NL2020806B1

NL2020806B1 - Rubber composition for tyres with good wet grip and rolling resistance properties

Info

Publication number: NL2020806B1
Application number: NL2020806A
Authority: NL
Inventors: Markovic Neven; Reuvekamp Louis
Original assignee: Apollo Tyres Global R & D Bv
Priority date: 2018-04-20
Filing date: 2018-04-20
Publication date: 2019-10-28
Also published as: WO2019201790A1

Abstract

The present invention relates to a cross—linkable rubber 5 composition comprising a rubber component and a resin component; wherein the resin component comprises a blend of at least two resins wherein the first resin is a coumarone—indene resin, and the second resin is a resin selected from the group of C5 resins, C9 resins, polyterpene resins, or a mixture thereof; wherein the 10 ratio of the second resin to the coumarone—indene resin is in a range of 2 1:10 to £ 10:1, the ratio referring to the respective weight (w/w).

Description

C08L 9/06 (2018.01) C08L 9/00 (2019.01) C08L 45/02 (2019.01) C08L 57/02 (2019.01) C08K 3/36 (2019.01) B60C 1/00 (2019.01) (© Afsplitsing van aanvraag , ingediend @ Voorrang:

(4A Aanvraag ingeschreven: 28 oktober 2019 (43) Aanvraag gepubliceerd:

oktober 2019 © Octrooischrift uitgegeven:

oktober 2019 © Octrooihouder(s):

Apollo Tyres Global R&D B.V. te Enschede © Uitvinder(s):

Neven Markovic te Enschede Louis Reuvekamp te Enschede © Gemachtigde:

M.A.T. Beck MSc LL.B te Heverlee

54) Rubber composition for tyres with good wet grip and rolling resistance properties

5^ The present invention relates to a cross-linkable rubber composition comprising a rubber component and a resin component; wherein the resin component comprises a blend of at least two resins wherein the first resin is a coumarone-indene resin, and the second resin is a resin selected from the group of C5 resins, C9 resins, polyterpene resins, ora mixture thereof; wherein the ratio of the second resin to the coumarone-indene resin is in a range of > 1:10 to < 10:1, the ratio referring to the respective weight (w/w).

NL B1 2020806

Dit octrooi is verleend ongeacht het bijgevoegde resultaat van het onderzoek naar de stand van de techniek en schriftelijke opinie. Het octrooischrift komt overeen met de oorspronkelijk ingediende stukken.

Rubber composition for tyres with good wet grip and rolling resistance properties

The present invention relates to a cross-linkable rubber composition comprising a rubber component and a resin component, a method of preparing a cross-linkable rubber composition comprising a rubber component and a resin component, a crosslinked rubber composition obtained by cross-linking such a rubber composition, a method of preparing a tyre and a tyre.

Tyre performances are highly dependent on its construction parts. A tyre tread is one of the most important component of a pneumatic tyre. It is the only part of the pneumatic tyre which has to be in contact with a road. Therefore, variety of performances such as wet grip, abrasion resistance and low rolling resistance are dependent on the rubber composition of the tread for a pneumatic tyre.

It is well known in rubber compounding that there is a trade-off between wet grip and rolling resistance. The tread compound can be optimized to exhibit good wet grip by using high Tg polymers like SBR but it normally results in high rolling resistance. On the other hand, tuning the rubber compound by using low Tg polymers like BR to reduce rolling resistance possibly leads to impairment in wet grip. Several types of resins are therefore introduced to increase the wet grip properties but these often have a negative effect on the rolling resistance. In order to obtain high performance tyres, all properties need to be improved simultaneously.

The researchers are constantly in search for new solutions and materials for finding a way to enhance above mentioned properties at a same time. It has been described in the prior art to use resin to improve wet traction. The prior art shows that the higher the concentration of a resin used the better the wet grip evaluated by tan δ at 0°C. Also, resins applied in higher concentration bring high shift of glass transition temperature (Tg) of the compound.

WO2015124681A1 describes a rubber composition based on at least one diene elastomer, a reinforcing filler, a vulcanisation system and a combination of plasticisers, said combination of plasticisers comprising more than 15 phr (parts by weight per hundred parts of elastomer) of hydrocarbonated resin having a glass transition temperature (Tg) of between -40°C and 20°C and a resin having a Tg higher than 20°C, the total amount of plasticiser being higher than, or equal to, 40 phr, and the amounts of reinforcing filler and plasticiser being such that the ratio of the total amount of filler and the total amount of plasticiser ranges between 1.3 and 2.

WO2015124684A1 describes a rubber composition based on at least one diene elastomer, 110 to 160 phr of reinforcing filler, a vulcanisation system and a plasticising system comprising at least one hydrocarbonated resin having a Tg of between -40°C and 20°C, the total amount of plasticiser being higher than, or equal to, 70 phr.

WQ2017001614A1 describes a rubber composition made up of: at least one diene elastomer; 50 to 160 phr of inorganic reinforcement filler; a vulcanisation system; a plasticising system including at least one hydrocarbon resin having a Tg of from -40 °C to 20 °C; as the coupling agent, a hydroxysilane polysulphide having the general formula (I): (HO)a R(3-a) Si— R' — Sx— R'— Si R(3-b) (OH)b where the groups R, which can be the same or different, are hydrocarbon groups preferably comprising 1 to 15 carbon atoms, the groups R', which can be the same or different, are divalent bonding groups preferably comprising 1 to 18 carbon atoms, a and b, which can be the same or different, are equal to 1 or 2, and x is a number no lower than 2; and a primary amine of formula (IV): R-NH2 where R is a straight or branched hydrocarbon group including 8 to 24 carbon atoms, said composition being free from or including less than 0.5 phr of guanidine derivative.

WQ2017001616A1 describes a rubber composition based on at least one diene elastomer, a reinforcing filler, a vulcanisation system and a plasticising system, said reinforcing filler comprising predominantly by weight a very high specific surface area silica, having a CTAB specific surface area greater than 170 m2/g and said plasticising system comprising at least more than 15 phr of a hydrocarbon resin having a Tg between -40°C and 20°C.

Although the wet grip is increased by the use of the resins in the rubber composition for tyres as disclosed by the state of the art, it also increases the rolling resistance which makes its not compatible to be used as a compound for the tread of a summer tyre. Therefore, the object to be achieved by this invention is to provide improvement in wet grip and at the same time in the rolling resistance.

The object is achieved by a cross-linkable rubber composition according to claim 1, a method of preparing a cross-linkable rubber composition according to claim 11, a cross-linked rubber composition according to claim 12, a method for preparing a tyre according to claim 14 and a tyre according to claim 15. Advantageous embodiments are the subject of the dependent claims. They may be combined freely unless the context clearly indicates otherwise .

Accordingly, a cross-linkable rubber composition is provided, the cross-linkable rubber composition comprising a rubber component and a resin component. The resin component comprises a blend of at least two resins wherein o the first resin is a coumarone-indene resin, and o the second resin is a resin selected from the group of C5 resins, C9 resins, polyterpene resins, or a mixture thereof, wherein the ratio of the second resin to the coumaroneindene resin is in a range of h 1:10 to T 10:1, the ratio referring to the respective weight (w/w).

It has surprisingly been found that improved performance of a tyre regarding wet grip and rolling resistance can be provided by such blends of resins. A combination of the second resin and the coumarone-indene resin in a tyre tread compound showed a balanced improvement in the wet grip and the rolling resistance. The amount of resins may be applied instead of oil in the composition.

According to one embodiment of the invention, the rubber component is selected from the group of solution styrene butadiene rubber (SSBR), butadiene rubber (BR) or a mixture thereof. The SSBR rubber component may contain one type of styrene butadiene rubber (SBR) rubber or several different types. Preferably, at least one type of SBR rubber is manufactured according to the solution process (SSBR or solution SBR). Likewise, the BR rubber component may contain one type of BR rubber or several different types.

According to one embodiment of the invention, the amount of the rubber component is, per hundred parts by weight of rubber (phr), in a range of L 1 to T 100 phr.

It is further understood that in formulations discussed in connection with the present invention the phr amount of all rubber components adds up to 100.

The cross-linkable rubber composition according to the invention comprises cross-linkable groups in the individual rubber components. They may be cross-linked (cured, vulcanised) by methods known to a skilled person in the rubber technology field. The cross-linkable rubber compositions may be sulphurvulcanizable and/or peroxide-vulcanizable. Other vulcanization systems may also be used. If desired, additional additives besides TPE can be added. Examples of usual additives are resins, stabilizers, antioxidants, lubricants, fillers, dyes, pigments, flame retardants, conductive fibres and reinforcing fibres. According to one embodiment of the invention, the second resin has an average molecular weight M_w in a range of b 880 g/mol to 4500 g/mol, preferably between 5 1000 g/mol to b 2500 g/mol, more preferably between b 1200 g/mol to 2000 g/mol and most preferably it is A1500 g/mol.

In embodiments, the Coumarone-Indene (CI) resin may have a low or very low softening point, for example of 30°C, and/or the second resin may have a high softening point. A use of resin dual blends comprising low Tg and high Tg may further support a balanced improvement in the wet grip and the rolling resistance.

According to one embodiment of the invention, the second resin is selected from the group of C5 resins with a softening point in a range of b 100 °C to 110°C, C9 resins with a softening point in a range of b 85 °C to 140°C or polyterpene (PT) resins with a softening point in a range of b 105 °C to 125°C (ring and ball method according to ASTM D3461), or a mixture thereof.

Commercially available C5 resins are, for example, Piccotac 1098, Piccotac 1115, Impera R1507, Impera R1508, Impera R1607, Impera R1608 from Eastman Chemical Company, Quintone A100, Quintone K100, Quintone C200H, Quintone C210 from Zeon etc.

a Methyl styrene (AMS) resins with a softening point in a range of b 85 °C to 140 °C are a preferred group of C9 resins.

Commercially available C9 resins are, for example Sylvatraxzx 4401 from Kraton Corporation, Impera P1505, Picco A100, Picco A120, Picco A140 from Eastman Chemical Company, Kristalex 3070, Kristalex 3085, Kristalex 3100, Kristalex F115, Piccotex 75, Piccotex 100 from Eastman Chemical Company etc.

Commercially available Terpene resins are, for example, Sylvagum TR90 and Sylvatraxx 4125 from Kraton Corporation; Dercolyte A 115, Dercolyte A 125, Dercolyte S 115 from DRT (les Dérivés Résiniques et Terpéniques).

According to one embodiment of the invention, the coumarone indene resin has a softening point in a range of 2 10 °C to 1 30

C (ring and ball method according to ASTM D3461).

Representative of coumarone-indene resins are, for example,

Novares C10 and Novares C30 from RUTGERS Resins BV.

According to one embodiment of the invention, the amount of coumarone-indene resin is in a range of 2 1 phr to 1 29 phr, preferably in a range of 2 5 to 25 phr, more preferably in a range of 2 10 phr to h 20 phr, and most preferably it is 15 phr.

According to one embodiment of the invention, the amount of the second resin is in a range of 2 1 phr to 1 29 phr, preferably in a range of 2 5 to i 25 phr, more preferably in a range of 2 10 phr to :2 20 phr, and most preferably it is 15 phr.

According to one embodiment of the invention, the total amount of coumarone-indene resin and second resin is in a range of 2 20 to phr, and most preferably it is 30 phr. In embodiments, the amount of coumarone-indene resin is at least 10 phr of a total amount of 30 phr to 40 phr of a dual blend with the second resin. Advantageously, 10 phr of CI resin in the blend leveled the rolling resistance performance. In the dual blends a concentration of 15 phr CI improved the tyre performance prediction. In embodiments, the amount of each of the CI resin and the second resin are 15 phr. With 15 phr of each of these resins the recipes achieved optimized results.

According to one embodiment of the invention, the ratio of the second resin to the coumarone-indene resin is in a range of 2

1:10 to 10:1, preferably in a range of 2 1:5 to 1 5:1, more preferably in a range of 2 1:1 to T 2:1 the ratio referring to the respective weight.

According to one embodiment of the invention, the second resin is a polyterpene resin, and the ratio of the polyterpene resin to the coumarone-indene resin is in a range of 2 1:1 to 1 2:1.

The invention also relates to a method of preparing a crosslinkable rubber composition comprising the steps of:

- providing a rubber component;

- adding a blend of at least two resins wherein the first resin is a coumarone-indene resin, and the second resin is a resin selected from the group of C5 resins, C9 resins, polyterpene resins, or a mixture thereof, and wherein the ratio of the second resin to the coumarone-indene resin is in a range of 2 10:1 to 1:10, the ratio referring to the respective weight (w/w);

- adding curing agents.

Another aspect of the present invention is a cross-linked rubber composition obtained by cross-linking a rubber composition according to the invention.

In an embodiment, the cross-linked rubber composition has a tan delta at 0°C of 2 0.5 to T 0.7 (determined from dynamic mechanical analysis (DMA) measurements according to ISO 4664-1, frequency 10 Hz, 0.1% dynamic strain) and a tan delta at 60 °C of 2 0.1 to 0.16 (determined from dynamic mechanical analysis (DMA) measurements according to ISO 4664-1, frequency 10 Hz, 6 % dynamic strain).

The present invention also relates to a method of preparing a tyre, comprising the steps of:

- providing a tyre assembly comprising a rubber composition according to the invention;

- cross-linking at least the rubber composition according to the invention in the tyre assembly.

Another aspect of the invention is a tyre tread obtained by cross-linked rubber composition according to the invention.

The present invention also encompasses a tyre comprising a tyre tread, wherein the tyre tread comprises a cross-linked rubber composition according to the invention.

Examples of the invention

The invention will be further described with reference to the following examples, tables and figures without wishing to be limited by them.

In the figures show:

- Figure 1: A graph of the tand as a function of temperature (-80 to 25°C) for various dual blend resin compositions of the present invention as compared to a reference composition.

- Figure 2: A graph of the tand as a function of temperature (30 to 80°C) for various dual blend resin compositions of the present invention as compared to a reference composition.

- Figure 3: A graph of the tand as a function of temperature (-80 to 25°C) for PT/CI resin blend composition (1:1) of the present invention as compared to a reference composition.

- Figure 4: A graph of the tand as a function of temperature (30 to 80°C) for PT/CI resin blend composition (1:1) of the present invention as compared to a reference composition.

- Figure 5: A graph of the tand as a function of temperature (-80 to 25°C) for PT/CI resin blend composition (2:1) of the present invention as compared to a reference composition.

- Figure 6: A graph of the tan5 as a function of temperature (30 to 80°C) for PT/CI resin blend composition (2:1) of the present invention as compared to a reference composition.

In accordance with the preceding, cross-linkable rubber compositions were prepared. For the preparation of the composition according to the present invention two resins were used in the blend. One of the two resins was a coumarone-indene resin having a low softening point in all formulations and the other resins were high softening point resins.

Example 1:

One of the two resins was CI resin in all formulations and the other resins were high softening point resins. The recipes of dual resin blends which were compared for dynamic mechanical analysis included blends of CI and C9 resins, CI and polyterpene (PT) resins and CI and C5 resins. The total amount of resin was kept the same at 30 phr and equal concentration of two resins was used (ratio of 1:1 w/w).

The table below shows the compositions of the reference dual blend (Ref-DB), C9/CI dual blend resin, PT/CI dual blend resin, and C5/CI dual blend resin.

Table 1: Reference Compound and The Dual Resin Blends Compounds

Formulation

	Ref- DB15/15	C9/CI=15/15	PT/CI=15/15	C5/CI=15/15
(phr)
SSBR	75	75	75	75
BR	25	25	25	25
Silica	90	90	90	90
Silane	7,2	7,2	7,2	7,2
Processing Oil (TDAE)	32,5	2,5	32,5	2,5
Coumaroneindene resin	-	15	15	15
C9 resin	-	15	-	-
Polyterpene resin	-	-	15	-
C5 resin	-	-	-	15
ZnO	2,5	2,5	2,5	2,5
Stearic Acid	1	1	1	1
6PPD	2	2	2	2
Anti ozone wax	1,5	1,5	1,5	1,5
Sulphur	1, 4	1,4	1,4	1, 4
TBBS	1,7	1,7	1,7	1, 7
DPG	2	2	2	2

SSBR had a styrene content of 21% and 62.2% vinyl groups and a Tg of -25°C and Mooney Viscosity of 49.1MU.

BR was neodymium catalyzed polybutadiene with high amount of linear chains and mostly cis-1,4 butadiene conformation with a viscosity of 44MU.

The C9 resin was Impera 1505 from Eastman Chemical Company which had an average molecular weight M_w of 4285 g/mol, and a softening point of 119°C (ring and ball method according to ASTM D3461).

The polyterpene resin was Sylvatraxx 4125 from Kraton Corporation which had an average molecular weight M_w of 1090 g/mol, and a softening point of 125°C (ring and ball method according to ASTM D3461).

The C5 resin was Piccotac 1115 from Eastman Chemical Company had an average molecular weight M_B of 3800 g/mol, and a softening point of 110°C (ring and ball method according to ASTM D3461).

The coumarone-indene resin was C30 from Rutgers which had an average molecular weight M_s of 281 g/mol, had a softening point of 20 to 30°C (ring and ball method according to ASTM D3461).

Silica contained 7% bound water and had a surface area of 165m²/g. TESPT silane had a sulfur content of 22% and average 3.75 sulfur atoms in the sulphur chain.

TDAE oil had a viscosity of 410m²/s at 40°C and a Tg of -42°C.

Zinc Oxide had a density of 5.61 kg/1 and Stearic Acid with melting point between 68-70°C.

6PPD (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine) had a melting point of 56°C.

Paraffin wax with 2% polyethylene and congealing point of 62-72 °C was used.

Two accelerators were used; TBBS (N-tert-butylbenzothiazole-2sulphenamide) with melting point of 109°C and DPG (diphenyl guanidine) with melting point between 144 and 151°C and alkalinity of 10.2 on pH scale.

Sulfur containing 1% of a mineral oil with melting point of 115 °C and pH of 6.8.

Abbreviations used are: TESPT (tetrasulphide silane); TDAE (treated distillate aromatic extract; processing oil); TBBS (Ntert-butyl-2 benzothiazole sulfenamide); DPG (diphenyl guanidine); TBzTD (tetrabenzyl thiuram disulfide); 6PPD (N-1,3dimethylbutyl)-N-phenyl-p-phenylenediamine).

Measurement of Dynamic Mechanical Propertiesof Ref-DB blend in comparison to C9/CI, PT/CI and C5/CI resin blends

A dynamical spectrum of the compounds was collected by the instrument Metravib DMA +450 dynamic spectrometer in double shear mode. Measurements of the material dynamic behavior were run in two different settings. In the first set-up the temperature was varied, and in the second, a different strain was applied.

In the temperature variation method there were two sub steps. In the first sub step, the temperature was in the range of -80°C to 25°C and the dynamic strain was 0,1%. In the second sub step, the temperature was in the range of 25°C to 80°C but the dynamic strain was higher and it was set at 6%. The reason of the increased dynamic strain at higher temperatures was the effort to simulate the real tyre conditions for the rolling resistance prediction. In both sub test the frequency was constant at 10Hz.

The results of the dual blends dynamical mechanical analysis were very close to each other. The results depicted that in temperature sweep measurements from -80 to 25 °C (Figure 1) only C5-CI resins formulation created 5°C less Tg shift. The exception was not peculiar because the C5 and the CI resins individually are not known to highly shift the Tg. Surprisingly, the inventors found out that the results were equivalent to the other 30phr resin recipes and tan δ peaks were narrow and the peak heights were same. This indicated the domination of the CI resin in the blends since the tan δ maximum values of the single C9 and C5 resin compounds are known to be much lower. Additionally, the CI resin combined with the C5 did not increase incompatibility which inventors have presumed with C5 resin but it was completely opposite and the compatibility was enhanced. Moreover, it was not likely that the 15phr of a high softening point resins will efficiently phase separate and the PT-CI resin blend behaves as the PT formulation.

The most important anticipated outcome of DMA results in temperature range from 30 to 80°C (Figure 2) is lowering of the resin blends tan δ graphs compared to the Ref-DB. This means that going from lOphr in ternary blend to 15phr of the CI in dual resin blend brings not equal but improved rolling resistance prediction performance when compared to the results of single CI resin compounds. Also, there is no preference in the high softening point resin when it is mixed with the CI resin in this concentration. Furthermore even on this level of similarity there were insignificant but explainable variations. In tan δ results the C5/CI is the closest to the reference and at the same time with C5 resin alone in the recipes the worst rolling resistance is obtained. Negative energy dissipation influenced also the C9 resin where its tan δ curve is higher than the reference in whole temperature range. The lowest fuel consumption prediction parameter among dual rubber-resin blends has PTCI recipe since its constituent the PT resin tan δ matched the reference value around 70°C. The most interesting observation anyhow was the crossing of the C5high resin based blend with two other blends at around 35 °C. Nevertheless moduli of dual resin blends are significantly lower in comparison to the reference and marginal rise from other blends is observed with C9 based blend recipe.

Example 2: The table below shows the compositions of the reference compounds Cl and C2 and the resin blends II and 12.

Table 2: Reference Compound and The Dual Resin Blends Compounds

Formulation

	Refl5/15 (C 1)	PT/CI=15/15( Il)	Ref20/10(C 2)	PT/CI=20/10( 12)
(phr)
SSBR	75	75	75	75
BR	25	25	25	25
Silica	90	90	90	90
Silane	7,2	7,2	7,2	7,2
Processin g Oil (TDAE)	32,5	2,5	32,5	2,5
Coumarone -Indene resin	-	15	-	10
Polyterpe ne resin	-	15	-	20
ZnO	2,5	2,5	2,5	2,5
Stearic Acid	1	1	1	1
6PPD	2	2	2	2
Anti ozone wax	1,5	1,5	1,5	1, 5
Sulphur	1, 4	1, 4	1,4	1, 4
TBBS	1, 7	1,7	1,7	1,7
DPG	2	2	2	2

*phr - Parts per hundred rubber

Measurement of Dynamic Mechanical Properties

In a first test the dynamic mechanical properties of the reference compound Cl was compared with the compound II. A dynamical spectrum of the compounds was collected by the instrument Metravib DMA +450 dynamic spectrometer in double shear mode .

Measurements of the material dynamic behavior were run in two different settings. In the first set-up the temperature was varied, and in the second, a different strain was applied.

Table 3: Mechanical and Physical properties of Cl and II

Test	Unit	Refl5/15(Cl)	PT/CI=15/15(II)
Hardness		100	96
M300%		100	167
M300/M100	% Compared	. 100 to	142
Tensile Strength	reference	\| 100	132
Elongation at Break		100	82
DIN Abrasion		100	73

In a second test the dynamic mechanical properties of the reference compound C2 was compared with the compound 12. The tests as described above provided the following results.

Table 4: Mechanical and Physical properties of C2 and 12

Test	Unit	Ref20/10(C2)	PT/CI=20/10(12)
Hardness	% Compared to reference	100	108
M300%	100	219
M300/M100	100	146
Tensile Strength	100	147
Elongation at Break	100	74
DIN Abrasion	100	74

DMA results of compounds with resin blends in different ratios of PT:CI=1:1 (w/w) and PT:CI=2:1 (w/w) are depicted in Figures 3-6 respectively. The total amount of resins was 30phr. The tan δ graph at low temperatures (Figures 3 and 5) depicts that the Tg shift of the compound with increased concentration of PT resin is higher. Therefore this compound will have a better wet grip. However, tan δ at 0°C looks similar and by assessment based on this parameter both compounds will have similar improvement in wet grip.

DMA results at high temperatures (Figures 4 and 6) show that the higher the concentration of the CI resin the lower the tan δ at 60°C and consequently the better the rolling resistance. Furthermore with even smaller amount of CI resin it can be designed that the PT resin compound has no increased rolling resistance. Therefore, the application of PT and CI resin blend wet grip and rolling resistance performances can be tailored by the concentration of CI resin.

Claims

Conclusions

1.5 D5 is a product datasheet for Wingtack STS which is used in the examples of D2.

2. Inventive step · Νΐ: 537.3> <»®ρίΐΓ3ίει sitesQ Lfcly BÖfW (shsei Bj

WRITTEN OPINION Application number (SEPARATE SHEET) ________________________________________ NL2020806

2.1 The subject matter of claims 1 - TO and 12 is not novel and therefore not inventive either.

2.2 Each of D1-D4 may be considered as closest prior art (see 1.1-1.4).

2.2.1 D1 already anticipates the subject matter of claims 1-3, 6-9 and 12.

The Mw and softening points of the C5 / C9 resin is not disclosed, but the ranges given in dependent claims 4 and 5 do not appear to be inventive, no technical effect has been shown. Dependent claims 4 and 5 are therefore not considered to be inventive in view or D1. The same applies to the process according to claim 11 which appears to be a standard procedure. The same applies to the rubber composition according to claim 13. Since D1 is related to tires, claims 14 and 15 are not inventive either in view or D1.

2.2.2 D2 already anticipates the subject matter cf claims i-6. 8. 3 and 12.

A slightly lower amount of coumarone indene resin (equal to or lower than 29 phr as defined in dependent claim 7) does not appear inventive in view of D2 (in some of the examples, the amount of coumarone indene resin is 32 phr). Dependent claim 7 is therefore not considered to be inventive in view of D2. The same applies to the process according to claim 11 which appears to be a standard procedure. The same applies to the rubber composition according to claim 13. Since D2 is related to tires, claims 14 and 15 are not inventive either in view or D2.

2.2.3 D3 already anticipates the subject matter of claims 1-3,5-10 and 12.

A Mw range of 880-4500 g / mol for the second resin does not appear inventive in the absence of a surprising advantageous technical effect. Dependent claim 4 is therefore not considered to be inventive in view of D3, The same applies to the process according to claim 11 which appears to be a standard procedure. The same applies to the rubber composition according to claim 13. Since D3 is related to tires, ciaims 14 and 15 are not inventive either in view or D3.

1.4 D4 relates to rubber compositions for tires with good wet grip and rolling resistance properties (paragraphs 3, 5).

Examples 22-30 and comparative examples 14.15 (table 2) disclose compositions including a rubber component (NR / 8R). a coumarone indene resin (resin 1, softening point 1 Q * C) and a polyterpene resin (resin 2, softening point 115 ° C). The amount of both resins is below 29 phr. The weight ratio of polyterpene resin to coumarone indene resin is 5: 1 or 1: 1, The mixtures are cross-linked (paragraph 108).

Hence, D4 discloses all the technical features of claims 1-3, 5-10 and 12. These claims are therefore not novel about D4.

1.3 D3 related to rubber compositions for tires with good wet grip and rolling resistance properties (paragraphs 1.2).

Examples 17,18 and 20 (table 2) disclose compositions including a rubber component (SBR / BR). a coumarone indene resin (coumarone indene resin 1 (paragraph 118; Novares C10 which is also mentioned in the present application and which has a softening point of 5-15 ° C) and either a polyterpene resin (example 17; paragraph 125, softening point 115 ° C'i, or a terpene phenol resin (example 18; paragraph 126, softening point 115 ° C) or a C9 resin (example 20; paragraph 128, softening point 120 ° C) .The amount of ail resins is 4 phr and the weight ratio of the two resins is 1: 1 in all the examples The mixtures are cross-linked (paragraph 139).

Hence, D3 discloses all the technical features of claims 1-3, 5-10 and 12. These claims are therefore not novel about D3.

1.2 D2 relates to rubber compositions for tires with goad wet grip and rolling resistance properties (paragraphs 1.3).

Examples T2, C1 (table i). T8, C3 (table 3), T11 and C4 (table 4) disclose compositions including a rubber component (SBR or SBR / BR). a coumarone indene resin (paragraph 152; Novares C30 which is also mentioned in the present application) and a C5 / C9 resin (Wingtack STS). Said Wingtack STS has a softening point of 94 ° C and a Mw or 1600 g / mol (see D5, right column). The weight ratio of C5Z · Ν: 153? "3 ·· <» ερίΐΓ3ί0 siissQ (<fc! Y fÖfW (shsei 4y

C9 resin to coumarone indene resin is between 1: 5 and 5: 1 for examples T2, 01, T11 and 04. The amount of 05/09 resin is below 29 phr. The mixtures are crosslinked (paragraph 149)

Hence, D2 discloses all the technical features or claims 1-6,8,9 and 12. These claims are therefore not novel about D2.

1.1D1 relates to rubber compositions for tires with goad wet grip and railing resistance properties (paragraphs 1,2,5).

Examples C1-C4 and T3-T9 (table 1) disclose compositions including a rubber component (SSR or SBR / BR), a coumarone indene resin (Novares C30 which is also mentioned in the present application) and a C5 / C9 resin (Escorez 2173). In examples T3-T7, the amount, or coumarone indene resin is below 29 phr. In almost all the examples, the amount of C5 / C9 resin is below 29 phr. The weight ratio of C5 / C9 resin to coumarone indene resin is between 1: 5 and 5: 1. The mixtures are crosslinked (paragraph 112)

Hence, D1 discloses all the technical features or claims 1-3, 6-9 and 12. These claims are therefore not novel about DI.

1. Novelty

1/3

Figure 1: Dynamic properties vs. temperature (-80 to 25 ° C), Resin dual blends (--- Ref-DB,

....... C9-CI-30, - - - PT-CI, ---- C5-CI)

Figure 2: Dynamic properties vs. temperature (30 to 80 ° C), Resin dual blends (--- Ref-DB,

....... C9-CI-30, - - - PT-CI, ..... - C5-CI)

2/3

Figure 3

Temperature [° C]

Figure 4

3/3

Figure 5

Figure 6

Rubber composition for tires with good wet grip and rolling resistance properties

The present invention relates to a cross-linkable rubber

Composition comprising a rubber component and a resin component; where the resin component consists of a blend of at least two resins the first resin is a coumarone-indene resin, and the second resin is a resin selected from the group of C5 resins C9 resins, polyterpene resins, or a mixture thereof; whether the 10 ratio of the second resin to the coumarone-indene resin is in a range or h 1:10 to C 10: 1, the ratio referring to the respective weight (w / w).

COOPERATION TREATY (PCT)

REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE

IDENTIFICATION OF THE NATIONAL APPLICATION CHARACTERISTICS OF THE AUTHORIZED APPLICANT APO4334NL Dutch eanwaag ». jn ^ 'êttihgs8s.tötö _; 2020806 20’04-2018 .................................................. .................................................. ................ Invoked voon angsöstum Applicant (Name ^ A polio Tires Global R&D B, v, Date of request for examination of By cfe International QodomooR authority international type he request to conduct an investigation of internal sewage type teecjekend nr. 28-07-2018 SN71685 I. CLASSIFICATION OF THE SUBJECT (for teepa »&> rt j van vasschiiteutte dassiiicatiss, "Ite ctassi ^ eaitesymh ^ and opswi) According to the Inlarnalkins e-eiaseificutie (IPC) C08L9 / 06; C08LS / OO; C08L45 / O2: C08L5ZO2; C08K3 / 36'B60C1W tl. TECHNICAL FIELDS EXAMINED Mini-Investigation investigated Classifcalie system C · assi a t; esym beien IPC C08L; C08K; B60C Researched »aritfen. · · 1οΰΐ (ΐβ @ ίΐι'ί8! Ί0. <1ίΐηίί & minimum deeirmenlati e. for zöyet Efergi figure döcïjmertjsri .in rte GncterzöGhfe area .apfjenörnen. ttl. NO RESEARCH POSSIBLE FOR CERTAIN CONCLUSIONS (remarked r, p IV. LACK OF UNIT OF INVENTION (comments on refinancing «Uai.i)

Form PCT / iSA 201 A (11/2000)

RESEARCH REPORT ON THE RESULT OF THE STUDY ON THE STATE OF THE TECHNOLOGY OF THE INTERNATIONAL TYPE OF FIUmtnw of t> w an on.cferzoèii according to the state of the art

HL 202Θ806

a. OssiReATfE w hëtOüëwwrr ::.:; :: ': ::':.: '':;: ::. ::.: Inv. C08L9 / 05 C08L9 / 00 C08L45 / 02 CO8L57 / 02 C08K3 / 36 B60C1 / 00 ADO. Follow® taiemaöorrste öfassiftöaite of patents ("IPS) or anyway according to national» oiassrfeafe ai "according to the 1PÖ. ft. WPE ^ PPHT6O8B! 6P ^ FROM PE T «PHWK Researched irwnwn documentation (oiassftcatfe followed by isosasifesttesymfeoiw) C08L C08K B60C Ondarzf> & hte doDnirnentatie dan cte döcurnerrtatffe, vöö? tfenjeiiiks dw? unsters, for zewer tawitón m de oncterzötïbte g ^ hi ^ efen zb »C’pgönotmn Electranisoke data files consulted during the investigation (name of the data files and, where practicable, keywords drawn) EPO-Internal, WPI Data C. VA »'BÉIAMS öEACMTÊ ÓÖCÜMÊNTÊ» Category ¹⁵ do & wrnsritafïj everóuea: with & anciu <d> ng of ap & weai ve bei From betang for · no X, D X, D WO 2015/124681 A1 (MICHELIN & CIE [FR]; MICHELIN RECH TECH [CH]) August 27, 2015 (2015-03-27) mentioned in the application «Paragraph axis [0O01J. [0002], [0005], [0112] * * examples C1-C4J3-T9 * * table 1 * WO 2017/001616 A1 (MICHELIN & CIE [FR]; MICHELIN RECH TECH [CH]) January 5, 2017 (2017-01-05) mentioned in the application * examples T2, C1, T8X3, T11, C4 * * tables 1,3,4 * * alineas [0001], [0003] »[0149], [0152] * - / - I 0, II-15 I 0, II-15 | V & rtk ^ e ctaeiim & ntett wötdön mentioned in the transport of box C J Laden Viin dsïaifcta ootrooifanrötë are verir.ald in ear; hijiage 'Spectate östegoneSn vandeitacumenten η · » _M tedterringsdidum <χ r.fe vootrsrigsdarurn yapubiiseenrte:. ,,; <. .: -.: -:, -,. . j literature that is quite enchanting for fis otarooiaenvrsge, ^A * belonging Iferattar d® da stand vati rr to _A. _uft <j venfreidter terhataenns van dsteeorre or testate * does not affect the principle that the invention 'Ö * in the scirooanwere avoiding' X 'the éottaioefe was not new or not tavénttaf besettamta mta ütiytmta mta ütiytamta mta ütiytamta mta ütiytamta mta ütiytamta mta ütiytamta mta ütiyta mta ütiytamta mta ütiytmt opuf after the «dtetansedata», opatahte vari this itaataur in which the same liftyinding is:>»»:> hrever. ....... The original is not at all inventive in relation to X * ewandefe rsdeneh veirrtdtófe iftefa, óur _{vaB com} ^ n _S tta of this title with other gswteercfe i, Ά><i<„i» 1 „U literature of the same category, where the combination for xy: rutaochottehite • taBrf. v® the taotawk _{v (Amep} 'p' fusissfi tfe yöörrang & datbm and the iiddteningSdsiiuta gdpubliceetae ictwstuut 'iid contains the same oettaoitamife or similar tastasmblblate' Daiut '*' wind research after * '0¾ state of the toe stretch of in ^ rnafionaisJ type vyerrf yo ^ ooid November 8, 2018 Verz & 'xkJfltcm van net nappon from net research into the state of the art of intemi ^ niwrf Name and address of the instarsffe Europear · Patent Qttirte, P.ft.'5818 Patenttaan-2 ifL 228ö HV Siiawiï ·: ' Tel. i + 31 "? G) 340-ZG.1Ö, fcr: (+ 31-7Ö) M0-3016 The competent amütenaftr from Bergen, Mare

FCW'Wtef F.C'T / iöA / Sül ^ c-t-deb ^ a) nianu & frX ^) page 1 of 2

RESEARCH REPORT ON THE RESULT OF THE RESEARCH ON THE STATE OF THE TECHNOLOGY OF THE INTERNATIONAL TYPE 'Numfnw van t> etv «itceK w a ontferzoai <to the state of tk technique

HL 202Θ806

0 (Continued) OF SSLANG <3-DOCUMENTS Gategoii® "" 'G »eite« de0Aun> Srtta »<: ®verrK®: egg BWt ^ aaeKSMidèige ^ Vsè.Sp & eiaatVS}) mischievous z (j« 4ie pAseBQAS: Van betang food ccifichjai »no. X: X a US 2014/155521 A1 (MIYAZAKI TATSUYA [JP]) 5 June 2014 (2014-06-05) * examples 17.18.20; table 2 * * axis [0001], [0002], [0118], [Ö125], Γ0126], [01281, [01391 *] US 2015/011676 A1 (MIYAZAKI TATSUYA [ÓP]) January 8, 2015 (2015-G1-08) * alineas [0G03], [0005], [Q108] * * examples 22-30, comparative 14, 14; table 2 * TOTAL Cray Valley: Technical Data Sheet Wingtack STS ”, 31 inaart 2016 (2016-03-31), ΧΡ0Θ2786349, Found on the Internet: URL: www. c ray from 11 ey. c oni / docs / TD S / w i ng t a c k - s ts.pdf [found on 2018-11-081 * right column or * 1-15 1-15 4.5

CT / 100 ^; A / 2Ü1 page 2 of 2 'Number èönïietcm ^ iènÈfejzisek naar de stand jas ·· de teahniek

RESEARCH REPORT ON THE RESULT OF THE STUDY ON THE TECHNOLOGY OF THE INTERNATIONAL TYPE kiSosmatte on tenders of the dezrsifcfe oatruoifamilki

called Botrooigeschnft in the report Date of publication agreement (s) gesfted (en ') Date of publication WO 2015124681 Al 27-08-2015 FR 3017879 Al WO 2915124681 A1 28-98-2015 27-08-2015 WO 2017001616 Al 05-91-2 ( Al FR 3038320 A1 US 2018186979 A1 WO 2017001616 Al 09-05-2018 06-01-2017 05 -7-2018 05-01-2017 US 2014155521 Al 05-06-2014 CN 103732670 A EP 2740757 A1 EP 33359G5 A1 0P 5559234 B2 OP 2013053296 A US 2014155521 Al WO 2G13021694 A1 16-04-2014 11-06-2014 20-96-2918 23-07-2014 21-03-2013 95-06-2014 14-02-2013 US 2015011676 Al 08-01-2015 CN 10427726 A DE 102014212680 A1 JP 6173078 B2 OP 2015013974 A US 2015911676 Al 14-91-2015 08-91-2015 02-08-2017 22-01-2015 98-01-2915 W ** '«.» M> w W. * »W «R« ww w »w w w w w w w w w, w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w * «S * W rt · W» '* rS »W' .¾¾ W '

FchKiJbR-r «January 2öü4 '<

WRITTEN OPINION

Fife No. SN71685 i Filing I Prferitydiïte feöy ^ tftvi ^ Wil i Application no. 04.2018 NL2020806 intarnotional Patent C-axis' afieatiors JPC>

INV. C03L9.06 C08L9.O0 C08L45 / 02 C08L57.02 CÜ8K336 B60CW0

Applicant

Apollo Tires Global R&D B.V.

This opinion contains inöföattons related to the following items:

K Box No. i D Box no. II □ Box No. Ki □ Box No. IV B Box No. V Basse of the opinion Priority Non-eslablishrnenl or opinion with regard to novelty, inventive step and industrial applicability Lack of unity of invention Reasoned statement with regard to novelty, inventive step or industrial applicability: citations and explanations supporting such statement □ Box No. Vi B Box No. Vi! □ Box No. Fish I Certain documents cited Certain detects in the application Certain observations on the application

£ xatri irW van Bergen, Marc

Form NL237A (Dekbladi (July £ 006})

Applfcafcn riurrttw

WRITTEN OPINION

Box No. IBasis of this opinion

T, This opinion has been established on the basis of the latest set of claims before the start of the search.

2. With regard to any nucleotide and / or amino acid sequence disclosed in the application and necessary to the claimed invention, this opinion has been established on the basis of:

a, type of material:

□ a sequence listing □ tablets) related to the sequence listing b, format of material:

□ on paper □ in eiectronic form c, time or filihgiumishing:

□ contained in the application as filed.

□ filed together with the application in electronic form.

Furnished subsequently or ths purposes of search.

3. □ In addition, in the case that more than one version or copy of a sequence listing andbr table related thereto has been filed or furnished, the required statements that the information in the subsequent or additional copies is identical to that in the application as Filed or does not go beyond the application as filed, as appropriate, were furnished.

4. Additional comments:

Bex no. V Reasoned statement with regard to novelty, inventive step or industrial applicability; Citations and explanattens supporting such statement

t, Statement Novelty Yes: Claims No 'Claims 11, 13-15 1-10, 12 Inventive step Yes ^- Claims No; Claims 1-15 Industrial applicability Yes. Claims Nd; Claims 1 15

.2., Citations and explanations see separate sheet

NL23ZB (Jüty 2006}

Application mimiw

WRITTEN OPINION

Box No; VII Certain defects in the application see separata sheet

NL23ZB (Jüty 2006]

Re Item V

Reference is made to the fallowing documents:

D1: WO 2015/124681 A1 (MICHELIN & CIE [FR] MICHELIN RECH TECH [CH]) 27 August 2.015 (2015-08-27) mentioned in the application

D2: WO 2.017 / 001616 A1 (MICHELIN & CIE [FR]; MICHELIN RECH TECH [CH]) mentioned January 5, 2017 (2017-01-05) in the application

OS: US 2014/155521 A1 (MIYAZAKI TATSUYA [JP]) June 5, 2014 (2014-06-05)

D4; US 2015/011676 A1 (MIYAZAKI TATSUYA [JP]) Jan. 8, 2015 (2015-01-08)

D5: TOTAL Cray Valley: Technical Data Sheet Wingtack STS ”,, March 31, 2016 (2016-03-31), XP002786349. Found on the Internet: URL: www.crayva! Ley.com/ docs / TDS / wingtack-sts.pdf [found on 2018-11 -08]

A cross-linkable rubber composition comprising a rubber component and a resin component;

characterized in that the resin component comprises a mixture of at least two resins, wherein

- the first resin is a coumarone-indene resin, and

- the second resin is a resin selected from the group of C5 resins, C9 resins, polyterpene resins or a mixture thereof;

wherein the ratio of the second resin to the coumarone endene resin is in the range of h1: 10 to h10: 1, the ratio referring to the respective weight (w / w).

The cross-linkable rubber composition of claim 1, wherein the rubber component is selected from the group of styrene butadiene rubber solution (SSBR), butadiene rubber (BR) or a mixture thereof.

The cross-linkable rubber composition of claim 1 or 2, wherein the amount of the rubber component, per hundred parts by weight of rubber (phr), is in a range of hl to hl00 phr.

The cross-linkable rubber composition of any one of claims 1 to 3, wherein the second resin has an average molecular weight Mw in a range of h880 g / mol to ^ 4500 g / mol.

The cross-linkable rubber composition of any one of claims 1 to 4, wherein the second resin is selected from the group of C5 resins with a softening point in a range from h10 ° C to hHO ° C, C9 resins with a softening point in a range of h85 ° C to hl40 C or polyterpene resins with a softening point in a range of hl05 ° C to hl25 ° C (ball method rings according to ASTM D3461), or a mixture thereof.

The cross-linkable rubber composition of any one of claims 1 to 5, wherein the coumarone indene resin has a softening point in a range of 210 ° C to 130 ° C (ring and ball method according to ASTM D3461).

The cross-linkable rubber composition of any one of claims 1 to 6, wherein the amount of coumarone-indene resin is in a range of 21 phr to 129 phr.

The cross-linkable rubber composition of any one of claims 1 to 7, wherein the amount of the second resin is in a range from 21 phr to 129 phr.

The cross-linkable rubber composition of any one of claims 1 to 8, wherein the ratio of the second resin to the coumarone indene resin is in a range of 21: 5 to 15: 1, the ratio referring to the respective weight .

The cross-linkable rubber composition of any one of claims 1 to 9, wherein the second resin is a polyterpene resin, and the ratio of the polyterpene resin to the coumaron-indene resin is in a range of 21: 1 to 12: 1.

A method for preparing a cross-linkable rubber composition according to any of claims 1 to 10, comprising the steps of:

- providing a rubber component;

- adding a mixture of at least two resins, wherein the first resin is a coumarone-indene resin, and the second resin is a resin selected from the group of C5 resins, C9 resins, polyterpene resins or a mixture thereof, and wherein ratio of the second resin to the coumarone-indene resin is in a range of 210: 1 to 11:10, the ratio referring to the respective weight (w / w);

- adding curing agents.

A cross-linked rubber composition, characterized in that it is obtained by cross-linking a rubber composition according to any of claims 1 to 10.

Cross-linked rubber composition according to claim 12 with a tan delta at 0 ° C from b0.5 to T0.7 (determined from dynamic mechanical analysis (DMA) measurements according to ISO 4664-1, frequency 10 Hz, 0.1% dynamic voltage) and a tan delta at 60 ° C from b0.1 to T0.16 (determined from dynamic mechanical analysis (DMA) measurements according to ISO 4664-1, frequency 10 Hz, 6% dynamic voltage).

A method for manufacturing a tire, comprising the steps of:

- providing a tire assembly comprising a rubber assembly according to any one of claims 1 to 10;

- crosslinking at least the rubber composition according to any one of claims 1 to 10 in the tire assembly.

A tire comprising a tire tread, characterized in that the tire tread comprises a cross-linked rubber composition according to any one of claims 12 or 13.

2.2.4 D4 already anticipates the subject matter of claims 1-3, 5-10 and 12.

For the same reasons as pointed out under 2.2.3, the subject matter of claims 4.11 and 13-15 is not considered to be inventive about D4 either.

WRITTEN OPINION (SEPARATE SHEET)

Application number

Re Item VII

The relevant background art disclosed in D3 and D4 is not mentioned in the description nor are these documents identified therein.

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