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WO2002022700A2 - Oligomere ou polymere dendritique durcissable par rayonnement - Google Patents

Oligomere ou polymere dendritique durcissable par rayonnement Download PDF

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Publication number
WO2002022700A2
WO2002022700A2 PCT/SE2001/001894 SE0101894W WO0222700A2 WO 2002022700 A2 WO2002022700 A2 WO 2002022700A2 SE 0101894 W SE0101894 W SE 0101894W WO 0222700 A2 WO0222700 A2 WO 0222700A2
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radiation curable
polymer
propanediol
acid
dendritic
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WO2002022700A3 (fr
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Bo Pettersson
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Perstorp Specialty Chemicals AB
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Perstorp Specialty Chemicals AB
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Priority to AU2001286351A priority Critical patent/AU2001286351A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds

Definitions

  • the present invention refers to a radiation curable dendritic oligomer or polymer nominally having at least one acrylic double bond and nominally at least one tertiary amine group. In a further aspect, the present invention refers to a process for production of said radiation curable dendritic oligomer or polymer. In yet a further aspect, the present invention refers to a radiation curable composition comprising said radiation curable dendritic oligomer or polymer.
  • Radiation curable coatings are a class of industrial coatings having in recent years expanded rapidly. The rapid growth of radcure coatings in relation to the total coatings market is a matter certain significant advantages over for instance traditional solventborne coatings. Radiation curable coatings are solvent-free and will not give any major emissions to the atmosphere. Hence, VOC emissions can be drastically reduced if an industrial coater replaces solventborne systems with the solvent-free radcure technology. Furthermore, radiation curable coatings have a very high reactivity and are energy efficient as they do not need to be heated. At the same time investment costs to convert from solventborne technology to radcure technology is low. This means that production costs can be reduced by using radcure coatings instead of solventborne systems. Radiation curable coatings can in other words offer an environmental solution as well as reduce production costs. The most industrially viable class of radiation curable coatings today are acrylate and methacrylate functional polymers, oligomers and monomers.
  • Photoinitiators are in general rather expensive and in some cases toxic. They give rise to degradation products after cure, which degradation products can give the cured coating an unpleasant odour. Remaining degradation products of photoinitiators can also impart the UN-stability of the cured coating and give rise to yellowing and coating degradation from natural exposition to UV light. Degradation products originating from photoinitiators can furthermore present a health hazard and can therefore restrict the use of radiation curable coatings in for instance food packaging applications.
  • dendritic acrylates of a particular molecular design.
  • a dendritic acrylate oligomer or polymer partly derivatised with at least one tertiary amine yields, without or with extremely low amounts of photoinitiators, coatings with excellent reactivity and film properties.
  • Said dendritic acrylates can be cured with low intensity UN lamps (80W/cm) under air atmosphere. Obtained coatings have very good film hardness, scratch resistance and chemical resistance.
  • Dendritic polymers are known to give excellent properties to various resin systems including coatings as disclosed in for instance the Swedish patents nos. 468 771, 502 634, 503 342, 503 622, 504 879 and 509 240 as well as in the International Patent Applications WO 97/23538 and WO 97/23539 and WO 96/07688, all teaching various types of dendritic polyesters with and without chain termination as well as the use and properties of said polyesters in applications such as binders, thermosets, thermoplastics and lubricants.
  • Dendritic polymers are, furthermore, disclosed in WO 95/20619 teaching dendritic macromolecules prepared from halogen cyanide units and EP 0 115 771 teaching dendritic polyamidoamines and dendritic polyethers.
  • the state of the art is excellently compiled in for instance "Dendritic Molecules - Concepts ⁇ Syntheses • Perspective" by G.R. ⁇ ewkome, C. ⁇ . Moorefield and F. N ⁇ gtle - VCH Verlagsgesellschaft mbH, 1996.
  • the densely branched polymer structure of dendritic molecules yields polymers with exceptionally low viscosity, yet high molecular weights.
  • the branched structure also results in a very high functionality at any given molecular weight.
  • the high functionality in combination with excellent rheological properties, makes it possible to tailor oligomers and polymer acrylic bouble bonds, which combine a high acrylate functionality and hence reactivity with auditority to incorporate tertiary amines which are known to reduce air inhibition and promote radical polymerisation.
  • dendritic acrylate oligomer or polymer according to the invention unique combination of high acrylate functionality in combination with pendant tertiary amine groups promoting polymerisation, yields an acrylate oligomer that can give excellent coating properties without the use of photoinitiators.
  • Acrylic acid, acrylic and acrylate are obove and hereinafter understood as any of the four commonly available unsaturated acids, propenoic acid (acrylic acid, vinyl formic acid), 2-methylpropenoic acid (methacrylic acid) and 2-butenoic acid (crotonic acid or ⁇ -methyl acrylic acid) in its cis (isocrotonic acid) and trans form (crotonic acid) or as derived from derivatives and reaction products of any of said four unsaturated acids.
  • Dendritic acrylates have previously been disclosed in publications as above and do indeed, due to the high functionality in combination with a high molecular weight and a low viscosity, promote reactivity well above state of the art radcure oligomers and polymers.
  • dendritic acrylates used as starting materials according to the invention is illustrated in enclosed embodiments.
  • reactive diluents are used together with an acrylic oligomer or polymer to adjust for instance the viscosity.
  • reactive diluents these might start to negatively influence the overall reactivity of a dendritic acrylate/reactive diluent formulation when cured under air atmosphere with low intensity UN lamps.
  • Tertiary amines are today admixed to acrylate based radiation curable formulations for two main reasons: i) They counteract air inhibition, provided that the particular amine contains asbtractable ⁇ -hydrogens, by formation of peroxy radicals, which can participate and trigger radical polymerisation of acrylic groups. Tertiary amines can therefore be used together with ⁇ orrish I type photoinitiators to reduce air inhibition and thereby increase cure speed. ii) They can act as co-synergists together with ketones of the benzophenone type, wherein the excited keto groups abstract a hydrogen from the amine, whereby two radicals are formed promoting radical polymerisation of acrylic groups and the like. This is the so called ⁇ orrish II type of photopolymerisation.
  • the blooming effect can be overcome by Michael addition of a secondary amine to an conventional acrylate functional monomer or oligomer yielding so called acrylated amines. They have the advantage of promoting higher cure speed, while the blooming effect is removed due to the fact that the acrylate amine will be an integral part of the cured network.
  • acrylated amines are available and are typically used in 5-10% by weight of a total formulation, together with 5-10 % by weight of either ⁇ orrish I or ⁇ orrish II type photoinitiators or mixtures thereof. Even though current acrylate amines are in fact prepolymers, they cannot be used as the sole oligomer or polymer component due to their adverse effects on mechanical properties compared to standard UN oligomers and polymers. Acrylated amines are further discussed in Chemistry and Technology of UV and EB formulations for Coatings, Inks & Paints, vol. II, Chapter IV, pp 153-157 "Acrylated Amines", by ⁇ .S. Allan, M.S. Johnsson, P.K.T.
  • Amine and nitril terminated dendrimers of polyamine type are disclosed in "AstramolTM Polypropyleneimine Dendrimers as Norrish Type II Amine Synergists", by j. jansen and H. Hartwig, RadTech '98, North America, pp 207-214, wherein primary amine termination was converted to tertiary amines by Micheal addition of phenoxyethyl acrylate.
  • the polymer backbone of the examplified dendrimers are of polyamine type. Acrylic double bonds are not present in disclosed molecules and said molecules are hence not radiation curable acrylic functional oligomers or polymers. The particular products examplified are therefore significantly different from the amine terminated dendritic acrylates according to the present invention.
  • the present invention accordingly refers to a radiation curable dendritic oligomer or polymer nominally having at least one terminal group of Formula (A)
  • Rj and R 2 individually are hydrogen or methyl and wherein R 3 and R 4 individually are alkyl, aryl, alkylaryl, arylalkyl, alkylalkoxy or arylalkoxy, wherein said alkyl, said alkoxy and/or said aryl optionally has one or more hydroxyl groups.
  • Said alkyl is preferably and indenpendently linear or branched alkanyl having 1-24 carbon atoms, linear or branched alkenyl having 3-24 carbon atoms, cycloalkanyl having 3-24 carbon atoms, branched cycloalkanyl having 4-24 carbon atoms, cycloalkenyl having 3-24 carbon atoms or branched cycloalkenyl having 4-24 carbon atoms and wherein said alkoxy preferably is ethoxy, propoxy, butoxy and/or phenylethoxy nominally comprising 0.2-50, such as 1-20 or 2-12 units of respective alkoxy.
  • R 3 and R 4 are in especially preferred embodiment individually methyl, hydroxymethyl, ethyl, hydroxyethyl, butyl, hydroxybutyl, propyl, hydroxypropyl, pentyl, hydroxypentyl, hexyl, hydroxyhexyl, heptyl, hydroxyheptyl, octyl, hydroxyactyl, nonyl, hydroxynonyl, phenyl or hydroxyphenyl.
  • the nominal percentage groups of Formula (A) to groups of Formula (B) is prefeably between 50:50 and 95:5, such as a nominal percentage of between 60:40 and 90:10 or 70:30 and 80:20.
  • the radiation curable dendritic oligomer or polymer according to the present invention can also in various embodiments, in addition to said at least one group of Formula (A) and said at least one group of formula (B), nominally comprise at least one terminal group comprising at least one oxygen, sulphur, phosphorus, nitrogen and/or halide, such as F, CI and/or Br, atom.
  • These embodiments include a radiation curable dendritic polymer nominally comprising at least one additional terminal hydroxyl, carboxyl, anhydride, alkenyl, ester, ether, thioester, thioether and/or thiol group.
  • the radiation curable dendritic oligomer or polymer of the present invention is in preferred embodiments a radiation curable dendritic polyester built up from at least one dendritic polyester, nominally having at least two terminal hydroxyl groups, which dendritic polyester per se is built up from ester units optionally in combination with ether units or is a radiation curable dendritic polyether built up from at least one dendritic polyether, nominally having at least two terminal hydroxyl groups, which dendritic polyether per se is built up from ether units optionally in combination with ester units.
  • Embodiments of said dendritic polyester having said at least two terminal hydroxyl groups include dendritic polyesters built up from a core molecule, having one or more hydroxyl and/or epoxide groups, and one or more dendrons bonded to said group or groups.
  • Said dendron preferably comprises two or more branching generations built up from at least one hydroxy and/or epoxyfunctional carboxylic acid, having at least one carboxyl group and at least two hydroxyl and/or epoxide groups, and optionally one or more spacing generations built up from at least one monohydroxy or monoepoxyfunctional monocarboxylic acid and/or from at least one lactone.
  • Said core molecule can for instance be a 1,3-propanediol, such as a 2-alkyl-l ,3-propanediol, 2,2-dialkyl- 1 ,3-propanediol, 2-hydroxy-2-alkyl- 1 ,3-propanediol, 2-hydroxyalkyl-2-alkyl- 1 ,3-propanediol, 2,2-di(hydroxyalkyl)- 1 ,3 -propanediol, 2-hydroxy- alkoxy-2-alkyl-l,3-propanediol, 2,2-di(hydroxyalkoxy)- 1,3 -propanediol or a dimer, trimer or polymer of a said 1,3-propanediol.
  • 1,3-propanediol such as a 2-alkyl-l ,3-propanediol, 2,2-dialkyl- 1 ,3-propaned
  • Alkyl is here preferably and independently alkanyl or C 2 -C 12 alkenyl and said alkoxy likewise preferably and independently ethoxy, propoxy and/or butoxy comprising 1 to 50, such as 1 to 20, units of respective alkoxy.
  • Said core molecule can suitably be exemplified by 2-methyl- 1,3-propanediol,
  • 1,3-propanediol and at least one alkylene oxide such as a reaction product between trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolethane, ditrimethylolpropane or dipentaerythritol and ethylene oxide, propylene oxide and/or butylene oxide, at a molar ratio alcohol to alkylene oxide of between 1:0.2 and 1:50, such as between
  • core molecule examples include alcohols such as ethylene glycol, propylene glycol, glycerol, anhydroennea-heptitol, 5-alkyl-5-hydroxyalkyl-
  • epoxides such as a glycidyl ester of a saturated mono functional carboxylic or fatty acid having for instance 1-24 carbon atoms, a glycidyl ester of an unsaturated mono functional carboxylic or fatty acid having for instance 3-24 carbon atoms, a glycidyl ester of a saturated or unsaturated di, tri or polyfunctional carboxylic acid having for instance 3-24 carbon atoms, a glycidyl ether of a saturated mono functional alcohol having for instance 1-24 carbon atoms, a glycidyl ether of an unsaturated mono functional alcohol having for instance 2-24 carbon atoms, a glycidyl ether of a saturated or unsaturated di, tri or polyfunctional alcohol having for instance 3-24 carbon atoms, a glycidyl ester of a saturated mono functional carboxylic or fatty acid having for instance 1-24 carbon atoms, a glycidyl ester of an unsaturated mono functional alcohol
  • Epoxide is here to be understood as any compound comprising at least one epoxy group.
  • Said dendron linked to said core comprises in especially preferred embodiments at least one generation built up from at least one di, tri or polyhydroxyfunctional monocarboxylic acid selected from the group consisting of dimethylolpropionic acid, ⁇ , ⁇ -bis(hydroxy- methyl)buryric acid, ⁇ , ⁇ -bis(hydroxymethyl)valeric acid, ⁇ , ⁇ -bis(hydroxy)propionic acid, 3,5-dihydroxybenzoic acid, ⁇ , ⁇ , ⁇ -tris- (hydroxymethyl)acetic acid, citric acid and/or heptonic acid and optionally at least one generation built up from at least one monohydroxyfunctional monocarboxylic acid and/or at least one lactone, such as hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid, glycolide, ⁇ -valerolactone, ⁇ -propiolactone and/or ⁇ -caprolactone.
  • di, tri or polyhydroxyfunctional monocarboxylic acid selected from the group consisting of dimethylolpropionic acid,
  • said dendritic polyester having said at least two terminal hydroxyl groups include polyester dendrons comprising at least one generation built up from at least one hydroxy and/or epoxyfunctional carboxylic acid, having at least one carboxyl group and at least two hydroxyl and/or epoxide groups, and optionally one or more spacing generations built up from at least one monohydroxy or monoepoxyfunctional monocarboxylic acid and/or from at least one lactone.
  • Said polyester dendron is in its preferred embodiments equal or similar to a dendron linked to a core molecule and disclosed above.
  • Embodiments wherein said radiation curable dendritic oligomer or polymer is built up from a dendritic polyether having at least two terminal hydroxyl groups include a dendritic polyether built up by thermally initiated cationic ring-opening polymerisation of at least one oxetane having at least two reactive groups of which at least one is an oxetane group.
  • Said at least one oxetane is preferably an oxetane of a 2-alkyl-2-hydroxyalkyl- 1,3-propanediol, a 2,2-di(hydroxyalkyl)- 1,3-propanediol, a 2-alkyl-2-hydroxyalkoxy- 1,3-propanediol, a 2,2-di(hydroxyalkoxy)-l,3- -propanediol or a dimer, trimer or polymer of any of said 1,3-propanediols.
  • Alkyl is here preferably and independently linear or branched alkanyl or alkenyl having 3 to 24, such as 4 to 12, carbon atoms and said alkoxy is preferably and independently ethoxy, propoxy or butoxy comprising 0.2 to 50, such as 1 to 20 or 2 to 12, units of respective alkoxy.
  • Said oxetane can suitably be exemplified by oxetanes of trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolethane, ditrimethylolpropane and dipentaerythritol and ethoxylates and/or propoxylates of a said alcohol.
  • a dendritic polyester or polyether having said at least two terminal hydroxylgroups may furthermore be partially chain terminated by reaction with at least one alkanyl, cycloalkanyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl or aryl compound selected from the group consisting of a mono, a di, a tri and a polyfunctional saturated or unsaturated carboxylic acid.
  • the present invention refers to a process for production of a radiation curable dendritic oligomer or polymer as disclosed above.
  • Said process comprises the Steps of (i) aciylation, by addition of at least one compound having at least one acrylic double bond to a dendritic oligomer or polymer nominally having at least two terminal hydroxyl groups, said acrylation being performed at a ratio hydroxyl groups to acrylic double bonds yielding a dendritic acrylate oligomer or polymer nominally having at least one acrylic double bond, and (ii) addition of at least one secondary amine to the dendritic acrylate ologomer or polymer yielded in Step (i) at a ratio amine to acrylic double bonds yielding an amine termianated dendritic acrylate oligomer or polymer having at least one acrylic double bond and at least one tertiary amine group.
  • Said acrylation in Step (i) is in various embodiments of said process preferably and most suitably performed employing acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid or a to a said acid corresponding anhydride or halide.
  • Embodiments of the present process include addition in Step (ii) of at least one secondary amine being a compound of Formula (C)
  • R 5 and R 6 individually is alkyl, aryl, alkylaryl, arylalkyl, alkylalkoxy, arylalkoxy, said alkyl and/or said aryl optionally having one or more hydroxyl groups.
  • Alkyl is here preferably and indenpendently linear or branched alkanyl having 1-24 carbon atoms, linear or branched alkenyl having 3-24 carbonatoms, cycloalkanyl having 3-24 carbon atoms, branched cycloalkanyl having 4-24 carbon atoms, cycloalkenyl having 3-24 carbon atoms or branched cycloalkenyl having 4-24 carbon atoms and said alkoxy is preferably ethoxy, propoxy, butoxy and/or phenylethoxy nominally comprising 0.2-50, such as 1-20 or 2-12 units of respective alkoxy .
  • Said secondary amine is suitably exemplified by a dialkylamine or diarylamine, such as dimethylamine, methylethylamine, diethylamine, dibutylamine, diphenylamine, ethylphenylamine, cyclohexylamine, diethanolamine and diisopropanolamine.
  • the dendritic oligomer or polymer, nominally having said at least two terminal hydroxylgroups, of said process is in preferred embodiments a dendritic polyester built up from ester units optionally in combination with ether units or a dendritic polyether built up from ether units optionally in combination with ester units as herein previously disclosed, discussed and exemplied.
  • the present invention refers to a radiation curable composition
  • a radiation curable composition comprising a radiation curable dendritic oligomer or polymer as previously disclosed in an amount of at least 0.1%, such as 0.5-80%, 0.5-50% or 1-25%, by weight.
  • Said composition comprises optionally in addition to said radiation curable dendritic oligomer or polymer comprises at least one linear or branched radiation curable monomer, oligomer or polymer, such as at least one linear or branched acrylic monomer, oligomer or polymer having at least one, preferably at least two acrylic double bonds and/or
  • Embodiments of said composition of the present invention include compositions comprising, in addition to said radiation curable dendritic oligomer or polymer, at least one reactive diluent, such as at least one acrylic ester of a 2-alkyl-l,3-propanediol, a 2,2-dialkyl-l,3-propanediol, a 2-hydroxy-2-alkyl- 1,3 -propanediol, a 2-hydroxyalkyl-2-alkyl- - 1,3-propanediol, a 2,2-di(hydroxyalkyl)-l,3-propanediol, a 2-hydroxyalkoxy-2-alkyl- -1,3 -propanediol or a 2,2-di(hydroxyalkoxy)- 1,3 -propanediol.
  • Alkyl is here independently
  • C J -C J2 alkanyl or C 2 - 2 alkenyl and alkoxy likewise independently ethoxy, propoxy or butoxy nominally comprising 0.2 to 50, such as 1 to 20 or 2 to 12, units of respective alkoxy.
  • 1:0.2 and 1:50 such as between 1:1 and 1:20.
  • composition of the present invention can, furthermore, comprise at least one Norrish I or Norrish II type photoinitiator, preferably in an amount of at most 1% by weight and/or at least one acrylated amine, preferably in an amount of at most 10%), such as 5-10%, by weight of the total formulation.
  • Said acrylated amine is preferably of the type disclosed and discussed in Chemistry and Technology of UV and EB formulations for Coatings, Inks & Paints, vol. II, Chapter IV, pp 153-157 "Acrylated Amines", by N.S. Allan, M.S. Johnsson, P.K.T. Oldring and S. Salim, SIT A Technology Ltd, London, UK, 1991.
  • Example 1 Preparation of a dendritic polyester acrylate according to an embodiment of Step
  • Example 2 and 3 Preparation of an embodiment of a dendritic oligomer/polymer according to the present invention. Preparation is perfomed according to an embodiment of the process of the present invention.
  • Examples 4-6 Evaluations of products obtained according to Examples 1-3 in comparison with reference substances.
  • Graph 1 Chemical resistance of dendritic acrylates vs. conventional oligomer acrylates as a function of number of passages under irradiation source.
  • Graph 2 Pencil hardness of cured dendritic acrylate oligomers vs. reference acrylates with and without acrylate amine.
  • Graph 3 Film hardness (pendulum hardness) of dendritic acrylate oligonmers vs. reference acrylates with and without acrylate amine. Pendulum hardness is measurred using a K ⁇ nig pendulum and reported as K ⁇ nig seconds.
  • Graph 4 Chemical resistance of diluted dendritic acrylates and reference acrylates.
  • Graph 5 Scratch resistance of diluted dendritic acrylates and reference acrylates.
  • Graph 6 Film hardness of PEOTA-diluted dendritic acrylates and reference acrylates.
  • Graph 7 Chemical resistance of diluted dendritic acrylate and reference acrylate when admixing 0.1 % of benzophenone to a coating formulation.
  • Graph 8 Scratch resistance of diluted dendritic acrylates and reference acrylate with addition of0.1% benzophenone.
  • Graph 9 Film hardness of diluted dendritic acrylates and reference acrylate/amine with 0.1% addition of benzophenone.
  • Example 2 was repeated with the difference that 20 mole% of dibutylamine instead of 15 mole% was charged. Obtained amine terminated dendritic acrylate was a highly viscous, yellow and odour-free product at room temperature and exhibited following product characteristics:
  • Examples 1-3 The products obtained in Examples 1-3 were heated to 50°C and then coated with a Meyer "2" bar to a film thickness of 12 ⁇ m on steel planels of the dimensions 152 x 75 x 0.25 mm.
  • references were also evaluated.
  • One of said references was a commercial polyester oligomer/polymer acrylate (1000 g/mole, 4 mmole/g of unsaturation) of high reactivity.
  • the second was a mixture of 90 pph of the commercial reference according to above and 10 pph of a commercial acrylate amine, of the type disclosed in Chemistry and Technology of UV and EB formulations for Coatings, Inks & Paints, vol. II, Chapter IV, 157 "Acrylated Amines", by N.S. Allan, M.S. Johnsson, P.K.T. Oldring and S.
  • Coating formulations comprising the products obtained in Examples 1-3 were prepared. Respective dendritic oligomer/polymer were diluted with pentaerythritol ethoxylate tetraacrylate (PEOTA) as reactive diluent in a 1:1 weight ratio. The reactive diluent content was hence 50%> by weight of the total formulations. The reference oligomer/polymer described and evaluated in Example 4 were also in the same manner diluted with PEOTA to a reactive diluent content of 50% by weight.
  • PEOTA pentaerythritol ethoxylate tetraacrylate
  • Example 5 is an extension of Example 5 and examplifies that extremely reactive coatings can be obtained according to the invention, when large amounts of reactive diluents are present, by minute additions of a photoinitiator.
  • the diluted dendritic acrylate according to Example 2 were evaluated in the presence of a very low amount of photoinitiator. 0.1% by weight of benzophenone was added to said diluted dendritic acrylate and compared with the diluted reference (see Example 4) comprising acrylate amine.
  • Coatings were prepared and evaluated in the same manner as described in Example 4. Obtained film properties are given in Graphs 7-9 below.
  • Graphs 7-9 again confirm the unique performance of radiation curable coatings comprising amine terminated dendritic acrylates according to the present invention.
  • a very small addition (0.1%) by weight - normally used levels of benzophenone in radation curing coatings are approx. 5% by weight) of benzophenone yields coatings having extremely good chemical resistance, very good scratch resistance as well as high film hardness.
  • the coatings comprising an amine terminated dendritic acrylate according to the present invention yield - with or without photoinitiator - coating properties that are superiour to coatings based on state of the art commercial technology.
  • UV-curing of neat oligomers in air at 20m/min, 80 /cm
  • Reference acrylate poly er/acrylated amine Reference acrylate

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Abstract

Oligomère ou polymère dendritique durcissable par rayonnement qui peut être obtenu par ajout d'au moins d'une amine secondaire à au moins une double liaison acrylique dans un oligomère ou polymère acrylate dendritique. Ledit oligomère ou polymère durcissable par rayonnement possède essentiellement au moins une double liaison acrylique et au moins un groupe amine tertiaire. Dans un autre aspect, la présente invention concerne un procédé de production dudit oligomère ou polymère dendritique durcissable par rayonnement. Ledit procédé consiste à acryler un polymère dendritique ayant essentiellement au moins deux groupes hydroxyle terminaux, puis à ajouter par réaction de Michael au moins une amine secondaire à au moins une double liaison acrylique. Dans un autre aspect encore, la présente invention concerne une composition durcissable par rayonnement contenant ledit oligomère ou polymère dendritique.
PCT/SE2001/001894 2000-09-13 2001-09-06 Oligomere ou polymere dendritique durcissable par rayonnement Ceased WO2002022700A2 (fr)

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EP1616897A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouveaux co-initiateurs polymeriques
EP1616922A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouvelles compositions durcissables par rayonnement
EP1674499A1 (fr) * 2004-12-21 2006-06-28 Agfa-Gevaert Compositions durcissables par irradiation
US7189456B2 (en) 2004-03-04 2007-03-13 Transitions Optical, Inc. Photochromic optical article
US7258437B2 (en) 2005-09-07 2007-08-21 Transitions Optical, Inc. Photochromic multifocal optical article
US7396861B2 (en) 2004-07-15 2008-07-08 Agfa Graphics Nv Radiation curable compositions
US7507785B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Polymeric co-initiators
US7507773B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Radiation curable compositions
US7538144B2 (en) 2004-07-15 2009-05-26 Agfa Graphics, N.V. Photoreactive polymers
US7666331B2 (en) 2005-08-31 2010-02-23 Transitions Optical, Inc. Photochromic article
EP1940984A4 (fr) * 2005-10-18 2011-01-12 Perstorp Specialty Chem Ab Composition a durcissement double
WO2010133289A3 (fr) * 2009-05-19 2011-02-24 Byk-Chemie Gmbh Macromonomères à base d'oxétane à insaturation terminale et leur procédé de production
WO2010133288A3 (fr) * 2009-05-19 2011-03-03 Byk-Chemie Gmbh Polymères pouvant être obtenus à partir de macromonomères à base d'oxétane, procédé pour les préparer et leur utilisation en tant qu'additifs dans des agents de revêtement et des matières plastiques
WO2011033262A1 (fr) 2009-09-17 2011-03-24 Unilever Plc Utilisation de copolymères d'addition ramifiés pour durcir des systèmes
EP1616899B2 (fr) † 2004-07-15 2014-07-02 Agfa Graphics N.V. Nouveaux polymères photoréactifs
JP2015509099A (ja) * 2012-01-20 2015-03-26 オルネクス ベルギウム ソシエテ アノニム アミノ光反応性バインダー
US10005717B2 (en) 2012-01-20 2018-06-26 Allnex Belgium S.A. Photo-reactive binder
US10189930B2 (en) 2013-07-23 2019-01-29 Allnex Belgium S.A. Polymeric photoinitiators
CN110615894A (zh) * 2019-06-15 2019-12-27 威海晨源分子新材料有限公司 一种超支化聚酯胺及其在水性涂料中的应用
US10633553B2 (en) 2015-10-16 2020-04-28 Basf Se Energy curable high reactivity multi vinylether or acrylate functional resins
CN115279845A (zh) * 2020-03-04 2022-11-01 阿科玛英国有限公司 光引发剂乳液

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AU2004289940B2 (en) * 2003-11-12 2008-03-13 Perstorp Specialty Chemicals Ab Radiation curable waterborne composition
US7189456B2 (en) 2004-03-04 2007-03-13 Transitions Optical, Inc. Photochromic optical article
US7507773B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Radiation curable compositions
EP1616922A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouvelles compositions durcissables par rayonnement
US7396861B2 (en) 2004-07-15 2008-07-08 Agfa Graphics Nv Radiation curable compositions
US7507785B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Polymeric co-initiators
EP1616899B2 (fr) † 2004-07-15 2014-07-02 Agfa Graphics N.V. Nouveaux polymères photoréactifs
US7538144B2 (en) 2004-07-15 2009-05-26 Agfa Graphics, N.V. Photoreactive polymers
CN1721478B (zh) * 2004-07-15 2010-06-16 爱克发印艺公司 新型可辐射固化组合物
EP1616897A1 (fr) * 2004-07-15 2006-01-18 Agfa-Gevaert Nouveaux co-initiateurs polymeriques
EP1674499A1 (fr) * 2004-12-21 2006-06-28 Agfa-Gevaert Compositions durcissables par irradiation
US7666331B2 (en) 2005-08-31 2010-02-23 Transitions Optical, Inc. Photochromic article
US7258437B2 (en) 2005-09-07 2007-08-21 Transitions Optical, Inc. Photochromic multifocal optical article
EP1940984A4 (fr) * 2005-10-18 2011-01-12 Perstorp Specialty Chem Ab Composition a durcissement double
WO2010133289A3 (fr) * 2009-05-19 2011-02-24 Byk-Chemie Gmbh Macromonomères à base d'oxétane à insaturation terminale et leur procédé de production
KR101526528B1 (ko) * 2009-05-19 2015-06-05 비와이케이-케미 게엠베하 옥세탄계 마크로모노머로부터 수득가능한 폴리머, 그의 제조방법 및 코팅제와 플라스틱에 있어서 첨가제로서의 그의 용도
JP2012527497A (ja) * 2009-05-19 2012-11-08 ベーイプシロンカー ヘミー ゲゼルシャフト ミット ベシュレンクター ハフトゥング 末端不飽和のオキセタン系マクロモノマー及びその製造方法
US8501880B2 (en) 2009-05-19 2013-08-06 Byk-Chemie Gmbh Polymers obtainable from oxetane based macromonomers, method for the production thereof, and the use thereof as additives in coating agents and plastics
WO2010133288A3 (fr) * 2009-05-19 2011-03-03 Byk-Chemie Gmbh Polymères pouvant être obtenus à partir de macromonomères à base d'oxétane, procédé pour les préparer et leur utilisation en tant qu'additifs dans des agents de revêtement et des matières plastiques
US8883942B2 (en) 2009-05-19 2014-11-11 Byk-Chemie Gmbh Terminally unsaturated, oxetane-based macromonomers, and methods for the production thereof
WO2011033262A1 (fr) 2009-09-17 2011-03-24 Unilever Plc Utilisation de copolymères d'addition ramifiés pour durcir des systèmes
JP2015509099A (ja) * 2012-01-20 2015-03-26 オルネクス ベルギウム ソシエテ アノニム アミノ光反応性バインダー
US10000446B2 (en) 2012-01-20 2018-06-19 Allnex Belgium S.A. Amino photo-reactive binder
US10005717B2 (en) 2012-01-20 2018-06-26 Allnex Belgium S.A. Photo-reactive binder
US10189930B2 (en) 2013-07-23 2019-01-29 Allnex Belgium S.A. Polymeric photoinitiators
US10633553B2 (en) 2015-10-16 2020-04-28 Basf Se Energy curable high reactivity multi vinylether or acrylate functional resins
CN110615894A (zh) * 2019-06-15 2019-12-27 威海晨源分子新材料有限公司 一种超支化聚酯胺及其在水性涂料中的应用
CN115279845A (zh) * 2020-03-04 2022-11-01 阿科玛英国有限公司 光引发剂乳液

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AU2001286351A1 (en) 2002-03-26
WO2002022700A3 (fr) 2002-05-30

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