WO1998043134A1

WO1998043134A1 - (e.g. ink or varnish) composition polymerisable and/or crosslinkable under radiation exposure by cationic and/or radical process, with an organic matrix base, of a diluent and a photoinitiator

Info

Publication number: WO1998043134A1
Application number: PCT/FR1998/000566
Authority: WO
Inventors: Stefan Breunig; Jean-Marc Frances
Original assignee: Rhodia Chimie
Priority date: 1997-03-25
Filing date: 1998-03-20
Publication date: 1998-10-01
Also published as: AU7049698A; FR2761368A1; EP0970405A1; FR2761368B1

Abstract

The invention aims at improving such compositions by proposing a non-toxic diluent harmless to reactivity and by making these compositions translucent, free from metallic impurities and capable of constituting light-polymerisable varnish with good properties of ductility for levelling and surface coating. This aim is achieved by the invention which proposes a composition comprising an organic polymerisable matrix A, containing cyclo-aliphatic epoxide resins or not, acrylates, alkenyl-ethers or polyols, a silicon diluent B with viscosity less than 100 MPa's, a radical and/or cationic (onium salt) photoinitiator C, optionally a light-sensitising material D, a pigment E and another additive F; provided that when A = cyclo-aliphatic epoxide resin, B has a metal concentration not more than 100 ppm. The invention also concerns the use of the silicon diluent B for preparing a composition crosslinkable by cationic and/or radical process, under UV radiation, in the presence of a photoinitiator (ink or varnish).

Description

The field of the invention is that of the invention. The field of the invention is that of the field of the invention. crosslinkable and / or polymerizable photopolymer systems under irradiation, in particular under UV irradiation or by electron beam, usable, in particular, to form coatings, such as inks or varnishes.

These compositions are of the type of those comprising an organic matrix, the constituents of which carry reactive polymerization / crosslinking functions, as well as a photo-initiator or photo-initiator which, after absorption of energy, for example UV, releases an acid. strong: H ⁺ (cationic pathway) or a free radical (radical pathway). Cationic photoinitiators thus allow the initiation and propagation of cationic chain polymerizations, while radical photoinitiators (PA) allow the initiation of chain polymerizations by the formation of free radicals.

In certain applications of coatings or inks (or even dark varnishes), additives are used, such as pigments, which are capable of appreciably increasing the viscosity of the compositions, so much so that they can no longer be spread and handled. . It goes without saying that these are crippling drawbacks for the applications considered. To remedy this, diluents have been incorporated into these compositions, in order to reduce their viscosity.

In the case of clear varnishes, diluents or co-reactants are sought which are capable of improving the flexibility of the coatings, without reducing the reactivity of the systems. The diluents most commonly used to date, in compositions of photopolymerizable inks or varnishes, are products of the vinyl ether type (in particular divinyl ether) or of the limonene type (in particular epoxidized limonene).

Although these products meet a certain number of specifications requested in the specifications of the diluent, namely in particular the miscibility with the organic matrix or the organic resin, the transparency or the inexpensive character, these known diluents are faulty with regard to the considerations respect for the environment, safety and industrial constraints.

Indeed, these products are particularly volatile (low flash point less than or equal to 110 ° C), toxic, even dangerous, because explosive and flammable. These known diluents, of the vinyl ether or epoxidized limonene type, are, moreover, irritants and sensitizers.

In addition, they do not make it possible to reach sufficiently high polymerization rates, which would make it possible to reduce the concentrations of photoinitiator, which would greatly relieve the cost of the compositions.

Furthermore, through patent application EP 0 389927, there are known photopolymerizable coating compositions comprising organic cycloaliphatic polyepoxides, associated with an α-ω-epoxycycloaliphatic functionalized siloxane, present in an amount allowing acceleration of crosslinking. The photo-initiators used are onium salts.

This composition is presented as having an improved crosslinking speed. The α-ω-cycloaliphatic functional epoxy siloxane is therefore in fact used as an accelerator for the polymerization of polymerizable coating systems, based on cycloaliphatic polyepoxides polymerizable under UV. This patent application discloses, in particular, compositions based on:

- 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, which constitutes the polymerizable matrix,

an agent making it possible to reduce the energy required for the photopolymerization, said agent consisting of dimethyldisiloxane α-ω-3,4-epoxycyclohexyl-1-ethyl,

- And a photoinitiator consisting of (4-octyloxyphenyl) phenyliodonium-hexafluoro-antimonate in solution in 2-ethyl-1,3-hexanediol.

The drawback of this type of composition is due to their turbid and colored appearance, therefore non-transparent. They also contain a significant amount of metal, which is not unrelated to the problem of lack of translucency and transparency and which, moreover, is likely to disturb the polymerization mechanism.

The cc-co-epoxidized dimethyldisiloxanes are, moreover, known as monomers which can be polymerized cationically under UV, in the presence of photo-initiators of the omnium salt type. CRIVELLO's article published in J. Polym. Sci. : Part A: Polym. Chem., 1994, Vol. 32, 683-697 deals with this subject and shows that the cycloaliphatic epoxy functions are more reactive in cationic polymerization under UV than conventional epoxy functions.

The article by RP ECKBERG & KD RTOLNG in Polym. Mater. Sci. Eng., 1989, 60, 222-7 discloses the cationic polymerization / crosslinking, under UV activation and in the presence of onium salt type photoinitiator, of mixtures of α, ω-epoxidized dimethyldisiloxanes (M ^E M ^E ) with cycloaliphatic epoxides of formula:

According to this document, there is no marked effect of M ^E M ^E with respect to the efficiency of the polymerization / crosslinking rate for M ^E M ^E concentrations of less than 45% in weight relative to the mixture M ^E M ^E / CY 179 (fig. 1). Such concentrations are not such as to promote the use of M ^E M ^E , since this additive cannot be preponderant in the formulation, as soon as the polymer / crosslinker becomes unsuitable for the applications intended for it (eg anti-coating - adherent paper, varnish, inks).

In addition, the crosslinked products obtained from such mixtures M ^E M ^E / CY 179 suffers from the major drawback of being brittle, which is unacceptable in many applications. Finally, these compositions are also affected by metallic turbidity and pollution defects, like the compositions according to EP 0 389 927.

It is therefore clear that the state of the art does not meet the specifications expected for polymerizable and / or crosslinkable compositions under irradiation, such as those intended for ink and varnish applications. In particular, the prior art does not disclose, or even suggest means for regulating (diluents) the viscosity of the photopolymerizable pigment inks, which are not toxic and which do not harm the reactivity of the composition.

Similarly, there are no harmless additives in the field of light photopolymerizable varnishes which are capable of improving the the flexibility of the coatings, the spreading and the surface condition, without hampering the photopolymerization and / or crosslinking.

It should also be observed that the prior art does not provide a satisfactory solution as regards, on the one hand, the problems of transparency and translucency and, on the other hand, the presence of metallic impurities, d on the other hand, in the photopolymerizable compositions considered.

Finally, the state of the art is even poorer in the case where the reactive polymerization functions are not epoxy but, for example, either alkenyl ether (e. G. Vinyl ether) - cationic route -, or acrylate or hydroxy - radical route -.

In this state of knowledge, one of the essential objectives of the present invention is to overcome the existing deficiencies, by providing photopolymerizable compositions by cationic and / or radical route, which meet the expectations of their fields of application, in particular as regards concerns inks and varnishes. Having set this objective, the Applicant had the merit, on the one hand, of isolating and selecting a silicone compound of the functionalized di or oligosiloxane type and, on the other hand, of implementing, in an original manner, this compound as a diluent in photopolymerizable compositions, for example in inks or varnishes. Thus, the invention which is the subject of the present application relates to a polymerizable and / or crosslinkable composition under irradiation, preferably actinic and / or by electron beam (s), by cationic and / or radical route, characterized in that it includes:

A. at least one polymerizable and / or at least partially polymerized organic matrix, comprising (co) monomers and / or (co) oligomers and / or (co) polymers chosen from those having epoxy reactive (frA) functions ( α,) and / or acrylate (α ₂ ) and / or alkenyl-ether (_) and / or hydroxy (α ₄ ), excluding cycloaliphatic epoxides (α _π ); B. at least one silicone diluent with reduced viscosity ηr at 25 ° C less than or equal to 200 mPa.s, preferably 150 mPa.s and, more preferably still, 100 mPa.s and comprising:

• at least one motif of formula (I):

in which :

- a = 0, 1 or 2,

- R ° is identical or different to its similars of the same exponent and represents an alkyl, cycloalkyl, aryl, vinyl, hydrogen, alkoxy radical, preferably a lower C ₆ alkyl,

Z is an organic substituent comprising at least one reactive function frB, epoxy and or acrylate and / or alkenyl ether and / or hydroxy, with the condition that at least part of the functions frB is of the same nature as at least one part of the functions frA of the matrix A,

• and at least two silicon atoms,

C. an effective amount of at least one cationic and / or radical photoinitiator, D. optionally at least one photosensitizer,

E. optionally at least one pigment,

F. possibly at least one other additive.

Except in the case where the matrix A comprises compounds carrying reactive functions frA of the cycloaliphatic epoxide type, the choice of silicone B as diluent of the composition is likely to solve the viscosity problems in dark inks and varnishes and , flexibility, spreading or sliding in clear photopolymerizable varnishes, under UV, by cationic and / or radical route.

In addition, diluent B, used in accordance with the invention, has the advantage of being economical, non-toxic, non-irritant, non-sensitizing and therefore easy to handle. In addition, this diluent B does not disturb either the transparency or the reactivity of the photopolymerizable composition. It is, moreover, surprising to note that the concept according to the invention of functionalized silicone diluent, with di or oligosiloxane skeleton, is applicable not only when the reactive functions frA of the matrix are of epoxy type (cationic route), but also when frA = alkenyl ether (cationic), frA = acrylate or frA = epoxy (radical route).

It should be noted that for frA = OH, the condition that the compound or compounds of said matrix comprise at least 20 OH per molecule, must be respected. These will then be polyols.

According to a variant of the invention, in which the cycloaliphatic epoxides are not excluded from the list of possible constituents for the matrix A, it is preferable to use a diluent B having a metal concentration less than or equal to 100 ppm, preferably at 50 ppm and, more preferably still, at 20 ppm.

This characteristic of the purity of the diluent B gives the composition transparency and translucency properties, which are particularly valuable for varnish applications, or even inks in certain cases.

Thus, even more preferably, the diluent B is selected so that it has a coloring less than or equal to 200 Hazen, preferably 150 Hazen and, more preferably still, 100 Hazen, this diluent B being, in addition or alternatively, soluble at a rate of at least 5%, preferably at least 10% and, more preferably still, of 20% by weight in the matrix A, this percentage of solubility being expressed relative to the mass of matrix A and not of mixture A + B.

According to another advantageous characteristic of the invention, the silicone diluent B is obtained by hydrosilylation of a synthon carrying an ethylenically unsaturated function and a frA function using a hydrogenated silicone oil, in the presence of a heterogeneous catalytic composition, comprising at least one metal chosen from the group consisting of Co, Rh, Ru, Pt, Ni, deposited on an inert support. In this method of obtaining diluent B by hydrosilylation, the silicone oil is reacted with different or identical synthons containing a hydrocarbon ring in which is included an oxygen atom. This reaction is carried out in the presence of a heterogeneous catalytic composition comprising a metal chosen from the group consisting of cobalt, rhodium, ruthenium, platinum, palladium and nickel deposited on an inert support. Preferably, the metal of the catalytic composition is platinum. The amount of metal contained in the heterogeneous catalytic composition is between 0.005% and 5% relative to the weight of the inert support. This amount of metal is also between 1 and 1000 ppm relative to the weight of the silicone oil. By convention, the term heterogeneous catalytic composition is understood to mean a catalytic composition which may be solid or liquid, which is not dissolved in the reaction medium, ie that the reaction medium comprises at least two phases, one of which is formed by the catalytic composition.

The metal is deposited on various inert supports such as carbon black, carbon, alumina, treated or untreated silica, barium sulphate or even crosslinked silicones. Advantageously, the particle size of the catalytic supports is greater than 10 μm in order to have good filterability which does not require filtration aids. Thus, this particle size is such that the filtration time can be considerably reduced.

The synthons contain at least one hydrocarbon ring in which an oxygen atom is included and have the formula: - (1)

in which :

the symbols W are identical or different and correspond to a divalent hydrocarbon radical chosen from linear or branched alkylene radicals having from 1 to 12 carbon atoms, one of the symbols W can be a free valence; the symbol Y corresponds to a free valence or a divalent radical chosen from linear or branched alkylene radicals having from 1 to 12 carbon atoms and which may contain a heteroatom, preferably an oxygen atom; the symbol Rj corresponds to a hydrogen atom or monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 12 carbon atoms and, preferably, a hydrogen atom or a methyl radical;

(2)

in which :

the symbols W are identical or different and correspond to a divalent hydrocarbon radical chosen from linear or branched alkylene radicals having from 1 to 12 carbon atoms, one of the symbols W can be a free valence;

- the symbol Y corresponds to a free valence or a divalent radical chosen from linear or branched alkylene radicals having from 1 to 12 carbon atoms and which may contain a heteroatom, preferably an oxygen atom;

- the symbol Ri corresponds to a hydrogen atom or monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to

12 carbon atoms, and preferably a hydrogen atom or a methyl radical; (3)

in which :

the symbols W are identical or different and correspond to a divalent hydrocarbon radical chosen from linear or branched alkylene radicals having from 1 to 12 carbon atoms and which may contain at least one hydroxyl function; one of the symbols W can be a free valence for (V) and the two symbols W can be simultaneously a free valence for (VI);

- the symbols W are identical or different and correspond to a divalent hydrocarbon radical chosen from linear or branched alkylene radicals having from 1 to 12 carbon atoms; at least one of the symbols W can be a free valence;

- the symbol Rj corresponds to a hydrogen atom or monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 12 carbon atoms, and preferably a hydrogen atom or a methyl radical; and (4)

in which : - the symbols W are identical or different and correspond to a free valence and a divalent hydrocarbon radical chosen from linear or branched alkylene radicals having from 1 to 2 carbon atoms;

- the symbol Z corresponds to a divalent radical chosen from a carbon atom or a heteroatom.

Preferably, the hydrocarbon ring in which the hydrogen atom is included has at most 8 atoms in said cycle. In addition, the best results are obtained in accordance with the hydrosilylation process of the invention with synthons containing only one hydrocarbon ring in which an oxygen atom is included. In particular, the synthons used and giving good results (see examples below) have the formula:

In general, the synthons reacting with the silicone oil are identical synthons. The molar ratio of the silicone oil / synthons is between 0.01 and 100, preferably between 0.1 and 10.

Different types of heterogeneous catalytic compositions can be used. By way of nonlimiting examples, platinum on carbon black or carbon can be used such as the catalytic composition containing 2.5% of platinum by weight deposited on the CECA 2S support developed by the company CECA, the catalytic composition SCAT 20 (1% Pt) from the company Engelhard or the catalytic composition 88 231 (1% Pt) from the company Heraeus. In this case, platinum can be deposited on this type of support by depositing chloroplatinic acid followed by neutralization and reduction. Likewise, the use of platinum on alumina, preferably of the α type such as the catalytic composition CAL 101 (0.3% of Pt, SCS9 support consisting of α-alumina) sold by the company Procatalyse or the catalytic composition 88 823 of HERAEUS (0.5% Pt on α-alumina) gives good results. This process for obtaining diluent B used in the composition according to the invention can be implemented according to various variants. It is thus in particular possible to use a first embodiment in which all of the reactants and of the catalytic composition are mixed in the reaction medium ("batch" type). A second embodiment of this process can be a continuous mode with a fixed bed of heterogeneous catalytic composition over which the silicone oil to be functionalized and the synthon pass. This type of implementation is advantageous in the case where the grain size of the inert support of the catalytic composition is greater than 100 μm. An example of the first embodiment is given below: (a) an amount of 5 to 5000 ppm, preferably from 10 to 100 ppm, of heterogeneous catalytic composition relative to the total mass of the reactants is introduced under gas inert in the reaction medium; (b) the synthon is introduced into the reaction medium;

(c) said medium is heated to a temperature between 25 ° C and 200 ° C, and preferably between 50 ° C and 160 ° C;

(d) the silicone oil is then introduced over a period of between 0 and 24 hours, preferably between 2.5 and 5 hours; the synthon / silicone molar ratio being between 1 and 1.10.

(e) the reaction mass is then filtered in order to separate the heterogeneous catalytic composition and the functionalized silicone oil, and;

(f) the functionalized silicone oil is finally devolatilized.

This process can be carried out in bulk, which means that the reaction between the silicone oil and the synthon takes place in the absence of solvent. However, many solvents such as toluene, xylene, octamethyltetrasiloxane, cyclohexane or hexane can be used.

Furthermore, the molar quantity of synthon poured during step (b) is less than that which is used for a conventional process of the prior art. Advantageously, the synthon / silicone oil molar ratio is between 1 and 1.05 and this without harming the quality of the functionalized oils obtained and the yield of the reaction.

Step (e) of filtration makes it possible, if necessary, to remove any trace of turbidity from the functionalized silicone oil obtained. On the other hand, the heterogeneous catalytic composition can be recovered then reused again, without requiring regeneration, with or without washing, and without there being any noticeable drop in activity of its performance.

As regards the preferred structural characteristics of diluent B, it should be noted that this diluent corresponds to at least one of the following general formulas:

in which :

• T = R ^{3 or} Si (R ³ ) _u (frB) _v ,

• x + y = 3; x = 1 to 3; y = 0 to 3;

• b + c = 2; b, c = 0, l or 2;

• u + v = 3; u, v = 0 to 3;

• 0 <n <15,

• R ² , R ³ are identical or different and correspond to the same definition as that given above for R ° of formula (I), the lower alkyls and / or alkoxyls in

and R ₃ , respectively,

• frB being as defined above in the passage devoted to the substituent Z of formula (I),

- (frB) (R ⁴ ) _eSi0 - - (R), - Si - O-

(1.2)

in which :

• d + e = 2; d = lou2; e = 0, lou2;

• o + p <15, preferably <10; o> 1;

• R ⁴ , R ⁵ are, respectively and jointly, identical or different between them and correspond to the same definition as R ² given above.

The reactive functions frB of diluent B, more particularly used in the context of the invention, are of epoxy, vinyl ether or acrylate nature. More precisely, these frB are, for example, chosen from the following radicals:

- (CH ₂ ) ₃ - O-CH = CH— R

• with R ⁶ :

- linear or branched alkylene in CC _dd , optionally substituted,

- or arylene, preferably phenylene, optionally substituted, preferably by one to three C 1 -C 6 alkyl groups,

• with R ⁷ = linear or branched C _j -Cg alkyl.

As examples of diluent B, consisting of at least one di, oligo or polysiloxane functionalized frB, mention may be made of those of the following formulas:

(n <10)

(n <10)

The silicone diluent B according to the invention is of less importance quantitatively, compared to the matrix A, which constitutes the predominant element of the composition. As regards the latter, these constituents belong to at least one of the following species:

OL _y Λ cycloaliphatic epoxides, taken alone or as a mixture between them:

- epoxides of 3,4-epoxycyclohexylmethyl-3 ', 4'- epoxycyclohexane carboxylate type:

- or Bis (3,4-epoxycyclohexyl) adipate, being particularly preferred; α 1.2) non-cycloaliphatic epoxides, taken alone or as a mixture between them:

• epoxides of the type of those resulting from the condensation of Bis-phenol A and of epichlorohydrin and of the type:

- di and triglycidyl ethers of alkoxylated Bisphenol A of 1,6 hexane diol, of glycerol, of neopentyl glycol and of propane trimethylol,

- or digly ci dy 1 ethers of Bisphenol A,

• epoxides of alpha-olefins, NOVOLAC epoxies, soybean oil and linseed epoxies, epoxy polybutadiene, being particularly preferred, α '2) acrylates, taken alone or as a mixture between them; e. g. :

• epoxy acrylates, preferably the oligomer of Bisphenol-A- epoxydiacrylate (EBECRYL 600),

• acryloglycero-polyester, preferably a mixture of trifunctional acrylate oligomer obtained from glycerol and polyester (EBECRYL 810), • multifunctional acrylates, preferably pentaerythrityl triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDODA), trimethylolpropane ethoxylate triacrylate, thiodiethylene glycol diacrylate, tetraethylene glycol diacrylate (TTEGDA), tripropylene glycol diacrylate (TRPGDA ), triethylene glycol diacrylate (TREGDA), trimethylpropane trimethacrylate (TMPTMA),

• acrylo-urethanes,

• acrylo-polyethers, • acrylo-polyesters,

• unsaturated polyesters,

• acrylo-acrylics, being particularly preferred, eg, ₎ alkenyl ethers, linear or cyclic, taken alone or as a mixture between them:

• vinyl ethers, in particular divinyl triethylene glycol ether (RAPIDCURE® CHVE-3, GAF Chemicals

Corp.), cyclic vinyl ethers or acrolein tetramers and / or dimers and vinyl ether of the following formula:

• propenyl ethers,

• and butenyl ethers, being very particularly preferred, α ₄₎ polyols: taken alone or as a mixture between them, preferably the compound of formula given below:

Examples of reactive monomers and / or oligomers and / or polymers, functionalized by epoxy and / or by an ethylenically unsaturated radical, such as an acrylate (cf. patent application EP 0 690 074). The initiation of photopolymerization and / or crosslinking of the composition according to the invention is made possible thanks to the presence of the cationic and / or radical photoinitiator C.

The cationic photoinitiators can be chosen from onium borates (taken alone or as a mixture between them) of an element from groups 15 to 17 of the periodic table [Chem. & Eng. News, vol.63, N ° 5, 26 of February 4, 1985] or of an organometallic complex of an element from groups 4 to 10 of the periodic table [same reference], Δ whose cationic entity is selected from: 1) the onium salts of formula (I): [(R ¹ ) n - A - (R ² ) _m ] ⁺ (I) formula in which:

• A represents an element from groups 15 to 17 such as for example: I, S, Se, P or N,

• Ri represents a carbocyclic or heterocyclic Cg-C20 aryl radical _. said heterocyclic radical possibly containing as heteroelements nitrogen or sulfur,

• R2 represents R ^ or a linear or branched C 1 -C 30 alkyl or alkenyl radical; said radicals R 1 and R 3 being optionally substituted by a C1-C25 alkoxy, C1-C25 alkyl, nitro, chloro, bromo, cyano, carboxy, ester or mercapto group,

• n is an integer ranging from 1 to v + 1, v being the valence of the element A,

• m is an integer ranging from 0 to v - 1 with n + m = v + 1, 2) the oxoisothiochromanium salts described in patent application WO 90/11303, in particular the sulfonium salt of 2-ethyl-4-oxoisothiochromanium or of 2-dodecyl-4-oxoisothio-chromanium,

3) the sulfonium salts in which the cationic entity comprises: 3 _d at least one polysulfonium species of formula III.1:

Ar ¹ - S - Ar ³ - Ar ³ - S— Ar '(ΠLI)

Ar Ar

in which :

the symbols Ar *, which may be identical or different from each other, each represent a monovalent phenyl or naphthyl radical, optionally substituted with one or more radicals chosen from: a linear or branched C \ - \ 2 alkyl radical, preferably in CJ-CÔ, a linear or branched C1-C6 alkoxy radical, preferably C -CÔ, a halogen atom, a group -OH, a group -COOH, an ester group - COO-alkyl where the alkyl part is a linear or branched residue in Ci - Ci 2, preferably in Ci-Cé, and a group of formula -γ4-Ar where the symbols Y ^* and Ar2 have the meanings given just below,

the symbols Ar2, which may be identical or different from each other or with Arl, each represent a monovalent phenyl or naphthyl radical, optionally substituted with one or more radicals chosen from: a linear or branched Ci -Ci 2 alkyl radical, preferably in Cj-Cg, a linear or branched alkoxy radical in Ci -Ci 2, preferably in Ci-Cg, a halogen atom, a group -OH, a group -COOH, an ester group - COO-alkyl where the part alkyl is a linear or branched residue in Ci -Ci 2, preferably in Ci-Cg, - the symbols Ar ^> , which may be identical or different from each other, each represent a divalent phenylene or naphthylene radical, optionally substituted with one or more radicals chosen from: a linear or branched C 1 -C 2, preferably C 1 -C 6 alkyl radical, a linear or branched C 1 -C 2, preferably C 1 -C 2 alkoxy radical, a halogen atom, -OH group, -COOH group, ester group - COO-alkyl in which the alkyl part is a linear or branched residue in C -C 12, preferably in C1-C6, t is an integer equal to 0 or 1, with the additional conditions that:

+ when t = 0, the symbol Y is then a monovalent radical γl representing the group of formula:

Y '-S— Ar'

Ar where the symbols Ar * and Ar2 have the meanings given above,

+ when t = 1:

O on the one hand, the symbol Y is then a divalent radical having the following meanings γ to Y ^:

• γ: a grouping of formula:

+

where the symbol Ar2 has the meanings given above,

• Y-: a simple valential link,

• Y ^: a divalent residue chosen from:

_o-. -s-. -s-. -vs- . o o a linear or branched C 1 -C 2 alkylene residue, preferably in

CI-CÔ, and a residue of formula - Si (CH3) 2θ -, O on the other hand, in the case only where the symbol Y represents Y ^ or Y ^, the radicals Ar ^ and Ar (terminals) have, in addition the meanings given above, the possibility of being linked together by the remainder Y 'consisting in ¹ a simple valential link or in Y ¹ a divalent remainder chosen from the rests cited in connection with the definition of Y ^, which is installed between the atoms of carbon, facing each other, located on each aromatic cycle in an ortho position with respect to the carbon atom directly linked to the S ⁺ cation;

3 ₂ and / or at least one monosulfonium species having a single cationic center S ⁺ per mole of cation and consisting in most cases in species of formula:

1 ⁺ 1

Ar ¹ S— Ar ¹ (III.2)

Ar in which Ar ^ and Ar2 have the meanings given above with regard to the formula (III-1), including the possibility of directly linking together only one of the radicals Ar to Ar2 in the manner indicated above with regard to the definition of the additional condition in force when t = 1 in formula (H), calling on the remainder Y ¹ ;

4) the organometallic salts of formula (IV):

(LlL ² L ³ M) ⁺ q (IV) formula in which:

• M represents a metal from group 4 to 10, in particular iron, manganese, chromium, cobalt ...

• L ^ represents 1 ligand linked to the metal M by π electrons, a ligand chosen from the ligands η ^ -alkyl, η ^ - cyclopendadienyl and η ^ - cycloheptratrienyl and the η ^ - aromatic compounds chosen from the ligands η ^ -benzene substituted and the compounds having from 2 to 4 condensed cycles, each cycle being able to contribute to the valence layer of the metal M by 3 to 8 π electrons;

• L represents a ligand linked to metal M by π electrons, a ligand chosen from the ligands

chosen from the ligands η6-benzene optionally substituted and the compounds having from 2 to 4 condensed cycles, each cycle being capable of contributing to the valence layer of the metal M by 6 or 7 π electrons; • L ³ represents from 0 to 3 identical or different ligands linked to the metal M by σ electrons, ligand (s) chosen from CO and NO2 ^"1" ; the total electronic charge q of the complex to which L ^, L and 1 contribute? and the ionic charge of the metal M being positive and equal to 1 or 2; Δ the anionic borate entity having the formula:

[BX _a Rbl- formula in which:

- a and b are integers ranging for a from 0 to 3 and for b from 1 to 4 with a + b = 4, - the symbols X represent:

* a halogen atom (chlorine, fluorine) with a = 0 to 3,

* an OH function with a = 0 to 2,

- the symbols R are identical or different and represent:

> a phenyl radical substituted by at least one electron-withdrawing group such as for example OCF3, CF3, NO2, CN, and / or by at least 2 halogen atoms (especially fluorine), and this when the cationic entity is an onium an element from groups 15 to 17,

> a phenyl radical substituted by at least one element or an electron-withdrawing group, in particular a halogen atom (especially fluorine), CF3, OCF3, NO2, CN, and this when the cationic entity is an organometallic complex of an element of the groups 4 to 10

> an aryl radical containing at least two aromatic rings such as, for example, biphenyl or naphthyl, optionally substituted with at least one element or an electron-withdrawing group, in particular a halogen atom (especially fluorine),

OCF3, CF3, NO2, CN, whatever the cationic entity.

Without being limiting, more details are given below as to the subclasses of onium borate and organometallic salt borate more particularly preferred in the context of the use in accordance with the invention. Thus, as regards the borate anionic entity, the species which are particularly suitable are the following: r [B (C ₆ F ₅ ) - 5 '[B (C ₆ H ₃ (CF ₃ ) ₂ ) - v [ (C ₆ F ₅ ) ₂ BF ₂ ] - 6 '[B (C ₆ H ₃ F ₂ ) ₄ ] - y [B (C ₆ H ₄ CF ₃ ) ₄ ] - T [C ₆ F ₅ BF ₃ ] -

4 '[B (C ₆ F ₄ OCF ₃ ) ₄ ] -

With regard to the cationic entity of the photoinitiator, there are:

1) onium salts of formula (I),

2) the oxoisothiochromanium salts of formula (II), 3) the mono and / or polysylfonium salts of formula (III.1) and / or (LII.2), 4) the organometallic salts of formula (IV).

The first 1) are described in numerous documents, notably in patents US-A-4,026,705, US-A-4,032,673, US-A-4,069,056, US-A- 4,136,102, US-A- 4,173,476. Among these, the following cations will be particularly favored:

[() 2l] ⁺ [C ₈ Hi7-O-Φ-I-Φ] ⁺ [(Φ-CH ₃ ) ₂ I] ⁺

[Cι ₂ H ₂₅ -Φ-I-Φ] ⁺ [(C ₈ Hi7-O-Φ) ₂ I] ⁺ [(C ₈ H ₁₇ -O-Φ- I-Φ)] + [(Φ) 3 S ] ⁺ [(Φ) ₂ -S-Φ-OC ₈ Hι ₇ ] ⁺ [(CH ₃ -Φ-I-Φ-CH (CH ₃ ) ₂ ] + [Φ-S-Φ-S- (Φ) ₂ ] ⁺ [(Cι ₂ H ₂₅ -Φ) 2 l] ⁺ [(CH ₃ -Φ-I-Φ-OC ₂ H ₅ ] + As regards the second family of cationic entities of formula (II) and oxoisothiochromanium type, it preferably comprises cations corresponding to the structure D ₁ which is defined on page 14 of application WO-A-90/11303 and has the formula (II):

where the radical R ⁶ has the meaning given in this WO application in connection with the symbol R ¹ ; a cationic entity of this type which is more preferred is that where R ⁶ represents an alkyl radical, linear or branched, C _j -C ^. As oxoisothiochromanium salts which are particularly suitable, mention will be made in particular the sulfonium salt of 2-ethyl-4-oxoisothiochromanium or 2-dodecyl-4-oxoisothiochromanium.

As regards the cationic polysulfonium entities (III.1), it will be specified that the cationic polysulfonium entity preferably comprises a species or a mixture of species of formula (III.1) in which:

the radicals Ar ^, identical or different from each other, each represent a phenyl radical, optionally substituted by a linear or branched C1-C4 alkyl radical or by the group of formula:

the radicals Ar, identical or different from each other and with Ar ^, each represent a phenyl radical, optionally substituted by a linear or branched C1-C4 alkyl radical,

the radicals Ar ³ each represent an unsubstituted para-phenylene radical,

- t is equal to O or 1, with the additional conditions according to which: + when t = 0, Y = Y ^{1 =} :

- S ⁺ - Ar ¹

I 2 Ar where the radicals Ar ^ and Ar have the preferred meanings given just above in this paragraph; + when t = 1:

O on the one hand, Y = Y ² to Y ⁴ with:

. γ2 =

where the radical Ar has the preferred meaning given just above in this paragraph,

• Y ³ = a valential link,

• Y ⁴ = - O— or —S—, and O on the other hand, when Y = Y ³ or Y ⁴ and when we then wish to use radicals Ar ^ and Ar (terminals) linked together, we install a bond Y 'consisting of a valential bond or the rest - O -.

The mono-sulfonium species, when there are any, which fall within the framework of this preferential modality are the species of formula (IV) in which the symbols Ar ^ and Ar2 have the preferred meanings indicated above in the preceding paragraph , including, when these radicals are directly linked together by a remainder Y ¹ , the installation of a valential link or the rest - O -.

As examples of cationic sulfonium entities, particular mention may be made of:

mixtures, in variable quantities, of species 5 + 2 + optionally 2, mixtures, in variable quantities, of species 5 with species 10 of formula

10

The borate anionic entity is preferably chosen from anions of formula [BX ^] - in which: - the symbols X represent a fluorine atom,

the symbols R, which are identical or different, represent a phenyl radical substituted by at least one electron-withdrawing group chosen from OCF3, CF3, NO2 and CN, and / or by at least two fluorine atoms.

Knowing that the borate anionic entity of formula [BX..R - is preferably chosen from the following anions: l ', 2', 3 ', 4', 5 ', 6', 7 ', borates of polysulfonium, which will be used very preferably, are the salts formed by the association of the following cations and anions: Cation Anion

5 V i ^y

5 4! mixtures 5 + \ 0 V mixtures 5 + 10 3_ mixtures 1 + 10 __ [

These polysulfonium borates can be prepared by exchange reaction between a salt of the cationic entity (halide such as for example chloride, iodide) with an alkali metal salt (sodium, lithium, potassium) of the anionic entity.

The operating conditions (respective quantities of reagents, choice of solvents, duration, temperature, stirring) are within the reach of those skilled in the art; these must make it possible to recover the desired polysulfonium borate in solid form by filtration of the precipitate formed or in oily form by extraction using an appropriate solvent.

The procedures for the synthesis of halides of cationic entities of formula (III.l) are described in particular in: "Polymer Bulletin (Berlin)", vol. 14, pages 279-286 (1985) and US-A-4,400,541.

According to an alternative concerning the preparation of polysulfonium borates, the latter can be prepared directly by reaction between a diarylsulfoxide and a diarylsulfide according to the teaching described in: "J. Org. Chem.", Vol. 55, pages 4222 - 4225 (1990).

These new polysulfonium borates can be used, as they are obtained at the end of their preparation process, for example in solid or liquid form or in solution in an appropriate solvent, in monomer / oligomer / polymer compositions which are intended to be polymerized and / or crosslinked cationically and under activation, for example UV.

The mono-sulfonium species (III.2) mentioned above may be in particular the co-products which are formed at the time of the preparation of the polysulfonium cations and whose presence can be more or less avoided. Up to 99%, more generally up to 90% and even more generally up to 50 mol% (of cation) of the polysulfonium species of formula (III. 1) can be replaced by monosulfonium species (HΣ.2) .

As regards the fourth type of cationic entity, it is described in US patent A-4,973,722, US-A-4,992,572, European patent applications EP-A-203,829, EP-A- 323 584 and EP-A-354 181. The organometallic salts most readily used in practice are in particular: (η5 - cyclopentadienyl) (η ^ - toluene) Fe ⁺ 'le (η5 - cyclopentadienyl) (η ^ - methyl-1- naphthalene) Fe ⁺ >. (η - cyclopentadienyl) (η ^ - cumene) Fe ⁺ > bis (η - mesitylene) Fe ⁺ 'bis (η "- benzene) Cr ⁺ -

There may be mentioned, as examples of photoinitiators of the onium borate type, the following products: [(Φ) ₂ 1] ⁺ , [B (C ₆ F ₅ ) ₄ ] - [(C ₈ H ₁₇ ) -O-Φ-I-Φ)] ⁺ , [B (C ₆ F ₅ ) ₄ ] ^"

[C ₁₂ H ₂₅ -Φ-I-Φ] +, [B (C ₆ F ₅ ) ₄ ] "[(C ₈ H ₁₇ -O-Φ) ₂ I] ⁺ , [B (C ₆ F ₅ ) ₄ ] -

[(C ₈ H ₁₇ ) -O-Φ-I-Φ)] ⁺ , [B (C ₆ F ₅ ) ₄ ] - [(Φ) ₃ S] ⁺ , [B (C ₆ F ₅ ) ₄ ] ^"

[(Φ) ₂ S-Φ-OC ₈ H ₁₇ ] +, [B (C ₆ H ₄ CF ₃ ) ₄ ] - [(C ₁₂ H ₂₅ -Φ) ₂ I] ⁺ , [B (C ₆ F ₅ ) -

[(Φ) ₃ S] +, [B (C ₆ F ₄ OCF ₃ ) ₄ ] "[(Φ-CH ₃ ) ₂ I] +, [B (C ₆ F ₅ ) ₄ ] - [(Φ-CH ₃ ) ₂ 1] ⁺ , [B (C ₆ F ₄ OCF ₃ ) ₄ ] "[CH ₃ -Φ-I-Φ-CH (CH ₃ ) ₂ ] ⁺ , [B (C ₆ F ₅ ) ₄ ] -

. (η ⁵ - cyclopentadienyl) (η ⁶ - toluene) Fe ⁺ , (C_Ε $) 4] -

(η5 - cyclopentadienyl) (η ^ - methyll-naphthalene) Fe ⁺ , [B (C6F5) 4] "(η5. cyclopentadienyl) (η ^ - cumene) Fe ⁺ , [B (C6F5) 4]"

As another literary reference to define the onium borates 1) and 2) and the organometallic salt borates 4), selected as photoinitiator in the context of SPL use according to the invention, mention may be made of the entire content of the applications for Patent EP 0 562 897 and 0 562 922. This content is fully incorporated by reference in the present description. As another example of an onium salt which can be used as photoinitiator C, mention may be made of those disclosed in American patents US 4 138 255 and US 4 310 469 (CRIVELLO).

It is also possible to use other cationic photoinitiators, e. g. : - those sold by UNION-CARBIDE (photo-initiator 6990 and 6974 triarylsulfonium hexafluoro-phosphate and hexafluoroantimonate),

- the iodonium salts hexafluorophosphate or hexafluoro-antimonate,

- or the ferrocenium salts of these different anions.

The radical photoinitiators used are based on benzophenones. We can cite, by way of examples, those marketed by CEBA-GEIGY:

- IRGACURE 184,

- IRGACURE 500,

- DAROCURE 1173,

- IRGACURE 1700, - DAROCURE 4265,

- IRGACURE 907,

- IRGACURE 369,

- IRGACURE 261,

- IRGACURE 784 DO, - IRGACURE 2959,

- IRGACURE 651.

The radical photoinitiators can contain one or more phosphorus atoms, such as those marketed by CIBA-GEIGY (IRGACURE 1700) or BASF (LUCIRIN TPO). In accordance with the invention, the proportions of compounds A, B, C are as follows:

• A: 59-97.99%, preferably 70-97.9%,

• B: 39-1%, preferably 29-1%;

• C 2-0.01%, preferably 1-0.1%. Various combinations are possible with regard to the matrix A and the diluent B of the composition according to the invention. Preferably, the latter comprises:

- a matrix (A) based on a mixture of at least one of the following species: epoxides (α,), acrylates (α ₂ ), vinyl ethers (0C ₃ ), polyols (α ₄ ), preferably ( α,) and (α ₂ ), - and a silicone diluent (B) whose frB are epoxy and / or acrylate and / or vinyl ether and / or hydroxy, preferably epoxy and / or acrylate. It goes without saying that, in the case where the species used are (0C _j ) and / or (oc-,), then the photoinitiator (C) is of the cationic type, while, for the species (o ^) and (α ₄ ) the photoinitiator (C) is radical. In practice, it will thus be possible, for example, to combine monomers and / or oligomers and / or polymers of the matrix A with epoxy and acrylate frA functions, with a first diluent B with epoxy functions and a second diluent B with acrylate functions.

According to a variant, the epoxy and acrylate frA functions can be carried by different comonomers from the matrix A.

Advantageously, the photoinitiator C is used in solution in an organic solvent (accelerator), preferably chosen from proton donors and, more preferably still, from the following groups: isopropyl alcohols, benzylic alcohols, diacetone alcohol, butyl lactate and their mixtures. In addition to the photo-initiator (s) C, the composition according to the invention can optionally comprise at least one photo-sensitizer D selected from (poly) aromatic products - optionally metallic - and heterocyclic products and, preferably, chosen from the following product list: phenothiazine, tetracene, perylene, anthracene, diphenyl-9-10-anthracene, thioxanthone, 2-chlorothioxanthen-9-one, 1-chloro 4 propoxy 9H-thioxanthen-9-one, isopropyl-OH-thioxanten -9-one, mixture of isomers 2 and 4, 2-isopropyl-9H - thioxanthen-9-one, benzophenone, [4- (4-methylphenylthio) phenyl] phenylmethanone, 4-benzyl-4'-methyldiphenylsulphide, acetophenone, xanthone, fluorenone, anthraquinone, 9, 10-dimethylanthracene, 2-ethyl-9, 10-dimethyloxyanthracene, 2,6-dimethyl-naphthalene, 2,5-diphenyl-1-3-4-oxadiazole, xanthopinacol, 1,2-benzanthracene, 9-nitro-anthracene, and mixtures thereof. By effective amount of initiator system is meant, within the meaning of the invention, the amount sufficient to initiate crosslinking. Advantageously, the effective amount corresponds to 1.10- ^4-1, preferably from 1.10 ° to 1.10 ^-1 and even more preferably from 1.10 ° to 1.10 ^{* 2} moles of photoinitiator per 1 mole of

When using a photo-sensitizer D, the appropriate concentration ranges for the latter are:

- 1.10- ⁴ to 1.10- ¹ mole / mole of frA and frB,

- preferably from 1.10 ^-4 to 1.10 ^-2 mole / mole of frA and frB, - and, more preferably still, from 1.10 ^-4 to 1.10 ^-3 mole / mole of frA and frB.

To illustrate what the optional ingredients can be, which are the pigments E in the composition according to the invention, mention will be made, for example, of the following products: titanium dioxide, kaolin, calcium carbonate, black iron oxide, salts of barium nitrogen, aluminum pigments, calcium borosilicate, carbanzole violet, azo pigments, red iron oxide, yellow iron oxide, diazo, naphthol, carbon black, bayrite, dianisidine, monoarylide, pyrazolone, toluidine, red calcium, Ca salts nitrogenous, nitrogenous Ba salts, diarylide, monoarylide, phthalocyanine, benzimidazoline, bronze powder, rhodamine.

The pigmented compositions according to the invention are, e. g., inks. Titanium dioxide produces a white ink.

As regards the other optional additives F, mention may be made, by way of examples, of dyes, fillers (silicones or not), surfactants, mineral reinforcing fillers (siliceous or not), bactericides, inhibitors of corrosion, binding bases, organosilicon compounds or epoxy compounds, such as alkoxysilanes, epoxycycloaliphatics or epoxyetheraliphatics.

Concerning more particularly the case of varnishes, these are, of course, free of pigments in the case where they are clear varnishes. In general, the varnishes comprise at least one surfactant and, advantageously, a particular combination of monomer, oligomer and polymer products in the matrix A, namely at least one cyclo aliphatic epoxide and, optionally, at least one epoxide obtained from condensation. bisphenol A and an epichlorohydrin. In a manner known per se, varnishes can include in their compositions: flexibilization agents and / or leveling agents (products marketed by BYK CHEMIE or EFKA CHEM., For example BYK 306, 307, 361, EFKA 31, EFKA 35 ) and / or adhesion promoting agents: eg silanes of the GLYMO type:

According to an advantageous characteristic of the invention, the flexibilization agent (s) and / or the leveling agent (s) and / or the adhesion promoter (s), can comprise, in whole or in part _l the reactive diluent B, eg formula 1.1, as described above.

Diluent B can therefore assume the functions fulfilled by these various functional additives. This multifunctionality is all the more interesting since it does not require an overload in diluting B. Low doses are sufficient.

According to another of its aspects, the present invention relates to a silicone diluent B, as defined above, for the preparation of a composition preferably an ink or a varnish, polymerizable and / or crosslinkable under irradiation, preferably actinic and / or by electron beam, by cationic and / or radical route, said composition comprising, in addition, the compounds A and C and, optionally, D, E and F referred to above. The examples which follow will make it possible to better understand the invention and to highlight all of its advantages and to glimpse some of its variant embodiments.

EXAMPLES

I - RAW MATERIALS:

I.l - MATRIX (A):

- α - Monomers with frA = epoxy

(MI) is marketed by the company UNION-CARBIDE (UVR 6105 and 6110). - α ₂ - frA: oligomer / epoxyacrylate of the type:

(AC1) Bisphenol with oligomeric epoxydiacrylate (EBECRYL 600).

- α ₂ - Monomers with frA = acrylate: mixture of trifunctional oligomer acrylate obtained from glycerol and polyester marketed, for example, by the BELGIAN CHEMICAL UNION (UCB) (EBECRYL 810) (AC2).

- α ₄ - Monomers with frA = OH:

(Tl) is marketed by the company UNION CARBIDE (TON 301).

1.2 - THINNER (B): 1)

This siloxane a) can be obtained by hydrosilylation of vinylcyclohexene-monoxide with tetramethyldihydrogeno-1,3-disiloxane, at a flash point of 200 ° C. 2)

1.3 - PHOTO-PRIMER C:

Photoinitiator (PI) (bis + 90% w / w and mono. 10% w / w)

20% in butyl lactate.

The cationic photoinitiator used has the following formula:

The radical photoinitiator (P3) used is that marketed by CIBA-

GEIBY (DAROCURE 1173).

P2 is soluble in P3.

PI, P2, P3 are used in the form of a solution in butyl lactate or isopropanol.

1.4 - PHOTOSENSITIZER (D):

CPTX = chloro-l-propoxy-4-thioxanthone.

1.5 - PIGMENT (E): Concentrated pigment base. A concentrated pigment base is obtained by dispersing:

- 700 parts of titanium oxide of rutile type marketed by DUPONT (R960),

- 3.5 parts of a dispersant marketed by ZENECA (SOLSPERSE 24000C)

- 296.5 parts of cycloaliphatic epoxy resin (Ml) sold by UNION-CARBIDE (UVR6105), in a 2 liter capacity reactor fitted with three-bladed central agitation. The concentrated pigment base is obtained by mixing Vi hour after casting the titanium oxide powder on the resin / dispersant mixture preheated to 40 ° C.

- TO OTHER ADDITIVES (F):

- Leveling agent marketed by the company BYK (BYK 306, BYK 307 or BYK 361) or by the company EFKA (EFKA 35).

- Wetting agent based on polyether silicone sold by the company OSI (SILWET L 7640 or L7644).

EVALUATION OF THE PROPERTIES OF THE COMPOSITION.

- RAPPsA test - crosslinking speed:

An illustration of the different crosslinking speeds is given from films from 4 to 25 μm thick obtained on a UV bench equipped with a lamp.

FUSION type H. The crosslinking speed is recorded at a given running speed and at a measured radiation dose. It is also possible to crosslink in a 2 mm thick layer from a high pressure Hg arc lamp connected to an optical fiber of 8 mm in diameter, sold by the company EFOS (ULTRACURE 100SS). The optical fiber is connected to the measuring tank of a RAPRA device (VNC or Vibrating Needle Curemeter). The vibrating needle plunges into the epoxy matrix (1 cm ³ ) and a potential difference is measured according to the degree of crosslinking at a given frequency of vibration, which is 40 Hz. When irradiated, the medium reaches the point of gel very quickly. This results in a variation of the measured potential. The potential variation curve is recorded throughout the UV exposure and the time value which corresponds to 95% of the total variation (T95) is reported, for example 0.6 minutes in fig. 1 attached. - Test at the MEK:

This MEK methyl ethyl ketone test consists of measuring the number of round trips that can be made on the surface of the varnish with a paper (cellulose wadding) soaked in methyl ethyl ketone (MEK) before the varnish is completely degraded.

- Flexibility of the layers by folding on a cylindrical mandrel according to AFNOR standard n ° T30-040.

EXAMPLE 1:

The diluent a) is perfectly miscible in the epoxy (Ml) or polyol (Tl) matrix. We study the behavior of crosslinking under ultraviolet light of different formulations in the presence of a sulfonium borate of formula (PI). The three formulations produced include:

- (FI) 5 P (a)

95 P (Ml)

- (F2) 10 P (a)

90 P (Ml) - (F3) 20 P (a)

80 P (Ml)

- (FT) control formulation 100 P (Ml) 0.5 p of a wetting agent based on polyether silicone sold by the OSI company (SILWET L7640 or L7644) and a photoinitiator solution are added to these formulations. in vinyl lactate, so as to have a given concentration, the value of which is specified further on in Table 1. The crosslinking in a thick layer (RAPRA (VNC)) and in a thin layer is studied. Films of 5, 10, 20 μm are produced using threaded coating bases (Bar 0, 2 or 3) on an aluminum support. A few drops of composition are used and the aluminum support is degreased by cleaning with propanol or isopropanol. Vibratory needle crosslinking tests are carried out in a tank with a size of 10 x 10 x 40 mm using 1 cm ³ of composition poured into the tank. The bottom of the tank is connected to a mercury vapor lamp (high pressure) via an optical fiber. The needle plunges up to 2 mm from the bottom of the tank which receives the light beam.

The results obtained during the various crosslinking tests on exposure to ultraviolet light are collated in Table I below.

With the FUSION lamp (type "H"), the minimum duration of exposure is recorded at a given scrolling speed to go from the liquid state to the non-sticky solid state. The degree of crosslinking of the films obtained by the methyl ethyl ketone (MEK) test is also defined. With the mercury arc lamp, in the case of cross-linking in a thick layer of 2 mm with RAPRA (vibrating needle), the minimum duration of exposure is recorded to reach 95% of cross-linking (T 95 defined above). ).

TABLE I

* passes = number of passes required at the speed considered to obtain a dry touchdown on the surface, ** MEK:> 200. After 100 round trips the film is still intact. Storage time at 20 ° C after irradiation after which the measurement is made. All additive formulations crosslink perfectly in the presence of this epoxy silicone, the viscosity of which is 50 mPa.s.

EXAMPLE 2:

We now compare the speed of crosslinking and the nature of the network obtained after adding Tl in the matrix (A) in addition to Ml which improves the flexibility of the resin after crosslinking.

The ratio [OH] / [epoxy] = 1/4.

The new control formulation (F'T) becomes:

- 85 p of (Ml),

- 15 p of (Tl). Different quantities of silicone diluent (a) are added:

- (F'1) 80.75p of (Ml),

14.25 p of (Tl), P of (a),

(F2) 76.5 p of (Ml),

13.5 p of (Tl),

10 p of (a),

(F'3) 68 p of (Ml),

12 p of (Tl),

20 p of (a). 0.5 p of the same wetting agent (SILWET L7640) as in the previous example is added and a known fixed amount of photoinitiator. We use the same lamps as before. The results obtained during the various tests are collated in Table II below. TABLE II

* 1 pass. conveyor limit running speed which allows a dry touch on the surface in a single pass, ** MEK: storage time at 20 ° C after irradiation after which the measurement is made (1 hour). Maximum number of round trips that the film can support. It can be seen, in particular, that the silicone (a) makes it possible to increase the speed of crosslinking, the hardness of the films, while improving the impact resistance (front). In particular, it is not necessary to add a lot of silicone (a) <30% w / w to obtain a spectacular effect.

EXAMPLE 3

The incidence of (a) added in an organic matrix based on cycloaliphatic epoxides (Ml), polyol (Tl) and in the presence of a leveling agent (BYK 306) is also evaluated.

In this example, the photoinitiator is an iodonium borate of formula (P2) added in solution at 33% w / w in isopropanol:

The following formulations were evaluated using RAPRA (see Tables III and Table IV) for 0.5% and 1% of photoinitiator, respectively.

TABLE El

TABLE IV

EXAMPLE 4 Formulation and evaluation of white inks containing a reactive diluent of the type of those claimed according to the invention.

This concentrated pigment base is formulated with or without diluent siloxane (a).

TABLE V

* CPTX = chlorine 1 propoxy4thioxanthone used as photo-sensitizer. The photoinitiator is added in the form of an isopropanolic solution.

The various constituents are added and mixed until complete dissolution of the thioxanthone CPTX, before addition of the concentrated pigment base. The drying of the inks is evaluated on a UV bench from the company FUSION fitted with a mercury lamp doped with gallium. This lamp, which has a power of 120W / cm, was calibrated using a Powerpuck cell from the company EIT, so as to determine the intensity and the dose received as a function of the running speed of the bench. At the running speed of 23 m / min the sample receives:

UVA (320-390 nm) = 0.157 J / cm ² ; UVB (280-320 nm) = 0.068 J / cm ² ; UVC (250-260 nm) = 0.013 J / cm ² ; UW (390-440 nm) = 0.490 J / cm ² . At the running speed of 43 m / min the sample receives:

UVA (320-390 nm) = 0.088 J / cm ² ; UVB (280-320 nm) = 0.038 J / cm ² ; UVC (250-260 nm) = 0.006 J / cm ² ; UW (390-440 nm) = 0.416 J / cm ² . The resistance to solvents of the inks obtained after drying of films of 12 μm ± 3 is measured, by measuring the number of necessary round trips made using a cloth soaked in solvent to disintegrate the ink layer, 1 hour. after exposure and 24 hours after exposure. In this case the solvent used is methyl ethyl ketone (MEK).

TABLE VI

EXAMPLE 5 Hybrid formulations of the matrix (A) based on epoxy / acrylate with an epoxy diluent.

Table VII below gives the compositions of tests F12 to FI 7.

TABLE Seen

_S. peeling of _. these hybrid formulations:

The drying of the inks is evaluated on a UV bench from the IST Company fitted with two 200W / cm lamps. A gallium-doped mercury lamp and an undoped mercury lamp.

At the running speed of 23 m / min the sample receives:

UVA (320-390 nm) = 0.372 J / cm ² ; UVB (280-320 nm) = 0.334 J / cm ² ;

UVC (250-260 nm) = 0.044 J / cm ² ; UW (390-440 nm) = 0.662 J / cm ² . At the running speed of 43 m / min the sample receives:

UVA (320-390 nm) = 0.145 J / cm ² ; UVB (280-320 nm) = 0.145 J / cm ² ;

UVC (250-260 nm) = 0.018 J / cm ² ; UW (390-440 nm) = 0.343 J / cm ² . At the speed of 100 m / min, the calibration is not significant, taking into account the response time of the cell. Measuring the resistance to solvents of the inks obtained after drying 12 μm films on aluminum (Bar n ° 2) by noting the number of necessary round trips made using a cloth soaked in solvent to disintegrate the layer ink after V_ hour. In this case, the solvent used is methyl ethyl ketone (MEK). The evaluation results without nitrogen cover are as follows. TABLE VIII

* Membership according to NFT 30038: 5 + 0% membership,

0 = 100% membership. The siloxane diluent (a) allows, thanks to its low viscosity, to facilitate spreading on the support and the mixture of the constituents.

The formulas, using the reactive diluent noted (a) have a particularly interesting behavior on drying. They lead to better adhesion without major loss of setting speed and solvent resistance.

EXAMPLE 6 Radical formulations with a matrix (A) based on acrylates.

The drying of the inks is evaluated on a UV bench from the IST Company equipped with two 200 W / cm lamps. A gallium-doped mercury lamp and an undoped mercury lamp.

The calibration of the lamps is the same as before.

The formulas used are described in Table IX below. TABLE IX

* Membership according to NFT 30038: 5 = 0% membership,

0 = 100% membership. The evaluation results without nitrogen cover are as follows. The siloxane diluent (P) allows very good incorporation of ACl without harming the polymerization.

Claims

CLAIMS:

1 - Composition which can be polymerized and / or crosslinked under irradiation, preferably actinic and / or by electron beam (s), cationically and / or free radical, characterized in that it comprises: A. at least one organic polymerizable matrix and / or at least partially polymerized, comprising (co) monomers and / or (co) oligomers and / or (co) polymers chosen from those having reactive (frA) epoxy (oc _j ) and / or acrylate ( α ₂ ) and / or alkenyl ether (α ₃ ) and / or hydroxy (α ₄ ), excluding cycloaliphatic epoxides (oc _n );

B. at least one silicone diluent with reduced viscosity ηr at 25 ° C less than or equal to 200 mPa.s, preferably 150 mPa.s and, more preferably still, 100 mPa.s and comprising: • at least one motif of formula (I):

in which :

- a = 0, 1 or 2,

- R ° is identical or different to its similars of the same exponent and represents an alkyl, cycloalkyl, aryl, vinyl, hydrogen, alkoxy radical, preferably a lower alkyl

C _j -C ₆ ,

- Z is an organic substituent comprising at least one reactive (frB), epoxy and / or acrylate and / or alkenyl ether and / or hydroxy function, with the condition that at least part of the functions (frB) is of the same nature that at least part of the functions (frA) of the matrix A, • and at least two silicon atoms, C. an effective amount of at least one cationic and / or radical photoinitiator, D. optionally at least one photosensitizer, E. optionally at least one pigment,

F. possibly at least one other additive.

2 - Composition according to claim 1, characterized:

• in that cycloaliphatic epoxides are not excluded from the list of possible constituents for the matrix (A),

• and in that the diluent (B) has a metal concentration of less than or equal to 100 ppm, preferably 50 ppm and, more preferably still, 20 ppm.

3 - Composition according to claim 1 or 2, characterized in that the diluent (B) has a color less than or equal to 200 Hazen, preferably 150

Hazen and, more preferably still, at 100 Hazen and / or is soluble at a rate of at least 5%, preferably at least 10% and, more preferably still, at least 20% by weight in the matrix A.

4 - Composition according to any one of claims 1 to 3, characterized in that the silicone diluent B is obtained by hydrosilylation of a synthon carrying an ethylenically unsaturated function and a FrA function using a silicone oil, in the presence of a heterogeneous catalytic composition comprising a metal chosen from the group consisting of Co, Rh, Ru, Pt, Ni deposited on an inert support. 5 - Composition according to any one of claims 1 to 4, characterized in that the diluent (B) corresponds to at least one of the following general formulas:

in which :

• x + y = 3; x = 1 to 3; y = 0 to 3;

• b + c = 2; b, c = 0, 1 or 2;

• u + v = 3; u, v = 0 to 3;

• 0 <n ≤ 15; R ² , R ³ are identical or different and correspond to the same definition as that given for R ° of formula (I), the alkyls and / or the lower alkoxyls C _r C ₆ being particularly preferred as radicals R ₂ and R ₃ , respectively, frB being as defined above in the passage devoted to the substituent Z of formula (I),

- (frB) (R ⁴ ) _eS iθ - (R), - Si— O-

(1.2)

in which :

• d + e = 2, d = 1 or 2, e = 0, 1 or 2,

• o + p <15, preferably <10; o> 1,

6 - Composition according to any one of claims 1 to 5, characterized in that the frB are chosen from the following radicals:

- (CH ^* , 2), 3— O— CH = CH— R with R ⁶ : - linear or branched C _j -C ₁₂ alkylene, optionally substituted,

- or arylene, preferably phenylene, optionally substituted, preferably by one to three C _j -C ₆ alkyl groups,

• with R ⁷ = linear or branched C ^ Cg alkyl.

7 - Composition according to any one of claims 1 to 6, characterized in that the diluent (B) consists of at least one polysiloxane functionalized frB of the following formula:

(n <10)

(n <10)

O CH,

, CC = CH ₂

O CH,

8 - Composition according to any one of claims 1 to 7, characterized in that the constituents of the matrix A belong to at least one of the following species: ^α ι.n cycloaliphatic epoxides, taken alone or as a mixture between them:

- or Bis (3,4-epoxycyclohexyl) adipate, being particularly preferred; _{l 2)} non-cycloaliphatic epoxides, taken alone or as a mixture between them: • epoxides of the type of those resulting from the condensation of Bis-phenol A and of epichlorohydrin and of the type:

- or diglycidyl ethers of Bisphenol A,

• alpha-olefin epoxides, NOVOLAC epoxies, soybean and linseed oil epoxies, polybutadiene epoxide, being particularly preferred, α ^ acrylates, taken alone or as a mixture between them; e. g. :

• acryloglycero-polyester, preferably a mixture of trifunctional acrylate oligomer obtained from glycerol and polyester (EBECRYL 810),

• multifunctional acrylates, preferably pentaerythrityl triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDODA), trimethylolpropane ethoxylate triacrylate, thiodiethylene glycol diacrylate, tetraethylene glycol diacrylate (TTEGDA), tripropylene glycol diacrylate (TRPGDA ), triethylene glycol diacrylate (TREGDA), trimethylpropane trimethacrylate (TMPTMA),

• acrylo-urethanes,

• acrylo-polyethers, • acrylo-polyesters,

• unsaturated polyesters,

• acrylo-acrylics, being particularly preferred, o ^ ₎ alkenyl-ethers, linear or cyclic, taken alone or as a mixture between them: vinyl ethers, in particular divinyl triethylene glycol ether (RAPIDCURE® CHVE-3, GAF Chemicals Corp.), cyclic vinyl ethers or acrolein tetramers and / or dimers and vinyl ether of the following formula:

• propenyl ethers,

• and butenyl ethers, being very particularly preferred, α ^• .4) polyols taken alone or as a mixture between them, preferably the compound of formula given below:

9 - Composition according to any one of claims 1 to 8, characterized in that the proportions of compounds A B / C are as follows:

• At 59-97.99%, preferably 70-97.9%,

• B 39-1%, preferably 29-1%;

• C 2-0.01%, preferably 1-0.1%.

10 - Composition according to any one of claims 1 to 10, caracteπsee

• in that it includes:

- a matrix (A) based on a mixture of at least one of the following species: epoxides (c. _j ), acrylates (α ₂ ), vinyl ethers (α ₃ ), polyols (oc ₄ ), preferably (α,) and (α ₂ ), - and a silicone diluent (B) whose frB are epoxy and / or acrylate and / or vinyl ether and / or hydroxy, preferably epoxy and / or acrylate,

• and in that, in the case where the species used are (α _j ) and / or (0 ₃ ), then the photoinitiator (C) is a cationic polyamino acid, while, for the species (0) and (α ₄ ) the polyamino acid is radical.

11 - Use of the silicone diluent (B), as defined in one of claims 1, 3, to 7, for the preparation of a composition preferably an ink or a varnish, polymerizable and / or crosslinkable under irradiation, preferably actinic and / or electron beam, cationic and / or radical, said composition further comprising the compounds A and C and, optionally, D, E and F referred to in claim 1.