EP3551699A1

EP3551699A1 - Solid oleaginous compositions

Info

Publication number: EP3551699A1
Application number: EP17817811.7A
Authority: EP
Inventors: Anupam AMAR; Louis PLANCQ
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Onetech SAS
Priority date: 2016-12-07
Filing date: 2017-12-06
Publication date: 2019-10-16
Also published as: FR3059672A1; US20190292369A1; WO2018104658A1; KR102531170B1; US11697735B2; FR3059672B1; CN110050035A; KR20190089008A; CN110050035B

Abstract

The invention relates to an oleaginous composition that is solidified at ambient temperature and in divided form, comprising an oil, including at least one hydrocarbon oil of petroleum origin, and at least one chemical organogelator additive. The invention also relates to the use of the composition as a plasticiser, in particular in tyre production, or as a solvent, in particular in ink production. The invention further relates to a method for transporting and/or storing and/or handling oleaginous compositions that are solid at ambient temperature and in divided form.

Description

SOLID OIL COMPOSITIONS

The present invention relates to cold and divided solid oil compositions and their use as a plasticizer, especially for the manufacture of tires and as a solvent, in particular for the manufacture of inks. It also relates to a method for transporting and / or storing and / or handling cold solid oil compositions and in divided form.

State of the art

Plasticizers are essential components in the formulation of elastomers, especially rubber-based compositions. The main role of the plasticizer is to give the elastomer flexibility and processability. It reduces the glass transition temperature of the elastomer, making it flexible even at low temperatures.

Solvents are essential components in the formulation of inks, especially compositions based on polymeric resin. The main role of the solvent is to wet and solubilize the dye used in the inks and also to disperse it in the polymer resins used in the inks.

Plasticizers for elastomers and solvents for inks are often oils of natural or synthetic origin, in particular mineral oils derived from the distillation of petroleum.

Plasticizing oils represent a large part of the plasticizer materials used in the field of elastomers.

The solvent used for the inks is the main constituent of the inks.

In the field of plasticizers and in the field of inks, oils are products that must be stored and transported in heated containers.

The transport of these plasticizing oils or solvent oils for inks is today carried out by insulated tanker trucks or in iso-containers for reheating by means of a heat transfer fluid or a vapor network. The user must be equipped with storage bins also kept hot until the oil is used. These constraints result in significant energy costs and equipment costs for both the oil supplier and the customer. In addition, the temperature maintenance of the plasticizing oil or solvents for inks during a given period may affect the properties of the oil, including the aging properties and thus change the final performance of the products in which the oil is incorporated. It is known that low molecular weight organogellators can gel liquids thermoreversibly. However, it is not possible to predict which organogelling agent is able to gel which liquid. In addition, the presence of an organogelator in a liquid has an influence on the properties of this liquid and the purpose of the invention is to formulate a plasticizing oil or a solvent oil for inks in gel form without its usual properties. are modified by the presence of gelling additives.

WO 2008/107551 teaches bitumen compositions comprising an organogelator additive and having thermoreversible viscosity and hardness characteristics. It is known, in particular from WO 2016/016320, to use organogelators for conditioning bitumens in cold and divided solid forms. However, the composition of a bitumen is very far from that of an oil and the targeted applications are very different.

JP 2010 126635 discloses the use as a lubricating composition of a base oil additive with a derivative of benzylidene sorbitol. The compositions obtained are in the form of a gel capable of reversibly liquefying by the application of a shear stress and have a consistency equal to 1 or 2 according to the NLGI scale.

US 5,186,972 discloses lubricating compositions comprising a gelling agent. Placed below a certain temperature, these compositions then pass from the liquid state to a gelled state.

The object of the present invention is to provide an oil composition, usable as a plasticizer or as an ink solvent, which is in divided form and solid at room temperature and which can be made fluid by simple heating. In particular, an object of the invention is to provide an oil composition, which can be used as a plasticizer or as a solvent, which is in divided form and which is solid at ambient temperature and which can be incorporated respectively in an elastomer composition or in an an ink. In particular, an attempt has been made to develop an oil composition in solid form and in divided form comprising a organogelator whose presence does not significantly modify the use properties of the plasticizing oil and elastomer compositions in which it is incorporated but also does not modify the use properties of the solvent for inks and compositions of inks in which it is incorporated.

Another object of the invention is to propose a method for transporting and / or storing and / or handling at ambient temperature an oil in solid form and in divided form.

Another object of the invention is to provide a method for easy handling of the oil during handling operations.

Another object of the invention is to provide an ecological and economical method for transporting an oil and to avoid the use of additional means for maintaining the temperature of this oil during its transport and / or storage and / or handling. Summary of the invention

The invention relates to a solid oil composition at room temperature comprising:

80% to 99.9% of at least one oil chosen from a hydrocarbon oil of petroleum or synthetic origin and mixtures thereof, preferably an oil of petroleum origin, advantageously chosen from aromatic oils and paraffinic oils,

0.1% to 10%, of at least one organogelling additive,

• 0% to 10% of one or more other additives,

the percentages being expressed by weight relative to the total mass of the composition.

According to a preferred embodiment, the hydrocarbon oil is chosen from hydrocarbon oils of petroleum origin.

According to a particular embodiment, the solid oil composition according to the invention further comprises an oil of vegetable origin. According to a first preferred variant, the hydrocarbon oil is chosen from aromatic oils having an aromatic content of between 30 and 95% by weight, advantageously between 50 and 95% by weight, more preferably between 60 and 95% by weight relative to the total mass of the aromatic oil.

According to a further preferred embodiment, the aromatic oil has a kinematic viscosity at 100 ° C of between 0.1 and 150 mm ² / s, advantageously between 5 and 120 mm ² / s, more advantageously between 7 and 90 mm ² / s.

According to a second preferred variant, the hydrocarbon oil is chosen from paraffmic oils having a total content of paraffinic compounds of at least 50% by weight relative to the total mass of the paraffinic oil.

According to a first preferred embodiment, the organogelling additive is a compound of general formula (I):

Ar1-R-Ar2 (I),

in which :

Ar 1 and Ar 2 represent, independently of one another, a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and optionally substituted by one or more C 1 -alkyl groups; -C20, and

R represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate and anhydride functions.

According to a second preferred embodiment, the organogelling additive is a compound of general formula (II):

R- (NH) _n CONH- (X) _m -NHCO (NH) _n -R '(II), wherein

the groups R and R ', which may be identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, optionally substituted by one or more hydroxyl groups or amino groups, and optionally comprising heteroatoms such N, O, S, C5-C24 hydrocarbon rings and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms, such as N, O, S, hydrocarbon rings; C5-C24 and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

n and m are integers having a value of 0 or 1 independently of one another.

According to a preferred embodiment, the composition comprises from 0.2% to 5% by weight, more preferably from 0.5% to 3.5% by weight of organogelling additive relative to the total mass of the composition. According to a preferred embodiment, the composition is in the form of granules or loaves.

The invention further relates to a kit comprising at least:

a solid oil composition at room temperature as described above and in detail below, and

a capsule comprising at least one additive.

The invention also relates to a method for preparing a solid oil composition at room temperature as described above and in detail below, comprising the following steps:

(i) having an oil chosen from a hydrocarbon oil of petroleum or synthetic origin, chosen from aromatic oils, paraffinic oils and their mixtures, and heating it with stirring at a temperature of between 70 and 250 ° C., preferably between 140 and 200 ° C, (ii) adding an organogelling additive and heating with stirring at a temperature between 70 and 250 ° C, preferably between 140 and 200 ° C, (iii) optionally adding one or more other additives and stirring the mixture at a temperature between 70 and 250 ° C, preferably between 140 and 200 ° C,

(iv) shaping the composition, for example in the form of granules or loaves,

(v) cool to room temperature.

The invention also relates to a method for transporting and / or storing and / or handling a solid oil composition at room temperature and in divided form as described above and in detail below, or a kit comprising such a composition, the composition being transported and / or stored and / or handled in the form of breads or granules solid at room temperature.

The invention also relates to the use of a solid oil composition at room temperature and in divided form as described above and in detail below, or a kit comprising such a composition, for the manufacture of tires.

The invention also relates to the use of a solid oil composition at room temperature and in divided form as described above and in detail below, or a kit comprising such a composition, for the formulation of an ink.

The storage, transportation and handling of oils, in particular plasticizing oils and solvent oils for inks, in solid form at room temperature and in divided form have many advantages: on the one hand, energy costs and costs of reduced equipment for transport and storage, on the other hand a transport of these oils over longer distances, especially in geographical areas difficult to access, but also less constraints of inventory management and production shutdowns. detailed description

The expression "consists essentially of" followed by one or more characteristics, means that may be included in the process or material of the invention, in addition to the components or steps explicitly listed, components or steps that do not significantly modify the properties and characteristics of the invention.

The expression "between X and Y" includes the terminals, unless explicitly stated otherwise. This expression therefore means that the target range includes X, Y values and all values from X to Y.

By "solid oil composition at room temperature" is meant a composition having a solid appearance at ambient temperature under conditions of transport and / or storage and / or handling. Specifically, it means a solid oily composition which retains its solid appearance throughout transport and / or storage and / or handling at room temperature, that is to say a solid oil that does not flow to a solid. a temperature of up to 80 ° C, preferably from 5 ° C to 70 ° C, preferably from 10 ° C to 70 ° C, more preferably from 10 ° C to 60 ° C, still more preferably from 15 ° C to 50 ° C, and pressure forces from the conditions of transport and / or storage and / or handling.

By "cold solid oil composition and divided form" is meant a solid composition at room temperature which is packaged in a divided form, that is to say in the form of units distinct from each other, that they are called granules or loaves. The oily composition according to the invention is also referred to indifferently in the present description "solid oily composition" or "solid oil".

The oily composition according to the invention is referred to indifferently in the present description "oily composition cold solid and divided form" or "oily composition additive". By "penetrability" is meant here the measurement of penetration of solid oils by a cone, which is carried out according to ASTM D217 at 25 ° C. This characteristic of penetrability is expressed in tenths of a millimeter (dmm or 1/10 mm). The cone penetration, measured at 25 ° C, according to the ASTM D217 standard test, represents the measurement of the penetration into a solid oil sample, after a time of 5 seconds, of a cone with a pointed tip. standardized mass, placed without constraints on the surface of a container comprising at least 0.4 kg of solidified oil. This operation is carried out three times and the measurement of the penetration of the solidified oil results from the average of these three measurements.

The solid oils according can also be characterized by their consistency. This consistency characteristic is measured according to the ASTM D4950 standard and is expressed according to the NLGI (National Lubricating Grease Institute Index) scale. The penetrability and consistency of an oil are two related parameters whose correspondence is given in the following table:

Preferably, the solid oil composition according to the invention has a penetrability at 25 ° C., measured according to the ASTM D217 standard, ranging from 50 to 160 1/10 mm, preferably from 55 to 150 1/10 mm, more preferably ranging from 65 to 135 1/10 mm.

Oil

The oil can be of any type, it is chosen according to the intended subsequent application. It can be a hydrocarbon oil of petroleum origin, a hydrocarbon oil of synthetic origin or their mixture.

Preferably the oil is a hydrocarbon oil of petroleum origin. It can be of aromatic or paraffinic type.

According to one embodiment, the oil is composed of 90 to 100% by weight of at least one hydrocarbon oil of petroleum origin, advantageously from 95 to 100%, more preferably from 98 to 100%, by weight of from minus a hydrocarbon oil of origin oil. Even more advantageously, the oil consists of a hydrocarbon oil of petroleum origin or a mixture of hydrocarbon oils of petroleum origin.

In a first embodiment of the invention, the hydrocarbon oil of petroleum origin is chosen from aromatic oils.

More preferably, the aromatic oils have a content of aromatic compounds of between 30 and 95% by weight, advantageously between 50 and 95% by weight, more advantageously between 60 and 95% by weight relative to the total weight of the aromatic oil (SARA method: Saturated / Aromatic / Resins / Asphaltenes).

More preferably, the aromatic oils have a content of saturated compounds of between 1 and 20% by weight, advantageously between 3 and 15% by weight, more preferably between 5 and 10% by weight (SARA method: Saturated / Aromatic / Resins Asphaltenes).

More preferably, the aromatic oils have a content of resin compounds of between 1 and 10% by weight, advantageously between 3 and 5% by weight, (SARA method: Saturated / Aromatic / Resins / Asphaltenes).

The contents of saturated compounds, resins and aromatics mentioned in the present application are determined according to ASTM D2140, in% by weight relative to the mass of the oil.

More preferably, the aromatic oils have a kinematic viscosity at 100 ° C of between 0.1 and 150 mm ² / s, advantageously between 5 and 120 mm ² / s, more advantageously between 7 and 90 mm ² / s (Method ASTM D 445).

More preferably, the aromatic oils have a kinematic viscosity at 40 ° C. of between 100 and 10,000 mm ² / s, advantageously between 200 and 7,500 mm ² / s, more advantageously between 250 and 6,000 mm ² / s (Method ASTM D 445).

More preferably, the aromatic oils have a Cleveland flash point greater than or equal to 150 ° C., advantageously between 150 ° C. and 600 ° C., more advantageously between 200 ° C. and 400 ° C. (EN ISO 2592 method). More preferably, the aromatic oils have an aniline point of between 20 ^° C. and 120 ^° C., advantageously between 40 ^° C. and 120 ^° C. (ASTM D611 method) More preferably, the aromatic oils have a density of 15 ° C. between 400 kg / m ^"and 1500 kg / m ^J, advantageously between 600 kg / m ³ and 1200 kg / m ^3, more preferably between 800 kg / m ³ and 1000 kg / m ³ (ASTM D4052)

According to this advantageous embodiment, the aromatic oil comprises aromatic extracts of petroleum residues obtained by extraction or dearomatization of residues of distillations of petroleum fractions.

The aromatic extracts are secondary products of the process of refining crude oils, obtained especially from the products of the vacuum distillation of atmospheric residues. They result from a single or double extraction of the raffinate that can be used in lubricants by means of a polar solvent. The different extracts are classified in different categories according to their process of obtaining and are the following ones:

- DAE (Distillate Aromatic Extract in English, or distillate aromatic extract)

- MES (Mild Extract Solvate in English or soft extraction solvent),

- Treated Distillate Aromatic Extract (TDAE),

- RAE (Residual Aromatic Extract in English or residual aromatic extract),

- TREE (Treated Residual Aromatic Extract in English or residual aromatic extract treated)

For example, the aromatic oils that can be used according to the invention can be chosen from the following products marketed by TOTAL under the names Plaxolene 50® (also known under the name SCRIPTANE NW 50®), Plaxolene TD346® and Plaxolene MSI 32®. .

The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil at the origin of the aromatic oil and the refining process used.

For example, Plaxolene 50 ® or SCRIPTANE NW 50 ® is an RAE (Residual Aromatic Extract) that presents:

a density at 15 ° C of between 980 kg / nr and 1010 kg / m ³ (ASTM Method D4052), a flash point (Cleveland) of approximately 230 ° C (EN ISO 2592 method), a kinematic viscosity at 100 ° C of between 60 and 85 mm ² / s (ASTM Method D 445),

aniline point between 53 and 65 ° C (ASTM D611 method).

For example, Plaxolene TD346 ® is a TDAE (Treated Distillates Aromatic Extract) that presents:

a density at 15 ° C of between 940 kg / m ³ and 970 kg / m 2 (ASTM Method D4052),

a flash point (Cleveland) of about 220 ° C (EN ISO 2592 method),

a kinematic viscosity at 100 ° C of between 16 and 23 mm ² / s (Method

ASTM D 445),

aniline point between 64 and 72 ° C (ASTM Method D61 1).

For example, Plaxolene MSI 32 ® is a MES (Mild Extract Solvate) that presents:

a density at 15 ° C of between 895 kg / m 2 and 925 kg / m ³ (ASTM Method D4052),

- a flash point (Cleveland) of about 230 ° C (EN ISO 2592 method),

a kinematic viscosity at 100 ° C of between 13 and 17 mm ² / s (ASTM Method D 445),

aniline point between 85 and 100 ° C (ASTM D611 method).

According to a second advantageous embodiment, the oil is a paraffinic oil comprising mainly paraffinic extracts of petroleum residues. According to this specific embodiment, advantageously, the oil comprises a total content of paraffinic compounds of at least 50% by weight, preferably at least 60% by weight, for example between 50% and 90%. >, preferably between 60%> and 90%>, more preferably between 50% and 80% and in particular between 55% and 75% or in particular between 60%> and 75%>.

In a more specific embodiment, the oil also contains a total content of naphthenic compounds which does not exceed 25%, for example between 5% and 25%, and in particular between 10% and 25%>.

In a more specific embodiment, the oil also contains a total content of aromatic compounds which does not exceed 25%, for example between 5% and 25%, and in particular between 8% and 18%>. In a particularly preferred embodiment, the oil is a paraffinic oil, comprising the respective contents:

(i) a total content of paraffinic compounds of between 50% and 90%;

(ii) a total content of naphthenic compounds of between 5% and 25%; and (iii) a total content of aromatic compounds of between 5% and 25%.

In a more particularly preferred embodiment, the oil is a paraffinic oil, comprising the respective contents:

(i) a total content of paraffinic compounds of between 60% and 75%;

In a still preferred embodiment, the oil is a paraffinic oil, comprising the respective contents:

(i) a total content of paraffinic compounds of between 60% and 75%;

(ii) a total content of naphthenic compounds of between 15% and 25%; and (iii) a total content of aromatic compounds of between 10% and 15%.

In a preferred embodiment of the invention, the paraffmic oils are derived from distillation deasphalting cuts under reduced pressure (vacuum residue, RSV) crude oil (hereinafter referred to as "DAO oil"). The principle of deasphalting is based on a separation by precipitation of a petroleum residue in two phases: i) a phase called "deasphalted oil", also called "oil matrix" or "oil phase" or DAO (DeAsphalted Oil in English); and ii) a phase called "asphalt". Oils corresponding to the characteristics below and usable according to the invention are obtained by vacuum residue deasphalting processes (RSV) from petroleum refining, for example by deasphalting with a C 3 solvent. C6, preferably with propane. Deasphalting processes are well known to those skilled in the art and are described for example in FR3014111, US 2004/0069685, US 4,305,812 and US 4,455,216 or in Lee et al., 2014, Fuel Processing Technology 119: 204-210.

In Lee et al., 2014, Fuel Processing Technology 119: 204-210, residues from vacuum distillation (RSV) are separated according to their molecular weight in the presence of C ₃ to C ₆ solvent (eg propane). The so-called DAO oil thus obtained is rich in paraffin, has a very low asphaltenes content, a temperature of evaporation between 440 ° C and 750 ° C and API gravity much higher than vacuum residues.

The API gravity or API gravity of an oil (API gravity) can be obtained from the following formula (1):

with:

- G _API , the API gravity of the oil considered (expressed without unit), and

- d, the density at 16 ° C (60 ° F) of the oil in question (expressed without unit) taking water as a reference.

The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil at the origin of the DAO oil and the refining process used. Those skilled in the art know how to determine the respective contents of paraffinic, naphthenic and aromatic compounds of a DAO oil for example using the SARA fractionation method also described in Lee et al 2014, Fuel Processing Technology 119: 204-210 and thus selecting the appropriate DAO oil for the preparation of the gelled oil composition according to the invention.

The contents of paraffmic, naphthenic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in% by weight relative to the weight of the oil.

In a third embodiment of the invention, the hydrocarbon oil of petroleum origin is a mixture of aromatic oils as described above and paraffmic oils as described above.

According to another embodiment, the oily composition may further comprise an oil of vegetable origin.

For example, vegetable oils can be chosen from rapeseed, sunflower, soybean, flax, olive, palm, castor oil, wood, corn, squash, grape seed oil. , jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and mixtures thereof.

Preferably, the oil of petroleum origin represents at least 80% by weight of the oil present in the solid oil compositions, preferably at least 90% by weight, still more preferably at least 95% by weight, and advantageously at least 99% by weight.

The organogelling additive

The solid oil composition at room temperature and in divided form according to the invention comprises at least one chemical additive chosen from organogelling additives.

In particular, the solid oil composition at room temperature and in divided form comprises at least one chemical organogelling additive in an amount adapted so that this composition is solid at room temperature and in divided form. In one embodiment of the invention, the organogelling chemical additive is an organic compound. Advantageously, the organogelling additive has a molar mass less than or equal to 2000 gmol ^-1 , preferably a molar mass less than or equal to 1000 gmol ^-1 .

In this first embodiment, according to a first variant, the organogelling additive is a compound of general formula (I):

Ar1-R-Ar2 (I),

in which :

Ar 1 and Ar 2 represent, independently of one another, a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group and optionally substituted with one or more alkyl groups;

R represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate and anhydride functions. Ar 1 and / or Ar 2 are preferably substituted with at least one alkyl group of 1 to 10 carbon atoms, advantageously at one or more ortho positions with respect to the hydroxyl group (s), more preferably Ar 1 and Ar 2 are 3,5-dialkyl-4-hydroxyphenyl groups, advantageously 3,5-di-tert-butyl-4-hydroxyphenyl groups.

Preferably, R is in the para position with respect to a hydroxyl group of Ar1 and / or Ar2.

An example of a compound of formula (I) is 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.

According to a second variant of this first embodiment, the organogelling additive is a compound of general formula (II):

R- (NH) _n CONH- (X) _m -NHCO (NH) _n -R '(II), wherein

the groups R and R ', which may be identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, optionally substituted by one or more hydroxyl groups or amino groups, and optionally comprising heteroatoms such as N, O, S, C5-C24 hydrocarbon rings and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms such as N, O, S, C5-hydrocarbon rings; C24 and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

n and m are integers having a value of 0 or 1 independently of one another.

According to this variant, when the integer ma has a value of 0, then the groups R- (NH) _n CONH and NHCO (NH) _n -R 'are covalently linked and together form a CONH-NHCO hydrazide bond. The group R, or the group R ', then represents at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms, an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic system, partially aromatic or entirely aromatic, each ring comprising 5 or 6 atoms. Still according to this variant, when the integer ma has a value of 1, then the group R, the group R 'and / or the group X, represent at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic ring system, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms.

Preferably, the group R and / or R 'represent an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, especially chosen from C4H9, C5H11, C9H19, C11H23, C12H25, C17H35, C18H37, C21H43, C22H45 groups.

According to a first preferred embodiment, the group X represents a linear, saturated hydrocarbon-based chain comprising from 1 to 22 carbon atoms, advantageously from 1 to 12 carbon atoms, more preferably from 1 to 10 carbon atoms. Preferably, the group X is selected from C2H4 groups, C ₃ H _6.

According to a second preferred embodiment, the group X may also be a cyclohexyl group or a phenyl group, the radicals R- (NH) _n CONH- and -NHCO (NH) _n -R 'may then be in the ortho, meta position. or para. Furthermore, the radicals R- (NH) _n CONH- and -NHCO (NH) _n -R 'may be in the cis or trans position with respect to each other. In addition, when the radical X is cyclic, this ring may be substituted by groups other than the two main groups R- (NH) _n CONH- and -NHCO (NH) _n -R '.

According to a third preferred embodiment, the X group represents two cycles of 6 carbons, optionally substituted, connected by a CH ₂ group, these rings being aliphatic or aromatic. In this case, the group X is for example:

Advantageously, according to this variant, the organogelator additive is a compound of general formula (II) chosen from derivatives hydrazides such as compounds C5H11- CONH-NHCO-C 1 ₅ Hi, C9H19-CONH-C9H19-NHCO, C iH ₂₃ -CONH-NHCO-Ci iH _23, Ci7H3 ₅ -CONH-NHCO-Ci7H _35, or H43-C21-CONH NHCO-C21H43; diamides such as N, N ^* -éthylènedi (laurylamide) of the formula C ₁₁ H ₂₃ -CONH-CH ₂ -CH ₂ -NHCO- C _{1 1M} _31, N, N ^* -éthylènedi (myristylamide) of the formula C ₁₃ H ₂₇ -CONH-CH ₂ -CH ₂ - NHCO-C13H27, N, N ^* -éthylènedi (palmitamide) of the formula H ₃ Ci ₅ i-CONH-CH2-CH ₂ - NHCO-Ci ₅ H ₃ i N, N ^* -éthylènedi (stearamide) of the formula Ci ₇ H ₃₅ -CONH-CH ₂ -CH ₂ - NHCO-Ci ₇ H _35; and ureide derivatives such as 4,4'-bis (dodecylaminocarbonylamino) diphenylmethane of the formula C ₁₂ H ₂₅ -NHCONH-C ₆ H 4 -CH 2 -C ₆ H 4 -NHCONH-C ₁₂ H 2 ₅ .

According to a third variant, the organogelling additive is a compound of formula (III):

(R-NHCO) _x -Z- (NHCO-R ') _y (III),

in which,

R and R ', which are identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, which may be optionally substituted, and optionally comprising heteroatoms such as N, O, S, rings; C ₅ -C ₂₄ hydrocarbonaceous hydrocarbons and / or C ₄ -C ₂₄ hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S,

Z represents a tri-functionalized group chosen from the following groups:

x and y are different integers, of value ranging from 0 to 3 and such that x + y = 3.

Preferably, when x is 0 and Z is Z ₂ , the compound of formula (III) is N 2, N 4, N 6 -tridecylmelamine having the following formula with R 'representing the group C 9 H 19:

Other preferred compounds corresponding to formula (III) are such that x is equal to 0, Z represents Z ₂ and R 'represents a linear saturated hydrocarbon-based chain of 1 to 22 carbon atoms, preferably 2 to 18 carbon atoms, preferably 5 to 12 carbon atoms.

Other preferred compounds corresponding to formula (III) are such that: y is 0 and Z is Zi, the compounds then have the formula:

with R selected from the following groups, taken alone or in mixtures:

Other preferred compounds corresponding to formula (III) are such that: y is 0, Z represents Z ₁ and R represents a linear saturated hydrocarbon-based chain of 1 to 22 carbon atoms, preferably 8 to 12 carbon atoms. carbon atoms.

In a fourth variant, the additive organogelator is a reaction product of at least one polyol C ₃ -C ₂ and at least one aldehyde C ₂ -C _12. Among the polyols that may be used, mention may be made of sorbitol, xylitol, mannitol and / or ribitol. Preferably, the polyol is sorbitol. Advantageously, according to this variant, the organogelling additive is a compound which comprises at least one function of general formula (IV):

R

(IV)

with:

x is an integer,

R is selected from alkyl C ₁ -C ₁₂ alkenyl, C ₂ -C ₁₂ aryl, C ₆ - C ₁₂ aralkyl or C ₇ -C _12, optionally substituted by one or more halogen atoms, one or more C ₁ -C ₆ alkoxy groups.

According to this variant, the organogelling additive is advantageously a sorbitol derivative. By "sorbitol derivative" is meant any reaction product, obtained from sorbitol. In particular, any reaction product obtained by reacting an aldehyde with D-sorbitol. This condensation reaction produces sorbitol acetals, which are derivatives of sorbitol. 1,3: 2,4-Di-O-benzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:

The sorbitol derivatives may thus be all the condensation products of aldehydes, especially aromatic aldehydes with sorbitol. Sorbitol derivatives of general formula will then be obtained:

where Ari and Ar ₂ are optionally substituted aromatic rings.

Among the derivatives of sorbitol, other than 1,3: 2,4-Di-O-benzylidene-D-sorbitol, there can be found, for example, 1,3,3,4,5,6-tri-O-benzylidene- D-sorbitol, 2,4-mono-O-benzylidene-D-sorbitol, 1,3,2,4-bis (p-methylbenzylidene) sorbitol, 1,3,2,4-bis (3,4-bis), dimethylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (p-propylbenzylidene) sorbitol, 1,3,2,4-bis (p-butylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethoxylbenzylidene) sorbitol, 1,3,2,4-bis (p-chlorobenzylidene) sorbitol, 1,3,2,4-bis (p-bromobenzylidene) sorbitol, 1,3: 2,4-Di-O-methylbenzylidene-D-sorbitol, 1,3: 2,4-Di-O-dimethylbenzylidene-D-sorbitol, 1: 3: 2,4-Di-O- (4) -methylbenzylidene) -D-sorbitol, 1,3: 2,4-Di-O- (4,3-dimethylbenzylidene) -D-sorbitol. Preferably, according to this variant, the organogelling additive is 1,3: 2,4-Di-O-benzylidene-D-sorbitol.

According to a fifth variant, the organogelling additive is a compound of general formula (V):

R "- (COOH) _z (V),

in which R "represents a linear or branched, saturated or unsaturated chain comprising from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms, and z is an integer ranging from 2 to at 4. Preferably, the group R "is a saturated linear chain of formula C _w H _2w with w an integer ranging from 4 to 22, preferably from 4 to 12.

According to this variant of the invention, the organogelling additives corresponding to the formula (V) can be diacids (z = 2), triacids (z = 3) or tetracides (z = 4). The preferred organogelling additives according to this variant are diacids with z = 2. Preferably, according to this variant, the diacids (V) have the general formula HOOC-C _w H _2w -COOH with w an integer ranging from 4 to 22, preferably from 4 to 12.

Advantageously, according to this variant, the organogelling additive is a diacid chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, the acid suberic or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12. More preferably, the organogelling additive is sebacic acid or 1,10-decanedioic acid with w = 8.

The diacids may also be diacid dimers of unsaturated fatty acid (s), that is to say dimers formed from at least one unsaturated fatty acid, for example from a single fatty acid. unsaturated or from two different unsaturated fatty acids. The diacid dimers of unsaturated fatty acid (s) are conventionally obtained by intermolecular dimerization reaction of at least one unsaturated fatty acid (reaction of Diels Aid for example).

Preferably, only one type of unsaturated fatty acid is dimerized. They derive, in particular, from the dimerization of an unsaturated fatty acid, in particular C ₈ to C 34, especially C ₁₂ to C ₂₂ , in particular C ₁₆ to C 20, and more particularly C ₁₈ .

A preferred fatty acid dimer is obtained by dimerization of linoleic acid, which can then be partially or fully hydrogenated.

Another preferred fatty acid dimer has the formula HOOC- (CH ₂ ) 7 -CH = CH- (CH ₂ ) ₇ -COOH. Another preferred fatty acid dimer is obtained by dimerization of methyl linoleate. In the same way, it is possible to find triacids of fatty acids and tetracides of fatty acids, obtained respectively by trimerization and tetramerization of at least one fatty acid.

According to a sixth variant, the organogelling additive is a compound of general formula (VI):

in which,

the groups Y and Y 'represent, independently of one another, an atom or a group chosen from: H, - (CH ₂ ) q -CH ₃ , - (CH ₂ ) q -NH ₂ , - (CH ₂ ) q- OH, - (CH ₂ ) q-COOH or

with q an integer varying from 2 to 18, preferably from 2 to 10, preferably from 2 to 4 and p an integer greater than or equal to 2, preferably having a value of 2 or 3.

Among the preferred organogelling additives of formula (VI), mention may be made of the following compounds:

Preferably, according to this variant, the organogelling additive of general formula (VI) is:

According to a seventh variant of this embodiment, the organogelling additive is a compound of general formula (VII):

R-NH-CO-CO-NH-R '(VII)

in which R and R ', which may be identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, which may be substituted, and comprising optionally heteroatoms, such as N, O, S, C5-C24 hydrocarbon rings and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S. It will not be departing from the scope of the invention by combining several different chemical additives such as various organogelling additives of formula (I), (II), (III), (V),

(VI) and (VII), the reaction products of at least one C ₃ -C ₁₂ polyol and at least one C ₂ -C ₁₂ aldehyde, in particular those comprising a group of formula (IV), in the composition oil.

Advantageously, the oil composition comprises at least one organogelling additive chosen from the compounds of formula (I), the compounds of formula (II) and the compounds of formula (V).

More preferably, the oil composition comprises at least one organogelling additive selected from compounds of formula (I) or compounds of formula (II).

Preferably, the oil composition comprises an organogelling additive in which the additive is 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.

According to an advantageous embodiment, the oil composition according to the invention comprises at least two organogelling additives.

According to a first variant of this embodiment, the oil composition according to the invention comprises at least one first organogelling additive of formula

(V) and at least one second organogelling additive selected from: organogelling additives of formula (I); organogelling additives of formula (II); organogelling additives of formula (III); organogelling additives of formula (V); organogelling additives of formula (VI); organogelling additives of formula

(VII) and the reaction products of at least one C ₃ -C ₁₂ polyol and at least one C ₂ -C ₁₂ aldehyde, in particular those comprising a group of formula (IV), the second organogelling additive being distinct from first additive organogelling.

Preferably, and according to this first variant, the oil composition according to the invention comprises at least one first organogelling additive of formula (V) and at least one second organogelling additive chosen from: the organogelling additives of formula (I) and the organogelling additives of formula (II).

According to a second variant of this embodiment, the oil composition according to the invention comprises at least one first organogelling additive of formula (II) and at least one second organogelling additive chosen from: the organogelling additives of formula (I); organogelling additives of formula (II); organogelling additives of formula (III); organogelling additives of formula (V); organogelling additives of formula (VI); the organogelling additives of formula (VII) and the reaction products of at least one C ₃ -C 12 polyol and at least one C ₂ -C 12 aldehyde, in particular those comprising a group of formula (IV), the second additive organogelling being distinct from the first organogelling additive.

According to a third variant of this embodiment, the oil composition according to the invention comprises at least one first organogelling additive of formula (I) and at least one second organogelling additive chosen from: organogelling additives of formula (I); organogelling additives of formula (II); organogelling additives of formula (III); organogelling additives of formula (V); organogelling additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C 3 -C 12 polyol and at least one C 2 -C 12 aldehyde, in particular those comprising a group of formula (IV), the second organogelling additive being distinct from the first organogelling additive.

Preferably, and according to this third variant, the second organogelling additive is chosen from the organogelling additives of formula (II) and the organogelling additives of formula (V).

Advantageously, the oil composition comprises from 0.1% to 10% by weight, preferably from 0.2% to 5% by weight, more preferably from 0.5% to 3.5% by weight of chemical additive. organogelator with respect to the total mass of the composition.

Composition of solid oil at room temperature and in divided form

The oil composition is solid at room temperature and in divided form. It comprises the oil, the organogelling additive (s) and, if appropriate, other additives. Advantageously, the oil composition comprises, or is essentially composed of:

80% to 99.9% by weight of at least one oil chosen from: hydrocarbon oils of petroleum or synthetic origin, preferably of petroleum origin, advantageously chosen from aromatic oils and paraffinic oils,

0.1% to 10% by weight, of at least one organogelling chemical additive,

0% to 10% by weight of one or more other additives,

relative to the total mass of the composition. Preferably, the oil composition comprises, or is essentially composed of:

85% to 99.8% by weight of at least one oil, chosen from: hydrocarbon oils of petroleum or synthetic origin, preferably of petroleum origin, advantageously chosen from aromatic oils and paraffinic oils,

0.2% to 5% by weight, of at least one chemical organogelling additive,

0% to 10% by weight of one or more other additives,

relative to the total mass of the composition. More preferably, the oil composition comprises, or is essentially composed of:

86.5% to 99.5% by weight of at least one oil chosen from: hydrocarbon oils of petroleum or synthetic origin, preferably of petroleum origin, advantageously chosen from aromatic oils and paraffinic oils, 0.5% to 3.5% by weight of at least one organogelling chemical additive,

• 0% to 10% by weight of one or more other additives relative to the total mass of the composition.

According to a first preferred embodiment, the organogelling additive is chosen from those corresponding to formula (I), in particular 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] ] propionyl)] propionohydrazide.

Advantageously according to this embodiment, the oil composition comprises, or is essentially composed of:

85% to 99.9% by weight of at least one hydrocarbon oil of petroleum origin, preferably of petroleum origin, advantageously chosen from aromatic oils and paraffinic oils,

0.1% to 5% by weight of at least one organogelling chemical additive of formula (I), advantageously 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] ] propionyl)] propionohydrazide,

0% to 10% by weight of one or more other additives,

86.5% to 99.8% by weight of at least one hydrocarbon oil of petroleum origin, preferably of petroleum origin, advantageously chosen from aromatic oils and paraffinic oils,

0.2% to 3.5% by weight of at least one organogelling chemical additive of formula (I), advantageously 2 ', 3-bis [(3- [3,5-di-tert-butyl] 4-hydroxyphenyl] propionyl)] propionohydrazide,

0% to 10% by weight of one or more other additives,

relative to the total mass of the composition.

Other additives

According to one variant of the invention, it is possible to incorporate into the oil composition all kinds of additives usually used for the formulation, depending on the intended application, since these additives do not interfere with gelation.

The amount of additive in the oil composition is calculated according to the amount of oil that will be implemented for the intended application and the amount of additive expected in this application. Usually, the additives are incorporated in amounts ranging from 0.1 to 10% by weight based on the total weight of the oil composition.

Application for tire manufacturing

The oily composition according to the invention may further comprise one or more additives forming part of the formulation of elastomer compositions, in particular of rubber, it is possible to add pigments, colorants, vulcanization, vulcanization-retarding agents, silica, fatty acids such as stearic acid, silanes, carbon black, etc.

According to one embodiment of the invention, the oil composition also comprises at least one compound chosen from transition metal oxides, such as oxides of magnesium, calcium, cadmium, lead and cobalt. zinc, especially zinc oxide ZnO.

Zinc oxide is commonly used to catalyze the vulcanization of rubber. Application for the manufacture of inks

The oily composition according to the invention may further comprise one or more additives included in the ink formulation, for example surfactants, fillers, stabilizers, drying or semi-drying oils, rheology improving agents, anti-oxidant additives, drying accelerators, anti-abrasion agents, gelling agents, etc.

By way of example of drying or semi-drying oils, mention may be made of linseed oil, tung oil and safflower oil.

Preferably, the oily composition according to the invention is used in the manufacture of printing inks, in particular inks for printing in flat form (or else offset printing) which is divided into three types: heat-inks. set, inks for sheet-fed sheet machines, cold-set inks (newspaper inks).

Process for preparing the solid oil composition

The solid oil compositions at ambient temperature according to the invention may be prepared, for example, according to the following process comprising the steps of:

(I) having an oil, for example DAO or RAE oil, and heating it with stirring at a temperature between 70 and 250 ° C., preferably between 140 and 200 ° C., for example from 10 minutes to 30 ° C. minutes,

(ii) adding an organogelling additive and heating with stirring at a temperature between 70 and 250 ° C, preferably between 140 and 200 ° C, for example from 30 minutes to 2 hours,

(iii) optionally adding one or more other additives and heating with stirring at a temperature between 70 and 250 ° C, preferably between 140 and 200 ° C, for example, from 5 minutes to 20 minutes,

(iv) shaping the composition, for example in the form of granules or loaves,

(v) cool to room temperature.

The order of steps (i) to (iii) can be changed. Solid oil granules at room temperature

For the purposes of the invention, the term "oil granules" can also be defined as a solid oil at room temperature packaged in a divided form, that is to say in the form of small units called balls, granules or particles.

The oil granules according to the invention are obtained by shaping an oil composition as described above according to any known process, for example according to the manufacturing method described in document US Pat. No. 3,026,568, US Pat. WO 2009/153324 or WO 2012/168380. According to a particular embodiment, the shaping of the granules can be carried out by draining, in particular using a drum.

Other techniques can be used in the process for manufacturing room temperature solid oil granules according to the invention, in particular molding, extrusion, etc.

Preferably, the oil granules according to the invention may have within the same population of granules, one or more forms chosen from a cylindrical, spherical or ovoid shape. The size of the oil granules according to the invention is such that the longest average dimension is preferably less than or equal to 50 mm, more preferably from 3 to 30 mm, even more preferably from 5 to 20 mm. The size and shape of solid oil granules at room temperature may vary depending on the manufacturing process employed. For example, the use of a die makes it possible to control the manufacture of granules of a chosen size. Sieving allows the selection of granules according to their size. The oil granules are preferably transported and / or stored in bulk in bags of 1 kg to 30 kg or 500 kg to 1000 kg commonly called "Big Bag", said bags being preferably in hot melt material or in boxes of 5 kg to 30 kg or in drums of 100 kg to 200 kg.

According to one embodiment of the invention, the oil granules according to the invention are covered on at least a portion of their surface with an anti-caking agent, preferably over their entire surface. Solid oil bread at room temperature

According to one embodiment of the invention, the solid oil composition at room temperature and in divided form is in the form of bread. For the purposes of the invention, the oil composition in the form of bread is also called "oil bread".

By solid oil bread at ambient temperature is meant an oil composition block according to the invention having a mass of between 1 kg and 1000 kg, preferably between 1 kg and 200 kg, more preferably between 1 kg. and 50 kg, even more preferably between 5 kg and 25 kg, more preferably between 10 kg and 30 kg, said block being advantageously parallelepipedic, preferably being a block.

The oil cake according to the invention preferably has a volume of between 1000 cm ³ and 50 000 cm ³ , preferably between 5000 cm ³ and 25 000 cm ³ , more preferably between 10 000 cm ³ and 30 cm ^3. 000 cm ³ , more preferably between 14 000 cm ³ and 25 000 cm ³ .

When the oil bread according to the invention is handled manually by a person, the mass of the oil bread can vary from 1 to 20 kg, and from 20 to 50 kg in the case of handling by two people. When the handling is carried out by mechanical equipment, the mass of the oil bread according to the invention can vary from 50 to 1000 kg.

The oil cake according to the invention is manufactured from the oil composition as described above according to any process known industrially, for example by extrusion, by molding, or according to the manufacturing method described in the US document. 2011/0290695.

The oil cake according to the invention is advantageously packaged in a hot-melt film according to any known method, preferably a film made of polypropylene, polyethylene or a mixture of polyethylene and polypropylene. The oil composition according to the invention packaged in bread packaged in a hot melt film has the advantage of being ready for use, that is to say that it can be directly heated in the melter without prior unpacking, for example for the manufacture of elastomer compositions. The hot melt material which melts with the oil composition according to the invention does not affect the properties of said oil composition. The oil cake according to the invention may also be covered with anti-caking compound as defined below.

In this variant, the preferences, the advantages, the various embodiments described for the anti-caking compounds also apply.

The oil bread according to the invention can also be packaged in a carton according to any known method.

In particular, the oil bread according to the invention is packaged in a carton by hot casting the oil composition according to the invention in a carton whose wall of the inner face is silicone and then cooled, the dimensions of the carton being adapted to the mass and / or the volume of the desired oil bread.

When the oil bread according to the invention is packaged in a hot-melt film or is packaged in a carton, the applicant has demonstrated that the deterioration of said hot-melt film or said carton during the transport and / or storage at ambient temperature of said baking bread. The oil according to the invention did not cause creep of the oil composition. Therefore, the oil bars according to the invention retain their original shape and do not stick to each other during their transport and / or storage at room temperature despite the fact that the hot melt film or cardboard is damaged. The absence of creep of the oil composition according to the invention in the form of bread during its transport and / or its storage at ambient temperature is due to the presence of the organogelling additive (s) within the oil composition. .

The anti-caking compound:

Optionally, as stated above, the oil composition according to the invention in solid form divided at room temperature, for example in the form of granules or solid oil buns at room temperature, can be partially coated with one or more anti-caking compounds.

The anti-caking compound is of mineral or organic origin. By "anti-caking agent" or "anti-caking compound" is meant any compound which limits, reduces, inhibits, delays, agglomeration and / or adhesion of granules or loaves to one another during their transport and / or storage and / or handling at room temperature and in the case of granules, also ensures their fluidity during handling. More preferably, the anti-caking compound is chosen from: talc; the fines, also called "fillers", generally of diameter less than 125 μιη, such as fine silicones, with the exception of fine limestones; sand such as fountain sand; cement ; carbon; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; the ashes of rice balls; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silicates, silicon hydroxides and other silicon oxides; silica fumes; plastic powder; lime; the plaster ; rubber crumb; polymer powder, such as styrene-butadiene copolymers (SB), styrene-butadiene-styrene copolymers (SBS) and mixtures of these materials.

Advantageously, the anti-caking compound is chosen from: fines, generally of diameter less than 125 μιη; wood residues such as lignin, conifer needle powders and conifer cone powders; silica fumes; their mixtures.

Preferably, the mass of anti-caking agent covering at least a part of the surface of the granules or loaves of oil is between 0.2% and 10% by weight, preferably between 0.5% and 8%. in bulk, more preferably between 0.5% and 5% relative to the total mass of oil composition according to the invention, in said granules or said loaves or balls.

The anti-caking layer covering the granules or the oil bars according to the invention is preferably continuous so that at least 90% of the surface of the granule or oil cake is the invention is coated with at least one anti-caking agent, preferably at least 95%, more preferably at least 99%. The anti-caking layer must be thick enough for it to be continuous.

The granules or loaves of oil solid at room temperature are covered with anti-caking agent according to any known method, for example according to the process described in document US Pat. No. 3,026,568. Oil composition kit solid cold and divided form

Another object of the invention relates to a kit comprising at least:

an oily solid composition with cold and in divided form as defined above,

a capsule comprising at least one additive as defined above.

According to one embodiment of the invention, the cold-solid and divided-form oily composition is in the form of a loaf.

According to one embodiment of the invention, the oily composition in the form of bread comprises on one of its faces, a cavity for accommodating all or part of the capsule.

According to one embodiment of the invention, the capsule is housed in all or part in the cavity removably.

According to this embodiment, the capsule may be a soft-shell capsule, in particular a sachet, or a hard-shell capsule.

Preferably, the envelope of the capsule is made of heat-fusible plastic film, in particular polyethylene, or silicone.

Another subject of the invention relates to the use of the kit as defined above in the process for preparing an oily composition ready for application according to the invention.

According to one embodiment of the invention, the oily composition in the form of bread and the capsule forming the kit as defined above are used in the process for preparing an oily composition simultaneously or consecutively.

In a variant, when the oily composition in the form of bread and the capsule forming the kit as defined above are used consecutively in the process for preparing an oily composition, the said oily composition in the form of bread is heated beforehand and then the capsule is added. In this variant, before the heating of the oily composition bread, the capsule is dislodged from the cavity present on one of the faces of the bread.

In another variant, the oily composition in the form of bread and the capsule forming the kit as defined above are used simultaneously in the process for preparing an oily composition. Method of transporting and / or storing and / or handling the solid oil composition at room temperature and in divided form

Another subject of the invention also relates to a method for transporting and / or storing and / or handling the solid oil composition at room temperature and in divided form, the composition being transported and / or stored and / or handled in the form of loaves or granules of solid oil composition at room temperature. The solid oil composition at room temperature and in divided form is as described above.

Preferably, the additive oil composition of the invention is transported and / or stored at room temperature for a period greater than or equal to 2 months, preferably 3 months.

According to one embodiment of the invention, the ambient temperature solid oil composition of the invention is transported and / or stored at a temperature below 80 ° C. In particular, the transport and / or storage temperature corresponds to the ambient temperature. By ambient temperature is meant the temperature which is reached during the transport and / or storage of the oil composition according to the invention without said composition being heated by any type of process. Thus, the ambient temperature can reach high temperatures, below 80 ° C during summer periods, especially in geographical regions with a hot climate.

Advantageously, the ambient temperature is 5 ° C to 70 ° C, preferably 10 ° C to 70 ° C, more preferably 10 ° C to 60 ° C, even more preferably 15 ° C to 50 ° C.

The solid oil compositions at room temperature and in divided form according to the present invention are remarkable in that they allow the transport and / or storage and / or handling of oil at ambient temperature under optimum conditions, particularly without creep of said solid compositions during their transport and / or storage and / or handling, even when the ambient temperature is high and without degrading the properties of the composition, or even improving them. Use of solid plasticizing oil compositions at room temperature

Plasticizer is a substance incorporated in a material to increase its malleability, flexibility or density. Plasticizers are incorporated into the rubber and also contribute to the mechanical properties of the elastomer after vulcanization. The plasticizing oils can be introduced up to 30% in a tire formulation. They bring several benefits to the formulator:

Better transformability of the elastomer, improved mechanical performance, improved cold properties. The solid plasticizing oil compositions of the invention make it possible to provide these same properties to compositions based on elastomer, in particular for the formulation of tires. No degradation of the performances in this application has been observed, despite the presence of the organogelling additive (s).

The plasticizing oil compositions of the invention can be used in any type of elastomer composition, whether of natural or synthetic origin. The elastomer-based composition may be based on natural rubber (NR) or synthetic rubber, such as cis-1,4-linked synthetic polyisoprenes (IR), polybutadienes (BR), butadiene-based copolymers. styrene (SBR), styrene-butadiene-styrene copolymers (SBSR), butadiene-isoprene copolymers (BIR), isoprene-styrene copolymers (SIR), styrene-butadiene-isoprene copolymers (SBIR), ethylene-propylene-diene monomer (EPDM), polyurethanes (PUR) and a mixture of two or more of these elastomers.

The elastomer composition, in particular the tire composition, may also include fillers such as carbon black or silica, or other additives such as vulcanizing agents, vulcanization retarding agents.

For the manufacture of tires, the elastomer compositions are presently used in the form of unvulcanized rubber bales, which are heated in admixture with the additives. The solid plasticizing oil composition according to the invention can also be introduced into the reactor in solid form. This solid formulation has the advantage of facilitating the determination of the plasticizing oil, but also other additives that can be introduced into the oil composition. plasticizers, such as vulcanizing agents, vulcanization retarding agents, fillers.

Use of solid solvent oil compositions at room temperature in ink compositions.

In inks, petroleum oils, particularly viscous aromatic oils, are used as the solvent for coldset type ink compositions. Coldset inks, also described as newspaper inks, are inks that dry by absorption into the porous substrate.

These ink compositions are usually composed of pigments, performance additives, resin binders and solvents. Generally, the pigments represent from 5 to 30% by weight, the resinous binders represent from 15 to 60% by weight, the performance additives represent from 1 to 10% by weight and the solvents, for example the hydrocarbon solvents, the naphthenic oils the viscous aromatic oils and mixtures thereof are from 30 to 70% by weight, based on the total mass of the ink composition. In the inks, the solvents have the function of making it possible to adjust the kinematic viscosity of the composition, to solubilize the resin or resins, and to adjust the fluidity of the ink.

More specifically, viscous aromatic oils are used to wet the dye, for example carbon black, to solubilize and disperse it in the polymeric resins of the ink.

The various embodiments, variants, preferences and advantages described above for each of the objects of the invention apply to all the objects of the invention and can be taken separately or in combination.

The invention is illustrated by the following examples given without limitation.

Experimental part :

EXAMPLE 1 Measurement of the Penetrability of Oily Compositions With Additive I- Raw Materials Oil :

Plaxolene 50®: RAE oil, that is to say an aromatic oil, sold by the company TOTAL under the trademark Plaxolène 50 ® but also marketed under the trademark SCRIPT ANE NW 50 ®.

Plaxolene 50 ® or SCRIPT ANE NW 50 ® is an RAE (Residual Aromatic Extract) that presents:

a density at 15 ° C of between 980 kg / m ^J and 1010 kg / m ³ (ASTM Method 1) 4052).

- a flash point (Cleveland) of about 230 ° C (EN ISO 2592 method),

a kinematic viscosity at 100 ° C of 60 to 85 mm ² / s (ASTM Method D 445),

an aniline point between 53 and 65 ° C. (ASTM D611 method). RAE oil: RAE oil, that is to say an aromatic oil, marketed by the company Luberef.

DAE oil: DAE oil, that is to say an aromatic oil, marketed by the company Paramo.

Organogelators:

We used :

Compound A1: 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl)] propionohydrazide (CAS 32687-78-8) sold by the company BASF under the trademark Irganox MD 1024.

II- Characterization methods:

Penetration: ASTM D217 at 25 ° C. III- Preparation of oil compositions according to the invention

The oil compositions according to the invention are prepared according to the following general method: (i) The oil is heated, for example to 170 ° C;

(ii) adding the organogelling additive and mixing for example between 15 min and 2 h, more specifically between 15 min and 1 h at 170 ° C with a stirring speed of between 400 and 500 rpm;

(iii) When the organogelling additive is completely dissolved, the stirring is stopped and the liquid is poured into molds and allowed to cool to room temperature.

Compositions of solid oil at room temperature C1 to C6 according to the invention are prepared according to the process described above with constituents and proportions (in percentage by mass relative to the total mass of oil composition) as follows:

Table 1: Cold solid oily compositions according to the invention

The compositions C 1 to C 6 are cast in a mold and then left to cool to room temperature. After observing the solidification of the compositions C1 to C6 in the mold, the compositions C1 and C6 are demolded and compositions C1 to C6 are obtained in the form of a solid cake at room temperature.

The penetrability of compositions C1 to C6 was measured to determine the solidification of these compositions. The penetrability values of compositions C1 to C6 vary from 65 to 135 dmm (Table 1). The lowest penetration value (65 dmm) is obtained with the composition containing the aromatic oil Plaxolene 50 ®. Therefore, in view of the penetrability values of compositions C1 to C6, it is observed that the addition of an organogelling additive in a hydrocarbon oil makes it possible to solidify this oil at ambient temperature, which thus makes it possible to transport and / or store and / or handle at room temperature this oil in the form of bread or granules without creep.

Example 2 Measurement of the Creep Resistance of the Oil Compositions According to the Invention

450 g of the C3 oil composition are prepared according to the method of preparation described in Example 1 and then the composition is hot cast in a mold and allowed to cool. It takes the form of a solid oil bread at room temperature measuring 15.5 cm in length, 9.5 cm in width and 4 cm in thickness. The oil bread is then removed from the mold and stored at room temperature.

After twelve months of storage at room temperature, the penetrability of the oil cake is measured. It is 75 dmm.

The oil bread is placed under a mass weight equivalent to ten times the mass of an oil bread, ie 4.5 kg. After a week under these conditions, no creep is observed.

Thus, it is clear that the solid oil breads at room temperature can be stored for a long time without creep, their penetrability being stable over time.

Claims

A solid oil composition at room temperature comprising:

80% to 99.9% of at least one oil chosen from a hydrocarbon oil of petroleum origin chosen from aromatic oils, paraffinic oils and their mixtures,

0.1% to 10%, of at least one organogelling additive,

• 0% to 10% of one or more other additives,

2. The composition of claim 1 further comprising an oil of plant origin.

3. Composition according to any one of the preceding claims wherein the hydrocarbon oil is chosen from aromatic oils having an aromatic content of between 30 and 95% by weight, preferably between 50 and 95% by weight, more preferably between 60 and 95% by mass relative to the total mass of the aromatic oil.

4. Composition according to claim 3, wherein the aromatic oil has a kinematic viscosity at 100 ° C of between 0.1 and 150 mm ² / s, advantageously between 5 and 120 mm ² / s, more advantageously between 7 and 90 mm ² / s.

5. Composition according to any one of claims 1 and 2 wherein the hydrocarbon oil is selected from paraffmic oils having a total content of paraffmic compounds of at least 50% by weight relative to the total mass of the oil paraffinic.

6. Composition according to any one of the preceding claims wherein the organogelling additive is a compound of general formula (I):

Ar1-R-Ar2 (I),

in which : Ar 1 and Ar 2 represent, independently of one another, a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and optionally substituted by one or more C 1 -alkyl groups; -C20, and

7. Composition according to any one of the preceding claims wherein the organogelling additive is a compound of general formula (II):

R- (NH) _n CONH- (X) _m -NHCO (NH) _n -R '(II), wherein

the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms, such as N, O, S, C5 hydrocarbon-based rings; -C24 and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

n and m are integers having a value of 0 or 1 independently of one another.

8. Composition according to any one of the preceding claims, which comprises from 0.2% to 5% by weight, more preferably from 0.5% to 3.5% by weight of organogelling additive relative to the total mass of the composition.

9. Composition according to any one of the preceding claims, in the form of granules or loaves.

10. Kit comprising at least:

an ambient temperature solid oil composition according to any one of claims 1 to 9,

a capsule comprising at least one additive.

A process for preparing an ambient temperature solid oil composition according to any one of claims 1 to 9, comprising the steps of:

(I) having an oil chosen from a hydrocarbon oil of petroleum or synthetic origin, chosen from aromatic oils, paraffinic oils and their mixtures and heating it to a temperature of between 70 and 250 ° C., preferably between 140 and 250 ° C. and 200 ° C,

(ii) adding an organogelling additive and heating the mixture to a temperature between 70 and 250 ° C, preferably between 140 and 200 ° C,

(iii) optionally adding one or more other additives and heating the mixture to a temperature between 70 and 250 ° C, preferably between 140 and 200 ° C,

(iv) shaping the composition, for example in the form of granules or loaves,

(v) cool to room temperature.

12. A method of transporting and / or storing and / or handling a solid oil composition at room temperature and in divided form according to any one of claims 1 to 9, or a kit comprising such a composition. according to claim 10, the composition being transported and / or stored and / or handled in the form of solid loaves or granules at ambient temperature.

13. Use of a solid oil composition at room temperature and in divided form according to any one of claims 1 to 9 or a kit comprising such a composition according to claim 10 for the manufacture of tires.

14. Use of a solid oil composition at room temperature and in divided form according to any one of claims 1 to 9 or a kit comprising such a composition according to claim 10 for the formulation of an ink.