Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/18—Suspension polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

• the invention describes (meth) acrylate polymers, preferably benzophenone-containing (meth) acrylate polymers, for use as polymer-bound photoinitiators or in UV-curable resins.
• Benzophenone and low molecular weight benzophenodehevates are widely used photoinitiators. Upon irradiation, radicals form, which can cause the polymerization or crosslinking of ethylenically unsaturated monomers.
• US 5,900,472 A describes copolymerizable benzophenone derivatives for use as photoinitiators. Benzophenone derivatives having two to four (meth) acrylate groups are shown as well as UV-curable coatings which are obtainable by reaction of the polyvalent benzophenone derivatives with (meth) acrylate under the action of radiation. According to US 5,900,472 A, the coatings obtainable using the polyvalent benzophenone derivatives are superior to known coatings with known photoinitiators insofar as they show a reduced tendency to "bleed.” To date, unused photoinitiator has tended to exhibit this phenomenon , which limited its application to just a few options.
• the polymer-bound benzophenones according to Carlini et al. may adversely affect the viscosity of the printing inks. Too high a viscosity can lead to a disturbed reaction kinetics and imperfect curing or delayed curing of the printing inks. task
• the polymers should be obtainable from simple basic building blocks by simple methods.
• the polymers should be as reactive as possible and react as completely as possible when used as a photoinitiator.
• the new polymers should also be adjustable or controllable with respect to their reactivity.
• the polymers should have as little tendency to bleed or migrate. They should thus be integrated as permanently as possible, for example, in a resulting coating or coating.
• the new photoinitiators should also be suitable as additives to UV-curable printing inks, above all for the printing of food packaging.
• R 1 is hydrogen or methyl
• R 2 is oxygen or NH
• R 3 is a radical of the general formula II
• R 7 , R 8 , R 9 are independently hydrogen or methyl, n is an integer from zero to two hundred, o and p are independently an integer from zero to two, where for the
• R 4 is a bond, oxygen, NH, O-CO-O, HN-CO-O, HN-CO-NH or sulfur;
• R 5 is hydrogen, halogen or a moiety having from one to 20 carbon atoms optionally substituted with oxygen, nitrogen and / or sulfur, where m is an integer from one to five; and
• R 6 is an aryl or heterocyclyl radical;
• Such a polymer as a photoinitiator or as an additive in the curing of UV-curable resins, allows the creation of highly advantageous coatings or coatings.
• the polymer does not tend to migrate from the food wrap to the packaged food.
• the polymer-bound photoinitiators according to the invention are largely odorless.
• the viscosity of the printing inks is not or only insignificantly influenced by the amount usually to be added to the inks, so that the curing kinetics are not disturbed. This in turn allows the application of the ink having the photoinitiator of the invention on existing standard printing systems.
• the monomer composition comprises one or more (meth) acrylates a) of the general formula (I).
• the proportion of (meth) acrylates a) in the monomer mixture is in the range from 0.1 to 99.9 percent by weight, based on the total weight of the polymerizable constituents (sum of a) and b)).
• the monomers of formula (I) are present in an amount in the range of 0.5 to 50 weight percent, especially in an amount in the range of 2.0 to 35.0 weight percent, and most preferably in the range of 5.0 to 30 , 0 percent by weight in the monomer mixture before, in each case based on the total weight of the polymerizable components (sum of a) and b)).
• (meth) acrylates means both methacrylates or acrylates and a mixture of methacrylates and acrylates.
• the monomer a) is at least one compound of the general formula
• R 1 is hydrogen or methyl
• R 2 is oxygen or NH
• R 3 is a radical of the general formula II
• R 7 , R 8 , R 9 are independently hydrogen or methyl, n is an integer from zero to two hundred, o and p are independently an integer from zero to two, and in the event that the sum of n and o and p is zero then R 3 is a bond;
• R 4 is a bond, oxygen, NH, O-CO-O, HN-CO-O, HN-CO-NH or sulfur;
• R 5 is hydrogen, halogen or a moiety having from one to 20 carbon atoms optionally substituted with oxygen, nitrogen and / or sulfur, where m is an integer from one to five;
• R 6 is aryl or heterocyclyl which is conveniently located in conjugation with the adjacent carbonyl group
• the radical R 1 is a methyl group.
• compounds of formula (I) wherein R 3 and / or R 4 are selected such that the connection of the polymerizable ethylenically unsaturated function of spacers in the form of ethylene oxide or propylene oxide residues performs.
• R 3 is selected such that the sum of the indices n + o + p is greater than zero.
• o and p are chosen to be zero, while n is an integer greater than zero, more suitably greater than five and even more preferably greater than ten.
• radicals R 7 to R 9 are chosen in a suitable variant so that they are all hydrogen.
• a particularly favorable process variant is achieved when using compounds of the formula (I) in which R 1 is methyl, R 2 is oxygen, R 4 is a bond, p and o are zero, R 7 is hydrogen and the index n is one integer in the range of 1 to 50, more preferably 2 to 20 and even more preferably 5 to 10 means.
• R 5 is hydrogen, halogen or radicals having up to 20 carbon atoms optionally substituted with oxygen, nitrogen and / or sulfur, where m is from one to four.
• Particularly useful variants of the invention use compounds of the formula (I) in which all four R 5 are hydrogen.
• R 6 is an aryl radical or a heterocyclyl radical. Particularly suitably R 6 is an aryl radical. R 6 is particularly preferably a phenyl radical.
• the linkage of the residue fragment -R-R-R- with the aromatic can take place in the o- m- or p-position to the carbonyl function on the atomate.
• the para, ie 1 -4-linkage Preferably, the monomer a) is at least one benzophenone (meth) acrylate of the general formula (T)
• R 1 , R 3 and R 5 and m can assume the meaning given above for formula (I).
• R 10 can independently of R 5 assume the meanings of R 5 , namely hydrogen, halogen or a radical having one to 20 carbon atoms, which is optionally substituted by oxygen, nitrogen and / or sulfur, wherein q is one to five.
• a very particularly preferred embodiment of the invention is directed to those processes in which compounds a) which correspond to the general formula (I ") are used as compounds a) at least one benzophenone (meth) acrylate of the monomer a) general formula I "
• R 1 , R 5 and R 10 and m and q have the meanings already given in the formulas (I) and (I 1 ).
• halogen is meant the radicals fluorine, chlorine, bromine or iodine.
• the radicals having 1 to 20 carbon atoms include, but are not limited to, (C 1 -C 20) -alkyl, (C 2 -C 20) -alkenyl, (C 2 -C 20) -alkynyl, aryl or heterocyclyl, where the aryl- or heterocyclyl radicals unsubstituted or may be provided with up to three, in the case of fluorine up to the maximum number of identical or different radicals and in said alkyl, alkenyl or alkynyl radicals one or more, preferably up to three non-adjacent saturated carbon units may be replaced by heteroatom units, such as oxygen or sulfur, and further wherein 3 to 6 atoms of these optionally modified as above hydrocarbon radicals can form a cycle and these hydrocarbon radicals with or without the specified variations, optionally with a or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halo preferably fluorine,
• (C 1 -C 20) -alkyl means an unbranched or branched hydrocarbon radical having 1 to 20 carbon atoms, such as. B.
• Octyl or the 1, 1, 3, 3-tetramethylbutyl radical; , as well as z.
• (C 2 -C 20) alkenyl e.g., the vinyl, allyl, 2-methyl-2- propenyl or 2-butenyl group; as well as For example, the 2-pentenyl, 2-decenyl or the 2-eicosenyl group;
• (C 2 -C 20) -alkynyl for example, the ethynyl, propargyl, 2-methyl-2-propynyl or 2-butynyl group; as well as The 2-pentynyl or 2-decynyl group;
• aryl is an isocyclic aromatic radical having preferably 6 to 14, in particular 6 to 12, C atoms, for example phenyl, naphthyl or biphenylyl, preferably phenyl.
• aryloxy is meant, for. The phenoxy or 1- or 2-naphthyloxy group
• arylthio is meant z. B. the phenylthio or 1- or 2-naphthylthio group;
• (C 3 -C 8) -cycloalkoxy denotes a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group which is linked via an oxygen;
• (C 3 -C 8) -cycloalkylthio means a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group linked via a sulfur atom.
• heterocyclyl means a heteroaromatic or heteroaliphatic ring system
• heteroaromatic ring system is an aryl radical in which at least one CH group is replaced by N and I or at least two adjacent CH groups are replaced by S, NH or O.
• Benzisothiazole benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran,
• Cinnoline 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine,
• heteroaliphatic ring system a heteroaliphatic ring system
• Group NR "is replaced and R" is hydrogen. (C 1 -C 4) -alkyl or aryl;
• heterocyclyloxy denotes one of the abovementioned heterocyclic radicals which are linked via an oxygen atom
• compositions are characterized in that R 1 is methyl.
• compositions wherein R 2 is oxygen are also compositions wherein R 2 is oxygen.
• compositions wherein R is a bond.
• compositions wherein all R 5 are hydrogen are hydrogen.
• compositions wherein R 6 is phenyl.
• methacryloyloxybenzophenone or benzophenone methacrylate as component a) to produce a polymer B) for the composition according to the invention.
• the compounds of the formulas (I), (I 1 ) and (I ") are either commercially available or are prepared by processes known in the literature The possible processes of preparation include, for example, the transesterification of (meth) acrylates with the corresponding alcohols or alcohol precursors -Links.
• the monomer composition further comprises one or more ethylenically unsaturated comonomers b) which can be copolymerized with, but different from, a).
• the proportion of the comonomers is preferably in the range from 99.9 to 0.01% by weight, in particular 50.0 to 99.5, advantageously 65.0 to 98.0% by weight and particularly preferably 70.0 to 35 , 0 wt .-%, based on the weight of the polymerizable
• suitable comonomers b) correspond for example to the formula (III):
• Aryl (meth) acrylates such as benzyl methacrylate or
• Phenyl methacrylate wherein the aryl radicals may each be unsubstituted or substituted up to four times;
• Methacrylates of halogenated alcohols such as
• Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;
• Vinyl esters such as vinyl acetate
• Styrene substituted styrenes having an alkyl substituent in the side chain, such as. ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, Vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-viny
• Maleic acid and maleic acid derivatives such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide;
• Fumaric acid and fumaric acid derivatives Acrylic acid and (meth) acrylic acid; Dienes such as divinylbenzene.
• Hydroxyalkyl (meth) acrylates such as
• Glycol dimethacrylates such as
• Methacrylates of ether alcohols such as
• Ethoxymethyl methacrylate and ethoxylated (meth) acrylates which preferably have 1 to 20, in particular 2 to 8, ethoxy groups;
• Aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylatamides such as
• Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as
• heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloyloxyethyl) -2-pyrrolidone;
• Particularly suitable comonomers b) include, but are not limited to, methacrylates, acrylates, styrenes, and mixtures comprising two or more components of the foregoing groups.
• (meth) acrylates are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenylethyl (meth) acrylate), 3,3,5-thmethylcycl
• (meth) acrylic acid (meth) acrylamide, N-methylol (meth) acrylamide, monoesters of maleic and succinic acid with hydroxyethyl methacrylate and the phosphoric acid ester of hydroxyethyl (meth) acrylate, the proportion of which is usually subordinate.
• the polymer of the invention can also be obtained by polymerization of two or more different monomers of the type b).
• component b) is selected from (meth) acrylate monomers. It is very particularly preferred that component b) is methyl methacrylate.
• component b) comprises n-butyl methacrylate.
• Particular polymers according to the invention are also obtainable using a component b) which is selected from (meth) acrylates having 3 to 5 carbon atoms in the ester group. These include, inter alia, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate and n-pentyl methacrylate. Of the monomers mentioned, n-butyl methacrylate is particularly preferred.
• Particular polymers of the invention are also characterized in that b) a mixture of monomers comprising methyl methacrylate and n-butyl methacrylate.
• Very particularly preferred polymers according to the invention are obtainable by copolymerization of benzophenone methacrylate, methyl methacrylate and n-butyl methacrylate.
• the polymers according to the invention are obtained by free-radical polymerization.
• the usual free-radical polymerization is described in detail in, inter alia, Ullmanns' Encyclopedia of Industrial Chemistry, Sixth Edition.
• the polymerization is started by using at least one polymerization initiator for the radical polymerization.
• the azo initiators well known in the art, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 1,1-azobiscyclohexanecarbonitrile, organic peroxides such as dicumyl peroxide, diacyl peroxides such as Dilauroyl peroxide, Peroxyd icarbonate, such as diisopropyl peroxydicarbonate, peresters, such as tert. Butyl peroxy-2-ethylhexanoate, and the like.
• Polymerization initiators include in particular the following compounds:
• dibenzoyl tert. Amyl peroxy-2-ethylhexanoate, tert. Butyl peroxy-2-ethylhexanoate, tert. Butyl peroxy-isobutyrate and mixtures of the aforementioned polymerization initiators.
• the polymers of the invention can be obtained in bulk or in solution. Preferably, however, is their receipt by polymerization by the suspension polymerization, the so-called bead polymerization.
• water-insoluble monomers are suspended in water by mechanical stirring.
• the polymerization is started in the monomer droplets by adding an "oil-soluble” initiator.
• suspending agents such as, for example, B. Ba2SO4, poly (vinyl alcohol) or similar. prevented.
• the polymer is in the form of small beads (50-400 microns) dispersed in water.
• the polymerization for the preparation of the polymers according to the invention can be carried out either in the presence or absence of a chain transfer agent.
• the polymerization is carried out in the presence of a chain transfer agent or so-called regulator.
• chain transfer agents it is possible to use typical species described for free-radical polymerizations, as known to the person skilled in the art.
• mercaptans such as, for example, n-butylmercaptan, n-dodecylmercaptan, 2-mercaptoethanol.
• the molecular weight of the benzophenone (meth) acrylate-containing copolymer of the invention is critical.
• the weight-average molecular weight MW is in the range of greater than or equal to 1,000 g / mol to less than or equal to 50,000 g / mol. If the MW is below 1, 000 g / mol, it may cause odor nuisance by the photoinitiator. In addition, migration security may not be sufficient. If the MW is above 50,000 g / mol, the viscosity of a printing ink becomes too high, so that either a disturbed reaction kinetics of the curing process or the addition of, for example, reactive diluents (monomers) to the printing ink formulation becomes necessary, with the known consequential problems.
• the amounts of monomers, polymerization initiator, chain transfer agent and, if appropriate, solvent are preferably selected such that a weight average molecular weight in the range from 1,000 to 20,000 g / mol, preferably in the range from 1 to 10,000 and 10,000 g / mol, preferably in the range of 1, 500 to less than 10,000 g / mol, advantageously in the range of 2,000 to 3,500 g / mol, in particular in the range of 2,500 to 3,500 g / mol is obtained. Particular preference is also given to molecular weights of less than 5,000 g / mol. These values are each based on the weight-average molecular weight (Mw).
• Mw weight-average molecular weight
• gel permeation chromatography also known as size exclusion chromatography (SEC)
• SEC size exclusion chromatography
• an osmometric method such as vapor phase osmometry can be used to determine molecular weights.
• SEC size exclusion chromatography
• osmometric method such as vapor phase osmometry
• the methods mentioned are described, for example, in: PJ. Flory, “Principles of Polymer Chemistry” Cornell University Press (1953), Chapter VII, 266-316, and “Macromeolecules, to Introduction to Polymer Science", FA Bovey and FH Winslow, Editors, Academic Press (1979), 296-312, and WW Yau, JJ. Kirkland and DD BIy, "Modern Size Exclusion Liquid Chromatography, John Wiley and Sons, New York, 1979.
• gel permeation chromatography is used to determine the molecular weights of the polymers presented herein. It is measured against polymethylacrylate standards
• the glass transition temperature of the polymer-bound benzophenones according to the invention can vary over a certain range.
• the glass transition temperatures are suitably at Tg> 40 ° C determined by DSC according to DIN EN / SO 6721 -2.
• Tg is below 40 ° C.
• the polymerization to obtain the polymers according to the invention can be carried out at atmospheric pressure, underpressure or overpressure.
• the polymerization temperature is not critical. However, it is generally in the range of -20 ° - 200 ° C, preferably in the range of 0 ° - 180 ° C, favorably in the range of 50 ° - 180 0 C, particularly preferably in the range of 50 ° - 130 ° C , and in particular in the range of 60 ° - 120 ° C.
• the polymerization is preferably carried out at a constant reaction temperature, which is preferably around during the entire polymerization reaction less than + -20 0 C, more preferably less than + -10 0 C, in particular by less than + - 5 ° C, to the desired temperature varies.
• the polymerization vessel is preferably with a
• Polymerization initiator the temperature of the temperature control over the previously set temperature, preferably by 2 to 10 ° C, in particular by 5 to 10 0 C, lowered.
• the copolymer of the invention can be used particularly suitably as a UV initiator for polymerization reactions. It may be of particular advantage if the polymer is present as a solution in a reactive diluent.
• reactive diluents are understood to mean those media which, on the one hand, are capable of dissolving the polymer-bound UV initiator and on the other hand, during a polymerization reaction initiated by the polymeric UV initiator, to participate in the reaction and be polymerized into the polymers to be prepared.
• Very particularly suitable reactive diluents for the use of the polymer according to the invention include, for example, polyvalent (meth) acrylates. Suitable polyvalent (meth) acrylates include di- or triacrylates, among others.
• tripropylene glycol diacrylate very particular preference is given, for example, to tripropylene glycol diacrylate.
• concentration of the ready-to-use solution can be easily adapted to the desired application depending on the desired reactivity of the UV initiator. Concentrations ranging from 10 to 70 percent (w / w) have been found to be favorable. Particularly preferred are 20 to 50 percent solution (w / w) in preferably tripropylene glycol diacrylate.
• the rate of initiation / crosslinking can be particularly advantageously further improved by combined use with an accelerator amine or adapted to the desired target speeds.
• the benzophenone-containing polymer according to the invention is used together in combination with an amine, wherein the amine is selected from the group of low molecular weight amines, polymeric amines and polymerizable amines.
• NDEA N-methyl diethanolamine
• DMAEMA 2-diethylaminoethyl methacrylate
• the polymer-bound initiator according to the invention can preferably also be successfully used as an additive to UV-curable resins, in particular as an additive to printing inks.
• a composition of a printing ink that is favorable in the context of the invention comprises: A.) colorants, B.) UV-curable binders, C.) customary auxiliaries, such as agents for influencing rheology, drying, gloss and surface hardness, and D.) based on the sum of the weight from A.) to D. ) 0.1 to 30% by weight of a polymer-bound initiator of the invention.
• a particularly suitable ink variant comprises according to the invention
• composition comprising the components A) to D) in the following amounts:
• a special composition includes:
• UV-luminescent paste 5% by weight UV-luminescent paste
• the polymer-bound photoinitiator is particularly suitably such that it represents a content of about 5 wt .-% benzophenone, based on the total printing ink formulation.
• the colorants A) that can be used with great success include inorganic pigments such as mineral pigments, eg. B. Milori blue, titanium white, iron oxide pigments; like metal pigments, eg. Aluminum powder (silver bronze PM1), brass powder (gold bronze PM2), Cu-Zn alloys, copper bronze; like interference pigments, e.g. Nacreous, pearlescent and fire-colored bronzes; like carbon pigments, e.g. As pigment blacks, Farbruße, each coarse and / or fine-grained; organic pigments such as azo pigments, couplings of mono- and diazo compounds and laked, isoindoline pigments, phthalocyanine pigments, special pigments based on polycyclic compounds, eg.
• inorganic pigments such as mineral pigments, eg. B. Milori blue, titanium white, iron oxide pigments
• metal pigments eg.
• binders B include in non-exhaustive list, inter alia:
• Fats, oxidatively drying or non-drying oils and alkyd resins prepared therefrom such as.
• B. fat drying oils of vegetable origin eg. Linseed oil, wood oil, soybean oil, ricinoleic oil, tall oil and their derivatives (grafted, hydrogenated or dehydrated oils, oil-resin cements, fatty acid-modified alkyd resins (phthalic acid + glycerol + drying oils), free fatty acids, fatty alcohols, etc.), gold leaf varnish (by prolonged heating of linseed oil);
• solvents and / or diluents include, but are not limited to: Hydrocarbons, mineral oils, alcohols, glycols, glycol ethers, esters, ketones, water; especially ethanol, denatured with methyl ethyl ketone or cyclohexane, ethyl acetate, 2-propanol, 1-methacryl-2-propanol, 1-ethoxy-2-propanol, water acetone, benzines including cycloaliphatics, dipropylene glycol monomethyl ether, ethoxypropyl acetate, isopropyl acetate, methoxypropyl acetate, methyl ethyl ketone, methoxypropyl ketone, 1 - propanol, propyl acetate, propylene glycol, diacetone alcohol, cyclohexanone, methyl isobutyl ketone, toluene and / or xylene.
• Useful excipients include fillers such as calcium carbonate (chalk PW18), alumina hydrate (PW24), barium sulphate (PW21 heavy duty), silica (silica SiO 2 PW27), aluminum silicate (kaolin PW19) or Magnesium silicate (talcum PW26) or mixtures of two or more of the aforementioned fillers;
• Waxes, z Natural waxes such as carnauba wax or ozokerite wax; synthetic waxes, z. Natural waxes such as carnauba wax or ozokerite wax; synthetic waxes, z. Natural waxes such as carnauba wax or ozokerite wax; synthetic waxes, z. Natural waxes such as carnauba wax or ozokerite wax; synthetic waxes, z. Natural waxes such as carnauba wax or ozokerite wax; synthetic
• Waxes such as PE waxes, oxidized carboxy group-containing PE waxes, fluorinated
• Waxes Waxes, PTFE waxes, petroleum waxes, paraffin gels, ceresin wax;
• Fatty acid amides such as.
• oleic amide or stearic acid amide oleic amide or stearic acid amide
• Plasticizers such as. B. Products of natural (eg castor oil, epoxidized soybean oil) or of synthetic origin such as phthalic acid esters (dibutyl phthalate (DBP), diisobutoyl phthalate
• DiBP dioctyl phthalate
• DOP dioctyl phthalate
• DIDP diisooctyl phthalate
• dicyclohexyl phthalate dicyclohexyl phthalate
• Diisononyl phthalate Diisononyl phthalate
• abietates abietates
• benzoates adipates
• sebacates phosphates and / or
• Dry substances such.
• B. liquid dryers such as oil-soluble metal soaps (octanoates,
• Resinate, naphthenates, tallates, linoleates such as.
• Dry pastes disersions of inorganic salts in oils, Mg salts milled in linseed oil varnishes
• Drying retarder antioxidants such as. Oxines, substituted phenols, aromatic amines and naphthols;
• wetting agents such. B. anionic wetting agents, for. As salts of acids, in particular
• fatty acids e.g. B. quaternary ammonium compounds
• nonionic surfactants such as ethoxylated alkylphenols
• amphoteric wetting agents such as fatty acids; cationic wetting agents, e.g. B. quaternary ammonium compounds; nonionic surfactants, such as ethoxylated alkylphenols; and amphoteric wetting agents such.
• Neutralizing agents such as Acrylates, ammonia or amino alcohols
• Crosslinker z. Polyisocyanates or polyachthynes, photoinitiators other than D);
• Antifoam agents complexing agents and other additives.
• the polymerization is conducted as follows.
• the entire amount of water and the aluminum sulfate are heated with stirring and nitrogen transfer to 80 0 C.
• soda solution is added in one go to precipitate the aluminum hydroxide.
• the addition of the auxiliary distributor takes place as a 1% solution.
• the pH of the water phase is checked. This is 5.5.
• the monomer solution is added all at once (in batch form). After the temperature maximum stirring is continued for 1 h at 90 ° C. It is then cooled to 40 ° C and acidified with 20 ml of 50% sulfuric acid.
• the batch is cooled further, drained on a porcelain chute with paper round filter (grade MN 616, retention range 4-12 microns) and washed neutral with 5 L of deionized water.
• the bead polymer is dried for about 20 h at 50 0 C (tray drying).
• MMA methyl methacrylate
• BMA n-butyl methacrylate
• the KGV determination was performed using a Malvern Mastersizer 2000 (with or without the use of ultrasound).
• the glass transition temperature was determined in accordance with EN ISO 11357.
• the determination of the glass transition temperature Tg was carried out according to the method defined in ISO 1 1357-2.
• the weight-average molecular weights Mw of the (meth) acrylate polymers according to the invention were determined by means of SEC (size exclusion chromatography) for hydrophobic polymers.
• SEC size exclusion chromatography
• Tetra hydrofu ran is permanently distilled, aerated with helium and pumped in a circle
• PMMA eg from PSS (Mainz) and Fa.
• PETG pentaerythritol tetrathioglycolate
• EHTG 2-ethylhexyl thioglycolate
• the polymer solutions were weighed into test tubes of 20 g. In the middle of the test tubes, a tube was fixed with a lid. In this tube, diethylene glycol as a carrier liquid was about. 6 cm filled. The thermocouples were placed in the middle tube and the samples placed at a distance of 2.5 cm from the lamps. This results in a radiant power of 1 mW / cm 2 .
• a basic experimental setup is shown in the attached FIG.
• FIG. 2 shows the temperature / time profile for the polymerization of tripropylene glycol diacrylate using 37.5% by weight of the polymeric photoinitiators characterized in Table 2; 3 shows the temperature / time curve for the polymerization of tripropylene glycol diacrylate, using 37.5 wt .-% of the characterized in Table 2.
• MDEA N methyl-diethanolamine
• UV-PZ stands for the maximum temperature reached in the individual polymerizations.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerisation Methods In General (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2009
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