IE42085B1 - Photopolymerisable compositions - Google Patents
Photopolymerisable compositionsInfo
- Publication number
- IE42085B1 IE42085B1 IE1980/75A IE198075A IE42085B1 IE 42085 B1 IE42085 B1 IE 42085B1 IE 1980/75 A IE1980/75 A IE 1980/75A IE 198075 A IE198075 A IE 198075A IE 42085 B1 IE42085 B1 IE 42085B1
- Authority
- IE
- Ireland
- Prior art keywords
- composition
- acid
- photosensitiser
- photopolymerisable
- photopolymerisable composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 93
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001450 anions Chemical class 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 46
- -1 tetrafluoroborate ion Chemical class 0.000 claims description 36
- 230000005855 radiation Effects 0.000 claims description 29
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 abstract description 3
- 239000003112 inhibitor Substances 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 28
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 239000002904 solvent Substances 0.000 description 17
- 229920003319 Araldite® Polymers 0.000 description 13
- 239000003085 diluting agent Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 238000001879 gelation Methods 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 6
- 150000002924 oxiranes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- MEYARNKYUHUVBB-UHFFFAOYSA-N 2-hydroxy-1-[2-(hydroxymethyl)phenyl]-2-phenylethanone Chemical compound OCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 MEYARNKYUHUVBB-UHFFFAOYSA-N 0.000 description 2
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- POJPQMDDRCILHJ-UHFFFAOYSA-N 1,1,1,2,2,2-hexabromoethane Chemical compound BrC(Br)(Br)C(Br)(Br)Br POJPQMDDRCILHJ-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001663 electronic absorption spectrum Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ARZLUCYKIWYSHR-UHFFFAOYSA-N hydroxymethoxymethanol Chemical class OCOCO ARZLUCYKIWYSHR-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08G85/00—General processes for preparing compounds provided for in this subclass
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Photopolymerisable compsn. contains >=1 constituent which is polymerisable or hardenable by acids and a photosensitiser having the formula: where A is S, Se or Te; n is 1 or 2; R1, R2, and R3 are each independently an opt. substd. hydrocarbyl radical or a heterocyclic radical or two of R1, R2 and R3 form a heterocycle with A and the other one of them is hydrocarbyl; Xn- is the anion of an acid which is able to polymerise or harden the above constituent. The compsns. are used for printing plates, printed circuits etc. The compsns. can be stored for long time in the dark without gelification and therefore do not require an inhibitor in this respect. Also the compsn. avoids the use of toxic cpds. such as transition metal carbonyls and N-nitrosamines used in previous process.
Description
This invention relates to photopolymerisable compositions comprising one or more materials, which may be monomeric or polymeric, which can be polymerised or cured by treatment with acids. Such materials are commonly referred to, and are referred to herein, as acid-polymerisable or acid-curable materials and examples of suitable materials are epoxide monomers, episulphide monomers, polyepoxides or epoxy resins, polyepisulphides or episulphide resins, phenol/ formaldehyde resins, melamine/formaldehyde resins, urea/formaldehyde resins, cyclic ethers and thio-ethers (other than epoxides and episulphides) and polymers thereof, lactones, styrene, vinyl ethers and thio-ethers and resins which contain a cross-linking agent to cross-link or cure the resin when treated with acid.
The invention relates in particular to compositions comprising one or more acid-polymerisable or acidcurable materials and at least one photosensitiser which initiates polymerisation or curing of the composition when the composition is exposed to radiation of suitable wavelength.
It is well known that acid-curable resins such as phenol resins and amino resins can be cured by irradiation with ultra-violet, actinic or electromagnetic radiation in the presence of a compound which generates an acid (which term includes’ Lewis acids) when exposed to ultraviolet radiation. Examples of compounds which have been proposed for use in such compositions are halogen- 2 <3088 containing compounds, for example bromoform, carbon tetrabromide, hexabromoethane, 2,5-dimethyl- -tribomoacetophenone, 2,2,2-trichloro-4'-tertiarybutyl acetophenone, halomethylated benzophenones, a-methylol benzoin sulphonic acid esters and aryl diazonium salts of metal halogenides.
It is also well known that epoxy resins can be cured by irradiation in the presence of a substance which generates a Lewis acid when exposed to suitable radiation. Substances which have been proposed for use in epoxy materials include transition metal carbonyls and α,β-unsaturated nitrosamines as well as a-methylol benzoin sulphonic acid esters and aryl diazonium salts of metal halogenides mentioned above. The aryl diazonium salts of metal halogenides have also been proposed for polymerisation of epoxide monomers, The photosensitive substances proposed hitherto for incorporation in acid-polymerieable or acid-curable materials are activated to release an acid upon exposure to ultra-violet or electromagnetic radiation or actinic radiation comprising a high proportion of ultra-violet radiation. However, the compositions proposed hitherto have not proved satisfactory. Transition metal carbonyls are toxic and slow acting and their use is undesirable. Generally, N-nitrosamines are carcenogenic and slow acting, Use of aryl diazonium salts of metal halogenides results in compositions which polymerise rapidly and which are subject to * 3 42085 premature gelation and cannot be stored satisfactorily for any length of time even in the dark. It has been proposed to incorporate stabilisers or gelation inhibitors into epoxy materials containing aryl diazonium salts of metal halogenides in order to inhibit premature gelation of the compositions and confer storage ability in the dark; this increases the cost of the compositions and moreover does not yield entirely satisfactory results even under carefully controlled storage conditions. Moreover the aryl diazonium salts generate nitrogen gas when the composition is irradiated and the resulting cured material may contain undesirable gas bubbles.
We have now found that incorporation of some salts of sulphur, selenium or tellurium into acidpolymerisable and/or acid-curable materials provides photopolymerisable compositions which overcome the disadvantages of the compositions proposed hitherto. Thus, for example, compositions containing the photo20 sensitisers can be stored for prolonged periods in the dark without noticeable gelation occurring and the need to provide gelation inhibitors is obviated.
According to the present invention, there is provided a photopolymerisable composition comprising at least one acid-polymerisable or acid-curable material and as photosensitiser at least one salt of formula - 4 42085 (I) wherein A is sulphur, selenium or tellurium, n is 1 or 2, R|, Rj and R3, which may be the same or different, each is a hydrocarbon or substituted hydrocarbon group or heterocyclic group or two of the groups R^, R2 and R^ together with the element A are a heterocyclic structure, the other group R being a hydrocarbon or a substituted hydrocarbon group, and X11 is an anion derived from an acid which is capable of polymerising or curing the acid-polymerisable or acid-curable material.
Upon exposure of the photopolymerlsable composition to radiation of suitable wavelength, the photosensitiser is activated to yield a catalyst species capable of polymerising or curing the composition to yield a polymeric material, and according to a further aspect of the present invention there is provided a process for the preparation of a polymeric material which comprises subjecting a photopolymerisable composition as described in the immediately preceding paragraph to radiation of wavelength such as to activate the photosensitiser and polymerise or cure the composition.
The radiation may be ultra-violet or electron beam radiation, or may include wavelengths ih the visible and the ultra-violet regions of the spectrum.
The wavelength of the radiation suitably may be, for example, in the range from 200 my to 600 my. We prefer 4208S to employ radiation of wavelength in the range from 200 mu to 400 m u. Sunlight may be used as the « radiation although the optimum wavelength of the radiation for any particular composition will depend upon the particular photosensitiser employed in that composition. The optimum wavelength in any particular case is easily determined by simple experiment, for example by determining the electronic absorption spectrum of the photosensitiser.
In the photosensitisers of formula I. the groups R may be, for example, alkyl, cycloalkyl, aryl, alkaryl, or aralkyl groups or substituted derivatives thereof. Preferably each of the groups R is an aryl or substituted aryl group or one of the groups R may be an alkyl group. Examples15 of substituents which may be present in the groups R, are halogen, alkoxy, -COOR, -COR, -NOj, -NO, -OH and -SH, In the case where one or more of the groups R in the photosensitiser is an alkyl or substituted alkyl group, it may contain from 1 to 20 carbon atoms, preferably from 2 to 6 carbon atoms. We prefer to employ salts wherein at least one, and preferably at least two, of the groups.R is an aryl or alkaryl or substituted aryl or alkaryl group, especially the phenyl group or a group containing a phenyl group, for example -CH2CO Ph where Ph is the phenyl group. The preferred salts are sulphonium salts, i.e. salts of formula I wherein A is sulphur.
The anion Xn in the photosensitiser may be, for example, a halogen-containing complex ion selected from - 6 42085 Cl 0^ and metal halogenides. The metal halogenide may be, for example, a polyhalide o£ boron, antimony, tin, silicon, phosphorus, arsenic, bismuth or iron.
Examples of suitable anions are tetrafluoroborate III (BF4), hexachloroantimonate V (S6cig), hexafluoroantimonate V (S<»F6-), hexachlorostannate IV (SnClg ), hexafluorophosphate (PFg ), hexafluoroarsenate (AsFg), tetrachloroferrate III (FeCl^) and pentachlorobismuthate III (BiCl5").
Photosensitisers containing the anions described above, i.e. the perchlorate ion and metal halogenide ions, are suitable for polymerising or curing all types of acid-polymerisable or acid-curable materials. The invention is not restricted, however, to use of photosensitisers containing these anions but includes use of photosensitisers which are capable of polymerising or curing some acid-polymerisable or acid-curable materials but not others. For example, salts (I) containing halide anions are capable of polymerising or curing urea/formaldehyde resins and melamine/formaldehyde resins but may not satisfactorily polymerise or cure epoxy resins and epieulphide resins. The ability of a particular salt to polymerise or cure a material depends upon the nucleophilicity of its anion; ealts containing strongly nuc .eophilic anions which readily form covalent bonds with carbon atoms to yield stable compounds, for example halide ions, in general will polymerise or cure urea/formaldehyde and melamine/formaldehyde resins but may not polymerise or cure epoxy resins and episulphide resins. Examples of other anions of this type are CF^COO", SOgF", ArS03- (where Ar is an aromatic group, e.g. the toluyl group), NO^ and the picrate ion. We do not exclude the possibility that some of these anions will provide photosensitisers which will also cure epoxy resins. The ability of a particular photosensitiser to cure the particular material depends upon the ability of the corresponding proton acid, i.e. the proton acid containing the same anion as the photosensitiser, to cure that material. In general if the acid polymerises or cures the material, then the corresponding salt containing the same anion also will be capable of polymerising or curing the material. Thus the suitability of a particular salt for use with a particular acid-polymerisable or acid-curable material generally is readily determined simply by mixing the corresponding proton acid with the material.
It is believed that the photosensitiser releases acid upon exposure to suitable radiation, for example ultraviolet light. The preferred anions for polymerising or curing epoxy and episulphide materials, on account of the rapid rate of polymerisation or curing which is induced, are BF^ , PFg , AsFg~ and SbFg".
The photosensitisers used in this invention are normally solids at ordinary temperatures and they are usually incorporated in the acid-polymerisable or acidcurable material in the form of a solution in an inert 420SS liquid diluent, that is a liquid diluent which is chemically inert towards the ingredients of the composition. Any inert liquid diluent in which the photosensitiser is sufficiently soluble may be used, and examples of suitable diluents are halogenated hydrocarbons, e.g. methylene chloride, ketones, e.g. acetone, and alcohols, e.g. ethanol. We prefer to employ a liquid diluent of low boiling point, e.g. below 150°c, in order to facilitate removal of the diluent from the composition. The amount of the diluent used is not critical but preferably is just sufficient to dissolve the appropriate amount of the photosensitiser. After incorporation of the photosensitiser in the composition, the diluent may he removed, if desired, before the composition is irradiated. Removal .of the diluent prior to irradiating the composition may be desirable in cases where the diluent is a solvent for the acid-polymerisable or acid-curable material. In the case where the material is, or contains, a monomer, the photosensitiser may be soluble in the material and a diluent may not be required.
The amount of the photosensitiser is not critical but will usually be from 0.01% to 10.0%, and preferably from 0.5% to 5.0% by weight based on the weight of acid-polymerisable and/or acid-curable material in the composition. In general increasing the amount of the photosensitJ ser results in an increase in the rate of polymerisat-j on or curing achieved although in practice there is little point in using an amount of greater than 10% by weight. The photosensitiser preferably should be soluble in the resin into which it is incorporated and the solubility of a particular photosensitiser in the resin may limit the amount of that salt which can be incorporated. The polymerisation or curing reaction initiated by irradiating the composition is exothermic and use of too large an amount of the photosensitiser may result in a very rapid rise in temperature and loss of control over the reaction conditions. The optimum amount of the photosensitiser will usually be about 3% to 5% by weight but will depend upon the particular salt and acid-polymerisable or acidcurable material employed and the radiation source, and can be determined by simple experiment.
In general, polymerisation or curing of the composition proceeds readily when the composition is irradiated at ambient temperature although the reaction is exothermic and may be accompanied by a rise in temperature of the composition. The rate of polymerisation or curing in general is increased by irradiating the composition at an elevated temperature.
Any acid-polymerisable or acid-curable material may be employed in the present invention. Mixtures of acid-polymerisable and/or acid-curable materials may be employed, as also may mixtures of one or more acidpolymerisable or acid-curable materials and resins which are not acid-curable, for example alkyd resins. 43085 Materials containing acid-polymerisable cyclic groups may be employed, notably cyclic ethers for example lactones and acrolein tetramer and especially epoxides and episulphides, and polymers thereof containing polymerisable cyclic groups. Epoxides and episulphides containing from 2 to 20 carbon atoms are suitable, for example ethylene oxide, ethylene sulphide, propylene oxide and propylene sulphide, as also are compounds containing two or more epoxide or episulphide groups.
Epoxy and episulphide resins may be used, for example the epoxy resins commonly known as Araldite ('’R.T.M.’1) epoxy resins. Other acid-curable resins which may be used include phenolic resins, for example phenol/formaldehyde resins, aminoplastics for example urea/formaldehyde and melamine/ formaldehyde resins, methylol compounds, methylol ethers of polycarboxylic acid amides, for example derivatives of polyacrylic and polymethacrylic acid amides, alkyd resins containing urethane groups and resins containing carbonic acid esters of N-methylolamides. Acidpolymerisable or acid-curable ethylenically unsaturated materials may also be used, for example styrene, vinyl carbozole, vinyl ethers and diketene (which is both ethylenically unsaturated and a lactone). Resinous materials containing cross-linking agents which can be cured by acids are included.
The compositions of the invention may be used in any of the applications for which acid-curable resin compositions are normally employed, provided that, if the composition is to be polymerised or cured in situ, irradiation of the composition is possible. Thus the compositions may be used, for example, for forming surface coatings on a variety of substrates, e.g. wood, paper, metals and textiles, and in printing inks. They may be used as adhesives in applications where they can be subjected in situ to radiation, for example in the formation of laminates wherein one or both of the lamina is permeable to radiation, e.g. glass lamina and some plastics lamina. The compositions have the property that only those regions contacted by radiation are polymerised or cured so that they may be used for example in the production of decorative articles having a contoured surface by exposing parts of the surface to radiation to cure those parts and subsequently removing uncured material from the surface. Thus they may be used, for example in the production of printing plates and printed circuits. The compositions of the invention may contain foaming agents and they may be foamed prior to irradiating them so that subsequently irradiating them cures or sets the foam.
When a resin composition according to the invention is irradiated, polymerisation or curing commences at the exposed surface and spreads inwardly. The depth of cure achieved is limited by the depth of penetration of the composition by the radiation. This property can be utilised in the production of skinned materials such as skinned foams. Thus for example a foamable resin composition may be irradiated prior to foaming to form a thin surface layer of cured material which is nonfoamable and the remainder of the composition may then be foamed to yield a foam having an integral skin. One or more surface of the composition may be skinned in this way. Foams having contoured skinned surfaces may be produced.
The compositions of the invention may contain inert fillers and pigments provided these do not prevent penetration of the composition by the radiation used to activate the sulphonium salt. If desired, the composition may contain one or more additional photosensitisers, for example to render the composition activatable by radiation which would not activate the sulphonium salt in the absence of the additional photosensitiser.
The invention is illustrated but in no way limited by the following examples.
Example 1 0.3 g of diphenyl ethyl sulphonium tetrafluoroborate was dissolved in a few ml of acetone and the solution was mixed into 9.7 g of an epoxy resin available as Araldite (R.T.M.) MY753 epoxy resin from Ciba-Geigy. The mixture was painted on a steel plate and left to stand for 10 minutes to allow the acetone to evaporate and then the coated plate was exposed to radiation from two 2 kw Phillips (R.T.M.)HTQ7 lamp tubes, known as the HTQ light printing lamp placed at a distance of 8 inches from the plate. The spectral energy output of the lamp, expressed as wavelength in fflp (energy %) was 248 (1.7), 254-8 (3.5), 265 (3.7), 270 (0.7), 275 (0.7), 280 (1.7), 289 (1.0), 2.97 (3.0), 302 (4.7), 313 (12.1), 334 (1.4), 366 (20.6), 405 (6.1), 436 (12.4), 492 (0.7), 546 (11.2), 578 (14.8). After two minutes the plate was removed and was found to be coated with a hard (pencil hardness >4H), solventresistant film. Solvent resistance was determined by rubbing the film with tissue soaked in acetone 20 times and noting the visible effect, if any, produced by this treatment.
A further mixture as above was prepared and stored in a dark bottle in a dark cupboard at ambient temperature. After 3 months the composition exhibited no noticeable signs of gelation and was curable by irradiation as if it had been freshly prepared.
Example 2 The procedure of Example 1 was repeated using 0.3 g of triphenyl sulphonium tetrafluoroborate and 9.7 g of an epoxy resin available as Araldite CT200 epoxy resin from Ciba-Geigy. The resin was a solid, and was employed as a solution in a 1:1 mixture of acetone and xylene.
After 2 minutes irradiation, a hard (pencil hardness 5H), solvent resistant coating was produced.
Example 3 The procedure of Example 1 was repeated using 0.3 g of diphenyl ethyl sulphonium tetrafluoroborate and 9.7 g of an epoxy resin available as Araldite MY750 epoxy resin. After 2 minutes irradiation, a hard, solventresistant film had been produced. - 14 4 2085 Example 4 The procedure of Example 2 was repeated using 0.3 g of diphenyl ethyl sulphonium tetrafluoroborate instead of the triphenyl sulphonium tetrafluoroborate. A hard (5H), solvent resistant film was obtained after 2 minutes irradiation.
In a further experiment the above procedure was repeated except that the coated plate was irradiated image-wise through holes in a sheet of aluminium foil out of which a variety of shapes had been cut. After 1¾ minutes irradiation, the coated plate was washed with cold acetone which resulted in removal of composition which had not been irradiated, leaving raised areas of a hard film in shapes corresponding to the shapes of the holes in the aluminium foil through which the coated plate has been irradiated.
Example 5 A liquid mixture of 0.3 g of diphenyl ethyl sulphonium tetrafluoroborate and 9.7 g of acrolein tetramer P J-CH,COO-f h was painted onto a steel plate X) z XT and the coated plate was irradiated as is described in Example 1. After 3 minutes irradiation the plate was removed and the coating had set into a hard (5H), solid film which was not fully resistant to acetone.
Example 6 The procedure of Example 2 was repeated except that the amount of the triphenyl sulphonium tetrafluoroborate was increased to 5% by weight of the composition and irradiation was 30 seconds instead of 2 minutes.
A solvent-resistant film of pencil hardness 6H was obtained.
Example 7 The procedure of Example 1 was repeated but 'using Araldite CT179 epoxy resin instead of Araldite MY753 resin and using triphenyl sulphonium tetrafluoroborate.
A solvent-resistant film of pencil hardness 6H was obtained. f In a further experiment the amount of the triphenyl sulphonium tetrafluoroborate was increased to 5% by weight and irradiation was for 30 seconds instead of 2 minutes. A solvent-resistant film of pencil hardness 6H was obtained.
Example 8 0.3 g of triphenyl sulphonium tetrafluoroborate was dissolved in a few ml of acetone and the solution was mixed into 9.7 g of a urea/formaldehyde resin-alkyd resin mixture comprising a mixture of 2 parts of butylated urea/formaldehyde and 3 parts of tall oil alkyd in a mixture of solvents (solids content 44% by weight). The mixture was painted onto a steel plate and allowed to stand for 10 minutes to allow the solvent to evaporate and then the painted plate was irradiated as described in Example 1 for 1 minute. A solvent-resistant film of pencil hardness 6H was obtained.
Example 9 The procedure of Example 8 was repeated but using diphenyl ethyl sulphonium tetrafluoroborate, and - 16 42085 irradiation was for 2 minutes. A solvent-resistant film of pencil hardness 6H was obtained.
Example 10 The procedure of Example 8 was repeated using tri5 phenyl sulphonium hexachloroantimonate instead of the tetrafluoroborate. After 1 minute of irradiation, a solvent-resistant film of pencil hardness 6H had been obtained.
Example 11 The procedure of Example 5 was repeated using 0.3 g of triphenyl sulphonium chloride instead of the diphenyl ethyl sulphonium tetrafluoroborate. After irradiation for 3 minutes, the sample was found to be a solventresistant film of a pencil hardness 6H.
Example 12 A variety of sulphonium salts were employed to cure Araldite CY179 epoxy resin using the procedure described in Example 1. The sulphonium salt employed, its concentration by weight based on the epoxy resin and the time for which the sample was irradiated are shown in the Table below. In each experiment, a hard (pencil hardness >4H), solvent-resistant film was obtained.
TABLE Sulphonium Salt Cone11. (% w/w) Exposure Time (seconds) Ph^.PF^ 2 20 Ph^.PEg® 410 * (ch3)3^.bp40 2 210 (ch3)3^.bf® 4 210 (HO ΟΗ2ΟΗ2)3^.ΒΡ4Θ 2 270 Η?Κ ^-COCH,^(CH,CH,OH) 9.BFd® 2 120 X—H2N ^COCH2fficH2CH2OH) 2 · ΒΕ>4θ 4 120 (Ph3^)2. SnClg 180 240 • BE, 120 120 Sulphonium Balt Concn. Exposure Time. (%w/w) (seconds) OH.BF OH.BI·’ Sulphonium Salt Concn* Exposure Time (% w/w) (seconds) . 25 R® L? PF.
(CH3)2S-COO CH2CH3. BF^ 2 150 130 © Ph3S Cone11' (% w/w) Exposure Time (seconds) 180 Ph3S © Ph3s SbF AsF 24u <£> IO * Exposure Time Sulphonium Salt Cone11 * (% w/w) (seconds) * 180 120 12o * In these experiments a tack-free film was obtained after 2 to 3 seconds.
Example 13 0.3 g of triphenyl selenium tetrafluoroborate ) ft :-Ph is dissolved in a few ml of acetone and the solution is mixed into 9.7 g of an epoxy resin available as Araldite CY179 epoxy resin from Ciba-Geigy. The mixture is painted on a steel plate and left to stand for 10 minutes to allow the acetone to evaporate and then the coated plate is exposed to radiation from two 2 kw Phillips HTQ7 lamp tubes, known as the HTQ light printing lamp placed at a distance of 8 inches from the plate. The spectral energy output of the lamp, expressed as wavelength in mp (energy %) was 248 (1.7), 254-8 (3.5), 265 (3.7), 270 (0.7), 275 (0.7), 280 (1.7), 289 (1.0), 2.97 (3.0), 302 (4.7), 313 (12.1), 334 (1.4), 366 (20.6), 405 (6.1), 436 (12.4) 492 (0.7), 546 (11.2), 578 (14.8). After two minutes the plate is removed and found to be coated with a solvent-resistant film of pencil hardness >4H. Solvent resistance is determined by rubbing the film with tissue soaked in acetone 20 times and noting the visible effect, if any, produced by this treatment.
Example 14 The procedure described in Example 1 was employed to cure the resins identified below by their trade names, using as photosensitiser triphenyl sulphonium hexafluorophosphate in an amount of 4% by weight based on the resin (0.08 g of photosensitiser dissolved in 0.5 g acetone and mixed with 2 g of the resin). In each experiment a hard, solvent resistant film was obtained.
Resin Exposure Time (seconds) Epicote 816 (Shell)(R.T.M.) Epicote 828 (Shell) Araldite LY558 (Ciba) Araldite CT200 (50% w/w solution in a 1:1 acetone: xylene mixture) Araldite MY 753 Urea/formaldehyde resin (as in Example 8) Cibamin ML 1000 GB (R.T.M.) (a methylated melamine-formaldehyde resin) Example 15 The procedure described in Example 1 was repeated using the epoxy resins, photosensitisers and exposure times listed below. In each experiment a hard, acetoneresistant film was produced.
Resin Photosensitiser (2g) (in 0.5 ml acetone) Araldite LY 558 dimethyl-(p-hydroxy-mtolyl) sulphonium hexafluorophosphate 105 Cone (g) 0.08 0.04 Epicote 828 Epicote 828 Epicote 828 Exposure Time (seconds) Example 16 The procedure described in Example 1 was repeated except that the epoxy resin used was Araldite GY 250 epoxy resin. The exposure time was 60 seconds after which time a hard, solvent-resistant film had been produced.
Example 17 A solution of triphenyl sulphonium tetrafluoroborate (0.008 g) in methylene chloride (3 g) and 2.2 g of isobutyl vinyl ether was irradiated in a glass vial placed at the centre of 8 x 20 w Philips black-light" fluoroscent tubes circularly disposed (diameter = 8 inches) and surrounded by a cylindrical reflector made of a polished metal sheet.
After about 30 seconds exothermic reaction resulted, demonstrated by boiling of the mixture. The colour of the mixture gradually changed to yellow and then red and a greenish fluoresence was observed. After about 2 minutes a rather viscous mass resulted caused by polymerisation of the vinyl ether.
Example 18 A solution of triphenyl sulphonium tetrafluoroborate (0.02 g) and N-vinyl carbazole (2.5 g) in methylene chloride (3.5 ml) was irradiated as in Example 17.
After about 25 seconds exothermic reaction resulted accompanied by a colour change and fluorescence, and the solution became rather viscous after 2 minutes as a result of polymerisation of the N-vinyl carbazole. 2 0 8 5 Example 19 The procedure of Example 17 was repeated using 0.02 g triphenyl sulphonium tetrafluoroborate in 2 ml of propylene sulphide. After 10 minutes of irradiation the solution became warm and after a further 5 minutes a solid clear mass had been produced.
Example 20 A mixture was prepared as described in Example 1 and stored in a dark bottle in a dark cupboard at ambient temperature. After 12 months the composition exhibited no noticeable signs of gelation and was curable by irradiation as if it had been freshly prepared.
Compositions prepared as described in Example 1 but using the'following epoxy resins were stored as above for a period of 12 months.
Araldite MY 750 Araldite CT 200 Araldite CY 250 Cibamin ML 1000 GB In each experiment the composition showed no noticeable signs of gelation and was cu-rable by irradiation as if it had been freshly prepared.
Claims (1)
1.CLAIMS : 4. A photopolymerisable composition comprising at least one acid-polymerisable or acid-curable material and as photosensitiser at least one salt of formula r Ί © R. - A 1 I R-, Rn (i) 2 J n wherein A is sulphur, selenium or tellurium, n is 1 or 2, R^, R 2 and R^, which may be the same or different, each is a hydrocarbon or substituted hydrocarbon group or heterocyclic group or two of the groups R^, R 2 and R 3 together with the element A are a heterocyclic structure the other group R being a hydrocarbon or a substituted hydrocarbon group, and X© is an anion derived from an acid which is capable of polymerising or curing the acid-polymerisable or acidcurable material. A photopolymerisable composition as claimed in claim 1 wherein in the photosensitiser the element A is sulphur. A photopolymerisable composition as claimed in claim 1 or 2 wherein the amount of the photosensitiser is from 0.01% to 10% by weight based on the weight of the acid-polymerisable or acid-curable material. A photooolymerisable composition as claimed in claim 3 wherein the amount of the photosensitiser 4 2 0 8 5 is from 0.05% to 5% by weight based on the weight of the acid-polymerisable or acid-curable material. 5. A photopolymerisable composition as claimed in claim 4 wherein the amount of the photosensitiser is from 3% to 5% by weight based on the weight of the acid-polymerisable or acid-curable material. 6. A photopolymerisable composition as claimed in any one of the preceding claims wherein the anion jj© is a halogen-containing complex ion selected from CIO^ and metal halogenides. 7. A photopolymerisable composition as claimed in claim 6 wherein the anion x*^ is a polyhalide of boron, antimony, tin, silicon, phosphorus, arsenic, bismuth or iron. 8. A photopolymerisable composition as claimed in claim 7 wherein the anion x®^ is the tetrafluoroborate ion. 9. A photopolymerisable composition as claimed in any one of the preceding claims wherein the photosensitiser is soluble in the acid-polymerisable or acid-curable material. 10. A photopolymerisable composition as claimed in any one of the preceding claims wherein in the photosensitiser at least one of the groups R is an aryl group or substituted aryl group. 11. A photopolymerisable composition as claimed in claim 10 wherein in the photosensitiser each of the groups R is an aryl group or substituted aryl group. 4308S 12. A photopolymerisable composition as claimed in claim 10 wherein two of the groups R are aryl groups or substituted aryl groups, the other group R being an alkyl group. 13. A photopolymerisable composition as claimed in claim 10, 11 or 12 wherein the photosensitiser contains at least one phenyl group. 14. A photopolymerisable composition as claimed in any one of the preceding claims wherein the acidcurable material comprises an epoxy resin. 15. A photopolymerisable composition as claimed in any one of claims 1 to 13 wherein the acidpolymerisable material is an acid-polymerisable monomer. 16. A photopolymerisable composition substantially a;: described herein with particular reference to any one of Examples 1 to 11. 17. A photopolymerisable composition substantially as described herein with particular reference to Example 12. 18. A photopolymerisable composition as described herein with particular reference to Example 13. 19. A polymeric composition derived from a photopolymerisable composition as claimed in any one of claims 1 to 18 by subjecting the photopolymerisable composition to radiation of wavelength such as to activate the photosensitiser and polymerise or cure the composition. 43085 21. 10 23. 15 25. A polymeric composition as claimed in claim 19 which is in the form of a surface coating on a substrate. A process for the preparation of a polymeric composition which comprises subjecting a photopolymerisable composition as claimed in any one of claims 1 to 18 to radiation of wavelength such as to activate the photosensitiser and polymerise or cure the composition. A process as claimed in claim 21 wherein the radiation comprises ultra-violet radiation. A process as claimed in claim 21 or 22 wherein the wavelength of the radiation is in the range from 200 microns to 600 microns. A process as claimed in claim 21 substantially as described herein with particular reference to the Examples. A polymeric composition as claimed in claim 20 substantially as described herein with particular reference to the Examples.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB40682/74A GB1526923A (en) | 1974-09-18 | 1974-09-18 | Photopolymerisable compositions |
GB759875 | 1975-02-24 |
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IE42085L IE42085L (en) | 1976-03-18 |
IE42085B1 true IE42085B1 (en) | 1980-06-04 |
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IE1980/75A IE42085B1 (en) | 1974-09-18 | 1975-09-11 | Photopolymerisable compositions |
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JP (1) | JPS6057442B2 (en) |
DE (1) | DE2541709C2 (en) |
DK (1) | DK415875A (en) |
FR (1) | FR2285423A1 (en) |
IE (1) | IE42085B1 (en) |
IT (1) | IT1042624B (en) |
NL (1) | NL179654C (en) |
NZ (1) | NZ178699A (en) |
SE (1) | SE425399B (en) |
Families Citing this family (20)
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US4069054A (en) * | 1975-09-02 | 1978-01-17 | Minnesota Mining And Manufacturing Company | Photopolymerizable composition containing a sensitized aromatic sulfonium compound and a cationacally polymerizable monomer |
US4108747A (en) * | 1976-07-14 | 1978-08-22 | General Electric Company | Curable compositions and method for curing such compositions |
US4102687A (en) * | 1977-02-14 | 1978-07-25 | General Electric Company | UV Curable composition of a thermosetting condensation resin and Group VIa onium salt |
GB1604953A (en) * | 1977-08-05 | 1981-12-16 | Gen Electric | Photocurable compositions and method for curing |
GB1604954A (en) * | 1977-08-05 | 1981-12-16 | Gen Electric | Photocurable compositions and method for curing |
US4273668A (en) * | 1977-09-14 | 1981-06-16 | General Electric Company | Arylsulfonium salt-solvent mixtures |
GB1596000A (en) * | 1977-09-14 | 1981-08-19 | Gen Electric | Heterocyclic onium salts their preparation and their use for photopolymerisable organic materials |
US4218531A (en) * | 1978-02-08 | 1980-08-19 | Minnesota Mining And Manufacturing Company | Addition of ethylenically unsaturated materials to control odor in photopolymerizable epoxy compositions |
US4186108A (en) * | 1978-02-08 | 1980-01-29 | Minnesota Mining And Manufacturing Company | Liquid compositions containing triarylsulfonium complex salts and oxyethylene material |
DE2966764D1 (en) * | 1978-10-27 | 1984-04-12 | Ici Plc | Polymerisable compositions, derived coatings and other polymerised products |
US4231886A (en) * | 1979-01-29 | 1980-11-04 | Minnesota Mining And Manufacturing Company | Ester solutions of complex salts |
DE2967466D1 (en) * | 1979-02-12 | 1985-07-18 | Gen Electric | Coating method and curable compositions |
SE8901048D0 (en) * | 1989-03-23 | 1989-03-23 | Becker Wilhelm Ab | polymerisation |
DE3909688A1 (en) * | 1989-03-23 | 1990-09-27 | Espe Stiftung | METHOD FOR GLUING OR POOLING SUBSTRATES AND DEVICE FOR CARRYING OUT ITSELF |
DE69029104T2 (en) | 1989-07-12 | 1997-03-20 | Fuji Photo Film Co Ltd | Polysiloxanes and positive working resist |
US6723483B1 (en) | 1999-12-27 | 2004-04-20 | Wako Pure Chemical Industries, Ltd. | Sulfonium salt compounds |
CN1297537C (en) * | 2000-08-30 | 2007-01-31 | 和光纯药工业株式会社 | Sulfonium salt compound |
JP4448730B2 (en) | 2004-04-20 | 2010-04-14 | 富士フイルム株式会社 | Photosensitive composition, compound used for photosensitive composition, and pattern formation method using the photosensitive composition |
WO2011096458A1 (en) | 2010-02-05 | 2011-08-11 | Canon Kabushiki Kaisha | Negative photosensitive resin composition, pattern formation method, and liquid discharge head |
EP2531890B1 (en) * | 2010-02-05 | 2019-08-28 | Canon Kabushiki Kaisha | Photosensitive resin composition, method for producing structure, and liquid discharge head |
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US3412046A (en) * | 1965-07-01 | 1968-11-19 | Dexter Corp | Catalyzed polyepoxide-anhydride resin systems |
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1975
- 1975-09-11 IE IE1980/75A patent/IE42085B1/en unknown
- 1975-09-16 NZ NZ178699A patent/NZ178699A/en unknown
- 1975-09-17 FR FR7528525A patent/FR2285423A1/en active Granted
- 1975-09-17 SE SE7510390A patent/SE425399B/en not_active IP Right Cessation
- 1975-09-17 IT IT27334/75A patent/IT1042624B/en active
- 1975-09-17 DK DK415875A patent/DK415875A/en not_active Application Discontinuation
- 1975-09-17 NL NLAANVRAGE7510920,A patent/NL179654C/en not_active IP Right Cessation
- 1975-09-18 DE DE2541709A patent/DE2541709C2/en not_active Expired
- 1975-09-18 JP JP50113094A patent/JPS6057442B2/en not_active Expired
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FR2285423A1 (en) | 1976-04-16 |
AU8489975A (en) | 1977-03-24 |
NL7510920A (en) | 1976-03-22 |
SE7510390L (en) | 1976-03-19 |
JPS5156885A (en) | 1976-05-18 |
JPS6057442B2 (en) | 1985-12-14 |
NL179654B (en) | 1986-05-16 |
FR2285423B1 (en) | 1979-08-31 |
IE42085L (en) | 1976-03-18 |
DE2541709C2 (en) | 1985-02-21 |
DE2541709A1 (en) | 1976-04-01 |
NL179654C (en) | 1986-10-16 |
IT1042624B (en) | 1980-01-30 |
DK415875A (en) | 1976-03-19 |
NZ178699A (en) | 1978-03-06 |
SE425399B (en) | 1982-09-27 |
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