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
  • G03F7/0037—Production of three-dimensional images
• • 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
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
• • 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
• • 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

Definitions

• the present invention relates to thermally stable photocurable compositions comprising cationic photoinitiators.
• Cationically curable compositions comprising corresponding initiator compounds are known in the art.
• Sulfonium salts as photoinitiators are for example described in WO 03/008404 and WO 03/072567, while for example WO 98/02493 and US 6306555 disclose iodonium salt photoinitiator compounds.
• Cationic systems or photocurable compositions comprising cationic photoinitiators
• cationic photoinitiators are known to have a problem of having insufficient storage stability.
• epoxy resins containing iodonium salt cationic photoinitiators exhibit poor shelf life stability (dark stability).
• Lewis bases are employed to enhance shelf life of these systems, but this approach inhibits the photocure response.
• a stabilized cationic photoinitiator system comprising amines is for example suggested in WO 99/35188, while GB 2198736 discloses nitroxyl compounds as stabilizers in radically polymerizable formulations.
• cationic photocurable compositions with improved shelf life stability comprising at least one cationically polymerizable compound, at least one onium salt photoinitiator and at least one compound selected from the group consisting of the organic phosphorus stabilizers and the hindered nitroxyl stabilizers.
• the present cationically polymerizable compounds are those which can be cationically polymerized using alkyl- or aryl-containing cations or protons.
• Typical examples are cyclic ethers, for instance epoxides, as well as vinyl ether and hydroxyl-containing compounds.
• the present cationically polymerizable compounds are for example cycloaliphatic epoxy compounds, glycidyl ethers, oxetane compounds, vinyl ethers, acid-crosslinkable melamine resins, acid-crosslinkable hydroxymethylene compounds and acid-crosslinkable alkoxy- methylene compounds.
• the present cationically polymerizable compounds are those described in U.S. Pat. Nos. 6,306,555 and 6,235,807, the disclosures of which are hereby incorporated by reference.
• All customary epoxides may be used, such as aromatic, aliphatic or cycloaliphatic epoxy res- ins. These are compounds having at least one, preferably at least two, epoxy groups in the molecule. Typical examples are the glycidyl ethers and ⁇ -methylglycidyl ethers of aliphatic or cycloaliphatic diols or polyols, e.g.
• ethylene glycol propane-1,2-diol, propane-1,3- diol, butane-1,4-diol, diethylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane or 1,4-dimethyIolcyclohexane, or of 2,2-bis(4-hydroxycyclohexyl)propane and N,N-bis(2-hydroxyethyl)aniline; the glycidyl ethers of di- and polyphenols, typically of re- sorcinol, of 4,4'-dihydroxyphenyl-2,2-propane, of novolaks or of 1,1,2,2-tetrakis(4-hydro- xyphenyl)ethane.
• Illustrative examples are phenyl glycidyl ether, p-tert-butyl glycidyl ether, o- icresyl glycidyl ether, polytetrahydrofuran glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl - glycidyl ether, C 12 ⁇ 5 alkyl glycidyl ether, cyclohexanedimethanol diglycidyl ether.
• N-glycidyl compounds typically the glycidyl compounds of ethylene urea, 1 ,3- propylene urea or 5-dimethylhydantoin or of 4,4'-methylene-5,5'-tetramethyldihydantoin, or e.g. triglycidyl isocyanurate.
• glycidyl compounds are the glycidyl esters of carboxylic acid, preferably di- and polycarboxylic acids. Typical examples are the glycidyl esters of succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, tetra- and hexa- hydrophthalic acid, isophthalic acid or trimellitic acid, or of dimerised fatty acids.
• polyepoxides which are not glycidyl compounds are the epoxides of vinyl cyclohexane and dicyclopentadiene, 3-(3',4'-epoxicyclohexyl)-8,9-epoxy-2,4-dioxaspiro- [5.5]undecane, of the 3',4'-epoxycyclohexylmethyl ester of 3,4-epoxycyclohexane carboxylic acid, butadiene diepoxide or isoprene diepoxide, epoxidised linolic acid derivatives or epoxi- dised polybutadiene.
• epoxy resins are, for example, epoxy resins of bisphenol A and bisphenol F, e.g. Araldit ® GY 250 (A), Araldit ® GY 282 (F), Araldit ® GY 285 (F) (supplied by Ciba Specialty Chemicals).
• the monofunctional -olefin epoxides having an un- branc ed chain consisting of 10, 12, 14 and 16 carbon atoms are particularly suitable.
• the epoxy resins may be diluted with a solvent, for example when the application is carried out by spraying.
• the epoxy resin is used in solvent-free state. Resins that are viscous to solid at room temperature can be applied hot.
• All customary vinyl ethers may be used, such as aromatic, aliphatic or cycloaliphatic vinyl ethers. These are compounds having at least one, preferably at least two, vinyl ether groups in the molecule.
• Typical examples of vinyl ethers suitable according to this invention are triethylene glycol divinyl ether, 1,4-cycIohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, the propenyl ether of propylene carbonate, dodecyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, ethylene glycol monovi- nyl ether, butanediol monovinyl ether, hexanediol monovinyl ether, 1,4- cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether,
• hydroxyl-containing compounds are polyester polyols, such as poly- caprolactones or polyester adipate polyols, glycols and polyether polyols, castor oil, hydroxy- functional vinyl and acrylic resins, cellulose esters, such as cellulose acetate butyrate, and phenoxy resins.
• the present cationically polymerizable compounds are cycloaliphatic epoxides or epoxides based on bisphenol A.
• the cationically polymerizable compounds are diglycidyl ethers of bisphenol A, bisphenol F or bisphenol S.
• leasfi is meant to define one or more than one, for example one or twOiOr three, preferably one or two.
• the onium salt photoinitiators are for example iodonium salt compounds as disclosed in U.S. Pat. Nos. 6,306,555 and 6,235,807, the disclosures of which are hereby incorporated by reference.
• the iodonium salt photoinitiators are of the formula (RH-R 2 ) + .
• (A " ) (I) where Ri and R 2 are each independently of the other phenyl which is unsubstituted or is substituted OH I by C ⁇ -C 2 alkyl, C ⁇ -C 2 alkoxy, -N0 2 , -Cl, -Br, -CN, -COOR 3 , -SRs or — 0-CH 2 -CH-R 4 ,
• R-i and R 2 together are a radical n is a number from 0 to 6;
• R 3 is hydrogen or CrC ⁇ alkyl;
• FU is C ⁇ -C ⁇ 8 alkyl or phenyl;
• R 5 and Re are -CN, or R 5 is -N0 2 , and
• R 6 is phenyl;
• R 7 and Re are each independently of the other C 1 -C 24 alkyl, CrC 24 alkoxy, -N0 2 , -Cl, -Br, -CN, -COORs, or -SR 3 ; and
• a " is an anion selected from the group consisting of (BF 4 ) ⁇ , (SbF 6 ) ⁇ , (PF 6 ) “ , (B(C 6 F 5 )) 4 " , CrC 2 oalkylsulfonate, C 2 -C 2 ohaloalkylsulfonate, unsubstituted C 6 -C 10 arylsulfonate, camphor- sulfonate, C C 2 o-perfIuoroalkylsulfonylmethide, C 1 -C 20 -perfluoroalkylsulfonylimide, and C 6 - Cioarylsulfonate substituted by halogen, -N0 2 ,, CrCi 2 alkyl, d-C 12 halo-alkyl, C C ⁇ 2 alkoxy or by COORi.
• onium salt in the presently claimed compositions in particular iodonium salts with ani- ons selected from the group consisting of (BF ) ⁇ , (SbF 6 ) “ , (PF 6 ) “ , (B(C 6 F 5 )) 4 " , CrC 2 oalkylsulfonate, C 2 -C 2 ohaloalkylsulfonate, unsubstituted C 6 -C 0 arylsuHonate, camphor- sulfonate, C ⁇ -C2o-perfluoroalkylsulfonylmethide, CrC 2 o-perfluoroalkylsulfonylimide, and C 6 - Cioarylsulfonate substituted by halogen, -N0 2 , Ci-Cttalkyl, d-C ⁇ halo-alkyl, C C 12 alkoxy or by COOR1 are used.
• Alkylsulfonate is RS0 3 " wherein R is linear or branched alkyl as described above. Examples thereof include methylsulfonate, ethylsulfonate, propylsulfonate, pentylsulfonate and hexyl- sulfonate.
• Haloalkylsulfonate is RSO 3 " wherein R is halo-substituted C 2 -C2oalkyl, C2-C10-, C 2 -C 8 - or C 4 - C 8 -alkyl. Examples thereof include C 2 F 5 S0 3 " , C F 9 S0 3 " and C 8 F 17 S0 ⁇ .
• R is C 6 -C ⁇ 0 aryl, e.g. phenyl or naphthyl.
• Alkyl-substituted arylsulfonates are, for example, toluenesulfonate, 2,4,6-trimethylbenzene- sulfonate, 2,4,6-tris(isopropyl)benzenesulfonate, 4-tert-butylbenzenesulfonate and 4-dodecyl- benzenesulfonate.
• Halo-substituted arylsulfonates are, for example, 4-chlorobenzenesulfonate, 4-fluoro- benzenesulfonate, 2,4,6-trifluorobenzenesulfonate and pentafluorobenzenesulfonate.
• Camphorsulfonate is 3 X ⁇ v>
• Perfluoroalkylsulfonylmethide is R ⁇ — SO ⁇ C — SO j R,, , perfluoroalkylsulfonylimide is SQ 2 -R C
• R a — SOj- -SOjR R a — SOj- -SOjR, , wherein R a , R b and R c independently of one another are d- C 2 operfluoroalkyl which is unsubstituted or is substituted by N(R d )(R ⁇ ), or R a , R b and R c are phenyl substituted by CF 3 ; or R a and R together are C ⁇ -C 6 -perfluoroalkylene, which optionally is interrupted by -0-; R d and R e independently of one another are C ⁇ -C ⁇ 2 alkyl or R d and R e together are CrC 6 perfluorolkylene, which optionally is interrupted by O or N(C ⁇ -C ⁇ 2 -alkyl).
• Perfluoroalkyl is alkyl which is fully substituted by fluoro, i.e. the hydrogen atoms are re- placed by fluoro.
• Examples of such anions are (C 2 F 5 S ⁇ 2 ) 2 N “ , (C 4 F 9 SO 2 ) 2 N “ , (C 8 F 17 S0 2 ) 3 C “ , (CF 3 S0 2 ) 3 C " , (CF 3 S0 2 ) 2 N “ , (C 4 F 9 S0 2 ) 3 C " , F 2 C-SO z
• Substituted phenyl is substituted at the phenyl ring one to five times, for example one, two or three times, in particular one or two times, preferably once.
• Ri and R 2 are each independently of the other phenyl which is unsubstituted or substituted by CrC 24 alkyl, CrC 2 alkoxy, -N0 2 , -Cl, -Br, -CN, -COOR 3 or -SR3.
• the present iodonium comounds are those where Ri and R 2 are C C 2 alkyl- or CrC 24 alkoxy-substituted phenyl.
• the anions are for example SbF 6 ⁇ or PF 6 " or (B(C 6 F 5 )) ⁇ anions.
• Illustrative examples of iodonium salt compounds are bis(4-hexylphenyl)iodonium hexafluoroantimonate; bis(4-hexyiphenyl)iodonium hexafluorophosphate; (4-hexylphenyl)phenyIiodonium hexafluoroantimonate; (4-hexylphenyl)phenyl- iodonium hexafluorophosphate; bis(4-octylphenyI)iodonium hexafluoroantimonate; (4-sec- butylphenyl)-(4'-methylphenyl)iodonium hexafluorophosphate; (4-iso-proylphenyl)-(4'-methyl- phenyl)iodonium hexafluorophosphate; [4-(2-hydroxytetradecyloxy)phenyl]phenyliodonium hexa
• iodonium photoinitiators are 4-isobutylphenyl-4'-methylphenyl- iodonium hexafluoro-phosphate; 4-isobutylphenyl-4'-methylphenyliodonium pentafluoroethyl- sulfonate; 4-isobutylphenyI-4'-methylphenyliodonium tresylate; 4-isobutylphenyl-4'-methyl- phenyliodonium nonaflate; 4-isobutylphenyl-4'-methylphenyliodonium tosylate; 4-isobutyl- phenyl-4'-methyl-phenyliodonium 4-methoxyphenylsulfonate; 4-isobutylphenyl-4'-methyl- phenyliodonium 4-chlorophenylsulfonate; 4-isobutylphenyl-4'-methylphenyl-4'-methylphenyl
• onium salt photoinitiators suitable in the context of the present invention further are for example sulfonium salt compounds as disclosed for example in WO 03/008404 or WO 03/072567, the disclosures of which are hereby incorporated by reference.
• R ⁇ oo, R101 and R 10 2 are each independently of the others unsubstituted phenyl, or phenyl sub ⁇
• R103 is a direct bond, S, O, CH 2 , (CH 2 ) 2 , CO or NR 109 ;
• R KM , R-105, 106 and R107 independently of one another are H, CrC 20 alkyl, C 3 -C 8 cycloalkyl, CrC ⁇ alkoxy, C 2 -C 2 oalkenyl, CN, OH, halogen, CrC 6 alkylthio, phenyl, naphthyl, phenyl-C C alkyl, ⁇ aphtyl-CrC 3 alkyl, phe ⁇ oxy, naphthyloxy, phenyl-C ⁇ -C 7 alkyloxy, naphtyl-d- Csalkyloxy, phenyl-C 2 -C 6 alkenyl, naphthyl-C 2 -C 4 alkenyl, S-phenyl, (CO)R 109 , O(CO)R 109J (CO)
• R108 is CrC ⁇ alkyl, C C- 2 ohydroxyalkyl
• R109 is H, C ⁇ -C ⁇ 2 alkyl, d-C ⁇ hydroxyalkyl, phenyl, naphthyl or biphenylyl;
• R110 is a direct bond, S, O or CH 2 ;
• R111, R112. R113 and Rn 4 independently of one another have one of the meanings as given for
• R w ; or Rm and R ⁇ 13 are joined to form a fused ring system with the benzene rings to which they are attached;
• Z A is an anion, especially PF 6 , SbF 6 , AsF 6 , BF 4 , (C 6 F 5 ) 4 B, Cl, Br, HS0 4 , CF 3 -S0 3 , F-S0 3 ,
• the onium salt photoinitiators are present from about 0.05% to about 15% by weight, based on the weight of the composition.
• the onium salt photoinitiators are present from about 0.1% to about 10%, or from about 0.5% to about 5% by weight, based on the weight of the composition.
• the present onium salt compounds are present from about 0.1% to about 5%, or from about 0.1% to about 15%, or from about 0.5% to about 10% or from about 0.5% to about 15%, based on the weight of the composition.
• compositions according to the invention may comprise mixtures of one or more different onium salts, e.g. mixtures of one or more different iodonium salts, mixtures of one or more different sulphonium salts or mixtures of one or more different iodonium and sulphonium salts.
• organic phosphorus stabilizers are as disclosed for example in U.S. Pat. No. 6,444,733, the disclosure of which is hereby incorporated by reference.
• Organic phosphorus stabilizers are known and many are commercially available.
• the present organic phosphorus stabilizers are of the formula (1), (2), (3), (4), (5), (6) or (7),
• Ai if n is 2, is C 2 -C 18 alkylene; C 2 -C ⁇ 2 alkylene interrupted by oxygen, sulfur or-NR ⁇ -; a
• Ai if n is 3, is a radical of the formula H 2 C—
• a L if n is 4, is — C-C-C— ;
• H 2 c— H 2 A 2 is as defined for A 1 if n is 2;
• B is a direct bond, -CH 2 -, -CHR ⁇ -, -CRsiR & r, sulfur, C 3 -C 7 cycloalkylidene, or cyclohexyl- idene which is substituted by from 1 to 4 C C alkyl radicals in position 3, 4 and/or 5;
• D L if p is 1 , is C C 4 alkyl and, if p is 2, is -CH 2 OCH 2 -;
• D 2 if p is 1, is C ⁇ -C alkyl;
• E, if y is 1, is CrC 18 alkyl, -OR5 1 or halogen;
• E, if y is 2, is -0-A 2 -0-, E, if y is 3, is a radical of the formula R5 4 C(CH 2 0-) 3 or N(CH 2 CH 2 0-) 3 ;
• Q is the radical of an at least z-valent alcohol or phenol, this radical being attached
• R51, R52 and R53 independently of one another are CrC 18 alkyl which is unsubstituted or substituted by halogen, -COOR 54 , -CN or -CONR ⁇ R ⁇ ; C 2 -C ⁇ 8 alkyl interrupted by oxygen, sulfur or-NR ⁇ -; C 7 -C 9 phenylalkyl; C 5 -C 12 cycloalkyl, phenyl or naphthyl; naphthyl or phenyl sub- stituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon at-
• oms or by C 7 -C 9 phenylalkyl; or a radical of the formula in which m is an integer from the range 3 to 6;
• R M is hydrogen, C ⁇ -C ⁇ 8 alkyl, C 5 -C ⁇ 2 cycloalkyl or C7-C 9 phenylalkyl,
• R 55 and R56 independently of one another are hydrogen, C ⁇ -C 8 alkyl or Cs-C ⁇ cycloalkyl, R OT and R58, if q is 2, independently of one another are C ⁇ -C 4 alkyl or together are a
• R ⁇ is hydrogen, C C 9 alkyl or cyclohexyl
• Res is hydrogen or methyl and, if two or more radicals R & and R ⁇ ⁇ are present, these radicals are identical or different,
• X and Y are each a direct bond or oxygen
• Z is a direct bond, methylene, -C(R 66 ) 2 - or sulfur, and
• the organic phosphorus stabilizers are for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioc- tadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol di- phosphite(D), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (E), bisisodecyloxy-
• the organic phosphorus stabilizers are for example tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyI) ethyl phosphite (G), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (D), tetrakis(2,4-di-tert-butylphenyl)4,4 , -biphenylene-diphosphonite (H), 2,2',2"-nitrilo[triethyltris(3,3'5,5'-tetra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite] (B), compound (J), compound (K) or compound (L).
• Hindered nitroxyl stabilizers or hindered nitroxides, are well known in the art and are disclosed for example in U.S. Pat. Nos. 6,337,426, 5,254,760, the relevant disclosures of which are hereby incorporated by reference.
• the present hindered nitroxyl stabilizers are of the formula wherein d and G 2 are independently alkyl of 1 to 4 carbon atoms or are together pentame- thylene; and
• Z, and Z 2 are each methyl or Z ⁇ and Z 2 together form a linking moiety which may or may not contain heteroatoms or carbonyl groups and which additionally may be substituted by hy- droxy, cyanohydrin, amino, alkoxy, amido, ketal, carboxy, hydantoin, carbamate, or a ure- thane group.
• the present hindered nitroxyl stabilizers are of the formula
• R 91 is hydrogen, C C 18 alkyl or said alkyl optionally interrupted by one or more oxygen atoms, C ⁇ -C ⁇ alkenyl, C 6 -C ⁇ 0 aryl, C 7 -C 18 aralkyl, glycidyl, a monovalent acyl radical of an ali- phatic.cycloaliphatic or aromatic carboxylic acid, or a carbamic acid, for example an acyl radical of an aliphatic carboxylic acid having 2-18 carbon atoms, of a cycloaliphatic carboxylic acid having 5-12 carbon atoms or of an aromatic carboxylic acid having 7-15 carbon at-
• R 91 is C ⁇ -C ⁇ 2 alkylene, C 4 -C ⁇ 2 alkenylene, xylylene, a divalent acyl radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid or of a dicarbamic acid, for example an acyl radical of an aliphatic dicarboxylic acid having 2-18 carbon atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms; or R 9 ⁇ is — , wherein
• D 5 ⁇ and D52 are independently hydrogen, an alkyl radical containing up to 8 carbon atoms, an aryl or aralkyl radical including 3,5-di-t-butyl-4-hydroxybenzyl radical;
• D 53 is hydrogen, or an alkyl or alkenyl radical containing up to 18 carbon atoms, and
• R9 1 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic tricarboxylic acid
• R 91 is a tetravalent acyl radical of a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid including 1,2,3,4-butanetetracarboxylic acid, 1 ,2,3,4-but-2-ene- tetracarboxylic , and 1 ,2,3,5- and 1 ,2,4,5-pentanetetracarboxyIic acid;
• Rg 2 is hydrogen, C ⁇ -C ⁇ 2 alkyl, C 3 -C 7 cycloalkyl, C 7 -C 9 aralkyl, C 2 -C 18 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; when p, is 1, R 93 is hydrogen, CrC 8 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl, unsubstituted or substituted by a cyano, carbonyl or carbamide group, aryl, aralkyl, or it is glycidyl, a group of the formula -CH 2 -CH(OH)-Z a or of the formula -CO-Z a or -CONH-Z a wherein Zg is hydrogen,
• T 8 and T 9 are independently hydrogen, alkyl of 1 to 18 carbon at ⁇ oms, or T 8 and T 9 together are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene, for instance T 8 and T 9 together are 3-oxapentamethylene; and when pi is 3, R 93 is 2,4,6-triazinyl.
• Typical nitroxyl stabilizers include bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4- hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-ethoxy-1-oxyl-2,2,6,6-tetramethylpiperid ⁇ ne, 4-propoxy-1-oxyl-2,2,6,6-tetramethyIpiperidine, 4-acetamido-1-oxyl-2,2,6,6-tetramethylpiperl ⁇ dine, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl- 2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethyl- hexanoate, 1-oxyI-2,2,6,6-tetramethylpiperidin-4-yl stearate,
• Nitroxyl stabilizers are for example bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4- hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine, 4-ethoxy-1 -oxyl-2,2,6,6-tetramethylpiperidine, 4-propoxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-acetamido-1-oxyl-2,2,6,6-tetramethylpiper- idine, 1-oxyl-2,2,6,6-tetramethylpiperidine, and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one.
• nitroxyl stabilizers are bis(1-oxyI-2,2,6,6-tetramethyl- piperidin-4-yl) sebacate or 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine.
• Alkenylene is unsaturated alkylene.
• Alkenyl is unsaturated version of alkyl.
• Alkanoyl is a branched or unbranched radical, for example formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, ico- sanoyl or docosanoyl.
• Alkenoyl is unsaturated alkanoyl.
• Arylene is for instance phenylene or naphthylene each unsubstituted or substituted by Ci- C 4 alkyl is, for example, 1,2-, 1,3- or 1,4-phenylene or 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6- or 2,7- naphthylene. For instance 1,4-phenylene.
• Cycloalkylene is for example substituted by from 1 to 3, especially 1 or 2, branched or un- branched CrC alkyl groups, and is, for example, cydopentylene, methylcyclopentylene, di- methylcyclopentylene, cyclohexylene, methylcyclohexylene, dimethylcyclohexylene, tri- methylcyclohexylene, tert-butylcyclohexylene, cycloheptylene or cyclooctylene. Preference is given to cyclohexylene and tert-butylcyclohexylene.
• Alkyl is linear or branched and is typically C ⁇ -C 12 alkyl, C C 8 alkyl, C ⁇ -C 6 alkyl or CrC 4 -alkyl. Typical 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, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or icosyl.
• Alkoxy is linear or branched radicals, typically methoxy, ethoxy, propoxy, isopropoxy, n- butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4- trimethylpentyloxy, 2-ethyl hexyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy or icosyloxy, in particular methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert- butyloxy, octyloxy, preferably methoxy and octyloxy.
• Halogen is fluorine, chlorine, bromine or iodine, especially chlorine or fluorine, preferably fluorine.
• Haloalkyl is a mono- or poly-halo-substituted alkyl.
• the alkyl moiety can be substituted by a plurality of identical halogen atoms or, alternatively, by different halogen atoms.
• CrCzoalkyl is mono- or poly-halo-substituted, there are, for example, from 1 to 3, or 1 or 2, halogen substituents present on the alkyl moiety.
• Alkylene is linear or branched. Typical examples are methylene, ethylene, propylene, iso- propyle ⁇ e, n-butylene, sec-butylene, isobutylene, tert-butylene, pentylene, hexylene, hepty- lene, 2,4,4-trimethyl pentylene, 2-ethylhexylene, octylene, nonylene, decylene, undecylene, dodecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene or icosylene.
• Cycloalkyl is for example cyclopropyl, cyclopentyl, cyclohexyl or cyclooctyl, especially cyclopentyl or cydohexyl, preferably cyclohexyl.
• Phenylalkyl is, for example, benzyl, ⁇ -methyl benzyl, ⁇ , ⁇ -dimethylbenzyl or 2-phenylethyl.
• benzyl and , ⁇ -dimethylbenzyl are examples of benzylalkyl.
• Cycloalkylidene is for example substituted by from 1 to 3, for instance 1 or 2, branched or unbranched C ⁇ -C 4 alkyl groups, and is for example cyclopentylidene, methylcyclopentylidene, di- methylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcydohexylidene, cycloheptylidene or cyclooctylidene.
• cyclohexylidene and tert-butylcyclohexylidene is for example cyclohexylidene and tert-butylcyclohexylidene.
• the stabilizers according to this invention are effective at very low levels.
• the stabilizer is chosen for optimal balance of shelf stability and photocure response. At the effective low lev- els of stabilizer, the photocure response is not inhibited.
• the present stabilizers are present from about 50 ppm to about 3 pph, by weight, based on the weight of the onium salt photoinitiator.
• the present stabilizers are present from about 100 ppm to about 2 pph, from about 200 ppm to about 2 pph, from about 250 ppm to about 1 pph, or from about 750 ppm to about 1 pph by weight, based on weight of the onium salt phtoinitiator.
• the present stabilizers may be employed to provide shelf life stability to a formulated cationically photocurable composition, or likewise, may be added directly to an onium salt photoinitiator, and thereby provide shelf life stability to a subsequent formulated curable composition .
• a cationic photoinitiator composition comprising at least one onium salt photoinitiator and at least one compound selected from the group consisting of the organic phosphorus stabilizers and the hindered nitroxyl stabilizers.
• Sensitizers may be present in the compositions of this invention and are, for example, compounds of the aromatic hydrocarbon class, typically anthracene and its derivatives, of the group of the xanthones, benzophenones and the derivatives thereof, such as Michler's ke- tone, Mannich bases or bis(p-N,N-dimethylaminobenzylidene)acetone.
• Thioxanthone and the derivatives thereof are also suitable, typically isopropylthioxanthone or dyes, such as ac- ridines, triarylmethanes, e.g. malachite green, indolines, thiazines, e.g.
• Aromatic carbonyl compounds are particularly suitable, such as benzophenone, thioxanthone, anthraquinone and 3- acylcuomarine derivatives, and also 3-(aroylmethylene thiazolines, as well as eosine, rho- danine and erythrosine dyes.
• Preferred sensitisers are those selected of the group consisting of the anthracenes, xan- thones, benzophenones and thioxanthones, preferably isopropylthioxanthone.
• Suitable sensitisers are 2,4-diethylthioxanthone; isopropylthioxanthone mixture of
• electron donor compounds such as, for example, alkyl- and aryl- amine donor compounds
• Such compounds are, for example, 4-di-meth- ylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid, 4-dime- thylaminobenzoin, 4-dimethyIaminobenzaldehyde, 4-dimethylaminobenzonitrile and 1,2,4-tri- methoxybenzene.
• Such donor compounds are preferably used in a concentration of from 0.01 to 5%, especially in a concentration of from 0.05 to 0.50%, based on the formulation.
• Thioxanthones thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthio- xanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanth- one, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxy- carbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1 -chloro-4-propoxy-thio- xanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxy- carbonyl-3-ethoxythioxanthone, 1 -ethoxycarbonyl-3-aminothioxan
• Benzophenones benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'- dimethoxy-benzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-di- methyl-aminobenzophenone, 4,4'-diethylaminobenzophenone, 4-methyIbenzophenone, 2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)-benzophenone, 3,3'-dimethyl-4-meth- oxybenzophenone, methyl-2-benzoyl benzoate, 4-(2-hydroxyethylthio)-benzophenone, 4-(4- tolylthio)benzophenone, 4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2- hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-prop
• 3-Acylcoumarins 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(prop- oxy)coumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl- bis[5,7-di-(propoxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-di- ethyl-aminocoumarin), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl- 5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxy-coumarin, 3-benzoyl-5,7-di(methoxyethoxy)- coumarin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-
• Sensitizers are present in the formulation to be cured in an amount of about 0.05 to about 10% by weight, e.g. of about 0.1 to 5% by weight, preferably of about 0.1 to 2 % by weight, based on the weight of the curable formulation.
• compositions according to the invention may additionally comprise further photoinitiators, such as, for example, cationic photoinitiators, photo acid formers in amounts of from 0.01 to 15%, for example from 0.1 to 5%, by weight, based on the weight of the composition.
• photoinitiators such as, for example, cationic photoinitiators, photo acid formers in amounts of from 0.01 to 15%, for example from 0.1 to 5%, by weight, based on the weight of the composition.
• cationic photoinitiators and acid-formers are phosphonium salts, diazonium salts, pyridinium salts, sulfonium salts, ferrocenium salts, e.g. ( ⁇ 6 -isopropylbenzene)( ⁇ 5 -cyc- lopentadienyl)-iron-ll hexafluorophosphate RTM lrgacure 261, nitrobenzylsulfonates, alkyl- and aryl-N-sulfonyloxyimides and further known alkylsulfonic acid esters, haloalkylsulfonic acid esters, 1 ,2-disulfones, oxime sulfonates, benzoin tosylate, tolylsulfonyloxy-2-hydroxy-2-meth- yl-1-phenyl-1-propanone and further known beta-ketosulfones, beta-sulfony
• Additional additives may be present in ⁇ the curable compositions of this invention.
• Such additional additives are added to the compositions in amounts customary in the art and generally known to the skilled person.
• Typical examples of such additives are light stabilizers such as UV absorbers, typically those of the hydroxyphenylbenztriazole, hydroxyphenyl- benzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type. These compounds may be used singly or in admixture with or without the addition of sterically hindered amines (HALS).
• HALS sterically hindered amines
• customary additives include thermal inhibitors, optical brighteners, fillers and pigments, as well as white and colored pigments, dyes, antistatics, adhesion promoters, wetting agents, flow auxiliaries, lubricants, waxes, anti-adhesive agents, dispersants, emulsifiers, antioxi- dants, fillers, e.g. talcum, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, thickeners, matting agents, antifoams, and other adjuvants customary, for example, in lacquer and coating technology.
• the present compositions may comprise dyes and/or white or colored pigments.
• inorganic and organic pigments are known to the person skilled in the art; some examples thereof are titanium dioxide pigments, for example of the rutile or anatase type, carbon black, zinc oxide, such as zinc white, iron oxides, such as iron oxide yellow, iron oxide red, chromium yellow, chromium green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow and cadmium red.
• titanium dioxide pigments for example of the rutile or anatase type
• carbon black zinc oxide, such as zinc white
• iron oxides such as iron oxide yellow, iron oxide red, chromium yellow, chromium green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow and cadmium red.
• organic pigments are mono- or bis-azo pigments, and metal complexes thereof, phthalocyanine pigments, polycyclic pigments, such as, for example, perylene, anthraquinone, thioindigo, quinacridone and triphenyl methane pigments, and diketo-pyrrolo-pyrrole, isoindolinone, e.g. tetrachloro-isoindolinone, isoindoline, dioxazine, benzimidazolone and quinophthalone pigments.
• phthalocyanine pigments polycyclic pigments, such as, for example, perylene, anthraquinone, thioindigo, quinacridone and triphenyl methane pigments, and diketo-pyrrolo-pyrrole
• isoindolinone e.g. tetrachloro-isoindolinone
• isoindoline dioxazine
• the pigments can be used individually or in admixture in the formulations. Depending upon the intended use, the pigments are added to the formulations in amounts customary in the art, for example in an amount of from about 1 to about 60% by weight, or from about 10 to about 30% by weight, based on the total weight.
• the formulations may, for example, also comprise organic dyes of a wide variety of classes. Examples thereof include azo dyes, methine dyes, anthraquinone dyes and metal complex dyes. Customary concentrations are, fon example, from about 0.1 to about 20%, especially from about 1 to about 5%, based on the total weight.
• the pigments, latent pigments or dyes or differently colored precursors of such pigments and dyes that are added may be so selected that they undergo a color change in the presence of the acid formed from the onium salt as a result of irradiation.
• Such compositions then show, by the color change, that they have been irradiated and can be used, for example, as irradiation dose indicators, e.g. for UV radiation, electron beams, X-rays, etc.
• additives will depend upon the field of use in question and upon the properties desired for that field.
• the additives described above are customary in the art and are accordingly used in amounts customary in the art.
• the present curable compositions may also comprise thermally curable components.
• the present curable compositions may also comprise free-radically polymerizable components such as ethylenically unsaturated monomers, oligomers or polymers. Suitable materials contain at least one ethylenically unsaturated double bond and are capable of undergoing addition polymerization.
• compositions of this invention When free-radically polymerizable components are added to the compositions of this invention, it may be advantageous to add one or more suitable free-radical photoinitiator, for example benzophenone and derivatives thereof, acetophenone and derivatives thereof or mono- or bis-acylphosphine oxides.
• suitable free-radical photoinitiator for example benzophenone and derivatives thereof, acetophenone and derivatives thereof or mono- or bis-acylphosphine oxides.
• Free-radically curable compounds and free-radical photoinitiators are for example disclosed in U.S. Pat. No. 6,306,555, incorporated herein by reference.
• compositions according to the invention can be used in numerous applications, for ex- ample in cationically radiation curable printing inks, in cationically radiation curable coating compounds which may or may not be pigmented, in cationically radiation curable adhesives, coatings and moldings, including glass fiber reinforced and carbon fiber reinforced composites and inner and outer layers of printed circuit boards.
• compositions according to the invention include also adhesives, as used, for example, for adhesive bonding (DVD bonding) in the manufacture of digital versatile disks (DVD) and as described, for example, in: WO 99/66506, WO 99/63017, JP 11241055 A2 Heisei, JP 11181391 A2 Heisei, WO 98/31765, and also as radiation curable laminating adhesives for flexible packaging (see, e.g., US 5328940), optical adhesives (e.g. German Patent Applica- tion DD 225985) and pressure sensitive adhesives (e.g. U.S. Pat. No. 4,988 741 and EP 115870).
• adhesives as used, for example, for adhesive bonding (DVD bonding) in the manufacture of digital versatile disks (DVD) and as described, for example, in: WO 99/66506, WO 99/63017, JP 11241055 A2 Heisei, JP 11181391 A2 Heisei
• compositions according to the invention are advantageously used where there is a need for hard coatings, adhesive bonds or photopolymerized dimensionally stable three dimensi- onal moldings (e.g. for rapid prototyping) having good adhesion to paper, glass, metal, silicon, polycarbonate, acrylate polymers and other polymer substrates, and that exhibit only slight shrinkage during curing.
• This curable compositions of this invention are employed for example for coating materials, in printing colors, clear coating formulations, white enamels, such as for wood or metals, or for paints, e.g. for paper, wood, metal or plastics.
• compositions according to the invention may be used for a variety of purposes, for example as printing inks, such as screen-printing inks, flexo printing inks or offset printing inks, as clear lacquer, as colored surface-coating compositions, as white surface-coating compositions, e.g.
• galvano-resists etch resists or permanent resists, liquid films and dry films, as photostructurable dielectrics, and as solder masks for electronic circuits, as resists in the manufacture of color filters for any type of screen or for producing structures in the manufacture of plasma displays and electroluminescent displays, in the manufacture of optical switches, optical gratings (interference gratings), in the coating or sealing of electronic components, e.g. as electroinsulating com- pounds, or as coatings for optical fibers, for* coil coating, as indicator systems for UV radiation, X-rays and electron beams, and in the manufacture of three-dimensional articles, e.g. for stereolithography and for composites, e.g. for composites reinforced with glass or carbon or graphite fibers.
• the compositions are also suitable for the manufacture of optical lenses, e.g. contact lenses or Fresnel lenses, and also in the manufacture of medical apparatus, aids or implants.
• the photocurable compositions according to the invention are suitable, for example, as coating materials for all kinds of substrates, for example wood, textiles, paper, ceramics, glass, marble, plastics, such as polyester, polyethylene terephthalate, polyolefins or cellulose ace- tate, especially in the form of films, and metals, such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or Si0 2 , to which a coating is to be applied or an image is to be applied by image- wise exposure, or to which a structured resist layer is to be applied.
• the coating of the substrates can be effected by applying a liquid composition, a solution or suspension to the substrate.
• the choice of solvent and the concentration are governed chiefly by the nature of the composition and by the coating method.
• the solvent should be inert, that is to say it should not enter into any chemical reaction with the components and it should be capable of being removed again upon drying after the coating operation.
• suitable solvents are ketones, ethers and esters, such as methyl ethyl ketone, isobu- tyl methyl ketone, cyclopentanone, cyclohexanone, 2-he ⁇ tanone, methyl amyl ketone, N- methylpyrrolidone, gamma-butyrolactone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2- ethoxyethanol, l-methoxy-2-propanol, 1,2-dimethoxyethane, acetic acid ethyl ester, acetic acid n-butyl ester, propylene glycol monomethyl ether acetate, lactic acid e
• the formulation is applied uniformly to a substrate by known coating methods, for example by spin-coating, immersion, knife coating, curtain pouring, brush application or spraying, especially by electrostatic spraying and reverse-roll coating, and by electrophoretic deposition. It is also possible to apply the photosensitive layer to a temporary flexible support and then coat the final substrate, e.g. a copper-laminated printed circuit board, by transferring the layer by lamination.
• coating methods for example by spin-coating, immersion, knife coating, curtain pouring, brush application or spraying, especially by electrostatic spraying and reverse-roll coating, and by electrophoretic deposition.
• the photosensitive layer to a temporary flexible support and then coat the final substrate, e.g. a copper-laminated printed circuit board, by transferring the layer by lamination.
• the amount applied (layer thickness) and the type of substrate used (layer substrate) depend of the desired field of application.
• the layer thickness is usually in the range from about 0.1 to about 100 ⁇ m, for example from about 0.1 ⁇ m up to about 50 ⁇ m, e.g. from about 4 ⁇ m to about 15 ⁇ m.
• suitable substrates are in particular metals, such as aluminium or tinplate.
• UV irradiation is usually carried out with light having a wavelength in the range of 200 nm to 600 nm.
• Suitable radiation includes e.g. sun light or light from artificial light sources.
• Light sources to be used include a great number of a very wide range of types. Suitable light sources are point sources as well as arrays of reflector lamps (lamp carpets).
• Typical examples are: carbon arc lamps, xenon arc lamps, mercury (medium, high and low pressure) lamps, where desired doped with metal halides (metal halide lamps), microwave-excited metal vapor lamps, excimer lamps, super- actinic neon lamps, fluorescent lamps, argon filament lamps, flash bulbs, photographic flood light lamps, electron beams and X-rays.
• the distance between the lamp and the substrate to be irradiated can vary depending on the end use requirement and type of lamp or lamp intensity, e.g. from about 2 cm to about 150 cm.
• Laser light sources are also suitable, e.g. excimer laser. It is also possible to use laser in the visible range.
• the radiation sensitive compositions according to the invention are used, for example, as negative resists that have very high photosensitivity and that can be developed in an aqueous alkaline medium without swelling. They are suitable as photoresists for electronics, such as galvanoresists, etch resists, and in liquid and dry films, solder resists, as resists in the production of color filters for any type of screen, or to form structures in the manufacture of plasma displays and electroluminescent displays, in the manufacture of printing plates, e.g. offset printing plates, in the manufacture of printing molds for letterpress printing, flatbed printing, intaglio printing, flexo printing or screen-printing molds, the production of relief copies, e.g.
• compositions can also be used as photostructurable dielectrics, for encapsulating mate- rials or as an ⁇ insulating coating in the manufacture of computer chips, printed' icircuits and other electrical or electronic components.
• the possible layer supports and processing conditions for the coated substrates vary accordingly.
• compositions according to the invention are also used in the manufacture of single or multi layer materials for image recording or image reproduction (copies, reprography), which may be monochromatic or polychromatic. Included therein are materials for holographic storage of information, e.g. for holographic images or 3-dimensional holographic data storage. Such materials can also be used in color test systems. In that technology it is also possible to use formulations that comprise microcapsules and, to produce the image, a ther- mal step can be carried out after the exposure step. Such systems and technologies and their use are described, e.g., in U.S. Pat. No. 5,376,459.
• the layer thicknesses for photographic materials and offset printing molds are generally from about 0.5 ⁇ m to 10 ⁇ m, and for printed circuits from 1.0 ⁇ m to about 100 ⁇ m.
• the invention relates also to the use of the present compositions in the manufacture of surface coating compositions, printing inks, printing plates, dental compounds, stereolithography resins, adhesives, anti-adhesive coatings, color filters, resist materials or image recording materials.
• the invention relates also to a coated substrate that is coated on at least one surface with a composition according to the invention, and to a method for the production of relief images wherein a composition according to the invention is applied to a substrate and is then exposed image wise.
• image wise exposure includes irradiation through a mask that contains a predetermined pattern, for example a diapositive, a metal mask, a chrome mask on a transparent support, exposure by means of a laser beam that is moved, for example controlled by a computer, over the surface of the coated substrate and in that manner produces an image, ⁇ and irradiation with computer-controlled electron beams. Images can also be produced by interference between two beams or images, for example for holographic uses. It is also possible to use liquid crystal masks that can be actuated pixel by pixel to produce digital images, as described, for example, by A. Bertsch, J.Y. Jezequel, J.C. Andre in Journal of Photochemistry and Photobiology A: Chemistry 1997, 107, pp. 275-281 and by K.-P. Nicolay in Offset Printing 1997, 6, pp. 34-37.
• compositions of this invention can be used in photoresists.
• Resist systems can be obtained by image wise exposure of formulations comprising the present components and a subsequent development step.
• photoresist is not limited to the chemically enhanced resists described in greater detail below, but includes all resist materials in which reactions are initiated by the radiation-chemical production of acid and that, in a development step, result in a difference in solubility between exposed and non-exposed regions.
• resists that can be processed in an aqueous medium, as described, for example, in U.S. Pat. No. 5,998,092 and in SPIE, Vol. 3999, pp. 569-578 (2000) as well as resists based on a Pinacol rearrangement, as described, for example, in SPIE, Vol. 3999, pp. 62-73 (2000).
• the invention relates also to a photoresist composition that comprises at least one onium salt photoinitiator and an effective stabilizing amount of at least one compound selected from the group consisting of the organic phosphorus stabilizers and the hindered nitroxyl stabilizers.
• a chemically enhanced photoresist is to be understood as being a resist formulation in which the radiation sensitive component provides a catalytic amount of acid, which in turn catalyzes a chemical reaction of at least one acid sensitive component of the resist. This results in a difference in the solubility of the irradiated and non irradiated portions of the resist.
• an acid molecule can initiate reactions at many sites because it diffuses through the reactive polymer matrix from one reaction site to the next, provided it is not captured or destroyed by secondary reactions. Even a low acid concentration is therefore sufficient to obtain large differences in solubility between irradiated and non-irradiated portions of the resist.
• latent acid compound It is therefore generally sufficient to add only a small amount of latent acid compound. It is necessary, however, for the latent acid donors to be chemically and thermally stable until they are being irradiated. It is also necessary for the latent catalysts to be readily soluble in the liquid resist formulation and in the solid resist film in order to avoid the formation of particles which would adversely affect the use of the resists in microelectronic processing processes.
• compositions according to the invention comprise components that increase the solubility of the composition in the developer after irradiation and optionally after thermal aftertreatment, then it is a positive photoresist.
• the invention accordingly relates also to a positive photoresist. If, however, the components of the composition lower the solubility in the developer after irradiation and optionally after thermal aftertreatment, then it is a negative photoresist.
• the invention accordingly relates also to a negative photoresist.
• the proportion of the onium salt compounds in the positive resist formulation is advantageously from about 0.01 to about 20% by weight, based on the solids content in the photoresist.
• Acid sensitive components that form negative resists are generally compounds that are capable of undergoing a crosslinking reaction with themselves and/or with one or more further components in the composition when they are catalyzed by an acid (e.g. the acid formed by exposure of the onium salt compounds in the presence of the stabilizers according to the in- vention).
• Compounds of that kind are, for example, the known acid-curable resins, such as acrylate, polyester, alkyd, melamine, urea, epoxy and phenolic resins or mixtures thereof. Amino resins, phenolic resins and epoxy resins are especially suitable.
• Acid-curable resins of that kind are generally known and are described, for example, in "Ullmann's Encyclopadie der ischen Chemie", Edition 4, Vol. 15 (1978), pp. 613 - 628.
• the crosslinking components should advantageously be present in a concentration of about from 2 to 40% by weight, preferably from 5 to 30% by weight, based on the solids content of the negative resist formulation.
• the concentration of the onium salt compounds in the negative resist is advantageously from about 0.1 to about 30% by weight, especially up to about 20% by weight, preferably from about 1 to about 15% by weight, based on the total solids content of the compositions.
• compositions according to the invention are dissolved in a suitable solvent be- fore application to the substrate.
• suitable solvents include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, ⁇ -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 2- ethoxyethyl acetate, 2-ethoxyethanol, diethyl glycol dimethyl ether, ethylene glycol mono- ethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methylmethoxy propionate, eth- ylethoxy propionate, methyl pyruvate, ethyl pyruvate, propyl
• esters such as 2- methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol mono- methyl ether acetate, methylmethoxy propionate, ethylethoxy propionate and ethyl lactate.
• a surfactant may be added to the solvent.
• suitable surfactants are non-ionic surfactants, such as polyoxyethylene alkyl ethers, e.g. polyoxyethylene lauryl ether, poly- oxyethylene stearyl ether, polyoxyethylene acetyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers, e.g. polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene/polyoxypropylene block copolymers, sorbitol/fatty acid esters, e.g.
• the proportion of surfactant in the composition is about 2 parts by weight or less, e.g. 0.1 part by weight or less, per 100 parts by weight of solids content in the composition.
• the surfactants may be used individually or in combinations.
• composition according to the invention is applied uniformly to a substrate by means of generally known methods already described above. Suitable layer thicknesses have also already been indicated above.
• the solvent is usually removed by heating and a layer of the photoresist remains on the substrate.
• the drying temperatures must, of course, be lower than the tem- peratures at which constituents of the resist formulation can decompose or react. Normally the drying temperatures vary within a range of about from about 60 to about 160°C.
• the exposure of the coated substrates has already been described above. After exposure and, if necessary after the thermal treatment, the exposed sites of the com- position (in the case of the positive resist) or the non-exposed sites of the composition (in the case of the negative resist) are removed using a developer in a manner generally known to a person skilled in the art.
• the coating is preferably heated before development. It is also possible to carry out heating during the exposure. Generally temperatures of from about 60 to about 160°C are used. The optimum duration of heating depends upon the heating method used and can be determined by the person skilled in the art by simple experiments. It normally ranges from a few seconds to several minutes, e.g. from about 10 to about 300 seconds when a heating plate is used, and, e.g., from about 1 to about 30 minutes when a circulated-air oven is used.
• Aqueous-alkali developer fluids customary in the art can be used for that purpose. Examples thereof include sodium and potassium hydroxide, the corresponding carbonates, hydrogen carbonates, silicates and metasilicates, metal- free bases, such as ammonium compounds, or amines, such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamines, e.g.
• the developer solutions are normally up to 0.5N, but are generally diluted before use in a suitable manner.
• solvents having a normality of about from 0.1 to 0.3 are very suitable.
• the choice of developer will depend upon the nature of the photocurable coating, especially upon the nature of the crosslinking agent or the resulting photolysis products.
• the aqueous developer solutions may, if necessary, also comprise small amounts of wetting agents and/or organic solvents.
• Examples of typical organic solvents that may be added to the developer solutions include cyclohexanone, 2-ethoxyethanol, toluene, acetone, isopropanol and mixtures of two or more such solvents.
• a typical aqueous/organic developer system is a system based on Butylcel- losolve RTM /water.
• the invention relates also to a method of manufacturing a photoresist by (1) applying a composition as described above to a substrate; &
• the photoresist compositions can be used on all types of substrate and with all irradiation techniques known to the person skilled in the art.
• semiconductor substrates can be used, such as silicon, gallium arsenide, germanium, indium antimonide; also substrates covered by oxide or nitride layers, such as silicon dioxide, silicon nitride, titanium nitride, siloxanes, and metal substrates and metal-coated substrates coated with metals such as aluminium, copper, tungsten, etc.
• the substrate can also be coated with polymeric mate- rials, for example with organic antireflective coatings, insulation layers and dielectric coatings made of polymeric materials.
• the photoresist layer can be irradiated by all customary techniques, such as direct writing, i.e. with a laser beam or projection lithography in step-and repeat mode or scanning mode, or by contact printing through a mask.
• a large number of optical conditions can be selected, such as coherent, partially coherent or incoherent radiation.
• the mask used to produce the pattern can be a hard mask or a flexible mask.
• the mask can indude transparent, semi-transparent and opaque patterns.
• the pattern size can include also patterns that are at or below the resolution limit of the projection optics and are arranged on the mask in a certain manner in order to modify the aerial image, intensity and phase modulation of the radiation after having it has passed through the mask. This indudes phase-shift masks and half-tone phase-shift masks. a*
• the process for forming an image on the photoresist composition can be used to generate patterns of any desired geometry and shape, for example dense and isolated lines, contact holes, channels, incisions, dots, etc.
• the invention relates also to the use of the present onium salt compounds in the presence of the stabilizers as photolatent acid donors in the polymerization or crosslinking of cationically or acid-catalytically polymerizable or crosslinkable compounds or to increase the solubility of compounds that increase their solubility in a developer under the action of acid, and also to a method for the photopolymerization or crosslinking of cationically or acid-catalytically polymerizable or crosslinkable compounds under the action of electromagnetic radiation, in which method the onium salt compounds in the presence of the stabilizers are used as photolatent acid donors.
• the UV irradiation to release the acid is generally effected with light of a wavelength of from about 157 to about 600 nm.
• Suitable radiation is present, for example, in sunlight or light from artificial light sources.
• a large number of widely varying types of light source may be used.
• Point sources and also planiform radiators (lamp carpets) are suitable. Examples thereof include: carbon arc lamps, xenon arc lamps, medium-, high- and low-pressure mercury lamps, doped where appropriate with metal halides (metal halide lamps), microwave- excited metal vapor lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flashlamps, photographic flood lights, electron beams and X-rays.
• Laser light sources for example excimer lasers, are also suitable. Lasers in the visible range can also be used.
• the distance between the lamp and the substrate to be exposed can vary according to the intended use and the type and strength of the lamp and may be, for example, from about 2 cm to about 150 cm.
• a method for curing a cationically polyerizable composition comprises applying a compositon comprising r at least one cationically polymerizable compound, at least one onium salt photoinitiator and at least one compound selected from the group consisting of the organic phosphorus stabilizers and the hindered nitroxyl stabilizers to a substrate and exposing the composition for a suitable time to ultraviolet radiation.
• a photocurable composition is prepared with a 25:25:50 weight mixture of resins R2:R3:R1 and 2.7 pph, by weight, of cationic photoinitiator PH.
• the fresh composition exhibits a viscosity of 16 cps.
• the unstabilized formulation exhibits a viscosity of 46 cps.
• a stabilized formulation with 0.025 pph nitroxyl stabilizer N01 has a viscosity of 23 cps.
• Photocurable compositions are prepared with a 3:1 weight ratio of resins R2:R3.
• the samples are tested for oven stability at 80°C.
• the samples contain 2.7 pph by weight photoinitiator PH. Without stabilizers, samples gel between 12 and 14 days. With an added 0.25 pph by weight nitroxyl stabilizer N01, the sample does not gel until 35 days. With an added 1 pph by weight of either of organic phosphorus stabilizer OP2 or OP3, the samples gel at about the 27 day. With 1 pph by weight of the organic phosphorus stabilizer OP1 , the sample does not gel until day 39.
• Photocurable compositions are prepared with a 3:1 weight ratio of resins R2:R3.
• the samples are tested for oven stability at 80°C.
• the samples contain 1 pph by weight photoinitiator PI2 and 0.5 pph by weight the sensitizer isopropylthioxanthone. Shelf life stability of formulations containing further additives is shown below.

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• 2005
  • 2005-01-17 WO PCT/EP2005/050157 patent/WO2005070989A2/en not_active Ceased
  • 2005-01-17 KR KR1020067017287A patent/KR20070004649A/ko not_active Ceased
  • 2005-01-17 JP JP2006550160A patent/JP2007523974A/ja active Pending
  • 2005-01-17 EP EP05701522A patent/EP1709099A2/en not_active Withdrawn
  • 2005-01-21 US US11/040,716 patent/US20050165141A1/en not_active Abandoned
  • 2005-01-26 TW TW094102282A patent/TW200538481A/zh unknown
• 2007
  • 2007-05-14 US US11/803,274 patent/US20070225395A1/en not_active Abandoned

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