Liquid bis(acyl)phosphine oxide photoinitiator d1492 and its application in radiation-curable compositions

FIELD: chemistry.

SUBSTANCE: claimed invention relates to bis(acyl)phosphine oxide of formula (I) and based on it radiation-curable compositions, which can be applied in the chemical industry: , where R represents C1-C18 alkyl.

EFFECT: claimed are novel effective polymerisation photoinitiators and based on them compositions.

24 cl, 5 ex, 3 tbl

 

The technical field to which the invention relates

The present invention relates to liquid photoinitiators based on bis(acyl)phosphinoxide and to radiation-curable compositions containing these photoinitiators.

The level of technology

Curing irradiation opaque compositions are used in many industries including, but not limited to, materials for fiber optics and coatings for various substrates such as concrete, metal, ceramics, glass, plastic, composites and textiles. Common types of radiation-curable compositions are the compositions, curable via free-radical polymerization. In these compositions the radiation (e.g. UV radiation) is absorbed by the composition with exercise curing or polymerization by generating free radicals. Curing of the composition is carried out using photoinitiators that absorb UV energy, and interact with the generation of free radicals, which in turn, interact with the double bonds in the composition (e.g., acrylate groups) with the formation of new free radicals (i.e., in the form of stages of initiation). The newly formed free radicals then interact with other centers of double bonds in the polymerization or p�pepper cross-linking (i.e., hardening) of the uncured liquid composition at the stage of distribution. Usually, the polymerization reaction is complete when free radicals interact with other free radicals instead of interaction with other active centers with the formation of new free radicals. This stage is usually referred to as the completion stage. In view of the above, it is obvious that the choice of photoinitiator is important to the success of the process of free-radical polymerization.

Review of photoinitiators for UV curing are described in "A Compilation of Photoinitiators Commercially Available for UV Today" by Dr. Kurt Dietliker, of Ciba Specialty Chemicals PLC, SITA Technology Limited (2002), which is incorporated herein by reference in its entirety. In April 2009 Ciba Holding AG was acquired by BASF.

Curable by irradiation of the composition is widely used in the industry of optical fibers and receiving optical fibers, tapes and cables. For example, the optical fiber typically cover at least two radiation-curable coatings directly after the optical fiber is obtained in the device for drawing the fiber in order to maintain the original character of the glass and protect it sufficiently for you to collect on a round spool. Directly after coating on the fiber pokr�Thiais quickly cured by exposure to radiation (usually ultraviolet light). Currently, the industry requires greater productivity and, for this reason, more high-curable opaque compositions.

Cured by the irradiation of materials for exterior coatings for the matrix and beam formation could further support and protect individual filament fibers coated when individual threads come together in a ribbon of optical fibers, cables, optical fibers and associated structures. In addition, radiation-curable inks can be used for color marking of individual strands of optical fiber. All of these types of materials relating to optical fibers, are cured by irradiation, and can serve as materials for coatings and/or cables.

Examples of radiation-curable inner primary coating is described in U.S. patent No. 5336563, Coady et al., and outer primary coatings (e.g., secondary coatings) in U.S. patent No. 4472019, Bishop et al. Additional aspects of coating technology for optical fibers is described, for example, in U.S. patents №№ 5595820, Szum; 5199098, Nolan et al.; 4923915, Urruti et al.; 4720529, Kimura et al.; and 4474830, Taylor et al., each of which is incorporated herein by reference in its entirety.

The following applications for U.S. patent describing and claiming illustrative curable about�teaching coverts composition, included as references in their entirety: application for a U.S. patent 11/955935, filed December 13, 2007, published as US 20080226916 September 19, 2008; application for U.S. patent 11/955838, filed December 13, 2007, published as US 20080241535 October 23, 2008; application for U.S. patent 11/955547, filed December 13, 2007, published as US 20080226912 September 19, 2008; application for U.S. patent 11/955614, filed December 13, 2007, published as US 20080226914 September 19, 2008; application for U.S. patent 11/955604, filed December 13, 2007, published as US 20080226913 September 19, 2008; application for U.S. patent 11/955721, filed December 13, 2007, published as US 20080233397 25 September 2008; patent application U.S. 11/955525, filed December 13, 2007, published as US 20080226911 19 September 2008; patent application U.S. 11/955628, filed December 13, 2007, published as US 20080226915 September 19, 2008; and application for U.S. patent 13/955541, filed December 13, 2007, published as US 20080226909 19 September 2008.

Curable by irradiation of coating materials are used as coatings for concrete and metal. UV-curable coatings for concrete are discussed, for example, in the article "UV Curable Concrete Coatings", Jo Ann Arceneaux, Ph. D., Cytec Industries Inc., Smyrna, Georgia, presented at Federation of Societies for Coatings Technology, "Coatings for Concrete Conference: "coating the World of Concrete", on 2 February 2009 at the Westin Casuarina Las Vegas Hotel in Las Vegas, Nevada, and in the article, "Field-Applied, UV-Curable Catings for Concrete Flooring," by Peter T. Weissman, published in the January/February/March 2009 RADTECH Report.

Cover UVoive® Instant Floor Coatings (available from DSM) are providing high performance coating systems with fast curing for concrete floors that have the following features and benefits:

- the ability to virtually instant cure makes possible a direct passage - even forklifts;

is a one - component system without mixing, without limitation to a life in a cooked condition or without by-products;

- utverjdenie coating protects concrete against damage under dirt, wear and chemicals; and

- the cured coating UVoive® Instant Floor Coatings are easy to clean - especially from traces tire forklifts.

The use of radiation-curable coatings for concrete floors means that maintenance costs will be lower due to the simplicity of cleaning. Cover UVoive® Instant Floor Coatings are VOC, zero value (the concentration of volatile products do not contain solvents and are 100% solids. Cover UVoive® Instant Floor Coatings are cured with getting a shiny, durable finish, which shows excellent resistance to recarpeting and impacts. They are available in both transparent and pigmented systems and ocvered�tsya instantly when using the device for irradiation of UV light, specially designed for use with UVoive® Instant Floor Coatings. See: http://www.uvolvecoatings.com.

Cover UVaCorr® Corrosion-Resistant UV Coatings for Tube & Pipe (products UVaCorr®, available from DSM) are a high performance radiation-curable coating systems used to improve the corrosion resistance of pipes and pipelines. Cover UVaCorr® are available in both transparent and colored coatings and are used to protect pipes and pipelines during storage and transportation. Product line UVaCorr®, now certified for use in the system Venjakob™ Ven Spray Pipe (trade name Venjakob), provides several advantages in performance compared to conventional coatings for pipes and piping, solvent-based and water, including: instant curing for high speed machining; coating with 100% solids for a higher level of coverage when applying and no VOC; best resistance to salt spray, to improve performance; and less need for equipment at lower energy requirements. See: http://www.dsm.com/en_US/html/dsmd/uvention_tube.htm

To reach the maximum speed of curing when curing with UV light is required, at least one photoinitiator (�toinitiate may not be needed during curing, electron beam). To obtain the appropriate balance of surface and bulk curing you can use several photoinitiators. For further discussion of the use of several photoinitiators, see U.S. patents Nos. 6438306 and 7276543. When the radiation-curable composition of the present invention there are several photoinitiators, as found suitable for use are the regular classes of photoinitiators.

You can use solid photoinitiators type of monoolefinic, such as LUCIRIN™ TPO (2,4,6-trimethylbenzoyl)diphenylphosphine), commercially available from BASF, which shows the relatively high curing rate. However, the use of solid commercial LUCIRIN™ TPO can cause unwanted effects of crystallization in opaque compositions (e.g., during aging), which can lead to clogging and loss of optical transparency (apparently detected under a light microscope).

Certain photoinitiators are known to cause yellowing, in particular, during long-term aging of the cured compositions under conditions of photolytic aging (e.g., UV or fluorescent light). Heat can also cause yellowing. Change the overall color and yellowing in particular, is undesirable and rejected in industrial�items. Therefore, a photoinitiator, which would not give harmful crystalline effects and continue to provide rapid curing, but it led to yellowing, does not satisfy sufficiently the most stringent industry requirements.

Attempts to use purified LUCIRIN™ TPO, but are costly purification step. Other solid photoinitiators based phosphine oxides (for example, CGI 403, Ciba) can show a less harmful effect crystallization, but they may also have a lower curing rate. Consequently, it is desirable to obtain photoinitiators that can provide both a high curing rate and good optical clarity.

Other desirable properties of performance for curable by irradiation environments include: to be a liquid at ordinary temperatures and have a sufficiently low viscosity for excellent coating; to provide high performance at high speed curing; provide sufficient strength and superior flexibility; demonstrate very little physical change during temperature changes within wide limits; to provide superior heat resistance and superior resistance to hydrolysis; show long-term reliability with a small Fi�demand changes over time; show excellent resistance to chemicals, such as acids and alkalis; to exhibit low moisture absorption and water; demonstrate excellent resistance to light, showing the smallest possible color change/fading over time; and demonstrate high resistance to oils. In addition, the increased need for processing speed of the cured materials makes it necessary coverts composition, which should be cured quickly stable manner. Thus, for faster curing materials applied as a coating, to be used a photoinitiator (photoinitiators), which decomposes quickly.

On the filing date of the present application, in this area, there were no photoinitiator, which provides an excellent balance of all these critical properties. For example, a large number of photoinitiators based phosphine oxides described, for example, in U.S. patents №№ 5218009, Rutsch et al. and 5534559, Leppard et al. However, these patents do not suggest any specific types of photoinitiators that would address the above problems and provide an excellent balance of properties.

Lined patent application of Japan No. 190712/1989 describes a composition comprising acylphosphatase as a composition of a photo-curable resin, which realizes high performance with fast ocvered�research Institute. However, this composition does not necessarily cured with a sufficiently high speed so as to sufficiently increase the productivity of optical fibers, while maintaining at the same time, the characteristics required for the coating material for optical fibers.

Another composition containing bis-acylphosphatase proposed in laid the patent application of Japan No. 259642/1996 as composition fotoallergiyami resin, which exhibits high performance by curing at a high speed. However, bis-acylphosphatase containing long-chain aliphatic group as described in the patent application of Japan, has a poor solubility in the resin compositions and, therefore, can not dissolve in the resin compositions in an amount sufficient to ensure a high cure speed.

The U.S. patents Nos. 6136880 and 6359025 and the application for European patent EP 0975693, Snowwhite et al., describe radiation-curable composition for optical fibers containing solid type photoinitiators bis-acylphosphatase (BAPO).

Bis-acylphosphatase (i.e., bis(2,4,6-trimethylbenzoyl)phenylphosphine) (BAPO) is a very strong photoinitiator when sitoindosides polymerization of ethylene-unsaturated compounds in radiation-curable compositions. It has a higher coefficient of pogles�tion, than acylphosphatase such as TPO or TPO-L, and thus, as a rule, leads to superior speed fototerapia. However, BAPO is a solid product having a low solubility in a wide variety of monomers and oligomers, which limits its use in some applications.

In an attempt to overcome the drawbacks of solid BAPO, reported liquid mixtures of photoinitiators with BAPO (bis-allfashion (BAP). For example, see "Liquid Bis-Acylphosphint Oxide (BAPO) Photoinitiators" by C. C. Chiu from Chitec Technology, presented at RADTECH 2010 Monday 24 may 2010.

The report Chiu described liquid mixture BAPO and BAP (collectively known as "LMBAPO"). Although a liquid mixture of BAPO photoinitiators and BAP (i.e., LMBAPO) usually has the properties of cured films, similar to solid BAPO, LMBAPO suffers from poor chemical stability, which limits its industrial application.

Thus, there is still not satisfied the need for photoinitiators suitable for radiation-curable compositions, demonstrating the critical balance of performance properties, including the existence in the liquid state for radiation-curable compositions.

Summary of the invention

In the first variant of implementation, the present invention provides a liquid bis(acyl)phosphinoxide of formula (I):

where R is a C1-C18alkyl and where R is optionally substituted.

In the second variant of implementation, the present invention provides a radiation-curable composition containing a liquid bis(acyl)phosphinoxide of formula (I).

In the third variant of implementation, the present invention provides a bis(acyl)phosphinoxide of formula (I):

where R is a C1-C18alkyl and where R is optionally substituted, this bis(acyl)phosphinoxide is liquid at 20°C.

In the fourth embodiment of the present invention provides a bis(acyl)phosphinoxide of the third embodiment, where R is a C1-C6alkyl and where R is preferably selected from the group consisting of methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl and hexyl.

In the fifth variant implementation, the present invention provides a bis(acyl)phosphinoxide of the third embodiment, where R is a C1-C3alkyl and where R is preferably selected from the group consisting of methyl, ethyl and n-propyl, more preferably, R represents ethyl.

In the sixth variant implementation, the present invention provides a radiation-curable composition containing a bi�(acyl)phosphinoxide according to any one of the third - the fifth embodiments and at least one component that is polymerizable by free radical mechanism.

In the seventh variant implementation, the present invention provides a radiation-curable composition of the sixth embodiment, where the specified composition selected from the group consisting of a covering composition for optical fibers and coating compositions suitable for radiation curing, the concrete and coating compositions suitable for radiation curing, on the metal.

In the eighth variant implementation, the present invention provides a covering composition for optical fibers of the seventh embodiment where the covering composition for optical fibers selected from the group consisting of a primary coating, secondary coating, the coating containing paint, exterior coating, a buffer coating and a matrix coating.

In the ninth variant implementation, the present invention provides a radiation-curable composition according to any one of the sixth to eighth embodiments, where the composition is cured using UV light generated by a conventional UV light source.

In the tenth version of the implementation, the present invention provides a radiation-curable composition according to any one of sixth�wow - ninth embodiments, where the composition is cured by means of light generated by the light source based on LED (led).

In the eleventh variant implementation, the present invention provides a radiation-curable composition according to any one of the sixth to tenth embodiments, where the composition further comprises at least one additional photoinitiator.

In the twelfth variant implementation, the present invention provides a radiation-curable composition of the eleventh embodiment, where at least one additional photoinitiator is selected from the group consisting of photoinitiators, which are solid at 20°C, and photoinitiators, which are liquid at 20°C.

In the thirteenth variant implementation, the present invention provides a radiation-curable composition of the twelfth embodiment, where the solid photoinitiators selected from the group consisting of 4-methyl benzophenone, p-phenylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenylamine, 4,4'-(tetracycline)benzophenone, 4,4'-(tetracycline)benzophenone, benzophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one, 1-hydroxycyclohexanone, 2,2-dimethoxy-2-Hairdryer�of acetophenone, 4-2-hydroxyethoxy)phenyl-(2-propyl)ketone, comparison and 2,4,6-trimethylbenzene.

In the fourteenth variant implementation, the present invention provides a radiation-curable composition of the twelfth embodiment, where the liquid photoinitiators selected from the group consisting of 2,4,6-(trimethylsiloxy, phenylphosphine)oxide, diethoxyacetophenone, 2-hydroxy 2-methyl-1-phenyl-propane-1-she, methylphenylglycidate and acelerando benzophenone.

In the fifteenth variant implementation, the present invention provides a radiation-curable composition of the twelfth embodiment, where at least one additional photoinitiator is a bis(acyl)phosphine.

In the sixteenth variant implementation, the present invention provides a radiation-curable composition of the twelfth embodiment, where at least one additional photoinitiator is a stable bis(acyl)phosphine.

Detailed description of the invention

In this application, the following abbreviations have the indicated meanings:

A-189γ mercaptopropionylglycine, available from Momentive
ACCLAIM 4200 the polypropylene glycol, MW = 4200, available from Bayer
BAPbis(acyl)phosphine
BAPObis(acyl)phosphinoxide
BHT2,6-di-tert-butyl-4-METHYLPHENOL, available from Fitz Chem.
DBTDLdibutylamino dilaurate, available from OMG Americas
HEAhydroxyethylacrylate, available from BASF
1RGACURE 819bis(2,4,6-trimethylbenzoyl)phenylphosphine, available from Ciba Specialty Chemicals (now owned by BASF)
IRGANOX 1035teotitlan bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) available from Ciba, Inc. (now owned by BASF)
LMBAPOA mixture of bis(acyl)phosphinoxide and bis(acyl)phosphine
MONDIJR TDS100% 2,4-isomer of toluene diisocyanate, available from Bayer
SR-339A2-phenoxyethylacrylate
SR-349ethoxylated (3) bisphenol diacrylate, available from Sartomer
SR-504D ethoxylated nonylphenolic, available from Sartomer
TINUVIN 123bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, available from Ciba, Inc. (now owned by BASF)
TPO2,4,6-
TPO-L2,4,6-(trimethylsiloxy, phenylphosphine)oxide

In this description uses a number of terms that are well known to specialists in this field. However, for purposes of clarity will be determined by the number of terms.

As used herein, the term "unsubstituted" means that no Deputy or that the only substituents are hydrogen atoms.

"Acyl" means an alkyl group-CO-or a group aryl-CO where the alkyl or aryl group is as described herein, examples of acyl include acetyl and benzoyl. The alkyl group preferably represents C1-C6alkyl or optionally substituted aryl group. The group may represent an end group or a bridging group.

"Alkoxy" refers to-O-alkyl group in which alkyl is defined herein. Preferably, alkoxy is C1-C6al�oxy. Examples include, but are not limited to methoxy and ethoxy. The group may represent an end group or a bridging group.

"Alkyl" as a group or part of a group refers to straight or branched aliphatic hydrocarbon group, preferably, to the C1-C18the alkyl, more preferably C1-C12the alkyl, more preferably C1-C9the alkyl, most preferably C1-C6unless noted otherwise. Examples of corresponding straight and branched C1-C6alkyl substituents include methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl, hexyl, and the like. The group may represent an end group or a bridging group.

"Alkylthio" refers to the group-SR, in which R represents an alkyl group, as defined herein. The group may represent an end group or a bridging group.

"Aryl" as a group or part of a group, means (i) optionally substituted monocyclic or condensed polycyclic, aromatic carbocycle (ring structure having ring atoms that are all carbon atoms), preferably having from 5 to 12 atoms per ring. Examples of aryl groups include phenyl, naphthyl, and the like; (ii) optionally substituted �aztechno saturated bicyclic aromatic carbocyclic residue, in which phenyl and C5-C7cycloalkyl or C5-C7cycloalkenyl groups are condensed with the formation of cyclic structures, such as tetrahydronaphthyl, indenyl or indanyl. The group may represent an end group or a bridging group. Other illustrative aryl groups described herein.

"Halogen" represents chlorine, fluorine, bromine or iodine.

"Heteroalkyl" refers to premiani or branched alkyl group, preferably having from 2 to 14 carbon atoms, more preferably from 2 to 10 carbon atoms in the chain, one or more of them are replaced by a heteroatom selected from S, O, P and N. the Illustrative heteroalkyl include simple alkyl ethers, secondary and tertiary alkyl amines, amides, alkylsulfate, and the like. The group may be a terminal group or a bridging group. As used herein, reference to the conventional circuit, when it is used in relation to the bridging group, refers to straight chain of atoms connecting the two end positions of the bridging group.

"Heteroaryl" either by itself or as part of a group, refers to groups containing an aromatic ring (preferably 5 - or 6-membered aromatic ring) having one or more heteroatoms as calcev�x atoms on the aromatic ring with the remaining ring atoms are carbon atoms. Corresponding heteroatoms include nitrogen, oxygen and sulfur. Examples of heteroaryl include thiophene, benzothiophene, benzofuran, benzimidazole, benzoxazole, benzothiazole, benzisothiazole, naphto[2,3-b]thiophene, furan, isoindole, santolan, phenoxathiin, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, isoindole, 1H-indazole, purine, quinoline, isoquinoline, phthalazine, naphthiridine, quinoxaline, cinnoline, carbazole, phenanthridine, acridine, fenesin, thiazole, isothiazol, phenothiazines, oxazol, isooctanol, furazan, phenoxazine, 2-, 3 - or 4-pyridyl, 2-, 3-, 4-, 5- or 8-chinolin, 1-, 3-, 4 - or 5-ethenolysis, 1-, 2 - or 3-indole and 2 - or 3-thienyl. The group may represent an end group or a bridging group.

The authors found that the liquid bis(acyl)phosphinoxide of formula (I):

where R is a C1-C18alkyl and where R is optionally substituted, is liquid at 20°C. the Presence of a liquid bis(acyl)phosphinoxide of formula (I) eliminates the disadvantages of solid photoinitiators.

Bis(acyl)phosphinoxide photoinitiators of formula (I) are liquid, thereby the drawbacks of solid photoinitiators (for example, ΒAΡΟ sold commercially as IRGACURE® 819 of Ciba (now owned by BASF), which is a solid product). For example, liquid bis(acyl)phosphinoxide� photoinitiators of the present invention demonstrate the ease of handling, good compatibility with resins and pigments, no problems with crystallization and the dangers of fine dust.

The authors found that the liquid bis(acyl)phosphine photoinitiators of formula (I) can be incorporated into radiation-curable covering composition for optical fibers and cured by irradiation coverts composition suitable for radiation curing, the concrete and curing irradiation opaque compositions suitable for radiation curing, on the metal.

Adhering to one of the embodiments of the present invention, the group R in bis(acyl)phosphine of formula (I) represents C1-C18alkyl, where R is optionally substituted.

The authors found that bis(2,4,6-trimethylbenzoyl)phosphine oxides of the formula (I) containing C1-C18alkyl group which is optionally substituted, provide a photoinitiator in a liquid state.

In some embodiments, the group R of the compound of formula (I) is optionally substituted by one or more substituents. Appropriate substituents include, for example, alkyl groups, aryl groups (e.g. phenyl), heteroalkyl group and heteroaryl group. As an example, when the aryl group is a phenyl, the phenyl group can�t have the following structure:

where each substituent is Ancan independently represent any substituent selected from the group consisting of a hydrogen atom, C1-C6alkyl, C1-C6alkylaryl, C1-C6alkoxy, C5-C10aryl, alkylaromatic, alkyloxyaryl, heteroalkyl, heteroaryl, heteroatomic and halogen, and wherein n represents the number of substituents on A phenyl ring and n is an integer from 0 to 5 (i.e., up to the maximum number of centers of substitution on the phenyl group, which is mono-, di-, tri-, Tetra - or Penta-substituted, as needed. In addition, the phenyl group optionally are substituted in any suitable position, for example, are ortho-, meta-, para-substituted.

The person skilled in the art will notice that the value of n varies with the Deputy.

In one of variants of implementation, where the group R is substituted, each substituent can independently be any Deputy selected from the group consisting of a hydrogen atom, C1-C6alkyl, C1-C6alkylaryl, C1-C6alkoxy, C5-C10aryl, alkylaromatic, alkyloxyaryl, heteroalkyl, heteroaryl and heteroatomic, and n is from 1 to the maximum number of Centro� of substitution, demand.

The corresponding C1-C6alkyl substituents include, for example, linear and branched C1-C6alkyl groups, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neo-pentyl, hexyl, isohexyl, second-hexyl, neo-hexyl, and the like.

As an illustration, appropriate substituents include groups, which selects the electron, including, but not limited to, Halogens, nitrile group and a carbonyl group. Furthermore, respective substituents also include groups, donating an electron, including but not limited to, hydroxy group and amino group, including substituted amino groups (e.g., -NHR, and-NHR2where R represents an alkyl group).

The corresponding aryl groups and heteroaryl groups include phenyl group, naftalina group, antarctilyne group, fornillo group, benzofuranyl group, isobenzofuranyl group, pyrrolidino group, pyridyloxy group, personilnya group, pyrimidinyl group, pyridazinyl group, indolenine group, isoindolyl group, imidazolidinyl group, pyrazolidine group, hyalinella group, athinodorou group, chinoxalin group, chinazoline group, sinolinding, Teofilo group, benzothiazoline group, criminology group, benzimidazolyl group, indazolinone group, benzoxazolyl group, benzisoxazole group, benzothiazolyl group, parinello group, and benzo[c]Teofilo group.

In one embodiment, the implementation of the aryl group is a phenyl group, naftalina group or antarctilyne group.

In one of the embodiments of the aryl group and/or heteroaryl group is substituted. Illustrative of the substituted aryl group represents, for example, substituted phenyl group. The appropriate substituted phenyl groups include methylphenyl group, ethylphenyl group, dimethylphenyl group, trialkyltin group, isopropylphenyl group, tert-butylphenyl group, methoxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, diethoxyaniline group, isopropoxyphenyl group and dimethoxyaniline group.

In one embodiment, the implementation trialkyltin group is trimethylaniline group.

In another embodiment of trimethylaniline group is a 2,4,6-trimethylphenyl group.

The corresponding alkyl groups include C1-C18alkyl group, C1-C12alkyl�s group, C1-C9alkyl group, C1-C6alkyl groups and C1-C3alkyl groups, as is well known to specialists in this field.

Relevant heteroalkyl the group include alkoxygroup or allylthiourea, where alkoxy - or allylthiourea is optionally substituted.

In one of the embodiments, heteroalkyl group is alkoxygroup. Relevant alkoxygroup include, for example, C1-C18-alkoxygroup. In one of the embodiments, alkoxygroup selected from C1-C12-alkoxygroup, or C1-C9-alkoxygroup, or C1-C6-alkoxygroup or C1-C3-alkoxygroup. Illustrative C1-C18-alkoxygroup. Illustrative alkoxygroup include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, Deut-butoxy, pentox, hexose, heptose, actoxy, nonoxy, decoke, undecane and dodecane.

In one embodiment, the implementation heteroalkyl group is allylthiourea. Illustrative ancilliary include, for example, C1-C6-alkylthio, such as methylthio, ethylthio and propylthio. In one of the embodiments, allylthiourea represents C1-C18-alkylthio.

Bis(acyl)phosphine oxides according to the present �the turbine zobretenie can be synthesized using any suitable method, known to the person skilled in the art. The proposed scheme of the synthesis is depicted herein in figure 1. Without any desire to be limited to the specific synthesis of bis(acyl)phosphine oxides of the present invention can be obtained by converting solid BAPO (1) illustrative bis(acyl)phosphine oxides of the present invention (e.g., compound (2); Scheme 1).

Scheme 1

In another embodiment, the implementation, the present invention provides a radiation-curable composition containing a bis(acyl)phosphinoxide, as described herein.

Curable by irradiation of the composition of the present invention contain at least one component that is polymerizable by free radical mechanism. As the polymerizable by free radical mechanism component, radiation-curable compositions of the present invention typically contain an acrylate group. Other relevant polymerizable by free radical mechanism components include, for example, methacrylate group, acrylamide, methacrylamide, vinylamine, groups of simple vinyl ether and other ethylene-unsaturated residues, known to specialists in this field.

In one of the embodiments, the present invention preduster�describes radiation-curable covering composition for optical fibers containing bis(acyl)phosphinoxide of formula (I) and at least one component that is polymerizable by free radical mechanism. Covering composition for optical fibers of the present invention can be any suitable for use covering composition for optical fibers. In one of variants of implementation, covering composition for optical fibers selected from the group consisting of a primary coating, secondary coating, the coating containing paint, exterior coating, a buffer coating and a matrix coating.

In another embodiment, the implementation, the present invention provides a radiation-curable coverts composition suitable for radiation curing, the concrete containing bis(acyl)phosphinoxide of formula (I) and at least one component that is polymerizable by free radical mechanism.

Commercially available radiation-curable coverts composition for concrete is known to the person skilled in the art. For example, look http://www.uvolvecoatings.com/.

In another embodiment, the implementation, the present invention provides a radiation-curable coverts composition suitable for radiation curing on metal containing bis(acyl)phosphine of formula (I) and at least one component that is polymerizable by free radical mechanisms�.

Conventional opaque compositions for metal known to specialists in this field. For example, look http://www.dsm.com/en_US/html/dsmd/uvention_tube.htm.

In one of the embodiments, the present invention provides a radiation-curable covering composition for optical fibers or radiation-curable opaque compositions suitable for radiation cure on concrete and coating compositions suitable for radiation curing on metal, where the compositions contain at least one component that is polymerizable by free radical mechanism, and a combination of at least two photoinitiators, where at least one photoinitiator is a bis(acyl)phosphinoxide of formula (I) and at least one photoinitiator is a conventional photoinitiator (for example, 2,4,6-trimethylbenzoyl)phenylphosphine), or consists of them.

If you stick to one aspect of the present invention, radiation-curable composition is a liquid. In one of the embodiments, the combination of bis(acyl)phosphinoxide of formula (1) and a conventional photoinitiator is a liquid at a temperature higher than about 15°C.

As used herein, the term "about" means ±10% of set value.

Curable by irradiation coverts com�osili of the present invention are designed to be cured using a conventional UV radiation. However, it may be desirable curing ready claimed coverts compositions using light from a light emitting diode (LED). The authors develop a covering compositions which are curable under the action of light generated by the LED source.

The use of ultraviolet mercury arc lamp for emitting ultraviolet light suitable for curing radiation-curable coatings applied to the optical fiber, is well known. UV arc lamps emit light by using an electric arc discharge for excitation of mercury that is in the environment of inert gas (e.g., argon), for generating ultraviolet light, which carries the cure. Alternatively, you can also use microwave energy to excite mercury lamps in an inert gas to generate ultraviolet light. In the present patent application is filed arc discharge excited by microwave radiation of a mercury lamp, plus modified forms of these mercury lamps with various additives (metallic iron, gallium, and the like) are defined as mercury lamps.

However, the use of ultraviolet mercury lamps as the radiation source suffers from several disadvantages, including the problem�s environment because of the mercury and the generation of ozone as a byproduct. In addition, mercury lamps typically have a lower energy conversion factor, require some time to heat up, produce heat during operation, and consume large amounts of energy compared to LED. In the production of optical fibers with a coating of heat generated by a mercury UV lamps, can adversely affect the liquid coating so that if the coating prepared with the exception of the presence of volatile products, these volatile products may be brought and deposited on the surface of the quartz tube, blocking the irradiation with UV liquid coating on the fiber that slows down the curing of the liquid coating to a solid state. In addition to this, mercury lamps have a broad spectrum of the output, in addition to UV radiation, and a large part of this spectrum is not suitable for curing and can damage the substrate, and is a danger to personnel.

Accordingly, we investigate alternative sources of radiation.

The light emitting diodes (LED) are semiconductor devices which use the phenomenon of electroluminescence to generate light. LED consists of a semiconductor material doped with impurities to produce the p-n junction capable of emitting light when positive holes interact with negative� electrons, when applied voltage. Wavelength of emitted light is determined by the materials used in the active region of the semiconductor. Typical materials used in semiconductors LED, include, for example, elements of Group 13 (III) and 15 (V) of the Periodic table. These semiconductors are referred to as semiconductors III-V and include, for example, semiconductors GaAs, GaP, GaAsP, AlGaAs, InGaAsP, AlGaInP and InGaN. Other examples of semiconductors used in LED, include compounds from Group 14 (IV semiconductor-IV) and Group 12-16 (II-VI). The choice of materials is based on many factors, including the desired wavelength of emission, the parameters of performance and cost.

Early LED used gallium arsenide (GaAs) for emitting infrared (IR) radiation and red light of low intensity. Progress in materials science has led to the development of LED, capable of emitting light with higher intensity and shorter wavelengths, including other colors of visible light and UV light. You can create a LED that emit light over the entire range, starting from about 100 nm to about 900 nm. Currently known sources of UV light based on the LED emit light with wavelengths in the range between about 300 and about 475 nm, and the common peak spectral output at 365 nm, 390 nm and 395 nm. Smot�and guide "Light-Emitting Diodes" by E. Fred Schubert, 2ndEdition, © E. Fred Schubert 2006, published by Cambridge University Press. If you use lamps based on LED for curing covering composition, a photoinitiator in the coverts of the composition is selected so that it was sensitive to the wavelength of light emitted by the lamp based on LED.

Lamps based on LED advantages compared to mercury lamps in applications for curing. For example, the lamp based on LED does not use mercury to generate UV light and, as a rule, are far less than the mercury arc UV UV lamp. In addition, the lamp based on LED sources are instant on/off without requiring warm-up time, which contributes to low energy consumption lamps based on LED. Lamps based on LED also generate much less heat, higher efficiency of energy conversion, have a longer life time of the lamps, and are mostly monochromatic, emitting a desired wavelength of light, which is determined by the choice of semiconductor materials used in LEDs.

Several manufacturers offer lamps-based LEDs for commercial applications during curing. For example, Phoseon Technology, Summit UV, Honle UV America, Inc., IST Metz GmbH, Jenton International Ltd., Lumios Solutions Ltd., Solid UV Inc., Seoul Optodevice Co., Ltd, Spectronix Stock Corporation, Luminus Devices Inc. and Clearstone Technologies, are some �W manufacturers, offering lamps based on LED for curing compositions for inkjet printing of PVC-compositions for flooring, opaque compositions for metals, plastic coating compositions and compositions of adhesives.

Curing using LED radiation-curable coatings for optical fiber describe and claim in the temporary patent application U.S. 61/287567, filed December 17, 2009, and PCT International application PCT US2010/60652, filed December 16, 2010, both entitled "D1429 BT LED Curing of Radiation Curable Optical Fiber Coating Compositions", both of which are incorporated herein by reference, in their entirety.

In one of the embodiments of the present invention provides a radiation-curable composition, where the composition is cured under UV-light generated using a conventional UV light source.

In another embodiment of the present invention provides a radiation-curable composition, where the composition is cured by means of light generated by the light source based on LED.

In one of the embodiments of the present invention provides a radiation-curable covering composition for optical fibers. As used herein, a coating for optical fiber" refers to the primary coating (t� is, inner primary coatings), secondary coatings (i.e., outer primary coatings), coatings containing paint, external coatings, matrices, coatings and materials for receiving cables (to link to the beams). Covering composition for optical fibers of the present invention contains at least one radiation-curable oligomer, at least one radiation-curable monomer diluent, at least one liquid bis(acyl)phosphine of the photoinitiator of formula (I) and additives, or consists of them. Details about curing irradiation opaque compositions for optical fibers is described, for example, in U.S. patent No. 6136880, Snowwhite et al., which is incorporated herein by reference in its entirety.

Examples of radiation-curable inner primary coating is described in U.S. patent No. 5336563, Coady et al., and outer primary coatings (e.g., secondary coatings) - U.S. patent No. 4472019, Bishop et al. Additional aspects of coating technology for optical fibers is described, for example, in U.S. patents №№ 5595820, Szum; 5199098, Nolan et al.; 4923915, Urruti et al.; 4720529, Kimura et al.; and 4474830, Taylor et al., each of which is incorporated herein by reference in its entirety.

The article "UV-CURED POLYURETHANE-ACRYLIC COMPOSITIONS AS HARD EXTERNAL LAYERS OF TWO-LAYER PROTECTIVE COATINGS FOR OPTICAL FIBRES", written by W. Podkoscielny and . Tarasiuk, Polim.Tworz.Wielk, Vol. 41, Nos. 7/8, p. 448-55, 1996, NDN-131-0123-9398-2 describes an optimization study of the synthesis of UV-curable urethane-acrylic oligomers and their use as hard protective coatings for optical fibers. Received in Poland oligotherapy, diethylene glycol, colorvision (Izocyn T-80) and the diisocyanate, in addition to the hydroxyethyl - and hydroxypropyl-(meth)acrylates, are used for the synthesis. Active solvents (butyl, 2-ethylhexylacrylate and 1,4-potentialability or mixtures thereof) and 2,2-dimethoxy-2-phenylacetophenone added as photoinitiators to these urethane-acrylic oligomers, which are active in the polymerization of the double bond. Composition of UV-irradiated in an atmosphere containing no oxygen. IR spectra of the compositions are recorded, and some of the physical and chemical and mechanical properties (density, molecular weight, viscosity as a function of temperature, refractive index, gel content, glass transition temperature, shore hardness, young's modulus, tensile strength, elongation at break, heat resistance and the diffusion coefficient of water vapor) is determined before and after curing.

The article "PROPERTIES OF ULTRAVIOLET CURABLE POLYURETHANE-ACRYLATE", written by M. Koshiba; K. K. S. Hwang; S. K. Foley; D. J. Yarusso; and S. L. Cooper; published in J. Mat. Sci., 17, No. 5, May 1982, p. 1447-58; NDN-131-0063-1179-2; describes the research that is carried out about �of otnosheniya between chemical structure and physical properties of UV-curable polyurethane-acrylates based isophorondiisocyanate and TDI. Prepare two systems with different molecular weight soft segment and with different content of agent for crosslinking. The results of dynamic mechanical studies show that it is possible to obtain one - or two-phase materials, depending on the molecular weight of soft segment. When the last parameter is increased, the Tg of the polyol is shifted towards lower temperatures. The increase in the use of either N-vinylpyrrolidone (NVP), or diacrylate of polyethylene glycol (PEGDA) causes an increase of the young's modulus and ultimate tensile strength. Cross stitching NVP increases the strength of two-phase materials, and high temperature peak shifts the Tg to higher temperatures, but PEGDA does not cause such effects. The properties of the two systems at break properties are broadly similar.

Generally, in the production of radiation-curable coatings for use on optical fiber, to obtain a urethane oligomers using isocyanates. In many references, including U.S. patent No. 7135229, "RADIATION-CURABLE COATING COMPOSITION", issued on 14 November 2006, DSM IP Assets B. V., (column 7, lines 10-32) provides for the concept intended to guide the person skilled in the art how to synthesize urethane oligomers: the polyisocyanates suitable for use in obtaining compositions �of the present invention, can be aliphatic, cycloaliphatic or aromatic and include diisocyanates, such as 2,4-colorvision, 2,6-colorvision, 1,3-silenciosamente, 1,4-xylylenediisocyanate, 1,5-naphthalenedisulfonate, m-phenylendiamin, p-phenylendiamin, 3,3'-dimethyl-4,4'-diphenylmethane, 4,4'-diphenylmethane, 3,3'-dimethylphenylsilane, 4,4'-biphenylenediisocyanate, 1,6-hexadienal, a diisocyanate, methylene bis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylenediamine, bis(2-isocyanate-ethyl)fumarate, 6-isopropyl-1,3-phenyldiazonium, 4-diphenylmethanediisocyanate, liaindizecign, hydrogenated diphenylmethane, hydrogenated xylylenediisocyanate, tetramethylethylenediamine and 2,5 (or 6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane. Among these diisocyanates, 2,4-colorvision, a diisocyanate, silenciosamente and methylene bis(4-cyclohexylsulfamate) are particularly preferred. These diisocyanate compounds are used either individually or in combination of two or more.

In many of these compositions using a urethane oligomer having chemically active end of the polymer main chain. In addition, the compositions generally contain reactive diluents, photoinitiators, to make compositions are UV-curable, and each�e relevant Supplement.

Published applications PCT patent WO 2205/026228 A1, published September 17, 2004, "Curable Liquid Resin Composition", Sugimoto, Kamo, Shigemoto, Komiya and Steeman, describes and claims a curable liquid resin composition containing: (A) a urethane (meth)acrylate having a structure originating from a polyol and a weighted average molecular weight of 800 g/mol or more but less than 6000 g/mol, and (B) urethane(meth)acrylate having a structure originating from a polyol, and weighted average molecular weight of 6000 g/mol or more but less than 20,000 g/mol, where the total amount of the component (A) and component (B) is 20-95 wt%. from the curable liquid resin composition and the content of the component (B) is 0.1-30 wt%. from the component (A) and component (B) in its entirety.

The variety of materials proposed for use as the polymer main chain urethane oligomer. For example, polyols, such as hydrocarbon polyols, polyols of polyethers, polycarbonatediol and polyol polyesters used in the urethane oligomers. The polyol polyesters are particularly attractive due to their commercial availability, stability to oxidation and diversity in the design characteristics of the coating by means of constructing the main circuit. The use of polyol polyesters as the polymer main chain in urethaneacrylate �oligomere describe for example, in U.S. patents№№ 5146531, 6023547, 6584263, 6707977, 6775451 and 6862392, as well as in European patent 539 030 A.

The problem with the cost, use and handling of urethane precursors lead to the use in the compositions of the coatings not containing urethane oligomers. For example, not containing urethane acrylates oligomers of polyesters used in radiation-curable coating compositions for optical glass fiber. Japanese patent 57-092552 (Nitto Electric) describes a coating material for all optical fibers containing di(meth)acrylate polyester, ester where the main chain has an average molecular weight of 300 or more. German Patent Application 04 12 68 60 A1 (Bayer) describes a matrix material for the tape of the three fibers consisting of acrylate oligomer complex polyester, 2-(N-butyl-carbamyl)acrylate as a reactive diluent and 2-hydroxy-2-methyl-1-phenyl-propane-1-one as photoinitiator. The patent application of Japan No. 10-243227 (publication No. 2000-072821) describes the curable liquid resin composition containing an acrylate oligomer complex polyester, which consists of polyether diol with two end dicyclomine or anhydrides and with the end in the form of hydroxyethylacrylate. U.S. patent No. 6714712 B2 describes radiation-curable coverts composition containing the oligomer meth�of crylate complex polyester and/or alkyd, containing a polyacid residue or anhydride, an optional reactive diluent, and optionally a photoinitiator. Also Mark D. Soucek and Aaron H. Johnson describe the use hexahydrophthalic acid to impart hydrolytic stability to "New Intramolecular Effect Observed for Polyesters: An Anomeric Effect", JCT Research, Vol. 1, No. 2, p. 111 (April 2004).

Curable by irradiation of the composition of the present invention can contain one or more photoinitiators. In addition to a liquid bis(acyl)phosphine of formula (I), a radiation-curable composition can further contain any suitable for the use of a photoinitiator. Illustrative examples of solid bis(acyl)phosphine oxides that can be included in the composition are, for example, bis(2,4,6-trimethylbenzoyl)phenylphosphine (below abbreviated referred to as "BTBPO"); bis-(2,6-dimethylbenzoyl)vinylphosphonate; bis(benzoyl)vinylphosphonate; bis-(2,6-dimethoxybenzoyl) phenylphosphine; and bisantis(2,4,6-trimethyl)phenylphosphine.

Photoinitiators, other than those represented by the formula (I) can together be used as the photoinitiator in the curable liquid resin composition of the present invention. Can also be added photosensitizer, as needed. Appropriate photosensitizers known to specialists in this field and include ant�ahenny, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-Melantrich, thioxanthones and xanthones, such as isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dietitican and 1-chloro-4-propoxyimino, methylbenzofuran (DAROCUR™ MBF from Ciba (now owned by BASF)), methyl-2-benzoylbenzoate (CHIVACURE™ OMB from Chitec), 4-benzoyl-4'-methyldiphenylamine (CHIVACURE™ BMS from Chitec), 4,4'-bis(diethylamino)benzophenone (CHIVACURE™ EMK from Chitec).

Examples of the photoinitiator which can be used include 1-hydroxycyclohexanone, 2,2-dimethoxy-2-phenylacetophenone, Canton, fluorenone, benzaldehyde, fluorene, anthraquinone, include naphtha, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, the ketone of Michler, simple benzoylpropionic ether, simple antinational ether, benzyldimethylamine, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-he, 2-hydroxy-2-methyl-1-phenylpropan-1-he, thioxanthone, dietitican, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-he, 2,4,6-, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentanediol and commercially available products such as IRGACURE® 184, 369, 651, 500, 907, 1700, 1850, (Ciba Specialty Chemicals, Inc. (now owned by BASF)), LUCIRIN™ TPO (BASF), DAROCUR™ 1173 (Ciba Specialty Chemicals, Inc., now belonging� BASF), EBECRYL™ P36 (Cytec Surface Specialties, Inc.), and such.

Examples of usable solid photoinitiators (solid photoinitiators are solid at 20°C), which can be additionally included in the radiation-curable compositions containing bis(acyl)phosphine oxides of the present invention include 4-methyl benzophenone, p-phenylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenylamine, 4,4'-(tetracycline)benzophenone, 4,4'-(tetracycline)benzophenone, benzophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methyl-propane-1-it, 1-hydroxycyclohexyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 4-(2-hydroxyethoxy)phenyl-(2-propyl)ketone, comparison and 2,4,6-trimethylbenzene.

Examples of usable liquid photoinitiators (liquid photoinitiators are liquid at 20°C), which can be additionally included in the radiation-curable compositions containing bis(acyl)phosphine oxides of the present invention include 2,4,6-(trimethylsiloxy,phenylphosphine)oxide, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-he, methylphenylglycidate and acrylaway benzophenone.

A photoinitiator, typically contained in the composition at a concentration of 0.05 wt%. or above, preferably more than 0.1 wt.%, and more preferably, more than 1% of the mass. As rules�, the number will be approximately 15% of the mass. or less, preferably, about 10 wt%. or less, and more preferably 5% by mass. or less, to improve the speed of curing the curable liquid resin composition and durability of the cured product. The amount will vary depending on the application. When considering "effective amount" can be considered to several factors, including the nature of other components in the composition, the type of material (e.g., inner or outer primary coating), film thickness, the magnitude of the lack of yellowing, which may be acceptable, the value of surface hardening in comparison with the volumetric composition is transparent or colored, and the like. The number will be selected to provide an optimum balance of properties for a particular application, key properties, including good curing rate, no yellowing in nature and no harmful crystallization.

Is preferred the exclusion of atmospheric oxygen during the polymerization, which can be accomplished by purging the N2or by adding paraffin or similar waxy substances, which upon the occurrence of polymerization, migrate to the surface due to the lack of solubility in the polymer and form a transparent captured�, which prevents the penetration of air into the system. The inhibitory effect of atmospheric oxygen can also be overcome by combining accelerators (or synergistic) with photoinitiators. Examples of such accelerators or photosensitizers include secondary and/or tertiary amines, such as dimethylethanolamine, triethanolamine, benzyldimethylamine, dimethylaminoethylacrylate, N-phenylglycine, N-methyl-N-phenylglycine, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoyl acid, methyl(4-dimethylaminobenzoate), ethyl-(4-dimethylaminobenzoate), isoamyl-(4-dimethylaminobenzoate), 2-ethylhexyl-(4-dimethylaminobenzoate), calironia amines and commercially available products such as MDEA EBECRYL™ p 104, 115, 7100, ADDITOL™ EHA and ADDITOL™ EPD (Cytec Surface Specialties, Inc.).

Curable by irradiation of the composition of the present invention, including variants of implementation, where the radiation-curable composition contains several photoinitiators, represent liquid compositions.

The following examples further illustrate the present invention but, of course, should not be construed as limiting the scope thereof in any way.

Example 1

This example illustrates the synthesis of liquid bis(2,4,6-trimethylbenzoyl)-n-butoxyethoxy, i.e. bis(acyl)phosphinoxide really hard�the acquisition.

Butyllithium (140,6 ml, 0,225 mol, 1.6 M) was added dropwise in a nitrogen atmosphere at 0°C for a period of 30 minutes to a solution of Diisopropylamine (31.9 per ml, 0,225 mol) in 80 ml of tetrahydrofuran. This solution was added dropwise at -30°C for a period of 90 minutes to a solution of 2,4,6-trimethylbenzaldehyde (20,5 g, 0,112 mol) and di-n-butyl hydrophosphate (19,8 g, is 0.102 mol) in 200 ml of tetrahydrofuran. After stirring the mixture for 2 h at -30°C, was added toluene (80 ml) with stirring. The solution was washed with water at room temperature, and the aqueous phase is separated. The organic phase is dried over magnesium sulfate, filtered, and concentrated using a rotary evaporator.

The product was dissolved in tetrahydrofuran (200 ml) at room temperature and added zinc bromide (22.5 g, 0.1 mol). To the mixture is added dropwise 2,4,6-trimethylbenzoyl (20.7 g, 0,113 mol). After 4 hours the reaction mixture was diluted

the phases were separated. The organic phase is dried over magnesium sulfate, filtered, and concentrated using a rotary evaporator.

Examples 2-5

These examples illustrate the radiation-curable composition containing a liquid photoinitiators based on bis(acyl)phosphinoxide of the present invention.

For obtaining said compositions were used the components specified in the following table 1.

Using these components was preparing radiation-curable compositions according to the invention for use as primary coatings for optical fibers. Compositions were prepared in the standard manner. The composition of the compositions (examples 2 and 3) are shown in table 2 below.

Also preparing radiation-curable compositions according to the invention for use as secondary coatings and dyes. Compositions were prepared in the standard manner. The composition of the compositions (examples 4 and 5) are shown in table 3 below.

All references, including publications, patent applications and patents cited in this document thereby are incorporated by reference to the same extent as if each reference individually and specifically indicated as incorporated by reference, and they are reproduced herein in their entirety.

This paper describes preferred embodiments of the present invention, including the best known authors of the mode of implementing the present invention.

Variations of those preferred embodiments may be obvious to specialists in this field when reading the preceding descriptions. The authors expect�Ute, professionals in this field use these options accordingly, and the authors propose that the present invention may be implemented otherwise than specifically described herein. Accordingly, the present invention includes all modifications and equivalents of the subject matter set forth in the claims appended to the description, as allowed by applicable law. Moreover, any combination of the above-described elements in all possible variations covered by the present invention, unless herein otherwise provided, or is not clearly contrary to the context.

1. Liquid bis(acyl)phosphinoxide of formula (I):

where R is a C1-C18alkyl and where R is unsubstituted.

2. Bis(acyl)phosphinoxide according to claim 1, where R is a C1-C6alkyl.

3. Bis(acyl)phosphinoxide according to claim 2, where R is selected from the group consisting of methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl and hexyl.

4. Bis(acyl)phosphinoxide according to claim 2, where R is a C1-C3alkyl.

5. Bis(acyl)phosphinoxide according to claim 4, where R is selected from the group consisting of methyl, ethyl and n-propyl.

6. Bis(acyl)phosphinoxide according to claim 5, where R represents ethyl.

7. Curable by irradiation of a composition comprising a bis(acyl)f�spinosad according to any one of claims. 1-6 and at least one component that is polymerizable by free radical mechanism.

8. Curable by irradiation of a composition according to claim 7, where the specified composition selected from the group consisting of a covering composition for optical fibers and coating compositions suitable for radiation curing on concrete, and coating compositions suitable for radiation cure on metal.

9. Curable by irradiation of a composition according to claim 8, wherein said composition is a covering composition for optical fibers.

10. Curable by irradiation of a composition according to claim 9, representing a covering composition for optical fibers, where this covering composition for optical fibers selected from the group consisting of a primary coating, secondary coating, the coating containing paint, exterior coating, a buffer coating and a matrix coating.

11. Curable by irradiation of a composition according to claim 8, wherein said composition is a coating suitable for radiation curing on the concrete.

12. Curable by irradiation of a composition according to claim 8, wherein said composition is a coating suitable for radiation cure on metal.

13. Curable by irradiation of a composition according to any one of claims. 7-12, where the composition is curable under the action of UV light, generated�already listed conventional UV light source.

14. Curable by irradiation of a composition according to any one of claims. 7-12, where the composition is curable under the action of light generated by the light source based on LED.

15. Curable by irradiation of a composition according to any one of claims. 7-12, where the composition further comprises at least one additional photoinitiator.

16. Curable by irradiation of a composition according to claim 13, wherein the composition further comprises at least one additional photoinitiator.

17. Cured by irradiating the composition of claim 14, where the composition further comprises at least one additional photoinitiator.

18. Cured by irradiating the composition of claim 15, where at least one additional photoinitiator is selected from the group consisting of solid and liquid photoinitiators of photoinitiators.

19. Cured by irradiating the composition of claim 16, where the at least one additional photoinitiator is selected from the group consisting of solid and liquid photoinitiators of photoinitiators.

20. Cured by irradiating the composition of claim 17, where at least one additional photoinitiator is selected from the group consisting of solid and liquid photoinitiators of photoinitiators.

21. Curable by irradiation of a composition according to any one of claims. 18-20, where the solid photoinitiators selected from the group consisting of 4-methylbenz�of venona, p-phenylbenzophenone, 4,4-bis(dimethylamino)benzophenone, 4-benzoyl-4-methyldiphenylamine, 4,4-(tetracycline)benzophenone, 4,4-(tetracycline)benzophenone, benzophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methyl-propane-1-one, 1-hydroxycyclohexanone, 2,2-dimethoxy-2-phenylacetophenone, 4-(2-hydroxyethoxy)phenyl(2-propyl)ketone, comparison and 2,4,6-trimethylbenzene.

22. Curable by irradiation of a composition according to any one of claims. 18-20, where the liquid photoinitiators selected from the group consisting of 2,4,6-(trimethylsiloxy, phenylphosphine)oxide, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-she, methylphenylglycidate and acelerando benzophenone.

23. Curable by irradiation of a composition according to any one of claims. 18-20, where at least one additional photoinitiator is a bis(acyl)phosphine.

24. Curable by irradiation of a composition according to any one of claims. 18-20, where at least one additional photoinitiator is a stable bis(acyl)phosphine.



 

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16 cl, 7 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to polymer coatings, namely, to a halogen-hydrocarbon polymer coating for electric devices. A printed circuit board (PCB) includes a substrate, including an insulation material. The PCB additionally includes multitudes of electroconductive printing paths, connected to at least one substrate surface. The PCB additionally includes a multi-layered coating, precipitated on at least one substrate surface. The multilayered coating covers at least a part of a multitude of the electroconductive paths and includes at least one layer of the halogen-hydrocarbon polymer. The PCB additionally includes at least one electric component, connected by a solder connection to at least one electroconductive printing path, with the solder connection being soldered through the multilayered coating in such a way that the connection adjoins the multilayered coating.

EFFECT: prevention of oxidation or corrosion of metal surfaces, capable of preventing the formation of strong solder connections or capable of reducing a service term of the said connections.

39 cl, 18 dwg

FIELD: transport.

SUBSTANCE: invention relates to coatings on surfaces of vehicle or building panels providing the sound or vibration attenuation. The coating includes a latex particle containing a product of reaction of itaconic acid and/or itaconic anhydride and monobasic alcohol or monoepoxide or monoamine. Methods of such coatings application are described, particularly for inhibition of the sound and vibration transfer through the substrate.

EFFECT: invention makes possible to use cost effective raw material from renewable or alternative sources.

18 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to paint and coatings industry, in particular to varnish compositions based on cationic oligostyrol (COS), used in preparation of fast-drying road-marking paints. Dry residue of varnish composition includes disperser, plasticizer and COS, obtained by styrol oligomerisation in aprotic organic solvent (AOS) at temperature 14-55°C and initial concentration of styrol in charge 14-50 wt % in presence of complex of Friedel-Crafts acid (FCA) with promoting additive (PA) with molar ratio FCA:PA=5.3÷14.3:1, with further FCA deactivation with Lewis base and separation of target product by AOS distillation. In varnish composition used is COS, obtained with application as FCA water-free aluminium chloride, and mixture, consisting of, wt %:17.7÷33.5 of α-phenylethanol, 19.0÷60.4 of propylene oxide, 10.7÷40.4 of thiophene and 6.2÷18.5 of water.

EFFECT: reduction of cost of vanish compositions due to reduction of price and volumes of dosing of plasticisers and dispersers in them and reduction of temperature of preparation of vanish compositions.

2 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved methods of producing alkyl esters of methacrylic acid as a reaction product, particularly to a method in which a) a reaction mixture which contains an amide of methacrylic acid, water, sulphuric acid and at least one alkanol undergoes esterification in one or more reaction spaces, b) the crude reaction product, in at least one fractionation column, is subjected to a separation process to obtain a reaction product which contains water, alkyl methacrylate and alkanol, c) the reaction product obtained at step b) is condensed in one or more heat-exchangers, d) the condensate is separated in at least one separation device into an organic phase and an aqueous phase, e) the organic phase is washed with water to obtain a washed organic phased and flush water and f) the separated aqueous phase, along with the flush water, is returned to at least one reaction space. The invention also relates to an apparatus for producing alkyl esters of methacrylic acid, at least having i) one or more reaction spaces in which a reaction mixture, which contains an amide of methacrylic acid, water, sulphuric acid and alkanol, undergoes esterification, ii) at least one fractionation column in which the reaction product is subjected to separation, iii) one or more heat-exchangers in which the reaction product subjected to separation is condensed, iv) at least one separation device in which the condensate is separated into an organic phase and an aqueous phase, v) at least one washing column in which the organic phase is washed with water, vi) at least one liquid-conducting connection between the separation device and at least one reaction space, through which the separated aqueous phase, optionally along with flush water, is returned to at least one reaction space.

EFFECT: high efficiency.

18 cl, 11 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to polyamide-based printed films which are used as casings for food products, particularly artificial sausage casing. Disclosed is a printing ink system for printing on (co)polyamide-based films. Said system contains a radically curable primer ink and UV radiation radically curable printing ink which forms an almost colourless layer of primer ink. The primer ink contains a reactive compound which, in one molecule, contains a group capable of bonding with a (co)polyamide surface and an ethylenically unsaturated group which can undergo radical-initiated polyaddition. The invention also discloses a (co)polyamide-based single- or multilayer film which is printed with said printing ink system and a method for production thereof.

EFFECT: printing ink system enables to print on (co)polyamide-based food films with high adhesion to the film, resistance to friction, scratching even without an additional lacquer coat, mechanical and thermal processing, resistance to migration of ink components, which prevents foreign odours from food products.

27 cl, 1 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of black printing inks. Proposed method comprises production of carbon black by pyrolysis of hydrocarbon gas stock in mix with the products of combustion of hydrocarbon fuel gas and air combusted in combustion chamber at air excess factor ≈0.7-0.9, tempering of pyrolysis products by demineralised water, cooling in heat exchange and carbon black separation. Produced carbon black is mixed with thin mineral oil to reach 8-10 sPs Larey viscosity of suspension. Ink fluid components are mixed with carbon black suspension. Produced mix is subjected to cavitation in hyper turbulent flow for homogenisation in closed space of straight-flow hydrodynamic cavitator to Larey viscosity of 3-4 sPs.

EFFECT: simplified and intensified process, higher quality of ink, lower power input.

5 cl, 1 dwg, 1 ex

FIELD: physics, computer engineering.

SUBSTANCE: group of inventions relates to a printing layer of a security element for a data medium. The printing layer comprises elastic microcapsules. The microcapsules have inside them a cholesteric phase-forming liquid crystal which is fixed by a compressible elastomer having at least two areas distinguished by elastic properties. In an uncompressed initial state of the elastomer, the cholesteric phase on said areas has the same specified winding pitch of its spiral structure. Said areas exhibit identical optical properties. With uniform mechanical pressure on the printing layer, said areas experience different deformation and begin to differ by the winding pitch of the spiral structure of the cholesteric phase, thereby reflecting radiation of different colours. The printing layer becomes visible to a person. The invention also describes a method of making a printing layer, a security element, a data medium and a transfer element, having said security element.

EFFECT: invention provides high degree of security of a data medium.

12 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a photoinitiator, a method for production and use thereof and a coating composition. The photoinitiator is a compound of formula: (PI-Sp)n-BB (I), where PI is a thioxanthone group, optionally including additional substitutes in the Sp group; Sp is a spacer link selected from a group consisting of or , BB is a backbone chain link selected from a group consisting of

The method of producing the photoinitiator includes the following steps: (a) optionally substituted thioxanthone, containing at least one hydroxy group, reacts with epichlorohydrin or haloacetic acid ester; (b) the compound from step (a) reacts with the corresponding backbone chain link containing a functional group, or the compound from step (a) reacts with a compound containing a functional group, and the obtained intermediate then reacts with the corresponding backbone chain link; optionally (c) obtaining derivatives of the compounds from step (b). The photoinitiator is used to cure a coating composition, preferably printing ink containing a polymerisable component.

EFFECT: invention enables to obtain a photoinitiator with good curing activity, faint odour and good compatibility with other components of the composition.

10 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a layered material coated with printing paint or printing lacquer. The printing paint or printing lacquer contains as binder at least one non-radiation cured aromatic polycarbonate based on geminally disubstituted dihydroxydiphenyl cycloalkane and as binder solvent at least one radiation cured monomer selected from a group comprising acrylates, methacrylates, vinyl ethers and nitrogen-containing compounds with an ethylene double bond. Said binder is dissolved in the solvent. After curing, the solvent remains in the printing ink or printing lacquer in a chemically cross-linked state.

EFFECT: invention provides high adhesion of the printing ink or printing lacquer to a base, prevents drying thereof on template glass during printing, the need for dilution thereof with a solvent and the undesirable washing off of paint from the print during pressure moulding.

16 cl, 11 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to use of a composition which contains: a) 0.1-20 wt % binder which contains a polycarbonate derivative based on geminally disubstituted dihydroxydiphenyl cycloalkane, b) 30-99.9 wt % solvent, c) 0-10 wt %, with respect to dry mass, dye or mixture of dyes, d) 0-10 wt % functional material or mixture of functional materials, e) 0-30 wt % additives and/or auxiliary substances or a mixture thereof, as jet printing ink. The invention also relates to a method of producing a composite and a composite which contains a polymer layer on which there is a jet printing layer of said composition.

EFFECT: invention is aimed at producing agents which enable to use jet printing in making counterfeit protected documents and/or valuable documents based on polycarbonate layers, and which enable to deposit jet printing layers on layers which meet all optical requirements, which can be coloured, wherein lamination does not deteriorate optical properties of the layers and said layers do not act as a separating layer and facilitate formation of a monolithic composite.

31 cl, 2 tbl, 2 dwg, 8 ex

FIELD: chemistry.

SUBSTANCE: printed paint composition contains aliphatic acid-modified polyester (A) with an attached polybasic acid. The polyester (A) has degree of modification of 35-65 wt %, hydroxyl number of 60-200 mg KOH/g, acid number of 10-60 mg KHO/g and weight-average molecular weight with respect to styrene of 3000-30000, a pigment component and a solvent. Also disclosed is a method of coating a seamless can with said paint composition.

EFFECT: paint composition has high stability, compatibility with coating varnish and high adhesion to the surface of a seamless can while providing good characteristics of coating film.

5 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic latent catalytic compounds which are suitable as catalysts in polyaddition or polycondensation reactions which are catalysed by a Lewis acid type catalyst, particularly for cross-linking a blocked or non-blocked isocyanate or an isothiocyanate component with a polyol or a polythiol to form polyurethane. Polyaddition or polycondensation reactions are initiated by that a catalyst is released while holding in electromagnetic radiation in wavelength range of 200-800 nm. The latent catalytic compound has formula I or II, Me(FG)(m-x)Ax (I); Ax(FG)(m-1-x)Me-O-Me(FG)(m-1-x)Ax (II), where Me is Sn, Bi, Al, Zr or Ti; m is an integer from 1 to the coordination number of Me; x is an integer from 0 to (m-1); A is a C1-C20 alkyl, halogen, C7-C30 aralkyl, C1-C20 alkoxy group, C2-C10 alkanoyloxy group, C6-C18 aryl or C6-C18 aryl, which is substituted with one or more C1-C20 alkyls; and under the condition that if x is greater than 1, A are identical or different; and FG independently represents a group of formula (Z), (B), (C), (D), (E), (F), (G), (L) or (M)

,

where values of radicals are given in the claim. The invention also relates to a polymerisable composition and a method for polymerisation in the presence of said catalytic compounds. The invention enables to initiate the reaction only if desired by external activation, such as heating or light.

EFFECT: widening the operating window with a polymer mixture until the chain reaction begins.

12 cl, 14 tbl, 67 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyamide-based printed films which are used as casings for food products, particularly artificial sausage casing. Disclosed is a printing ink system for printing on (co)polyamide-based films. Said system contains a radically curable primer ink and UV radiation radically curable printing ink which forms an almost colourless layer of primer ink. The primer ink contains a reactive compound which, in one molecule, contains a group capable of bonding with a (co)polyamide surface and an ethylenically unsaturated group which can undergo radical-initiated polyaddition. The invention also discloses a (co)polyamide-based single- or multilayer film which is printed with said printing ink system and a method for production thereof.

EFFECT: printing ink system enables to print on (co)polyamide-based food films with high adhesion to the film, resistance to friction, scratching even without an additional lacquer coat, mechanical and thermal processing, resistance to migration of ink components, which prevents foreign odours from food products.

27 cl, 1 ex

FIELD: printing.

SUBSTANCE: carrier based on high-density polymer is decorated with ink for printing, comprising at least one pigment and one binder. The binder is an oxygenised polyolefin wax in the form of an aqueous emulsion, and the wax has a Brookfield viscosity of less than 5000 mPa*s at 150°C and a pH level of 28 to 32 mg KOH/g, and the said ink has a viscosity of less than 2000 mPa*s at 25°C. The ink is applied in a continuous or discrete manner on at least one surface of the carrier. The subject of the invention is also a decorated carrier based on high-density polymer, a multi-layered product, and a method of manufacturing of a multi-layered product with a coating of the said ink.

EFFECT: creation of the ink of simpler composition and easier to use.

16 cl, 1 dwg, 4 tbl

FIELD: textiles and paper.

SUBSTANCE: non-woven fabric is proposed, on the visible surface of which the ink composition is applied comprising from about 40 wt % to about 80 wt % of the dry weight of the ink of linking agent - aziridine oligomer with at least two aziridine functional groups. Also an absorbing article is proposed comprising a liquid-permeable upper layer, an absorbing core and a liquid-impermeable lower layer that contains the specified non-woven fabric with the said applied ink composition. The application of ink on the non-woven fabric can be carried out by the method of flexography or a method of ink-jet printing.

EFFECT: printed non-woven fabric has high resistance to abrasion even in case of its contacting with fatty substance.

16 cl, 2 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to (meth)acrylate polymer, which is obtained by polymerising a mixture comprising a) 0.1 to 99.9 wt % of at least one (meth)acrylate of general formula where residues R1-R6 and m assume values given in the description, and b) 99.9 to 0.1 wt % of one or more ethylenically unsaturated monomers which are different from (a) and are compolymerisable with (a), wherein components (a) and (b) constitute 100 wt % of the polymerisable components of the mixture, wherein MW of the polymer ranges from ≥1000 to ≤50000 g/mol. The formed polymers can be used as UV initiators for polymerisation reactions used in printing ink.

EFFECT: obtaining (meth)acrylate polymers which can be used as polymer initiators or ink additives.

26 cl, 2 tbl, 3 dwg, 11 ex

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