein as being important. For example, a tanδ property is the ratio of the viscous contribution to the elastic contribution for a viscoelastic rubber

subjected to a dynamic deformation. Such properties are typically represented

in a form of a curve(s) as a plot of tanδ values versus temperature. For a tire with good wet skid resistance, a tread rubber with a tanδ

maximization (a maximization of a tanδ value of a tanδ vs temperature curve)

is desired in a temperature range, or region, of about -45⁰C. to about +1O⁰C. Also, for a tire to have good wet grip, wet skid resistance, it is desired that the composition have a high tanδ between the temperatures of from about 0 to about 3O⁰C. Further, for a tire to have low resistance to rolling and thus provide better gas mileage as discussed above, it is desired that the composition have a low tanδ between the temperatures of from about 60 to about 80 ⁰C.

The composition of the present invention has any tanδ from about 60 to about 8O⁰C. The tanδ from about 60 to about 8O⁰C is less than 0.1400, preferably less than 0.13, more preferably less than about 0.12 and most preferably less than 0.11. For example, at any temperature from about 60 to about 8O⁰C (including about 60, 65, 70, 75, and 8O⁰C), it is preferable that the tanδ of the composition be less than 0.1400, preferably less than 0.13, more preferably less than about 0.12 and most preferably less than 0.11. In a preferred embodiment, the composition contains a terpene phenol resin and has a tanδ at about 6O⁰C of about 0.139 or less, preferably about 0.135 or less, more preferably about 0.128 or less, most preferably about 0.112 or less.

In another preferred embodiment, the composition contains a terpene phenol ^■esin and has a tanδ at about 7O⁰C of about 0.129 or less, preferably about 0.125 or less, more preferably about 0.120 or less, most preferably about

0.115 or less.

The composition of the present invention has any tanδ from about 0 to about 3O⁰C. The tanδ from about 0 to about 3O⁰C is greater than about 0.16, preferably greater than about 0.165, more preferably greater than about 0.17 and most preferably greater than about 0.175. For example, at any temperature from about 0 to about 3O⁰C (including about 0, 5, 10, 15, 20, 25 and 3O⁰C), it is preferable that the tanδ of the composition be greater than 0.1600, preferably greater than 0.165, more preferably less than about 0.17 and most preferably greater than 0.175. In a preferred embodiment, the composition contains a terpene phenol resin and has a tanδ at about 0⁰C of about 0.205 or more, preferably about 0.21 or more, more preferably about 0.22 or more, most preferably about 0.23 or more. In another preferred embodiment, the composition contains a terpene phenol resin and has a tanδ at about 2O⁰C of about 0.166 or more, preferably about 0.169 or more, more preferably about 0.171 or more, most preferably about 0.174 or more.

The composition of the present invention may have a reduced or increased tanδ at 70⁰C as compared to a composition not containing any resin

according to the present invention and/or to a composition containing Koresin in the place of the resin according to the present invention. However, it is

preferable that the composition of the present invention has a tanδ at 7O⁰C that is at least 3%, preferably at least 4%, more preferably at least 5%, most

preferably at least 10% less than the tanδ at 7O⁰C of a composition not

containing any resin according to the present invention and/or to a composition

containing Koresin in the place of the resin according to the present invention.

The composition of the present invention may have a reduced or increased tanδ at 2O⁰C as compared to a composition not containing any resin according to the present invention and/or to a composition containing Koresin in the place of the resin according to the present invention. However, it is preferable that the composition of the present invention has a tanδ at 2O⁰C that is at least 2%, preferably at least 7%, more preferably at least 10%, most preferably at least 15% greater than the tanδ at 2O⁰C of a composition not containing any resin according to the present invention and/or to a composition containing Koresin in the place of the resin according to the present invention.

The composition of the present invention may contain an effective amount of the resin. An effective amount means, for the purposes of herein, an amount of resin that is capable of allowing the composition to obtain any of the above-mentioned preferable performance and physical characteristics. More preferably, an effective amount of resin in the composition allows the

composition to attain the above-mentioned abrasion resistance and tanδ

/alues. Further, a composition containing the effective amount of resin, when

ncorporated into a tire according to the present invention, bestows upon the tire an increased abrasion resistance, an decreased resistance to rolling, and

an increased wet skid resistance or wet grip.

The term "phr" where used herein, and according to conventional practice, refers to parts of a respective material per 100 parts by weight of rubber, or elastomer.

The presence of the tackifier mentioned above with a rubber blend is considered herein to be beneficial because of observed viscoelastic properties of the tread rubber composition such as complex and storage modulus, loss modulus tan. delta and loss compliance at different temperature/frequency/strain as hereinafter generally described. The properties of complex and storage modulus, loss modulus, tan. delta and loss compliance are understood to be generally well known to those having skill in such art. They are hereinafter generally described.

The present invention is explained in more detail with the aid of the following embodiment examples.

EXAMPLES

Example 1

Synthesis of TP 115, a Terpene-Phenol Resin for Tire Tread Formulation

Testing having 115⁰C Softening Point

I. Raw Materials

Alpha pinene, phenol, boron trifluoride, xylene, water, sodium carbonate, and sodium hypophosphite.

II. Procedure

H-A. Dehydration of Solvent and Phenol:

(i) Charge 191 g of xylene to a 1.0 Liter Morton flask equipped with an agitator, a Dean-Stark trap attached to a condenser, and a thermocouple probe assembly with an inlet for nitrogen.

(N) Add 52.5 g of phenol to the xylene

(iii) Fill up the DS trap with xylene.

(iv) Place an electric heating mantle under the Morton flask. Begin

heating and bring contents to reflux.

(v) When refluxing begins, any water being removed from the solution

will begin collecting at the bottom in the Dean-Stark trap. Allow

contents to reflux for 2 hours. H-B. Polymerization:

(i) Cool the contents to ambient temperature and charge 1.4-1.5 g of boron trifluoride gas. (ii) The gas will form a complex with phenol and the solution will acquire a red-brown color, (iii) Once the gas has been charged, resume a gentle flow of nitrogen through the flask and gradually begin to warm contents to 67⁰C. (iv) At 67⁰C, begin adding drop-wise 197.5 g of alpha pinene. (v) As the reaction initiates, the temperature in the flask with rise; allow it to rise to 70⁰C and then maintain the entire polymerization process at

70-72⁰C. (vi) Feed the alpha pinene over a period of 2.5 to 3 hours under a nitrogen atmosphere, with agitation, and at 70-72⁰C.

U-C. Neutralization of Catalyst:

(i) Quench the reaction by adding an aqueous solution of sodium

carbonate (1.5 g) and sodium hypophosphite (0.5 g) in 10OmL of water.

(ii) Heat contents to 75-8O⁰C and agitate for 10 minutes.

(iii) Allow layers to separate and draw off the aqueous layer.

(iv) Add 100 imL of water to the reaction flask again and wash the mixture; repeat steps (ii) and (iii) above.

H-D. Distillation and Stripping to Softening point:

Transfer the resin solution to a tared 4-neck round bottom flask. Equip the flask with an agitator, a condenser via a 3-way take-off adapter, a

thermocouple assembly, and a sparge tube for nitrogen sparging. Insert the sparge tube below the surface of the solution and beging nitrogen sparge (~ 2000 cc/min.) Begin agitation and start heating using an electric heating mantle. Distill off the solvent between 140 and 17O⁰C, and continue heating to 245⁰C. When the contents reach 245⁰C, terminate the sparge and maintain a nitrogen purge. Lower heating mantle and draw out a sample (1-2 ml_) of the hot resin for softening point. Obtain a softening point (base s.p.) and resume heating and nitrogen sparge. Continue sparging at 245⁰C to strip out residual terpene-phenol dimers (residual in the TP resin), and sample as needed for s.p. measurements till target s.p. (112-118⁰C) is reached. At target s.p., lower mantle, discontinue nitrogen sparge and pour sample out for color, final softening point, and obtain a final resin yield.

A typical synthesis affords a resin with a softening point of 115⁰C, a neat color of 6-7 Gardner at an overall yield of 85-90%

Example 2

The following Commercial Products: Koresin (from BASF); Sylvalite RE

104 (from Arizona Chemical Company); SLYVARES TR5147 (from Arizona

Chemical Company); SLYVARES TP 105 (from Arizona Chemical Company);

and SLYVARES 525 (from Arizona Chemical Company), were tested

according the DIN standard listed in the table below (DIN Nos: 53505, 53504,

53507), all of which are hereby incorporated, in their entirety, herein by

reference, to test the physical properties thereof (see Table 1 below) when formulated in a rubber composition according to attached report. The tan d

(e.g. tanδ) analysis is described in the report attached hereto. The difference

between the vulcanization presented below and the vulcanization in the attached report is that the vulcanization was performed under conditions

where the 2 mm thick fims have been cured for 17 minutes at 160⁰C in a hot platen press.

W

Table 1. Rubber compositions containing different resins as compared

to Koresin (a standard in the art) and their performances and physical

characteristics.

The compositions of Table 1 are exactly set forth as in the formulation of Table 3, except that a BR Buna® CB 24 is replaced with BR Buna® CB 10.

The tan d (or tanδ) reported above comes from the curve in Figure 1 which is a graph of these rubber formulations tan delta as a function of

temperature when containing the above-mentioned tackifiers.

Example 3

Various Terpene Phenol resins have been compared below in a silica tread rubber compound by mechanical and visco-elastic data. When applied in

quantities of 4 parts resin on 100 part rubber, the Mooney viscosity, the vulcanization behaviour and most of the mechanical do not change significantly. There are significant differences in the visco-elastic behaviour. TP115 shows the best modification of the rubber compound in increasing damping for braking and reducing damping for rolling resistance. While TP95 increases damping in both relevant temperature zones, TP resins with high OH value such as TP300 and TP2040 HME exhibit higher rolling resistance without improving wet braking whereas TP2019 does not show any effect. Average SP of around 105 to 115 with low OH value seems to be an optimum in regard to dynamic tyre properties while high polarity is detrimental especially combined with high softening point.

In addition, the compound containing TP2040HME shows significantly better abrasion resistance than the other resins and the reference.

Surprisingly it was found that a lower softening point Terpene Phenol

resin (Sylvares TP105) was performing similar to an AMS type resin. Terpene phenol resins are known in the industry as tackifier resins, however with much

less tackification effect than Alkylphenol Novolaks and are applied in various

compounds for sidewall, innerliners, or Apex. They are not known as compound modification resin like aliphatic, naphthenic or aromatic (modified)

Hydrocarbon resins from fossil or renewable resources.

In order to verify the effect, a series of terpene phenol resins have been selected and subjected to a comparative study in which a typical silica tread compound was used as matrix and the mechanical data and the visco-elastic data were generated. The resin selection criteria were softening point and polarity expressed by their OH value (See Table.2)

Table 2. Softening point (SP) and OH value of various resins used in to make the rubber compositions.

Experimental: Table 3: Compound compositions used

Compound preparation:

The compounds were prepared in 4 steps with a laboratory internal mixer from Werner&Pfleiderer GK 1.5 E with intermeshing geometry and a laboratory 2

roll mill of Berstorff (150x350 mm). The process parameters were as followed:

Step 1 Basic mixture in internal mixer Filling factor 70%

Pre-set temperature 65°C Rotor speed 60 rpm

Mixing time 6 min.

From 0' to 1' polymers (s-SBR +Br)

1' to 3' ²J₃ Silica, ²/₃ silane, ZnO₁ Stearic acid, Antooxidants, wax, resin

3' to 6' V₃ Silica, V₃ mineral oil T_max (display): approx. 140 ⁰C

Step 2 and Step 3 (Remilling) in internal mixer

Filling factor 70%

Pre-set temperature 65°C

Rotor speed 60 rpm

Mixing time 3 min. T_max Step2 (Display): approx. 130 - 135 ⁰C

T_max Step3(Display): approx. 120 - 125 ⁰C

Step 4 Productive step

Pre-set temperature 65°C Cylinder speed 16:20 rpm Mixing time 7 min.

Vulcanisation was carried out at 160 ⁰C up to t_go in a platen press.

Test methods

All methods were carried out by standardized methods (see table 4 for names of methods)

Results:

In Table. 4 all the relevant data characterising the process-ability (Mooney

viscosity and Vulcametry), mechanical data and data concerning the heat build up and the durability (Flexometer) are shown.

Table 4. All relevant physical and performance data (e.g.Viscosity, vulcanisation, mechanical data and durability data) for compositions containing the resins mentioned above as placed in the composition parameters of Table 3 above.

Method Dim. Reference TP 95 TP105 TP 115 TP 300 TP 2019 TP 2040 HME

Viscosity

Mooney ISO289-1 ML (1+4) 72.80 71.40 59,5 73.70 72.9 70.6 70.2

Vulcanisation

Torque min ISO6502 dNm 3.06 3.21 2,46 2.98 2.99 3.04 2.89

Torque max ISO6502 dNm 22.97 19.93 22,57 23.68 23.27 23.27 23.55

Δ Torque ISO6502 dNm 19.91 23.14 20,11 20.70 20.28 20.38 20.66 tso ISO6502 min 15.11 16.16 14,50 14.58 15.8 15.01 15.53

Mechanical properties Reference TP 95 TP105 TP 115 TP 300 TP 2019 TP 2040 HME

Hardness ISO868 Shore A 69 ± 0.4 68 ± 0.4 66 ± 0,6 68 ± 0.4 69 ± 0,5 70 ± 0,8 70 ± 0,5

Ball Rebound @ RT ISO₄662 32 ± 0.4 30 ± 0.3 31 ± 0,7 30 ± 0.2 30 ± 0,4 29 ± 0,3 29 ± 0,1

Ball Rebound @ 70 °C ISO4662 52 ± 0.3 52 ± 0.6 51 ± 1,0 53 ± 0.5 51 ± 0,7 51 ± 0,7 50 ± 0,5

Δ Ball rebound 20 22 20 23 21 22 21

Tensile Strength ISO37 MPa 20.0 + 1.2 19.1 ± 1.2 19,5 + 1,1 19.5 + 1.6 20,8 ± 1,3 19,8 + 1,2 21,1 ± 0,5

Elongation at break ISO37 % 370 ± 18 365 ± 18 431 ± 18 372 + 24 381 ± 21 383 ± 18 391 ± 9

Tensile Strength @

50% Elongation ISO37 MPa 1.7 ± 0.0 1.7 ± 0.0 1,4 ± 0,0 1.7 ± 0.0 1.7 ± 0.0 1.6 + 0.0 1.7 + 0.0

100% Elongation ISO37 MPa 3,2 ± 0.0 3.2 ± 0.0 2,6 ± 0,0 3.2 ± 0.1 3.3 ± 0.0 3.0 + 0.0 3.2 + 0.1

200% Elongation ISO37 MPa 8.6 ± 0.1 8.3 ± 0.1 6,6 ± 0,0 8.2 ± 0.1 8.7 ± 0.1 8.0 ± 0.1 8.4 ± 0.3

300% Elongation ISO37 MPa 15.3 ± 0.1 14.8 ± 0.1 12,1 ± 0,1 14.8 ± 0.2 15.4 ± 0.1 14.5 + 0.1 15.1 ± 0.4

Tear Resistance ISO37 N/mm 16.1 ± 1,8 17.5 ±1.4 14,9 ± 1,0 16.2 + 1.5 17.1 ± 2.2 17.5 + 2.4 18.0 ± 1.6

DIN Abrasion ISO37 mm3 97 ± 5 94 ± 4 98 + 5 99 + 7 97 ± 2 93 ± 4 90 ± 3

Spec. Density ISO1183-1 g/cm3 1.2049 1.2650 1.1946 1.2063 1.2065 1.2049 1.2065

Flexometer Reference TP 95 TP105 TP 115 TP 300 TP 2019 TP 2040 HME delta T 25 ISO4666 ⁰C 28.8 + 0.4 28.5 ± 0.3 27,2 ± 0,1 28.3 + 0.3 29.1 ± 0.4 28.5 ± 0,5 28.7 ± 0.4

Max Temperature ISO4666 ⁰C 150.2 ± 0.8 149.4 ± 0.3 147,9 ± 0,1 149.5 ± 0.3 150.6 ± 0,7. 149.1 ± 0,5 149.6 ± 0.8

Flow ISO4666 % 2.47 ± 0.23 2.17 ± 0.07 2,98 ± 0,05 2.41 + 0.22 2.63 ± 0.26 2.50 + 0.30 2.23 + 0.16

Permanent set ISO4666 % - 6.62 ± 0.22 - 6.15 ± 0.15 - 6.96 ± 0.10 - 6.40 ± 0.20 - 6.68 ± 0.28 - 6.51 ± 0.30 - 6.24 ± 0.40 Viscoelastic Properties (DMA Measurements)

In Figures 2 and 3. the tan δ curves of the low softening point TP resins are

compared to the reference not containing resin. In Figures 2 and 3, Terpene phenol with approximately the same softening point, but different OH values are compared. As can be clearly seen, TP95 shifts the tan δ upwards in both most interesting temperature ranges, i.e. 0 to + 30 and 60 to 80 ⁰C, without changing the tan δ peak itself either in the height and its temperature position. The higher damping in the 0 to +20 ⁰C temperature represents better wet braking capability, however the increased damping at the 60 to 80 ⁰C temperature range relates to higher rolling resistance which is highly negative. On the contrary, TP115 generates an ideal change of the tan δ curve, higher the wet braking zone and lower in the rolling resistance zone. Also, the peak shift to slightly temperatures is also of interest. The peak height is related to abrasion and wear resistance. All tan δ curves have approx. the same peak height, there should be no difference in abrasion resistance which is confirmed by the DIN abrasion data. The compound containing TP105 has been excluded for reasons explained earlier. The other example of TP105 shown is only added for reference. The data were acquired by earlier work

(DIK05A0386) in which another Butadien rubber (Buna CB 10) was used which is now not anymore available. Therefore the curves cannot be directly

compared. For better clarity the relevant values of tan δ are tabulated in Table 5 which are

represented in Figures 2 and 3.

Table 5 tan δ values at selected temperatures of silica tread compounds

containing 4php resin, for comparison data from the resin SA85 which is already commercialized for this application containing compound is included.

Temp (°C) Reference TP 95 TP105 TP115 TP300 TP2019 TP2040HME SA85

0 0.2130 0.2346 0.2368 0.2421 0.2119 0.2214 0.2084 0.2388

20 0.1657 0.1899 0.1973 0.1777 0.1747 0.1750 0.1730 0.1980

50 0.1263 0.1449 0.1512 0.1249 0.1385 0.1284 0.1367 0.1498

60 0.1177 0.1354 0.1382 0.1149 0.1309 0.1180 0.1271 0.1351

70 0.1111 0.1288 0.1284 0.1051 0.1250 0.1112 0.1231 0.1257

As used throughout, ranges are used as a short hand for describing each and every value that is within the range, including all subranges therein.

Numerous modifications and variations on the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the accompanying claims, the invention may be practiced otherwise than as specifically described herein.

All of the references, as well as their cited references, cited herein are hereby incorporated by reference with respect to relative portions related to the subject matter of the present invention and all of its embodiments

Claims

We claim:

1. A composition, comprising

At least one polymer selected from the group consisting of a rubber polymer or copolymer; and at least one resin.

2. The composition according to Claim 1, wherein the at least one resin is selected from the group consisting of a rosin ester, terpene phenolic resin, terpene phenol, pentaerythritol rosin ester, a modified terpene resin, terpene resin, a polyterpene, and a phenol modified copolymer of styrene and alpha methyl styrene.

3. The composition according to Claim 1, wherein the resin is a terpene phenol resin.

4. The composition according to Claim 1, wherein the resin is a terpene phenol resin having a softening point as determined by Ring & Ball of from 75 to 15O⁰C.

5. The composition according to Claim 1, wherein the resin is a terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 13O⁰C.

6. The composition according to Claim 5, wherein the resin has an OH value of from 5 to 150.

7. The composition according to Claim 5, wherein the resin has an OH value of from 30 to 50.

8. The composition according to Claim 3, wherein the resin has an OH value of from 5 to 150.

9. The composition according to Claim 3, wherein the resin has an OH value of from 30 to 50.

10. The composition according to Claim 9, wherein the resin is a terpene phenol resin having a softening point as determined by Ring & Ball of from 75 to 15O⁰C.

11. The composition according to Claim 9, wherein the composition contains an effective amount of resin.

12. The composition according to Claim 9, wherein the composition further contains at least one filler.

13. The composition according to Claim 9, wherein the composition further contains at least one filler selected from the group consisting of silica, alumina, and carbon black.

14. The composition according to Claim 9, further comprising a coupling agent.

15. The composition according to Claim 14, wherein the coupling agent comprises a silane.

16. The composition according to Claim 9, wherein the composition has an abrasion resistance as measured the DIN Abrasion method ISO37 of from 80 to 100 mm³.

17. The composition according to Claim 9, wherein the composition has an abrasion resistance as measured the DiN Abrasion method ISO37 of from 80 to 100 mm³, a tanδ at 7O⁰C of about 0.129 or less, and a tanδ at 2O⁰C of about 0.205 or more.

18. The composition according to Claim 9, wherein the composition has an abrasion resistance as measured the DIN Abrasion method ISO37 of from 80 to 100 mm³; a tanδ at 7O⁰C that is at least at least 5%less than the tanδ at 7O⁰C of a composition not containing any resin; and has a tanδ at 2O⁰C that is at least 5% greater than the tanδ at 2O⁰C of a composition not containing any resin.

19. A tire, comprising

A tread composition wherein the tread composition contains at least one rubber polyer, at least one rubber copolymer, or mixtures thereof, and an effective amount of at least one terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 13O⁰C and having a OH value of from 30 to 50; the tread composition having an abrasion resistance as measured by the DIN Abrasion method ISO37 of from 80 to 100 mm³, a tanδ at 7O⁰C of about 0.129 or less, and a tanδ at 2O⁰C of about 0.205 or more, wherein

the tire has a reduced resistance to rolling and an increased wet skid

resistance.

20. A tire, comprising

A tread composition wherein the tread composition contains at least one rubber polyer, at least one rubber copolymer, or mixtures thereof, and an effective amount of at least one terpene phenol resin having a softening point as determined by Ring & Ball of from 90 to 13O⁰C and having a OH value of from 30 to 50; the tread composition having an abrasion resistance as measured the DIN Abrasion method ISO37 of from 80 to 100 mm³; a tanδ at 7O⁰C that is at least at least 5%less than the tanδ at 7O⁰C of a composition not containing any resin; and has a tanδ at 2O⁰C that is at least 5% greater than the tanδ at 2O⁰C of a composition not containing any resin, wherein the tire has a reduced resistance to rolling and an increased wet skid resistance.