COMPOSITION COMPRISING ESTERS

Abstract

The present invention relates to a composition for use as a plasticizer composition in a formulation for a tire or a technical rubber good or for use as an extender oil for decreasing the mooney-viscosity and/or the glass transition temperature (T.sub.g) of a polymer composition and its corresponding use. The invention also relates to the use of one or more than one ester as well as a process of preparing a formulation for making a tire or a technical rubber good or making a tire or a technical rubber good or preparing a polymer composition having a decreased mooney-viscosity. Moreover, the invention also relates to a formulation for making a tire or a technical rubber good and a corresponding tire or to technical rubber good.

Claims

1. Composition for use as a plasticizer composition in a formulation for a tire or a technical rubber good or for use as an extender oil for decreasing the moony-viscosity and/or the glass transition temperature (T.sub.g) of a polymer composition, wherein the composition comprises as ingredients one or more than one ester selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters, and one or more than one resin selected from the group consisting of coumarone-indene resins, petroleum hydrocarbon resins and phenol formaldehyde resins, wherein the total amount of said esters and said resins is above 80% by weight, based on the total amount of the composition.

2. Composition according to claim 1, wherein the total amount of said esters selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters, and said resins is above 90% by weight, preferably above 95% by weight, based on the total amount of the composition.

3. Composition according to claim 1, wherein the proportion of the total amount of said esters selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters is 40% by weight or lower, based on the total amount of said esters and said resins, preferably 30% by weight or lower, more preferably in the range of from 10 to 25% by weight.

4. Composition according to claim 1, wherein said one or at least one of said more than one esters selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters is a compound of formula (I) ##STR00004## wherein R1 is a substituted or unsubstituted aryl radical having a total number of 22 carbon atoms or less, preferably having a total number of 10 carbon atoms or less, preferably selected from the group consisting of substituted and unsubstituted phenyl, or a substituted or unsubstituted, branched or linear, alkyl radical having a total number of 22 carbon atoms or less, preferably selected from the group consisting of ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and benzyl, more preferably 2-ethyl-hexyl, and R2 is a substituted or unsubstituted, branched or linear, saturated or unsaturated aliphatic hydrocarbon radical having a total number of 21 carbon atoms or less, preferably a linear, saturated or unsaturated aliphatic hydrocarbon radical having 21 carbon atoms or less, more preferably a linear, unsaturated aliphatic hydrocarbon radical having 21 carbon atoms or less and one, two or three double bonds, wherein R2 most preferably is a linear, unsaturated aliphatic hydrocarbon radical having 17 carbon atoms or less and one double bond.

5. Composition according to claim 1, wherein said one or at least one of said more than one esters selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters is a compound of formula (I) ##STR00005## wherein R1 is a substituted or unsubstituted, branched or linear, alkyl radical having a total number of 22 carbon atoms or less, preferably selected from the group consisting of ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and benzyl, more preferably 2-ethylhexyl, and R2 is a substituted or unsubstituted, branched or linear, saturated or unsaturated aliphatic hydrocarbon radical having a total number of 21 carbon atoms or less, preferably a linear, saturated or unsaturated aliphatic hydrocarbon radical having 21 carbon atoms or less, more preferably a linear, unsaturated aliphatic hydrocarbon radical having 21 carbon atoms or less and one, two or three double bonds, wherein R2 most preferably is a linear, unsaturated aliphatic hydrocarbon radical having 17 carbon atoms or less and one double bond.

6. Composition according to claim 1, wherein said one or at least one of said more than one fatty acid alkyl esters is selected from the group consisting of alkyl arachidonate, alkyl linoleate, alkyl linolenate, alkyl laurate, alkyl myristate, alkyl oleate, alkyl caprate, alkyl oleate, alkyl stearate, alkyl palmitate, alkyl caprylate alkyl caproate, alkyl butyrate, and alkyl behenate, preferably the one or at least one of said more than one fatty acid alkyl esters is 2-ethylhexyl oleate.

7. Composition according to claim 1, obtainable by mixing with the other ingredient(s) of the composition one or more than one resin having a softening point according to ASTM D3461-14 in the range of from 5 to 50 C., preferably in the range of from 20 to 35 C., and being selected from the group consisting of coumarone-indene resins, petroleum hydrocarbon resins and phenol formaldehyde resins.

8. Composition according to claim 7, obtainable by mixing with the other ingredient(s) of the composition one or more than one resin having a softening point according to ASTM D3461-14 in the range of from 5 to 50 C., preferably in the range of from 20 to 35 C., and being selected from the group consisting of coumarone-indene resins and petroleum hydrocarbon resins.

9. Composition according to claim 1, comprising 2-ethylhexyl oleate, and one or more than one resin selected from the group consisting of coumarone-indene resins and petroleum hydrocarbon resins, wherein the total amount of 2-ethylhexyl oleate and said resins selected from the group consisting of coumarone-indene resins and petroleum hydrocarbon resins is above 95% by weight, based on the total amount of the composition, and wherein the proportion of the total amount of said 2-ethylhexyl oleate is 35% by weight or lower, based on the total amount of said 2-ethylhexyl oleate and said resins, wherein the proportion of the total amount of said 2-ethylhexyl oleate is more preferably in the range of from 10 to 25% by weight.

10. Method of a composition according to claim 1 (i) as an extender oil for decreasing the mooney-viscosity of a polymer composition and/or (ii) as an extender oil for decreasing the glass transition temperature (T.sub.g) of a polymer composition and/or (iii) as a plasticizer composition in a formulation for a tire or a technical rubber good, preferably in a formulation for a tire comprising one or more fillers selected from the group consisting of silica and carbon black.

11. (canceled)

12. Process of (a) preparing a formulation for making a tire or a technical rubber good or (b) making a tire or a technical rubber good or (c) preparing a polymer composition having a decreased mooney-viscosity and/or glass transition temperature (T.sub.g), the process comprising the following steps: providing one or more than one ester selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters, providing one or more than one resin selected from the group consisting of coumarone-indene resins, petroleum hydrocarbon resins and phenol formaldehyde resins, mixing said one or more than one esters and said one or more than one resin selected from the group consisting of coumarone-indene resins, petroleum hydrocarbon resins and phenol formaldehyde resins with further ingredients, and wherein the process comprises: preparing a composition according to claim 1 by pre-mixing said one or more than one ester selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters with said one or more than one resin selected from the group consisting of coumarone-indene resins, petroleum hydrocarbon resins and phenol formaldehyde resins, mixing said composition with said further ingredients.

13. Process according to claim 12, wherein one or more of said further ingredients are selected from the group consisting of natural and synthetic rubbers, reinforcing filler, non-reinforcing filler, vulcanization accelerators, pigments, antioxidants, antiozone waxes, cross-linking agents, organic or inorganic coloring agents, activators, and silane coupling agents, wherein said reinforcing filler or said non-reinforcing filler is preferably selected from the group consisting of silica and carbon black.

14. Formulation for making a tire or a technical rubber good, obtainable by a process according to claim 12.

15. Tire or technical rubber good, obtainable by a process according to claim 12 and preferably additionally comprising one or more further ingredients selected from the group consisting of natural and synthetic rubbers, reinforcing filler, non-reinforcing filler, vulcanization accelerators, pigments, antioxidants, antiozone waxes, cross-linking agents, organic or inorganic coloring agents, activators, and silane coupling agents, wherein said reinforcing filler or said non-reinforcing filler is preferably selected from the group consisting of silica and carbon black.

Description

EXAMPLES

[0155] Determination Methods

[0156] 1. Cure Characteristics

[0157] The cure characteristics (e.g. the curing times T50, t90 and the parameter Fmin-Fmax [dNm]) were determined at 170 C. according to DIN 53529 (part 3) by using, for example, an Alpha Technologies Rheometer MDR 2000.

[0158] 2. Mooney Viscosity

[0159] The mooney viscosity (e.g. parameters I-Value [MU] and ML (1+4) [MU]) was determined according to DIN 53523/3 at 100 C. by using, for example, a Rubber Process Analyzer MV 2000.

[0160] 3. Hardness

[0161] The hardness was determined before and after ageing the samples in air for 70 h at 100 C. according to DIN ISO 7619-1 by using, for example, a Zwick 3114/5 (Shore A).

[0162] 4. Mechanical Properties

[0163] The mechanical properties (elongation at break, tensile strength, 100% Modulus and 200% Modulus) were determined according to DIN 53504 (by using a Zwick tensile test machine, for example, a Zwick 5109 or Zwick Z005 mit X-Force HP). The rebound was determined according to DIN 53512 (by using, for example, a Zwick 5109). The tear strength was determined by DIN 34-1:2004.

[0164] 5. Dynamic Properties

[0165] The dynamic properties (for example, tan 60 C. indicating changes in the rolling resistance and tan 0 C. indicating changes in the wet grip) were determined according to DIN 53513 (by using, for example, a Gabo Eplexor 500N).

[0166] 6. Abrasion

[0167] The abrasion was determined according to ISO 4649 by using, for example, a Zwick 6103.

[0168] 7. Ageing Processes

[0169] The ageing processes were conducted in air or in IRM 902 ASTM reference oil (CAS-number: 64742-52-5) at different temperatures for different periods (i.e. ageing time) in a laboratory airing cupboard.

[0170] 8. Glass Transition Temperature

[0171] The glass transition temperature was determined according to ISO 11357-2.

[0172] Chemicals Used: [0173] Rubbers: [0174] (1) Buna VSL 5025-0 HM is a solution styrene-butadiene-rubber (S-SBR) and available from the company ARLANXEO. [0175] (2) Buna SB 1500 is an emulsion styrene-butadiene-rubber (E-SBR) and available from the company ARLANXEO [0176] (3) Bayprene 110 is a neodymium butadiene-rubber and available from the company ARLANXEO, [0177] (4) Bayprene 230 is chlorprene rubbers (CR) and available from the company ARLANXEO, [0178] (5) Buna CB 24 is chlorprene rubbers (CR) and available from the company ARLANXEO, and [0179] (6) Sprintan SLR 4602 is a functionalized styrene-butadiene-rubber (SBR) and available from the company Trinseo. [0180] Silica: [0181] (1) Ultrasil 7000 GR available from Evonik Industries AG; [0182] (2) Hi-Sil 233, [0183] (3) Hi-Sil 210 available from PPG. [0184] Carbon blacks (available from Orion Engineered Carbons) [0185] (1) N 234, [0186] (2) N 330, [0187] (3) N 550. [0188] Silane coupling agent: Si 69 available from Evonik Industries AG. [0189] Zinc oxide: ZnO RS available from Grillo Zinkoxid GmbH. [0190] Magnesium oxide: Elastomag 170 MgO available from Akrochem Corporation. [0191] Stearic acid available from NOF Corporation. [0192] Antiozone wax: Negozone 3457 available from Hansen & Rosenthal KG [0193] TDAE available from Hansen & Rosenthal KG [0194] Antioxidants: [0195] (1) Vulkanox HS available from ARLANXEO: [0196] (2) Vulkanox 4020 available from ARLANXEO: [0197] (3) Rhenofit OCD available from RheinChemie Additives. [0198] Curing Agents: [0199] (i) Vulcanisation accelerators: [0200] (1) Vulkacit CZ available from ARLANXEO; [0201] (2) Vulkacit D available from ARLANXEO; [0202] (3) Rhenogran MTT-80 available from RheinChemie Additives. [0203] (ii) Vulcanisation activator: Rhenogran HPCA-50 available from RheinChemie Additives [0204] (iii) Vulcanisation agent: Rhenogran S-80 available available from Rhein Chemie Additives

[0205] Compositions According to the Invention:

[0206] The following compositions of the invention (see table 1a, entries C4, C5, C6, C7, C8 and C9, below) for the use as plasticizers have been used as such in a formulation for a tire or a technical rubber good (see examples hereinbelow).

[0207] In the case of C5.1 and C7.1, the corresponding formulations (for example F5.1 and F7.1 for the formulation of a silica tire, see below) have not been pre-mixed before they were added in the first step of the corresponding mixing protocol (see TABLE 2 and TABLE 5 below). However, C5 and C5.1 have the same ester/resin ratio and C7 and C7.1 have the same ester/resin ratio.

TABLE-US-00001 TABLE 1a Compositions and ingredients for use as plasticizers or as an extender oil content content composition ester ingredient (wt.-%) resin ingredient (wt.-%) C4 2- 20 petroleum-based hydrocarbon- 80 ethylhexyloleate resin; polymer of aromatic C9-/ C10-hydrocarbons C5 2- 30 petroleum-based hydrocarbon- 70 ethylhexyloleate resin; polymer of aromatic C9-/ C10-hydrocarbons C6 2- 20 coumarone-indene resin; polymer 80 ethylhexyloleate of carbon-based aromatic C9-/ C10-hydrocarbons C7 2- 30 coumarone-indene resin; polymer 70 ethylhexyloleate of carbon-based aromatic C9-/ C10-hydrocarbons C8 1,4-butanediyl- 20 petroleum-based hydrocarbon- 80 (9Z,9Z)-bis(-9- resin; polymer of aromatic C9-/ octadecenoate) C10-hydrocarbons C9 Decahydro-2- 30 petroleum-based hydrocarbon- 70 naphtyl-9- resin; polymer of aromatic C9-/ octadecenoate) C10-hydrocarbons

[0208] The compositions C4 to C9 shown in table 1 can also be used as extender oils.

[0209] Mixing process of formulations for silica tires:

[0210] The investigated tire tread formulations are presented in TABLE 1 (for silica tires) and TABLE 3 (for carbon black tires). The compounds depicted in TABLE 1 were mixed in an internal mixer in accordance with the mixing procedures described in TABLE 2 and the compounds depicted in TABLE 3 were mixed according to the TABLE 5. The curing to agents (Vulcanisation accelerators, Vulcanisation activators and Vulcanisation agent) were added in a two-roll mill at 50 C. The silica tire treads were prepared according to ISO 5794/3. The resulting formulations were vulcanised at the rheometer optimum at 170 C. to give the corresponding silica or carbon black tire.

[0211] The investigated formulations for technical rubber goods are presented in TABLE 4 (axle boots). The compounds were mixed in an internal mixer in accordance with the mixing procedures as described in TABLE 5. The curing agents (Vulcanisation accelerators, Vulcanisation activators and Vulcanisation agent) were added in a two-roll mill at 50 C. The resulting formulations were vulcanised at the rheometer optimum at 170 C. to give the corresponding rubber good (axle boots, rolls and gaskets, or hoses).

TABLE-US-00002 TABLE 1 Ingredients (including composition according to the invention) of formulations for silica tires phr (parts per hundred rubber) Ingredients F1 F2 F4 F5 F5.1* F6 F7 F7.1* F8 F9 Rubber 1 100 0 100 100 100 100 100 100 0 0 Rubber 6 0 100 0 0 0 0 0 0 100 100 Silica 1 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 Silane coupling 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 agent Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Antioxidant 1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Antioxidant 2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Vulcanisation 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 accelerator 1 Vulcanisation 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 accelerator 2 Vulcanisation 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 agent TDAE 37.5 37.5 C4 37.5 37.5 C5 37.5 37.5 37.5 C6 37.5 C7 37.5 37.5 *ester and resin have not been pre-mixed before they mixing protocol 1 below). Thus, both ingredients (ester and resin) were separately added into the mill and not as a composition.

TABLE-US-00003 TABLE 2 Mixing steps for silica tire compounds (including composition according to the invention) First step: internal mixer, 60 C., 100 rpm.sup.a) Mixing sequence 0.0 min rubber 1 1.0 min silica 1 + silane coupling agent 2.0 min silica 1 + silane coupling agent + composition.sup.b) 4.0 min Zinc oxide + Stearic acid 5.0 min sweep 6.0 min dump Second step (after 24 h at 23 C.): internal mixer, 60 C., 140 rpm.sup.a) Mixing sequence 0.0 min mix from the first step 5.0 min dump Third step (after 24 h at 23 C.): open mill, 20 C., 10/10 rpm.sup.a) Mixing sequence 0.0 min vulcanisation agents and accelerators 6.0 min cross blend and sheet off .sup.a)rpmrotation per minute .sup.b)TDAE, C4, C5, C6, C7,

[0212] Mixing process of formulations for carbon black tires and for technical rubber goods:

TABLE-US-00004 TABLE 3 Ingredients (including composition according to the invention) of formulations for carbon black tires phr (parts per hundred rubber) Ingredients B1 B4 B5 B6 B7 B8 B9 Rubber 2 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Carbon black 1 60.0 60.0 60.0 60.0 60.0 60.0 60.0 Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Antioxidant 1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Antioxidant 2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Vulcanisation 1.8 1.8 1.8 1.8 1.8 1.8 1.8 accelerator 1 Vulcanisation 2.0 2.0 2.0 2.0 2.0 2.0 2.0 accelerator 2 Vulcanisation 1.5 1.5 1.5 1.5 1.5 1.5 1.5 agent TDAE 37.5 C4 37.5 C5 37.5 C6 37.5 C7 37.5 C8 37.5 C9 37.5

TABLE-US-00005 TABLE 4 Ingredients (including composition according to the invention) of formulations for technical rubber goods (axle boots) phr (parts per hundred rubber) Ingredients AB1 AB4 AB5 AB6 AB7 Rubber 3 100.0 100.0 100.0 100.0 100.0 Carbon black 2 50.0 50.0 50.0 50.0 50.0 Zinc oxide 2.0 2.0 2.0 2.0 2.0 Stearic acid 0.5 0.5 0.5 0.5 0.5 Antioxidant 3 2.0 2.0 2.0 2.0 2.0 Vulcanisation accelerator 3 1.0 1.0 1.0 1.0 1.0 Vulcanisation activator 4.2 4.2 4.2 4.2 4.2 TDAE 25.0 C4 25.0 C5 25.0 C6 25.0 C7 25.0

TABLE-US-00006 TABLE 5 Mixing steps for carbon black tire or for a technical rubber goods (including composition according to the invention) First step: internal mixer, 50 C., 50 rpm.sup.a) Mixing sequence 0.0 min rubber.sup.b) 2.0 min carbon black + composition.sup.c) 3.0 min carbon black + composition.sup.c) 5.0 min Zinc oxide + Stearic acid 7.0 min sweep 10.0 min dump Second step (after 24 h at 23 C.): open mill, 20 C., 10/10 rpm.sup.a) Mixing sequence 0.0 min vulcanisation agents and accelerators 6.0 min cross blend and sheet off .sup.a)rpmrotation per minute .sup.b)Rubber 2, 3, 4, 5 .sup.c)TDAE, composition C4, composition C5, composition C6, composition C7, composition C8 or composition C9 for carbon black tires and TDAE, composition C4, composition C5, composition C6 or composition C7 for technical rubber goods (axle boots)

Example 1 (Silica Tires)

[0213] Example 1 shows a comparative evaluation of seven formulations for a silica tire and of the corresponding resulting silica tires of such formulations prepared with either TDAE (as reference) or different compositions according to the invention. The formulation F1 comprised the reference oil TDAE; the other six formulations comprised compositions according to the invention. The same amount of TDAE oil or of a composition according to the invention was added to the other ingredients of the formulation for silica tires as described in table 1 above. The obtained formulations were mixed and vulcanized as described in TABLE 2 above. The results of the cure characteristics of the different resulting formulations as well as the hardness before and after ageing, the mechanical and dynamical properties, and abrasion loss of the corresponding resulting tires are summarized in TABLE 6 below.

TABLE-US-00007 TABLE 6 Silica formulations F1* F4 F5 F5.1 F6 F7 F7.1 Cure characteristics of silica tire formulations T50 [min] 4.5 3.8 3.8 3.5 3.5 3.7 3.7 t90 [min] 17.2 17.3 17.3 16.6 16.4 17.1 17.8 Fmax-Fmin [dNm] 13.8 12.4 12.4 12.6 12.3 12.4 12.5 Properties of resulting silica tires Hardness [Shore A] at 23 C., before ageing 57 58 58 54 57 57 54 after ageing for 70 h at 100 C. 60 60 61 57 58 58 57 Mechanical properties Rebound [%] 16 14 19 18 16 21 20 Elongation at break [%] 260 240 260 330 300 290 300 Tensile strength [MPa] 12.1 16.7 16.6 18 18.2 16.7 16.3 100% Modulus [MPa] 2.5 3.7 3.1 2.3 2.8 2.8 2.4 200% Modulus [MPa] 8.0 12.9 10.9 8.0 9.7 9.3 8.5 Dynamic properties Rolling resistance: Tan 60 C. 0.100 0.064 0.063 0.0814 0.072 0.071 0.081 Tan 60 C., Normalized 100 64 63 81 72 71 81 Change [%] 0 +36 +37 +19 +28 +29 +19 Wet grip: Tan 0 C. 0.841 1.071 0.830 0.826 0.963 0.668 0.670 Tan 0 C., Normalized 100 127 98 98 115 79 79 Change [%] 0 +27 2 2 +15 21 21 Abrasion loss [mm.sup.3] 152 128 132 n.d. 128 129 n.d. *reference: with TDAE as plasticizer; n.d. = not determined

[0214] The measurements of the mechanical properties of a tire of the present invention showed that all compositions according to the present invention (C4, C5, C6, C7) improved the tensile strength of the resulting silica tire compared to a silica tire prepared with TDAE. The following improvements in terms of tensile strength were observed [0215] 38% for silica tires prepared with formulation F4, [0216] 37% for silica tires prepared with formulation F5, [0217] 50% for silica tires prepared with formulation F6 [0218] and [0219] 38% for silica tires prepared with formulation F7,
in each case compared to a silica tire prepared with TDAE (see formulation F1 in table 6).

[0220] A higher tensile strength indicates a better filler dispersion and therefore a better filler polymer interaction, which is leading to better final properties of the tire, as for example tensile strength.

[0221] An advantage of the formulations F5 and F7 comprising premixed compositions C5 and C7, respectively, are the higher values for the 100% Modulus and 200% Modulus, in comparison with F5.1 and F7.1.

[0222] The use of compositions C4, C5, C6 and C7 of the present invention (in the corresponding formulations) caused a significant increase in the 100% Modulus and 200% Modulus as well as a decrease of the rolling resistance (Tan 60) of the resulting tires in comparison with tires prepared with TDAE (silica formulation F1).

[0223] TABLE 6 also shows the comparison between two key parameters often used in the tire industry to predict compound performance, rolling resistance and wet grip, namely tan 60 C. and tan 0 C. Lower tan 60 C. indicates a lower rolling resistance and a higher tan 0 C. is indicative for a better wet grip.

[0224] As shown in TABLE 6, formulations according to the invention improved (i.e. decreased) the tan 60 C. to a large extent. Generally, the pre-mixed compositions improved overall properties if compared with the not pre-mixed compositions. formulation F4 (resin and fatty acid ester were pre-mixed) improved the tan 60 C. of the resulting silica tire by +36%,

formulation F5 (resin and fatty acid ester were pre-mixed) by +19%,
formulation F6 (resin and fatty acid ester were pre-mixed) by +28%
and
formulation F7 (resin and fatty acid ester were pre-mixed) by +29%,
in each case in comparison to the tan 60 C. values of silica tires prepared with TDAE (see formulation F1 in table 6). Thus, pre-mixing ester and resin is advantageous.

[0225] Additionally, formulations F4 and F6 according to the invention drastically improved the tan 0 C. Formulation F4 increased (i.e., improved) the tan 0 C. by +27%, formulation F6 by +15. Formulations F4 and F6 comprise compositions C4 and C6, wherein the proportion of the total amount of esters selected from the group consisting of fatty acid alkyl esters and fatty acid aryl esters is in the range of from 10 to 25% by weight, based on the total amount of said compositions (consisting of ester ingredient and resin ingredient).

[0226] Furthermore, a decreased abrasion loss was measured for tires prepared with formulations F4, F5, F6 and F7 comprising premixed compositions. Lower values for abrasion loss were obtained for tires prepared with premixed compositions of the invention in comparison with the reference tire (see formulation F1) prepared with TDAE (see last row of Table 6). Moreover, the hardness of the comparative tire and tires of the invention was not changed significantly.

[0227] Thus, silica tires made with a formulation of the present invention have superior properties in comparison with a reference formulation using TDAE as plasticizer composition.

Example 2 (Carbon Black Tires)

Formulations B4 to B7 (as Examples for Formulations of the Invention)

[0228] Example 2 shows a comparative evaluation of five formulations for carbon black tires and the corresponding resulting carbon black tires of such formulations prepared with either TDAE (as reference) or different compositions according to the invention. The formulation B1 contained the reference oil TDAE; the other four formulations contained compositions according to the invention. The same amount of TDAE oil or of a composition according to the invention was added to the other ingredients of the formulation for silica tires as described in table 3 above. The obtained formulations were mixed and vulcanized as described above in TABLE 5 above. The results of the cure characteristics of the different formulations and the hardness before and after ageing, the mechanical and dynamical properties of the corresponding resulting tires are summarized in TABLE 7 below.

TABLE-US-00008 TABLE 7 Carbon black tire formulations B1* B4 B5 B6 B7 Cure characteristics of carbon black tire formulations T50 [min] 1.6 1.0 1.1 0.9 1.0 t90 [min] 2.9 1.7 1.8 1.6 1.6 Fmax-Fmin [dNm] 9.1 6.9 7.0 6.8 6.7 Properties of resulting carbon black tires Hardness [Shore A] at 23 C., before ageing 50 47 48 49 46 after ageing for 70 h at 55 55 54 56 55 100 C. Mechanical properties Rebound [%] 37 38 39 38 38 Elongation at break [%] 710 790 800 780 790 100% Modulus [MPa] 1.1 0.9 0.8 0.8 0.9 Dynamic properties Rolling resistance: Tan 60 C. 0.307 0.320 0.288 0.301 0.295 Tan 60 C., 100 104 94 98 96 Normalized Change [%] 0 4 +6 +2 +4 Wet grip: Tan 0 C. 0.236 0.268 0.264 0.274 0.276 Tan 0 C., 100 113 112 116 117 Normalized Change [%] 0 +13 +12 +16 +17 *reference: with TDAE as plasticizer

[0229] As indicated in TABLE 7 for carbon black tires made according to a process of the present invention, the hardness before and after ageing and the mechanical properties were not significantly affected by the use of compositions of the present invention in comparison to carbon black tires prepared with TDAE as plasticizer composition (formulation F1).

[0230] However, the experimental results depicted in TABLE 7 clearly show that compositions of the present invention improved significantly the wet grip (tan 0 C.) as well as the rolling resistance (tan 60 C.) of all carbon black tires made according to a process of the present invention (see formulations B4 to B7 in TABLE 7) in comparison to carbon black tires prepared with TDAE as plasticizer composition.

[0231] Formulation B4 (resin and fatty acid ester were pre-mixed) improved the tan 0 C. of the resulting silica tire by +13%,

formulation B5 (resin and fatty acid ester were pre-mixed) by +12%,
formulation B6 (resin and fatty acid ester were pre-mixed) by +16%
and
formulation B7 (resin and fatty acid ester were pre-mixed) by +17%, in each case in comparison to the tan 0 C. of silica tires prepared with TDAE (see formulation B1 in table 7).

[0232] Thus, carbon black tires made with a formulation of the present invention have superior properties in comparison with state-of-the-art formulations using TDAE as plasticizer composition.

Formulations B8 and B9 (as Examples of Formulations of the Invention):

[0233] Similar results were obtained when the carbon black tires were prepared with the compositions B8 and B9 comprising esters different from 2-ethylhexyloleate. The results for the rolling resistance (tan 60 C.) and the wet grip (tan 0 C.) are shown in TABLE 8 and TABLE 9.

TABLE-US-00009 TABLE 8 Dynamic properties of resulting carbon black tires Carbon black tire formulations Rolling resistance: B1 (reference) B8 B9 Tan 60 C. 0.307 0.301 0.305 Tan 60 C., Normalized 100 98 99 Change [%] 0 +2 +1

TABLE-US-00010 TABLE 9 Dynamic properties of resulting carbon black tires Carbon black tire formulations wet grip: B1 (reference) B8 B9 Tan 0 C. 0.236 0.256 0.245 Tan 0 C., Normalized 100 108 104 Change [%] 0 +8 +4

[0234] The rolling resistance of carbon black tires prepared with the formulations B8 and B9 were decreased (i.e. improved) by 2% compared to a carbon black tire prepared with TDAE as plasticizer composition.

[0235] The wet grip of carbon black tires prepared with the formulations B8 and B9 were increased by +8%, respectively +4% compared to a carbon black tire prepared with TDAE as plasticizer composition.

Example 3 (Technical Rubber Goods-Axle Boots)

[0236] Example 3 shows a comparative evaluation of five formulations for technical rubber goods and the corresponding resulting technical rubber goods, both prepared with either TDAE or a composition AB4, AB5, AB6 and AB7 according to the invention. The formulation AB1 contained the reference oil TDAE; the other four formulations contained compositions according to the invention. The same amount of TDAE oil or of a composition according to the invention was added to other ingredients of the formulation for silica tires as described in table 4 above. The obtained formulations were mixed and vulcanized as described above in TABLE 5 above. The results of the cure characteristics of the different formulations and the hardness before and after ageing, the mechanical and dynamical properties of the corresponding resulting tires are summarized in TABLE 10 below.

TABLE-US-00011 TABLE 10 Formulations for technical rubber goods (axle boots) AB1* AB4 AB5 AB6 AB7 Cure characteristics of formulations for technical rubber goods (axle boots) T50 [min] 4.2 3.7 3.8 3.6 3.8 T90 [min] 15.6 15.7 15.5 15.5 15.7 Fmax-Fmin [dNm] 11.8 11.6 11.6 11.5 11.6 Properties of resulting technical rubber goods (axle boots) Hardness [Shore A] at 23 C., before ageing 61 61 61 63 62 after ageing in hot air for 72 h at 62 64 64 65 65 120 C. Change in hardness [%] +2 +5 +5 +3 +5 Mechanical properties Tear strength [N/mm] 16 24 18 19 13 Elongation at break [%] at 23 C., before ageing 370 370 380 370 370 after ageing in hot air for 72 h at 360 400 390 400 390 120 C. Change in elongation[%] 3 +8 +3 +8 +5 100% Modulus [MPa] at 23 C., before ageing 2.7 2.9 2.7 2.9 2.8 after ageing in hot air for 72 h at 3.0 3.0 2.9 3.0 2.9 120 C. Change in 100% Modulus [%] +11 +3 +7 +3 +4 Tensile strength [MPa] at 23 C., before ageing 17.8 18.3 17.7 18.2 18.2 after ageing in hot air for 72 h at 18.0 20.0 19.2 20.0 19.0 120 C. Change in Tensile strength [%] +1 +9 +8 +10 +6 *reference: with TDAE as plasticizer

[0237] The results set forth in TABLE 10 show that the use of compositions of the present invention in a formulation for a technical rubber good increases the tear strength of the obtained technical rubber good (i.e. axle boots as in TABLE 10 above) due to an improved polymer network. This is also indicated by the 100% Modulus which is very low after ageing in hot air in comparison to axle boots prepared with TDAE.

[0238] Additionally, and in comparison with aged technical rubber goods prepared with TDAE as plasticizer composition, the elongation at break of aged technical rubber goods is increased (i.e. improved) when compositions of the present invention are present in a formulation for the technical rubber good.

[0239] The use of compositions of the invention in a formulation for a technical rubber good improves the technical properties of aged technical rubber goods by having a lower 100% Modulus compared to an aged technical rubber good reference. As a consequence, the life time of the technical rubber goods of the present invention (i.e. comprising a formulation of the present invention) is increased.

Example 4 (Use of a Composition of the Invention as Extender Oil)

[0240] Tables 13 and 14 show the values of the resulting mooney viscosity after the addition of [0241] (i) composition C7 (as an example of a composition of the invention) [0242] or [0243] (ii) TDAE (as a comparative example)
to different rubbers. Composition C7 was added to NR (resulting in a NR mixture), ENR 25 (resulting in a ENR 25 mixture) and Buna VSL 5025-0 HM (resulting in a Buna VSL 5025-0 HM mixture), see tables 13 to 14.

[0244] The addition of compositions of the invention decreases the mooney viscosity of the resulting mixture due to the plasticizing effect of the compositions of the invention. This indicates a better compatibility or interaction of the compositions of the invention with the polymer chains.

[0245] Tables 13 and 14 illustrate that the addition of a composition of the invention to polymer compositions decreases the mooney viscosity of the resulting compositions to a larger extent than the addition of the bench mark plasticizer (TDAE).

TABLE-US-00012 TABLE 13 Mooney Viscosity (MUmooney Unit) as influenced by addition of composition C7 mooney viscosity of amount mooney viscosity mooney viscosity Buna VSL of composition of NR of ENR 25 mixture 5025-0 HM C7 [phr] mixture [MU] [MU] mixture [MU] 0 47 45 69 10 38 33 41 30 23 19 19 50 14 12 11 70 10 7 7

TABLE-US-00013 TABLE 14 Mooney Viscosity (MUmooney Unit) by addition of composition TDAE mooney viscosity of Buna amount of mooney viscosity mooney viscosity VSL 5025-0 composition of NR of ENR 25 mixture HM mixture C7 [phr] mixture [MU] [MU] [MU] 0 47 45 69 10 40 40 52 30 25 22 27 50 18 13 16 70 12 8 10

[0246] Without wishing to be bound to any theory, it is believed that by the addition of compositions of the invention to a rubber mixture, the free volume in the system and the polymer chain mobility increase while the intermolecular forces between the chains decrease [see also J. A. Brydson, Rubber Materials Elsevier Applied Science, New York, 1988]. Therefore, a drop in glass transition and viscosity of the mixture will occur associated with changes in rheological and physical properties of the rubber melts as well as of the corresponding cured materials [see also G. R. Hamed, Rubber Chem. Technol., 54 (1981) 576]. The glass transition temperature of the resulting mixture comprising the rubber and a composition of the invention decreases until the phase separation is reached (see Table 15 and Table 16).

[0247] The compatibility of compositions of the invention with different rubbers was investigated by studying how the addition of different amounts of compositions of the invention to different rubber mixtures as defined in table 15 effects the glass transition temperature of the resulting rubber mixture.

[0248] An analogous experiment was done with TDAE of which the results are shown in table 16.

[0249] The results of are shown in tables 15 and 16.

TABLE-US-00014 TABLE 15 Glass transition (in C.) as influenced by addition of composition C7 of the invention amount of composition T.sub.g of NR T.sub.g of ENR 25 T.sub.g of Buna VSL 5025-0 C7 [phr] mixture ( C.) mixture ( C.) HM mixture ( C.) 0 63 40 19 10 67 47 35 30 73 59 50 50 73 69 64 70 74 68 78

[0250] The data of table 15 shows that the addition of composition C7 of the invention to a rubber mixture results in a decrease in the glass transition temperature.

[0251] The strongest decrease in the glass transition temperature was observed for the rubber mixture Buna VSL 5025-0 HM mixture by 59 C. (compare first value in the last column of table 15 with the last value in the last column of table 15).

TABLE-US-00015 TABLE 16 Glass transition (in C.) by addition of composition TDAE amount of composition T.sub.g of NR T.sub.g of ENR 25 T.sub.g of Buna VSL 5025- TDAE [phr] mixture ( C.) mixture ( C.) 0 HM mixture ( C.) 0 63 40 19 10 63 39 20 30 62 41 25 50 61 43 27 70 61 43 30

[0252] An addition of the composition C7 up to 30 phr into the NR rubber lowers the T.sub.g of the resulting mixture by 10 C., while a similar addition of TDAE leads to unchanged glass transition temperature (compare second column of table 15 with first column of table 16).

[0253] An addition of the composition C7 up to 50 phr into the ENR 50 lowers the T.sub.g of the resulting mixture by 19 C. while an similar addition of TDAE lowers the glass transition temperature by only 3 C. (compare third column of table 15 with third column of table 16).

[0254] An addition of the composition C7 up to 70 phr into Buna VSL 5025-0 HM mixture lowers the T.sub.g of the resulting mixture by 59 C. while a similar addition of TDAE lowers the glass transition temperature by only 11 C. (compare fourth column of table 15 with fourth column of table 16).

[0255] These results show that compositions of the invention are very compatible with rubbers and can be used as extender oils for decreasing the mooney-viscosity and the glass transition temperature T.sub.g of polymers compositions. In particular, the resulting drop of the mooney-viscosity and the glass transition temperature T.sub.g due to the addition of a composition of the invention is much stronger than the decrease of the mooney-viscosity and the glass transition temperature T.sub.g due to the addition of a TDAE (compare last row of table 15 with last row of table 16).

[0256] Additionally, the strong decrease in glass transition temperature of rubber mixtures as described in table 15 shows that compositions of the invention can be advantageously used in a formulation for making a tire, preferably a winter or snow tire, in order to adjust the corresponding mechanical and dynamic properties of the resulting tire. In particular, flexible tire materials better absorb mechanical shocks and have more contact with the road surface, thus having a better traction.

[0257] Without wishing to be bound by any theory, a measure for the rigidity of a tire is the glass transition temperature of the tire material. The tire material usually is for example a vulcanized rubber mixture or a vulcanized formulation for making a tire according to the invention. The lower the glass transition temperature of an unvulcanized rubber mixture (to be used as a starting material for producing the tire) the lower is the glass transition temperature of the corresponding tire material as produced, i.e. comprising the vulcanized rubber mixture. As a consequence, the temperature, at which the tire becomes rigid (less flexible) and thus brittle, is reduced as well.

[0258] It is thus advantageous to reduce the glass transition temperature of an unvulcanized rubber mixture in order to reduce the glass transition temperature of the corresponding tire material, e.g. a vulcanized formulation of the invention or a vulcanized polymer composition (for an example of a polymer composition see rubber mixtures as in table 15), so that the corresponding tire can be safely used at low temperatures, in particular at temperatures below 0 C. or even below 10 C.

Example 5 (Use of a Composition of the Invention as Extender Oil)

[0259] Example 5 shows a comparative evaluation of three silica tire formulations (F2 (reference), F8 and F9; see table 1 for the concentrations of the different ingredients) containing different compositions as extender oil (TDAE as a reference composition; compositions C4 and C5 according to the invention). Formulation F2 contains the reference oil TDAE. Formulation F8 contains composition C4 according to the invention and formulation F9 contains composition C5 according to the invention. The same amount of oil was added to the other ingredients of the formulation for silica tires as defined in table 4 above.

[0260] The obtained formulations were mixed and vulcanized as described above in TABLE 2. Cure characteristics, hardness before and after ageing, mechanical and dynamical properties, and abrasion tests were conducted on the rubber formulations F2, F8 and F9. The results are summarized in TABLE 17 below.

TABLE-US-00016 TABLE 17 Silica formulations F2 (reference) F8 F9 Cure characteristics of silica tire formulations T50 [min] 4.4 3.0 3.0 t90 [min] 14.9 14.4 14.2 Fmax-Fmin [dNm] 13.8 13.5 13.4 Properties of resulting silica tires Hardness [Shore A] at 23 C., before ageing 55 56 54 after ageing for 70 h at 100 C. 56 58 56 Mechanical properties Rebound [%] 31 29 35 Elongation at break [%] 320 300 290 Tensile strength [MPa] 17.4 18.6 17.3 100% Modulus [MPa] 2.6 2.9 2.9 200% Modulus [MPa] 8.5 9.9 9.8 Dynamic properties Rolling resistance: Tan 60 C. 0.064 0.045 0.049 Tan 60 C., Normalized 0.064 0.064 Change [%] +30 +23 Wet grip: Tan 0 C. 0.572 0.611 0.461 Tan 0 C., Normalized 0.572 0.572 Change [%] +7 19 Abrasion loss [mm.sup.3] 150 143 136

[0261] An overall good performance of compositions according to the invention in SBR functionalized polymer tires (comprising rubber (6) Sprintan SLR 4602 available from the company Trinseo, see above) was observed.

[0262] As in Example 1, the presence of compositions C4 or C5 (compositions of the present invention) in formulations F8 and F9, respectively, reduced the tan 60 C. value (i.e., the rolling resistance) of the obtained tire in comparison with the reference. The presence of composition C4 in formulation F8 reduced the tan 60 C. of the obtained tire by +30% and the presence of composition C5 in formulation F9 reduced the tan 60 C. of the obtained tire by +23%.

[0263] Additionally, the presence of composition C4 in formulation F8 increased the tan 0 C. of the obtained tire by +7%, in comparison with the reference.

[0264] Furthermore, an improved abrasion was measured for tires prepared with formulations F8 and F9, comprising compositions C4 or C5, respectively (see last row of table 17). Lower values of abrasion were obtained in comparison with the reference formulation comprising TDAE at almost unchanged hardness of the tire compounds (see rows 9 and 10 of table 17).