MXPA99007982A - Radiation-curable, cyanoacrylate-containing compositions - Google Patents

Abstract

A radiation-curable composition which includes a cyanoacrylate component or a cyanoacrylate-containing formulation;a metallocene component;and a polymerizingly effective amount of a photoinitiator to accelerate the rate of cure is provided.

Description

COMPU THESE WITH CYANOACRILATE. CURIABLE BY RADIATION BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a radiation curable composition that includes a cyanoacrylate component or a cyanoacrylate-containing formulation, a metallocene component and an amount of polymerizing photoinitiator effective to accelerate the rate of cure.

Brief description of the related technology In general, cyanoacrylates are fast curing materials that generate a clear, hard and glassy resin that is very useful as a sealant, coating and particularly as a glue to bond various substrates [see, for example. H .V. Coover, D .W. Dreifus and J .T. O'Connor, "Cyanoacrylate Adhesives" in the Handbook of Adhesives, 27, 463-77, I. Skeist, ed. , Van Nostrand Reinhold, New York, 3rd. (1 990)] ~~ Generally, upon contact with substrates having a surface nucleophile, the cyanoacrylate-containing compounds spontaneously polymerize and form a cured material. This cured material shows excellent properties as glue for materials such as metals, plastics, elastomers, fabrics, woods, ceramics, etc.

The compounds containing cyanoacrylate are then considered as a very versatile type of glue, which cure at room temperature and have a single component. As indicated, the polymerization of the cyanoacrylate is usually initiated by a nucleophile. The anionic polymerization reaction of the cyanoacrylate continues until all the available cyanoacrylate monomer has been consumed and / or terminated by an acidic species. While the main mechanism by which cyanoacrylate monomers polymerize is anionic, it is also known that free radical polymerization occurs when there is prolonged exposure to heat or light of the appropriate wavelength. See, for example. Coover et al. supra. However, free radical stabilizers (for example quinones or sterically hindered phenols) are generally included in cyanoacrylate-containing glues formulations to prolong their shelf life. Thus, typically the degree of free radical polymerization in any commercial compound containing cyanoacrylates is minimal and in fact is particularly undesirable by, at least, the ratio specified above. In conventional polymerisable compositions that do not contain cyanoacrylate monomers, radiation curing usually has certain advantages over other known curing methods. Among them are: shorter time of curing, elimination of solvent (which reduces environmental pollution and conserves raw materials and energy) and induces low thermal stress of the substrate. Also, curing by radiation at room temperature prevents the degradation of certain heat sensitive polymers, which could occur during a thermal curing process. Radiation curable resin-based compositions are used in a multitude of applications in various industries, such as coatings, printing, electronics, medical accessories and engineering in general. Commonly, radiation curable compositions are used for glues, in which case the resin that is chosen is usually epoxy or acrylate based. Some of the best known resins, epoxy based and radiation curable, include cycloaliphatic and epoxy resins with bisphenol-A, epoxidized novolacs and glycidic polyethers. [See, e.g., U.S. Pat. UU 4,690,957 (Fujiokau) and European Patent Publication EP 278 685.] The common curing mechanism reported for such radiation-curable epoxy based compositions is by cationic polymerization. Well-known examples of radiation-curable acrylate-based resins are those having as their main structure urethanes, amides, imides, ethers, hydrocarbons, esters and siloxanes. fVer. eg, J. G. Woods, "Radiation-Curable Adhesives" (Curable Adhesives by radiation) in Radiation Curinq: Science and Technology (Radiation Curing: Science and Technology) 333-98, 371, S. P. Pappas, ed. , Plenum Press, New York (1992)]. The common curing mechanism of such acrylate based and radiation curable compositions is free radical polymerization. European Patent Publication EP 393 407 discloses a radiation curable composition that includes a slow-curing polymerizable cationic epoxide, a fast curing acrylic component polymerizable by free radicals and a photoinitiator. After exposing it to radiation, it is said that the photoinitiator is capable of generating cationic species which in turn initiate the polymerization of the epoxide and a species with free radicals which in turn initiates the polymerization of the acrylic component. The polymerizable acrylic component includes monofunctional acrylates and acrylate esters, such as, for example, acrylates with cyano group and acrylate esters, examples of which are 2-cyanoethyl acrylate (CH2 = CHCOOCH2CH2CN) and 3-cyanopropyl acrylate (CH2 = CHCOOCH2CH2CH2CN) ). [See page 5, lines 1 9 to 26.) The photoinitiator includes cationic salts or elements of the groups Va, Via and Vl la, as well as iron-arene complexes and generally metallocene salts, provided the material chosen as photoinitiator be able to generate both cationic species and species with free radicals when exposed to radiation. [See page 5, line 56, as well as page 7, line 1 5.) Other published information relating to photopolymerizable compositions includes formulations containing epoxy compounds and metal complexes, such as those described in U.S. Pat. UU No. 5,525,698 (Bdttcher). U.S. Pat. UU No. 4,707,432 (Gatechair) refers to a free radical polymerizable composition that includes (a) polymerizable partial esters of epoxy resins and acrylic acid and / or methacrylic acid, and partial esters of polyols and acrylic acid and / or methacrylic acid, and (b) a mixture of photoinitiators of a cyclopentadienyl iron complex and a sensitizer or photoinitiator, such as, for example, an acetophenone.

In "I norganic and Organometallic Photoinitiators" (inorganic and organometallic photoinitiators) of D.B. Yang and C. Kutal, in Radiation Curina: Science and Technoloav (Radiation Curing: Science and Technology), 21 -55, S. P. Pappas, ed. , Plenum Press, New York (1992), cyclopentadienyl complexes are analyzed with transition metals, paying particular attention to ferrocene and titanocene. In the absence of halogenated media, Yanq and Kutal report that ferrocene is photoinsert, although in the presence of such media and a vinyl source polymerization initiated by free radicals could occur. In "A Novel _Strategy for Photoinitiated Anionic Polymerization" (New strategy for photoinitialized ammonium polymerization), Macromolecules (Macromolecules) 24_, 6872-73 (1 991), the authors C. Kutal, P.A. Grutsch and D. B. Yang observe that "it draws attention that in the current catalog of photoinitiators those products that suffer a photochemical release of an ammonia initiator species are absent". The authors also stress that ethyl cyanoacrylate "is not affected by prolonged irradiation (24 hours) with light of wavelength greater than 350 nm" whereas in the presence of NCS ", it is observed that the cyanoacrylate solidifies immediately, in a process that is exothermic, although in that case the NCS "was not generated as a result of the irradiation, it was generated from the Reineckato anion by the excitation of the ligand field with light close to the ultraviolet / visible light spectrum. While metallocenes (such as ferrocenes) have been employed in acrylate-based anaerobic adhesive compositions [see, e.g., U.S. Pat. UU Nos. 3,855,040 (Maiofsky), 4,525,232 (Rooney), 4,533,446 (Conway) and EP '407], it is not believed that to date a composition of cyanoacrylate-based glues with a metallocene has been developed therein as defined in the present, particularly with respect to curing by a photoinitiated mechanism. Accordingly, it would be desirable for a photocurable composition that includes a cyanoacrylate component, a metallocene component and a photoinitiating component, to possess the benefits and advantages of the compositions with cyanoacrylate, and that will effect curing by at least one photoinduced polymerization mechanism.

BRIEF DESCRIPTION OF THE INVENTION The present invention fulfills the desire expressed above, since its composition includes a cyanoacrylate component or a formulation containing cyanoacrylate, a metallocene component and a photoinitiating component. Ideally, such compositions cure after exposure to radiation in the electromagnetic spectrum. Accordingly, in such radiation or photocurable compositions an amount of photoinitiator which carries out the polymerization effectively must be used. The photocurable compositions of this invention retain the benefits and advantages of traditional compositions containing cyanoacrylate, while the curing is effected by at least one photoinduced polymerization mechanism, thereby providing the compositions (and the cured reaction products) which were formed in them) the benefits and advantages of curing by that mechanism. More specifically, the photocurable compositions according to this invention cures quickly, and in doing so, minimizes the possibility of a change in gloss or the appearance of cracks in the cured reaction product (certainly undesirable phenomena).

In another aspect of the present invention, there is provided a method for polymerizing a photocurable composition by applying a certain amount of the composition to the desired surface, and then exposing it to the radiation for a sufficient time to effect curing thereof. . In another aspect of the present invention, the cured reaction product formed from a photocurable composition is provided after exposure to a dose of radiation necessary to effect curing. The present invention will be better appreciated by those skilled in the art on the basis of a reading of the detailed description of the invention, below, and to the examples presented later for illustrative purposes.

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photocurable compositions that include a cyanoacrylate component or a cyanoacrylate-containing formulation, a metallocene component and an effective photoinitiator amount to accomplish polymerization. The cyanoacrylate component or the cyanoacrylate-containing formulation includes cyanoacrylate monomers that can be chosen with a variety of substituents, such as those represented by H2C = C (CN) -COOR, where R can be a group, alkyou C1 - 15; alkoxyalkyl; cycloalkyl; alz uenil; aralkyl; aril; allyl or haloalkyl. Preferably, the cyanoacrylate monomer is selected from: methyl cyanoacrylate; ethyl-2-cyanoacrylate; propyl cyanoacrylates; butyl cyanoacrylates; octyl cyanoacrylates; allyl-2-cyanoacrylates; β-methoxyethyl-2-cyanoacrylate or combinations thereof. A particularly desirable cyanoacrylate monomer for use herein is ethyl-2-cyanoacrylate. Various organometallic compounds can also be used in the present. The compounds of particular interest here can be represented by metallocenes within structure I: Mr -, where R, and R2 can be the same group or two different groups and can be present from one to four times in each ring in case of lock. a ring of five elements, and up to five times if it were a ring of six elements; R, and R2 can be selected from: H; any linear or branched alkyl, with 1 and up to 8 carbon atoms, such as, for example, CH 3, CH 2 CH 3, CH 2 CH 2 CH 3, CH (CH 3) 2, C (CH 3) 3 or the like; acetyl; vinyl; allyl; hydroxyl; carboxyl; - (CH2) n-OH where n can be an integer comprised in 1 and 8; - (CH2) "- COOR3, where n can be an integer between 1 and 8 and R3 can be any alkyl, linear or branched, having between 1 and 8 carbon atoms; H; Li; Na; or - (CH2) n *, where n 'can be an integer between 2 and 8; - (CH2) "- OR4, where n can be an integer between 1 and 8 and R4 can be any linear or branched alkyl, having between 1 and 8 carbon atoms; or - (CH2) n-N + (CH3) 3 X ", where n can be an integer between 1 and 8 and X can be CL, Br, I", CIO4"or BF4"; Yi and z may not be present at all, but when at least one of them is present, the other may be the same or different and may be selected among the groups: H, Cl ", Br", I ", cyano, methoxy, acetyl, hydroxy, nitro, trialkyl amines, triaryl amines, trialkyl phosphines, triphenylamine, tosyl and the like, A and A 'may be the same or different and may be C or N; m and m 'can be the same or different and can be 1 or 2; It is Faith, Ti, Ru, Co, Ni, Cr, Cu, Mn, Pd, Ag, Rh, Pt, Zr, Hf, Nb, V, Mo or others of the style. Of course, depending on the valence, the element represented by Me may have additional ligands - Yi and Y? - associated therewith beyond the carboxylic ligands shown above (such as, for example, where Me is Ti and Y and Y2 are CI).) As an option, the metallocene structure i can be modified to include variants such as: where R,, R2, Y1? Y2, A, A ', m, m' and I correspond to what was defined above. A particularly desirable example of such variant occurs when R., and R2 are both H; Y., and Y? they are both Cl; A and A 'are both N; m and m 'are both 2 and M? It's Ru.

Within the metallocene structure I, suitable metallocene materials of the metallocene II structure can be chosen: I I 0 where R,, R2 and Me correspond to what was previously defined. Particularly suitable metallocene materials of structure 1 can be chosen in which R.,, R2, Y,, Y2, m and 5 m 'are as defined above and Me is chosen from Ti, Cr, Cu, Mn, Ag, Zr , Hf, Nb, V and Mo. Ideally, the metallocene is chosen from the ferrocenes (ie, where the Me is Fe), such as, for example, ferrocene, vinyl ferrocenes, ferrocene derivatives - as would be the butyl ferrocenes. or the diarylphosphino metal complexed ferrocenes [ie, 1,1-bis (diphenylphosphino) ferrocene-palladium dichloride], titanocenes (ie, where the Mβ is Ti), such as, for example, bis (? 5-2.4 -cyclopentadien-1-yl) -bis- [2,6-difluoro-3- (1 H -pyrrol-1-yl) phenyl] titanium, marketed by Ciba-Geigy ? b Corporation of Tarrytown, New York under the trade name of "I RGACURE" 784I-C so chorno their derivatives and combinations thereof. A particularly desirable metallocene is ferrocene. Bis-alkyl methalocenes, for example, bis-alkyl ferrocenes (such as diferrocenyl ethane, propane, butane and the like) are also desirable for use herein, particularly because about half the equivalent weight of the material (as opposed to a non-bis-metallocene) ) can be used to obtain the desired results, with everything else without 0 changes. Of these materials, diferrocenil ethane is the most desirable. Of course other materials can be adapted very well to use them as a metallocene. For example, Me [CW3-CO- CH = C (0 ') - CW'3] 2, where Me is what was previously defined, and W and W can be the same or different, being able to be selected between H and halogens, such as, for example, F and Cl. Examples of such materials include platinum (II) acetyl acetonate ("PtACAC"), cobalt (II) acetyl acetonate ("CoACAC"), nickel (II) acetyl acetonate ("NiACAC"), and acetyl acetonate copper (I I) ("CuACAC"). Combinations of these materials can also be used. There are a number of photoinitiators that can be employed herein to provide the benefits and advantages of the present invention, to which reference was made above. The ? Photoinitiators increase the speed of the curing process when photocurable compositions as a whole are exposed to electromagnetic radiation. Certain metallocenes, such as the "I RGACU RE" 784DC, can perform a double function, acting as a metallocene and as a photoinitiator. Examples of photoinitiators suitable for use include, but are not limited to, commercially available photoinitiators produced by Ciba-Geigy Corp., of Tarrytown, New York, under the trademarks "IRGACU RE" and "DAROCUR", specifically " IRGACURE "1 84 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1 - [4- (methylthio) phenyl] -2-morpholinopropan-1 -one), 369 (2-benzyl-2-N, N -dimethylamino-1- (4-morpholinophenyl) -1-butanone, 500 (the combination of 1-hydroxycyclohexyl phenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (the combination of bis ( 2,6-dimethoxybenzoyl-2,4-, 4-trimethyl pentyl) phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanol), and 81 9 [bis (2,4 , 6-trimethylbenzoyl) phenyl phosphine oxide] and "DAROCU R" 1 1 73 (2-hydroxy-2-methyl-1-phenyl-1-propane) and 4265 (the combination of 2,4,6-trimethylbenzolldiphenyl oxide) of phosphine and 2-hydroxy-2-methyl-1-phenyl-propan-1 -one); and the photoinitiators with visible light [blue], dl-camphorquinone and "I RGACU RE" 784DC. Of course, combinations of these materials can also be used. Other photoinitiators useful herein include alkyl pyruvates, such as, for example, methyl, ethyl, propyl, and butyl pyruvates, and aryl pyruvates, such as pyruvates. of phenyl, benzyl and other derivatives of pyruvates duly substituted. Photoinitiators particularly suitable for use with the present include ultraviolet photoinitiators, such as for example 2,2-dimethoxy-2-phenyl acetophenone (eg, "IRGACURE" 651), and 2-hydroxy-2-methyl-1. phenyl-1-propane (for example, "DAROCUR" 1173), bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (for example, "IRGACURE" 819), and the combination of ultraviolet / visible photoinitiator (2,6-dimethoxybenzoyl-2,4-, 4-trimethylpentyl) phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one) (eg "IRGACURE" 1700), as well as the visible photoinitiator bis (? 5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium (for example, "IRGACURE" 784DC) . With respect to the formulation of the photocurable compositions, in general the components can be mixed together in any order that is convenient. Another option is that it may be desirable to prepare a premix of the metallocene component and the photoinitiator component. In this way, an already prepared premix of these components can be added to the cyanoacrylate component of the formulation, which will allow to have a quick and simple formulation of a part of a photocurable composition before dispensing and curing it.

For packaging and dispensing purposes, it would be desirable for the photocurable composition that met the requirements of the present invention to be relatively fluid and with good flowability. Variations in the viscosity of the same would also be desirable for certain applications and could be achieved immediately by routine changes in the formulation, leaving such changes in the hands of those people understood in the field. For example, common cyanoacrylate compositions to which a thickener or a viscosity modifier would not have been added will be low viscosity formulations (in the range of 1 to 3 cps). And while a composition with such viscosity (or one whose viscosity had been modified to have a viscosity five times greater) could be appropriate for a filling application, where there is a small light between the substrates that it is desired to join (for example, with light less than 0.1 mil) and / or in applications where a higher curing speed is desired, such viscosity could be too low for its use to be convenient in certain industrial applications. At least for this reason, the viscosity of the cyanoacrylate-containing compositions has sometimes been modified to a more appropriate value by the addition of polymethylmethacrylates and / or fumed silica. See, for example, US Patent. UU Us. 4,533,422 (Litke) and Re. 32,889 (Litke), whose statements are expressly incorporated herein by reference. A formulation with medium viscosity (for example, one that is in a range of 1 00 to 300 cps), could be more appropriate in those applications where greater control over the characteristics of the flow is desired, such as when it is desired to join pieces Molded polymer Finally, a high viscosity formulation (ranging from 600 to 1 000 cps) could be more appropriate in those applications where the substrates are more porous and / or have more light between them (for example, all light greater than 0 , 5 thousandths of an inch). Of course, the people understood in the field will be the ones who make the appropriate decisions regarding whether a viscosity modifier should be incorporated in the photocurable composition and, if so, which will be and at what levels they should be incorporated to achieve the viscosity desired for the application to which it is intended. In addition, it may be advisable to reinforce the cured curable compositions of the present invention by adding elastomeric gums as explained and claimed in US Pat. U U No. 4,440.91 0 (O'Connor), disclosures of which and which are hereby expressly incorporated herein by reference. It may also be advisable to improve the heat resistance of the compositions cured curable by the addition of anhydrides as explained and claimed in US Pat. UU No. 4,450, 265 (Harris) and in the documents cited therein, disclosures of each of them and which are hereby expressly incorporated therein, by reference. Moreover, the compositions of the present invention can be incorporated into a thixotropic paste by the addition of organic filler powder with a particle size of between 2 and 200 microns as indicated in US Pat. U U No. 4, 1 05.71 5 (Gleave) or can be thickened by the addition of a copolymer or a terpolymer resin in order to improve the peel strength as taught in US Pat. U U No. 4, 1 02,945 (Gleave), disclosures of each of which and hereby expressly incorporated herein by reference. Moreover, the compositions of the present invention can become more resistant to thermal degradation under high temperature conditions by the addition of certain sulfur-containing compounds, such as sulfonates, sulphonates, sulfates and sulphites, as set forth in U.S. Patent UU No. 5,328,944 (Attarwala), disclosures of which and which are hereby expressly incorporated therein, by reference. The addition of such compounds in the photocurable compositions of the present invention makes these compositions very suitable for applications in the _ that high temperature conditions occur, as occurs with the compounds for encapsulation, particularly where large volumes of curing are employed and the formation of non-sticky surfaces is required in less than five seconds. The inclusion of such materials in a photocurable composition according to the present invention could result in a formulation with very particular advantages for certain applications and which, at least in the case of viscosity modifiers, could be attractive from the point of view of security, since it would make it possible to reduce the amount of splashes or spills of the composition on the skin of the user or of third parties. In addition, as the pieces to be bonded with the compositions of the invention are fixed by exposure to UV radiation, there is less chance of the operator touching or coming into contact with the uncured substance. The relative percentage of the different components of the photocurable compositions according to this invention is a matter of choice of the persons understood in the field, depending of course on the identity of the particular components chosen for a specific composition. However, as a general guideline it is expressed that it is desirable that photocurable compositions include a metallocene, such as ferrocene, in a percentage between 0.005% and up to 4% or more (the desirable value is in the range of 0.01). % to 1, 5%) by weight of the total composition. It is also desirable that the compositions include a photoinitiator such as "IRGACURE" 1700 or 819, or "DAROCUR" 1 173 in amounts within the range of 0.125% to 10% by weight of the composition, where the desirable range is find between 2% and 4% or more, by weight, of the total composition. The rest of the composition is predominantly formed by the cyanoacrylate component, such as, for example, ethyl-2-cyanoacrylate. Of course, the total amount of all the components that make up the composition is 1 00%. A method for curing a photocurable composition according to this invention is also provided herein, the steps of which include (a) incorporation of a given volume of a photocurable compound into the desired substrate; and (b) subjecting the composition to sufficient radiation to effect curing thereof. The amount of photocurable compound incorporated should be sufficient to cure and form an adequate bond to the surfaces of the substrate between which it is applied. For example, the application of the photocurable composition could be achieved by dispensing it simply by dropping it or by applying it as a liquid jet, by brush, dipping it, etc. , to form a thin film. The application of the photocurable composition may depend on the flowability or the viscosity of the composition. In that In this case, as indicated above, viscosity modifiers may be incorporated into the composition. The compositions are dispensed, ideally, on a portion of the desired surface of a substrate to which another portion of another substrate is to be attached. The photocurable composition can be applied to certain portions of the surface of the substrate or over the entire surface of the entire substrate to be joined, which will depend on the particular application. The source of radiation that emits the electromagnetic waves is selected from: ultraviolet light, visible light, X-ray, electron beam, infrared radiation or a combination thereof. In general, ultraviolet light is the radiation of choice, where appropriate sources include "H", "D", "V", "X", "M" and "A" lamps, mercury arc lamps and xenon arch (such as those marketed by Loctite Corporation, Rocky Hill, Connecticut; UV Fusion Curing Systems, Buffalo Grove, Illinois; or Spectroline, Westbury, New York); ultraviolet radiation generated by microwaves; sunlight and fluorescent light sources. Any of these sources of electromagnetic radiation can be used together with their respective reflectors and / or filters, so as to focus the radiation emitted on a specific part of the substrate on which a photocurable composition has been dispensed and / or within a particular region. of the electromagnetic spectrum. Similarly, electromagnetic radiation can be generated directly and continuously or intermittently, to minimize the volume of accumulated heat. While here we often indicate that the electromagnetic radiation used to cure the photocurable compositions in the desired reaction products is in the ultraviolet region, that does not mean that other radiations of the electromagnetic spectrum are not suitable. For example, in certain situations it may be advantageous to apply radiation in the visible region of the electromagnetic spectrum, either alone or combined, for example, with radiation from the ultraviolet region of the spectrum. Of course, under the appropriate conditions, microwave radiation and / or infrared radiation could also be advantageously employed. To complete the curing, it may be necessary to apply higher or lower radiation intensities, more or less exposures, more or less prolonged exposure periods and / or greater or lesser distances from the source, all of which will depend, of course, of the particular components of a given composition. More specifically and with respect to the intensity of the radiation, the lamp chosen should have a power of at least 100 watts per inch (about 40 watts per cm), although the desirable is a power of at least 300 watts per inch (about 1 watt per inch). 20 watts per cm). Also, as the addition of a photoinitiator in the composition could vary the wavelength Within the spectrum of electromagnetic radiation at which curing occurs, it may be desirable to use a source of electromagnetic radiation whose variables (e.g., wavelength, distance, etc.) could be regulated at will. During the curing process, the composition will be exposed to a source of electromagnetic radiation that emits an amount of energy, measured in KJ / m2, determined by parameters that include: size, type and geometry of the source; duration of exposure to electromagnetic radiation; intensity of the radiation (and what portion of the radiation emitted within the region is the one that is appropriate for curing); Absorption of electromagnetic radiation by the materials involved in the process, such as substrates; finally, distance between the composition and the source of radiation. Those skilled in the art will surely have already determined that curing the composition can be optimized by choosing the appropriate values for these parameters and depending on the particular components of the composition. To effect curing, the source of electromagnetic radiation can remain stationary while the composition passes in front of it. As an option, a substrate coated with the photocurable composition can remain immobile while the source of electromagnetic radiation passes over or around it to realize the transformation of composition to reaction product. Another alternative is that both parts move or remain stationary, provided the photocurable composition is exposed to electromagnetic radiation for a sufficiently long period of time to effect curing. For the purpose described herein, the following commercial curing systems are well suited to this task: "ZETA" 7200 or 7400 ultraviolet radiation curing chamber (Loctite Corporation, Rocky Hill, Connecticut); Curing System Fusion UV F-300 B (Fusion UV Curing Systems, Buffalo Grove, Illinois); System for curing Hanovia UV (Hanovia Corp., Newark, New Jersey); BlackLight Model B-1 00 (Spectroline, Westbury, New York) and System for curing RC500 A Pulsed UV (Xenon Corp., Woburn, Massachusetts). In addition, a Sunlighter UV camera equipped with low intensity mercury vapor lamps and a turntable can also be used. The amount of energy needed for the process can be applied by exposing the composition to a less powerful source of electromagnetic radiation over a longer period and by making multiple exposures, or by exposing the composition to a more powerful source of electromagnetic radiation but for shorter periods. Also, each of these multiple exposures can be made by regulating the source at different intensities. In any case, the people understood in the field should choose a source of radiation electromagnetic suitable for the particular composition, and they should place the source at an appropriate distance from the composition so that, along with the exposure span, the transformation optimization is achieved. It may also be advisable to use a source of electromagnetic radiation that emits intermittently, for example, with a pulsating or strobe light, in order to ensure that a complete and total curing is carried out without causing an excessive increase in heat. When used, a photocurable composition according to this invention can be dispensed onto the desired substrate in the form of droplets or thin layer. The substrates on which the photocurable composition of the present invention can be applied include a wide range of various materials; basically, any material with which cyanoacrylates can be used is included. See above. The most desirable selection of these materials includes: acrylics, epoxies, polyolefins, polycarbonates, polysulfones (eg, polyether sulfone), polyvinyl acetates, polyamides, polyetherimides, polyimides and derivatives and copolymers thereof with which they could be mixed or compose traditional additives that assist in the processing facility or in the modification of the physical properties and characteristics of the material used as a substrate. Examples of copolymers that can be used as substrates include: acri Ion itrilo-butad ie no-estire no, reno-a crilonitri cellulose, aromatic copolyesters based on terephthalic acid, p, p-dihydroxydiphenyl and p-hydroxybenzoic acids, polyalkylene (such as polybutylene or polyethylene), terephthalate , polymethyl pentene, polyphenylene oxide or sulfide, polystyrene, polyurethane, polyvinyl chloride and others. In particular, among the most desirable copolymers are those which are capable of transmitting UV radiation and / or visible radiation. Of course other materials can also be used as a substrate, such as metals (stainless steel). The substrate coated with the composition may be placed inside an apparatus for curing by electromagnetic radiation, such as for example the ultraviolet radiation curing chamber "ZETA" 7200, which is equipped with an appropriate source of electromagnetic radiation -for example, ultraviolet- and at an appropriate distance from the substrate, for example, in the range of 1 to 2 inches, although a distance of about 3 inches is desirable. As indicated above, the substrate coated with the composition may remain in the same position or may be passed under the radiation source at the appropriate speed, such as, for example, at 1 and up to 60 seconds per foot, with about 5 seconds per foot. Said passage may be made one or more times or as necessary to achieve curing of the composition on the substrate. The exposure period may last a few seconds or less (for a single exposure) or may last for tens of seconds or more (either for a single exposure or for multiple passes) if desired, which will depend on the thickness of the composition to be cured and, of course, on the components of the composition itself. Of course, a reaction product is also provided with this invention. The reaction product is formed from photocurable compositions after exposing them to sufficient electromagnetic radiation to effect curing of the composition. The reaction product is formed quickly, ideally and usually without a decrease in the brightness or the appearance of cracks, see below. The reaction product of the photocurable composition can be prepared by dispensing a liquid or low viscosity photocurable composition, according to the present invention, onto a substrate and then contacting it with a second substrate and thus forming an assembled assembly. Then, the exposure to electromagnetic radiation of at least one of the substrates of the assembled assembly during an appropriate lapse should transform the photocurable composition into an adhesive reaction product. Also within the scope of the present invention is that the reaction products are prepared from a photocurable composition separated from the device and that after are placed on the surface of a substrate with which they were going to be used. In this way, the reaction products will be produced in the desired form, for example, in the form of a film or tape (adhesive film or coating film), which when applied to the chosen substrate will be bonded thereto. Many film manufacturing processes can be used to produce films of photocurable compositions that respond to the present invention, among which stand out: calendering, melting, rolling, pouring, coating, extrusion and thermoforming. For a non-exhaustive description of such processes, see Modern Plastics Encvclopedia 1 988 (Modern Enciclopledia de los Plásticos), 203-300, McGraw-Hill I nc. , New York (1988). With respect to pouring or coating, conventional techniques can be used, including: gravity coating, spraying, dipping, spinning, roller, brush or transfer. A film of photocurable composition can be prepared by extrusion or calendering, where the curing occurs by exposure to electromagnetic radiation before, concomitantly or, if the composition is sufficiently viscous, after passing through the extruder or the calender. After that, the film can be placed between the desired substrates and the construction of the device will be completed.

The viscosity of the photocurable composition can be controlled or modified in order to optimize its application by (in addition to the inclusion of the appropriate material to alter the viscosity thereof as indicated above) the temperature setting of (1) the composition itself, or of (2) the substrates on which the composition will be applied to assemble the device. For example, the temperature of the composition or of the substrate (s), as well as any combination thereof, can be decreased to increase the viscosity of the composition. In this way, the uniformity of the photocurable composition dispensed on the substrate can be increased by the use of laminating, centrifugation, pressure applied from the atmosphere (as when vacuum bagging is done), pressure applied by a heavy object, by rollers, etc. The substrates on which the photocurable compositions of the present invention are intended to be applied can be constructed with any of the materials mentioned above, which can be both flexible and inflexible. The type of substrate chosen based on its flexibility will depend, of course, on the application for which it will be used. More specifically, the substrates can be constructed with considerably inflexible materials, such as, for example, glass, laminated glass, tempered glass, optical plastics such as polycarbonates, acrylics and polystyrenes, and other alternative materials mentioned supra: they can also be built with flexible materials, such as "MYLAR" films or polyolefins, such as polyethylene or polypropylene, pipes, etc. The choice of the substrate material may influence the choice of the processing technique used to convert the photocurable composition into the cured reaction product or the type of assembled device. For example, when assembling a device with at least one flexible substrate, a composition may be advantageously applied on one end of the flexible substrate and then allowed to fill that end through a portion of another substrate, which is sized to receive that Flexible substrate portion. As a concrete example of such an application, we have polyolefin tubes used for medical purposes, where a portion of them are sized to be received by an acrylic luer seat. Also, roller-roller systems can be used where the flexible substrates are dispensed from rollers (which are aligned and rotate in opposite directions) that approach each other but leave a light between them. In this way, the photocurable composition can be dispensed or injected onto one of the flexible substrates at a point where the two flexible substrates are supplied from their respective rollers and approach each other, while being exposed to electromagnetic radiation for a period of time. long enough as to cure the composition and obtain the adhesive reaction product. The composition could be dispensed by an injection nozzle placed on one of the flexible substrate rolls. When circulating in front of the nozzle in the form of a tape in continuous movement, one of the flexible substrates may come into contact with the composition in the amount of adododa, for dospuos to be placed on the other flexible substrate. Since the photocurable compositions of the present invention are cured to form reaction products, as indicated by their description, a photoinitiated mechanism, both the composition and the surface of the substrate on which the composition is placed should be exposed to the radiation source. electromagnetic The choice of substrate could affect the speed and the degree to which curing of the photocurable compositions of the present invention occurs. For example, it is desirable that the substrates be perfectly joined to be virtually free of absorbing electromagnetic radiation. That is, the greater the degree of transmission capacity of electromagnetic radiation that the substrate has, the greater the speed and the degree of curing of the composition, leaving - of course - the rest of the variables equal.

The loss of the sorcerer or the appearance of cracks is observed when the compositions are cured to give reaction products but the curing itself is incomplete. That is to say, the loss of brightness refers to the evaporation of cyanoacrylate monomer (due to its relatively high vapor pressure) in uncured areas, the result of which is the formation of a precipitate on the surfaces adjacent to the junction line, which it is observed as a white turbidity. Cracking is the formation of stress cracks of certain synthetic materials, such as, for example, polycarbonates, acrylics and polysulfones, in this case due to the presence therein of cyanoacrylate monomer.

The result of an incomplete cure can be observed in the uses as a glue of the photocurable composition as a failure of the adhesion or the cohesion of the cured composition when applied to or between substrates. Such phenomena can be minimized or even eliminated by the use of transmitting substrates (as opposed to absorbents) of electromagnetic radiation, and by placing the source of electromagnetic radiation at a strategic site in order to increase the degree of exposure of the composition to said electromagnetic radiation. In a similar manner and to increase the degree of curing, additional sources of electromagnetic radiation can be used, or as indicated above, reflectors can be used which redirect dispersed or wandering electromagnetic radiation towards the desired parts of the substrate.

Accordingly, the compositions of this invention provide several benefits and advantages, among which stand out: a secondary curing system incorporated (ie, photoinitiation in addition to the common anionic initiation of the cyanoacrylate), which is particularly attractive in applications where some of the substrates that could be used in the set do not allow the transmission of light, making another type of glue (such as double cured acrylic glue) less desirable because it would require a second step that would entail heating, elimination of a (primary) primer for the substrate, which obviates the use of often flammable materials and invites the use of automated processes, and improvement of curing in general In view of the above description of the present invention, it is It is evident that the present information provides a wide variety of practical uses. They then identify, as do many of the advantages and benefits of the present invention. However, the examples of this invention are provided for illustrative purposes only and are not to be taken as limiting the various aspects of the information provided herein.

EXAMPLES Example 1 A photocurable composition was prepared according to the present invention, using for this purpose about 95.9 g of ethyl-2-cyanoacrylate, about 0.1 g of ferrocene and about 4 g of "DAROCU R" 1 1 73 as a photoinitiator. In general, commercially available compositions containing cyanoacrylate (such as "PRISM" Adhesive 4061, commercially manufactured by Loctite Corporation, Rocky Hill, Connecticut) are stabilized against premature anionic polymerization by the addition of an acidic material, such as, for example, trifluoride. of boron or methanesulfonic acid. In this example, therefore, the ethyl cyanoacrylate contained about 20 ppm of boron trifluoride as an acidic anionic stabilizer. Of course, for this purpose, larger or smaller amounts of boron trifluoride or other acidic anionic stabilizers can be added. In one case, the three components were added directly to a polyethylene container and mixed for about thirty minutes at room temperature. In another case, the cyanoacrylate was added to the polyethylene container and then a premix of the ferrocene in the "DAROCUR" photoinitiator was added thereto. In this second case the mixing was also allowed to continue for about thirty minutes at room temperature.

Once the photocurable composition was prepared and by means of a polyethylene pipette, a drop or 'pearl' (about 0.2 grams) of the composition was applied onto an acrylic ultraviolet light transmitting substrate (the substrate dimensions were approximately 1 x 1 x J3.25 inches, similar to those of the substrate marketed by Industrial Safety Co.). More specifically, the composition was applied on one end of a substrate and thereafter a second substrate (where each substrate was of the same material and had the same dimensions) was placed laterally, in an off-line position with respect to the first and so as to cover only the portion of the first substrate on which the composition had been applied. This procedure was repeated in triplicate. Then the two substrates were fastened by small clamps, which formed the assembly of assembled parts. This was introduced into a "ZETA" 7200 ultraviolet radiation curing chamber, equipped with a five-inch intermediate pressure mercury arc lamp (emitting light with a wavelength between 300 and 365 nm). The assembly of assembled pieces was placed in the chamber at a distance of the lamps of between 2 and 3 inches, exposing to ultraviolet light emitted during a period of five to fifteen seconds, as indicated in Table 1. After the indicated exposure time, it was observed that the composition, previously liquid, had cured to form a Solid reaction product. The thickness of the cured material, or bond line, was measured and turned out to be 1 to 3 mils. The data in Table 1 reflect the values obtained after a lapse of about 24 hours at room temperature before the test. Cured test pieces were then tested for shear strength (shear) with Instron Universal (Model 4206, Instron, Canton, Massachusetts) and according to the protocol established in ASTM D-1002. The Instron was used to measure the force required to separate the test pieces from one another. Thus, results of measurements generally between 2500 and 5000 psi were obtained. The force measured corresponds to the strength of the union of the cured reaction product, expressed in terms of pounds per square inch ("psi"). The limiting feature of the cured composition of the present invention appears to be the strength of the substrate on which it is applied and cured. Table 1 shows the averages of the measurements of the three test specimens formed by the two-piece assemblies. The data presented for Samples No. 1 to No. 3 of Table 1 reflect the compositions that were subjected to various initial exposures of electromagnetic radiation and the shear strength demonstrated by the reaction product after a lapse of about 24 hours before. to effect the measurements with the Instron. A second photocurable composition was prepared in the same way and according to the present invention, with about 2 grams of "I RGACURE" 651 in replacement of the photoinitiator "DAROCUR", where the rest of the composition came from more "PRISM" adhesive. Samples No. 4 to No. 6 of Table 1 reflect this second composition, which were subjected to the different initial exposures of electromagnetic radiation indicated. 'Tapia l Tables 2a and 2b below should be analyzed together. They establish several other formulations of photocurable compositions according to the present invention, which were prepared with cyanoacrylate "PRISM" Ad hesive 4061 and 0.1% by weight of ferrocene with photoinitiators indicated and the amounts thereof, the curing process employed and certain properties and characteristics of the reaction products formed therefrom. Each of these formulations (ie, Samples No. 7-1 0) was allowed to fully cure for a period of about 24 hours after the initial exposure to ultraviolet light. Table 2b shows the shear strength of the reaction products formed when these formulations are cured.

Table 2a UV absorbent substrates and the composition containing the photoinitiator "I RGACURE" 1 700, were superior to those measured in the compositions containing any of the other two photoinitiators ("DAROCUR" 1 1 73 in Sample No. 7 or "IRGACURE" "651 in Sample No. 8) after the lapse of 1 to 3 minutes indicated above. However, after curing for about 24 hours, the measurements of each of the assembled assemblies prepared with transmitting substrates or UV absorbers and with each of the aforementioned photoinitiators, were found practically within the same range, which was always much higher than the control ("PRISM" Adhesive 4061, Sample No. 1 0).

EXAMPLE 2 In this example, a photoinitiator capable of initiating polymerization was used for the formulation regardless of whether the substrate used was prepared with a transmitter material or with a UV light absorbing material. That is, the photoinitiator can be initiated by radiation in the visible region of the electromagnetic spectrum. More specifically, three formulations were prepared from "PRISM" Adhesive 4061, about 0.1% by weight of ferrocene and about 0.5% to 2% by weight of "IRGACURE" 1700 as photoinitiator. The amount of "PRISM" Adhesive 4061 (which contains ethyl-2-cyanoacrylate) chosen is Table 2b In Table 2b the resistance to shear was measured after exposure to electromagnetic radiation and after 1 to 3 minutes; the measurement was repeated after about 24 hours at room temperature. In short, we will say that the measurements of shear resistance performed on the test sets prepared with the composition containing the photoinitiator "I RGACURE" 1 700 (Sample No. 9) showed a relatively small difference between the test sets prepared with substrates that transmitted or absorbed UV. And the shear strength measurements of the test sets constructed with the found within the range of about 97.9% to 99.4% by weight of the composition. A fourth formulation consisted entirely of "PRISM" Adhesive 4061 and was used as control (reference).

The prepared formulations were applied to microscope "s / p" slides (marketed by Baxter Corporation, Deerfield, Illinois), which were then placed in the "ZETA" UV radiation curing chamber 7200. It was then observed that the formulations cured on the glass slides in a period of about 2 to 3 seconds. The formulations were then applied to acrylic substrates, both to the absorbent type and to the UV transmitter type. The formulations were applied to two sets of test samples, in triplicate, to both absorbent and UV transmitter substrates, which were then joined to form the assembled sets of the assay. These assemblies were then placed in the chamber for curing by UV radiation and exposed to UV radiation during the following intervals: 1, 2 and 5 seconds. After that, the test sets were kept at room temperature for a period of close to 1-3 minutes, to finally make the measurements of shear strength of each set. The determinations were made with a Universal Instron, as described in Example 1, supra. The second set of triplicate specimens was allowed to cure at room temperature for a period of about 24 hours. Failures in these specimens can occur either due to failure in the substrate (eg, substrate fracture), failure in cohesion (e.g., where a portion of the photocurable composition is separated due to the forces applied to the surfaces of both substrates) or a failure in adhesion (pTej., where the composition is separated due to the force applied on the surface of a substrate) The first formulation contained approximately 2% by weight of "I RGACURE" 1700, and the UV transmitter test that was exposed to UV radiation for 1 second exhibited a shear strength of about 2552 psi, with adhesive failure and cohesive failure; the corresponding test piece, UV absorbent, exhibited a shear strength of about 864 psi, with cohesive failure. The test piece, UV transmitter, which was exposed to UV radiation for 2 seconds, exhibited a shear strength of about 3292 psi, with adhesive failure and substrate failure; the corresponding test piece, UV absorber, exhibited a shear strength of about 2672 psi, with adhesive failure and failure in the substrate. The UV transmitting test piece that was exposed to UV radiation for 5 seconds exhibited a shear strength of about 291 0 psi, with adhesive failure; the corresponding test piece, UV absorber, exhibited a shear strength of about 1 698 psi, with adhesive failure and substrate failure. The UV transmitting test piece that was exposed to UV radiation for 1 second and then allowed to cure for 24 hours, exhibited a shear strength of about 2572 psi, with adhesive failure; the corresponding test piece, UV absorber, exhibited a shear strength of about 2466 psi, with adhesive failure. It was observed that the UV transmitting test piece that was exposed to UV radiation for 2 seconds and then allowed to cure for 24 hours, did not change with respect to the shear strength; the corresponding test piece, UV absorber, exhibited a shear strength of about 31 98 psi, with failure in the substrate. The UV transmitting test piece which was exposed to UV radiation for 5 seconds and then allowed to cure for 24 hours, exhibited a shear strength of about 381 2 psi, with failure in the substrate; the corresponding test piece, UV absorber, exhibited a shear strength of about 3502 psi, with failure in the substrate. The second formulation contained about 1% by weight of "I RGACURE" 1 700, and the UV transmitting test piece that was exposed to UV radiation for 1 second exhibited a shear strength of about 1272 psi, with adhesive failure; the corresponding test piece, UV absorbent, exhibited a shear strength of about 430 psi, with cohesive failure. The UV transmitting test piece that was exposed to UV radiation for 2 seconds exhibited a shear strength of about 2808 psi, with adhesive failure and cohesive failure; the corresponding test piece, UV absorber, exhibited a shear strength of about 2334 psi, with adhesive failure and failure in the substrate. The UV transmitting test piece that was exposed to UV radiation for 5 seconds exhibited a shear strength of about 2208 psi, with adhesive failure; the corresponding test piece, UV absorbent, exhibited a shear strength of about 1832 psi, with adhesive failure and cohesive failure. The UV transmitting test piece that was exposed to UV radiation for 1 second and then left to cure for 24 hours, exhibited a shear strength of about 2828 psi, with adhesive failure and substrate failure; the corresponding test piece, UV absorber, exhibited a shear strength of about 1742 psi, with cohesive failure. The UV transmitting test piece that was exposed to UV radiation for 2 seconds and then allowed to cure for 24 hours, exhibited a shear strength of about 2808 psi, with adhesive failure and cohesive failure; the corresponding test piece, UV absorbent, exhibited a shear strength of about 2538 psi, with adhesive failure and failure in the substrate. The UV transmitting test piece that was exposed to UV radiation for 5 seconds and then allowed to cure for 24 hours, exhibited a shear strength of about 2004 psi, with cohesive failure; the corresponding test piece, UV absorbent, exhibited a shear strength of about 3524 psi, with failure in the substrate.

The third formulation contained approximately 0.5% by weight of "I RGACURE" 1 700, and the UV transmitting test piece that was exposed to UV radiation for 1 second exhibited a shear strength of about 1776 psi, with adhesive failure; it was observed that the corresponding test piece, UV absorber, had not cured. The UV transmitting test piece that was exposed to UV radiation for 2 seconds, exhibited a shear strength of about 1830 psi, with cohesive failure; the corresponding test piece, UV absorber, exhibited a shear strength of about 654 psi, also with cohesive failure. The UV transmitting test piece that was exposed to UV radiation for 5 seconds exhibited a shear strength of about 2064 psi, with adhesive failure and cohesive failure; the corresponding test piece, UV absorber, exhibited a shear strength of about 904 psi, with adhesive failure and cohesive failure. The UV transmitting test piece that was exposed to UV radiation for 1 second and then allowed to cure for 24 hours, exhibited a shear strength of about 3124 psi, with adhesive failure and substrate failure; again, it was observed that the corresponding test piece, UV absorber, had not cured. The UV transmitting test piece that was exposed to UV radiation for 2 seconds and then allowed to cure for 24 hours, exhibited a shear strength of about 1 830 psi, with cohesive failure; the test piece _ The corresponding UV absorber exhibited a shear strength of about 2820 psi, with adhesive failure and substrate failure. The UV transmitting test piece that was exposed to UV radiation for 5 seconds and then allowed to cure for 24 hours, exhibited a shear strength of about 21 90 psi, with adhesive failure and cohesive failure; the corresponding test piece, UV absorbent, exhibited a shear strength of about 31 28 psi, with failure in the substrate. As the control composition, Adhesive 4061 cyanoacrylate adhesive "PRISM" was applied to both transmitting and UV absorbing test pieces. The exposure of both test pieces (transmitters and UV absorbers) to UV radiation for 5 seconds resulted in shear strength values of about 1 3 and 14 psi, respectively. The values of this order of magnitude reflect, without doubt, that the composition did not cure. After a lapse of about 24 hours at room temperature, the UV transmitting test piece exhibited a shear strength of about 1724 psi, while the test piece, UV absorber, exhibited a shear strength of about 2624 psi .

Example 3 For this example, additional compositions were prepared according to the present invention, which 4 evaluated in terms of their speed of curing, stability and strength of the union. Table 3, below, shows the components of those compositions. Table 3 In Table 3, Cp2 represents dicyclopentadienyl and Py2 represents bis (2-pyridyl). Also, about 50 ppm of BF3 and about 1000 ppm of hydroquinone were added to the ethyl-2-cyanoacrylate to minimize the chances of premature anionic polymerization and free radical formation, respectively. Samples No. 1 1-19 were prepared in the same manner as the samples described in Example 1, supra. Once prepared, about 10 mg of each sample was placed in an aluminum container and exposed to UV radiation emitted by a mercury lamp of intermediate pressure (intensity of 10 mW / cm2 and at a wavelength of 365 nm). The exposure occurred for about 10 minutes under isothermal conditions and at a temperature of about 30 ° C. The data shown below in Table 4, provide information on Samples No. 1 1 -1 9 in relation to its ability to cure when exposed to electromagnetic radiation. The response of these samples was determined with a DuPont 930 Differential Photo Calorimeter ('DPC'), which was connected to a universal Oriel 68805 current source. The induction time and maximum peak time are the UV exposure times required to induce a light curing reaction and to reach a maximum reaction, respectively. These data were measured from the beginning and at the time of the peak of the reaction enthalpy (or exothermic light curing reaction). Higher enthalpies indicate that the sample has a higher reactivity. Of course, a faster curing sample will have a shorter induction time, a peak peak time and a higher enthalpy. For example, Sample 1 1 required 1.1 seconds of UV exposure to induce UV curing, 4 seconds to reach the maximum curing reaction and generated 164 J / G of exothermic heat.

Table 4 As a control, ethyl-2-cyanoacrylate was exposed to UV radiation under the same conditions as the other samples, without a polymerization reaction being observed. Example 4 For comparison purposes, in this example, one-part compositions according to the present invention were prepared using various viscosities and photoinitiating compounds. Table 5 shows the components of these compositions.

Table 5 In Table 5, PM MA represents polymethyl methacrylate. Samples No. 20-24 were also prepared in the same manner as the samples described in Example 1, supra.

Once prepared, about 10 mg of each sample was placed in an aluminum container and exposed to UV radiation emitted by a mercury lamp of intermediate pressure (intensity of 1.0 mW / cm2 and at a wavelength of 365 nm) . The exposure occurred for about 10 minutes under isothermal conditions and at a temperature of about 30 ° C. The data shown below in Table 6, provide information on Samples No. 20-24 regarding its curing capacity when exposed to electromagnetic radiation. The response of these samples was determined with the DuPont 930 DPC. As a control, a sample of ethyl-2-cyanoacrylate thickened with PMMA was exposed to UV radiation and under the same conditions as those of the other samples: no reaction was observed of polymerization. . Table 6 The strength of the binding of the cured reaction product for each sample is included in Table 7, below.

Table 7 Example 5 The photocurable compositions of the present invention can be used in a wide variety of applications. For example, various medical equipment can be manufactured using the compositions of the invention, which includes, although not exhaustively, needles, tubes, masks and catheters. Needles, syringes, lancets, hypoderms, injectors, devices for collecting body fluids (blood, urine), cannula / mouthpiece assemblies and cannula / tube assemblies, such as those used in dialysis operations, constitute only some of the examples of medical needles that could be manufactured with the composition of this invention.

In general, in the manufacture of needles for which a cannula is inserted into a cavity inside the connection mouth and is for fixing there, the application of a predetermined quantity of compositions of the invention and the subjecting of the assembly to UV radiation allows a fast fixation that will cure in the shaded area by means of an ordinary anionic curing mechanism of the cyanoacrylate to achieve a totally strong bond within 24 hours. Moreover, with respect to needle devices that must be tested against all types of unauthorized manipulation and which must have a protective cover, the composition of the invention could be placed at the junction between the cover and the neck, which could be placed a connection mouth. Likewise, and with respect to tubes, devices for intravenous use, application of fluids and games for extractions (for application of medicines and for blood extraction) and suction tubes, are just some of the examples of tubes for medical use that can be manufacture with the composition of this invention. In such cases, the tubes and connectors can be assembled with the composition of this invention if one end of the tube is inserted into the appropriate receptacle of a connector. Avoiding the use of a primer or primer is of particular interest since the solvents used in conventional primer compositions could cause the product to The reaction formed by the conventional reactive adhesive compositions will be brittle and more susceptible to stress fractures. In contrast, the photocurable ability of the compositions of the present invention allows the parts to bond rapidly, which allows the traditional anionically initiated cyanoacrylate curing mechanism to occur without fear of compromising the integrity of the formed bond. Also, facial, anesthetic and surgical masks are just some of the examples of equipment used by medical personnel that could be manufactured with the composition of this invention. Likewise, catheters for balloon angioplasties and catheters are just some of the catheter examples that could be made with the compositions of this invention. Of course, there are other applications for the compositions of the present invention, beyond those specifically exemplified above and contemplated within the scope thereof, including, but not limited to, silk analysis and applications in disk drives; holographic uses where a hologram phase for optical information storage is prepared; Applications in magnetic sensors for door and window alarms, in which a magnet is adhered to the sensor frame using the compositions of the invention so as to fill the free space within the frame; fixing of gauges needles to supports pillars (eg .. in automotive applications); union of pieces that hold cartridges for batteries; speaker assembly [see, eg .. in the context of the "PRISM" adhesive Adhesive 4204 from Loctite, "Beyond a Simple Bond - Benefits of Adhesives Extend to Product and Process" (More than a simple union - The benefits of glues are incorporated into products and processes), Desiqn News (January 20, 1997)] for which the compositions of the invention can be used in at least five aspects of assembly: attachment of the centering spider (which aligns the coil of voice with the magnet) to the frame; fixation of the 'surround' (which connects to the box) to the frame; fixing of cables; Fixing the dust cover to the cone; and fixing the voice coil to the spider and the cone; applications in conjunction with lenses; applications where the occurrence of turbidity and cracking would be aesthetically unacceptable, as is the case in jewelry manufacturing tasks and in repair tasks where it is desirable to have a strip of cured material (as a reaction product of the compositions of the invention) to effect structural assemblies; applications in electronics and other applications where it would be desirable to eliminate the need to use a detonator (which can be expensive, contain products that affect the ozone layer and / or could complicate the assembly process), for example, the fixing of electronic cables, etc.

Also, electronic applications where the release of gases is a constant problem could use the photocurable compositions of this invention to decrease the heating time necessary to obtain a reaction product totally cured from the composition, thus decreasing the generation of gases that otherwise it would happen. Although the present invention has been exemplified as demonstrated above, it is clear that the intention is that the variations also fall within the spirit and scope of the present invention and that it be practiced according to the attached, with routine experimentation, not extraordinary Any variation and its equivalents should provide adequate, if not comparable, results when analyzed in relation to the results obtained with the previous examples. Accordingly, the intention is that such variations and equivalents are also encompassed by the claims mentioned below.

Claims (32)

1. REVIVALATION IS 1 . A composition comprising: (a) a 2-cyanoacrylate component, (b) a metallocene component, and (c) a photoinitiating component. The composition according to claim 1, which includes an amount of polymerizing photoinitiator effective to make it capable of photocuring upon exposure to electromagnetic radiation. 3. The composition according to claim 1, wherein the clanoacrilate component includes a cyanoacrylate monomer represented by H2C = C (CN) -COOR, wherein R can be a group: C1-15 alkyl; alkoxyalkyl; cycloalkyl; alkenyl; aralkyl; aril; allyl or haloalkyl. 4. The composition according to claim 1, wherein the cyanoacrylate monomer is selected from: methyl cyanoacrylate; ethyl-2-cyanoacrylate; propyl cyanoacrylates; butyl cyanoacrylates; octyl cyanoacrylates; allyl-2-cyanoacrylate; β-methoxyethyl-2-cyanoacrylate or combinations thereof. The composition according to claim 1, wherein the cyanoacrylate monomer is ethyl-2-cyanoacrylate. 6. The composition according to claim 1, wherein the metallocene component includes materials within The following structure: wherein R, and R2 may be present at least once in each ring, they may be the same group or two different groups and may be selected from: H; any alkyl, linear or branched, with 1 and up to 8 carbon atoms; acetyl; vinyl; allyl; hydroxyl; carboxyl; - (CH2) n-OH where n can be an integer between 1 and 8; - (CH2) n-COOR3, wherein n can be an integer between 1 and 8 and R3 can be H; Li; Na; any alkyl, linear or branched constituent having between 1 and 8 carbon atoms; or - (CH2) n., where n 'can be an integer between 2 and 8; - (CH ,,) "- OR ,,, wherein n can be an integer between 1 and 8 and R4 can be any alkyl, linear or branched, having between 1 and 8 carbon atoms; and - (CH?) p-N '(CH3) 3 X ", where n can be a number integer between 1 and 8 and X can be Cl ", Br", I ", CI04" or BF4"; Yi and Y2 may or may not be present at all, but when at least one of them is present, the other may be the same or different and may be selected from the groups: H, Cl ", Br *, I", cyano, methoxy, acetyl, hydroxy, nitro, trialkylamines, triarylamines, trialkylphosphines, triphenylamine and tosyl; A and A 'may be the same or different and can be C or N; mym 'can be the same or different and can be 1 or 2, and Me is selected from Fe, Ti, Ru, Co, Ni, Cr, Cu, Mn, Pd, Ag, Rh, Pt , Zr, Hf, Nb, V or Mo. 7. The composition according to the claim 1, wherein the metallocene component includes materials within the following structure: wherein R1 and R2 can be the same group or two different groups and can be selected from: H; any alkyl, linear or branched, with 1 and up to 8 carbon atoms, such as, for example, acetyl; vinyl; allyl; hydroxyl; carboxyl; - (CH2) n-OH where n can be an integer between 1 and 8; - (CH2) n-COOR3, wherein n can be an integer between 1 and 8 and R3 can be any alkyl, linear or branched, having between 1 and 8 carbon atoms; H; Li; Na; or - (CH2) n., where n 'can be an integer between 2 and 8; - (CH2) n-OR4, wherein n can be an integer between 1 and 8 and R4 can be any alkyl, linear or branched, having between 1 and 8 carbon atoms; or - (CH2) n-N + (CH3) 3 X ", where n can be an integer between 1 and 8 and X can be Cl ', Br", I ", CI04" or BF4", and Me is selected from the group consisting of Fe, Ti, Ru, Co, Ni, Cr, Zr, Hf, Nb, V or Mo. The composition according to claim 6, wherein Me is selected from a group consisting of You, Cr, Cu, Mn, Ag, Zr, Hf or Mo 9. The composition according to claim 1, wherein the metallocene component includes materials within the following structure: wherein R, and R2 can be present at least once in each ring, they can be the same or different and can be selected from: H; any alkyl, linear or branched, with 1 and up to 8 carbon atoms; acetyl; vinyl; allyl; hydroxyl; carboxyl; - (CH2) n-OH where n can be an integer between 1 and 8; - (CH2) n-COOR3, where n can be an integer between 1 and 8 and R3 can be H; Li; Na; any alkylic, linear or branched constituent, which has between 1 and 8 carbon atoms; or - (CH2) n., where n 'can be an integer number between 2 and 8; - (CH2) n-OR4, wherein n can be an integer between 1 and 8 and R4 can be any alkyl, linear or branched, having between 1 and 8 carbon atoms; or - (CH2) n-N + (CH3) 3 X ", where n can be an integer between 1 and 8 and X can be selected from Cl", Br, I, CIO, or B F,, Y, and Y2 may or may not be present, but when at least one of them is present, the other may be the same or different and may be selected among the groups: H, Cl ", Br", I ", cyano, methoxy, acetyl , hydroxy, nitro, triacylamines, triarylamines, trialkylphosphines, triphenylamine and tosyl, A and A 'can be the same or different and can be C or N; mym' can be the same or different and can be 1 or 2; and I am selected from Faith, Ti, Ru, Co, Ni, Cr, Cu, Mn, Pd, Ag; Rh, Pt, Zr, Hf, Nb, V or Mo. 1 0. The composition according to claim 9, wherein both R and R2 are H; both Y1 and Y2 are Cl; both A and A 'are N; both m and m 'are 2; Mß is Ru. eleven . The composition according to claim 1, wherein the metallocene is selected from a group consisting of complex metal diarylphosphine ferrocenes, bis-alkyl ferrocenes and Me [CW3-C0-CH = C (0") - CW'3] 2, where Me is Faith, Ti, Ru, Co, Ni, Cr, Cu, Mn, Pd, Ag, Rh, Pt, Zr, Hf, Nb, V or Mo, and W and W can be the same or different, being able The composition according to claim 1, wherein the metallocene component is selected from a group consisting of ferrocenes, titanocenes, as well as their derivatives and combinations thereof, is selected from H and a halogen. 3. The composition according to claim 1, wherein the metallocene is a ferrocene. The composition according to claim 1, wherein the photoinitiator component is one of the following groups: 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 - [4- (methylthio) phenyl] -2-morpholino propane 1 -one, benzophenone, 2-benzyl-2-N, N -dimeti the mino- 1- (4-morpholinophenyl) -1 -butanone, 2,2-dimethoxy-2-phenyl acetophenone), bis (2,6) -di methoxy be nzoi 1-2,4-, 4-trimethyl pentyl) phosphine oxide. 2-hydroxy-2-methyl-1-phenyl-propan-1-ene 2-hydroxy-2-methyl-1-phenyl-1-propane 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide bis (2, 4, 6 -trimethyl benzoyl) phenyl phosphine oxide 2-hydroxy-2-methyl-1-phenyl-propan-1 -one and the photoinitiators with visible light [blue], di-camphorquinone, alkyl pyruvates, aryl pyruvates and combinations of the same. The composition according to any of claims 1-14, wherein the source of electromagnetic radiation is selected from: ultraviolet light, visible light, X-ray, electron beam, infrared radiation or a combination thereof. The composition according to any of claims 1-14, for comprising a member selected from the group consisting of viscosity modifying agents, gum hardening agents, thixotropic agents, thermostabilizing agents and combinations thereof. The composition according to any of claims 1-14, wherein the composition is useful as an adhesive, sealant or coating. 8. A method for polymerizing a photocurable composition, wherein said method comprises the following steps: (a) providing an amount of the composition according to any of claims 1-14 and 17; and (b) subjecting the composition to effective electromagnetic radiation to effect curing of the composition. 9. The composition according to any of claims 1-14 and 17 in a one-part formulation. 20. The composition according to claim 2, wherein the cyanoacrylate component includes ethyl-2-cyanoacrylate present within the range of about 97.9% to 99.4% by weight of the total composition, the metallocene component is ferrocene, present in about 0.1 % by weight of the total composition and the photoinitiator component, includes the combination of bis (2,6-dimethoxybenzoyl-2, 4-, 4-trimethyl) pentyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl -propan-1 -one, which is present in an amount in the order of 0.5% to 2% by weight of the total composition. twenty-one . The composition according to claim 2, wherein the cyanoacrylate component includes ethyl-2-cyanoacrylate present within the range of about 98.71 5% and about 98.75% by weight of the total composition; BF3 in an amount within the range of about 0.04% to 0.075% by weight of the total composition; the metallocene component is ferrocene, present in about 0.02% by weight of the total composition and the photoinitiator component, which includes the combination of bis (2,6-dimethoxybenzoyl-2,4-, 4-trimethyl) pentyl phosphine oxide and -hydroxy-2-methyl-1-phenyl-propan-1 -one, which is present in an amount of the order of 1.2% by weight of the total composition. 22. A reaction product formed from the composition of any of claims 1 -17 and 1 9-21, after exposing the composition to effective electromagnetic radiation so as to effect curing of the composition. 23. An article prepared with a composition according to any of claims 1-17 and 19-21, selected from the group consisting of needles, syringes, lancets, hypoderms, injectors, devices for collection of body fluids, cannula / mouthpiece assemblies and cannula / tube sets, sets of tubes, devices for intravenous use, application of fluids and sets for extractions, suction tubes, anesthesia masks, facial masks and surgical masks, catheters for angioplasties and balloon type catheters, disc unit applications; magnetic sensors; cartridges for batteries; speakers, phase holograms, lenses and jewelry. 24. A method for using a composition according to any of claims 1-17 and 1-9-21 to manufacture an article, selected from the group comprising needles, syringes, lancets, hypoderms, injectors, devices for collecting fluid from the body, cannula / nozzle assemblies and cannula / tube assemblies, sets of tubes, devices for intravenous use, fluid application and extractions kits, suction tubes, anesthesia masks, face masks and surgical masks, catheters for angioplasties and catheters balloon type, applications in disk drives; magnetic sensors; cartridges for batteries; speakers, phase holograms, lenses and jewelry. 25. A method for using a composition according to any of claims 1-17 and 19-21 for repairing an article, selected from the group comprising needles, syringes, lancets, hypoderms, injectors, devices for collection of body fluids, cannula / manhole sets and cannula / tube sets, sets of tubes, devices for intravenous use, fluid application and sets for extractions, suction tubes, anesthesia masks, facial masks and surgical masks, catheters for angioplasty and balloon type catheters, applications in disk units; magnetic sensors; cartridges for batteries; speakers, phase holograms, lenses and jewelry. 26. A method for using a one-part composition, according to claim 1, in the assembly of an article which would normally be assembled by applying a detonator to a substrate followed by an adhesive composition. 27. The composition according to claim 1 6, 17 or 1 9, with a viscosity within the range between 1 and 1.5 cps. 28. The composition according to claim 16, 1 7 or 1 9, with a viscosity within the range between 1 00 and 300 cps. 29. The composition according to claim 16, 17 or 19, with a viscosity within the range between 600 and 1000 cps. 30. The composition according to the claim 26, for use in the manufacture of articles in which the application is carried out by 'refilling'. 31 The composition according to the claim 27, for use in the manufacture of articles having molded polymer parts that must be bonded together. 32. The composition according to claim 28, for use in the manufacture of articles having porous substrates and / or surfaces with a light greater than 12.7 microns between them.