Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
  • C07D335/12—Thioxanthenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
  • C07D339/08—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/76—Dibenzothiophenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
  • C07D335/12—Thioxanthenes
  • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
  • C07D335/16—Oxygen atoms, e.g. thioxanthones
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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 invention relates to sulfonium salts, to methods for their preparation, to formulations containing them and to their use as photoinitiators for radiation curable systems STATE OF THE ART
• UV-visible curable systems arises from some of its advantages such as the high speed of formation of the coating, its good adhesion to plastics and metals and its high flexibility
• curable systems generally contain a cationic polyme ⁇ sable material and an onium salt (sulfonium, phosphonium, lodonium salts) eventually dissolved in a reactive solvent
• Sulfonium salts can be utilised as initiators of cationic polymerisation after photochemical activation
• Heterocyclic ring containing a sulfonium salt in their structures were utilised as initiators of polymerisation activated by light or heat
• R is a C 5 -C 8 cycloalkyl substituted with another Cs-C ⁇ cycloalkyl radical
• X is an anion selected from PF 6 “ , AsF 6 “ , SbF 6 “ , SbF 5 OH “ ,
• the above-described compounds act as heat-sensitive initiators for cationic polymerisation
• Sulfonium salts are also utilised as photoinitiators for resists
• M " is a carboxylate or an organic sulfonate anion
• R is an unsubstituted or substituted aryl group
• X is O, S, N-R or a C ⁇ -C 3 alkylene
• M is selected from P, As, Sb, R is an aryl
• Z is selected from S, SO, CH 2 , C 2 H 4 , NR' wherein R' is C ⁇ -C 8 alkyl or C 6 -C ⁇ 3 aryl
• the compounds of formula (E) are cationic photoinitiators for a variety of monomers and ohgomers
• X is selected from: S, O, CH 2 , CO, single bond, N-R wherein R is H, or alkyl or aryl;
• Yi and Y are equal or different and are selected from: H, C ⁇ -C ⁇ linear or branched alkyl, cycloalkyl, O-alkyl, hydroxyl, halogen, S-alkyl, S-aryl;
• Z " is a group of the general formula MQ P wherein M is B, P, As or Sb; Q is F, CI,
• p is an integer from 4 to 6;
• A is a functional group of the general formula (II):
• the present invention is also directed to the sulfonium salts of formula (III)
• X is selected from S, O, CH 2 , CO, single bond, N-R wherein R is H, or alkyl or aryl,
• Y ⁇ ', Y 2 ', Y 3 ' are equal or different and are selected from H, Ci-C ⁇ linear or branched alkyl, cycloalkyl, O-alkyl, hydroxyl, halogen, S-alkyl, S-aryl, NR ⁇ 2 wherein R 1 and R are equal or different and are selected from H, linear or branched alkyl, cycloalkyl, aryl, L " is a group of the general formula MQ P wherein M is B, P, As or Sb,
• Q is F, CI, Br, I, or perfluorophenyl
• p is an integer from 4 to 6
• D is selected from: a C 2 -C 6 linear or branched alkoxyl or cycloalkoxyl eventually substituted with one or more groups selected from OH, OR, NH 2 , NHR, NR ⁇ , SH, SR, wherein R, R ⁇ ,
• R 2 can be equal or different and are selected from H, linear or branched alkyl, cycloalkyl, or aryl; a C 2 -C 6 linear or branched alkylthio or cycloalkylthio eventually substituted with one or more groups selected from SH, SR, OH, OR, NH 2 , NHR, NR ⁇ R 2 , wherein
• R, RL R 2 can be equal or different and are selected from H, linear or branched alkyl, cycloalkyl, or aryl;
• NR 3 R 4 wherein R 3 , R are equal or different and are selected from H; aryl; C Ci 2 linear or branched alkyl, the alkyl being eventually substituted with one or more groups selected from: OH, OR, NH 2 , NHR, NR ⁇ R 2 , SH, SR, wherein R, R1 , R2 are equal or different and are selected from H, linear or branched alkyl, cycloalkyl, or aryl.
• the present invention is further directed to radiation curable compositions containing as photoinitiators at least one sulfonium salts of the formula (I) or of the formula (III).
• Another object of the present invention is a method for the preparation of the sulfonium salts of formula (I) comprising the following steps: a) reacting at 0°-100°C a compound of the formula (IV):
• the preferred Lewis acid is aluminium trichloride
• the preferred mineral acid is sulfunc acid c) reacting the thus obtained compound of formula (IA) with a compound of formula (MB)
• R 1 -R 5 are equal or different and are selected from H, halogen atom (F, CI, Br, I), nitro, Ci -C ⁇ linear or branched alkyl, Ci -Ce linear or branched alkoxyl, S-C 1 -C ⁇ linear or branched alkylthio, and
• B" is selected from a C 2 -C 18 linear or a branched alkylene carrying at one of its end an heteroatom selected from O, S, N-R and at the opposite end a group chosen among NHR, SH, OH, the alkylene being eventually substituted with CI-C ⁇ linear or branched hydroxyalkyl, C1-C6 mercaptoalkyl, hydroxyl, ammo, or aminoalkyl, an alicychc group with two nitrogen atoms in the ring, wherein the first one is linked to the aryl group and the second one is substituted with a hydrogen atom, the alicyclic group being eventually substituted with hydroxyl, ammo, Ci-C ⁇ linear or a branched aminoalkyl, to obtain the compound of formula (IB)
• Still another object of the present invention is a method for the preparation of the sulfonium salts of formula (III) comprising the following steps a) reacting at 0°-100°C a compound of the formula (IVA)
• the compounds of formula (I) are those wherein X is selected from S,CO,CH 2 , single bond and B is selected from S, single bond, O,
• Y is H or Ci-C ⁇ linear or branched alkyl
• the compounds of formula (III) are those wherein D is
• - n is an integer from 2 to 10
• K is O, S or NR 3 and R ⁇ R 2 , R 3 are equal or different and are selected from H, linear or branched alkyl, cycloalkyl, aryl,
• the radiation curable compositions of the present invention contain the sulfonium salts in an amount of from 0 5 to 10 %, more preferably of from 0 5 to 5 %, w/w
• the sulfonium salts of formula (III) show a good solubility in the formulations and thus they can be added directly to the formulations without being previously dissolved in a solvent
• the radiation curable compositions of the invention polymerise by irradiation at a wavelength of 2000-7000 Angstrom
• the polyme ⁇ sable compound is a monomer or a pre-polymer belonging to the following categories epoxides, oxetanes, modified sihcones, vegetal epoxidised oil, epoxidised alkenes, cyclic ethers, vinyl ethers (such as ethylvmylether, t ⁇ ethyleneglycol divinylether, 4- epoxybutylvmylether), lactones, styrene, acrolem, vmylarene, vinyl compounds, spiro-ortocarbonate, phenol, formaldehyde It is a further object of the present invention to provide liquid formulations containing from 30 to 80% w/w of one or more sulfonium salts of general formula (I) or (III) in a solvent selected from the group consist
• the liquid formulations of the present invention preferably contain propylene carbonate as solvent
• the radiation curable compositions of the invention are utihzable for the coating of food packaging or of metallic surfaces
• sufonium salts are generally well described in many patents such as in US 5,012,001 and in US 4,684,671 , where the use of condensation reactions between a reactant bearing a sulfoxide group and another compound, electron rich, able to undergo an electrophihc substitution reaction is described Normally a strong mineral acid (e g sulfu ⁇ c acid), eventually in combination with a strong dehydrating agent (e g P 2 Os), promotes the formation of the electrophilic group
• a strong mineral acid e g sulfu ⁇ c acid
• a strong dehydrating agent e g P 2 Os
• the sulfonium salts prepared as described in the examples were tested in radiation curable compositions to measure their reactivity and the concentration of low molecular weight fragmentation products (benzene in particular) released during irradiation
• composition A contained as photomitiator a mixture of b ⁇ s-[4-(d ⁇ phenylsulfon ⁇ o)-phenyl]-sulf ⁇ de dihexafluorophosphate and was prepared by adding to Composition A' a 50% solution of said photomitiator in propylene carbonate
• the resulting radiation curable compositions were spread on an aluminium support as a 12 micron thick film and irradiated with a high-pressure mercury lamp having energy of 700 mJ
• Example 9 The photomitiator of Example 9 was directly dissolved in Composition A' to obtain two radiation curable compositions containing the photomitiator in the desired amount (2 and 4%)
• Example 9 The photomitiator of Example 9 was then dissolved in propylene carbonate to obtain a 50% w/w solution The solution was added to Composition A' to obtain a radiation curable composition containing 4% by weight of the photomitiator Compostion A (containing 4% of photomitiator) was again used as the reference The results are reported in Table 3
• the sulfonium salts of the invention possess a reactivity that is similar or greater of the reference
• the content of benzene in the polymerised radiation curable compositions was measured The content of benzene was determined by headspace GC, a capillary column CP-select 624 CB, 30m x 0,32 mm id, film 1 ,8 ⁇ m and FID detector at 250°C The samples were cut into small pieces, charged in a head space vial containing DMSO, then warmed up for 30' at 95°C and injected

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polymerization Catalysts (AREA)
• Polymerisation Methods In General (AREA)
• Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
• Epoxy Resins (AREA)

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Cited By (23)

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• 2002
  • 2002-07-04 AT AT02767172T patent/ATE438638T1/de not_active IP Right Cessation
  • 2002-07-04 AU AU2002331332A patent/AU2002331332A1/en not_active Abandoned
  • 2002-07-04 WO PCT/EP2002/007415 patent/WO2003008404A2/en not_active Ceased
  • 2002-07-04 US US10/484,358 patent/US7230121B2/en not_active Expired - Lifetime
  • 2002-07-04 DE DE60233234T patent/DE60233234D1/de not_active Expired - Lifetime
  • 2002-07-04 CN CNB028145038A patent/CN1269812C/zh not_active Expired - Fee Related
  • 2002-07-04 BR BRPI0205767-0B1A patent/BR0205767B1/pt not_active IP Right Cessation
  • 2002-07-04 JP JP2003513963A patent/JP4480393B2/ja not_active Expired - Lifetime
  • 2002-07-04 KR KR1020037003928A patent/KR100918556B1/ko not_active Expired - Fee Related
  • 2002-07-04 ES ES02767172T patent/ES2329345T3/es not_active Expired - Lifetime
  • 2002-07-04 EP EP02767172A patent/EP1417198B1/en not_active Expired - Lifetime
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