Method for production of the coatings having the strong adhesion

FIELD: chemical industry; methods of production of the coatings with the strong adhesion.

SUBSTANCE: the invention is pertaining to the method of production of the coatings with the strong adhesion on the inorganic or organic substrate, which provides, that one inorganic or organic substrate is subjected to the treatment with the low-temperature plasma, the corona discharge or the treatment with the gaseous flame, at the normal atmospheric pressure deposit on the inorganic or organic substrate one or several photoinitiating agents or the mixtures of the at least one ethylene- unsaturated with the monomers and-or the oligomers containing at least one ethylene- unsaturated group, or the solutions, suspensions or emulsions of the above indicated substances using the suitable methods; the above indicated substances are not necessary subjected to drying and-or to the electromagnetic irradiation; and either on the preliminary so treated substrate deposit the composition including at least one ethylene- unsaturated monomer or the oligomer and the coating is subjected to hardening under action of the UF/ the visual rays emission or the electron beam; or on the substrate with such a preliminary coating made out of the photoinitiating agent they apply the printing ink coating and dry it. The method has the high efficiency and allows to produce the coating with the good adhesion and is suitable for to production of the products made out of the various plastics materials and-or metals or the glass types with the coatings having the good adhesion.

EFFECT: the invention ensures the high efficiency of the method, production of the highly adhesive coatings suitable for manufacture of the products made out of the various plastics materials, metals or the glass types.

18 cl, 19 ex

 

The invention relates to a method for coating with strong adhesion on inorganic or organic substrates, in which these substrates treated with low temperature plasma, corona or flame treatment, at normal pressure applied on inorganic or organic substrates, one or more photoinitiators, and such substrates with pre-coating photoinitiator cover composition containing at least one ethylene unsaturated monomer or oligomer, and floor utverjdayut using radiation. In addition, the invention relates to a device for implementing the method, to the use of photoinitiators upon receipt of such layers of coatings and to the coating with strong adhesion.

The adhesion properties of coatings (e.g., finishing, pigments, printing inks or adhesives) on inorganic or organic substrates, especially on non-polar substrates, such as polyethylene, polypropylene or fluorinated polyolefins, often do not meet the requirements. For this reason, it is necessary to conduct additional processing in order to obtain satisfactory results. The adhesion can be enhanced by the initial application of the special primer, the so-called primers, and only then on top put the desired treatment is used.

An additional possibility is the impact on the substrates to be coated, plasma treatment or corona discharge with subsequent coating of substrates, and between these two operations can be carried out the process of vaccination, for example, acrylate monomers (see J.Polym. Sci., Part A: Polym. Chem. 31, 1307-1314 (1993)).

Obtaining low-temperature plasma and stimulated plasma deposition of thin organic or inorganic films in vacuum conditions and at normal pressure has been known since some time. Basic principles and applications described, for example, article ..Bell, "Fundamentals of Plasma Chemistry" in Proc. "Technology and Application of Plasma Chemistry", Ed. by J.R.Holahan and ..Bell, Wiley, New York (1974) and article .Suhr, Plasma Chem. Plasma Process 3 (1), 1, (1983).

In addition, in the plasma it is possible to conduct polymerization, which leads to the deposition of polymer films, which can be used as a primer. Basic principles and applications described, for example, .Biederman, Y.Osada "Plasma Polymerization Processes," in "Plasma technology 3" edited L.Holland, Elsevier, Amsterdam 1992.

It is also known that the surface of the plastics can be subjected to plasma processing, and the result is plotted in the subsequent finishing has improved adhesion to plastic substrates. This is described .J.Jacobasch and others in the publishing Farbe+Lack 99 (7), 602-607 (1993) for low-temperature plasma is s in vacuum conditions and J.Friedrich and other in the Surf. Coat. Technol. 59, 371-6 (1993) plasma in conditions from vacuum to normal pressure, while the low-temperature plasma enters the corona discharge.

The way that the similar type mentioned above is known from the document WO 00/24527. This method is described plasma processing of substrates with direct deposition from the vapor phase and prevents photoinitiator in vacuum. However, a drawback of this method is that for vapour deposition requires the use of a vacuum unit and due to the low deposition rate, this method is not effective and not suitable for industrial applications that require high performance.

In this field of technology there is a need for methods of pretreatment of substrates that can be easily implemented in practice and not too expensive in terms of cost of equipment, which improves the subsequent coating these substrates.

According to the invention is installed, the floor fototerapia compositions with particularly good adhesion can be obtained by applying photoinitiator on the substrate to be coated, then the substrate is subjected to plasma processing (plasma low pressure and/or at normal pressure), the treatment by corona discharge or flame treatment, and dried and/or about ucaut substrate, treated in this way. On substrates with such preprocessing is applied coating that cures. The resulting coating has unexpectedly good adhesion, which does not deteriorate in an appreciable degree even after several days of storage or exposure to sunlight.

Consequently, the invention relates to a method for coating with strong adhesion on inorganic or organic substrates, in which:

a) an inorganic or organic substrate is processed by low-temperature plasma, corona or flame treatment,

b) at normal pressure applied on the inorganic or organic substrate, one or more photoinitiators or mixture of photoinitiators with monomers and/or oligomers containing at least one ethylene unsaturated group, or solutions, suspensions or emulsions of the above substances, and

C) using suitable methods, the above substances are optionally dried and/or subjected to electromagnetic radiation.

The method is simple to implement and provides high performance in a unit of time, since there are no long stage of deposition and slow processes stitching. This method is especially well adapted for the manufacture of products made of various plastics, and/or m is for metal, or types of glass, which so without preprocessing would have a different degree of adhesion to other components or which in the case of traditional priming treatment have different affinity for the primer.

In the method according to the invention after application of photoinitiator (or photoinitiators), or a solution or dispersion in a solvent or the monomer on the substrate, which is pre-treated by plasma, corona or flame, and after any stage of the drying process for evaporating any solvent used, is the stage of fixing photoinitiator under the action of radiation in the ultraviolet (UV) or visible region of the spectrum. In the context of the present invention, the term "drying" includes both: how to remove solvent, and the consolidation of photoinitiator.

It is therefore of interest is a method of obtaining coatings with good adhesion to inorganic or organic substrates, in which:

a) an inorganic or organic substrate is processed by low-temperature plasma, corona or flame treatment,

b) at normal pressure applied on the inorganic or organic substrate, one or more photoinitiators, or a mixture of photoinitiators with monomers and/or oligomers containing at least one of ethylene nenasi the military group, or solutions, suspensions or emulsions of the above substances, and

C) using suitable methods, the above substances are optionally dried and/or subjected to electromagnetic radiation with the aim of securing photoinitiator.

At the stage of) the above-described preferred methods is optimal drying and removing the solvent. This stage can be excluded, for example, when the solvent is not used. At the stage b) preferred methods must be implemented pinning photoinitiator under the action of electromagnetic waves, especially radiation in the UV/visible region of the spectrum. In the following described suitable device for drying and exposure.

In addition, the invention relates to a method for coating with strong adhesion on inorganic or organic substrates, in which:

a) an inorganic or organic substrate is processed by low-temperature plasma, corona or flame treatment,

b) at normal pressure applied on the inorganic or organic substrate, one or more photoinitiators, or a mixture of photoinitiators with monomers and/or oligomers containing at least one ethylene unsaturated group, or solutions, suspensions or emulsions of the above substances, and

C) using suitable methods, is shown above substances optionally dried and/or subjected to electromagnetic radiation, and either

G1) on the substrate with such pre-coating photoinitiator applied composition comprising at least one ethylene unsaturated monomer or oligomer, and floor utverjdayut under the action of UV/visible radiation or an electron beam; or

G2) on the substrate with such pre-coating photoinitiator coated printing ink and dried.

The preferred method of obtaining coatings with good adhesion to the inorganic or organic substrate, in which:

a) an inorganic or organic substrate is processed by low-temperature plasma, corona or flame treatment,

b) at normal pressure applied on the inorganic or organic substrate, one or more photoinitiators, or a mixture of photoinitiators with monomers and/or oligomers containing at least one ethylene unsaturated group, or solutions, suspensions or emulsions of the above substances, and

C) using suitable methods, the above substances are optionally dried and/or subjected to electromagnetic radiation, and either

G1) on the substrate with such pre-coating photoinitiator applied composition comprising at least one ethylene unsaturated monomer or oligomer, and floor utverjdayut under the action of UV/videosaishwarya or an electron beam; or

G2) on the substrate with such pre-coating photoinitiator coated printing ink and dried.

Process stage b) in each of the above methods is preferably carried out at normal pressure.

If the process stage b) in each of the methods described above) uses a mixture of photoinitiators with monomers or/and oligomers, the use of mixtures of one or more photoinitiator monomers is preferred.

Possible ways of obtaining plasma under vacuum conditions is well described in the literature. Electricity can be entered inductive or capacitive manner. This may be direct current or alternating current, the frequency of the alternating current can vary from a few kHz to interval MHz. In addition, the possible energy in the microwave range (GHz).

The basics of obtaining and maintaining plasma is described, for example, review papers ..Bell and .Suhr mentioned above.

As the main gas plasma can be used, for example, helium, argon, xenon, N2About2H2water vapor or air.

The method according to the invention is essentially not sensitive to the method of supply of electricity.

The method may be performed periodically, for example, in a rotating drum, or continuously in the case of films, filaments is or textile fabric. Such methods are known and described in the prior art.

Furthermore, the method can be carried out in conditions of corona discharge. Corona discharge is formed in conditions of normal pressure, and the most frequently used ionized gas is air. But in principle can also be used for other gases and their mixtures, as described, for example, in the journal of Coating, t, No. 12, 426 (2001). The advantage of using air as the ionized gas in the corona discharge is that the process can be led in the outdoor unit, and, for example, the film can be extracted continuously between the corona electrodes. Such technological design is known and described, for example, in the journal J.Adhesion Sci. Technol, T. 7, No. 10, 1105, (1993). Three-dimensional products can be processed with a plasma jet, and the contours of the product are tracked using robots.

Professionals in this area of technology known gas-flame processing of substrates. Appropriate industrial device, for example, flame treatment films, commercially available. Under this treatment, the film moves on a cooled cylindrical roller after the device for firing processing, which consists of a system of burners arranged in parallel, usually along the entire length of the cylindrical roller. Details can be found in the br is Surah firms producing device for fire treatment (e.g., issuing firms CI, Flame treaters are, Italy). The choice of parameters is determined by the specific type of the processed substrate. For example, the temperature of the flame, its intensity, time, distance between the substrate and the burner, the nature of the combustible gas, air pressure and humidity, consistent with the type of the considered substrate. As the combustible gases can be used, for example, methane, propane, butane or a mixture of 70% butane and 30% propane.

Solid inorganic or organic substrates to be processed can be of any shape. Preferably the substrate has the form of a textile fabric, fibers, films or three-dimensional products. For example, the substrate may be a thermoplastic, elastomeric, internally crosslinked or crosslinked polymer, metal oxide, ceramic material, glass, metal, leather or cloth.

Pretreatment of the substrate by treatment with plasma, corona or flame may be implemented, for example, directly after the extrusion of the fiber or film, and immediately after the extrusion of the film.

Preferably the inorganic or organic substrate is a thermoplastic, elastomeric, internally crosslinked or crosslinked polymer, a metal oxide, ceramic material, glass or metal, the person is but thermoplastic, elastomeric, internally crosslinked or crosslinked polymer.

Examples of thermoplastic, elastomeric, internally crosslinked or crosslinked polymers listed below.

1. Polymers of mono - and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, as well as polymerization products of cycloolefins, such as cyclopentene or norbornene; and also polyethylene (which optionally can be crosslinked), e.g. high density polyethylene (HDPE), high molecular weight high density polyethylene (VM-HDPE), ultrahigh molecular weight high density polyethylene (SVM-HDPE), medium-density polyethylene (PASP), low density polyethylene (LDPE), and linear polyethylene of low, very low and extremely low density (LLDPE), (PAOP) and (PANP).

Polyolefins, i.e. the polymers of mono-olefins, which in the example mentioned in the previous paragraph, especially polyethylene and polypropylene, can be obtained in various ways, especially using the following methods:

a) free-radical polymerization (normally under high pressure and high temperature);

b) catalytic polymerization, the catalyst usually contains one or more metals from groups IVb, Vb, VIb or VIII. Typically, these metals have one or more ligands, such as hydroxy is s, the halide, alcoholate, esters, ethers, amines, alkali, alkenyl and/or arily, which can have either πor σ-coordination. Such metal complexes may be in free form or can be mounted on carriers, for example on activated magnesium chloride, titanium chloride (III), aluminium oxide or silicon oxide. Such catalysts can be soluble or insoluble in the polymerization medium. These catalysts can be active in the polymerization or can be used for more activators, for example, altimetry, metal hydrides, alkylhalogenide metals, alkylperoxide or allylmethylamine, the metals being elements of groups Ia, IIa and/or IIIa. The activators can be further modified, for example, groups: ester, a simple ester, amine or similair. Such catalytic systems are usually referred to as metallocene or single center catalysts (SSC) firms Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont).

2. Mixtures of the polymers mentioned in paragraph 1, for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of polyethylenes of different types (for example LDPE/HDPE).

3. Copolymers of mono - and diolefins with each other or with other vinyl monomers, for example ethylene/propylene the e copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene copolymers and butene-1, propylene/isobutilene copolymers, copolymers of ethylene and butene-1, ethylene/hexenoic copolymers, ethylene/methylpentene copolymers, ethylene/heptanone copolymers, ethylene/okanoya copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkylacrylate copolymers, ethylene/alkylmethacrylamide copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide, or copolymers of ethylene and acrylic acid and its salts (ionomers)and ternary copolymers (terpolymers) of ethylene with propylene and a diene, such as hexadiene, Dicyclopentadiene or ethylidenenorbornene; and also mixtures of such copolymers with each other or with polymers mentioned in paragraph 1, for example, copolymers of polypropylene-ethylene/propylene copolymers, LDPE-ethylene/vinyl acetate, copolymers, LDPE-ethylene/acrylic acid copolymers, LLDPE-ethylene/vinyl acetate, copolymers, LLDPE-ethylene/acrylic acid and alternate or statistically structured copolymers polyalkylene with carbon monoxide and their mixtures with other polymers, for example polyamides.

4. Hydrocarbon resins (for example, C5-C9), including hydrogenated modifications (for example, glue is the following resins) and mixtures of polyalkylene and starch.

5. Polystyrene, poly(p-methylsterol), poly(α-methylsterol).

6. Copolymers of styrene or α-methylstyrene with denami or acrylic derivatives, for example styrene/butadiene, styrene/Acrylonitrile, styrene/alkylmethacrylamide, styrene/butadiene/alkylacrylate and methacrylate, styrene/maleic anhydride, styrene/Acrylonitrile/methyl acrylate; mixtures of high impact strength consisting of copolymers of styrene and another polymer, such as polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and also block copolymers of styrene, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene-butylene/styrene or styrene/ethylene-propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene copolymers polybutadiene/styrene or polybutadiene/Acrylonitrile, styrene and Acrylonitrile (or Methacrylonitrile) on polybutadiene; styrene, Acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, Acrylonitrile and maleic anhydride or maleic acid imide on polybutadiene; styrene and maleic acid imide on polybutadiene, styrene and alkylacrylate or alkylmethacrylamide on polybutadiene, styrene and Acrylonitrile on ethylene/propylene/diene copolymers (APDS), styrene and Acrylonitrile on polyalkylacrylate the x or polyalkylacrylate, styrene and Acrylonitrile on acrylate/butadiene copolymers, and mixtures thereof with the copolymers mentioned in paragraph 6, these known copolymers, such as, for example, a copolymer of Acrylonitrile, butadiene and styrene (ABS), a ternary copolymer of methyl methacrylate, butadiene and styrene (MBS), as well as copolymers ASA and AES.

8. Halogenated polymers, for example polychloroprene, chlorinated rubber, chlorinated and commercially available brominated copolymer of isobutylene/isoprene (galouti rubber), chlorinated or chlorosulphurized polyethylene, copolymers of ethylene and chlorinated ethylene Homo - and copolymers of epichlorohydrin, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride (PVC), grades, polivinilhlorid, polyvinylidene fluoride; and copolymers such as vinyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate.

9. Polymers produced from α, βunsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, or polymetylmetacrylate, polyacrylamides and shockproof polyacrylonitrile modified with butyl acrylate.

10. The copolymers of the monomers mentioned in paragraph 9, with each other or with other unsaturated monomers, for example, copolymers of Acrylonitrile/butadiene, Acrylonitrile/alkylacrylate copolymers, Acrylonitrile/alkoxy is alkylacrylate copolymers, copolymers of Acrylonitrile/vinylchlorid or terpolymer Acrylonitrile/alkylmethacrylamide/butadiene.

11. Polymers made from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate or maleate, polyvinyl butyral, polyarylate, polyallylamine; and their copolymers with olefins mentioned in paragraph 1.

12. Homo - and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropyleneoxide or their copolymers with bisglycinate ethers.

13. Polyacetals, such as Polyoxymethylene and those polyoxymethylenes which contain comonomers, for example ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenyleneoxides (PFD) and sulfides and their mixtures with polymers of styrene or polyamides.

15. Polyurethanes made from polyethers, polyesters and polybutadienes containing terminal hydroxyl groups, on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and their original products.

16. Polyamides (PA) and copolyamids produced from diamines and dicarboxylic acids and/or from aminocarbonyl acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamide produced from m-xylene, Damian and adipic acid; a polyamide derived from a diamine and ISO - and/or terephthalic acid and optionally elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene-terephthalamide or poly-m-phenylenedimaleimide. Block copolymers of the aforementioned polyamides with polyolefins, copolymers of olefins, ionomers or chemically bonded or grafted elastomers; or with a simple polyethers, e.g. with polyethylene glycol, polypropyleneglycol or polytetramethylene. In addition, polyamides or copolyamids modified APDS or ABS; and polyamides condensed during processing ("polyamide system RIM").

17. Polyureas, polyimides, polyamideimide, simple polyetherimide, complex polyetherimide, polyvidone and polybenzimidazole.

18. Polyesters produced from dicarboxylic acids and glycols (deserty) and/or from hydroxycarbonic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylcyclohexane, polyhydroxybenzenes, and also block polyether-esters (simple-complex), made from polyethers with hydroxyl terminal groups; and also polyesters, modificar the bathrooms with polycarbonates or MBS.

19. Polycarbonates (PC) and complex politicalparty.

20. Polysulfones, simple polyethersulfone and polyetherketone.

21. Crosslinked polymers produced from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

22. Dry and not alkyd resins.

23. Unsaturated complex polyester resin produced from complex spoliation of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and their halogenated difficult flammable modifications.

24. Stitched acrylic resin produced from substituted acrylic esters, for example from epoxyacrylate, urethaneacrylate or complex poliefirakrilaty.

25. Alkyd resins, complex, polyester resins and acrylate resins which are crosslinked with melamine resins, mochevinnye resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resin produced from aliphatic, cycloaliphatic, heterocyclic or aromatic Picadilly compounds, for example, products: diglycidyl ethers of bisphenol-A, diglycidyl ethers of bisphenol-F, which is stitched using the m conventional hardeners, for example, anhydrides or amines, with or without accelerators.

27. Natural polymers such as cellulose, natural rubber, gelatin, or a polymer-homologous chemically modified derivatives such as acetates, propionate and butyrate cellulose, ethers of cellulose, such as methylcellulose; and colophony resins and derivatives.

Nov (multiple components) of the aforementioned polymers, for example PP/EPDS, PA/APDS or ABS, PVC/EVA (ethylene-vinyl acetate), PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/RHT, PVC/CPE, PVC/acrylates, RUM/thermoplastic polyurethane (PU), PC/thermoplastic PU, RUM/acrylate, POM/MBS, PFD/HIPS, PFD/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PFD, PBT/PC/ABS or PBT/PET/PC.

The substrate may consist, for example, that used in the field of commercial printing, sheet or roll printing, posters, calendars, letterheads, labels, packaging foil, tapes, credit cards, templates, hardware and other application of the substrate is not limited to non-food purpose. For example, the substrate may also be a material food purposes, for example, as a packaging material for food products, cosmetics, pharmaceuticals, and other

When the substrates are pre-treated in accordance with the methods of the invention, moreover, it is possible to adhese the Noah linking to each other or laminated, for example, substrates that tend to have poor mutual compatibility.

Within the context of the present invention the paper should also be considered as internally cross-linked polymer, especially in the form of cardboard, which can optionally be coated, for example, Teflon - Teflon®. Such substrates are, for example, are commercially available.

Thermoplastic, crosslinked or internally crosslinked plastic is preferably a polyolefin, polyamide, polyacrylate, polycarbonate, polystyrene or acrylic/melamine, alkyd or polyurethane surface treatment.

Polycarbonate, polyethylene and polypropylene are particularly preferred.

The plastic may be, for example, in the form of a film products injection molding, molded parts, fibers, nonwovens or textile fabric.

As inorganic substrates are considered here specifically glass, ceramic materials, metal oxides and metals. The substrates may be a silicate and oxide glass metalloids or metals, which preferably have the form of films or powders, which preferably have an average particle size of from 10 nm to 2000 μm. These particles can be compact or porous. Examples of oxides and silicates are SiO2, TiO2, rO 2, MgO, NiO, WO3, Al2O3La2About3, silica gels, clays and zeolites. In addition to metals, the preferred inorganic substrates include silica, alumina, titanium oxide, and glass, and mixtures thereof.

As metal substrates specifically addresses Fe, Al, Ti, Ni, Mo, Cr and steel alloys.

Photoinitiator suitable for use in the method according to the invention, in principle, can be any compounds and mixtures, which upon irradiation with electromagnetic radiation to form one or more free radicals. They include initiating system consisting of a set of initiators and systems that work independently from each other or synergistic. Besides coinitiators, such as amines, thiols, borates, Rostov, phosphine, carboxylates and imidazoles, it is also possible the use of sensitizers, for example acridine, xantinol, Riazanov, coumarins, thioxanthones, triazines and dyes. A description of these compounds and initiating systems can be found, for example, in the publications J.V. Crivello, Dietliker K.K., (1999): Chemistry &Technology of UV &EB Formulation for Coatings, Inks &Paints (Chemistry and technology of UV and electron beam formulations for coatings, printing inks and pigments) and in the book, Bradley G. (editor) volume 3: Photoinitiators for Free Radical & Cationic Polymerization (Photoinitiator for free radical and cationic poly is erinacei) 2nd Edition, John Wiley & Son Ltd. Photoinitiator, suitable for use in the method according to the invention at the stage b)can be either an initiator containing an unsaturated group, or an initiator that does not contain such a group

Such compounds and derivatives are obtained, for example, from compounds of the following classes: benzoin, benzylacetone, acetophenone, hydroxyacetophenone, aminoalkylindole, acylphosphatase, azinphosmethyl, acyloxymethyl, alkylamidoamines ketones, such as michler ketone, peroxide compounds, dinitrile compounds, the halogenated acetophenone, phenylglyoxylate, dimeric phenylglyoxylate, benzophenone, oximes and oxime esters, thioxanthone, coumarins, ferrocene, titanocene, onevia salt, sulfonate salt, itaniemi salts, diazonium salts, borates, triazine, bisimides, polysilane and dyes. In addition, it is possible to use combinations of the compounds mentioned classes of compounds with each other and combinations with the corresponding concierage systems and/or sensitizers.

Preferably photoinitiator is a compound of formula (I) or (Ia):

,

,

in which

(IN) means photoinitiator main structure;

But spasinou group or a simple bond;

(RG)of the mean hydrogen or at least one functional ethylene unsaturated group; and

(RG')represents a simple bond or a bivalent radical which contains at least one functional ethylene unsaturated group, or means a trivalent radical. Interest compounds of formula (I) or (Ia), in which (IN) is photoinitiator the basic structure of the formula (II) or (III):

R1mean group (A), (B), (C), or (III)

n denotes a number from 0 to 6;

R2represents hydrogen, C1-C12alkyl, halogen, group (RG)-A -, or, when R1mean group (A), two radicals R2in ortho-position to a carbonyl group can also together mean a group of-S - or;

the substituents R3and R4each independently mean C1-C6alkyl, C1-C6alkanoyl, phenyl or benzoyl, each radical is phenyl and benzoyl is unsubstituted or substituted with halogen, C1-C6the alkyl, C1-C6alkylthio or C1-C6alkoxy group;

R5means hydrogen, halogen, C1-C12alkyl or C1-the 12alkoxy or a group (RG)-A-;

R6is a OR9or N(R9)2or,,or SO2R9;

the substituents R7and R8each independently represent hydrogen, C1-C12alkyl, C2-C12alkenyl, C1-C12alkoxy, phenyl or benzyl, or R7and R8taken together, indicate With2-C6alkylen;

R9represents hydrogen, C1-C6alkyl or C1-C6alkanoyl;

R10means hydrogen, C1-C12alkyl or phenyl;

R11represents a C1-C4alkyl or; and

X1represents oxygen or sulphur.

(IN) means, for example,,,,,,,or,,,.

Group a in the compounds of formula (I) or (Ia) is, for example, a simple link, space the NSS group-Z-[(A 1)a-Y]c-[(A2)b-X]d-,,or

Groups X, Y and Z each independently represent a simple bond, -O-, -S-, -N(R10)-, -(CO)-, -(CO)O-, -(CO)N(R10)-, -O-(CO)-, -N(R10)-(CO)- or-N(R10)-(CO)O-.

Group A1and A2each independently represent a1-C4alkylen,3-C12cycloalkyl, phenylene, phenylene-C1-C4alkylen or1-C4alkylene-phenylene-C1-C4alkylen.

The indices a, b, C and d, each independently represent a number from 0 to 4.

Particular preference is given to compounds of the formula (I) or (Ia), in which the group a is a separating group-Z-[(CH2)a-Y]c-[(CH2)b-X]dand X, Y, Z, a, b, C and d have the above values.

In the compounds of formula (I) or (Ia)

(RG) represents hydrogen or RcRbC=CRa-especially RcRbC=CRa-;

(RG') means a simple link,orespeciallyand

each radical Ra, Rb, Remeans N or C1-C6alkyl, especially H or CH3.

Obtaining such photoinitiator compounds known specialist is m in this technical field and are described in numerous publications.

For example, compounds containing unsaturated groups can be obtained by reacting 4-[2-hydroxyethoxy)benzoyl]-1-hydroxy-1-mutilata (Irgacure® 2959, from the company Ciba Spezialitätenchemie) with isocyanates, containing acryloyl or methacryloyl group, or with other compounds containing acryloyl or methacryloyl group, see for example, US patent No. 4922004.

Industrial available unsaturated photoinitiators are, for example, 4-(13-acryloyl-1,4,7,10,13-pentaacetate)-benzophenone (Uvecryl R36 from the company UCB), chloride 4-benzoyl-N, N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethyltrimethylammonium (Quantacure ABQ from the company Great Lakes), and some unsaturated tertiary amines capable of copolymerization (Uvecryl P101, Uvecryl P104, Uvecryl P105, Uvecryl P115 from the company UCB Radcure Specialties) or capable of copolymerization aminoacridine (Photomer 4116 and Photomer 4182 from the company Ackros; Laromer LR8812 from BASF; CN381 and CN386 from the company Cray Valley).

The following publications are examples of suitable photoinitiator compounds containing ethylene unsaturated functional group, and receipt of them. Unsaturated, Aceto and benzophenone derivatives described, for example, in U.S. patent No. 3214492, US 3429852, US 3622848 and US 4304895, for example.

Also suitable are, for example,

and the other pic is service to copolymerization benzophenone, for example, from the company UCB, Ebecryl P36 or Ebecryl P38, diluted in 30% of diacrylate tripropyleneglycol.

Capable of copolymerization, ethylene unsaturated acetophenone connection can be found, for example, in patent US 4922004, for example

or.

2-Acryloyloxy were published in the journal Eur. Polym. J. 23, 985 (1987). Examples such asdescribed in the document DE 2818763. In addition, photoinitiated compounds containing unsaturated carbonate groups can be found in the document EP 377191. Already mentioned above, Uvecryl® P36 (from the company UCB) is a benzophenone associated with acrylic functional group with units of ethylene oxide (see Technical Bulletin 2480/885 (1985) from the company UCB or magazine New. Polym. Mat. 1, 63 (1987)):

.

Connection

published in the journal of Chem. Abstr. t, Ref. 283649,

In addition, in the document DE 19501025 given suitable ethylene unsaturated photoinitiated connection. Examples are 4-vinyloxycarbonyloxy, 4-vinyloxycarbonyloxy-4'-chlorobenzophenone, 4-vinyloxycarbonyloxy-4'-methoxybenzophenone, N-vinyloxycarbonyl-4-aminobenzophenone, vinyloxycarbonyloxy-4'-fermentation, 2-vinyloxycarbonyloxy-4'-methoxybenzo the northward, 2 vinyloxycarbonyloxy-5-fluoro-4'-chlorobenzophenone, 4-vinyloxycarbonyloxy, 2-vinyloxycarbonyloxy, N-vinyloxycarbonyl-4-aminoacetophenone, 4-vinyloxycarbonyloxy, 4-vinyloxycarbonyloxy-4'-methoxybenzyl, simple vinyloxycarbonyloxy ether, a simple 4-methoxybenzenediazonium ether, phenyl-(2-vinyloxycarbonyloxy-2-propyl)ketone, (4-isopropylphenyl)-(2-vinyloxycarbonyloxy-2-propyl)ketone, phenyl-(1-vinyloxycarbonyloxy)cyclohexylamine, 2-vinyloxycarbonyloxy-9-fluorenone, 2-(N-vinyloxycarbonyl)-9-aminofluorene, 2-vinylcarbazole, 2-(N-vinyloxycarbonyl)aminoanthracene, 2-vinyloxycarbonyloxy, 3-vinylcaprolactam or.

In the patent US 4672079, inter alia, disclosed obtaining 2-hydroxy-2-methyl(4-fenilpropionova), 2-hydroxy-2-methyl-n-(1-methylvinyl)propiophenone, p-vinylbenzenesulfonic, p-(1-methylvinyl)benzoylecognine.

Also suitable are described in the document JP Kokai Hei 2-292307 products of the interaction of 4-[2-hydroxyethoxy)benzoyl]-1-hydroxy-1-mutilata (Irgacure 2959 from the company Ciba Spezialitätenchemie) with isocyanates, containing acryloyl or methacryloyl group, for example,or(in which R is H or CH ).

Additional examples of suitable photoinitiators are:and

The following examples described W.Bäumer and others in the publishing Radcure '86, Conference Proceedings, 4-43 to 4-54:

,,

,and.

G. Wehner et al described in Radtech '90 North America connection

In the method according to the invention are also suitable connection, published in RadTech 2002, North America

,

where x, y and z represent average 3 (SiMFPI2) and

.

In the method according to the invention can be used either saturated or unsaturated photoinitiator. The use of unsaturated photoinitiator is preferred. In addition, in the method according to the invention can of course be used mixtures of different photoinitiators, for example, a mixture of saturated and unsaturated photoinitiators.

Professionals in this area of technology known photoinitiator without unsaturated groups, and a large number of such diverse photoinitiators commercially available. Generally in this way are suitable for any photoinitiator to the e after treatment with plasma, by corona discharge or flame, are fixed on the surface of the substrate treated in this way.

Values of the substituents defined in formula (I) and (Ia) in other radicals, is explained below.

With1-C12Alkyl is linear or branched and is, for example, With1-C8-With1-C6- or1-C4alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl and dodecyl, especially, for example, methyl or butyl.

Similarly With1-C6alkyl and C1-C4alkyl are linear or branched and have, for example, the above-mentioned values, until the appropriate number of carbon atoms. Specific1-C6alkyl substituents for benzoyl or phenyl are1-C4alkali, for example methyl or butyl.

Halogen represents fluorine, chlorine, bromine and iodine, especially chlorine and bromine, preferably chlorine.

When R1mean group (a) and two radicals R2in ortho-position to a carbonyl group can also together mean a group of-S - or - (C=O)-, are formed, for example, patterns having the basic structure of thioxanthone

or the basic structure is the anthraquinone

With1-C6Alkanoyl is linear or branched and is for example, With1-C4alkanoyl. Examples are formyl, acetyl, propionyl, butanoyl, Isobutanol, pentanol and hexanol, preferably acetyl. With1-C4Alkanoyl has the aforementioned values, until the appropriate number of carbon atoms.

With1-C12Alkoxy denotes linear or branched radicals and is, for example, With1-C8-With1-C6- or2-C4alkoxy. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-Butylochka, sec-Butylochka, isobutoxy, tert-Butylochka, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentane, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, n-Butylochka, sec-Butylochka, isobutoxy, tert-Butylochka, preferably methoxy. Similarly radicals With1-C8alkoxy, C1-C6alkoxy and C1-C4alkoxy are linear or branched and have, for example, the above-mentioned values, until the appropriate number of carbon atoms.

With1-C6Alkylthio means a linear or branched radical and is, for example, With1-C4alkylthio. Example and are methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutyric, tert-butylthio, pentylthio and hexylthio, especially methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutyric, tert-butylthio, preferably methylthio. Similarly, the radical With1-C4alkylthio is linear or branched and is, for example, the above-mentioned values, until the appropriate number of carbon atoms. Phenyl or benzoline radicals, substituted by halogen, C1-C6the alkyl, C1-C6alkylthio or1-C6alkoxy group, for example, have from one to five substituents, for example, mono-, di - or tizamidine radicals, especially di - or tizamidine phenyl ring. Preference is given, for example, 2,4,6-trimethylbenzoyl, 2,6-dichlorobenzoyl, 2,6-dimethylbenzoyl or 2,6-dimethoxybenzoyl.

With1-C6Alkylene and C2-C6alkylen represent a linear or branched alkylene, for example With2-C4alkylene, for example methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, pentile, hexylen. Preference is given To1-C4alkylene, for example, ethylene or butylene,,,or-C(CH3)2 2-as well as the methylene and ethylene.

Phenylene-C1-C4alkylen means phenylene, substituted C1-C4alkylene in one position of the aromatic ring, whereas With1-C4alkaliphile-C1-C4alkylene represents phenylene which is substituted With1-C4alkylene in two positions venereologia rings. Alkylene radicals are linear or branched and have, for example, the above-mentioned values, until the appropriate number of carbon atoms. Examples are

,,,and other

However alkylene group can also be located on different sides venereologia rings, for example, also in the 1,3-position.

Cycloalkyl represents, for example, With3-C12-With3-C8cycloalkyl, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, especially cyclopentyl and cyclohexyl, preferably cyclohexyl. However, With3-C12cycloalkyl also means the structural links such asin which x and y independently of one another denote a number from 0 to 6, and the sum of x+y≤6, orwhere x and y independently on the angle from each other mean a number from 0 to 7 and the sum of x+y≤ 7.

With2-C12Alkeneamine radicals can be mono - or polyunsaturated linear or branched and are, for example, With2-C8-With2-C6- or2-C4alkenyl. Examples are allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl and dodecenyl, especially allyl.

When R7and R8together represent a2-C6alkylen, they can form together with the carbon atom to which they relate, With3-C7cycloalkyl ring. Example3-C7cycloalkyl is cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, especially cyclopentyl or cyclohexyl, preferably cyclohexyl.

The group RcRbC=CRa- represents, for example, -CH=CH2or-C(CH3)=CH2preferably-CH=CH2.

After applying photoinitiator product can be stored or immediately processed further, and applied using well-known technologies: or (preferably) radiation-curable coating containing ethylene unsaturated communication, or a coating that is dried/utverjdayut some other way, for example, the ink for printing. Application can be made by pouring, immersion, spraying, coating, coating with a knife, is Yesenia roller or by centrifuging.

Unsaturated compounds radiation-curable compositions may contain one or more ethylene unsaturated double bonds. They may have low molecular weight (monomer) or high molecular weight (oligomers). Examples of monomers having a double bond are alkyl and hydroxyethylacrylate and methacrylates, for example methyl-, ethyl-, butyl-, 2-ethylhexyl - 2-hydroxyethylacrylate, isobutylacetate and methyl - and athletically. In addition, interest from siliconalley. Additional examples are Acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, complex, vinyl esters such as vinyl acetate, simple vinyl esters, such as isobutylphenyl ether, styrene, alkyl - and halogen styrene, N-vinyl pyrrolidone, vinyl chloride and vinylidenechloride.

Examples of monomers having more than one double bond are etilenglikolevye, 1,6-hexanediamine, propilenglikolstearat, dipropylenetriamine, tripropyleneglycol, neopentylglycol, hexamethylenediamine and diacrylate bisphenol-A, 4,4'-bis(2-acryloyloxyhexyloxy)diphenylpropane, trimethylolpropane, triacrylate pentaerythritol, tetraacrylate pentaerythritol, vinylacetat, divinylbenzene, divinylbenzene, diallylphthalate, triethylphosphate, triallyl socialurl, triacrylate Tris(hydroxyethyl)isocyanurate (Sartomer 368; from the company Cray Valley) and Tris(2-acrylonitril)isocyanurate.

In addition, radiation-curable systems can be used acrylic esters alkoxysilane polyols, such as triacrylate ethoxylated glycerol, triacrylate propoxyethanol glycerin, triacrylate of trimethylolpropane, triacrylate of trimethylolpropane, tetraacrylate of pentaerythritol, triacrylate of pentaerythritol, tetraacrylate of pentaerythritol, diacrylate of neopentylglycol or diacrylate of neopentylglycol. The degree of alkoxysilane polyols used may vary.

Examples of high molecular weight (oligomeric) polyunsaturated compounds are epoxy acrylate resins, polyester acrylate with groups or the group containing simple vinyl ether or epoxy groups, polyurethane and polymeric ethers. In addition, examples of unsaturated oligomers are unsaturated complex polyester resin, which is usually derived from maleic acid, phthalic acid and one or more diols and which have a molecular weight of approximately from 500 to 3000. In addition, can also be used simple vinyl ester monomers and oligomers and oligomers with mA is eachname terminal group and the main chain, which are polyesters, polyurethanes, polyethers, polyvinyl simple ethers and epoxides. In particular, it is especially suitable are combinations of oligomers and polymers containing groups of simple polyvinyl esters, which are described in the document WO 90/01512, however, can also be considered copolymers of monomers functionalized with maleic acid and simple vinyl ether. Such unsaturated oligomers can also be called prepolymers.

Especially suitable are, for example, esters of ethylene unsaturated carboxylic acids and polyols or polyepoxides, and polymers having ethylene unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and their copolymers, alkyd resins, polybutadiene and copolymers of butadiene, isoprene and copolymers of isoprene, polymers and copolymers having (meth)acrylic groups in side chains, and also mixtures of one or more of such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, taconova acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid. Preferred are acrylic and methacrylic acid.

Suitable polyols depict ablaut an aromatic and especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane and novolak and resole. Examples of polyepoxides are polyepoxide on the basis of these polyols, especially of aromatic polyols and epichlorohydrin. Also suitable as polyols are polymers and copolymers which contain hydroxyl groups in the polymer chain or in side groups, for example polyvinyl alcohol and its copolymers, or hydroxyalkyl esters of poly (methacrylic acid or their copolymers. In addition, suitable polyols are complex oligoesters having a hydroxyl terminal group.

Examples of aliphatic and cycloaliphatic polyols include alkylenedioxy, preferably containing from 2 to 12 carbon atoms, such as ethylene glycol, 1,2 - or 1,3-propandiol, 1,2-, 1,3 - or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3 - or 1,4-cyclohexanediol, 1,4-dihydroxyphenylglycol, glycerol, Tris(β-hydroxyethyl)amine, trimethylacetyl, trimethylolpropane, pentaerythritol, and dipentaerythritol sorbitol.

The polyols may be partially or fully tarifitsirovana one or more unsaturated carbon is Vym acid, it is possible that the free hydroxyl groups in partial esters will be modified, for example with the formation of ethers, or tarifitsirovana other carboxylic acids.

Examples of esters are:

triacrylate of trimethylolpropane, triacrylate of trimethyloctane, trimethacrylate of trimethylolpropane, trimethacrylate of trimethyloctane, dimethacrylate of tetraethyleneglycol, triethylene glycol dimethacrylate, diacrylate tetraethyleneglycol, diacrylate pentaerythritol, triacrylate pentaerythritol, tetraacrylate pentaerythritol, diacrylate of dipentaerythritol, triacrylate of dipentaerythritol, tetraacrylate of dipentaerythritol, pentacarinat of dipentaerythritol, hexagram of dipentaerythritol, actuariat of tripentaerythritol, pentaerythritol dimethacrylate, trimethacrylate pentaerythritol, dimethacrylate of dipentaerythritol, cerametallic of dipentaerythritol, octamethyl of tripentaerythritol, digitalnet pentaerythritol, traitement of dipentaerythritol, pentagonal of dipentaerythritol, exitement of dipentaerythritol, diacrylate of ethylene glycol, diacrylate 1,3-butanediol, dimethacrylate 1,3-butanediol, digitalnet 1,4-butanediol, triacrylate sorbitol, tetraacrylate sorbitol, triacrylate- modified pentaerythritol, cerametallic sorbitol, pentakill sorbitol, hexagram sorbitol, oligoesters acrylic and metallogenica, di - and tri-acrylates glycerol, 1,4-cyclohexanediacetic, bicarinate and mimetically of polyethylene glycol having a molecular weight of from 200 to 1500, and mixtures thereof. Also suitable as components are the amides of identical or different unsaturated carboxylic acids and aromatic, cycloaliphatic and aliphatic polyamine, preferably containing from 2 to 6, especially from 2 to 4, amino groups. Examples of such polyamines are Ethylenediamine, 1,2 - or 1,3-Propylenediamine, 1,2-, 1,3-or 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexylaniline, octylaniline, dodecylamine, 1,4-diaminocyclohexane, ISOPHORONEDIAMINE, phenylenediamine, biphenylamine, di-β-aminoacylase ether, Diethylenetriamine, Triethylenetetramine and di(β-aminoethoxy)- and di(β-aminopropoxy)ethane. In addition, suitable polyamines are polymers and copolymers, which may have additional amino group in the side chain, and oligoimide containing terminal amino groups. Examples of such unsaturated amides are: methylene-bisacrylamide, 1,6-hexamethylene-bisacrylamide, Diethylenetriamine-trimethacrylate, bis(methacryloyloxy)ethane, β-methacrylamidoethylene and N-[(β-hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters, and polyamides receive, for example, from maleic acid and diol is in or diamines. Maleic acid may be partially replaced by other dicarboxylic acids. They can be used together with ethylene unsaturated comonomers, for example styrene. In addition, polyesters and polyamides can be obtained from dicarboxylic acids and ethylene unsaturated diols or diamines, especially from those that have extra long chain, for example, from 6 to 20 carbon atoms. Examples of polyurethanes are those that are produced from saturated diisocyanates and unsaturated diols or unsaturated diisocyanates and saturated diols.

Polybutadiene and polyisoprene, and their copolymers are known. Suitable comonomers include, for example, olefins such as ethylene, propylene, butene, hexene, (meth)acrylates, Acrylonitrile, styrene and vinyl chloride. Polymers having a (meth)acrylate groups in the side chain, also known. Examples are products of the interaction of epoxy resins on the basis of novolak with (meth)acrylic acid; Homo - or copolymers of vinyl alcohol or hydroxyalkyl derivatives, which tarifitsirovana (meth)acrylic acid; and Homo - and copolymers of (meth)acrylates, which tarifitsirovana hydroxyalkyl(meth)acrylates.

In the context of the present invention, the term (meth)acrylate includes acrylates and methacrylates.

Acrylate or methacrylate of the giving is especially used as a mono - or polyethylene unsaturated compounds. Very particular preference is given to poly-unsaturated acrylate compounds such already mentioned above. Particular preference is given to the manner in which at least one ethylene unsaturated monomer (monomer or oligomer compositions curable by radiation, is a mono-, di, tri - or Tetra-functionalized acrylate or methacrylate.

Besides the fact that the composition contains at least one ethylene unsaturated monomer or oligomer, preferably, it also contains at least one photoinitiator or coinitiator for curing of UV/visible radiation. Therefore, the invention also relates to a method in which technological stage G1) on the pretreated substrate is applied photopolymerized composition containing at least one ethylene unsaturated monomer or/and oligomer and at least one photoinitiator and/or coinitiator, and is cured using radiation in the UV/visible region of the spectrum.

In the context of the present invention, the term radiation in the UV/visible region of the spectrum should be understood as electromagnetic radiation in the wavelength range from 150 nm to 700 nm. The preferred range of from 250 nm to 500 nm. Suitable lamps are well-known specialists in this field of technology, and they are available for sale.

Fo is chuvstvitelnosti compositions in accordance with the technological stage G1) usually extends from about 150 nm to about 600 nm (UV region). Can be used a large number of different types of light sources. Are suitable as point sources, and ploskovice emitters (matrix lamps). Examples are: lamp with a carbon arc, xenon-arc lamps, mercury arc lamps, medium pressure, high pressure, high pressure and low pressure, with additives, as appropriate, of the halides of the metals (metallogenesis lamp), lamp with pairs of metals and microwave-pumped, excimer lamp, transuranic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flash lamps, photographic floodlight lamps, light emitting diodes (LED), electron beams and x-rays. The distance between the lamp and irradiated the substrate may vary in accordance with the intended use and the type and power of lamp and may be, for example, from 2 cm to 150 see also, suitable are laser sources, for example excimer lasers, such as Krypton-F lasers for radiation with a wavelength of 248 nm. Can also be used lasers in the visible range. This method can also be used to produce printed circuits in the electronics industry, lithographic printed circuit boards or cards, letterpress printing, and photographic materials for image recording.

The above description of the right of radiation sources refers to the stage of exposure) (pinning photoinitiator) in the method according to the invention, and to the procedure of process stage g) (curing fotoallergiyami composition). In addition, the curing of the composition applied to the process stages G1 or G2)is likely to be conducted in daylight or with light sources equivalent to daylight.

Appropriate dose of radiation used in the method)is, for example, from 1 to 1000 MJ/cm2such as 1-800 MJ/cm2or, for example, 1-500 MJ/cm2for example, from 5 to 300 MJ/cm2preferably from 10 to 200 MJ/cm2.

As photoinitiator in the compositions, curable by radiation according to the technological stage G1), it is possible to use compounds of the formula I or Ia or any of the initiators and initiator systems known from the prior art.

In these compositions the preferred application of photoinitiators without unsaturated groups.

Typical examples are mentioned below, compounds that can be used separately or in mixture with each other. For example, benzophenone, benzophenone derivatives, acetophenone derivatives of acetophenone, for example α-hydroxyacetanilide or 2-hydroxy-2-methyl-1-phenylpropane, dialkoxybenzene, α-hydroxy - or α-aminoacetophenone, for example (4-methylthiophenyl)-1-methyl-1-morpholinoethyl, (4-morpholinomethyl)-1-benzyl-1-Dima is alminoprofen, (4-methylthiophenyl)-1-methyl-1-morpholinoethyl, (4-morpholinomethyl)-1-(4-methylbenzyl)-1-dimethylaminopropane, 4-aroyl-1,3-dioxolane, benzoylcholine ethers, and benzylacetone, for example, benzyldimethylamine, phenylglyoxylate and derivatives thereof, dimeric phenylglyoxylate, monoolefins, such as (2,4,6-trimethylbenzoyl)phenylphosphine, besatisfied, for example bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpent-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine or bis(2,4,6-trimethylbenzoyl)-(2,4-dipentylester)phosphine oxide, triarylphosphines, compounds ferrocene or titanocene, for example dicyclopentadienyl-bis(2,6-debtor-3-pyrrolidinyl)titanium and borate salts.

As coinitiators here are, for example, sensitizers, which shift or broaden the spectral sensitivity and, thus, cause the acceleration of photopolymerization. Specifically they are aromatic carbonyl compounds such as benzophenone, thioxanthone, especially isopropylthioxanthone, anthraquinone and derivatives 3-acicularis, terphenyls, tirikatene, and 3-(koimeterion)of thiazoline, quinone chamber, and eosinophile, rodnikovye and erythrosine dyes. For example, amines can also be considered as photosensitizers, when the layer of photoinitiator grafted coz the ACLs to the invention, contains a benzophenone or benzophenone derivative.

Further examples of photosensitizers are:

1. Thioxanthone

Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylamino, 2,4-dietitican, 2,4-dimethyldioxanes, 1 methoxycarbonylamino, 2-ethoxycarbonylmethoxy, 3-(2-methoxyethoxymethyl)thioxanthone, 4-butoxycarbonylamino, 3-butoxycarbonyl-7-methylthionine, 1-cyano-3-chlorothioxanthone, 1-etoxycarbonyl-3-chlorothioxanthone, 1-etoxycarbonyl-3-etoxification, 1-etoxycarbonyl-3-aminothiazole, 1-etoxycarbonyl-3-phenylsulfonylacetate, 3,4-di[2-(2-methoxyethoxy)etoxycarbonyl]thioxanthone, 1-etoxycarbonyl-3-(1-methyl-1-morpholinoethyl)thioxanthone, 2-methyl-6-dimethoxymethyl-thioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)thioxanthone, 2-morpholinoethoxy, 2-methyl-6-morpholinoethoxy, N-allithiamine-3,4-dicarboximide, N-artisticchardon-3,4-dicarboximide, N-(1,1,3,3-TETRAMETHYLBUTYL)thioxanthone-3,4-dicarboximide, 1 renoxification, 6-etoxycarbonyl-2-detoxification, 6-etoxycarbonyl-2-methylthionine, esters of thioxanthen-2-polyethylene glycol, chloride, 2-hydroxy-3-(3,4-dimethyl-9-oxo-N-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanamine;

2. Benzophenone

Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, ,4'-dichlorobenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzoate, 4-methylbenzophenone, 2,4,6-trimethylbenzene, 4-(4-methylthiophenyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate, 4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone, chloride, 4-benzoyl-N,N,N-trimethylindolenine, chloride, 2-hydroxy-3-(4-benzoylperoxy)-N,N,N-trimethyl-1-propanamine, monohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaacetate) benzophenone, chloride, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethylbenzylamine;

3. 3-Acicularis

3-Benzoyltartaric, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)coumarin, 3-benzoyl-6,8-dichloroaniline, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis[5,7-di(propoxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-isobutylamino, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxyaniline, 3-benzoyl-5,7-diputaciones, 3-benzoyl-5,7-di(methoxyethoxy)coumarin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyryl-7-diethylaminocoumarin, 5,7-dimethoxy-3-(1-naphtol)coumarin, 5,7-dimethoxy-3-(1-naphtol)coumarin, 3-benzoylbenzene[f]coumarin, 7-diethylamino-3-tenormin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin;

4. 3-(Koimeterion)of thiazoline

3-Methyl-2-benzoylmethylene-β-negotiation, 3-methyl-2-benzoylmethylene-Benz is thiazolin, 3-ethyl-2-propionitrile-β-negotiation;

5. Other carbonyl compounds

The acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylation, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthones, 2,5-bis(4-diethylaminobenzylidene)Cyclopentanone, α-(para-dimethylaminobenzylidene)ketones, such as 2-(4-dimethylaminobenzylidene)indan-1-one or 3-(4-dimethylaminophenyl)-1-indan-5-ispropanol, 3-phenylthiophene, N-methyl-3,5-di(ethylthio)phthalimide N-methyl-3,5-di(ethylthio)phthalimide.

In addition to these additives, it is possible that radiation-curable composition also contain additional additives, particularly light stabilizers. The nature and number of such additional additives are determined by the anticipated use of the examined coatings, and this refers to the competence of specialists in this field of technology.

In addition, the composition may also contain pigment, when you have chosen the right photoinitiator, and can be used, possibly colored pigments and white pigments.

The thickness of the applied layer of the composition may range from 0.1 to 1000 μm, especially from about 1 μm to 100 μm. At low layer thickness, in the range of less than 50 μm, pigmented compositions are also referred to as printing inks.

As light stabilizers can of batobalani UV absorbers, for example, from the class of hydroxyphenylacetate, hydroxyphenylpropionic, amide of oxalic acid or hydroxyphenyl-SIM.-triazine. Such compounds can be used individually or as mixtures with the use of sterically obstructed amines (SSA) or without them.

Examples of such UV absorbers and light stabilizers are:

1. 2-(2'-Hydroxyphenyl)benzotriazole. for example, 2-(2'-hydroxy-5'-were-benzotriazol, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazol, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazol, 2-(2'-hydroxy-5'-(1,1,3,3-TETRAMETHYLBUTYL)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyn-2'-hydroxy-5'-were)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazol, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, a mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl)benzotriazol, 2-(3'-tre the-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazol, 2-(3'-dodecyl-2'-hydroxy-5'-were)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctylmercaptoacetate)phenylbenzothiazole, 2,2'-methylene-bis[4-(1,1,3,3-TETRAMETHYLBUTYL)-6-benzotriazol-2-infenal]; products of transesterification of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3]2- where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2. 2-Hydroxybenzophenone, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy-derivative.

3. Esters of unsubstituted or substituted benzoic acids, for example, 4-tert-butylanisole, fenilsalitsilat, antifederalist, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylation, 2,4-di-tert-BUTYLPEROXY ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid, hexadecylamine ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid, octadecenoic ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 2-methyl-4,6-di-tert-BUTYLPEROXY ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid.

4. Acrylates, for example ethyl ester or isooctyl ester α-cyano-β,β-diphenylacetone acid, methyl ester α-methoxycarbonylamino acid, methyl ester or butyl ester α-cyano-β-m is Teal-p-methoxycatechol acid, methyl ether α-methoxycarbonyl-p-methoxycatechol acid, N-(β-methoxycarbonyl-β-cyanovinyl)-2-methylindolin.

5. Steric employed amines, for example bis(2,2,6,6-tetramethylpiperidine) sebacina, bis(2,2,6,6-tetramethylpiperidine)succinate, bis(1,2,2,6,6-pentamethylpiperidin)sebacina, bis(1,2,2,6,6-pentamethylpiperidin)new ether n-butyl-3,5-di-tert-butyl-4-hydroxybenzylidene acid, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-tert-octylamine-2,b-sodium dichloro-1,3,5-SIM-triazine, Tris(2,2,6,6-tetramethyl-4-piperidyl)-nitrilotriacetate, tetraeder (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic acid, 1,1'-(1,2-ethandiyl)bis(3,3,5,5-tetramethylpiperidine), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-sterilox-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidin)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)sebacina, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)succinate, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-morpholino-2,6-sodium dichloro-1,3,5-triazine, condensation product of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidine)-1,3,5-triazine and 1,2 bis(3-aminor is palamino)ethane, the condensation products of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin)-1,3,5-triazine and 1,2-bis(3-aminopropylene)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidin-2,5-dione.

6. The diamide of oxalic acid, for example, 4,4'-dactyloctenium oxalic acid, 2,2'-diethoxyaniline oxalic acid, 2,2'-dioctyloxy-5,5'-di-tert-butylaniline oxalic acid, 2,2'-didodecyl-5,5'-di-tert-butylaniline oxalic acid, 2-ethoxy-2'-ethylaniline oxalic acid, N,N'-bis(3-dimethylaminopropyl)amide of oxalic acid, 2-ethoxy-5-tert-butyl-2'-ethylaniline oxalic acid and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butylaniline oxalic acid, mixtures of ortho - and para-methoxy-as well as ortho - and para-ethoxy-disubstituted anilides oxalic acid.

7. 2-(2-Hydroxyphenyl)-1.3.5-triazine, for example, 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-proproxyphene)-6-(2,4-dimetilfenil)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-were)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butylacetophenone)phenyl]-4,6-bis(4-dimetilfenil)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxyphenyl)phenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-[4-(dodecyloxyethoxy-2-hydroxypropyl)oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine.

In addition to the above-mentioned light stabilizers, are also suitable other stabilizers, such as phosphites or phosphonites.

8. The phosphites and phosphonites. for example, triphenylphosphite, diphenylacetate, phenyldichlorophosphine, Tris(nonylphenyl)FOSFA, trilaurylamine, trioctadecyl, the diphosphite of diseasespecific, Tris(2,4-di-tert-butylphenyl)FOSFA, the diphosphite of diisodecylphthalate, the diphosphite and bis(2,4-di-tert-butylphenyl)of pentaerythritol, the diphosphite and bis(2,6-di-tert-butyl-4-were)of pentaerythritol, the diphosphite bis-isodecyloxy-pentaerythritol, diphosphite and bis(2,4-di-tert-butyl-6-were)of pentaerythritol, the diphosphite bis(2,4,6-tri-tert-butylphenyl)pentaerythritol, triphosphate of tristearate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-diphenylene-diphosphonic, 6-isooctane-2,4,8,10-Tetra-tert-butyl-N-dibenzo[d,g]-1,3,2-dioxaphospholane, 6-fluoro-2,4,8,10-Tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphospholane, bis(2,4-decret-butyl-6-were)methylphosphate, bis(2,4-decret-butyl-6-were)ethylphosphate.

Depending on the field of application can also be used for traditional prior art additives, such as antistatic agents, additives, increases the possibility fluidity, and adhesion promoters.

The composition applied to the process stages G1 or G2)are, for example, pigmented or non-pigmented surface coatings, ink, ink for inkjet printing; printing inks, such as inks for screen printing inks for offset printing inks for flexographic printing; or coating drying oil; or primer; or printed form, the form for offset printing, powder coating, adhesives or coatings for repair, composition varnish or sealant for repair.

The composition applied to the process stages G1)does not need to contain photoinitiator - for example, they can represent a traditional composition, cured by electron beam (without photoinitiator), which are known to the expert in this field of technology.

The substrates pre-treated according to the method of the invention, at a later stage G1) can be covered traditionally vodootvedenie compositions and solidified radiation in the UV/visible spectrum or an electron beam, or d2) can be provided with a conventional coating, such coating is dried, for example, air or thermally. In addition, drying of the substrate can be carried out, for example, by absorption, for example, due to the penetrating ability of the radiation.

Floor, antennae on the technological stage G2), preferably is a printing ink.

Such printing inks are known to experts in this field of technology, widely used in the printing process described in literature.

For example, they are pigmented printing inks and printing inks, colored dyes. For example, the ink may be a liquid or pasty dispersion that contains colorants (pigments or dyes), a binder, and optionally solvents and/or optional water and additives. In the liquid printing ink, a binder and additives (if used) is usually dissolved in the solvent. Usually the viscosity (measured in a Brookfield viscometer) for liquid printing inks comprise from 20 to 5000 MPa·with, for example, from 20 to 1000 MPa·C. For pasty printing inks viscosity change, for example, from 1 to 100 PA·s, preferably from 5 to 50 PA·C. the Specialists in this field of technology known components and composition of printing inks.

Suitable pigments, such as traditional formulation of printing inks are generally known and are described in detail in the prior art.

Printing inks contain pigments, suitable concentration, for example, from 0.01 to 40 wt.%, preferably from 1 to 25 wt.%, especially from 5 to 10 wt.%, calculated on the total mA is su ink.

Printing inks can be used, for example, metallography, flexography, screen printing, offset printing, lithography or continuous drip ink-jet-ink printing material pre-treated in accordance with the method of the invention, with the use of well-known compositions, for example, in publishing, packaging or transportation, logistics, advertising, printing money or documents in the field of office equipment.

Suitable inks are printing inks, solvent-based and printed with water-based paints. For example, of interest in printing inks water-based acrylate. It is implied that such printing inks may include polymers or copolymers, which are obtained by polymerization of at least one monomer containing the grouporand which dissolve in water or aqueous organic solvents. Suitable organic solvents are miscible with water, the solvents traditionally used specialists in this field of technology, for example alcohols, such as methanol, ethanol and the isomers of propanol, butanol and pentanol, ethylene glycol and its ethers, such as the methyl ether of ethylene glycol, and ethyl ether of ethylene glycol, and ketones, such as acetone, methyl ethyl ketone or cyclo, for example, isopropanol. Preferred solvents are water and alcohols.

Suitable printing inks contain, for example, as a binder, mainly acrylate polymer or copolymer, and the solvent chosen, for example, from the group consisting of water, alcohols C1-C5, ethylene glycol, 2-(C1-C5alkoxy)ethanol, acetone, methyl ethyl ketone, and any mixtures thereof.

In addition to binders, printing inks can also contain conventional additives known to the skilled in this technical field, in normal concentrations.

For metallographic or flexo printing ink is usually prepared by dilution of a concentrate of printing ink, and then it can be used in accordance with known essentially methods. For example, printing inks can also contain alkyd system, drying by oxidation.

Ink dries in a known manner, traditional art, not necessarily through the floor.

A suitable composition of the aqueous ink contains a pigment or combination of pigments, a dispersant and binder.

The scope of this invention, the dispersing agents include, for example, conventional dispersing agents such as water-soluble d is pergatory based on one or more of the condensation products arylsulfonic acid with formaldehyde or one or more water-soluble oxyalkylated phenols, nonionic dispersants or polymeric acids.

Condensation products arylsulfonic acid with formaldehyde can be obtained, for example, by sulfonation of aromatic compounds such as naphthalene or naphthaleneamine mixture, with subsequent condensation formed arylsulfonic acids with formaldehyde. Such dispersing agents are known and described, for example, in documents U.S. A-5186846 and Germany And-19727767. Suitable oxyalkylated phenols are also known and described, for example, in the documents US-A-4218218 and DE-A-19727767. Fit a non-ionic dispersing agents are, for example, adducts of alkalisation, the products of polymerization of vinylpyrrolidone, vinyl acetate or vinyl alcohol, and copolymers or ternary copolymers (terpolymers) vinylpyrrolidone with vinyl acetate and/or vinyl alcohol.

Additionally, there may be used, for example, polymeric acids, which act as dispersants and binders.

Examples of suitable binders which may be mentioned include monomers, prepolymers and polymers containing acrylate group containing vinyl groups and/or containing an epoxy group, and mixtures thereof. Additional examples are eliminability and siliconalley. In addition, acrylate compounds may be deionno modificarea is generated (for example, substituted amino groups) or ion modified (for example, equipped with acid groups or ammonium groups) and can be used in the form of aqueous dispersions or emulsions (see, for example, the document EP-A-704469, EP-A-12339). Moreover, in order to obtain the desired level of viscosity, solvent free acrylate polymers can be mixed with so-called reactive diluents, for example, monomers containing vinyl groups. In addition, suitable binders are compounds containing an epoxy group.

The printing ink composition may also contain as an optional component, for example, an agent that causes water retention (humidifier), for example, polyhydric alcohols, polyalkylene glycols, which lead composition in the state, especially suitable for ink-jet-ink printing.

It should be understood that the printing inks may also contain additional excipients that are traditional, especially for the (aqueous) ink for inkjet printing, in printing, and in the coatings industry, for example, stabilizers (such as glutaric dialdehyde acid and/or tetramethylethylenediamine), antioxidants, degassers/antifoaming agents, viscosity regulators, additives that improve the fluidity, agents against deposition, obuvki, improves Shine, lubricants, adhesion promoters, and substances that prevent the formation of surface film, matting agents, emulsifiers, stabilizers, hydrophobic agents, light stabilizers, additives that improve the manipulation, and antistatics. When such agents are present in the composition, their total content is usually ≤1 wt.% in the calculation of the weight of the product.

Printing ink, suitable for technological stage G2)include, for example, those that contain dye (with a total content of the dye, for example, from 1 to 35 wt.% calculated on the total weight of the paint). Dyes suitable for the dyeing of such printing inks, known to specialists in this field of technology, and they are widely available on the market, for example, from the company Ciba Spezialitätenchemie AG, Basel.

Such printing inks may contain organic solvents such as organic solvents, miscible with water, for example, alcohols, C1-C4, amides, ketones or ketaspire, ethers, nitrogen-containing heterocyclic compounds, polyalkylene glycols, C2-C6alkalophile and thioglycol, other polyols, such as glycerin and simple C1-C4alkalemia esters of polyhydric alcohols, usually in an amount of from 2 to 30 wt.% in the calculation of the total mass of the ink.

In addition, the printed ink can with what to keep, for example, soljubilizatory, for example, ε-caprolactam. For the purpose of regulating the viscosity of printing ink, by the way, can contain thickeners of natural or synthetic origin. Examples of thickeners include commercially available alginate thickeners, ethers, starch or esters flour carob. For example, printing inks contain thickeners in amounts of from 0.01 to 2 wt.% in the calculation of the total mass of the ink.

In addition, it is possible that printing inks contain buffer substances such as borax, borate, phosphate, polyphosphate or citrate, in amounts, for example, from 0.1 to 3 wt.%, in order to set the pH value equal to, for example, from 4 to 9, especially from 5 to 8.5.

As additional additives such printing inks may contain surfactants or moisturizers. Surface-active substances that attract attention include commercially available anionic and nonionic surfactants. Humectants, which attract attention in printing inks include, for example, urea or a mixture of sodium lactate (useful as 50-60%aqueous solution) and glycerol and/or propylene glycol, for example, in amounts of from 0.1 to 30 wt.%, especially from 2 to 30 wt.%. Moreover, the printing ink can also contain conventional additives which, for example, antifoaming agents or specific substances that inhibit the growth of fungi and/or bacteria. Such additives are typically used in amounts of from 0.01 to 1 wt.% in the calculation of the total mass of the ink.

In addition, the printed ink can be obtained in a traditional way, by co-mixing of the individual components, for example, in a given amount of water.

As already mentioned, depending on the application, it may be necessary to adapt accordingly, for example, viscosity or other physical properties of printing inks, especially those properties that affect the affinity of the ink to discussing the substrate.

In addition, the printing inks are suitable, for example, for use in recording systems of the type in which printing ink is squeezed out from the small holes in the form of droplets that are directed at the substrate on which is formed the image. Suitable substrates are, for example, textile fibre materials, paper, plastic or aluminum foil, pre-treated by the method according to the invention. Appropriate recording systems are, for example, a commercially available inkjet printing device.

Preference is given to printing methods, which use water printing ink.

The method according to the invention can be implemented in a wide range of pressures, the characteristics of the discharge are shifted with increasing pressure from a purely low-temperature plasma in the direction of the corona discharge and finally shifted to a purely corona discharge at atmospheric pressure of about 1000-1100 mbar (102-112 kPa).

Preferably the method is carried out when the process pressure is from 10-6mbar to atmospheric pressure (1013 mbar), especially in the range from 10-4up to 10-2mbar, in the form of a plasma method and at atmospheric pressure in the form of a method by corona discharge. Typically, the firing treatment is carried out at atmospheric pressure.

Preferably the method is carried out, using as a plasma gas, an inert gas or mixture of inert gas with a reactive gas.

When using corona discharge, preferably as a gas used for air, CO2and/or nitrogen. Especially preferably using air, N2, CO2Not, Ar, Kr, Xe, N2About2or H2Oh, separately or in a mixture.

Preferably the layer of deposited photoinitiator has a thickness in the range of, for example, from monomolecular layer, up to 500 nm, especially from 5 nm to 200 nm.

Plasma processing of inorganic or organic substrates (a) is preferably carried out in the period from 1 MS to 300 s, especially from 10 MS to 200 C.

In principle, it is advantageous when fot the initiator is applied as soon as possible after pretreatment plasma by corona discharge or flame, but for many tasks can also be acceptable stage of interaction b) after a time delay. However, it is preferable process stage b) is carried out immediately after process stage a) or within 24 hours after process stage a). Of interest is the way in which process stage C) is conducted immediately after process stage b) or within 24 hours after process stage b).

Pre-treated and coated photoinitiation substrate can be involved in process stage d) immediately after coating and drying in accordance with the process stages a), b) and C), or it can be stored in a pre-processed form.

Photoinitiator, or (where appropriate) a mixture of many photoinitiator, and/or coinitiators, is applied to the substrate pre-treated by corona discharge, plasma or flame, for example, in pure form, i.e. without additional additives, or in combination with monomer or oligomer, or in solution with the solvent. In addition, the initiator or mixture of initiators may be, for example, in the molten state. In addition, the initiator or mixture of initiators may, for example, dispergirujutsja, suspenderbelt or emulgirovanija in the water, and, if necessary, EXT what is dispersing agent. Of course, you can also use any mixture of the above components, photoinitiator, monomer, oligomer, solvent, water.

Suitable dispersing agents are, for example, any surface-active substances (surfactants), preferably anionic and nonionic surfactants, and polymeric dispersing agents are generally known to experts in this field of technology and is described, for example, in US patents No. 4 965294 and 5168087.

Suitable solvents are, in principle, is any substance in which photoinitiator (or photoinitiator) can be translated into a condition suitable for application either in solution or in suspension or emulsion. Suitable solvents are, for example, alcohols, such as ethanol, propanol, isopropanol, butanol, ethylene glycol, etc., ketones, such as acetone, methyl ethyl ketone, acetonitrile, aromatic hydrocarbons such as toluene and xylene, esters and aldehydes, such as ethyl acetate, ethyl formate, aliphatic hydrocarbons such as petroleum ether, pentane, hexane, cyclohexane, halogenated hydrocarbons such as dichloromethane, chloroform, or in the alternative, oil, natural oil, castor oil, vegetable oil, etc. and synthetic oils. This description in no case is not exhaustive and is given merely as an example.

Alcohols, water and esters are the preferred solvents.

Suitable monomers and oligomers are, for example, those described above in connection with fotoallergiyami composition.

Therefore, the invention also relates to a method in which photoinitiator or mixtures thereof with monomers or oligomers are used in combination with one or more liquids (such as solvents or water) in the form of solutions, suspensions and emulsions.

Also of interest is the way in which photoinitiator used in process stage b), or a mixture of photoinitiator was used in the molten state.

Therefore, after preprocessing by plasma, corona or flame in process stage b) is applied on the pretreated substrate, for example, 0.1 to 15%, for example, 0.1 to 5%, photoinitiator having an unsaturated group or, for example, 0.1 to 15%, for example, 0.1 to 5%, photoinitiator, for example, without unsaturated group, for example, 0.5 to 10% of such monomer as acrylate, methacrylate, vinyl ether, etc.

Applying photoinitiators or their mixtures with each other or with monomers or oligomers in the form of melts, solutions, dispersions, suspensions or emulsions, can be implemented in different ways. Application may be effected by dipping, spraying, coating, brush application, spray application knife, roller, is Catania, by centrifuging and fill. In the case of a mixture of photoinitiators with each other and with coinitiators and sensitizers can be used all possible ratios of mixing. When will be only one photoinitiator or a mixture of photoinitiator on the pre-processed substrate, the concentration of such initiators is, of course, 100%.

When photoinitiator applied in the form of a mixture with monomers or/and with solvents and/or water in the form of liquids, solutions, emulsions or suspensions, they are used, for example, in a concentration of from 0.01 to 99.9%, or from 0.01 to 80%, for example, 0.1 to 50%or 10-90%, based on the solution that will be applied. In addition, liquid, comprising photoinitiator may contain, for example, additives, such as antifoaming agents, emulsifiers, surfactants, agents, antifouling coatings, wetting agents and other additives, which are traditionally used in industry, especially in the industrial coatings and pigments.

There are many possible ways of drying coatings, all of which can be used in the method according to the invention. For example, can be used hot gases, IR emitters, microwave and radio frequency emitters, furnace and heated platens. In addition, the drying can be performed, n is the sample, by absorption, for example, due to the permeability of the substrate. This applies particularly to the drying process stage), but also applicable for drying, carried out at the technological stage D2). Drying may occur, for example, at temperatures from 0 to 300°With, for example from 20 to 200°C. Radiation coverage in order fixing photoinitiator on the technological stage) (and also for curing the composition on the technological stage G1)) can be performed, as already mentioned above, using any sources that emit electromagnetic radiation in this range, which can be used by photoinitiation. Usually these sources are light sources that emit in the wavelength range from 200 to 700 nm. Additionally, there may be used an electron beam. In addition to traditional radiators and lamps, can also be used lasers and LEDs (light emitting diodes). May be irradiated the entire coverage area or part of it. Partial irradiation is advantageous when only certain areas of coverage should be provided in the connecting state. In addition, the irradiation may be performed using a beam of electrons.

Drying and/or irradiation can be conducted in air or in an inert gas environment. As the inert gas is considered kazooba the hydrated nitrogen, however, it can also be used with other inert gases such as CO2or argon, helium, etc. or mixtures thereof. Suitable systems and devices known to specialists in this field of technology, and they are available for sale.

In addition, the invention relates to a device for implementing the method according to the invention, which is in accordance with the above described method improves the adhesion of such coatings. These devices include at least one processing module plasma module corona treatment or processing module flame, at least one module of the application, at least one drying module and at least one module of radiation.

In addition, the invention relates to the use of photoinitiators and photoinitiator systems in the method according to the invention.

The invention also relates to highly related coatings, which can be obtained in accordance with the above-described method.

Such strongly related coverage are important not only as protective films or coatings which may be optionally pigmented, but are also used in coatings for imaging, for example in the technology of resists and printed circuit boards. In the case of methods of forming the image exposure may be performed using a mask or by writing with the use of what Finance movable laser beam (direct laser image - LDI). After such partial irradiation may be followed by stage manifestations or washing on which parts of the coating are removed using solvents and/or water, or mechanically.

When the method according to the invention is used to produce coatings forming the image (image rendering), for example, upon receipt of printed circuit boards or circuit boards with electronic printed circuits, phase imaging can be carried out or the process stage b) or the process stage g).

At stage g) depending on the recipe used cover image formation can be a crosslinking reaction or, alternatively, the reaction, which changes the solubility of the composition.

Therefore, the invention also relates to a method in which part of photoinitiators, or mixtures thereof with monomers and/or oligomers deposited on process stage b), which turned out to be unstitched after irradiation in process stage b)are removed by treatment with a solvent and/or water and/or mechanically, and to the way in which after exposure to the process stages G1) parts of the coating are removed by treatment with a solvent and/or water, and/or mechanically.

In addition, you can use the methods of forming the image or on one of the two t geologicheskikh stages in), and G1) or sequentially, at both stages) and G1).

The following additional examples illustrate the invention but they are not intended to limit the invention to these examples. Here, as in the rest of the description and in the claims, parts and percentages relate to weight, unless otherwise indicated.

Example 1

The plasma processing is carried out in a plasma reactor at a frequency of 13.56 MHz and a variable power output from 10 to 100 watts. As the substrate using the film of low density polyethylene (LDPE) with a thickness of 150 μm. This substrate is subjected to argon-oxygen plasma (streams of gases: argon 10 STD. cm3/min, oxygen 2.5 STD. cm3/min) when radiated power of 20 W for 1 s at room temperature and a pressure of 5 PA. Then let the air and the sample removed. Using a knife with a thickness of 4 μm (the company Erichsen), is applied to the treated side of the film 1% ethanol solution of photoinitiator And having the following structural formula:

The samples are stored until the alcohol evaporates, and in a short time they become dry. Then the samples are irradiated using a UV processor (firm Fusion Systems) and mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min

Curing radiation epoxyacrylate composition consisting of 87,26% e is oxoacridine bisphenol a with 1,6-hexanediamine (GDDA), Ebecryl® 604 (firm UCB), 9,80% polyethylene glycol of diacrylate, SR® 344 (Sartomer company), and 0.98% acelerando silicone, Ebecryl® 350 (firm UCB) and 1.96% of 2-hydroxy-2-methyl-1-phenylpropane (Darocur® 1173; firm Ciba Spezialitätenchemie), put a knife on the substrate with such pre-coating receiving layer with the thickness of about 24 μm. Coated samples utverjdayut in the UV processor (firm Fusion Systems), using a mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and belt speeds of 15 m/min

The strength of adhesion is determined by cross-cutting coverage and detachment of the adhesive tape. In the case of untreated samples covering completely detached. The samples pre-treated photoinitiation, on the transverse cuts off only a very small fragments.

Example 2

Using the method of example 1, but the ethanol solution was applied to the mesh plate with which it is printed using a rotating rubber roller at a speed of 10 m/min

The sample pre-treated photoinitiation, on the transverse cuts off only a very small fragments; the adhesion is excellent.

Example 3

Using the method of example 1, but using aqueous suspension of L above photoinitiator, which is prepared as follows: dissolve 0.2% of Tween 40 (polyoxyethylene-20 - mono the FYR of sorbitol and palmitic acid) in distilled water. To the resulting solution add 0.5% photoinitiator A, and the mixture was stirred at 60°C for 1 hour. Turbid liquid cooled and filtered through a filter with air suction (with filter paper Macherey-Nagel MN615). Drying is carried out with the use of the hand dryer, and it ends in a few seconds. The sample pre-treated photoinitiation, on the transverse cuts off only a very small fragments; the adhesion is excellent.

Example 4

Using the method of example 2, but using aqueous suspension of L from example 3. The sample pre-treated photoinitiation, on the transverse cuts off only a very small fragments; the adhesion is excellent.

Example 5

The LDPE film from example 1 process 4 times by corona discharge in air using ceramic electrode (portable unit corona discharge type CEE 42-0-1 MD, width 330 mm, firm SOFTAL) at a distance of approximately 1-2 mm at a radiated power of 400 W and a processing speed of 10 cm/sec. Water slurry of example 3 is applied to the treated side of the film using 4 μm knife (the company Erichsen). Samples dried at 60°C for 15 minutes.

Curing radiation epoxyacrylate composition consisting of 87,26% epoxyacrylate bisphenol a with 1,6-hexanediamine (GDDA), Ebecryl® 604 (f the RMA UCB), 9,80% polyethylene glycol of diacrylate, SR® 344 (Sartomer company), and 0.98% acelerando silicone, Ebecryl® 350 (firm UCB) and 1.96% of 2-hydroxy-2-methyl-1-phenylpropane (Darocur® 1173; firm Ciba Spezialitätenchemie), put a knife on the substrate with such pre-coating receiving layer with the thickness of about 24 μm. Coated samples utverjdayut in the UV processor (firm Fusion Systems), using a mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and belt speeds of 15 m/min, the Strength of adhesion is determined by cross-cutting coverage and detachment of the adhesive tape. In the case of untreated samples covering completely detached. The samples pre-treated photoinitiation, on the transverse cuts off only a very small fragments.

Example 6

Using the method of example 5, but after drying conduct additional exposure. On the sample, which was pre-treated photoinitiation, dried and irradiated on the transverse sections were cut out only very small fragments; the adhesion was excellent. On unprocessed film adhesion was not observed.

Example 7

Using the method of example 5, but using aqueous 1% solution of initiator having the following structural formula:

On the sample, which was pre-treated photoinitiation,dried and irradiated, on transverse sections were cut out only very small fragments; the adhesion was excellent. On unprocessed film adhesion was not observed.

Example 8

In continuously operating device handle film of high density polyethylene with a thickness of 40 μm (Hostalen GF7740 F2no width of 15 cm between the rolls when the conveyor speed of 3 m/min. In the module Vetaphone Coronaplus type TF-415 (has 4 electrodes with a gap of 1-2 mm) film treated by corona discharge when radiated power 27 W·min/m2. Then put a suspension of L from example 3, using the roller causing the device (the video is of polished steel against the rubber roller), and then dried at 60°using the drying unit, consisting of a hot air blower and air diffuser length 80 cm, and the film wound on the roller. Curing radiation epoxyacrylate composition consisting of 87,26% epoxyacrylate bisphenol a with 1,6-hexanediamine (GDDA), Ebecryl® 604 (firm UCB), 9,80% polyethylene glycol of diacrylate, SR® 344 (Sartomer company), and 0.98% acelerando silicone, Ebecryl® 350 (firm UCB) and 1.96% of 2-hydroxy-2-methyl-1-phenylpropane (Darocur® 1173; firm Ciba Spezialitätenchemie), put a knife on the part of the film, receiving a layer thickness of about 24 μm. Coated samples utverjdayut in the UV processor (firm Fusion Systems), using a mercury vapor lamp with microwave excitation and when the disrupting power of 120 W/cm and belt speeds of 15 m/min The strength of adhesion is determined by the bend test and by separation of the adhesive tape. With this purpose, the coated film exactly is folded several times until the coating will not crack. Then impose and tear off the adhesive tape. In the case of untreated samples covering completely detached. The samples pre-treated photoinitiators and dried, the coating is not removed.

Example 9

Using the method of example 8, but in addition, the irradiation is carried out after drying and prior to the winding of the substrate on the roller. To this end UV lamp (IST-Metz, M 200 U1), having a nominal power of 120 W/cm, operates at 50% capacity.

The strength of adhesion is determined by the bend test and by separation of the adhesive tape. In the case of untreated samples covering completely detached. On the sample, which was pre-treated photoinitiation, dried and irradiated, the coating is not removed. The film itself does not stick to the roller.

Example 10

The piece of film LDPE treated in the same manner as described in example 8, by passing associated with adhesive film HDPE. In the case of untreated samples covering completely detached. The samples pre-treated photoinitiators and dried, the coating is not removed.

Example 11

In the plasma reactor described in example 1, PVC film (what thickness 400 μm) is subjected to an argon-oxygen plasma (streams of gases: argon + 10 STD. cm3/min, oxygen - 2.5 STD. cm3/min) when radiated power of 20 W for 10 s at room temperature and a pressure of 5 PA. Then let the air and the sample removed. Using the knife (4 μm), applied on the treated plasma side of the tape aqueous suspension of L from example 3 and the substrate is dried in a drying Cabinet at 60°C for 15 minutes

Curing radiation epoxyacrylate composition consisting of 87,26% epoxyacrylate bisphenol a with 1,6-hexanediamine (GDDA), Ebecryl® 604 (firm UCB), 9,80% polyethylene glycol of diacrylate, SR® 344 (Sartomer company), and 0.98% acelerando silicone, Ebecryl® 350 (firm UCB) and 1.96% of 2-hydroxy-2-methyl-1-phenylpropane (Darocur® 1173; firm Ciba Spezialitätenchemie), put a knife on the substrate with this pre-coating receiving layer with the thickness of about 24 μm. Coated samples utverjdayut in the UV processor (firm Fusion Systems), using a mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and belt speeds of 15 m/min, the Strength of adhesion is determined by cross-cutting coverage and detachment of the adhesive tape. In the case of untreated samples covering completely detached. The samples pre-treated photoinitiators and dried, nothing is removed when Stripping strength of adhesive tape.

Example 12

In the plasma reactor described in example 1, topped triftoratsetata film (thickness 250 μm) is subjected to an argon-oxygen plasma (streams of gases: argon + 10 STD. cm3/min, oxygen - 2.5 STD. cm3/min) when radiated power of 20 W for 30 s at room temperature and a pressure of 5 PA. Then let the air and the sample removed. Using the knife (4 μm), applied on the treated plasma side of the tape aqueous suspension of L from example 3 and the substrate is dried in a drying Cabinet at 60°C for 15 minutes and Then the sample utverjdayut in the UV processor (firm Fusion Systems), using a mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min

Curing radiation urethaneacrylate composition consisting of 68,62% diacrylate aliphatic urethane with GDATA, Ebecryl® 284 (firm UCB), 14,71% N-vinylpyrrolidone (ISP), 14,71% polyethylene glycol of diacrylate, SR® 344 (Sartomer company), and 1.96% of 2-hydroxy-2-methyl-1-phenylpropane (Darocur® 1173; firm Ciba Spezialitätenchemie), put a knife on the substrate with such pre-coating receiving layer with the thickness of about 24 μm. Coated samples utverjdayut in three cycles passing through a UV processor (firm Fusion Systems), using a mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and belt speeds of 15 m/min

The strength of adhesion is determined by separation of the adhesive tape. In the case of untreated samples covering completely detached even under irradiation. On the samples that were pre-obrabotkaponravilos, dried and irradiated, nothing is removed when Stripping strength of adhesive tape.

Example 13

Biaxially oriented polypropylene film (thickness 15 μm, Trespaphan) process 4 times by corona discharge in air using ceramic electrode (portable unit corona discharge type CEE 42-0-1 MD, width 330 mm, firm SOFTAL) at a distance of approximately 1-2 mm at a radiated power of 400 W and a processing speed of 10 cm/S.

Using a knife with a thickness of 4 μm (the company Erichsen), is applied to the treated side of the film 1% ethanol solution of photoinitiator example 1. After drying, the film is irradiated using a UV processor (firm Fusion Systems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min

Curing radiation urethaneacrylate composition consisting of 68,62% diacrylate aliphatic urethane with GDATA, Ebecryl® 284 (firm UCB), 14,71% N-vinylpyrrolidone (ISP), 14,71% polyethylene glycol of diacrylate, SR® 344 (Sartomer company), and 1.96% of 2-hydroxy-2-methyl-1-phenylpropane (Darocur® 1173; firm Ciba Spezialitätenchemie), put a knife on the substrate with such pre-coating receiving layer with the thickness of about 24 μm. Coated samples utverjdayut in the UV processor (firm Fusion Systems), using a mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and belt speeds of 15 m/min

The adhesion strength of opredelyaetsya bend test and by separation of the adhesive tape. In the case of untreated samples of the film is not sufficiently wetted surface (there are areas without cover) and the cover completely off. On the samples that were pre-treated photoinitiation, dried and irradiated, the coating is not removed.

Example 14

Biaxially oriented polypropylene film (thickness 20 μm) treated in the module, flame treatment, and the film moves with a linear velocity of 150 m/min, the roller is cooled to a temperature of 24°S, the distance between the flame and the film is 3.5 mm and the flame temperature ("temperature" ions flame) is equal to 745°C.

On the treated side of the film to cause 1% ethanol solution of photoinitiator example 1 at a flow rate of 30 m /h After drying, the film is irradiated using a UV processor (firm Fusion Systems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min

Curing radiation urethaneacrylate composition consisting of 68,62% diacrylate aliphatic urethane with GDATA, Ebecryl® 284 (firm UCB), 14,71% N-vinylpyrrolidone (ISP), 14,71% polyethylene glycol of diacrylate, SR® 344 (Sartomer company), and 1.96% of 2-hydroxy-2-methyl-1-phenylpropane (Darocur® 1173; firm Ciba Spezialitätenchemie), put a knife on the substrate with such pre-coating receiving layer with the thickness of about 24 μm. Coated samples Ammergau the UV processor (firm Fusion Systems), using mercury vapor lamp with microwave excitation when the radiated power of 120 W/cm and belt speeds of 15 m/min

The strength of adhesion is determined by the bend test and by separation of the adhesive tape. In the case of untreated samples covering completely detached. On the samples that were pre-treated photoinitiation, dried and irradiated, the coating is not removed.

Example 15

Use the procedure described in example 14, but photoinitiator And replace the initiator used in example 7. The strength of adhesion is determined by separation of the adhesive tape. In the case of untreated samples covering completely detached. On the samples that were pre-treated photoinitiation, dried and irradiated, nothing is removed when Stripping strength of adhesive tape.

Example 16

Biaxially oriented polypropylene film (thickness 15 μm, Trespaphan) process 4 times by corona discharge in air using ceramic electrode (portable unit corona discharge type CEE 42-0-1 MD, width 330 mm, firm SOFTAL) at a distance of approximately 1-2 mm, with radiated power of 600 W and a processing speed of 10 cm/S.

Using a knife with a thickness of 4 μm (the company Erichsen), is applied to the treated side of the film 1% ethanol solution of photoinitiator example 1. After drying, the film is irradiated using a UV processor (firm Fusion Sysems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min

Curing with radiation a composition consisting of 67,75% epoxyacrylate oligomer (Craynor® 152, the company Sartomer Company), 30% of tetrahydrofurfurylamine (Sartomer® 285, the company Sartomer Company), 2% 1-hydroxycyclohexanone (Irgacure® 184; firm Ciba Spezialitätenchemie) and 0.25% bis(2,4,6-trimethylbenzoyl)phenylphosphine (Irgacure® 819; firm Ciba Spezialitätenchemie) is applied onto a substrate such pre-coating. Then put the second, raw, duono-oriented polypropylene film (thickness 15 μm, Trespaphan), and the laminate is irradiated in a UV processor (firm Fusion Systems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and belt speeds of 15 m/min. And in this case the connection cannot be broken.

Example 17

Biaxially oriented polypropylene film (thickness 15 μm, Trespaphan) process 4 times by corona discharge in air using ceramic electrode (portable unit corona discharge type CEE 42-0-1 MD, width 330 mm, firm SOFTAL) at a distance of approximately 1-2 mm, with radiated power of 600 W and a processing speed of 10 cm/S.

Using a knife with a thickness of 4 μm (the company Erichsen), is applied to the treated side of the film 1% ethanol solution of photoinitiator example 1. After drying, the film is irradiated using a UV processor (firm Fusion Systems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 3 m/min

Curing with radiation a composition consisting of 67,75% epoxyacrylate oligomer (Craynor® 152, the company Sartomer Company), 30% of tetrahydrofurfurylamine (Sartomer® 285, the company Sartomer Company), 2% 1-hydroxycyclohexanone (Irgacure® 184; firm Ciba Spezialitätenchemie) and 0.25% bis(2,4,6-trimethylbenzoyl)phenylphosphine (Irgacure® 819; firm Ciba Spezialitätenchemie) is applied onto a substrate such pre-coating.

Then put the second biaxially-oriented polypropylene film treated by corona discharge, as described above, and the laminate is irradiated in a UV processor (firm Fusion Systems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min. And in this case the connection cannot be broken.

Example 18

Biaxially oriented polypropylene film (thickness 15 μm, Trespaphan) is treated by corona discharge and cover with ethanolic photoinitiator example 1, as described in example 17.

Curing with radiation a composition consisting of 70% epoxyacrylate oligomer (Craynor® 152, the company Sartomer Company) and 30% of tetrahydrofurfurylamine (Sartomer® 285, the company Sartomer Company), is applied to the substrate with such pre-coating.

Then put the second devuono-oriented polypropylene film treated by corona discharge as described above, and the laminate is irradiated in a UV processor (firm FusionSystems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min And in this case the connection cannot be broken.

Example 19

Biaxially oriented polypropylene film (thickness 20 μm) treated 4 times by corona discharge in air using ceramic electrode (portable unit corona discharge type CEE 42-0-1 MD, width 330 mm, firm SOFTAL) at a distance of approximately 1-2 mm at a radiated power of 600 W and a processing speed of 10 cm/S.

On the treated side of the film to cause 1% ethanol solution of photoinitiator example 1 at a speed of casting 30 m3/hour. After drying, the film is irradiated using a UV processor (firm Fusion Systems) with a mercury lamp with microwave excitation when the radiated power of 120 W/cm and the conveyor speed of 30 m/min

The aqueous composition consisting of 24,5% aqueous preparation of Cu-phthalocyaninato (β) pigment (UNISPERSE® Blue GN-PI; firm Ciba Spezialitätenchemie), 22,2% aqueous emulsion carboxylating acrylic copolymer (GLASCOL® LE 530, the company Ciba Spezialitätenchemie), 5.2% triethanolamine and 48.1% of the water applied with a knife with a layer thickness of approximately 2 μm on the substrate with a preliminary coating. Coated samples dried using an oven with hot air blower at a temperature of 60°and belt speeds of 15 m/min

The strength of adhesion is determined by separation of the adhesive tape. In the case of untreated samples covering completely detached. On the samples that were pre-treatments is through photoinitiation, dried and irradiated, the coating is not removed.

1. A method of producing coatings with good adhesion to inorganic or organic substrates, in which

a) an inorganic or organic substrate is processed by low-temperature plasma, corona or flame treatment,

b) at normal pressure applied on the inorganic or organic substrate, one or more photoinitiators, or a mixture of photoinitiators with monomers and/or oligomers containing at least one ethylene unsaturated group, or solutions, suspensions or emulsions of the above substances, and

C) using suitable methods, the above substances are optionally dried and/or subjected to electromagnetic radiation, and either

G1) on the substrate with such pre-coating photoinitiator put a composition including at least one teleoperation monomer or oligomer, and floor utverjdayut under the action of UV/visible radiation or an electron beam; or

G2) on the substrate with such pre-coating photoinitiator coated printing ink and dried.

2. The method according to claim 1, in which photoinitiator is a compound or composition of compounds of classes: benzoin, benzylacetone, acetophenone, hydroxyacetophenone, monoalkylphenol, acylphosphatase, azinphosmethyl, acyloxymethyl, peroxide compounds, dinitrile compounds, the halogenated acetophenone, phenylglyoxylate, dimeric phenylglyoxylate, benzophenone, oximes and oxime esters, thioxanthone, thiazoline, ferrocene, coumarins, dinitrile connection, titanocene, sulfonate salt, itaniemi salt, diazonium salt, onevia salts, borates, triazine, bisimides, polysilane and dyes, as well as relevant coinitiator and/or sensitizers.

3. The method according to claim 1, in which photoinitiator is a compound of formula (I) or (1A)

(IN) means photoinitiator main structure;

But spasinou group or a simple bond;

(RG) means hydrogen or at least one functional ethylene unsaturated group; and (RG') represents a simple bond or a bivalent radical which contains at least one functional ethylene unsaturated group, or means a trivalent radical.

4. The method according to claim 3, in which photoinitiator is a compound of formula (I) or (1A), in which

(IN) is photoinitiator the basic structure of the formula (II) or (III)

/img>

R1mean group (A), (B), (C), or (III)

n denotes a number from 0 to 6;

R2represents hydrogen, C1-C12alkyl, halogen, group (RG)-A -, or, when

R1mean group (A), two radicals R2in anthopology to a carbonyl group can also together mean a group of-S - or

the substituents R3and R4each independently mean C1-C6alkyl, C1-C6alkanoyl, phenyl or benzoyl, each radical is phenyl and benzoyl is unsubstituted or substituted with halogen, C1-C6the alkyl, C1-C6alkylthio or C1-C6alkoxygroup;

R5means hydrogen, halogen, C1-C12alkyl or C1-C12alkoxy or a group (RG)-A-;

R6is a OR9or N(R9)2oror SO2R9;

the substituents R7and R8each independently represent hydrogen, C1-C12alkyl, C2-C12alkenyl,1-C alkoxy, phenyl or benzyl, or R7and R8taken together, indicate With2-C6alkylen;

R9represents hydrogen, C1-C6alkyl or C1-C6alkanoyl;

R10means hydrogen, C1-C12alkyl or phenyl;

R11represents a C1-C4alkyl orand

X1represents oxygen or sulphur.

5. The method according to claim 4, in which in the compound of formula I or la (RG) means RcRbC=CRa-;

(RG') is aorand the substituents Ra, Rband Rceach independently represent hydrogen or C1-C6alkyl, especially hydrogen or methyl.

6. The method according to claim 1, in which photoinitiator (photoinitiator) or mixtures thereof with monomers or oligomers are used in combination with one or more liquids (such as solvents or water), in the form of solutions, suspensions and emulsions.

7. The method according to claim 1, in which the technological stage G1) on the pretreated substrate is applied photopolymerizable composition, which includes at least one ethylene unsaturated monomer or/and oligomer and at least one photoinitiator and/or coinitiator, and spend from eridania using radiation in the UV/visible region of the spectrum.

8. The method according to claim 1, in which the plasma gas used is an inert gas or mixture of inert gas with a reactive gas.

9. The method according to claim 8, in which air, N2, CO2Not, Ar, Kr, Xe, N2About2or H2Oh, used separately or in a mixture.

10. The method according to claim 1, wherein the layer of deposited photoinitiator has a thickness of 500 nm, preferably in the range from monomolecular layer to a layer thickness of 200 nm.

11. The method according to claim 1, in which process stage b) is carried out immediately after process stage a) or within 24 hours after process stage a).

12. The method according to claim 1, in which the concentration of photoinitiator or photoinitiators in process stage b) is from 0.01 to 99.5%, preferably from 0.1 to 80%.

13. The method according to claim 1, in which process stage C) is conducted immediately after process stage b) or within 24 hours after process stage b).

14. The method according to claim 1, wherein the drying in process stage C) is carried out in a furnace, hot gases, hot rollers, or infrared or microwave emitters, or by absorption.

15. The method according to claim 1, in which the irradiation on the process stage C) is carried out by the source, which emits electromagnetic radiation in the wavelength range from 200 nm to 700 nm, or electron beam.

16. The method according to claim 1, in which photoinitiator mixtures thereof with monomers and/or oligomers, which were applied to the process stages b) and was unstitched after irradiation in process stage b)is removed by treatment with a solvent and/or water, and/or mechanically.

17. The method according to claim 1, wherein after exposure to the process stages G1) part of the coating is removed by treatment with a solvent and/or water, and/or mechanically.

18. Coating with strong adhesion obtained by the method according to one of the preceding claims 1 to 17.



 

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11 cl, 2 dwg, 1 ex

FIELD: engines and pumps.

SUBSTANCE: sheet structure consists of several elements interconnected after coat application step A. Step B of local heating of sheet structure at preset points is performed till preset temperature prior to burning stage C and/or after it. Device to implement proposed method comprises means for local heating at preset points of sheet structure to preset temperature. Car body allows at least one localised heating at preset structural points where front frame is jointed to side member.

EFFECT: reduced costs, accelerated assembling of cars.

8 cl, 3 dwg

FIELD: process engineering.

SUBSTANCE: proposed plant consists of radiator 21 comprising several power emitting elements arranged on carrier. In one of the versions, said power emitting elements define the plane parallel to direction of travel of objects 8. Carrier or carriers and/or power emitting elements can move in that plane or parallel to it. In another version, power emitting elements are arranged on the carrier in the form of ring or along the circumference. Plant for deposition of powder coat can comprises deflecting element 18 to deflect charges and smooth power lines of electric field on object to be coated. Said deflecting element is arranged opposite appliance 16 for coat deposition, while path of locking element and object being coated is located between deflecting element and powder deposition device.

EFFECT: simple and efficient process, simplified design.

37 cl, 3 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to application of coats. Proposed method comprises producing first acetone-containing solvent. It includes also mixing terpene alcohol with said first solvent to produce second solvent with ignition point of, at least 140°F. Then, at least, one resin id dissolved in said second solvent to produce coat. Aforesaid resin is selected from the group including acrylic, epoxy, vinyl, siloxane, epoxy/siloxane, polyvinylbutyral, phenol, oil and acetobutyrate cellulose resins. It comprises, finally, application of said coat onto substrate.

EFFECT: better propertied on surface coating film.

15 cl

FIELD: process engineering.

SUBSTANCE: invention relates to radiating device designed to irradiate disc-shaped wood surfaces. Primarily, its relates to mean-density fibers in applying powder coating thereon. Proposed device incorporates, additionally, one control unit and, at least, one contactless temperature transducer. Said transducer serves to measure temperature of irradiated object in, at least, one zone of object irradiated surface. Unit and transducer (transducers) are configured to register measured temperature and control, at least, one power radiator. Surface to be irradiated is divided into multiple imaginary zones related to one or several temperature transducers. Radiating device may comprises several power radiators distributed across irradiated surface. Irradiators are, preferably, represented by heat radiators, particularly, IR-radiators, or radiators in near IR-band, arranged to displace on, at least, one driven carrier. In compliance with proposed method, moisture content in wood objects is increased to 7-7.8 wt %. Proposed plant is designed to implement described method.

EFFECT: valid data on temperature on entire surface of radiation.

23 cl, 9 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to device metal strip heating in direct-fired furnace. Device for induction preheating of metal strip is arranged ahead of direct-fired furnace in direction of metal strip feed. Air feed means are located ahead of aforesaid device for airing said strip.

EFFECT: higher quality and yield of finished products.

19 cl, 1 dwg

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