Aqueous disperse systems of photoinitiators and their use

Abstract: The invention relates to aqueous disperse systems of photoinitiators which are particularly useful in the photopolymerisation of aqueous disperse systems and emulsions of oligomers or polymers carrying photopolymerisable functionalities which are widely used in the field of dyes and packaging.

Description: Field of the invention The present invention relates to aqueous disperse systems of photoinitiators which are particularly useful in the photopolymerisation of aqueous systems comprising oligomers or polymers carrying photopolymerisable functionalities. These aqueous systems, which are largely used in the field of dyes and in the coating of wrappings are normally constituted by aqueous emulsions and/or dispersions of polyurethanes, polyesters, polyethers, polyols, polyacrylates as oligomers and/or polymers carrying acrylic- and methacrylic-, fumaric-, maleic-, vinyl-ethers unsaturations. Technical Problem The photopolymerisable systems commonly used in industry are constituted by oligomers and/or polymers carrying functionalities which can polymerise or copolymerise when diluted in the appropriate reactive solvents. With the expression reactive solvents are intended monomers having low molecular weight possessing various functionalities which have a good solving power and can therefore dissolve the oligomers and maintain the systems to a degree of viscosity appropriate for their use and which at the end of the polymerisation process remain included in the mass as integrant part of the polymeric matrix. Unfortunately the photoinitiate polymerisation, which is a very efficient process, does not permit the complete reaction of the monomer, and therefore the technical problem arises that the monomer can migrate and be extracted from the materials which come into contact with the photopolymerised masses. In view of the toxicity and unpleasant smell of the solvents commonly used, it is easy to understand the importance of this technical problem which entails a strong limitation of the possible use of this technology in very important fields like the coating of food-wrappings (direct or indirect) and the painting and finishing of those materials which come into contact with the users. State of the art In the last times various possible solutions in alternative to the photopolymerisable systems comprising the dilution in reactive solvents have been studied. Such solutions involve the use of oligomers or polymers carrying photopolymerisable functionalities which are dispersed or emulsifyed in water or if required diluted with water. With these systems it is possible to perform the photopolymerisation either immediately after the application of the liquid system or after having evaporated the water. In the case of aqueous emulsions or dispersions wherein the dry part represents 70-80% it is necessary to evaporate the water in order to obtain the coalescence of the system before performing the photopolymerisation on the resulting homogeneous film. Although it is necessary to add one further step to the process for preparing the final products (i.e. the water evaporation) in respect of the traditional processes, the use of aqueous systems is widely spread because it offers the advantage of avoiding the presence of inflamables monomers in the compositions on sale and also assures the absence of residue monomers in the final products. Anyhow, till now it has not been possible to solve satisfactorily the problems deriving from the use of the photoinitiators in aqueous systems. The normally used photoinitiators can not be easily included in systems dispersed in water. This disadvantage is particularly relevant with solids as for example: benzyl-dimethyl-ketal, benzophenone and 1-benzoyl-cyclohexanol. Normally the problem is avoided using liquid photoinitiators which are included in the aqueous dispersions or emulsions before their use. However the possibility of using only liquid photoinitiators represents a strong limitation since the users normally need a large flexibility to satisfy their various demands which request the employ of various photoinitiators. In other cases the photoinitiator is dissolved in the photopolymerisable mixture before its emulsion with water at the moment of use (autoemulsifying mixtures), but this solution involves a complicated process of production and therefore is not appreciated by the users. In still other cases the photopolymerisable mixture are delivered to the user with the photoinitiator already included. These mixtures, which do not require further manufacture, present the the disadvantage of a limited possibility of application since it is impossible to proportion or change the photoinitiator included during the production of the mixture. Typical examples of photoinitiators used in aqueous systems are 2-hydroxy-2-methyl-1-(p-dodecyl)propiophenone as described in the EPA-85,305, wherein the introduction of an aliphatic chain in the molecule, for lowering the melting point of the product under the room temperature, results in a dilution of its part active as photoinitiator and therefore reduces its efficacy in respect of the compound not presenting the lateral dodecyl-chain; or the 2-hydroxy-2-methyl-1-phenyl-propiophenone described in the USA Patent 4,347,111, which is too volatile and is therefore easily lost during the coalescence-process by evaporation of the aqueous phase; or again the 2-hydroxy-2-methyl-1-(4-hydroxy-ethoxy-phenyl)propiophenone, as described in the PCT-WO-86/05778, which is hydrophylic up to a certain degree but is obtained through a synthetic process, which is very complicated and therefore involves higher costs than those of other commonly used photoinitiators and therefore its use is limited. Unfortunately, considering that the photopolymerisation process takes place in an organic-phase (after coalescence) it is not profitable to use photoinitiators which are soluble in water. This kind of photoinitiators are not very compatible with the organic matrix of the systems to photopolymerize and therefore the results are not satisfying. Detailed description of the invention We have now found that it is possible to use the photoinitiators normally used in non aqueous photopolymerisable systems also for aqueous systems when such photoinitiators are used as emulsions and/or disperse systems in water. In the present text the term "disperse systems" means both disperse systems and emulsions. According to a fundamental characteristic of the present invention the aqueous disperse systems of photoinitiators free of any oligomers and polymers to be photopolymerised comprise at least a photoinitiator and at least a surface active agent, wherein the photoinitiator represents from 20% to 80% by weight and the surface active agent from 0.1% to 10% by weight of the disperse system. The aqueous disperse systems of photoinitiators according to the present invention are stable, easy to proportion and to include in the mixtures of oligomers or polymers which must be polymerised and with which they do not interfere electrokinetically. Such disperse systems of photoinitiators can have anionic, cationic or non-ionic character according to the surface active agents used. Normally it is preferable to use non-ionic aqueous disperse systems of photoinitiators because they are more compatible with all the photopolymerisable systems dispersed in water. The aqueous disperse systems of photoinitiators according to the present invention can contain a single photoinitiator or a mixture of them or also a couple of a photoinitiator and an hydrogen-donor (co-initiator). Among the photoinitiators useful for the aqueous disperse systems according to the present invention are benzoin ethers, benzyldimethylketal, 2,2-dialkoxy-acetophenones, alpha-hydroxy-alkyl-aryl ketones, arylglyoxylic acid esters, mono- and di-acyl-phosphine oxides, aromatic ketones, especially benzophenone, thioxanthones, antraquinones or the hexa-aryl-bis-imidazoles. As co-initiators can be used the compounds having a tertiary amino group with at least an hydrogen atom on the carbon atom linked to the nitrogen of the amino group. If the above said compounds are soluble in water, as for example the N-methyl-N,N-diethanolamine (MDEA) or the triethanolamine, they can also be added to the mass to polymerise instead of being added to the aqueous dispersion of the photoinitiator without presenting negative effects on the photopolymerisation reaction. On the other hand it is preferred to add to the aqueous dispersion of the photoinitiator, and especially during its preparation, those compounds which are not soluble in water, as for example the esters of p-dimethylamino-benzoic acid. The typical ratio in weight of photoinitiators and co-initiators in the aqueous disperse systems according to the present invention is comprised between 1:1 and 1:2.5. The surface active agents in the aqueous disperse systems according to the present invention have an emulsifying action, helping the wettability of the compounds to disperse in water, and also a dispersing action, preventing to reaggregate the drops of the dispersed phase. All the surface active agents normally available on the market can be used for the disperse systems according to the present invention, particularly suitable are the organic sulphonic acids and their salts, mono-alkyl-sulphates, quaternary ammonium salts, higher aliphatic alcohols or alkyl-phenoles condensed with ethylene oxide and/or propylene, partial esters of phosphoric acid with aliphatic alcohols and their salts. In the preferred embodiments of the aqueous disperse systems of photoinitiators according to the invention one or more dispersions stabilizers are added. Such stabilizers have a thickening action and impart to the dispersion pronounced thixotropic and pseudoelastic characteristics, with high stand viscosity and a viscosity proportionally decreasing with the increasing of the mechanical stress to which the disperse system is subjected. Among the substances having a stabilizing action useful in the aqueous disperse systems according to the present invention, are particuarly preferred the polymers and the copolymers of acrylic and metacrylic acid, maleic anhydride, polyvinylalcohol, ionic and non-ionic derivatives of cellulose and natural polysaccharides, among which particularly preferred are xanthane and its derivatives. The quantities of the various components the aqueous disperse systems of photoinitiators according to the present invention can vary in wide ranges always maintaining their efficiency. According to a fundamental characteristic of the present invention the photoinitiator (or the mixture of photoinitiators in the case that more then one are used) represents from 20% to 80% by weight of the disperse system and the surface active agent represents from 0.1% to 10% by weight. In the preferred embodiments of the invention, the photoinitiator, or the mixture of photoinitiators, represents from 30% to 60% by weight and the surface active agent from 0.5% to 2% by weight of the disperse system. When one or more stabilizers are added to the aqueous disperse system of the photoinitiator, their concentration is preferably comprised between 0.1 and 2% by weight of the aqueous disperse system. In the above described range of concentrations, the aqueous disperse systems of photoinitiators according to the present invention are stable, either in respect of viscosity or phase separation, and can be easily stored and put on the market. Their compatibility with the common aqueous systems of oligomers and/or polymers on the market is excellent and allows their inclusion in all the known aqueous systems. The aqueous disperse systems of photoinitiators according to the present inventions can also include other substances, over those already mentioned, which can help in their production or prevent their deterioration as for example antifoam, degasing, antibacterial and antimold agents. It is also possible to add to the aqueous disperse systems according to the invention all those auxiliaries which are commonly used in the aqueous systems which must be photopolymerised as thermic stabilizers, spreader, coalescence auxiliaries, pigments, photostabilizers. The aqueous dispersions according to the invention can be prepared according to the usual dispersing techniques, in particular by mechanical action with fast agitators or colloid mills. The inclusion of the aqueous disperse systems of photoinitiators according to the invention in the aqueous systems which must be photopolymerised is performed by mixing under mild mechanical action. The employing ratios between the photoinitiating dispersion and the aqueous system are based on the ratios of their dry parts. Normally the qualitity of photoinitiator used is comprised between 0.5% and 10% by weight in respect of the oligomer and/or polymer contained in the system to photopolymerise. The liquid compositions obtained after the mixing of the aqueous dispersion of photoinitiator and the aqueous system to photopolymerise are stable and can be easily stored if not immediately used and put on the market. The composition obtained can be applied in the usual way by rolling, spraying, curtain-spraying, brushing, blading, if necessary after thickening. The liquid film, however applied, is subjected to fast heating to evaporate the aqueous phase and produce the coalescence and afterwards is crosslinked by irradiation with UV-lamps. In some cases the heat of the lamps used for the crosslinking is sufficient to obtain the coalescence of the liquid film. In the following examples all the parts are in weight if not otherwise specified. The substaces used in the examples are available on the market under the following trading names : ESACURE (F.lli Lamberti Spa) SARTOMER (Sartomer Co. USA) PROXEL (ICI) RHODOPOL (Rhône-Poulenc) LAROMER (BASF) IRGACURE (Ciba-Geigy) DAROCURE (Merck) QUANTACURE (Ward Blekinsop) NEOREZ (PolyvinylChemie) ACRONAL (Rohm & Haas) TEXANOL (Kodak) PRESANTIL (F.lli Lamberti) ESAPAL (F.lli Lamberti Spa) EXAMPLE 1 To 65 parts of ESACURE KIP [75% of oligo-(4-alpha-hydroxy-isobutirryl)-alpha-methyl-styrene in diacrylated tripropylen-glycol] are added at 75°C 2 parts of nonylphenol condensed with 3 moles of ethylene oxide and 1 part of nonylphenol condensed with 9 moles of ethylene oxide, 0.2 parts of nonylphenol condensed with 100 moles of ethylene oxide, 1 part of N-methyldiethanolamine and 0.1 part of dodecyl alcohol condensed with 225 moles of ethylene oxide. To the homogeneous solution are added 50 parts of water and 10 parts of polyethyleneglycol 400 diacrylated (SARTOMER SR 344). The suspension is grinded for 10 minutes in a colloidal mill Ultraturrax cooling from 75°C to 30°C. At the end are added under agitation 0.4 parts of PROXEL GXL (ICI) and 13 parts of an aqueous solution 2.27% in weight of RHODOPOL 23. The dispersion obtained contains 34% in weight of alphahydroxyketonic oligomeric photoinitiator and has the following characteristics : Appearance : Liquid dispersion, viscous, homogeneous, white Viscosity : 2300 mPas at 20°C (Brookfield RVT 20 rpm) Stability : Stable for more than 4 months at 40 °C EXAMPLE 2 To 65 parts of ESACURE KB1(Benzyl-dimethyl-ketal) are added at 75°C 1 part of nonylphenyl condensed with 9 moles of ethylene oxide, 2 parts of nonylphenol condensed with 3 moles of ethylene oxide, 1 part of of sulphated sodium salt of nonylphenol condensed with 30 moles of ethylene oxide, 1 part of 2-ethyl-hexanoic acid. To the homogeneous solution are added under agitation 100 parts of deionized water and the mixture is grinded for 10 minutes in Ultraturrax cooling to 35°C. At the end are added under agitation 0.4 parts of PROXEL GXL (ICI) and 8 parts of an aqueous solution 2.27% by weight of RHODOPOL 23. The dispersion obtained contains 34.5% by weight of benzyldimethylketal and has the following characteristics : Appearance : Dispersion having pastous consistency, homogeneous, white color. Viscosity : 5000 mpas at 20°C (Brookfield RVT 20 rpm) Stability : Stable for more than 4 months at 40 °C EXAMPLE 3 To 94.5 parts of ESACURE TZT (80 parts of 2,4,6-trimethylbenzophenone and 20 parts of methylbenzophenone) are added 1.5 parts of ESAPAL NP 90 (nonylphenol condensed with 9 moles of ethylene oxide), 0.75 parts of nonylphenol condensed with 100 moles of ethylene oxide, 0.3 parts of dodecyl- alcohol condensed with 225 moles of ethylene oxide and 6 parts of N-methyl-diethanolamine. To the homogeneous solution are added under agitation 95 parts of deionized water. The mixture is grinded for 10 minutes in a colloidal mill Ultraturrax) without passing 35°C. At the end are added under agitation 0.75 parts of PROXEL GXL (ICI) and 19 parts of an aqueous solution 2.27% by weight of RHODOPOL 23. The dispersion obtained contains 44% by weight of photoinitiator and has the following characteristics : Appearance : White, homogeneous, milky liquid Viscosity : 900-1000 mPas at 20°C (Brookfield RVT 20 rpm) Stability : Stable for more than 4 months at 40°C EXAMPLE 4 The dispersion of benzophenone is obtained in an analogous manner as described in Example 3. The solution of the auxiliaries and the grinding in the colloidal mill Ultraturrax are performed at 60°C. The final characteristics of the dispersion are similar to those of the dispersion of the Example 3. EXAMPLE 5 To 100 parts of LAROMER PE 55 W (acrylated polyester by BASF; pH 4.5-5, viscosity 1000 mPas, dispersion at 50% in water) are added the photoinitiators according to the quantities reported in TABLE 1 so that in all cases 1.5 parts of photoinitiatotor (100% active) on 100 parts of resin are present. After agitation for 10 minutes, the composition is applied to a glass plate to a thickness of 100 micrometers. The plate is heated in oven at 100°C for 10 minutes and after cooling to ambient temperature is irradiated by passing it at 20 m/min under an 80 W Hanovia 6512-A-431 lamp, distance from the lamp 10 cm, for so many times as necessary for obtaining a tack free surface. The following characteristics are reported : reactivity (number of passages for obtaining a tack free surface) film appearance film color film residual smell. Photoinitiator parts % on system n.pass. Appearance Yellowing (ASTM D 1925) Smell I Product of Example 2 4.5 1 transp. 12 v.light BDMK 1.5 2 transp. 12 v.light Product of Example 1 4.4 1 transp. 8 absent ESACURE KIP (1) 2.0 1 transp. 8 absent IRGACURE KIP 184 (2) 1.5 3 transp. 8 aromat. DAROCURE 1173 (3) 1.5 3 transp. 8 absent DAROCURE 953 (4) 1.5 2 transp. 8 absent II(*) QUANTACURE QTX (5) 1.5 2 transp. 18 aminic QUANTACURE BTC (6) 1.5 3 opaque 12 aminic Product of Example 3 3.5 1 opaque 10 absent ESACURE TZT (7) 1.5 2 opaque 10 absent Product of Example 4 3.5 1 opaque 10 absent BZO 1.5 3 opaque 10 absent (1) oligo (4-alpha-2-hydroxyisobutirryl)-alpha methylstyrene, 75% in tripropyleneglycol diacrylate (Lamberti) (2) 1-benzoylcyclohexanol (Ciba-Geigy) (3) 2-hydroxy-2-methylpropiophenone (Merck) (4) 2-hydroxy-2-methyl-1-(p-dodecyl) propiophenone (Merck) (5) 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-tioxanthen-2-yloxy)-N,N,N-trimethyl-1-propan chloride (Ward Blekinsop) (6) 4-benzoyl-benzyl-N-trimethyl chloride (Ward Blenkinsop) (photoinitiator soluble in water) (7) 80% 2,4,6-Trimethylbenzophenone / 20% methylbenzophenone (Lamberti) BDMK : Benzyldimethylketal BZO : benzophenone The example shows that the dispersed photoinitiators prepared as described in the examples 1 - 4 are all very active and do not present side disadvantage. ESACURE KIP is very active. The others photoinitiators of Group II are very yellowing and not compatible (QUANTACURE QTX and BTC ) or slightly active (BZO). Example 6 To 100 g of NEOREZ KT 18C (aliphatic acrylated polyurethane as aqueous dispersion 38%, pH 7, viscosity: 26 mPas) are added various amounts of the photoinitiators indicated in Table 2 (in order to have 1.5 parts of photoinitiator, at 100% of active, for 100 parts of resin in each preparation) and the mixture is stirred (60 rpm with impeller) for a fixed time, after that a film to a thickness of 200 micrometers (wet) is applied to a glass plate. The plate is dried at 110°C for 5 minutes or for 20 minutes and is irradiated under an 80 W Hanovia 6512-A-431 lamp at 15 m/min. by two passages at 10 cm from the lamp. The resistence to MEK ( number of double rubs) on crosslinked films is measured. Photoinitiator Parts % on System 5 20 Dry. (min) 1 2 5 20 5 Stir. (min) I Product of Example 1 4.4 90 >200 180 180 178 ESACURE KIP 2.0 70 133 155 155 160 IRGACURE 184 1.5 30 40 25 30 77 DAROCURE 1173 1.5 40 40 40 40 40 Product of Example 2 4.5 164 130 190 185 185 BDMK 1.5 18 17 26 28 35 II Product of Example 3 3.5 50 75 85 85 83 ESACURE TZT 1.5 30 62 76 75 78 Product of Example 4 3.5 48 70 82 80 81 BZO 1.5 25 60 75 72 72 The example shows that, given the same concentration, the photoinitiators as aqueous dispersion impart to the photopolymerisable system an higher photochemical reactivity, in respect to those normally available on the market. It is also demonstrated that, even after long mixing times, the normal photoinitiators are not suitable for use in these systems, while with the aqueous dispersions of photoinitiators already after few minutes of agitation interesting properties are obtained. Even after longer drying times the normal photoinitiators do not impart to the films the wanted reactivity. EXAMPLE 7 To 100 g of LAROMER PE 55 W (BASF, see example 5) are added various quantity of the photoinitiators indicated in TABLE 3 and the mixture is subjected to mechanical agitation (80 rpm, impeller) for 1.2 and minutes. The dispersion is applied on glass to a thickness of 200 micrometers (wet) and dried in oven at 120° C for 7 minutes. After cooling it is irradiated under an 80 W Hanovia 6512-A-431 lamp at 20 m/min at 10 cm from the lamp. The reactivity (number of passages for obtaining a tack free surface) (see Table 3) and film hardness (at the maximum dosage of luminous energy received) according to the method of Koenig's Pendulum (DIN 53157) in seconds (see Table 4) are measured. The results reported in Table 3 show that, given the same concentration, the aqueous dispersed photoinitiators impart to the photopolymerisable system an higher reactivity in respect of the commercially available photoinitiators, independently from agitation time in the preparation of the mixtures. That means that the dispersions according to the present invention are highly compatible and easily included with a minimum of agitation. In this case also ESACURE KIP is very active since already diluted in diacrylated tripropylenglycol which promotes the dispersion. The results reported in Table 4 show that for the photoinitiators in aqueous dispersion the films hardness is higher than that obtained using the corresponding pure photoinitiators (with the only exception of ESACURE KIP for the reasons given in the above mentioned table). In so far as the compounds of group I are concerned, the hardness with the pure products is lower even after longer irradiation times (3 passages instead of 2). The same behaviour is noticed with the photoinitiators of group II, although, as it can be expected for the hydrogen extraction systems, the hardness is inferior than that measured with the photoinitiators by fragmentation. number of passages for a tack-free surface Photoinitiator parts % on system 1 2 5 agitation (min) I Product of Example 1 4.4 1 1 1 ESACURE KIP 2.0 2 1 1 IRGACURE 184 1.5 3 2 2 DAROCURE 173 1.5 3 2 3 Product of Example 2 4.5 1 1 1 BDMK 1.5 3 2 2 II Product of Example 3 3.5 1 1 1 ESACURE TZT 1.5 3 3 2 Product of Exmple 4 3.5 1 1 1 BZO 1.5 5 5 4 Hardness (Koenig's pendulum) (sec) Photoinitiator Parts % on system Number of passages Agitation (min) 1 2 5 Product of Example 1 4.4 2 27 27 31 ESACURE KIP 2.0 2 27 28 27 IRGACURE 184 1.5 3 21 23 28 DAROCURE 173 1.5 3 11 18 25 I a Product of Example 2 4.5 2 22 22 29 BDMK 1.5 2 22 22 29 II Product of Example 3 3.5 3 18 19 19 ESACURE TZT 1.5 3 15 16 16 II a (**) Product of Example 4 3.5 5 11 11 11 BZO 1.5 5 9 9 9 EXAMPLE 8 A water-paint for mural application is prepared by dispersing with a turbomixer "Molteni" (500 rpm) the following compounds in the given order (all the parts are by weight): Base Water parts 21.2 Sodium Hexametaphosphate parts 1 Acrylic disperdent parts 0.2 Antifoam parts 0.1 Rutile titanium bioxide parts 15 Calcium carbonate parts 15 Talc parts 4 ACRONAL 290 P (Rhom-Haas) parts 35 PRESANTIL (Antiflash rusting) parts 0.7 Diurethane thickener (20% in water) parts 1 Ethylene glycol parts 1 Coalescence agent (Texanol-Kodak) parts 0.5 Antifoam parts 0.2 Acrylic thickener parts 2.4 Ammonia 28 Bè parts 0.3 The formulation is completed by adding under mild agitation for 5 minutes (60 rpm) the other components. Finished Base parts 10 LAROMER PE 55 w parts 0.95 Product of example 1 parts 0.045 The base and the finished are applied on an asbestos cement panel to a thickness of 250 micrometers (wet). The film is dryed in darkness and then exposed to the sun light for 3 days in order that the absorbed energy is 3.5 J/cm 2 at 340 nm. The valuations are reported in Table 5 Characteristic Base Finished Film appearance polished compact polished compact Water repellency (Spray test) totally wettable impermeable Water resistance (100 double rubs) matted unchanged MEK resistance (100 double rubs) matted unchanged Stain resistance (suspension Fe 2 O 3 ) brown colourless Resistance to 2 double bending unchanged unchanged the results show that the photoinitiators in aqueous disperse systems of the present invention can be advantageously used in the resin dispersions (water-paint) for the building industry (or similar) to impart better properties to the coatings. It has been noticed that films containing the photopolymerisable resin and the photoinitiator show better superficial resistance thanks to the spread crosslinking without losing in flexibility. EXAMPLE 9 To a wood-lacquer, consisting of 36.5 parts of acrylated polyester and 6.5 parts of rutile titanium bioxide dispersed in 57 parts of water, are added 4.3 parts of a dispersion of photoinitiator (I) according to Example 1 (PID A) but containing also 4.3 parts of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide for 100 parts of PID A (PID A + APO). After agitation for 5 minutes and degasing for 4 hours the lacquer is applied to a thickness of 200 micrometers (wet), the water is evaporated for 20 minutes at 65°C and the resulting film is irradiated with a 80 W IST lamp (distance from the lamp 29 cm) at 3 m/min by three passages. After 4 hours the properties reported in Table 6 are measured and compared with the properties of films obtained by introducing the photoinitiators (II): Phot. Parts % on system Parts % phot. resin Hard. Koenig (sec) Mek (doub. rubs) Appea. Resist. nail-scratch (I)PID A+APO 4.3 - - - - - KIP - 4 45 >300 White polis. Total APO - 0.5 - - - - (II) KIP 2 4 - - - - APO 0.18 0.5 22 180 White Scratch rough surface grains The example shows that it is possible to obtain a total crosslinking also in the depth of strongly pigmented films prepared from aqueous disperse systems using dispersed photoinitiators, while using commercially available products the properties obtained are not useful for practical use. EXAMPLE 10 In this example are compared the properties of films obtained from two photocrosslinkable compositions containing the same photoinitiator (ESACURE KIP) and the same oligomer (ROSKYDAL 850 w - acrylated autoemulsifying polyester - Bayer) but differing in so far as the diluent is concerned. In one case the diluent is water (emulsified composition) in the other case is hexadiolacrylate (reactive diluent monomer, HDDA). The liquid mixtures are applied to glass in order to obtain crosslinked films to a thickness of 100 micrometers, after evaporation of water in oven at 100°C for 10 minutes and crosslinking through irradiation with a 80 W Hanovia 6512-A-431 lamp (distance from the lamp 10 cm) (2 passages). On the crosslinked film are evaluated: hardness (Koenig's pendulum DIN 53157), residual smell, weight lost and the extract in diethyl ether, as reported in Table 7. The example shows that an emulsified system permits to obtain characteristics similar to those of photocrosslinkable systems diluted in a reactive solvent but permits also to avoid the presence of smell and residual monomer in the crosslinked films. Components (mixed according to the given order) A B 1. ROSKYDAL 850 w 100 60 2. HDDA - 40 3. ESACURE KIP - 2 4. Water 60 - 5. Product of example 1 4.4 - Applied thickness wet (nanometer) 160 100 Hardness (Koenig) (sec) 60 65 Smell absent strong Weight loss at 120 °C 0.05% 2.5% Extract in diethyl ether absent 2.7%

Claims: Claims for the following Contracting States : CH, DE, FR, GB, LI, NL Aqueous disperse systems of photoinitiators free of any oligomers and polymers to be photopolymerised comprising at least a photoinitiator and at least a surface active agent, wherein the photoinitiator is present in an amount higher than 50% up to 80% by weight and the surface active agent from 0.1% to 10% by weight of the disperse system. Aqueous disperse systems according to claim 1, wherein the photoinitiator represents from 51% to 60% by wt. of the disperse system and the surface active agent from 0.5% to 2% by weight. Aqueous disperse systems according to claim 1, wherein the photoinitiator is a compound chosen in the group of benzoine ethers, benzyl-dimethyl-ketal, 2,2-dialkoxy-acetophenones, alpha-hydroxy-alkyl-aryl ketones, arylglyoxylic acid esters, mono- and di-acyl-phosphine oxides, or their mixtures; or aromatic ketones, tioxanthones, antraquinones or their mixture; or hexa-aryl-bis-imidazoles. Aqueous disperse systems according to claim 1, wherein the photoinitiator is coupled with an hydrogen donor (coinitiator), the weight ratio between the photoinitiator and the hydrogen donor (coinitiator) is comprised between 1:1 and 1:2.5. Aqueous disperse systems according to claim 3. wherein the photoinitiator is benzophenone or its alkyl derivative. Aqueous disperse systems according to claim 4. wherein the hydrogen donor (coinitiator) is a compound containing a tertiary amino group with at least an hydrogen atom on the carbon atom linked to the nitrogen of the amino group. Aqueous disperse systems according to claim 6. wherein the hydrogen donor (coinitiator) is a compound chosen in the group consisting of N-methyl-N,N-diethanolamine (MDEA) triethanolamine, p-dimethylamino-benzoic acid esters. Aqueous disperse systems according to claim 1. wherein the surface active agent is chosen in the group consisting of: organic sulphonic acids and their salts, mono-alkyl sulphates, quaternary ammonium salts, higher aliphatic alcohols or alkylphenols condensed with ethylene oxide and/or propylene, partial esters of phosphoric acid with aliphatic alcohols and their salts. Claims for the following Contracting States : AT, BE, ES, SE Aqueous disperse systems of photoinitiators free of any oligomers and polymers to be photopolymerised comprising at least a photoinitiator and at least a surface active agent, wherein the photoinitiator represents from 20% to 80% by weight and the surface active agent from 0.1% to 10% by weight of the disperse system. Aqueous disperse systems according to claim 1, wherein the photoinitiator represents from 30% to 60% by wt. of the disperse system and the surface active agent from 0.5% to 2% by weight. Aqueous disperse systems according to claim 1, wherein the photoinitiator is a compound chosen in the group of benzoine ethers, benzyl-dimethyl-ketal, 2,2-dialkoxy-acetophenones, alpha-hydroxy-alkyl-aryl ketones, arylglyoxylic acid esters, mono- and di-acyl-phosphine oxides, or their mixtures; or aromatic ketones, tioxanthones, antraquinones or their mixture; or hexa-aryl-bis-imidazoles. Aqueous disperse systems according to claim 1, wherein the photoinitiator is coupled with an hydrogen donor (coinitiator), the weight ratio between the photoinitiator and the hydrogen donor (coinitiator) is comprised between 1:1 and 1:2.5. Aqueous disperse systems according to claim 3. wherein the photoinitiator is benzophenone or its alkyl derivative. Aqueous disperse systems according to claim 4. wherein the hydrogen donor (coinitiator) is a compound containing a tertiary amino group with at least an hydrogen atom on the carbon atom linked to the nitrogen of the amino group. Aqueous disperse systems according to claim 6. wherein the hydrogen donor (coinitiator) is a compound chosen in the group consisting of N-methyl-N,N-diethanolamine (MDEA) triethanolamine, p-dimethylamino-benzoic acid esters. Aqueous disperse systems according to claim 1. wherein the surface active agent is chosen in the group consisting of: organic sulphonic acids and their salts, mono-alkyl sulphates, quaternary ammonium salts, higher aliphatic alcohols or alkylphenols condensed with ethylene oxide and/or propylene, partial esters of phosphoric acid with aliphatic alcohols and their salts.

Inventors: LI BASSI GIUSEPPE, NICORA CARLO, LI BASSI, GIUSEPPE, NICORA, CARLO
Applicants: LAMBERTI SPA, LAMBERTI S.P.A.
Application year: 1990
Main classification: C08F2
IPC codes: G03F7, C08F2