FR2761368A1 - COMPOSITION (E.G. INK OR VARNISH) POLYMERIZABLE AND / OR CROSSLINKABLE BY CATIONIC AND / OR RADICAL ARRAY, BASED ON ORGANIC MATRIX, SILICONE DILUENT AND PHOTO-PRIMER - Google Patents

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 photopolymer systems

  crosslinkable and / or polymerizable under irradiation, in particular under UV or electron beam irradiation, which can be used, in particular, to form coatings, such as

as inks or varnishes.

  These compositions are of the type comprising an organic matrix whose constituents carry reactive polymerization / crosslinking functions, as well as a photoinitiator or photoinitiator which, after absorbing energy, for example UV, releases a strong acid: H + (cationic route) or a free radical (radical route). The cationic photoinitiators thus allow the initiation and the propagation of cationic chain polymerizations, whereas the radical photoinitiators (PA) allow the triggering of polymerizations in

  chain by formation of free radicals.

  In some applications of coatings or inks (or even dark varnishes), additives, such as pigments, are used which are capable of appreciably increasing the viscosity of the compositions, to such an extent that they are no longer detectable and manipulable. . It goes without saying that these are prohibitive drawbacks for the applications in question. To remedy this, diluents have

  These compositions have been incorporated in order to reduce their viscosity.

  In the case of clear lacquers, diluents or coreagents are sought which can improve the flexibility of the coatings, without reducing the reactivity of the systems. The diluents most commonly used to date, in compositions of inks or photopolymerizable varnishes, are products of the vinylether type (in particular

  divinyl ether) or of the limonene type (in particular limonene epoxidized).

  Although these products satisfy a number of specifications required in the specifications of the diluent, namely in particular the miscibility with the organic matrix or the organic resin, the transparency or the inexpensive nature, these known diluents are fishing with regard to the considerations respect for

  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 vinylether or epoxidized limonene type, are, moreover, irritating and sensitizing. In addition, they do not achieve sufficiently high polymerization rates, which would reduce the concentrations of photoinitiator, which would greatly relieve the cost of the compositions. EP 0 389 927 also discloses photopolymerizable coating compositions comprising polyepoxides.

  organic cycloaliphatics, combined with a functionalized siloxane a-co-

  epoxycycloaliphatic, present in an amount allowing the acceleration of the

  crosslinking. The photoinitiators used are onium salts.

  This composition is presented as having an improved cure rate.

  The functional xa-o-cycloaliphatic epoxy siloxane is therefore in fact used as a polymerization accelerator for polymerizable coating systems, based on UV-polymerizable cycloaliphatic polyepoxides. This patent application discloses, in particular, compositions based on: - 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, which constitutes the polymerizable matrix, - an agent for reducing the energy required for the photopolymerization,

  said agent being dimethyldisiloxane α-o-3,4-epoxycyclohexyl-1-

ethyl,

  and a photoinitiator consisting of (4-octyloxyphenyl) phenyliodonium

  hexafluoro-antimonate solution in 2-ethyl-1,3-hexanediol.

  The disadvantage of this type of compositions is their turbid appearance and color, so not transparent. In addition, they contain a significant quantity of metal, which is not unrelated to the problem of lack of translucency and transparency and which

  additionally, is likely to disturb the polymerization mechanism.

  O-O-> epoxidized dimethyldisiloxanes are, moreover, known as

  cationically polymerizable monomers under UV, in the presence of

  initiators of the type omnium salts. The article by CRIVELLO published in J. Polym. Sci .: Part A: Polym. Chem., 1994, Vol. 32, 683-697 deals with this subject and shows that the cyclo-aliphatic epoxide functions are more reactive in cationic polymerization

  under UV than conventional epoxy functions.

  The article by R. P. ECKBERG & K. D. RIDING in Polym. Mater. Sci. Eng., 1989, 60, 222-7 discloses the cationic polymerization / crosslinking, under UV activation and in the presence of onium salt photoinitiator, of mixtures of α,--epoxidized dimethyldisiloxanes (MEME) with cycloaliphatic epoxides of formula: o

C [O (CY 179)

  According to this document, there is no marked effect of the MEME with respect to the effectiveness of the polymerization / crosslinking rate for MEME concentrations lower than

  % by weight relative to the mixture MEME / CY 179 (FIG 1).

  Such concentrations are not likely to promote the use of MEME, because this additive can not be preponderant in the formulation, just to make the polymer / crosslink unsuitable for the applications intended for it (e.g.

  non-stick paper, varnish, inks).

  In addition, the crosslinked products obtained from such mixtures MEME / CY 179 suffer from the major disadvantage of being brittle, which is unacceptable in good

number of applications.

  Finally, these compositions are also affected by turbidity and

  metal pollution, like the compositions according to EP 0 389 927.

  It must therefore be noted that the state of the art does not meet the specifications expected for the 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 regulating means (diluents) for the viscosity of photopolymerizable pigment inks, which are not toxic.

  and which do not interfere with the reactivity of the composition.

  Similarly, in the field of light-cured clearcoats, there are no harmless additives capable of improving the flexibility of the coatings, the spreading and the surface condition, without however

  hinder 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 (ie vinyl ether) - cationic pathway - or acrylate or hydroxy-pathway

radical -.

  In this state of knowledge, one of the essential objectives of the present invention is to overcome the existing shortcomings by providing cationic and / or radical photopolymerizable compositions which meet the expectations.

  their fields of application, particularly as regards inks and varnishes.

  Having fixed this objective, the plaintiff had the merit, on the one hand, of isolating and selecting a silicone compound of the di or oligosiloxane functionalized type and, on the other hand, of implementing, in an original way, this compound as a diluent in photopolymerizable compositions, for example in

inks or varnishes.

  Thus, the invention, object of the present application, relates to a polymerizable composition and / or crosslinkable under irradiation, preferably actinic and / or electron beam (s), cationically and / or radical, characterized in that it comprises: A. at least one polymerizable and / or at least partially polymerized organic matrix, comprising (co) monomers and / or (co) oligomers and / or (co) polymers selected from those having reactive functions (frA) epoxy (o,) and / or acrylate ({x2) and / or alkenyl-ether (a3) and / or hydroxy (cxa4), excluding cycloaliphatic epoxides (ol); B. at least one silicone diluent of reduced viscosity η at 25 ° C. of less than or equal to 200 mPa.s, preferably at least 150 mPa.s and, more preferably still, at 100 mPa.s, and comprising: at least one formula (I): Z - Si 'tR - O (3-a) 2 in which: - a = 0, 1 or 2, - R is identical to or different from those of the same exponent and represents an alkyl radical, cycloalkyl, aryl, vinyl, hydrogen, alkoxy, preferably lower alkyl

C-CC6,

  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 proviso that at least a part of the functions frB are of the same nature as at least a part of the functions frA of the matrix A, * and at least two silicon atoms, C. an effective quantity of at least one cationic and / or radical photoinitiator, D. optionally at least one photosensitizer, E. optionally at less a pigment,

  F. optionally at least one other additive.

  Except in the case where the matrix A comprises compounds bearing reactive functions frA of the cycloaliphatic epoxide type, the choice of the silicone B as diluent of the composition, is likely to solve the problems of viscosity in the inks and varnishes dark and , flexibility, spreading or sliding in the

  clear, photopolymerizable, UV, cationic and / or radical-type varnishes.

  In addition, the diluent B used in accordance with the invention has the advantage of being economical, non-toxic, non-irritating, non-sensitizing and therefore easy to handle. Moreover, this diluent B does not disturb neither the transparency nor the

  reactivity of the photopolymerizable composition.

  N. It is, moreover, surprising to note that the concept according to the invention of functionalized silicone diluent with a di or oligosiloxane backbone is applicable not only when the reactive functions frA of the matrix are of epoxy type (cationic pathway), but also when frA = alkenyl ether (cationic), frA = acrylate or frA = epoxy (radical route). It should be noted that for frA = OH, the condition according to which the compound or compounds of said matrix comprise at least 20H per molecule, must be

  respected. It 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 of less than or equal to 100 ppm, preferably at 50 ppm and more

  preferentially still, at 20 ppm.

  This characteristic of the purity of the diluent B confers on the composition, transparency and translucency properties, particularly valuable for the

  varnished applications, even inks in some cases.

  Thus, even more preferably, the diluent B is selected so that it has a coloring of 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 by at least 5%, preferably at least 10% and more preferably 20% by weight in the matrix A, this percentage of solubility being expressed relative to the mass of the matrix A and not of the 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 function frA to l using a hydrogenated silicone oil, in the presence of a heterogeneous catalytic composition, comprising at least one metal selected from the group consisting of Co, Rh, Ru, Pt, Ni deposited on a

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 selected from the group consisting of cobalt, rhodium, ruthenium, platinum, palladium and nickel deposited on a

  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 based on the weight of the silicone oil.

  By convention, heterogeneous catalytic composition is understood to mean a catalytic composition that can be solid or liquid, which is undissolved in the reaction medium, 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 sulfate or cross-linked silicones. Advantageously, the granulometric size of the catalytic supports is greater than 10 μm in order to have good filterability that does not require filtration aids. Thus, this particle size is such that it can be reduced

  considerably the filtration time.

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

(1)

y / R

WW W

  (I) and / or O (II) 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 being be a free valence - the symbol Y corresponds to a free valency 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 R1 corresponds to a hydrogen atom or a monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 12 carbon atoms and, preferably, from a hydrogen atom or a methyl radical; At (2) RI y Y CH / \ w

O = C C = O0

  (In) and / or (IV) 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 being able to 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 R1 corresponds to a hydrogen atom or a 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) Y

9 \

YRI

Y W W

IC HC-CH

CH H, C

W W W 'Wr

\ 0 / \ 0 /

  (V) and / or (VI) 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 functional group; hydroxyl; one of the symbols W which may be a free valence for (V) and the two symbols W may simultaneously be 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 'being 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 R1 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) o

(VII)

  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 a hydrocarbon ring in which an oxygen atom is included. In particular, the synthons used and giving good results (see examples below) have the formula: o o (VIII), (x), I (X), o o 0 \ d 0 0 0

O = C C = 0

(XIII), (XIV)

I1

H H

H OH

H H_

H

OH OH (XV),

(XVI) 40 (XVI) <and (XVII)

O 0

  In general, 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 are usable.

  By way of non-limiting examples, platinum on carbon black or carbon may be used such that the catalytic composition containing 2.5% platinum by weight deposited on the CECA 2S support developed by 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, the platinum can be deposited on this type of support by deposition of chloroplatinic acid followed by neutralization and reduction. Likewise, the use of platinum on alumina, preferably of the type such as

  that the catalytic composition CAL 101 (0.3% of Pt, support SCS9 consisting of

  alumina) marketed by Procatalyse or the catalytic composition

  88,823 of HERAEUS (0.5% Pt on ao-alumina) gives good results.

  This process for obtaining the diluent B used in the composition according to the invention can be implemented according to various variants. It is thus possible in particular to use a first embodiment in which all the reagents and the catalytic composition are mixed in the reaction medium ("batch" type). A second embodiment of this method may be a continuous mode with a fixed bed of heterogeneous catalytic composition over which pass the silicone oil to be functionalized and the synthon. 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 lim.

  An example of the first embodiment is given below: (a) an amount of 5 to 5000 ppm, preferably 10 to 100 ppm, of heterogeneous catalytic composition relative to the total mass of the reagents 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 of 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 molar ratio synthon / silicone being

between 1 and 1.10.

  (e) the reaction mass is then filtered 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 is carried out in the absence of solvent. However, many solvents such as toluene, xylene, octamethyltetrasiloxane, cyclohexane or

hexane can be used.

  Moreover, the molar amount of synthon poured during step (b) is less than that used for a conventional method of the prior art. Advantageously, the molar ratio synthon / silicone oil is between 1 and 1.05 and this without affecting the

  the quality of the functionalized oils obtained and the yield of the reaction.

  The filtration stage (e) makes it possible, where appropriate, to eliminate any trace of turbidity from the functionalized silicone oil obtained. On the other hand, the heterogeneous catalytic composition can be recovered and reused again, without requiring regeneration, with or without washing, and without noticeable decrease in

its performances.

  With regard to the preferred structural characteristics of diluent B, it should be noted that it satisfies at least one of the following general formulas: (1.1) (frB) (R) ySi- (frB) (R) y SiO Where T = R3 or Si (R3) u (frB) v, * x + y = 3; x = 1 to 3; y = 0 to 3; * b + c = 2; b, c = 0.1 I or 2; * u + v = 3; u, v = 0 to 3; * 0 <n <15, * R2, R3 are identical or different and meet the same definition as that given supra for R of the formula (I), the alkyls and / or lower alkoxyls C1-C6 being particularly preferred at as radicals R2 and R3, respectively, * frB being as defined above in the passage devoted to the substituent Z of the formula (I), frB) (R4) eSiO (R5) 2 -Si-O (I.2) in which: * d + e = 2; d = lou2; e = Ooul; * o + p <15, preferably <10; o> 1 * R4, R5 are, respectively and together, identical or different from each other and

  meet the same definition as R2 given above.

  The reactive functions frB of diluent B, more particularly

  In the context of the invention, they are of the epoxy, vinyl ether or acrylate type.

  More specifically, these frB are, for example, chosen from the following radicals

O ;; -CH-2 CH CH3

O 'D

o O 0; 0 o O Js; / O'- OCH2CHO) O) E

  - (CH2) t-O-CH = CH2; - (CH3) -O-R - O-CH = CH2

- (CH2) 3-O-CH = CH-R?

  with R 6: - C 1 -C 2 linear or branched alkylene, optionally substituted, or arylene, preferably phenylene, optionally substituted, preferably with one to three C 1 -C 6 alkyl groups,

  with R7 = linear or branched C1-C6 alkyl.

  As examples of diluent B, consisting of at least one di, oligo or polysiloxane functionalized with frB, mention may be made of those of the following formulas: Me Me e / Me a) OSisOzi% Si Me Me Me Me Me b) / o Me Me Me Me eMe MC) o if, O / if (Om) \ Me Me / (OMe) d) O / SM O (ome) (OMe) (n <10) Me MeJ If Me 0 e Me Me If O Me Si Me Me (OMe) M Me f) 0tz 0, M (OMe) (n <10) Me Me

Si-O- - Si-O-

Me g) - p (o + p) <10

0 0> 1

o

CH2 CH-CH2

o

CH2H2 CH2

CH3-i-CH3 h) CH-Si-CH3

CH2CH2 H2

O

CH CH-CH2

  ## STR2 ## ## STR2 ## ## STR13 ##

C-C = CH2

Bone

CH2CH2 CH2

CH3-Si-CH3 CH.-Si-CH3

/ CH2CH2H2

Bone

C-C = CH2

  The silicone diluent B according to the invention has a smaller importance in terms of quantity, compared with the matrix A, which constitutes the preponderant element of the composition. the latter, these constituents belong to at least one of the following species: X1.1) cycloaliphatic epoxides, taken alone or mixed with one another:

  epoxides of the 3,4-epoxycyclohexylmethyl-3 ', 4'-type

epoxycyclohexane carboxylate: o

0 O

  or Bis (3,4-epoxycyclohexyl) adipate, being particularly preferred; aX.2) non-cycloaliphatic epoxides, taken alone or in mixture with one another: * epoxides of the type resulting from the condensation of Bis-phenol A and epichlorohydrin and of the type: - di and triglycidyl ethers of alkoxylated bisphenol A 1.6 hexane diol, glycerol, neopentyl glycol and propane trimethylol, or diglycidyl ethers of Bisphenol A, the epoxides of alpha-olefins, epoxides NOVOLAC, epoxidized soybean and linseed oil, epoxidized polybutadiene, being particularly preferred ,

  (Y2) acrylates, taken by themselves or mixed together; e. g.

  epoxidized acrylates, preferably the oligomer of Bisphenol-A-

  epoxydiacrylate (EBECRYL 600), acrylo-glycero-polyester, preferably trifunctional acrylate oligomer mixture obtained from glycerol and polyester (EBECRYL 810), multifunctional acrylates, preferably pentaerythritol 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, * acrylic-polyesters, * unsaturated polyesters, * acrylo-acrylics, being particularly preferred, linear or cyclic 3>) alkenyl ethers, taken alone or as a mixture with one another vinyl ethers, in particular divinyl triethylene glycol ether (RAPIDCURE CHVE-3, GAF Chemicals Corp.), cyclic vinyl ethers, t tetramers and / or dimer acroleins and vinyl-ether of the following formula: Me Me Me Me Me

I / I /

  IVO- (C 2 CH 2 O) -CHH-CH 1 -Si Si-CH 2 CH 2 - (OCH 2 CH 2) -O-

O

  propenyl ethers, and butenyl ethers, being especially preferred, a) polyols: taken alone or in a mixture with one another, preferably the compound of formula given below: (C 2 H 5) -C-- Of WH Examples of monomers and / or oligomers and / or reactive polymers, functionalized epoxy and / or an ethylenically unsaturated radical, such as an acrylate

  (see patent application EP 0 690 074).

  The initiation of the photopolymerization and / or crosslinking of the composition according to the invention is made possible by the presence of the photoinitiator C

cationic and / or radical.

  The cationic photoinitiators may be chosen from onium borates (taken alone or in mixture with one another) of an element from groups 15 to 17 of the periodic classification [Chem. & Eng. News, vol.63, N 5, 26 of 4 February 1985] or an organometallic complex of an element of groups 4 to 10 of the Periodic Table [same reference], A whose cationic entity is selected from 1) the onium salts of formula (I): [(R 1) n - A - (R 2) m] + (I) in which: A represents an element from groups 15 to 17 such as for example: I, S, Se, Pou N, R1 represents a C6-C20 carbocyclic or heterocyclic aryl radical, said heterocyclic radical being able to contain, as heteroelements, nitrogen or sulfur,

  R2 represents R1 or a linear or branched C1-C6 alkyl or alkenyl radical;

  C30; said radicals R1 and R2 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 the patent application WO 90/11303,

  especially the sulphonium salt of 2-ethyl-4-oxoisothiochromanium or 2-

  dodecyl-4-oxoisothio-chromanium, 3) sulfonium salts in which the cationic entity comprises: at least one polysulfonium species of formula III. Embedded image in which: the symbols Arl1, 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 C1-C12, preferably C1-C6, alkyl radical; a linear or branched C1-C12, preferably C1-C6, alkoxy radical;

  halogen atom, -OH group, -COOH group, ester group-

  COO-alkyl where the alkyl part is a linear or branched C 1 -

  C12, preferably C1-C6, and a group of formula -Y4-Ar2 o the symbols Y4 and Ar2 have the meanings given just below, - the symbols Ar2, which may be identical or different from each other or with Ar1, each represent a monovalent phenyl or naphthyl radical, optionally substituted with one or more radicals chosen from: a linear or branched C1-C12, preferably C1-C6, alkyl radical, a linear or branched C1-C12 alkoxy radical, preferably in C1-C6, a

  halogen atom, -OH group, -COOH group, ester group-

  COO-alkyl wherein the alkyl part is a linear or branched C 1 -C 12, preferably C 1 -C 6, radical; the Ar 3 symbols, which may be identical to or different from each other, each represent a divalent phenylene or naphthylene radical, optionally substituted with a or more radicals chosen from: a linear or branched C 1 -C 12, preferably C 1 -C 6, alkyl radical, a linear or branched C 1 -C 12, preferably C 1 -C 6, alkoxy radical;

  halogen atom, -OH group, -COOH group, ester group-

  COO-alkyl wherein the alkyl part is a linear or branched C 1 -C 12 residue, preferably C 1 -C 6, t is an integer equal to 0 or 1, with the additional conditions according to which: + when t = 0 the symbol Y is then a monovalent radical yl representing the group of formula: + Y: -S-Ar '1 2 Ar2

  the symbols Ar1 and Ar2 have the meanings given below.

  before, + when t = 1: O on the one hand, the symbol Y is then a divalent radical having the following meanings y2 to Y4: y2: a group of formula: + -S- 1 2 Ar o the symbol Ar2 possesses the meanings given above, y3 a simple valency bond, y4 a divalent remainder selected from:

-O-, -S, -, --C-

O O

  a linear or branched C 1 -C 12, preferably C 1 -C 6, alkylene radical and a radical of the formula -Si (CH 3) 2 O, on the other hand, in the case only where the symbol Y represents Y 3 or Y 4, the radicals Ar1 and Ar2 (terminals) have, in addition to the meanings given above, the possibility of being interconnected by the remainder Y 'consisting in yV1 a simple valency bond or in y, 2 a divalent remainder selected from the remainders quoted about the definition of Y4, which is installed between the carbon atoms, facing each other, located on each aromatic ring in the ortho position with respect to the carbon atom directly connected to the S + cation; 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 the formula: + Ar 'S - Ar (III.2) Ar wherein Ar1 and Ar2 have the meanings given above with respect to formula (III.1), including the possibility of directly connecting one of the radicals Ar1 to Ar2 in the same manner as mentioned above with respect to the definition of the additional condition in force when t = 1 in formula (II), using the remainder Y '; 4) the organometallic salts of formula (IV): (L1L2L3M) + q (IV) in which: M represents a group 4 to 10 metal, in particular iron, manganese,

chrome, cobalt ...

  L1 represents 1 ligand bound to the metal M by ir electrons, ligand selected from 113-alkyl, 115-cyclopendadienyl and 13-cycloheptratrienyl ligands and 6-aromatic compounds selected from optionally substituted 6-benzene ligands and compounds having 2 with 4 condensed rings, each ring being able to contribute to the valence layer of the metal M by 3 to 8 electrons it; L 2 represents a ligand bound to the metal M by It electrons, a ligand selected from the R 7 -cycloheptatrienyl ligands and the R 6 aromatic compounds selected from the optionally substituted R 6 -benzene ligands and the compounds having 2 to 4 fused rings, each ring being able to contribute to the valence layer of metal M by 6 or 7 ir electrons; L3 represents from 0 to 3 identical or different ligands linked to the metal M by α electrons, ligand (s) chosen (s) from CO and NO2 +; the total electronic charge q of the complex to which L1, L2 and L3 contribute and the ionic charge of the metal M being positive and equal to 1 or 2; A borate anionic entity having the formula:

[BXa Rb] -

  formula in which: a and b are integers ranging from 0 to 3 and for b from 1 to 4 with a + b = 4, the X symbols 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 (particularly fluorine), and this when the cationic entity is an onium of an element of the groups

at 17,

  a phenyl radical substituted by at least one element or an electron-withdrawing group, especially 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 D 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, the following gives more details on the subclasses of onium borate and borate of organometallic salts more

  particularly preferred in the context of the use according to the invention.

  Thus, with respect to the borate anionic species, the most suitable species are the following:

  1 ': [B (C6F) 41- 5': [B (C6H3 (CF3) 2) 4] -

  2 ': [(C6Fs) 2BF 2] - 6': [B (C 6 H 3 F 2) 4] -

3 ': [B (C6H4CF3) 41-7': [C6F5BF3] -

4 ': [B (C6F4OCF3) 4] -

  As regards the cationic entity of the photoinitiator, there are: 1) onium salts of formula (I), 2) oxoisothiochromanium salts of formula (II), 3) mono and / or polysylfonium salts of formula (III.1) and / or (m.2),

  4) organometallic salts of formula (IV).

  The first 1) are described in many documents including

  in 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 preferred:

  [("D) 2I] + [C8H17-O-O-I-I] + [(4-CH3) 2 I] +

  [C12 H25-4-I-O] + [(C8H17-O-D) 2 I] + [(C8H17-O- <I-I - @)] +

  [(O) 3 S] + [(') 2-S-'DO-C8H17] + [(CH3-9b-I-O-CH (CH3) 2] + [<- S-O-S- ( <) 2] + [(C12H25-q>) 2I] + [(CH3-I-OC2H5] + As regards the second family of cationic entities of formula (II) and of oxoisothiochromanium type, it comprises preferably cations corresponding to the structure D1 which is defined on page 14 of the application WO-A-90/11303 and has the formula (II): CSs.4 (II) R6 o the radical R6 has the meaning given in this WO application with respect to the symbol R ', a cationic entity of this type which is more preferred is that where R 6 represents a linear or branched C 1 -C 20 alkyl radical, which are particularly suitable as oxoisothiochromanium salts. will mention in particular

  the sulphonium salt of 2-ethyl-4-oxoisothiochromanium or 2-dodecyl-4-

  oxoisothiochromanium. With regard to the polysulphonium cationic entities (III.1), it will be specified that the polysulfonium cationic entity preferably comprises a species or a mixture of species of formula (III.1) in which: the radicals Ar1, which are identical or different, each of them represents a phenyl radical, optionally substituted by a linear or branched C 1 -C 4 alkyl radical or by the group of formula: -OO or - the Ar 2 radicals, which are identical to or different from each other and with Ar 1, each represent a phenyl radical , optionally substituted by a linear or branched C 1 -C 4 alkyl radical, the Ar 3 radicals each represent an unsubstituted para-phenylene radical, 0 or 1 equal to 1, with the additional conditions according to which: + whent = o, wherein Ar 1 and Ar 2 have the preferred meanings given just above in this paragraph; + whent = l: O on the one hand, y = y2 to Y4 with y2 = + -S- Ar o the radical Ar2 has the preferred meaning given just above in this paragraph, Y3 = a valence, * Y4 = -O-- or -S-, and O on the other hand, when Y = Y3 or Y4 and when it is then desired to implement radicals Ar1 and Ar2 (terminals) connected to each other, a Y 'link is installed

  consisting of a valid link or the remainder O--.

  The mono-sulfonium species, if any, which come within the scope of this preferential mode are the species of formula (IV) in which the symbols Ar1 and Ar2 have the preferred meanings indicated above in the preceding paragraph, including, when these radicals are directly connected to each other

  by a remainder Y ', the installation of a valid link or the remainder --O--.

  Examples of sulfonium cationic entities include: O-vsSX, o. Q

00 to,

  6 N i <nq 1 6o + cn el% mi 0 <r-i N i a a 0 0 a0

V) C)

  5. the mixtures, in variable quantities, of the species 5 + 2 +, optionally the mixtures, in variable quantities, of the species 5 with the species of formula: [BXLRb] - in which: the symbols X represent a fluorine atom, the symbols R, 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.Ib] - is preferably chosen from the following anions: 1 ', 2', 3 ', 4', ', 6', 7'T, the borates of polysulfonium, which will be implemented very preferably, are the salts formed by the combination of the following cations and anions: i. Cation Anion 51 '

3 '

41

  mixtures 5 + 10 1 'mixtures 5 + 10 3' mixtures 5 + 10 4 'These polysulfonium borates can be prepared by an 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 species.

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

of a suitable solvent.

  The procedures for synthesizing the halides of the cationic entities of formula (III.1) are described in particular in: "Polymer Bulletin

  (Berlin) 14, pages 279-286 (1985) and US-A-4,400,541.

  According to an alternative concerning the preparation of polysulphonium borates, these can be prepared directly by reaction between a diarylsulfoxide and a diarylsulphide according to the teaching described in: "J. Org. Chem.",

Flight. 55, pp. 4222-425 (1990).

  These novel polysulphonium 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 a suitable solvent, in monomer / oligomer / polymer compositions. which are intended to be polymerised and / or

  cationically crosslinked and under activation, for example UV.

  The mono-sulfonium species (III.2) mentioned above can be in particular the co-products which are formed at the time of preparation

  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% by mole (of cation) of polysulfonium species of formula

  (II.1) may be replaced by monosulphonium species (III.2).

  With regard to the fourth type of cationic entity, it is found in US Pat. No. 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 which are more readily used in practice are in particular: (1-cyclopentadienyl) (R 6 -toluene) Fe +, (R 1 -cyclopentadienyl) (R 6 -methyl-1-naphthalene) Fe +, 10. (N-cyclopentadienyl) (n-6-cumene) Fe +, bis (116-mesitylene) Fe +, bis (16-benzene) Cr + Examples of photoinitiators of the onium borate type include: following products: [(D) 2 I1 +, [B (C6Fs) 4] - [(CsH17) -O- '> I - ()] *, [B (C6Fs) 41'

  [C, 2H25 -'- I -] +, [B (C6F5) 4] - [(CsH7-O-) 2I] +, [B (C6F5) 4] -

  [(CsHi7) -O -'- I -)] +, [B (C6F5) 4] - [(D) 3S] +, [B (C6F5) 4] -

  [(D) 2S-c-O-C8H17] +, [B (C6H4CF3) 4] - [(C12H2s- (I) 2I] +, [B (C6F5) 4] -

  [(") 3 S] +, [B (C6F4OCF3) 4] - [((I> -CH3) 2I] +, [B (C6F5) 4]

  [(cI-CH3) 2 I] +, [B (C6F4OCF3) 41- [CH3-cI-I-4-CH (CH3) 2] +, [B (C6F5) 4] -

* (rl5 - cyclopentadienyl) (16 - toluene) Fe +, [B (C6Fs) 4] -

  (t15-cyclopentadienyl) (11-methyl-naphthalene) Fe +, [B (C6Fs) 4] -

  (rl5 - cyclopentadienyl) (16-cumene) Fe +, [B (C6Fs) 4] Another literary reference for defining the onium borates 1) and 2) and the borates of organometallic salts 4), selected as photoinitiator in the part of the SPL use according to the invention, mention may be made of the entire content of patent applications EP 0 562 897 and 0 562 922. This content is entirely

  incorporated by reference in this disclosure.

  As another example of an onium salt that can be used as photoinitiator C, mention may be made of those disclosed in US Patents 4,138,255 and

US 4,310,469 (CRIVELLO).

  Other cationic photoinitiators, e. g.

  those marketed by UNION-CARBIDE (photoinitiator 6990 and 6974 triarylsulfonium hexafluoro-phosphate and hexafluoroantimonate), the salts of iodonium hexafluorophosphate or hexafluoro-antimonate,

  or the ferrocenium salts of these different anions.

  The radical photoinitiators used are based on benzophenones.

  As examples, those marketed by CIBA-GEIGY:

- IRGACURE 184,

- IRGACURE 500,

- DAROCURE 1173,

- IRGACURE 1700,

- DAROCURE 4265,

- IRGACURE 907,

- IRGACURE 369,

- IRGACURE 261,

- IRGACURE 784 DO,

- IRGACURE 2959,

- IRGACURE 651.

  Radical photoinitiators may contain one or more phosphorus atoms, such as those marketed by CIBA-GEIGY (IRGACURE 1700)

or BASF (LUCIRIN TPO).

  According to the invention, the proportions of compounds A, B, C are as follows: A: 59-97.99%, preferably 70-97.9%, B: 39-1%, preferably 1%;

  * C: 2-0.01%, preferably. 0.1%.

  Various associations are possible with regard to 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 (ao), acrylates (o2), vinyl ethers (a3), polyols (a4), preferably (ao,) and (oc2), 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 (oc1) and / or (% 3), then the photoinitiator (C) is of the cationic type, while. that for species (a2) and

  (0c4) the photoinitiator (C) is radical.

  In practice, it will thus be possible, for example, to associate monomers and / or oligomers and / or polymers of matrix A with epoxy and acrylate functions, with a first epoxy functional diluent B and a second acrylate functional diluent B. According to one variant, the epoxy and acrylate functions can be carried by comonomers that are different from the matrix A. Advantageously, the photoinitiator C is employed in solution in an organic solvent (accelerator), preferably chosen from proton donors and , more preferably still, from the following groups: isopropyl alcohols,

  benzyl alcohols, diacetone alcohol, butyl lactate and mixtures thereof.

  In addition to the photoinitiator (s) C, the composition according to the invention may comprise, optionally, at least one photosensitizer D selected from (poly) aromatic - optionally metallic products - and heterocyclic products and, preferably, chosen from the following list of products phenothiazine, tetracene, perylene, anthracene, 9-diphenyl-anthracene, thioxanthone, 2-chlorothioxanthen-9-one, 1-chloro-4-propoxy-9H-thioxanthen-9-one,

  isopropyl-OH-thioxanten-9-one, isomeric mixture 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-nitroanthracene, and mixtures thereof.

  For an effective amount of initiator system is meant, in the sense of the invention, the amount sufficient to initiate the crosslinking. Advantageously, this effective amount corresponds to 1.104 to 1, preferably from 1.10-3 to 1.10-1 and, more preferably still from 1.10-3 to 1.10-2 moles of photoinitiator per 1 mole of frA and frB. When using a photosensitizer D, the appropriate concentration ranges for the latter are: 1.104 to 1.10 mol / mole of frA and frB, preferably of 1.10.4 to 1.10 -2 mol. / mole of frA and frB,

  and, more preferably still, from 1.104 to 1.10-3 mol / mol of frA and frB.

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

  benzimidazoline, bronze powder, rhodamine.

  The pigmented compositions according to the invention are, e. g., inks. The

  Titanium dioxide makes it possible to obtain a white ink.

  With regard to the other optional additives F, mention may be made, by way of example, of dyes, fillers (silicones or not), surfactants, mineral reinforcing fillers (siliceous or non-siliceous), bactericides, inhibitors of corrosion, binding bases, organosilicon compounds or epoxidized compounds,

  such as alkoxysilanes, epoxycycloaliphatic or epoxyetheraliphatic.

  Concerning more particularly the case of varnishes, these are, of course, free of pigments in the case where it is clear varnish. In general, the lacquers comprise at least one surfactant and, advantageously, a particular combination of monomeric, oligomeric and polymeric products in the matrix A, namely at least one cycloaliphatic cyclohexyl and, optionally, at least one

  less an epoxide resulting from the condensation of bis-phenol A and epichlorohydrin.

  In a manner known per se, the varnishes may include in their compositions: flexibilizing 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: e. g. silanes of the GLYMO type: (MeO) 3SiOJ / '7 o or (EtO) 3Si O 7 or' '' i (OEt) 3 or V or OASi (OMe) 3 or 0 <According to an advantageous characteristic of the invention, the the flexibilizers and / or the leveling agent (s) and / or the adhesion promoter (s) may comprise, in whole or in part, the reactive diluent B, eg

  formula I. 1, as described supra.

  The diluent B can therefore assume the functions fulfilled by these various functional additives. This multifunctionality is all the more interesting because it does not

  requires no overload by 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, cationically and / or radically, said composition further comprising 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 its advantages and to glimpse some of its variant embodiments.

EXAMPLES

I - RAW MATERIALS:

  1.1 -MATRiMCE (A): - (l1 - Monomers to frA = epoxy: n to

ó [90-9 (M1 (M)

  (MI) is marketed by the company UNION-CARBIDE (UVR 6105 and

6110).

  - (a2 - frA: oligomer / epoxyacrylate of the type:

0 CH3 0

CH2 = C-C H2CH-CO CCH2CH2) = C-CHCH2

CH3 (AC1)

  Oligomeric epoxydiacrylate bisphenol (EBECRYL 600).

  - 2 - frA = acrylate monomers: Mixture of trifunctional oligomeric acrylate obtained from glycerol and polyester marketed, for example, by the BELGIAN CHEMICAL UNION

(UCB) (EBECRYL 810) (AC2).

- a4 -Monomers to frA = OH:

(C7H5) -C- 4 --- OQX 03 H

(ô & n01H (TI)

  (TI) is marketed by UNION CARBIDE (TON 301).

I.2 - DILuANr (B):

1)

Me Me e Me if si a) o0

  This siloxane a) can be obtained by hydrosilylation of the vinylcyclohexene-

  monoxide by tetramethyldihydrogeno-1,3-disiloxane, has a flash point of C. 2) Me Me e Me Me, Me j) osi, s oC o0 o

O O

1.3 - PHOTO-PRIMER C:

  Photo-initiator (P1) (bis + 90% w / w and mono 10% w / w) B (C6F5) 4 S 1s B (C6F5) 4

X N. (PI)

"bis"

"" 3 S E S 'B (C6F5) 4

(P1) "mono."

to 20% in butyl lactate.

  The cationic photoinitiator used has the following formula:

C C: B- F

CH3 CH3; B- F (P2)

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

GEIBY (DAROCURE 1173).

P2 is soluble in P3.

  P1, P2, P3 are used as a solution in butyl lactate or isopropanol.

1.4 - PHOTOSENSIBILUSA TEUR (D):

  CPTX = chloro-1-propoxy-4-thioxanthone.

1.5 - PIGMENT (E):

  Concentrated pigment base. A concentrated pigment base is obtained by dispersion of: 700 parts of rutile titanium oxide marketed by DuPont

(R960)

  - 3.5 parts of a dispersant marketed by ZENECA (SOLSPERSE

24000C)

  - 296.5 parts of cycloaliphatic epoxy resin (MI) marketed by

UNION-CARBIDE (UVR6105),

  in a 2-liter reactor equipped with a three-bladed central stirrer.

  The concentrated pigment base is obtained by mixing 1/2 hour after casting of the titanium oxide powder on the resin / dispersant mixture preheated with C.

I.6 - OTHER ADDI77FS (F):

  Leveling agent marketed by BYK (BYK 306, BYK 307

  or BYK 361) or EFKA (EFKA 35).

  - Wetting agent based on polyether silicone marketed by the OSI Company

(SILWET L 7640 or L7644).

  II - EVALUATION OF THE PROPERTIES OF THE COMPOSITION

  RAPRA test - crosslinking speed: An illustration of the different crosslinking speeds is given from films of 4 to 25 gm thick obtained on a UV bench fitted with a type H FUSION lamp. The crosslinking rate is recorded. at a given frame rate and at a measured irradiation dose. It is also possible to crosslink a thick layer of 2 mm from a high-pressure arc lamp Hg connected to an optical fiber 8 mm in diameter, marketed by the company EFOS (ULTRACURE 100SS). The optical fiber is connected to the tank of

  measuring a RAPRA (VNC or Vibrating Needle Curemeter) apparatus.

  The vibrating needle is immersed in the epoxy matrix (1 cm 3) and a potential difference is measured according to the degree of crosslinking at a given vibration frequency, which is 40 Hz. When irradiating, the medium reaches the freezing point. very quickly. This results in a variation of the measured potential. The potential variation curve is recorded throughout the UV exposure and the value of the time corresponding to 95% of the total variation is reported.

  (T95), ie for example 0.6 minutes in FIG. 1 annexed.

  - MEK test: 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 not be completely degraded. - Flexibility of the layers by folding on a cylindrical mandrel according to the standard

AFNOR n0 T30-040.

EXAMPLE 1

  The diluent a) is perfectly miscible in the epoxy matrix (M1) or polyol (Tl).

  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: - (F1) p (a) p (M1) (F2) p (a) p (MI) - (F3) p (a) p (M1) - (FT) formulation 100 In these formulations, 0.5 μ of a wetting agent based on silicone polyether marketed by the OSI Company (SILWET L7640 or L7644) and a photoinitiator solution in the vinyl lactate, are added to these formulations. way to have a

  concentration, the value of which is specified in Table 1 below. Thick-film cross-linking (RAPRA (V.

thin layer.

  Films of 5, 10, 20 μm are made using threaded coating bars (Bar 0, 2 or 3) on an aluminum support. We use a few drops of composition and we

  degreases the aluminum support by cleaning with propanol or isopropanol.

  Vibrating needle crosslinking tests are carried out in a tank of size 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) through an optical fiber. The needle plunges up to 2 mm from the bottom of the tank that receives the beam of light. The results obtained during the various crosslinking tests at the exposure of the

  ultraviolet light are collected Table I infra.

  With the FUSION lamp (type "H"), the minimum duration of exposure to a

  scrolling speed given to pass 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 vapor arc lamp, in the case of the 2 mm thick thick-layer crosslinking at RAPRA (vibrating needle), the

  minimum exposure time to reach 95% cross-linking (T 95 defined below)

above).

TABLE I

  Photo- MEK Rapra lamp (VNC "H" initiator test (FUSION) (test) ** dose: 1,1J / cmL (120W / cm) T95 in s Fl (5 pmn) 2.5.10-3 mol /> 52n / min 4h /> 200 FI (10 j5m) 52m / min 3 passes 4h /> 200 245 FI (10 gi2m) mn 2 mn2passes 4h /> 200 F2 (5) 2.5.10-3 mol / 1> 52 m / min 4h /> 200 F2 (10 m) 52 rn / min 3 passes 4h /> 200 245 F2 (10 Pm) 23 m / min 2 passes 4h /> 200 F3 (5 JIM) 2.5.103 mol / I> 52 m / mn 4h /> 200 F3 (10 lm) 52 nm / min 3 passes 4h /> 200 210 F3 (10 gm) ____ _23m / min 2 passes 4h /> 200 FT (5 min) 2.5.l0-3 molI> 52 m / min 4h /> 200 FT (10 gm) 52 m / min 3 passes 4h /> 200 245 tFT (10 EL) ._____ 23 m / min 2 passes 4h /> 200 * passes = number of passes required for speed considered to obtain a dry touch on the surface, ** MEK:> 200. At the end of 100 round trips the film is still intact.

  storage at 20 C after irradiation at the end of which the measurement is made.

  All the additive formulations crosslink perfectly in the presence of this silicone

  epoxidized whose viscosity is 50 mPa.s.

EXAMPLE 2

  We now compare the crosslinking speed and the nature of the network obtained after adding Tl in the matrix (A) in addition to M1 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 (MI),

- 15 p of (Ti).

  Various amounts of silicone diluent (a) are added: - (F'I) 80.75p of (Mi), 14.25p of (T1), p of (a), - (F'2) 76.5 p of (M1), 13.5 p of (Tl), p of (a), - (F '3) 68 p of (M1), 12 p of (Tl),

p of (a).

  0.5 μl of the same wetting agent (SILWET L7640) is added as in the example

  previous and a known fixed amount of photoinitiator.

  We use the same lamps as before.

  The results obtained during the different tests are shown in Table II infra.

TABLE II

  - ,. Lamp Resistance Hardness Test Photo- "Ht MEK Impact pencil / Film (e 'li) initiator (FUSION) (test) ** 24h': persoz: ..- (120w / cm) * .. inch-21l - 24 h F'1 (20 9m) 5.10-3 mol / 3 m / min: 1 h / 100 15 H / 269

1 pass.

  F'2 (20 μm) 5.10-3 mol / l 8 m / min: lh / 88 20 H / 250

1 pass.

  F'3 (20 mm) 5.10-3 mol / i 23 m / min: 1 h / 80 30 H / 346

I pass.

  F'T (20 nm) 5.10-3 mol / l 3 m / min: 1 h / 130 10 H / 230 1 pass. _ _ * I pass: speed limit of the conveyor which makes it possible to obtain a dry touch on the surface in a single pass, ** MEK: storage time at 20 C after irradiation at the end of which the measurement is

  done (1 hour). Number of maximum round trips limit that can support the film.

  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 achieve a dramatic effect.

EXAMPLE 3

  The incidence of (a) added in an organic matrix based on cycloaliphatic epoxides (MI), polyol (T1) and in the presence of

leveling (BYK 306).

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

-CH-I- '' + "-CH3; B FF F (P2)

C3

LF F 4

  The following formulations were evaluated in RAPRA (see Tables III and Table IV)

  for 0.5% and 1% of photoinitiator, respectively.

TABLE IH

  :. "" Reference .. :: .. "To .. F4 FS F6

M 1% 82.7 66.1 57.45

T 1% 14.7 11.6 10.40

Byk 306% 1.1 0.8 0.65

P2% 0.5 0.5 0.5

  a) in% O 20 30 Isopropanol% 1.0 1.0 1 Rapra (V.N.C) dose 0.4 J / cm T95 s 690 510 420

TABLE IV

I - -Reference F7 F8 F9

M1% 81.4 64.8 56.3

TI% 14.7 11.4 10.1

Byk 306% 1,1 0.8 0.6

P2% 1 1 1

  a) in% 0 Isopropanol% 2 2 2 Rapra (V.N.C) dose 0.4 J / cm T95 s 180 150 130 EXAMPLE 4: Formulation and evaluation of white inks containing a

  reactive diluent of the type claimed in accordance with the invention.

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

TABLE V

  Reference F10 Fll Pigment base E conc. % 78 78 Thinner a) in% 10 0

T1% 0 5

M1% 7.9 12.9

BYK 361% 1.5 1.5

P2% 1 1

CPTX *% 0.6 0.6

Isopropanol% I 1

  * CPTX = chloro-propoxy-thioxanthone used as photosensitizer.

  The photoinitiator is added in the form of an isopropanol solution.

  The different 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 of the company FUSION equipped 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 / cm2

  UVC (250-260 nm) = 0.013 J / cm 2; UVV (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; UVV (390-440 nm) = 0.416 J / cm2.

  The solvent resistance of the inks obtained after drying films of 12 μm 3 was measured by measuring the number of round-trips required using a cloth soaked in solvent to break up the ink layer, one hour later. exposure and 24 hours after exposure. In this case, the solvent used is methyl ethyl ketone

(MEK).

TABLE VI

  Speed; 23 mImn; 23 mImn; 43 mm; 43 mI / min; I formulation F10 FlL F10 Fll Reticulation OK 1 pass OK 1 pass OK 1 pass OK 1 pass MEK (lh) 70 25 30 5 MEK (24h)> 200 80> 200 50 0 (mm) smaller cylinder 3 mm 3 mm 3 numm 3 mm of the mandrel EXAMPLE 5 Hybrid formulations of the matrix (A) based on epoxy / acrylate

with an epoxy thinner.

  Table VII below gives the compositions of tests F12 to F17.

TABLE VII

  Reagents (%) F12- F13 F14 FIS F16 F17 Matrix A (AC2) 97 96 30 30 30 76 Mi 0 0 56 53.4 39 0

T1 0 0 10 9.6 7 0

  Diluent a) OOO 0 O 20 20 Photo- P2 0 1 I 1 initiator P3 3 3 3 3 3 3 Iso0 0 0 3 0 0 propanol Drying of these hybrid formulations: S ... ca..d ..... c .... ... s..o u..at o ..... h.y.b. d .: The drying of the inks is evaluated on a UV bench of the IST Company equipped with two lamps of 200 W / cm. A gallium-doped mercury lamp and a mercury lamp

undoped.

  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; UWVV (390-440 nm) = 0.662 J / cm2.

  At the running speed of 43 m / min the sample receives: UVA (320-390 nm) = 0.145 J / cm 2; UVB (280-320 nmn) = 0.145 J / cm 2;

  UVC (250-260 nm) = 0.018 J / cm 2; UVV (390-440 nm) = 0.343 J / cm2.

  At a speed of 100 m / min, the calibration is not significant, given the response time of the cell. The solvent resistance of the inks obtained after drying films of 12 prm on aluminum (Bar No. 2) is measured by noting the number of necessary round-trips carried out using a cloth soaked in solvent to break up the layer.

  of ink after 1/2 hour. In this case, the solvent used is methyl ethyl ketone (MEK).

  The evaluation results without nitrogen blanket are as follows.

TABLE VIII

  Reagents (%) F12 F13 F14 F15 F16 F17 V (m / min) 100 100 100 100 100 100

MEK> 100> 100 40 40 50 40

  Membership 3 3 1 1 0 0 V (m / min) 50 50 50 50 50 50

MEK> 100> 100 70 90 100 80

  Adhesion 3 3 1 1 3 3 * Adhesion according to NFT 30038: 5 + 0% adhesion, 0 = 100% adhesion. The siloxane diluent (a) makes it possible, thanks to its low viscosity, to facilitate the spreading on the

  support and mixing of 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 of the Company IST equipped with two lamps of 200 W / cm. A gallium-doped mercury lamp and a mercury lamp

undoped.

  The calibration of the lamps is the same as before.

  The formulas used are described in Table IX below.

TABLE IX

  Reagents% F18 F19 F20 F21 Matrix A "(ACI) 97 96 0 28.5 r (AC2) 0 0 85.3 59 Diluent (j) 0 10.9 7.5 Photoinitiator P3 3 4 3.7 5 V (m) / nmn) 100 100 100 100 MEK no surface cure no surface cure no surface cure 35 Adhesion * not relevant not concerned 5 5 V (m / min) 50 50 50 5 MEK no surface cure no surface cure 10 60 adhesion not concerned not concerned 5 5 * Adhesion according to NFT 30038: 5 = 0% adhesion, 0 = 100% adhesion.

  The evaluation results without nitrogen blanket are as follows.

  The siloxane diluent (P) allows a very good incorporation of ACI 1 without harming the polymerization.

Claims (8)

CLAIMS:   1- Polymerizable composition and / or crosslinkable under irradiation, preferably actinic and / or electron beam (s), cationically and / or radical, characterized in that it comprises: A. at least one polymerizable organic matrix and / or at least partially polymerized, comprising (co) monomers and / or (co) oligomers and / or (co) polymers selected from those having reactive functions (frA) epoxy (o,) and / or acrylate ( x2) and / or alkenyl ether (a3) and / or hydroxy (a4), with or without cycloaliphatic epoxides (c1,); B. at least one silicone diluent of reduced viscosity ir at 25 ° C. of less than or equal to 200 mPa.s, preferably at least 150 mPa.s and, more preferably still, at 100 mPa.s, and comprising: at least one formula (I): ## STR2 ## in which: a = 0, lamb2, R is identical to or different from those of the same exponent and represents an alkyl, cycloalkyl or aryl radical; vinyl, hydrogen, alkoxy, preferably a C1-C6 lower alkyl, - Z is an organic substituent having at least one   reactive function (frB), epoxy and / or acrylate and / or alkenyl-   ether and / or hydroxy, with the proviso that at least a part of the functions (frB) is of the same nature as at least a 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. optionally at least one other additive 2 - Composition according to claim 1, characterized: in that the 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 less than or equal to 100 ppm, preferably at 50 ppm and more   preferentially still, at 20 ppm.   3 - Composition according to claim 1 or 2, characterized in that the diluent (B) has a coloring of less than or equal to 200 Hazen, preferably 150 Hazen and, more preferably still, 100 Hazen and / or is soluble in at least 5%, preferably at least 10% and, more preferably still, at least% 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 with a silicone oil, in the presence of a heterogeneous catalytic composition comprising a metal selected from the group consisting of Co, Rh, Ru, Pt, Ni deposited on an inert support. 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: (1.1) (frB) (R3), Si-O frB) ( R2) c SiO] T wherein: * T = R3 or Si (R3) u (frB), * x + y3; 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 lower alkyls and / or lower alkoxyls Ci-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 the formula (I), frB) (R4) SOsE (R5) -Si 0 d 2o (1.2) in which: * d + e = 2, d = 1 or 2, e = 0 or 1, * o + p <15, preferably <10; o> 1, * R4, R5 are, respectively and jointly, identical or different from each other and   meet the same definition as R2 given above.   6 - Composition according to any one of claims I to 5,   characterized in that the frB are selected from the following radicals: O; OK-X / o; o -CH2-CH CH3 o o o O o <- O '/ o / -; OCH2CH2 --- O-   - (CH2) -O-CH = CH2; - (CH3) '- O-R-O-CH = CH2; - (CH2) --O-CH = CH-R   with R6: linear or branched C 1 -C 12 alkylene, optionally substituted, or arylene, preferably phenylene, optionally substituted, preferably with one to three C 6 -C 6 alkyl groups,   with R7 = linear or branched C1-C6 alkyl.   7 - Composition according to any one of claims 1 to 6,   characterized in that the diluent (B) consists of at least one functionalized polysiloxane frB of the following formula: Me Me Me Me Me Me Me Mee Mee MeMe ",,,,., JSi ,. .o If, b) OO Me Me Me Me Me Me Me Me Me c) if, 0   (OMe) Me M _ si i Si / iM d) o Me (OMe) (OMe) (n <10) Me Me Si, Me 0 I e) Me-si O Me if Me Me (OMe) Mee Me t Si -, Me (OMe) (n <10) Me Me Si-OSi-O Me g) p (o + p) <10 0 0> 1 O // \ / CH2 CH-CH2 O CH2CH2CH2 H2 CH3-Si-CH3 h) O CH-Si-CH3 CH2CH2H2 Bone CH2CH- CH2   ## STR2 ## wherein CH 2 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 -C-CCH 2 Ox o CH2CH2 CH2 CH 3 Si-CH 3 j) o 1 CH-Si-CH 3 CH2CH2 H2} O0 C-C-CH He l 2 0 CH3   It k) H2C = CHCOCH2 CH3 L -CH2CH2 Si O CH32   8 - Composition according to any one of claims I to 7,   characterized in that the constituents of the matrix A belong to at least one of the following species: ao.1) cycloaliphatic epoxides, taken alone or in mixture with one another:   epoxides of the 3,4-epoxycyclohexylmethyl-3 ', 4'-type epoxycyclohexane carboxylate: O O O   or Bis (3,4-epoxycyclohexyl) adipate, being particularly preferred; ao.2) non-cycloaliphatic epoxides, taken alone or in mixture with one another: * epoxides of the type resulting from the condensation of Bis-phenol A and epichlorohydrin and of the type: - di and triglycidyl ethers of alkoxylated bisphenol A 1.6 hexane diol, glycerol, neopentyl glycol and propane trimethylol, or diglycidyl ethers of Bisphenol A, the epoxides of alpha-olefins, epoxides NOVOLAC, epoxidized soybean and linseed oil, epoxidized polybutadiene, being particularly preferred ,   oc2) acrylates, taken by themselves or mixed with each other; e. g.   epoxidized acrylates, preferably the oligomer of Bisphenol-A-   epoxydiacrylate (EBECRYL 600), acrylo-glycero-polyester, preferably trifunctional acrylate oligomer mixture obtained from glycerol and polyester (EBECRYL 810), multifunctional acrylates, preferably pentaerythritol 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) Acryl-urethanes, acrylo-polyethers, acrylic-polyesters, unsaturated polyesters, acrylic-acrylics, being particularly preferred, linear or cyclic alkenyl ethers, 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: MeMe Me e Me 1/1   IFO- (CHCH2O) -CH2-CH2 Si-CH2CH-- (OCH2CH2) -O--   Especially preferred are propenyl ethers, and butenyl ethers. The polyols taken alone or in admixture with one another, preferably the compound of the formula given below: (C2H5) -C OLS-sN .X su H   9 - Composition according to any one of claims 1 to 8,   characterized in that 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%.   - Composition according to any one of claims 1 to 10,   characterized in that it comprises: - a matrix (A) based on a mixture of at least one of the following species: epoxides (ox), acrylates (x2), vinyl ethers (3), polyols ( a4), preferably (ao) and (a2), and a silicone diluent (B) whose frB are epoxy and / or acrylate and / or vinylether and / or hydroxy, preferably epoxy and / or acrylate, and that, in the case where the species used are (a1) and / or (o%), then the photoinitiator (C) is a cationic polyamino acid, while for the species (oa2) and (oa4) the polyamino acid is radical.   11 - Use of the silicone diluent (B), as defined in one of the   claims 1, 3, to 7, for the preparation of a composition preferably a   ink or varnish, polymerizable and / or crosslinkable under irradiation, preferably actinic and / or electron beam, cationically and / or radically, said composition further comprising compounds A and C and, optionally, , E and F referred to in claim 1.