EP1446454A1

EP1446454A1 - Crosslinkable adhesive silicone composition comprising as gelling agent a compound with cyclic amine function borne by a siloxane chain

Info

Publication number: EP1446454A1
Application number: EP02785565A
Authority: EP
Inventors: Scott Jackson; Alain Pouchelon
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2001-10-31
Filing date: 2002-10-30
Publication date: 2004-08-18
Also published as: BR0213917A; FR2831548A1; FR2831548B1; WO2003037987A1; US20050020738A1

Abstract

The invention more particularly concerns self-adhesive silicone elastomeric compositions crosslinked by addition reaction, having modified rheological properties. Thus the invention concerns a crosslinkable adhesive silicone composition comprising a polyorganosiloxane (POS) with ( alpha , omega -di-Vi polydimethylsiloxane) Si-Vi units; a crosslinking POS with SiH units; a platinum catalyst; a filler; and optionally an adherence promoter comprising vinyltrimethoxysilane, 3-glycidoxy-propyltrimehtoxysilane and butyl titanate and/or a cross-linkage inhibitor and/or a MMViDDViQ or MDViQ or MMViQ unsaturated POS. Said composition is characterized in that it further comprises a polyorganosiloxane having per mole at least a piperidinyl function. The invention aims at providing a crosslinkable elastomeric silicone composition having rheological properties fully adapted to enable successful use of the composition for bonding various substrates as well as for performing moulding operations requiring non-flowable materials.

Description

CROSSLINKABLE ADHESIVE SILICONE COMPOSITION COMPRISING

AS A THIXOTROPANT AGENT AN AMINE FUNCTIONAL COMPOUND

CYCLIC CARRIED BY A SILOXANIC CHAIN

The field of the present invention is that of silicone elastomer compositions crosslinkable by addition and / or condensation. The polyorganosiloxanes (POS) considered are of the cold vulcanizable type (RTV), knowing that conventionally they are in the form of two-component systems (RTV-2), the vulcanization of which, in the case of crosslinking by addition, can be depending on the use accelerated hot. These products are particularly known for their applications in the field of molding and reproduction; they can then be shaped by casting, injection, brushing, spraying ... depending on the uses.

In the context of the present invention, particular interest is given to self-adhesive silicone elastomer compositions crosslinking by addition reaction, which have modified rheological properties.

More specifically still, the present invention relates to crosslinkable adhesive silicone elastomer compositions comprising a thixotropic agent of POS type with piperidinyl function, giving these compositions a high flow threshold. By flow threshold is meant the ability of the product not to flow spontaneously under its own weight.

RTV type silicone adhesive elastomer compositions are now well known and have been the subject of various applications. Thus, the use of such compositions is known for the bonding of various substrates, of electrical / electronic components or of mechanical parts, in particular in the field of the automobile or of household appliances. Such a composition having good storage stability, viscosity in liquid form in line with the requirements for ease of application on the substrates to be bonded, high adhesive power, good temperature resistance, good stickiness stability. over time, while having a low cost price, is described in patent FR-A-2 775 481. If this composition turns out to be a silicone adhesive composition of choice for the aforementioned applications, it does not have characteristics rheological perfectly adapted for certain particular applications (anti-drip device, shaped joint in place ...) where the method of removal requires a product flow threshold. By analogy with molding applications, it would then be necessary to add thixotropic additives to the composition to allow the silicone elastomer compositions to be thickened to a fair extent without affecting their malleability, their fluidity necessary for their handling and in such a way that the composition, before crosslinking, does not flow spontaneously if this is not required. As thixotropic agent, there may be mentioned:

- an ultra fine silica in appropriate proportion; - hydroxylated and amino additives.

However, these additives have unacceptable drawbacks depending on the case. The drawback of silicas is that they cause both a large increase in the flow threshold and in viscosity.

The problem with hydroxylated and amino additives is that they do not induce the increase in the flow threshold desired for all types of compositions in the field. In addition, the amino derivatives inhibit the action of platinum catalysts, used in silicone compositions crosslinkable by addition.

Thus, an objective of the present invention is to develop a crosslinkable silicone elastomer composition, having rheological properties perfectly suited to allow the composition to be used successfully, both for bonding various substrates, and for producing molding operations requiring non-flowing materials.

Another objective is to obtain a composition which can be crosslinked by non-flowing polyaddition and, in addition, which may be self-adhesive in the case of bonding applications.

In addition, in the context of its use for bonding, the composition according to the invention must make it possible to obtain a solid assembly which is resistant to low stresses, and this as soon as it is put in place (bonding between the substrates). It must also make it possible to obtain good stability of the tackiness over time. In addition, in the context of molding and bonding applications, another objective is to obtain a composition which can be easily shaped and which is capable of retaining the shape thus formed at least for the time necessary for crosslinking. Finally, this composition must retain good mechanical properties and satisfactory thermal resistance. To achieve these objectives, the inventors had the merit of highlighting, in a completely surprising and unexpected manner, that the use in a crosslinkable silicone composition of a compound comprising at least one cyclic amine function, carried by a chain siloxane provides the composition with a strong increase in its flow threshold. The inventors are all the more deserving, that they have been against the prejudice according to which, amino compounds are traditionally inhibitors of platinum-based compounds, advantageously used to catalyze the crosslinking of silicone compositions, by addition. Thus, the present invention satisfies the above objectives, among others, by proposing, first of all, an adhesive silicone composition, crosslinkable of the type of those comprising:

(I) at least one polyorganosiloxane having, per molecule at least two alkenyl groups bonded to silicon;

(II) at least one polyorganosiloxane having, per molecule at least three hydrogen atoms bonded to silicon;

(III) a catalytically effective amount of at least one catalyst, composed of at least one metal belonging to the platinum group; (IV) optionally an adhesion promoter,

(V) a mineral filler,

(VI) optionally at least one crosslinking inhibitor,

(VII) optionally at least one polyorganosiloxane resin carrying siloxyl units Q and / or T and of alkenyl groups, this composition also comprises:

(VIII) at least one compound comprising at least one cyclic amine function carried on at least one siloxane chain, as a thixotropic additive, modifying the rheological properties of the composition by giving it a high flow threshold. Preferably, the cyclic amine function is a piperidinyl function.

Advantageously, the compound (VIII) is a polyorganosiloxane having per molecule at least one unit of general formula:

in which :

• the symbols R are identical or different and represent a monovalent hydrocarbon radical chosen from alkyl radicals having from 1 to 4 carbon atoms, phenyl and trifluoro-3,3,3 propyl;

• the symbols X are identical or different and represent a monovalent radical chosen from a hydroxyl group, an alkenyl radical and an alkoxy radical, linear or branched, having from 1 to 3 carbon atoms;

• Z represents a residue containing sterically hindered piperidinyl group (s) chosen from:

^ the formula remains:

in which :

- Ri is a divalent hydrocarbon radical chosen from: • alkylene radicals, linear or branched, having 2 to 18 carbon atoms;

• alkylene-carbonyl radicals of which the alkylene part, linear or branched, contains 2 to 20 carbon atoms;

• alkylene-cyclohexylene radicals in which the alkylene part, linear or branched, contains from 2 to 12 carbon atoms and the cyclohexylene part comprises a group -OH and optionally 1 or 2 alkyl radicals having from 1 to 4 carbon atoms;

• radicals of formula - R ⁴ -O-R5- in which the identical or different radicals R ⁴ and R ^ represent alkylene radicals having 1 to 12 carbon atoms;

• the radicals of formula -R -O-R5- in which the radicals R ⁴ and R ^ have the meanings indicated above and one of them or both is substituted by one or two OH group (s);

• the radicals of formulas -R ⁴ -COO-R ⁵ and -R ⁴ -OCO-R ⁵ - in which R ⁴ and R5 have the above meanings;

• the radicals of formula -R ⁶ -OR ⁷ -O-CO-R ⁸ - in which R ⁶ , R ⁷ and R ⁸ , identical or different, represent alkylene radicals having from 2 to 12 carbon atoms and the radical R ⁷ is optionally substituted with a hydroxyl group; - U represents -O- or -NR ^ -, R9 being a radical chosen from: a hydrogen atom; an alkyl radical, linear or branched, having from 1 to 6 carbon atoms; a divalent radical -Ri- having the meaning indicated above, one of the valential bonds being linked to the nitrogen atom of -NR ^ -, the other being connected to a silicon atom; and a divalent radical of formula:

in which Ri has the meaning indicated above, R ² and R ³ have the meanings indicated below and RIO represents an alkylene radical, linear or branched, having 1 to 12 carbon atoms, one of the valential bonds (that of RIO ) being connected to the nitrogen atom of -NR ^ -, the other (that of R *) being connected to a silicon atom;

- R ² are radicals, identical or different, chosen from alkyl radicals, linear or branched, having from 1 to 3 carbon atoms and phenyl;

- R ³ represents a hydrogen atom or the radical R ² ; and those of formula:

in which :

- R 'is chosen from a trivalent radical of formula:

. CO -

(CH ₂ ) -CH,

^* Ï ^J "\ where m represents a number from 2 to 20,

CO -

and a trivalent radical of formula:

where n represents a number from 2 to 20;

- U 'represents -O- or -NRU-, RU being a hydrogen atom or an alkyl radical, linear or branched having from 1 to 6 carbon atoms; - R ² and R ³ have the same meanings as those given in connection with formula (II);

• a is a number chosen from 0, 1 and 2; • b is a number chosen from 0, 1 and 2;

• the sum a + b is at most equal to 2.

This polyorganosiloxane (VIII) can also comprise at least one other siloxyl unit of formula: (R) _c (X) _d VSi (0) _{3- (c + c} (III)

in which :

• the symbols R and X have the same meanings as those given above with regard to formula (I);

• the symbol V represents: an alkyl radical, linear or branched, having 5 to 20 carbon atoms; a radical of formula - (CH2) _p -COO-Rl ² in which p represents a number of 5 to 20 and R ^ ² represents a linear or branched alkyl radical of 1 to 12 carbon atoms; a radical of formula - (CH2) -O-Rl3 in which q represents a number from 3 to 10 and R ^ represents a hydrogen atom, an ethylene oxide chain, a propylene oxide chain, a mixed oxide chain ethylene + propylene oxide or an acyl radical having from 2 to 12 carbon atoms;

• c is a number chosen from 0, 1 and 2;

• d is a number chosen from 0, 1 and 2;

• the sum c + d is at most equal to 2.

It can advantageously also include other siloxyl unit (s) of formula

(R) _e (X) _f If (0) 4 e _{± û} (IV)

in which :

• R and X have the same meanings as those given in relation to formula (I);

• e is a number chosen from 0, 1, 2 and 3;

• f is a number chosen from 0, 1, 2 and 3;

• the sum e + f is at most equal to 3.

Thus, preferably, the polyorganosiloxane (VIII) is a linear polydiorganosiloxane of average formula:

in which • the symbols R, Z and V have the meanings given above with regard to formulas (I) and (III);

• the symbol Y represents a monovalent radical chosen from the radicals R, Z, V and X;

14

• the symbols R are identical or different and represent a monovalent radical chosen from a radical R and a radical X as defined above with respect to formula (I);

• r, s and t are equal to zero or represent whole or fractional numbers greater than zero, with the additional condition that if r = 0, at least one of the two radicals Y represents the radical Z.

According to a preferred embodiment, the compound with piperidinyl function corresponds to the following formula:

in which: x "is between 0 and 1000, y" is between 1 and 50, the proportion of compound (VI) in the composition being preferably between 0.2 and 5%.

The present compound in the form of an oil advantageously makes it possible to obtain a composition whose Bingham threshold can reach 350 Pa.

The polyorganosiloxane (I) is by weight one of the essential constituents of the composition used according to the invention. Advantageously, it is a product having patterns of formula:

W _a Z ' _b SiQ ₄ . _{(a + b)} (VII)

2 in which :

W is an alkenyl group, preferably vinyl or allyl,

- Z 'is a monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst and chosen, preferably, from alkyl groups having from 1 to 8 carbon atoms included, advantageously, from methyl, ethyl, propyl groups and 3,3,3-trifluoropropyl and also among the aryl groups and, advantageously, among the xylyl and tolyl and phenyl radicals,

- a is 1 or 2, b is 0, 1 or 2 and a + b is between 1 and 3, preferably between 2 and 3, optionally at least part of the other units are units of average formula:

Z'cSiCYç (VIII)

2 in which Z 'has the same meaning as above and c has a value between 0 and 3, preferably between 2 and 3.

It is advantageous for this polydiorganosiloxane to have a viscosity at least equal to 100 mPa.s, preferably to 500 mPa.s and more preferably still between 500 and 100,000 mPa.s. Mention may be made, as example of compound (I), of poiydimethylsiloxane.

The polyorganosiloxane (I) can only be formed of units of formula (VII) or can additionally contain units of formula (VIII). Likewise, it can have a linear, branched, cyclic or network structure. Its degree of polymerization is preferably between 2 and 5000. Z 'is generally chosen from methyl, ethyl and phenyl radicals, at least 60 mol% of the radicals Z' being methyl radicals.

Examples of siloxyl units of formula (VII) are the vinyldimethylsiloxane unit, the vinylphenylmethylsiloxane unit and the vinylsiloxane unit.

Examples of siloxyl units of formula (VIII) are the SiO _4/2 , dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, methylsiloxane and phenylsiloxane units.

Examples of polyorganosiloxanes (I) are dimethylpolysiloxanes with dimethylvinylsilyl ends, methylvinyldimethylpolysiloxane copolymers with trimethylsilyl ends, methylvinyldimethylpolysiloxane copolymers with dimethylvinylsilyl ends, cyclic methylvinylpolysiloxanes.

The polyorganosiloxane (II) is preferably of the type of those comprising siloxyl units of formula: H _d L _e SiQ ₄ . _{(d + e)} (iχ)

2 in which:

- L is a monovalent hydrocarbon group, free from any adverse action on the activity of the catalyst and preferably chosen from alkyl groups having from 1 to 8 carbon atoms included and, advantageously, from methyl, ethyl and propyl groups and 3,3,3-trifluoropropyl and also among the aryl groups and, advantageously, among the xylyl and tolyl and phenyl radicals,

- d is 1 or 2, e is 0, 1 or 2, d + e has a value between 1 and 3, - possibly, at least part of the other units being units of average formula:

_g SiC _g (X)

2 in which L has the same meaning as above and g has a value between 0 and 3, preferably between 2 and 3.

The dynamic viscosity of this polyorganosiloxane is at least equal to 5, preferably 10, and more preferably still is between 20 and 1000 mPa.s. The dynamic viscosity, called "Newtonian", is the dynamic viscosity which is measured at 25 ° C, in a manner known per se, at a shear speed gradient sufficiently low for the measured viscosity to be independent of the speed gradient.

As examples of polyorganosiloxane (II), mention may be made of poly (dimethylsiloxane) (methylhydrogensiloxy) α, ω dimethylhydrogensosiloxane.

The polyorganosiloxane (II) can be formed only of units of formula (IX) or additionally comprises units of formula (X).

The polyorganosiloxane (II) can have a linear, branched, cyclic or network structure. The degree of polymerization is greater than or equal to 2. More generally, it is less than 5,000.

Group L has the same meaning as group Z above. Examples of units of formula (IX) are:

H (CH ₃ ) ₂ SiO _1/2 , HCH ₃ SiO _2/2 , H (C ₆ H ₅ ) SiO _2/2

The examples of units of formula (X) are the same as those given above for the units of formula (VIII).

Examples of polyorganosiloxane (II) are:

- dimethylpolysiloxanes with hydrogenodimethylsilyl ends, - copolymers containing dimethyl-hydrogenomethylpolysiloxane (dimethyl) units with trimethylsilyl ends,

- copolymers with dimethyl-hydrogenomethylpolysiloxane units with hydrogenodimethylsilyl ends, - hydrogenomethylpolysiloxanes with trimethylsilyl ends,

- cyclic hydrogenomethylpolysiloxanes.

The ratio of the number of hydrogen atoms bound to silicon in the polyorganosiloxane (I) to the number of alkenyl unsaturated groups of the polyorganosiloxane (II) is between 0.4 and 10, preferably between 0.6 and 5. The polyorganosiloxane (I) and / or the polyorganosiloxane (II) can be diluted in a non-toxic organic solvent compatible with silicones.

The networked polyorganosiloxanes (I) and (II) are commonly called silicone resins.

The bases of polyaddition silicone compositions may contain only linear polyorganosiloxanes (I) and (II) such as, for example, those described in the patents: US-A-3,220,972, US-A-3,697,473 and US-A -4,340,709 or contain both branched or networked polyorganosiloxanes (I) and (II), such as those described in the patents: US-A-3,284,406 and US-A-3,434,366.

According to a particular embodiment, use is made of: - at least one linear polyorganosiloxane (I) comprising chains formed of units of formula (VIII) where c = 2, blocked at each of their ends by units of formula (VII ) where a = 1 and b = 2, and at least one linear polyorganosiloxane (II) comprising in its structure at least three hydrogen atoms bonded to silicon, located in the chains and / or at the chain ends; and more preferably still:

at least one linear polyorganosiloxane (I) comprising chains formed of units of formula (VIII) where c = 2, blocked at each of their ends by units of formula (VII) where a = 1 and b = 2, and - at least one linear polyorganosiloxane (II) comprising chains formed of units of formula (IX) where d = 1 and e = 1 and optionally of units of formula (X) where g = 2, blocked at each of their ends by units of formula (IX) where d = 1 and e = 2.

The catalysts (III) are also well known. The platinum and rhodium compounds are preferably used. It is possible, in particular, to use the complexes of platinum and of an organic product described in patents US-A-3,159,601, US-A-

3,159,602, US-A-3,220,972 and European patents EP-A-0,057,459, EP-A-0,188,978 and

EP-A-0 190 530, the complexes of platinum and vinyl organosiloxanes described in the US-A-3,419,593, US-A-3,715,334, US-A-3,377,432 and US-A-3,814,730. The generally preferred catalyst is platinum. In this case, the quantity by weight of catalyst (III), calculated by weight of platinum-metal, is generally between 2 and 400 ppm, preferably between 5 and 200 ppm based on the total weight of the polyorganosiloxanes (I) and (II ).

In accordance with a provision of the invention, the composition can be used for bonding. In the context of this application, it is possible and even recommended to add to the composition an adhesion promoter (IV).

By cons, when the composition is used for molding, it does not include an adhesion promoter.

The promoter (IV), when used, comprises: (IV.l) at least one alkoxylated organosilane containing, per molecule, at least one C ₂ -C ₆ alkenyl group, (IV.2) at least one compound organosilicon comprising at least one epoxy radical,

(IV.3) at least one metal chelate M and / or a metal alkoxide of general formula: M (OJ) _n , with n = valence of M and J = linear or branched C ₂ -C ₆ alkyl Advantageously, the alkoxylated organosiloxane (IV.l) corresponds to the following general formula:

in which: - R " ¹ , R ' ² , R' ³ are hydrogenated or hydrocarbon radicals identical or different from each other and preferably represent hydrogen, a linear or branched C ^ Q _j alkyl or a phenyl optionally substituted by at least one C _[ -C ₃ alkyl,

A is a linear or branched C, -C ₄ alkylene or a divalent group of formula -CO-O-alkylene ..., where the alkylene residue is as defined above and the valence - is linked to Si via G ,

L is a valence bond or oxygen,

R ' ⁴ and R' ⁵ are the same or different radicals and represent an alkyl in

C, -C ₄ linear or branched, - x '= 0 or l, x = 0 to 4, preferably 0 or 1 and more preferably still 0. Without this being limiting, it can be considered that vinyltrimethoxysilane is a particularly suitable compound (IV.l). The organosilicon compound (IV.2), of the promoter (IV) is chosen:

- either among the products (IV.2a) of the following general formula:

in which: A. R ' ⁶ is a linear or branched C _[ -C ₄ _] alkyl radical,

J R ' ⁷ is a linear or branched alkyl radical

A. y is equal to 0, 1, 2 or 3, preferably to 0 or 1 and, more preferably still to 0, X 'is equal to:

with

* E and D which are identical or different radicals chosen from linear or branched C 1 -C ₄ alkylene,

* z which is equal to 0 or 1, * R ' ⁸ , R' ⁹ , R ^'10 which are the same or different radicals, representing hydrogen or a linear or branched C ₄ -C ₄ alkyl, hydrogen being more particularly preferred, 4 R'8, R ' ^Q _; R ′ ⁱ o can alternately constitute together with the two carbons carrying the epoxy, an alkyl ring having 5 to 7 members,

- or among the products (IV.2b) constituted by epoxyfunctional polydiorganosiloxanes comprising at least one unit of formula:

X ' _p G _q Si0 ₄ . _{(p + q)} (xπi)

2 in which:

A. X 'is the radical as defined above for formula (XII) JL G is a monovalent hydrocarbon group, free from any adverse action on the activity of the catalyst and preferably chosen from alkyl groups having JL of 1 to 8 carbon atoms included, advantageously, from methyl, ethyl and propyl groups and 3,3,3-trifluoropropyl and also among the aryl groups and, advantageously, among the xylyl and tolyl and phenyl radicals, A. p = 0, 1 or 2, JL q = 1, 2 or 3 JL p + q = 0, 1, 2 or 3.

Optionally, at least some of the other units of these polydiorganosiloxanes are units of average formula:

G _r Siθ ₄ . _r (XIV)

T in which G has the same meaning as above and ra has a value between 0 and 3, for example between 1 and 3. The compounds (IV.2) are therefore preferably epoxyalkoxysilicones and more preferably still epoxyalkoxymonosilanes (IV. 2 a). Examples of such compounds (IV.2) that may be mentioned: 3-glycidoxypropyltrimethoxysilane (GLYMO) - or 3,4-epoxycyclohexylethyltrimethoxysilane. As regards the last essential compound (IV.3) of the adhesion promoter (IV), the preferred products are those in which the metal M of the chelate and / or the alkoxide (IV.3) is chosen from the list next: Ti, Zr, Ge, Li, Mn. It should be emphasized that titanium is more particularly preferred. One can associate it, for example, an alkyl radical of butyl type. In practice, the adhesion promoter (IV) is for example:

- vinyltrimethoxysilane (VTMO) (IV.l), - 3-Glycidoxypropyltrimethoxysilane (GLYMO) (IV.2),

- and butyl titanate (IV.3).

From a quantitative point of view, it can be specified that the weight proportions between (IV.l), (IV.2) and (IV.3), when using an adhesion promoter, expressed in percentages by weight relative to the total of the three, are as follows: (IV.l) between 15 and 70 and preferably between 30 and 50,

(IV.2) between 15 and 70 and preferably between 30 and 50, (IV.3) between 5 and 25 and preferably between 10 and 20, it being understood that the sum of these proportions in (IV.l) , (IV.2), (IV.3) is equal to 100%. The charge (V) used consists of products chosen from siliceous materials (or not).

With regard to siliceous materials, they can play the role of reinforcing or semi-reinforcing filler. The reinforcing siliceous fillers are chosen from colloidal silicas, combustion and precipitation silica powders or their mixtures.

These powders have an average particle size generally less than 0.1 μm and a BET specific surface greater than 50 m ² / g, preferably between 100 and 350 m ² / g. Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used.

With regard to non-siliceous mineral materials, they can act as a semi-reinforcing or tamping mineral filler. Examples of these non-siliceous fillers which can be used alone or as a mixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, unexpanded vermiculite, calcium carbonate, l zinc oxide, mica, talc, zirconates, iron oxide, barium sulfate and slaked lime. These fillers have a particle size generally between 0.001 and 300 μm and a BET surface area of less than 100 m ² / g.

In a practical but nonlimiting manner, the filler used is quartz or a mixture of quartz and silica.

The load can be treated with all or part of at least one and / or the other of the compounds (IV.l) to (IV.3) of the promoter (IV).

In the case in particular of the use of a particulate siliceous mineral filler, the filler can advantageously be used in the form of the suspension obtained by treating the filler by applying the method in accordance with the teaching of the patent application WO -A-98/58997, providing for a two-stage treatment of the charge with a compatibilizing agent (chosen for example: in the case of the first treatment, from a silazane, a hydroxylated siloxane, an amine, an organic acid; and as regards the second treatment time, among a silazane) by operating in the presence of the component POS (I). In the case where such a treatment leads to a basic pH, a neutralizing agent such as for example a weak acid or a silica filler such as ground quartz can be added to the dispersion.

In terms of weight, it is preferred to use an amount of filler of between 20 and 50, preferably between 25 and 35% by weight relative to all of the constituents of the composition.

Advantageously, the silicone elastomer composition comprises at least one retarder (VI) of the addition reaction (crosslinking inhibitor), chosen from the following compounds: polyorganosiloxanes, advantageously cyclic and substituted with at least one alkenyl, tetramethylvinyltetrasiloxane being particularly preferred, pyridine, - organic phosphines and phosphites, unsaturated amides, alkyl maleates and acetylenic alcohols. These acetylenic alcohols, (Cf. FR-B-1 528 464 and FR-A-2 372 874), which are part of the preferred hydrosilylation reaction thermal blockers, have the formula:

R ¹⁵ - (R ¹⁶ ) C (OH) ≡ CH formula in which:

. R ¹⁵ is a linear or branched alkyl radical, or a phenyl radical; . R ¹⁶ is H or a linear or branched alkyl radical, or a phenyl radical; the radicals R ¹⁵ , R ¹⁶ and the carbon atom located at α of the triple bond possibly optionally forming a ring; the total number of carbon atoms contained in R ¹⁵ and R ¹⁶ being at least 5, preferably from 9 to 20.

Said alcohols are preferably chosen from those having a boiling point above 250 ° C. As examples, we can cite:. ethynyl-1-cyclohexanol 1; . 3-methyl-dodecy-1 ol-3; . trimethyl-3,7,11 dodécyne-1 ol-3; . diphenyl-1,1 propyne-2 ol-1; . 3-ethyl-6-ethyl nonyne-1 ol-3;

. 3-methyl-pentadecy-1 ol-3.

These α-acetylenic alcohols are commercial products. Such a retarder (VI) is present at a rate of 3000 ppm at most, preferably at the rate of 100 to 2000 ppm relative to the total weight of the organopolysiloxanes (I) and (II).

The composition used according to the invention may comprise at least one unsaturated POS resin (VII) comprising at least two alkenyl residues, preferably vinyls per molecule.

Advantageously, the POS resin (VII) comprises in its structure from 0.1 to 20% by weight of alkenyl group (s), said structure having at least two different units chosen from units of types M, D, T and Q, at least one of these patterns being a pattern of type T or Q. In practice, this resin (VII) preferably corresponds to one of the following three formulas:

(XV) MM ^Vi DD ^vi Q or MD ^vi Q (XVI) or MM ^Vi Q (XVII)

This resin (VII) participates in establishing the rheological, mechanical and adhesive properties of the composition. It is known that the siloxyl units Q play a relatively important role in this regard. Thus, in accordance with an advantageous arrangement of the invention. The resin (VII) contains units Q at a rate of at least 5%, preferably at least 7%, and even more preferably at a rate of 8 to 30%. According to a variant, the resin (VII) comprises siloxy units T. In a manner known per se, the silicone elastomer composition can be added with various conventional additives such as, for example, the dyes.

Even more advantageously, the composition according to the invention comprises at least one reinforcing filler, such as a silicic filler or a paste.

According to a particularly preferred embodiment, the composition used according to the invention involves the constituents (I) to (VIII) in the following proportions, in% by weight on a dry basis relative to the total mass: (I) l to 80 preferably 10 to 60

(II) 0.1 to 20 preferably 0.5 to 10

(III) 0.0002 to 0.04 preferably 0.0005 to 0.02 (IV.l) 0.01 to 5 preferably 0.05 to 2 (IV.2) 0.01 to 5 preferably 0, 05 to 2 (IV.3) 0.01 to 3 preferably 0.1 to 1

(V) 0 to 90 preferably 10 to 80

(VI) 0 to 0.5 preferably 0.005 to 0.3

(VII) 0 to 80 preferably 5 to 70

(VIII) 0.2 to 5%, preferably 0.5 to 2. According to another of its aspects, the present invention relates to a two-component precursor system of the silicone elastomer composition described above.

Such a precursor system is presented in two distinct parts A and B, intended to be mixed to form the composition, one of these parts A or B comprising the catalyst (III) and a single species (I) or (II) of polyorganosiloxane. Another characteristic of this precursor system is that its part A or B containing the compound (IV.l) of the promoter (IV) does not include the catalyst (III), that the resin (VII) can be used in the part A or part B or in both parts A and B, part A or B containing the POS (II) and the resin (VII) being free of catalyst (III), and that finally the thixotropic compound (VIII) can be used in part A or B, comprising the catalyst (III).

The viscosity of parts A and B and their mixture can be adjusted by varying the amounts of the constituents and by choosing polyorganosiloxanes of different viscosity.

Once mixed together, parts A and B form a ready-to-use silicone elastomer composition which can be applied to the substrates to be bonded or coated by any suitable means (for example doctor blade, nozzle, spray gun , brush, screen printing ...). The crosslinking of the composition applied to the support to be coated can be caused by thermal means and / or infrared radiation.

According to a remarkable characteristic of the use according to the invention, the substrates which can be bonded by the composition are made of thermoplastic or thermosetting polymer, preferably of phenoplast, of polyamide, of polyester, of ABS, of polycarbonate, of PVC, polyether, polyolefin or epoxy resin.

The substrates can also be metallic, it can be e.g. raw or treated aluminum, raw or treated steels, or lacquered metals.

Thus, the composition according to the invention is self-adhesive on aluminum (type AG3) and on steel (type Sollac R 1426) with a shear strength of 1 to 5 MPa and a 100% cohesive break in all cases.

The field of application of the use recommended by the invention is advantageously that of the bonding of construction parts of vehicles, in particular motor vehicles, or that of the bonding of construction parts of household appliances, in particular irons. In practice, bonding applications in the automotive industry can be:

- flexible bonding of plastic and metal parts under the engine hood and in the passenger compartment,

- bonding of optical units.

According to a variant, this field of application can also be that of bonding of electrical / electronic components, in particular in household appliances.

According to yet another variant, the field of application can also be that of molding shapes to be reproduced. Indeed, the low dripping of the composition according to the invention gives it a very particular interest for its application on parts or supports to be reproduced and therefore which need to be molded. The examples which follow describe the preparation of the crosslinkable silicone composition according to the invention. These examples will highlight its advantages. They refer to the drawings in which: FIG. 1 represents the curve of the evolution of the viscosity and the Bingham threshold of a composition, part A of the two-component comprising 2.5% of silica 200 m ² / g pretreated and additive with a POS oil with piperidinyl function.

FIG. 2 represents the curve of the evolution of the viscosity and the Bingham threshold of a composition, part A of the two-component comprising 10% of a dispersion of silica treated in situ and added with a POS oil with piperidinyl function.

EXAMPLES

EXAMPLE 1: FORMULATION OF PARTS A AND B OF A SILICONE COMPOSITION

TWO-COMPONENT CROSSLINK

Part A of the bicomponent In a reactor at room temperature:

- 41.6 parts by weight of a resin of type (VII) MM ^{V |} DD ^{V |} Q containing 0.9% by weight of vinyl groups (Vi) and consisting of 21% by weight of units (CH ₃ ) ₃ SiO ₀₅ , 0.2% by weight of units (CH ₃ ) ₂ ViSiO ₀₅ , 67.8% by weight of units ( CH ₃ ) ₂ SiO, 3% by weight of units (CH ₃ ) ViSiO and 8% by weight of units SiO ₂ - 24.8 parts by weight of a PDMS oil (I), blocked by units (CH ₃ ) ₂ ViSiO _{0 5} having a viscosity of 100,000 mPa.s and containing 0.005 SiVi function for 100g of oil

- 32.9 parts by weight of mineral filler (V), in the form of ground quartz of average particle size about 2 μm - 0.7 parts by weight of tetrabutyl orthotitanate (TBOT) (IV.3)

- 0.004 parts by weight of platinum (III) metal in the form of a metal complex known as the Karstedt catalyst

Part B of the two-component

In a reactor at room temperature:

- 26.8 parts by weight of a resin (VII) of structure MM ^V, DD ^{V |} Q containing 0.9% by weight of vinyl groups (Vi) and consisting of 21% by weight of units (CH ₃ ) ₃ SiOo ₅ , 0.2% by weight of units (CH ₃ ) ₂ ViSiO ₀₅ , 67.8% by weight of units ( CH ₃ ) ₂ SiO, 3% by weight of units (CH ₃ ) ViSiO and 8% by weight of units SiO ₂

- 14.1 parts by weight of a PDMS oil (I) blocked by patterns (CH ₃ ) ₂ ViSiO _{0 5} having a viscosity of 100,000 mPa.s and containing 0.005 SiVi function per 100g of oil 49 parts by weight by weight of mineral filler (V), in the form of ground quartz of average particle size about 2 μm

2.5 parts by weight of silica 200 m / g pretreated with a cyclic POS

3.9 parts by weight of a poly (dimethyl) (hydrogen methyl) siloxane (II) blocked by (CH ₃ ) ₂ HSiO _{0 units} . ₅ having a viscosity of 25 mPa.s and containing a total of 0.7 SiH function per 100g of oil

0.05 part by weight of EthynylCycloHexanol (VI)

1.8 parts by weight of vinyltrimethoxysilane (VTMO) (IV.l)

1.8 parts by weight of γ-glycidoxypropyltrimethoxysilane (GLYMO) (IV.2)

0.1 part by weight of black coloring base

The bicomponent is obtained by mixing at room temperature 100 parts of A and 100 parts of B.

EXAMPLE 2: RHEOLOGICAL AND MECHANICAL PROPERTIES OF PART A OF

ADDITIVE TWO-COMPONENT OF A PIPERIDINYL FUNCTION POS OIL (VIII)

For laboratory evaluations, the product is implemented using a pneumatic gun allowing the product contained in two-component cartridges (2x200cc) to be extruded: mixing is carried out using a static mixer placed immediately at the outlet of the cartridge.

The rheological and mechanical properties are evaluated by additivation of part A of the bicomponent, with a POS oil with piperidinyl function (VIII). Part B remains the same. The piperidinyl-functional POS has the formula:

in the form of an oil with a viscosity of approximately 10,000 mPa.s, comprising 0.25% by weight of nitrogen.

This oil is added to part A of the bicomponent at 0.5 (test 1), 1 (test 2) and 2% (test

3). The mixture is homogenized by hand using a spatula.

The rheological and mechanical performances of the composition thus obtained are measured in the following way:

- the rheological properties were measured on a CARRI MED rheometer, with a cone of 2.0cm diameter and an angle of 1 °. the flow threshold is determined by the computer of the apparatus by applying a Bingham fluid model.

- the mechanical properties were measured on H2 test pieces. To do this, a 2 mm film is produced: the product is crosslinked for 1 hour at 150 ° C. in a heating press. The test pieces are then taken: a shore A hardness measurement is carried out, then the mechanical properties (breaking strength, modulus, elongation are evaluated using a ZWICK type dynamometer with a tensile speed of 500 mm / min.

The results of these tests are collated in Table 1 below

Table 1

These results show that the addition of POS oil with piperidinyl function has an effect on the rheological properties of part A of the bicomponent. In fact, the higher the oil content, the higher the flow threshold. On the other hand, it can be seen that the addition of oil has no significant effect on the viscosity of composition A or on the mechanical properties of the two-component. EXAMPLE 3: RHEOLOGICAL AND MECHANICAL PROPERTIES OF PART A OF

TWO-COMPONENT COMPRISING 2.5% SILICA 200 M ² / G PRETREATED AND ADDITIVE OF A POS WITH PIPERIDINYL FUNCTION AS THIXOTROPANT ADDITIVE

The previous example is reproduced with the exception that 2.5% silica 200m ² / g pretreated is added to part A as reinforcing filler.

The test results are grouped in Table 2 below

Table 2

The results show that in the presence of silica in the composition of part A, the effect of POS oil with piperidinyl function (VIII) on the flow threshold, is reinforced compared to the action of the same oil. on a composition without silica as presented in Example 2. In the same way as in Example 2, the viscosity of the composition and the mechanical properties of the bicomponent are not significantly modified by the addition of l 'oil.

EXAMPLE 4 RHEOLOGICAL AND MECHANICAL PROPERTIES OF PART A OF TWO-COMPONENT COMPRISING VARIOUS RATES OF SILICA DISPERSION TREATED IN SITU AND

ADDITIVE OF A POS WITH PIPERIDINYL FUNCTION

Example 2 is reproduced except that different parts A are prepared, each comprising a different rate of reinforcing filler provided by the dispersion of silica. To each of these compositions is added POS oil with piperidinyl function, as defined in Example 2, at rates of 0.5, 1 and 2%. The dispersion of silica treated in situ is obtained as follows: In a laboratory mixer with a Z-arm, the following are introduced:

- 74 parts of PDMS completed (CH ₃ ) ViSiO ₀ . ₅ with a viscosity of 600 mPa,

- 2 parts of water,

- 30 parts of silica with a developed surface of 200 m ² / g.

After incorporation, 5 parts of hexamethyldisilazane are added. The mixing is continued for 1 hour, before heating the reactor to gradually remove the volatile compounds. Table 3 groups together the results obtained with part A comprising 10% of dispersion of silica treated in situ:

Table 3

Table 4 groups together the results obtained with part A comprising 15% dispersion of silica treated in situ:

Table 4 Table 5 groups together the results obtained with part A comprising 20% dispersion of silica treated in situ:

Table 5

The results presented in Table 3 show that in the presence of a dispersion of silica treated in situ, in part A of the two-component, the effect of the POS oil with piperidinyl function (VIII) on the flow threshold is reinforced. compared to the action of the same oil on a composition without dispersion of silica as presented in Example 2.

The comparison of the results in Tables 3, 4 and 5 show that the increase in the flow threshold is all the more important the higher the dispersion rate of silica in part A of the bicomponent.

The mechanical properties and the viscosity of the bicomponent with various rates of pasting are not modified by the addition of POS oil with piperidinyl function.

EXAMPLE 5 STUDY OF THE EVOLUTION OVER TIME OF THE RHEOLOGICAL PROPERTIES OF PART A OF THE TWO-COMPONENT COMPRISING 2.5% SILICA 200 M ² / G PRETREATED AND ADDITIVE OF A PIPERIDINYL POS

The various compositions described in Example 2 were the subject of a viscosity and Bingham threshold measurement after 0, 2, 7, 21, 50, 80 and 120 days of storage, in order to study the evolution in the time of the rheological properties, of the additive compositions relative to the control composition and therefore of determining the effects of the POS oil with piperidinyl function after storage. This evolution is represented in the form of a curve in FIG. 1. In this figure, the solid curves are the viscosity curves while the dashed curves are those of the Bingham threshold. The legend of the various symbols is as follows:

B control (part A comprising 2.5% of silica 200m ² / g pretreated) part A comprising 2.5% of silica 200m ² / g pretreated and 0.5% of oil

Piperidinyl POS

• part A comprising 2.5% pretreated silica 200m ² / g and 1% POS oil with piperidinyl function

_ part A comprising 2.5% of pre-treated silica 200m ² / g and 2% POS oil with piperidinyl function.

It can be seen that the evolution over time of the different parts A with added values is entirely equivalent to that of the control part A with no added values. The POS oil with piperidinyl function therefore has no effect over time on part A of the bicomponent, which comprises 200 m ² / g pretreated as an additive of silica. Part A of the bicomponent according to the invention therefore has rheological properties which are stable over time.

EXAMPLE 6 STUDY OF THE EVOLUTION OVER TIME OF THE RHEOLOGICAL PROPERTIES OF PART A OF THE TWO-COMPONENT COMPRISING 10% DISPERSION OF SILICA TREATED IN SITU AND ADDITIVE OF A POS WITH PIPERIDINYL FUNCTION

Example 5 is reproduced except that the parts A are equivalent to those tested in Example 4 and not include only a single rate of dispersion of silica at 10%.

The evolution over time of the rheological properties of the different compositions is represented in FIG. 2. In this figure, the solid curves are the viscosity curves while the dashed curves are those of the Bingham threshold. The legend of the various symbols is as follows: m control (part A comprising 10% of silica dispersion treated in situ) part A comprising 10% of silica dispersion treated in situ and 0.5% POS oil with piperidinyl function part A comprising 10% dispersion of silica treated in situ and 1% POS oil with piperidinyl function

• part A comprising 10% dispersion of silica treated in situ and 2% POS oil with piperidinyl function.

As in Example 5, it can be seen that the development over time of the different parts A with added colors is entirely equivalent to that of the control part A with no added colors. oil POS with piperidinyl function therefore has no effect over time on part A of the bicomponent, which comprises as an additive the dispersion of silica treated in situ.

The examples presented show that the composition developed by the applicant exhibits improved rheological properties, while retaining a viscosity allowing easy handling, first-order mechanical properties. The use of reinforcing fillers significantly improves the rheological properties, since the value of the flow threshold is multiplied by 4, and this without modifying the viscosity or the mechanical properties. Finally, the composition according to the invention, and in particular the part A which constitutes it, has very good stability over time.

Claims

1. Crosslinkable adhesive silicone composition, of the type comprising:

(III) a catalytically effective amount of at least one catalyst, composed of at least one metal belonging to the platinum group; (IV) optionally an adhesion promoter;

(V) a mineral filler, reinforcing or not;

(VI) optionally at least one crosslinking inhibitor,

(VII) and optionally at least one polyorganosiloxane resin carrying siloxyl units Q and / or T and of alkenyl groups, said composition being characterized in that it also comprises:

(VIII) at least one compound with a cyclic amine function carried on a siloxane chain, as a thixotropic additive, modifying the rheological properties of the composition by giving it a high flow threshold.

2. Composition according to claim 1, characterized in that the cyclic amine function of the compound (VIII) is a piperidinyl function.

3. Composition according to one of claims 1 or 2, characterized in that the compound (VIII) is a polyorganosiloxane having per mole at least one unit of general formula:

(R) _a (X) _b ZSiO s____

2 in which:

• the symbols R are identical or different and represent a monovalent hydrocarbon radical chosen from alkyl radicals, linear or branched, having from 1 to 4 carbon atoms, phenyl and trifluoro-3,3,3 propyl; “The symbols X are identical or different and represent a monovalent radical chosen from a hydroxyl group, an alkenyl radical and an alkoxy radical, having from 1 to 3 carbon atoms; Z represents a residue containing sterically hindered piperidinyl group (s) chosen from: the residues of formula:

in which :

- R is a divalent hydrocarbon radical chosen from: alkylene radicals, linear or branched, having from 2 to 18 carbon atoms; alkylene-carbonyl radicals of which the alkylene part, linear or branched, contains 2 to 20 carbon atoms; alkylene-cyclohexylene radicals in which the alkylene part, linear or branched, contains from 2 to 12 carbon atoms and the cyclohexylene part comprises a group -OH and optionally 1 or 2 alkyl radicals having from 1 to 4 carbon atoms; the radicals of formula - R ⁴ -O-R5- in which the identical or different radicals R ⁴ and R5 represent alkylene radicals having 1 to 12 carbon atoms; the radicals of formula -R ⁴ -OR ^ - in which the radicals

R ⁴ and R have the meanings indicated above and one of them or both are substituted by one or two OH group (s); the radicals of formulas -R ⁴ -COO-R ⁵ and -R ⁴ -OCO-R ⁵ - in which R ⁴ and R ^ have the above meanings; the radicals of formula -R ⁶ -OR ⁷ -O-CO-R ⁸ - in which R ⁶ , R ⁷ and R ⁸ , identical or different, represent alkylene radicals having from 2 to 12 carbon atoms and the radical R ⁷ is optionally substituted by a hydroxyl group;

- U represents -O- or -NR -, R "being a radical chosen from: a hydrogen atom; an alkyl radical, linear or branched, having 1 to 6 carbon atoms; a divalent radical -Ri- having the meaning indicated above, one of the valid links being connected to the nitrogen atom of -NR ^ -, the other being connected to a silicon atom; and a divalent radical of formula:

in which R has the meaning indicated above, R ² and R ³ have the meanings indicated below and RIO represents an alkylene radical, linear or branched, having 1 to 12 carbon atoms, one of the valential bonds (that of RO ) being connected to the nitrogen atom of -NR ^ -, the other (that of R) being connected to a silicon atom;

- R ³ represents a hydrogen atom or the radical R ² ; and those of formula:

in which: - R 'is chosen from a trivalent radical of formula:

where m represents a number from 2 to 20,

and a trivalent radical of formula:

where n represents a number from 2 to 20;

• a is a number chosen from 0, 1 and 2;

• b is a number chosen from 0, 1 and 2; "The sum a + b is at most equal to 2.

4. Composition according to the preceding claim, characterized in that the polyorganosiloxane (VIII) can also comprise at least one other siloxyl unit of formula: (R) _c (X) _d VSi (O) Hç ± di (III)

2

in which :

• the symbols R and X have the same meanings as those given above with regard to formula (I); “The symbol V represents: an alkyl radical, linear or branched, having 5 to 20 carbon atoms; a radical of formula - (CH2) p-COO-Rl in which p represents a number from 5 to 20 and R 1 represents a linear or branched alkyl radical of 1 to 12 carbon atoms; a radical of formula - (CH2) π-O-Rl3 in which q represents a number from 3 to 10 and R 3 represents a hydrogen atom, an ethylene oxide chain, a propylene oxide chain, a mixed oxide chain ethylene + propylene oxide or an acyl radical having 2 to 12 carbon atoms;

• c is a number chosen from 0, 1 and 2;

• d is a number chosen from 0, 1 and 2; "The sum c + d is at most equal to 2.

5. Composition according to one of claims 3 or 4, characterized in that the polyorganosiloxane (VIII) may further comprise other (s) siloxyl unit (s) of formula: (R) e (X) f If (O) _{4 g ± Q} (IV)

2 in which:

• R and X have the same meanings as those given in relation to the formula

(D; • e is a number chosen from 0, 1, 2 and 3;

• f is a number chosen from 0, 1, 2 and 3;

• the sum e + f is at most equal to 3.

6. Composition according to one of claims 3 to 5, characterized in that the polyorganosiloxane (VIII) is a linear polydiorganosiloxane of average formula:

in which :

• the symbols R, Z and V have the meanings given above with regard to formulas (I) and (III); "The symbol Y represents a monovalent radical chosen from the radicals R, Z,

V and X;

• the symbols R ⁴ are identical or different and represent a monovalent radical chosen from a radical R and a radical X as defined above with regard to formula (I); • r, s and t are equal to zero or represent whole or fractional numbers greater than zero, with the additional condition that if r = 0, at least one of the two radicals Y represents the radical Z.

7. Composition according to one of the preceding claims, characterized in that the compound (VIII) corresponds to the following formula:

in which - x "is between 0 and 1000,

- y "is between 1 and 50, the proportion by weight of the compound of formula (VI) in the composition preferably being between 0.2 and 5%.

8. Composition according to any one of the preceding claims, characterized in that the polyorganosiloxane (I) has units of formula:

W _a T _b SiQ ₄ _ _{(a + b)} (VII) 2 in which:

W is an alkenyl group, preferably vinyl or allyl,

Z'c SiO ^ (VIII) 2 in which Z 'has the same meaning as above and c has a value between 0 and 3, preferably between 2 and 3.

9. Composition according to any one of the preceding claims, characterized in that the polyorganosiloxane (II) comprises siloxy units of formula:

H _d L _β SiO _{± t≤} (IX)

2 in which:

- L is a monovalent hydrocarbon group, free from any adverse action on the activity of the catalyst and preferably chosen from alkyl groups having from 1 to 8 carbon atoms included and, advantageously, from methyl, ethyl and propyl groups and 3,3,3-trifluoropropyl and also among the aryl groups and, advantageously, among the xylyl and tolyl and phenyl radicals, - d is 1 or 2, e is 0, 1 or 2, d + has a value between 1 and 3, preferably between 2 and 3,

- optionally, at least some of the other units being units of average formula: .SiO ^ (X)

10. Composition according to any one of the preceding claims, characterized in that the promoter (IV) is based on:

(IV.l) at least one alkoxylated organosilane containing, per molecule, at least one C -C ₆ alkenyl group, (IV.2) at least one organosilicon compound comprising at least one epoxy radical, (IV.3) at least a metal chelate M and / or a metal alkoxide of general formula: M (OJ) _n , with n = valence of M and J = linear or branched C ₂ -C ₆ alkyl.

11. Composition according to the preceding claim, characterized in that the alkoxylated organosiloxane (IV.l) of the promoter (IV) corresponds to the following general formula:

in which :

R " ¹ , R ' ² , R' ³ are hydrogenated or hydrocarbon radicals identical or different from each other and preferably represent hydrogen, a linear or branched C ₄ -C ₄ alkyl or a phenyl optionally substituted with least one C _[-C ₃ alkyl, - a is a linear or branched alkylene C, -C ₄ -C ₄ or a divalent group of formula -CO-O-alkylene-, where the alkylene radical is as defined above before and valence— is related to Si via G,

L is a valence bond or oxygen, R ' ⁴ and R' ⁵ are identical or different radicals and represent a linear or branched C _r C ₄ alkyl,

- x '= 0 or l,

- x = 0 to 4, preferably 0 or 1 and more preferably still 0.

12. Composition according to any one of claims 10 or 11, characterized in that the organosilicon compound (IV.2), of the promoter (IV) is chosen - either from the products (IV.2a) of the following general formula:

in which: A R ′ ⁶ is a linear or branched C ₄ -C ₄ alkyl radical,

JL R ' ⁷ is a linear or branched alkyl radical

JL is equal to 0, 1, 2 or 3, preferably to 0 or 1 and, more preferably still to 0,

A X 'is equal to:

with E and D which are identical or different radicals chosen from linear or branched C ₄ -C ₄ alkylene, z which is equal to 0 or 1, R ' ⁸ , R' ⁹ , R ^'10 which are identical radicals or different representing hydrogen or a linear or branched C alkyl, hydrogen being more particularly preferred, * R ' ⁸ , R' ⁹ , R ^'10 can alternately constitute together with the two carbons carrying the epoxy, a alkyl ring having from 5 to 7 links, - either from the products (IV.2b) constituted by epoxyfunctional polydiorganosiloxanes comprising at least one unit of formula:

X ' _p G _q Si0 ₄ _ _{(p + q)} (XIII) in which :

JL X ′ is the radical as defined above for formula (IV.2 a) JL G is a monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst and preferably chosen from alkyl groups having

A from 1 to 8 carbon atoms included, advantageously, among the methyl, ethyl, propyl and 3,3,3-trifluoropropyl groups and also among the aryl groups and, advantageously, among the xylyl and tolyl and phenyl radicals, A p = 0, 1 or 2,

JL q = 1, 2 or 3 JL p + q = 0, 1, 2 or 3.

JL optionally at least part of the other units of these polydiorganosiloxanes are units of average formula:

G _r Si0 ₄ _ _r (XIV) ^~ 2 ^~ in which G has the same meaning as above and ra a value between 0 and 3, for example between 1 and 3.

13. Composition according to one of claims 10 to 12, characterized in that the metal M of the chelate and or of the alkoxide (IV.3) is chosen from the following list: Ti, Zr, Ge, Li, Mn, Ti being more particularly preferred.

14. Composition according to any one of the preceding claims, characterized in that the adhesion promoter comprises:

- vinyltrimethoxysilane (VTMO) (IV.l),

- 3-Glycidoxypropyltrimethoxysilane (GLYMO) (IV.2),

- and butyl titanate (IV.3).

15. Composition according to any one of the preceding claims, characterized in that the unsaturated resin (VII) comprises at least one vinyl per molecule and corresponds to one of the following three formulas:

(XV) or (XVI) R V ^V ^i,, Q, or (XVII) MM V _f ^V i ', Q

16. Composition according to any one of claims 10 to 15, characterized in that the constituents (I) to (VIII) are used in the following proportions, in% by weight on a dry basis relative to the total mass:

(I) l to 80 preferably 10 to 60

(II) 0.1 to 20 preferably 0.5 to 10

(III) 0.0002 to 0.04 preferably 0.0005 to 0.02

(IV.l) 0.01 to 5 preferably 0.05 to 2

(IV.2) 0.01 to 5 preferably 0.05 to 2

(IV.3) 0.01 to 3 preferably 0.1 to 1

(V) 0 to 90 preferably 10 to 80

(VI) 0 to 0.5 preferably 0.005 to 0.3

(VII) 0 to 80 preferably 5 to 70

(VIII) 0.2 to 5 preferably 0.5 to 2.

17. Two-component precursor system of the composition according to any one of claims, characterized: in that it is in two distinct parts A and B intended to be mixed to form the composition, in that one of these parts A and B comprises the catalyst (III) and a single species (I) or (II) of polyorganosiloxane, in that the part A or B containing the compound (IV.l) of the promoter (IV) does not include the catalyst ( III), in that the resin (VII) can be used in part A or part B or in both parts A and B, part A or B containing the POS (II) and the resin (VII ) being free of catalyst (III), and in that the thixotropic compound (VIII) can be used in part A or B, comprising the catalyst (III).

18. Use of the composition according to one of claims 1 to 17, characterized in that the field of application is that of the bonding of construction parts of vehicles, in particular motor vehicles, or that of the bonding of construction parts of Appliances.

19. Use of the composition according to any one of claims 1 to 17, characterized in that the field of application is that of bonding of electrical / electronic components, in particular in household appliances.

20. Use of a crosslinkable adhesive silicone composition, of the type of those comprising:

(I) at least one polyorganosiloxane having, per molecule at least two alkenyl groups bonded to silicon; (II) at least one polyorganosiloxane having, per molecule at least three hydrogen atoms bonded to silicon; (III) a catalytically effective amount of at least one catalyst, composed of at least one metal belonging to the platinum group; (V) a mineral filler, reinforcing or not; (VI) optionally at least one crosslinking inhibitor,

(VII) and optionally at least one polyorganosiloxane resin carrying siloxyl units Q and / or T and of alkenyl groups,

(VIII) at least one compound with a cyclic amine function carried on a siloxane chain, as a thixotropic additive, modifying the rheological properties of the composition by giving it a high flow threshold, characterized in that the field of application is that of molding.