EP1084456A1 - Heavy metal-free coating formulations - Google Patents

Heavy metal-free coating formulations

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Publication number
EP1084456A1
EP1084456A1 EP99919233A EP99919233A EP1084456A1 EP 1084456 A1 EP1084456 A1 EP 1084456A1 EP 99919233 A EP99919233 A EP 99919233A EP 99919233 A EP99919233 A EP 99919233A EP 1084456 A1 EP1084456 A1 EP 1084456A1
Authority
EP
European Patent Office
Prior art keywords
composition according
compound
compounds
alkyl
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99919233A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ljubomir Misev
Allan Francis Cunningham
Gisèle BAUDIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP99919233A priority Critical patent/EP1084456A1/en
Publication of EP1084456A1 publication Critical patent/EP1084456A1/en
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Definitions

  • the present invention relates to heavy metal-free UV-curable, cationically polymerisable compositions and to their use.
  • the technology has a demand for formulations which are radiation-curable, reactive, cationically curable, inexpensive, white and hardly yellowing, especially for use as coatings.
  • the photoinitiator (c) is, for example, a compound of formula I
  • R 2 , R 3 and R 4 are each independently of one another hydrogen, d-C 2 oalkyl or unsub- stituted or hydroxyl-substituted CrC 2 oalkoxy, with the proviso that at least one of R 1 ( R 2 , R 3 or R 4 is not hydrogen.
  • C,-C 20 Alkyl is linear or branched and is, for example, C C ⁇ 2 -, Cj-C ⁇ -, d-Ce- or d-C 4 alkyl.
  • Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dcdecyl, tetra- decyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.
  • Branched alkyl is preferred, in particular C 3 -C 8 -, C 3 -C 6 - and C 3 -C 4 alkyl.
  • R 2 and R 4 are, for example, d-C ⁇ alkyl, C C 8 alkyl or CrCealkyl, preferably d-dalkyl, such as isobutyl, or d-C ⁇ alkyl, such as dodecyl.
  • CrCjioAlkoxy is a linear or branched radical and is, for example, C ⁇ -C 12 -, C J -C B -, CrC 6 - or C C 4 alkoxy.
  • Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethypentyloxy, 2-ethyl- hexyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, hexadecyloxy or octadecyloxy, prefer ably methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butybxy, isobutyloxy, tert-butyloxy, more preferably me
  • Preferred compounds are, for example, n-C 4 -C 6 -, n-C C ⁇ -, n- C 2 -C 6 -, n-C C 4 - n-C 2 -C 4 alkoxy.
  • n-C 12 -C 20 Alkoxy is also interesting.
  • R 1 f R 2 , R 3 and R are branched CrC 2 oalkyl, preferably branched CrC 12 alkyl or branched C C 4 alkyl.
  • Preferred compounds of formula I are those, wherein R 2 and R 4 are d-C ⁇ alkyl, and R-, and R 3 are hydrogen.
  • R 2 is CrC 12 alkyl, preferably isobutyl or dodecyl, and R ⁇ , R 3 and R are hydrogen.
  • R 2 and R are C C 12 - alkyl, such as isobutyl or dodecyl.
  • Preferred compounds of formula I are those, wherein R 2 is CrC 4 alkyl if R,, R 2 and R 3 are hydrogen.
  • Other preferred compounds of formula I are those wherein R 2 is C C 4 alkoxy if R,, R 2 and R 3 are hydrogen.
  • Those compounds of formula I are also preferred wherein R 2 is C ⁇ 0 -C 20 alkoxy if Ri, R 2 and R 3 are hydrogen.
  • Examples of compounds of formula I are bis(4-hexylphenyl)iodonium hexafluorophosphate; (4-hexylphenyl)phenyl iodonium hexafluorophosphate; bis(4-octylphenyl)iodonium hexafluorophosphate; (4-octylphenyl)phenyl iodonium hexafluorophosphate; bis(4-decylphenyl)iodonium hexafluorophosphate; (4-isobu- tylphenyl)phenyl iodonium hexafluorophosphate; bis(4-isobutylphenyl)iodonium hexafluorophosphate; (4-dodecylphenyl)phenyl iodonium hexafluorophosphate; (2-hydroxydodecyloxy- phenyl)phenyl io
  • This invention also relates to (4-isobutylphenyl)phenyl iodonium hexafluorophosphate, in particular dissolved in propylene carbonate.
  • This literature also describes different methods for the preparation of the above- mentioned simple salts, for example the reaction of two aromatic compounds with iodyl sulfate in sulfuric acid; the reaction of two aromatic compounds with iodate in acetic acid, acetic anhydride, sulfuric acid; the reaction of two aromatic compounds with iodine acylate in the presence of an acid, or the condensation of a iodosyl compound, of a iodosyl diacetate or of a iodoyl compound with another aromatic compound in the presence of an acid.
  • the photoinitiator (c) is conveniently used in an amount from 0.05% to 15%, for example from 0.5% to 10%, preferably from 0.1 % to 5%, based on the composition.
  • the glycidyl ether components (a) used in the novel formulations are typically glycidyl ethers of polyvalent phenols obtained by reacting polyvalent phenols with an excess of chlorohyd- rin, such as epichiorohydrin (e.g. glycidyl ether of 2,2-bis(2,3-epoxypropoxyphenol)propane.
  • epichiorohydrin e.g. glycidyl ether of 2,2-bis(2,3-epoxypropoxyphenol
  • Other examples of glycidyl ether epoxides which can be used in connection with this invention are described, inter alia, in US 3018262 and in "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co., New York (1967).
  • glycidyl ether epoxides which can be used as component (a), for example glycidyl methacrylate, diglycidyl ether of bisphenol A, e.g. those obtainable under the tradenames EPON 828, EPON 825, EPON 1004 and EPON 1010, of Shell; DER-331 , DER-332 and DER-334, of Dow Chemical; 1 ,4-butanediol diglycidyl ether of phenolformaldehyde novolak, e.g.
  • alkyl glycidyl ether such as C 8 -C 10 glycidyl ether, e.g. HELOXY modifier 7, C 12 -C 14 glycidyl ether, e.g. HELOXY modifier 8, butyl gly
  • HELOXY modifier 65 polyfunctional glycidyl ethers, for example diglycidyl ether of 1 ,4-butanediol, e.g. HELOXY modifier 67, diglycidyl ether of neopentyl glycol, e.g. HELOXY modifier 68, diglycidyl ether of cyclohexanedimethanol, e.g. HELOXY modifier 107, trimethyloi- ethane triglycidyl ether, e.g. HELOXY modifier 44, trimethylolpropane triglycidyl ether, e.g. HELOXY modifier 48, polyglycidyl ether of aliphatic polyols, e.g. HELOXY modifier 84 (all HELOXY glycidyl ethers are available from Shell).
  • polyfunctional glycidyl ethers for example diglycidy
  • Suitable glycidyl ethers are those containing copolymers of acrylates, for example styrene glycidyl methacrylate or methyl methacrylate glycidyl acrylate. Examples are 1 :1 styrene/glycidyl methacrylate, 1 :1 methyl methacrylate/glycidyl acrylate, 62.5:24:13.5 methyl methacrylate/ethyl acrylate/glycidyl methacrylate.
  • the polymers of the glycidyl ether compounds can, for example, also contain other functionalities, provided they do not impair the cationic cure.
  • glycidyl ether compounds suitable as component (a) and commercially available from Ciba Spezialitatenchemie are polyfunctional liquid and solid novolak glycidyl ether resins, for example PY 307, EPN 1179, EPN 1180, EPN 1182 and ECN 9699. It is, of course, also possible to use mixtures of different glycidyl ether compounds as component (a).
  • the glycidyl ethers (a) are, for example, compounds of formula II
  • H x is a number from 1 to 6;
  • R 5 is a monovalent to hexavalent alkyl or aryl radical.
  • the glycidyl ethers (a) are preferably e.g. compounds of formula II
  • y is a number from 1 to 10; and R 6 is
  • the glycidyl ethers (a) are, for example, compounds of formula lla
  • R 7 is unsubstituted or d-C ⁇ alkyl-substituted phenyl; naphthyl; anthracyl; biphenylyl; C r C 2 o- alkyl; C 2 -C 20 alkyl which is interrupted by one or more than one oxygen atom; or a group of
  • R 5 is phenylene, CrC 2 oalkylene; C 2 -C 2 oalkyiene which is interrupted by one or more than
  • R 6 is or oxygen
  • Preferred glycidyl ethers are the compounds of formula lib
  • R 5 is phenylene, C C 20 alkylene; C 2 -C 20 alkylene which is interrupted by one or more than
  • R 6 is CrC 20 alkylene or oxygen.
  • Alkyl radicals are, for example, CrC 20 alkyl, CrC 8 -, C ⁇ -C 12 -, C C ⁇ o-, CrC 8 -, C C 6 - or C r C 4 alkyl. Meanings of these radicals are given above.
  • C C2oAlkylene is linear or branched and is, for example, C C ⁇ 8 -, C C 16 -, C C 1 -, C C ⁇ 2 -, C r C10-, C r C 8 -, CrC 6 -, C 2 -C 12 -, C 2 -C 8 -, C -C 8 - or C C 4 alkylene.
  • Examples are methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene, heptadecylene or octadecylene.
  • C ⁇ -C 20 Alkylene is preferably understood to mean e.g.
  • Halogen is fluoro, chloro and bromo, preferably bromo and chloro, most preferably bromo.
  • Halogen-substituted CrC ⁇ alkylene is, for example, _CH 2 " ⁇ 2
  • C 2 -C 20 Alkylene which is interrupted by one or more than one oxygen atom is also linear or branched and is interrupted, for example, one to nine times, one to five times or once or twice by non-consecutive oxygen atoms.
  • This gives structures such as -CH 2 -O-CH 2 -, -CH 2 CH 2 -O-CH 2 CH 2 -, -[CH 2 CH 2 O] y -, where y 1 -9, -(CH 2 CH 2 O)7CH 2 CH 2 -, or -CH 2 -CH(CH 3 )-O-CH 2 -CH(CH 3 )-.
  • Cycloalkylene is for example 1 ,4-, 1 ,3- or 1 ,6- cyclohexylene, or also
  • alkylene radicals are preferably in 1 ,4-position.
  • R 5 is preferably a group
  • R 6 is preferably CrC 12 alkylene, more preferably — C — , or oxygen.
  • component (a) are polyglycidyl ether and poly( ⁇ -methylglycidyl)ether which are obtainable by reacting a compound containing at least two free alcoholic and/or phenolic hydroxyl groups per molecule with the corresponding epichlorohydrin under alkaline conditions, or also in the presence of an acid catalyst with subsequent treatment with alkali. It is also possible to use mixtures of different polyols.
  • ethers can be prepared with poly(epichlorohydrin) from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene)glycol, propane-1 ,2-diol and poly(oxypropylene)glycols, propane-1 ,3-diol, butane-1 ,4-diol, poly(oxytetramethylene)glycols, pentane-1 ,5-diol, hexane-1 ,6-diol, hexane-2,4,6-triol, glycerol, 1 ,1 ,1 -trimethylolpropane, pen- taerythritol and sorbitol, from cycloaliphatic alcohols, such as resorcitol, quinitol, bis(4-hydro- xycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propan
  • these ethers from mononuclear phenols, such as resorcinol and hydroquinone, and from polynuclear phenols, such as bis(4-hydroxyphenyl)methane, 4,4-dihydroxydiphenyl, bis(4- hydroxyphenyl)sulfone, 1 ,1 ,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)- propane (bisphenol A) and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
  • mononuclear phenols such as resorcinol and hydroquinone
  • polynuclear phenols such as bis(4-hydroxyphenyl)methane, 4,4-dihydroxydiphenyl, bis(4- hydroxyphenyl)sulfone, 1 ,1 ,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphen
  • Suitable hydroxy compounds for the preparation of polyglycidyl ethers and poly( ⁇ -me- thylglycidyl)ethers are the novolaks obtainable by condensing aldehydes, such as formaldehyde, acetaldehyde, chloral and furfural, and phenols, such as phenol, o-cresol, m-cresol, p- cresol, 3,5-dimethylphenol, 4-chlorophenol and 4-tert-butylphenol.
  • aldehydes such as formaldehyde, acetaldehyde, chloral and furfural
  • phenols such as phenol, o-cresol, m-cresol, p- cresol, 3,5-dimethylphenol, 4-chlorophenol and 4-tert-butylphenol.
  • Poly(N-glycidyl) compounds can be obtained, for example, by dehydrochlorinating the reaction products of epichlorohydrin with at least two amines containing active hydrogen bound to amino nitrogen atoms, for example aniline, n-butyiamine, bis(4-aminophenyl)methane and bis(4-methylaminophenyl)methane.
  • Other suitable poly(N-glycidyi) compounds are triglycidyl isocyanurate and N,N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethylene urea and 1 ,3-propylene urea, and hydantoins, for example 5,5-dimethylhydantoin.
  • Poly(S-glycidyl) compounds are also suitable. Examples are the di-S-glycidyl derivatives of dithiols, such as ethane-1 ,2-dithiol and bis(4-mercaptomethylphenyl)ether.
  • suitable components (a) are also epoxy resins in which the glycidyl groups or ⁇ -me- thylglycidyl groups are bound to different kinds of heteroatoms, e.g. the N,N,O-triglycidyl de- rivative of 4-aminophenol, the glycidyl ether/glycidyl ester of salicylic acid or p-hydroxyben- zoic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin and 2-glycidyloxy-1 ,3-bis- (5,5-dimethyl-1-glycidylhydantoinyl-3)propane.
  • the N,N,O-triglycidyl de- rivative of 4-aminophenol the glycidyl ether/glycidyl ester of salicylic acid or p-hydroxyben- zoic acid
  • the diglycidyl ethers of bisphenols are preferred. Examples thereof are diglycidyl ethers of bisphenol A, such as ARALDIT GY 250, of Ciba Spezialitatenchemie, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S. Diglycidyl ether of bisphenol A is particularly preferred.
  • the composition can also contain a free-radically polymerisable material, including ethylenically unsaturated monomers, oligomers or polymers. Suitable materials contain at least one ethylenically unsaturated double bond, and are capable of undergoing addition polymerisation.
  • Such free-radically polymerisable materials include mono-, di- or polyacrylates and mono-, di- or polymethacrylates such as methylacrylate, methyl methacrylate, ethylacrylate, isopropyl methacrylate, n-hexylacrylate, stearylacrylate, allyl- acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1 ,3-propanedioldiacrylate, 1 ,3-propane- diol dimethacrylate, trimethylolpropanetriacrylate, 1 ,2,4-butanetrioltrimethacrylate, 1 ,4- cyclohexanedioldiacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, penta- erythritol te
  • radical photoinitiator(s) for example benzophenone and benzophenone derivatives, acetophenone and acetophenone derivatives, such as ⁇ -hydroxycyclohexylphenylketone or 2-hydroxy-2-methyl-1-phenylprcpanone, ⁇ -hydroxy- or ⁇ -aminoacetophenone, such as (4-methylthiobenzoyl)-1-methyl-1-mo ⁇ pholino ethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, 4-aroyl-1 ,3-dbxolanes, benzoinalkyl ether and benzilketal, such as benzildimethylketal, phenylglyoxalate and phe- nylglyoxalate derivatives, mono- or bisacylphosphin
  • novel compositions can also contain vinyl ether monomers such as cyclohexanedime- thanol divinyl ether or hydroxybutyl vinyl ether.
  • additional components may be, for example, hydroxy-functional components such as alcohols, polyester polyols, polyether polyols, castor oil and the like.
  • hydroxy-functional components such as alcohols, polyester polyols, polyether polyols, castor oil and the like.
  • aliphatic and cycloaliphatic polyols such as alkylenediols containing preferably 2 to 12 carbon atoms, e.g.
  • the polyols can be partially or completely esterified with one or different unsaturated carboxylic acids, it being possible for the free hydroxyl groups in partial esters to be modified, for example etherified or esterified, with other carboxylic acids.
  • esters are: trimethylol- propanetriacrylate, trimethylolethanetriacrylate, trimethylolpropanetrimethacrylate, trimethyl- olethanetrimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythri
  • Components (a) of particular interest are pure glycidyl ether formulations, i.e. mixtures consisting only of one or several different glycidyl ether compounds.
  • the titanium dioxide pigment (b) can be added to the novel compositions in a very wide range of forms. Thus, it can be incorporated, for example, in the form of fine particles or powders. The particle size is usefully from 100 to 400 nm, but is not restricted to these sizes.
  • the titanium dioxide pigments used are preferably surface-treated, for example with stabilisers, to increase their dispersibility.
  • Such stabiliser components are usually oxides or hydra- ted oxides of siiicium, magnesium or aluminium, or amines or other organic compounds. Examples thereof are cited in US 4054498.
  • the titanium dioxide can be present in different crystalline forms, it is preferred to use the rutile form which is also commercially available.
  • the amount of titanium dioxide component (b) in the polymerisable composition can vary within a wide range, depending on the desired opacity, for example from 5% to 60%, typically from 20 % to 55%, preferably from 40 % to 50%, based on the composition.
  • Suitable sensitiser compounds (d) are, for example, compounds from the class of the aromatic hydrocarbons, such as anthracene and its derivatives, from the group of the xanthones and their derivatives, benzophenones and their derivatives, for example Michler's ketone, Mannich bases or bis(p-N,N-dimethylaminobenzylidene)acetone.
  • Other suitable compounds are thioxanthone and its derivatives, such as isopropylthioxanthone, or dyes, such as acri- dines, triaryimethanes, e.g. malachite green, indolines, thiazines, e.g.
  • oxazines phenazines, e.g. safranin, or rhodamines.
  • Particularly suitable compounds are aromatic carbonyl compounds, such as the benzophenone, thioxanthone, anthraquinone and 3-acylcoumarine derivatives, and also 3-(aroylmethylene)thiazolines, as well as eosine, rhodamine and erythrosine dyes.
  • the sensitiser compound should be soluble in the photopolymerisable composition and should be free of functional groups which crucially influence the cationic crosslinking process.
  • the light absorption of the compounds should furthermore be in the range of about 300 to 1000 nm.
  • Suitable sensitisers are (as mentioned above to some extent) compounds of the following classes: ketones, coumarines (e.g.
  • ketocoumarine xanthones, acridines, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrines, aromatic polycyclic hydrogens, p-substituted aminostyryl ketone compounds, aminotriarylmethanes, merocya- nines, squarylium dyes and pyridinium dyes.
  • Preferred compounds are ketones (e.g. mono- ketone or ⁇ -diketone), ketocoumarines, aminoarylketones and p-substituted aminostyryl ketone compounds. For applications requiring a deep cure (e.g.
  • sensitisers having an extinction coefficient of less than about 1000 lmol '1 cm '1 , preferably of less than about 100 lmor 1 cm '1 , at the desired radiation wavelength for the photopolymerisation.
  • the ⁇ -diketones are one example of a class of sensitisers possessing these properties.
  • Suitable ketone sensitisers are, for example, those of formula IV
  • X is CO or CR a R b ,
  • R a and R are each independently of the other hydrogen, alkyl, alkaryl, or aralkyl; b is 1 or 2; and
  • a and Z are each independently of the other aryl, alkyl, alkaryl or aralkyl, which groups are unsubstituted or substituted, or A and Z together form a ring which is substituted or unsubstituted, cycloaliphatic, aromatic or heteroaromatic.
  • monoketones such as 2,2-, 4,4- or 2,4-di
  • Suitable diketones include aralkyldiketones such as anthraquinone, phenanthrenequinone, o-, m- and p-diacetylbenzene, 1 ,3-, 1 ,4-, 1 ,5-, 1 ,6-, 1 ,7- and 1 ,8-diacetylnaphthalene, 1 ,5-, 1 ,8- and 9,10-diacetylanthracene and the like.
  • aralkyldiketones such as anthraquinone, phenanthrenequinone, o-, m- and p-diacetylbenzene, 1 ,3-, 1 ,4-, 1 ,5-, 1 ,6-, 1 ,7- and 1 ,8-diacetylnaphthalene, 1 ,5-, 1 ,8- and 9,10-diacetylanthrac
  • Suitable diketones include 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, benzile, 2,2'-, 3,3'- and 4,4'-dihydroxy- benzile, furile, di-3,3'-indolylethanedione, 2,3-bornanedione (camphorquinone), biacetyl, 1 ,2-cyclohexanedione, 1 ,2-naphthaquinone, acenaphthaquinone and the like.
  • Preferred sensitisers are those of the group of the anthracenes, xanthones, benzophenones and thioxanthones, also including the derivatives of these compounds.
  • Thioxanthones are particularly preferred, in particular isopropylthioxanthone.
  • the sensitiser compound (d) is usefully added to the novel compositions in an amount from 0.1%-3%, e.g. from 0.2%-1.5%, preferably from 0.4%-1.0%.
  • the novel composition conveniently comprises 40-70% of the glycidyl ether component (a), 20-60% of the titanium dioxide (b), 0.5-10% of the photoinitiator (c) and 0.1-3% of the sensitiser compound (d).
  • additives may be added to the novel compositions besides components (a), (b), (c) and (d).
  • light stabilisers for example UV absorbers such as those of the hydroxyphenylbenztriazole, hydroxyphenylbenzophenone, oxalic acid amide or hydroxy- phenyl-s-triazine type. These compounds can be used separately or as mixtures, with or without addition of sterically hindered amines (HALS).
  • HALS sterically hindered amines
  • novel compositions can contain as additional additive, inter alia, an electron-donor compound.
  • an electron-donor compound examples of such compounds are described in US 5545676.
  • Examples thereof are 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid, 4-dimethylaminoben- zoin, 4-dimethylaminobenzaldehyde, 4-dimethylaminobenzonitrile and 1 ,2,4-trimethoxyben- zene.
  • compositions may contain as further additives dispersants, emulsifiers, antioxidants, light stabilisers, dyes, pigments, fillers, e.g. talcum, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, flow control agents, wetting agents, thickeners, flatting agents, antifoams, antioxidants and other auxiliaries customarily used in the paint system technology.
  • dispersants emulsifiers, antioxidants, light stabilisers, dyes, pigments, fillers, e.g. talcum, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, flow control agents, wetting agents, thickeners, flatting agents, antifoams, antioxidants and other auxiliaries customarily used in the paint system technology.
  • Suitable dispersants are, for example, high molecular weight organic compounds containing polar groups, such as polyvinyl alcohols, polyvinyl pyrrolidone or cellulose ether.
  • Suitable emulsifiers are non-ionic or ionic emulsifiers. The choice of the additives depends on the respective field of applications and on the properties desired in this field. The additives are standard in the technology and are thus used in amounts known to the skilled person.
  • novel compositions can be used in different fields, for example in coating materials, laminating adhesives, in printing inks, white enamel formulations, for example for wood or metal, or in paints used, inter alia, for paper, wood, metal or plastic materials.
  • compositions of this invention can be used to coat or bond substrates of all kinds, for example wood, textiles, paper, ceramics, glass, plastic materials, such as polyester, polyethylene terephthalate, polyolefins or cellulose acetate, in particular in the form of films, and metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2 to which a protective coating is to be applied.
  • plastic materials such as polyester, polyethylene terephthalate, polyolefins or cellulose acetate, in particular in the form of films, and metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2 to which a protective coating is to be applied.
  • the substrates can be coated by applying a liquid composition, a solution or suspension to the substrate.
  • a liquid composition a solution or suspension
  • the choice of solvent used and its concentration depends mainly on the type of composition and on the coating process used.
  • the solvent should be inert, i.e. it should not chemically react with the components and should be removable during drying after coating.
  • Suitable solvents are, for example, ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyciohexanone, N-methylpyrrolidone, di- oxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1 ,2-di- methoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate.
  • the formulation is uniformly applied to a substrate by known coating processes, for example centrifuging, dipping, knife application, curtain coating, brush application, screen printing, spraying, especially by electrostatic spraying and reverse roll coating.
  • the coating thickness and type of substrate depend on the desired field of application, The coating thickness is generally within the range from about 0.1 ⁇ m to higher than 100 ⁇ m, e.g. from 1 ⁇ m to 30 ⁇ m, preferably from 4 ⁇ m to 20 ⁇ m.
  • metal coating for example coating metal sheets and tubes, tins or bottle caps.
  • the metals to be coated can be uncoat- ed or precoated.
  • Suitable substrates are especially metals, such as aluminium or tinplate.
  • the novel white compositions are distinguished by having very good resistance to yellowing. Another advantage is that the heavy metal anions normally used in the technology, for example SbF 6 anions, are not present in these compounds.
  • novel formulations are cured by irradiation with light in the wavelength of 200-600 nm.
  • the formulation can be subjected to a heat treatment after irradiation.
  • the thermal aftertreatment is conveniently carried out in the temperature range from 50-250°C, e.g. from 100-220°C, preferably from 150-210°C.
  • this invention also relates to a process for the polymerisation of compositions described above, which comprises irradiating the composition with light in the wavelength of 200-600 nm, and to a corresponding process in which the irradiation is followed by a heat treatment.
  • the UV irradiation for curing the novel formulation is usually carried out using light in the wavelength from 200-600 nm.
  • Suitable radiation comprises, for example, sunlight or light from artificial light sources.
  • a large number of widely different types of light sources can be used, including point sources and arrays of reflector lamps. Examples are: carbon arc lamps, xenon arc lamps, mercury medium, high and low pressure lamps which are doped, where required, with metal halides (metal halogen lamps), microwave-excited metal vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon glow lamps, flash lamps, photographic floodlights, electron beams and X-rays.
  • metal halides metal halogen lamps
  • microwave-excited metal vapour lamps excimer lamps
  • superactinic fluorescent tubes fluorescent lamps
  • fluorescent lamps argon glow lamps
  • flash lamps photographic floodlights, electron beams and X-rays.
  • fusion lamps such as fusion H (main emissions: mercury medium pressure spectrum), fusion D (main emissions: 350-450 nm), fusion V (main emissions: 400-450 nm) or fusion M (main emissions: 360-370 nm and 400-410 nm).
  • the distance between lamp and substrate to be irradiated can vary depending on the purpose of application and type or strength of lamp, for example from 2 cm to 150 cm.
  • suitable lamps are laser light sources, for example excimer laser. It is also possible to use lasers in the visible range. Irradiation using fusion lamps, e.g. fusion H, fusion D, fusion V or fusion M, is particularly interesting.
  • This invention also relates to the use of the above compositions and to a process for the preparation of coatings, paints, printing inks, powder coatings, laminating adhesives, dental compositions, in particular white enamel formulations.
  • this invention relates to a coated substrate which is coated on at least one surface with one of the above compositions, and to a coated substrate to which the novel composition is applied at a coating thickness of at least 0.1 -100 ⁇ m, e.g. 1-30 ⁇ m, preferably 4-15 ⁇ m.
  • Example 1 Preparation of p-isobutylphenylphenyl iodonium hexafluorophosphate
  • the reaction mixture is stirred overnight at 40°C, cooled to room temperature and filtered.
  • the filter cake is washed with water and dried at 60°C under high vacuum, giving 372.4 g of hydroxy(tosyioxy)iodobenzene.
  • Example 3 (4-Octylphenyl)phenyl iodonium hexafluorophosphate Prepared from octylbenzene. The title product is obtained as a reddish oil.
  • the product contains about 8% of the 2-octyl isomeric product.
  • Example 4 (2,4-Dimethoxyphenyl)phenyl iodonium hexafluorophosphate Prepared from 1 ,3-dimethoxybenzene.
  • the title product is a solid having a melting point from 129-130°C.
  • 1 H-NMR measured in DMSO-de [ppm]: 8.19 (1 H, d, J 8.8Hz H 6 ), 8.07 (2H, m, H 26 ), 7.63 (1 H, m, H 4 ), 7.49 (2H, m, H 3 .
  • Example 5 (2,4-Diethoxyphenyl)phenyl iodonium hexafluorophosphate Prepared from 1 ,3-diethoxybenzene.
  • the title product is a solid having a melting point of 158°C.
  • the title product is a solid having a melting point of 125°C.
  • Example 7 Preparation of bis(p-isobutylphenyl)iodonium hexafluorophosphate
  • 211.2 g (1.57 mol) of isobutylbenzene and 140.3 g (0.65 mol) of potassium iodate are cooled to 0°C in a mixture of 1850 ml of acetic acid and 525 ml of acetic anhydride.
  • a mixture consisting of 385 ml of acetic acid and 310 ml of sulfuric acid is added dropwise.
  • Example 12 Bis[4(1 ,1-dimethylprop-1-yl)phenyl]iodonium hexafluorophosphate Prepared from 4(1 ,1-dimethylprop-1-yl)phenol.
  • Example 13 Bis(4-C 3 -C 14 alkylphenyl)iodonium hexafluorophosphate Prepared from a mixture of phenols substituted in 4-position by C 8 -C 1 alkyl.
  • Example 14 Preparation of p-butoxyphenylphenyl iodonium hexafluorophosphate
  • the reaction solution is stirred overnight at 40°C, cooled to room temperature and filtered.
  • the filter cake is washed with water and dried at 60°C under vacuum, giving 71.2 g of hydroxy(tosyloxy)iodobenzene.
  • Examples 15-16 are prepared in analogy to the method of Example 14, using the corresponding educts.
  • the compounds and their physical data are listed in the following Table 1.
  • a white enamel formulation is prepared by mixing the following components:
  • the mixture is heated to 60°C and shaken for 6 minutes. After heating it once more to 60°C and shaking it for another 6 minutes, it is stirred for 30 minutes at 60°C.
  • the formulation is applied to a 300 ⁇ m aluminium sheet using a 12 ⁇ m spiral applicator. Irradiation is carried out using a UV processor under two 80 W/cm mercury medium pressure lamps. The highest belt speed is determined at which the sample is cured with the surface still remaining tack- free. The higher the belt speed, the more reactive the formulation.
  • the yellowing of the coating is determined via the Yellowness Index (Yl) in accordance with ASTMD-1925-70. The lower the Yl value, the less yellowing of the coating.
  • This formulation is cured tack-free at a belt speed of 12.5 m/min. Immediately after irradiation, the measured Yl value is -2.5, and after the subsequent heat treatment it is -3.4.
  • a white enamel formulation is prepared by mixing the following components:

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  • Optics & Photonics (AREA)
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  • Epoxy Resins (AREA)
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EP99919233A 1998-04-24 1999-04-14 Heavy metal-free coating formulations Withdrawn EP1084456A1 (en)

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PCT/EP1999/002511 WO1999056177A1 (en) 1998-04-24 1999-04-14 Heavy metal-free coating formulations
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DE19961355A1 (de) 1999-12-17 2001-06-21 S & C Polymer Silicon & Compos Photoinitiatorsystem mit Titanocen-Initiatoren
DE19961347A1 (de) * 1999-12-17 2001-06-21 S & C Polymer Silicon & Compos Photoinitiatorsystem mit Acylphosphinoxid-Initiatoren
GB0516515D0 (en) * 2005-08-11 2005-09-21 Sun Chemical Bv A jet ink and ink jet printing process
JP5485583B2 (ja) * 2009-05-08 2014-05-07 株式会社日本触媒 ジアリールヨードニウム化合物の製造方法
EP2428501B1 (en) * 2009-05-08 2018-12-12 Nippon Shokubai Co., Ltd. Diaryliodonium salt mixture and process for production thereof, and process for production of diaryliodonium compound
CN104497277A (zh) * 2014-11-26 2015-04-08 南京凯泰化工科技有限公司 一种自由基光引发剂及其制备方法
RU2646003C2 (ru) * 2017-06-06 2018-03-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) Фотополимеризующаяся композиция для ускоренного формирования покрытий защитного назначения

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US4590281A (en) * 1983-03-09 1986-05-20 Nippon Petrochemicals Company Process for preparing aldehydes
EP0293633A2 (en) * 1987-05-06 1988-12-07 Nippon Petrochemicals Company, Limited 1,2-Di(4-isobutylphenyl)ethylene and its preparation and use as intermediate
EP0762207A2 (de) * 1995-09-11 1997-03-12 Basf Aktiengesellschaft Positivarbeitendes strahlenempfindliches Gemisch und Verfahren zur Herstellung von Reliefstrukturen

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US4399071A (en) * 1982-03-12 1983-08-16 General Electric Company Method for making diaryliodonium salts
DE4002682A1 (de) * 1990-01-31 1991-08-01 Herberts Gmbh Verfahren zum beschichten von substraten mit durch uv-strahlung haertbaren ueberzugsmitteln
TW460509B (en) * 1996-07-12 2001-10-21 Ciba Sc Holding Ag Curing process for cationically photocurable formulations

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Publication number Priority date Publication date Assignee Title
US4590281A (en) * 1983-03-09 1986-05-20 Nippon Petrochemicals Company Process for preparing aldehydes
EP0293633A2 (en) * 1987-05-06 1988-12-07 Nippon Petrochemicals Company, Limited 1,2-Di(4-isobutylphenyl)ethylene and its preparation and use as intermediate
EP0762207A2 (de) * 1995-09-11 1997-03-12 Basf Aktiengesellschaft Positivarbeitendes strahlenempfindliches Gemisch und Verfahren zur Herstellung von Reliefstrukturen

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CA2329012A1 (en) 1999-11-04
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BR9909890A (pt) 2000-12-26
JP2002513078A (ja) 2002-05-08

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