Classifications

• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

• the invention relates to a radiation- curable coating composition containing a radiation- curable resin composition and an aliphatic maleimide.
• Such a radiation-curable coating composition is described in "Initiator free polymerisations of donor acceptor monomer systems" by C.E. Hoyle, S. Jonsson, S.C. Clark, C. Miller and M. Shimose (Radtech Europe, June 97, Lyons). This describes a coating composition consisting of an acrylate-functional resin and an aliphatic maleimide. This composition cures under the influence of UV light.
• a drawback of such a coating composition is that it cures at a low rate.
• the aim of the invention is to provide a radiation-curable coating composition that has a higher curing rate.
• the radiation-curable coating composition also contains a tertiary amine. This ensures that the radiation-curable coating composition cures faster under the influence of radiation than the known radiation-curable coating composition described by Hoyle et al .
• EP-A-618,237 describes a coating composition based on an acrylate-functional resin and maleic anhydride. A drawback of the coating composition described in EP-A-618,237 is that it cures slowly, as a result of which the cured coating may also contain residual monomer in addition to residual photoactive compound.
• the radiation-curable resin composition consists of for example a reactive unsaturation connected to an electron-withdrawing group (a) , optionally combined with a reactive unsaturation connected to an electron-donating group (b) or a an allyl group-containing compound connected to an electron-donating group (c) or a mixture hereof (b+c) .
• the reactive unsaturation connected to an electron-withdrawing group (a) is characterised by the following structural element.
• X may be for example any one of the following groups: OR 4 , NR 4 R 5 , SR 4 .
• Ri,R 2 , R 3 may be for example independently of one another the following groups: H, C 1 -C 20 alkyl, aryl, substituted aryl, COOR 6 , CONR 6 R 7 , CH 2 COOR 6 , CH 2 OR s , OR 6 , NR 6 R 7 , SR 6 , Cl or CN, in which R 4 , R 5 , R 6 and R 7 are chosen from the following groups: H, C 1 -C 20 , alkyl (including linear and cyclic structures) , aryl, substituted aryl, O, S, N or P atoms-containing heterocyclic compounds, 0, S, N or P atoms-containing aromatic heterocyclic compounds, COY, CH 2 COY, CH 2 OY, CH 2 NYZ, CH 2 SY, CH 2 CH 2 0Y, CH 2 CH 2 NYZ CH 2 CH 2 SY,
• Y and Z can for example be chosen from any of the following groups H, C 1 -C 20 , alkyl (including linear and cyclic structures) , aryl, substituted aryl, 0, S, N or P atoms-containing heterocyclic compounds, 0, S, N or P atoms-containing aromatic heterocyclic compounds. Derivatives of these compounds can also be used, for example esters, urethanes, urea, thiourethanes and anhydrides.
• the reactive unsaturation connected to an electron-donating group (b) use is preferably made of a vinyl ether, a vinyl ester, a vinyl amide, a vinyl amine, a vinyl thioether or a vinyl thioester.
• allyl group-containing compound connected to an electron-donating group use is preferably made of an allyl ether, an allyl ester, an allyl amine or an allyl amide.
• the amount of reactive unsaturation connected to an electron-withdrawing group (a) in the radiation-curable curing resin is between 25% and 100%.
• the amount of reactive unsaturation connected to an electron-donating group (b) or an allyl group- containing compound connected to an electron-donating group (c) or a mixture hereof (b+c) in the radiation- curable curing resin is between 0% and 75%, depending on the amount of reactive unsaturation connected to an electron-withdrawing group (a) in the radiation-curable curing resin.
• the amount of reactive unsaturation connected to an electron-withdrawing group (a) in the radiation-curable resin is 100%.
• the amount of reactive unsaturation connected to an electron-withdrawing group (a) in the radiation-curable resin is 50% and the amount of reactive unsaturation connected to an electron-donating group (b) or an allyl group-containing compound connected to an electron-donating group (c) or a mixture hereof (b+c) in the radiation-curable resin is 50%.
• the reactive unsaturation connected to an electron-withdrawing group (a) may be connected to polymers or oligomers via R 4 .
• polymers or oligomers are polyurethanes , polyesters, polyacrylates, polyethers, polyolefins containing for example units from the group comprising ethylene, propene, butadiene and styrene, hydrocarbon polymers such as (co)polymers of cyclopentadiene, polysilicates, polycarbonates, polyvinyl esters, rubbers such as polyisoprene, natural rubbers and polyepoxides .
• Copolymers such as polyether urethanes, polyester urethanes, polyether carbonates and polyepoxide esters. Combinations of polymers or oligomers can also be used.
• the reactive unsaturation connected to the electron-withdrawing group (a) has another functionality besides R 4 , in the form of R lf R 2 or R 3 , for example C00R 6 , C0NR 6 R 7 , CH 2 COOR 6 or CH 2 OR 6
• the reactive unsaturation can be incorporated in the polymer or oligomer chain.
• examples of such polymers or oligomers are unsaturated polyesters in which fumarate, maleate, itaconate, citraconate or mesaconate functionalities are incorporated in the structure of the polymer or oligomer.
• the number of reactive unsaturations connected to an electron- attracting group in a polymer or oligomer is greater than 1.
• the reactive unsaturation connected to an electron-donating group (b) or the allyl group- containing compound connected to an electron-donating group (c) can be bound to the polymers or oligomers described above via ether, ester amine or amide bonds, or, in the case of a bifunctional reactive unsaturation connected to an electron-donating group or a bifunctional allyl compound, it can also be incorporated in a polymer or oligomer chain.
• the radiation-curable resin composition may also contain low-molecular compounds containing a reactive unsaturation.
• These low-molecular compounds contain a * reactive unsaturation in the molecule with side groups that may be aromatic, aliphatic or cycloaliphatic.
• These molecules may furthermore contain several functionalities, i.e. they may be mono- or multifunctional.
• ethyl acrylate ethyl methacrylate, methyl methacrylate, hexane diol diacrylate, hexane diol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate
• acrylamides such as acrylamide, N- methyl acrylamide, N-lauryl acrylamide, maleate esters such as ethyl maleate, diethyl maleate, methyl maleate, maleamides such as N,N' -bismaleamide, N,N' -dimethyl maleamide, fumarate esters such as ethyl fumarate, diethyl fumarate, fumaric amides, itaconic esters such as methyl itaconate, dimethyl itaconate, ethyl itaconate, itaconic amides, itaconic imides, citraconic esters such as methyl citraconate, diethy
• Aliphatic maleimides are characterised in that an aliphatic carbon is connected to the nitrogen atom of the maleimide, as represented in the following structure.
• R- L , R 2 , R 3 independently of one another, a choice can be made from for example the group comprising H, C x - C 20 alkyl, aryl, hydroxy, thiol, amines, ethers, thioethers, esters, thioesters, amides, thioamides, urethanes, thiourethanes and combinations of these functionalities.
• R l R 2 , R 3 may also form part of ring systems or they may be interconnected in this way, for example so that R ! -R 2 is C 5 H 10 and R 3 is H, i.e. cyclohexyl maleimide.
• the aliphatic maleimide may also contain more than one maleimide group, i.e. a bis, tris, tetra, penta, hexa, etc. maleimide. If the aliphatic maleimide contains more than one maleimide group, these maleimide groups may be connected via a chain comprising exclusively carbon. These maleimide groups may also be connected via other functionalities, such as amines, ethers, thioethers, esters, thioesters, amides, thioamides , urethanes and thiourethanes . The other functionalities may form part of oligo (polymer) chains such as polyethers, polyesters, polyurethane, polyethylene. Combinations of functional groups are also possible here, such as a polyether urethane.
• the aliphatic maleimide contains more than one maleimide group. According to a third preferred embodiment of the invention the aliphatic maleimide contains more than one maleimide group and a hydroxy, ether, ester or urethane functionality or combinations of these functionalities .
• the amount of maleimide in the present radiation-curable coating composition is not critical. Preferably the amount of maleimide used in this radiation-curable coating composition is between 0.1 and 15 wt.%, relative to the radiation-curable resin composition. With less than 0.1 wt.% maleimide the radiation-curable coating composition reacts too slowly. With more than 15 wt.% the properties of the cured radiation-curable coating composition are adversely affected.
• the tertiary amine may be an aromatic or an aliphatic tertiary amine.
• An advantage of an aliphatic tertiary amine is that this compound increases the reactivity of the curing reaction to an extra extent while the advantage of an aromatic tertiary amine is that it is much less volatile and is consequently bound better by the cured radiation-curable coating composition.
• the tertiary amine may contain other functionalities, for example hydroxy, thiol, ether, ester, nitrile, acrylate, vinyl, urethane and amide functionalities.
• the tertiary amine may also be a monomer, oligomer or polymer with a tertiary amine functionality.
• An example of a tertiary amine without other functionalities is triethylamine .
• Examples of tertiary amines with a hydroxy functionality are N,N- dimethyl ethanol amine, N-methyl diethanol amine (Genocure MDEA, RAHN) and triethanol amine.
• tertiary amine with an ether functionality is N- methylmorpholine.
• aromatic tertiary amines are 2-ethylhexyl-4-dimethylaminobenzoate (Quantacure
• oligomer (polymer) tertiary amines are derivatives of the Jeff amines, Actilane 584 (AKCROS) and Actilane 587 (AKCROS) .
• tertiary amines with a functionality that can co-react during the radiation curing, such as acrylates or vinyl ether functionalities, are Ebecryl P115 (UCB) , Ebecryl 7100 (UCB) , Genomer 5248 (RAHN) , Genomer 8275 (RAHN) , Genomer 5695 (RAHN) , Actilane 705 (AKCROS) , Actilane
• tertiary amines mentioned above can also be used, as can mixtures of the tertiary amines mentioned above.
• the amount of tertiary amine used in a radiation-curable coating composition is not critical.
• the amount of tertiary amine used in a radiation-curable coating composition is between 0.1 and 15 wt.%, relative to the radiation-curable resin composition. With an amount of tertiary amine of less than 0.1 wt. % the reaction rate of the curing reaction decreases substantially. With an amount of tertiary amine of more than 15 wt.% the tertiary amine can no longer be bound entirely in the cured radiation-curable coating composition.
• the radiation-curable coating composition according to the invention may also contain additives such as pigments, fillers and matting agents.
• the radiation-curable coating composition may also contain other photoactive compounds.
• Other photoactive compounds are ketonic and may be aromatic, such as xanthone, thioxanthone and benzophenone .
• Suitable aromatic ketones are Darocure 1173 (2 -hydroxy-2 -methyl-1- phenylpropane-1-one as the active component) , Irgacure 184 (hydroxy-eyelohexyl phenyl ketone as the active component) , Irgacure 369 (2-benzyl-2-dimethylamino-l- (morpholinophenyl) -butanone-1 as the active component) , acylphosphines such as Lucerine TPO (2,4,6- trimethylbenzoyl diphenyl phosphine oxide) . Chemical derivatives and combinations of these photoinitiators can also be used.
• xanthone, thioxanthone and benzophenone and their derivatives are employed as photoactive compounds in combination with the maleimide/tertiary amine combination.
• the radiation-curable coating composition can be cured by different kinds of radiation, such as UV and EB radiation.
• the most prefered irradiation source is ultraviolet light.
• Ultraviolet light is preferably high intensity light to provide a dosage to achieve reasonable curing rates .
• UV-curing equipment we refer to, for example, pages 161-234 of Chemistry and Technology of Uv and EB-formulations, volume 1, Oldring
• Suitable lamps employed to provide the desired high intensity and availability of wavelength and spectral distribution include for example that available from Fusion systems, Corp.
• the radiation-curable coating composition according to the invention can be used on different substrates, for example glass, paper, wood, plastic, metals such as aluminium and iron.
• a 10- ⁇ m-thick film was applied to a gold-coated aluminium plate. This plate was subsequently cured in the infrared machine using a dose of 500 mW/cm 2 and the conversion of the acrylate double bonds was followed.
• a 10- ⁇ m-thick film was applied to a gold-coated aluminium plate. This plate was subsequently cured in the infrared machine using a dose of 500 mW/cm 2 and the conversion of the acrylate double bonds was followed. A 97 % degree of conversion was obtained after 9.8 seconds.
• a 10- ⁇ m-thick film was applied to a gold-coated aluminium plate. This plate was subsequently cured in the infrared machine using a dose of 500 mW/cm 2 and the conversion of the acrylate double bonds was followed.
• a 100- ⁇ m-thick film was applied on a glass plate and subsequently cured with a total dose of 1 J/cm 2 under nitrogen using a Fusion VIP 308 as lamp. After irradiation a cured coating was obtained as indicated with the acetone double rub test . The cured film could withstand 100 acetone double rubs without being affected.
• a 100- ⁇ m-thick film was applied on a glass plate and subsequently cured with a total dose of 1 J/cm 2 under nitrogen using a Fusion VIP 308 as lamp. After irradiation the coating was not fully cured as indicated with the acetone double rub test. The coating was completely removed from the glassplate after 60 acetone double rubs .
• a 100- ⁇ m-thick film was applied on a glass plate and subsequently cured with a total dose of 1 J/cm 2 under nitrogen using a Fusion VIP 308 as lamp. After irradiation the coating was not fully cured as indicated with the acetone double rub test . The coating was completely removed from the glassplate after 72 acetone double rubs .
• Experiment IV and comparative example E as well as Experiment V and comparative example F clearly show that a cured coating is obtained employing the same dose by using the combination of an aliphatic maleimide and a tertiary amine.
• a 100- ⁇ m-thick film was applied on a glass plate and subsequently cured with a total dose of 1 J/cm 2 under nitrogen using a Fusion VIP 308 as lamp. After irradiation a cured coating was obtained as indicated with the acetone double rub test. The cured film could withstand 100 acetone double rubs without being affected.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Engineering & Computer Science (AREA)
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• Wood Science & Technology (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
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• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1997
  • 1997-07-18 NL NL1006621A patent/NL1006621C2/nl not_active IP Right Cessation
• 1998
  • 1998-07-03 WO PCT/NL1998/000382 patent/WO1999003930A1/en not_active Application Discontinuation
  • 1998-07-03 CA CA002297056A patent/CA2297056A1/en not_active Abandoned
  • 1998-07-03 EP EP98932622A patent/EP0996680A1/en not_active Withdrawn
  • 1998-07-03 JP JP2000503147A patent/JP2001510220A/ja active Pending
  • 1998-07-03 BR BR9811515-4A patent/BR9811515A/pt not_active IP Right Cessation
  • 1998-07-03 CN CN 98807374 patent/CN1264409A/zh active Pending
  • 1998-07-03 AU AU82457/98A patent/AU8245798A/en not_active Abandoned
  • 1998-07-03 KR KR1020007000408A patent/KR20010021844A/ko not_active Application Discontinuation

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