CA1137695A - Photopolymerizable compositions featuring novel co-initiators - Google Patents
Photopolymerizable compositions featuring novel co-initiatorsInfo
- Publication number
- CA1137695A CA1137695A CA000336005A CA336005A CA1137695A CA 1137695 A CA1137695 A CA 1137695A CA 000336005 A CA000336005 A CA 000336005A CA 336005 A CA336005 A CA 336005A CA 1137695 A CA1137695 A CA 1137695A
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- Prior art keywords
- coumarin
- composition
- carbonyl compound
- activator
- initiator
- Prior art date
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Abstract
Abstract A photopolymerizable composition, element and method of photopolymerizing are disclosed wherein the com-position comprises an addition polymerizable compound con-taining ethylenic unsaturation and a co-initiator including a photopolymerization activator and a coumarin having an absorption maximum between about 250 and about 550 nm and a
Description
~3~95 PHOTOPOLYMERIZABLE COMPOSITIONS FEATURING
NOVEL CO-INITIATORS
1) Field Or the Invention This invention relates to co-initiators used to photoinitiate the polymerlzation of addition polymerizable compounds containing ethylenic unsaturation.
NOVEL CO-INITIATORS
1) Field Or the Invention This invention relates to co-initiators used to photoinitiate the polymerlzation of addition polymerizable compounds containing ethylenic unsaturation.
2) Back~round o~ the Invention Mixed photoinitlators, sometimes known as co-initiators, have been disclosed for use with polymerizable lO monomers. Co-initiators usually comprise two compounds, a light-sensitive compound sometimes identifled as a sensi-tizer, and an activator compound which in the presence of the sensitizer is not significantly directly excited by the activating radiation, but instead forms a free-radical in 1~ response to the exposure of the sensitizer. The known classes of such activators include amines, sulfinic acid and sulfinic acid esters, sulfones, - and ~-dicarbonyls such as bornanedione and acetylacetone, phosphines, phosphites, stannates, and hexaarylbi-imidazoles.
An early example of a very effective co-initiator system has been Michler's ketone as the sensitizer, admixed with benzophenone as the activator, e.g. 3 as described in U.S. Patent No. 3,682,641. This mixture has long been considered an industry standard. More recently, a number of 25 aromatic carbonyl compounds have been disclosed as useful with amine activators to form co-photoinitiators of many kinds. Such mixtures are described in Ledwith, J. Oil Col.
Chem. Assoc~, 59, p. 157 and especially p. 162-164 (1976).
The carbonyls specifically identlfied are phenones, in-cluding cyclic ketones, such as benzophenone, fluorenones,anthraquinones and anthrones.
Such co-initiators have been highly effective in photopolymerization compositlons of var~ous klnds. However, notwithstanding such extensive uses, there has been a con-tinued need to achieve still faster speeds through the dis-covery of novel co-inltiator systems. That is, faster .speeds result either in reduced exposure tlmes or reduced amounts of exposure intensity, both of which are beneficial ' to the user.
~3~
U.S. 4~147,552~ l~sued April 39 1979, discloses 3 substituted coumarln compounds as ~ens4tlzers ~or pho~o-crossllnkable and pho~opolymer~able ethylenlcally unsatura-ted compounds. The patent ~urther mentions sensltlzlng mixtures of the coumarlns with other compQun~s lncludlng speci~ically 3,37--c~rbonylbls(7-diethylaminocoumarln) ~Col~
20-21), benzene chromlum trlcarbonyl, and a trlbromomethyl-ated polymer (~xample 14), particularly ~or the crosslinklng o~ polymers. Although these ~ensltlzing mlxtures have been 1~ round to be useful, speclric speed lmprovements ~rom theQe mixtures are reported ln the patent as generally r~sultln~
~rom the speed provided by the ~oumarln alone.
In accordance with the present lnvention khere ls 15 advantageously reatured a co-initiator compositlon and pho~o-polymerizable element conta~nlng an addition-polymerlzable compound, that ~e lmproved to provlde speeds that in many cases are superior to those available ~rom conventlonal co-lnitlator composltions, e.g., Mlchler's ketone adm~xed with 23 benzophenOne-In a related ~eature of the invention such lm-proved ~peeds are provided gor a great ~ariety o~ photo polymerization actlvators, both known and no~el.
In yet another reature of the inventlon, lmproved polymerization e~lclencles, i.e., a greater degree Or polymerlzatlon, are achieYed, at least with certaln add~-~ion-polymerlzable compounds.
~L lL37695i The aforesaid features of the invention are achieved by the use of an improved composition and an element using such composltion, comprising a carbonyl compound and a photopolymerization activator responsive in the presence of the photo-excited form of the carbonyl compound ~o form a free radical, the activator being selected from the ~roup consisting of an amine, an acetic acld derlvative, a phos-phineg a phosphite, a bismuthine, an arsene7 a stibene9 a sulfinic acid, a sulfinic acid ester, a sulfone, an ~- or ~-10 dicarbonyl, a ketone, a bi-imidazole, and a stannate. The improvernent comprises the use of a coumarin as the carbonylg such coumarin having an absorptive maximum between bout 250 " 1 and about 550 nm and a -CR substituent in the 3-position 15 wherein Rl is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, the coumarin and the activator being present in an amount sufficlent to pro~ide, when the compositlon is coated, dried and exposed 20 to a medium pressure mercury light source, a speed that is at least about one-firth that of the same composition coated, dried and exposed identically except with a co~initiator consisting Or Michler's ketone and benzophenone.
Such composition and element provide in many 25 instances, when exposed to activating radiation, a photo-polymerization speed not obtainable by conventional com positions.
Other ~eatures of the invention will become apparent upon reference to the following Description of the 30 Preferred Embodiments.
Description of the Preferred Embodiments The inventlon is based upon the discovery that certain coumarins are effective as the sensitizer portion of a co-initlator composition that also includes a free-radical 35 photopolymerization activator, in polymerizing addition polymerlzable compounds havlng ethylenic unsaturation wlth a speed that exceeds that achievable by the co-initiator composltion of Michler's ketone and benzophenone. In many 1~3~69~
-3a-instances, it is believed that the speed far exceeds that which is available ~rom any previously known co-initiator composition or system. This result is surprising~ in llght of the fact that a previously dlsclosed mlxture of a coumarin 5 with an amine compound, e.g., that of 3-benzoyl-7-methoxy-coumarin and 3,3'-carbonylbis(7-diethylamlnocoumarin), when used as a pho~oinitiator for the polymerization o~ such 3o . ~3~9~ii _4 unsaturated compounds, produces a speed of only about 0. o8 that of the speed produced by Michler's ketone plus benzo-phenone.
As used herein, a "co-initiator compositlon" ls a 5 subset of the class "photosensitizer" in that the former is~
used only to initiate addition polymerization o~ simple compounds or polymers. Without being limited to speciflc mechanisms, addition polymerlzation usually occurs through the production of free radicals. Photosensi~izers on the 10 other hand include both the function of sensitizing a single-event crosslinking of photopolymers as well as the addition polymerization of light sensitive materials Just noted.
The term "additlon polymerizable" or "addition-15 polymerization" refers to the chain reaction that occurs wherein a single photon causes the addition of more than one recurring unit to a growing polymer, ln contrast wlth single-event crosslinking wherein a single photon creates one and only one cross-link event.
As used herein, "carbocyc:Lic"~ "aryl" and "hetero-cyclic" include substituted as well as unsubstituted carbo-cyclic~ aryl and heterocyclic, respectively. Suitable substituents include alkoxy contain:Lng f`rom 1 to about 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, and 25 the like; sulfonates such as fluorosulfonate and the like;
cyano; dialkylamino such as dimethylamino, diethylamino and the like; halo such 2S chloro, bromo and the like; nitro;
hydroxy, and alkyl of from 1 to about 5 carbon atoms, such as methyl, ethyl, propyl and the like. Also, alkenyl 30 includes aryl or alkyl substituted alkenyl, for example styryl and the like.
The photopolymerizable composition of the in-vention comprises an additlon polymerizable compound con-taining ethylenlc unsaturation~ and a co-initiator composl-35 tion compr~sing an admlxture o~ a 3-substituted ketocoumarin and a photopolymerization activator responsive in the presence of the photoexclted coumarin. The activator is selected from the group set rorth in the Summary.
13~3769S
_~, Any compound contal~lng ethylenlc un~urat~on which ls addl~lon polymerizable can be used ~n the ~nven-tlon~ ~referred are ~lmple c~mpounds s or ~onomer~ as they are ~ometimes denomlnated9 contaln~ng ethylenic un~atur~-tlong as well as polymers ~ontal~lng ~nd groups or pen~ant ,, groups termlnating with ethylenic unsaturat~on. ~or e~ample, the phrase "additlon polymerizable co~poun~s" i~clude~
polymers ha~lng recurrln~ units wlth th~ structure X ~
OC-CT-C~2 9~
10 whereln R ls any ~oiety capable Or ~orming the backb~ne of a polymer and T is hydrogen or ~ethyl.
Other examples o~ userul ~dd1tlon polymerizable compounds contalning ethylenlc unsaturatlon ~ncluBe m~no~
meric acrylates, acrylamldes, methacrylates, ~ethacryl-15 amldes~ allyl compounds, ~lnyl ~thers~ vinyl ~ers, N-~inyl compounds, styrenes and crotonates. Many ~xa~ples ~ each Or these classes are well known, e.g., as llsted ln ~rltlsh Patent Spec~ atlon No. 1,~34,137 published November 29, 1978, Acrylonitrile is also useful.
H~ghly prererre~ as add~ltion polymerlzable com-pounds are the acrylate compounds as a class. Acrylates ror years have been used ln photopoly~nerlzatlon and a wide varlety have been identi~ied in the llterature. Partlcular-ly userul examples lnclude alkyl acrylates contalnlng ~rom 1 25 to about 10 and ~ost pre~erably 1 to about 5 carbon atoms ln the alkyl portion, such as methyl acrylate, ethyl meth-acrylate and the llke; pentaerythrltol trl- and tetraacry-lates and methacrylates; esters o~ polyols includ~ng ~lycol dlacryla~es a~d dlmethacrylates, ~uch as trlpr~pylene glycol
An early example of a very effective co-initiator system has been Michler's ketone as the sensitizer, admixed with benzophenone as the activator, e.g. 3 as described in U.S. Patent No. 3,682,641. This mixture has long been considered an industry standard. More recently, a number of 25 aromatic carbonyl compounds have been disclosed as useful with amine activators to form co-photoinitiators of many kinds. Such mixtures are described in Ledwith, J. Oil Col.
Chem. Assoc~, 59, p. 157 and especially p. 162-164 (1976).
The carbonyls specifically identlfied are phenones, in-cluding cyclic ketones, such as benzophenone, fluorenones,anthraquinones and anthrones.
Such co-initiators have been highly effective in photopolymerization compositlons of var~ous klnds. However, notwithstanding such extensive uses, there has been a con-tinued need to achieve still faster speeds through the dis-covery of novel co-inltiator systems. That is, faster .speeds result either in reduced exposure tlmes or reduced amounts of exposure intensity, both of which are beneficial ' to the user.
~3~
U.S. 4~147,552~ l~sued April 39 1979, discloses 3 substituted coumarln compounds as ~ens4tlzers ~or pho~o-crossllnkable and pho~opolymer~able ethylenlcally unsatura-ted compounds. The patent ~urther mentions sensltlzlng mixtures of the coumarlns with other compQun~s lncludlng speci~ically 3,37--c~rbonylbls(7-diethylaminocoumarln) ~Col~
20-21), benzene chromlum trlcarbonyl, and a trlbromomethyl-ated polymer (~xample 14), particularly ~or the crosslinklng o~ polymers. Although these ~ensltlzing mlxtures have been 1~ round to be useful, speclric speed lmprovements ~rom theQe mixtures are reported ln the patent as generally r~sultln~
~rom the speed provided by the ~oumarln alone.
In accordance with the present lnvention khere ls 15 advantageously reatured a co-initiator compositlon and pho~o-polymerizable element conta~nlng an addition-polymerlzable compound, that ~e lmproved to provlde speeds that in many cases are superior to those available ~rom conventlonal co-lnitlator composltions, e.g., Mlchler's ketone adm~xed with 23 benzophenOne-In a related ~eature of the invention such lm-proved ~peeds are provided gor a great ~ariety o~ photo polymerization actlvators, both known and no~el.
In yet another reature of the inventlon, lmproved polymerization e~lclencles, i.e., a greater degree Or polymerlzatlon, are achieYed, at least with certaln add~-~ion-polymerlzable compounds.
~L lL37695i The aforesaid features of the invention are achieved by the use of an improved composition and an element using such composltion, comprising a carbonyl compound and a photopolymerization activator responsive in the presence of the photo-excited form of the carbonyl compound ~o form a free radical, the activator being selected from the ~roup consisting of an amine, an acetic acld derlvative, a phos-phineg a phosphite, a bismuthine, an arsene7 a stibene9 a sulfinic acid, a sulfinic acid ester, a sulfone, an ~- or ~-10 dicarbonyl, a ketone, a bi-imidazole, and a stannate. The improvernent comprises the use of a coumarin as the carbonylg such coumarin having an absorptive maximum between bout 250 " 1 and about 550 nm and a -CR substituent in the 3-position 15 wherein Rl is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, the coumarin and the activator being present in an amount sufficlent to pro~ide, when the compositlon is coated, dried and exposed 20 to a medium pressure mercury light source, a speed that is at least about one-firth that of the same composition coated, dried and exposed identically except with a co~initiator consisting Or Michler's ketone and benzophenone.
Such composition and element provide in many 25 instances, when exposed to activating radiation, a photo-polymerization speed not obtainable by conventional com positions.
Other ~eatures of the invention will become apparent upon reference to the following Description of the 30 Preferred Embodiments.
Description of the Preferred Embodiments The inventlon is based upon the discovery that certain coumarins are effective as the sensitizer portion of a co-initlator composition that also includes a free-radical 35 photopolymerization activator, in polymerizing addition polymerlzable compounds havlng ethylenic unsaturation wlth a speed that exceeds that achievable by the co-initiator composltion of Michler's ketone and benzophenone. In many 1~3~69~
-3a-instances, it is believed that the speed far exceeds that which is available ~rom any previously known co-initiator composition or system. This result is surprising~ in llght of the fact that a previously dlsclosed mlxture of a coumarin 5 with an amine compound, e.g., that of 3-benzoyl-7-methoxy-coumarin and 3,3'-carbonylbis(7-diethylamlnocoumarin), when used as a pho~oinitiator for the polymerization o~ such 3o . ~3~9~ii _4 unsaturated compounds, produces a speed of only about 0. o8 that of the speed produced by Michler's ketone plus benzo-phenone.
As used herein, a "co-initiator compositlon" ls a 5 subset of the class "photosensitizer" in that the former is~
used only to initiate addition polymerization o~ simple compounds or polymers. Without being limited to speciflc mechanisms, addition polymerlzation usually occurs through the production of free radicals. Photosensi~izers on the 10 other hand include both the function of sensitizing a single-event crosslinking of photopolymers as well as the addition polymerization of light sensitive materials Just noted.
The term "additlon polymerizable" or "addition-15 polymerization" refers to the chain reaction that occurs wherein a single photon causes the addition of more than one recurring unit to a growing polymer, ln contrast wlth single-event crosslinking wherein a single photon creates one and only one cross-link event.
As used herein, "carbocyc:Lic"~ "aryl" and "hetero-cyclic" include substituted as well as unsubstituted carbo-cyclic~ aryl and heterocyclic, respectively. Suitable substituents include alkoxy contain:Lng f`rom 1 to about 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, and 25 the like; sulfonates such as fluorosulfonate and the like;
cyano; dialkylamino such as dimethylamino, diethylamino and the like; halo such 2S chloro, bromo and the like; nitro;
hydroxy, and alkyl of from 1 to about 5 carbon atoms, such as methyl, ethyl, propyl and the like. Also, alkenyl 30 includes aryl or alkyl substituted alkenyl, for example styryl and the like.
The photopolymerizable composition of the in-vention comprises an additlon polymerizable compound con-taining ethylenlc unsaturation~ and a co-initiator composl-35 tion compr~sing an admlxture o~ a 3-substituted ketocoumarin and a photopolymerization activator responsive in the presence of the photoexclted coumarin. The activator is selected from the group set rorth in the Summary.
13~3769S
_~, Any compound contal~lng ethylenlc un~urat~on which ls addl~lon polymerizable can be used ~n the ~nven-tlon~ ~referred are ~lmple c~mpounds s or ~onomer~ as they are ~ometimes denomlnated9 contaln~ng ethylenic un~atur~-tlong as well as polymers ~ontal~lng ~nd groups or pen~ant ,, groups termlnating with ethylenic unsaturat~on. ~or e~ample, the phrase "additlon polymerizable co~poun~s" i~clude~
polymers ha~lng recurrln~ units wlth th~ structure X ~
OC-CT-C~2 9~
10 whereln R ls any ~oiety capable Or ~orming the backb~ne of a polymer and T is hydrogen or ~ethyl.
Other examples o~ userul ~dd1tlon polymerizable compounds contalning ethylenlc unsaturatlon ~ncluBe m~no~
meric acrylates, acrylamldes, methacrylates, ~ethacryl-15 amldes~ allyl compounds, ~lnyl ~thers~ vinyl ~ers, N-~inyl compounds, styrenes and crotonates. Many ~xa~ples ~ each Or these classes are well known, e.g., as llsted ln ~rltlsh Patent Spec~ atlon No. 1,~34,137 published November 29, 1978, Acrylonitrile is also useful.
H~ghly prererre~ as add~ltion polymerlzable com-pounds are the acrylate compounds as a class. Acrylates ror years have been used ln photopoly~nerlzatlon and a wide varlety have been identi~ied in the llterature. Partlcular-ly userul examples lnclude alkyl acrylates contalnlng ~rom 1 25 to about 10 and ~ost pre~erably 1 to about 5 carbon atoms ln the alkyl portion, such as methyl acrylate, ethyl meth-acrylate and the llke; pentaerythrltol trl- and tetraacry-lates and methacrylates; esters o~ polyols includ~ng ~lycol dlacryla~es a~d dlmethacrylates, ~uch as trlpr~pylene glycol
3~ dlacrylates, tetrae~hylene ~lycol diacrylate, trlethyle~e glycol dlmethacrylate~ and the like; alkanedlol ~lacryaltes such as hexanedlol diacrylates and the llke; polyether dlacrylates such as that obS~lnable rrom VCB, a divi~lon o~
Chi~lque Chaus3ee de Charlerol, Bru~elæ, ~elglum under the 35 ~rade nsme "Ebecryl 210"; and mixtures Or the abo~e.
~3~69 Of the two components of the co-initiator composi-tion, the one which preferably predominates as the light-absorbing component is the coumarin. That ls, preferably greater than about 50% of the actlvatlng radiation, and ln 5 some cases, all of that radiation, is absorbed by the ~_ coumarin. In accordance with one aspect of the inventlon, the coumarin is a 3-ketocoumarln bearlng a variety o~
substituents ad~acent to the carbonyl group. A prêferred group of such coumarlns are those having the ~ormula R c_ R3 ~
wherein Rl is as defined above, and R2, R3 and R4 are the same or di~ferent and are each hydrogen; dialkylamlno or alkoxy containing from 1 to about 5 carbon atoms in the alkyl portion, such as dimethylamlno, diethylamino, methoxy, 15 ethoxy, n-propoxy and the llke; a heterocyclic group of one or more saturated or unsaturated rlngs containlng from about 5 to 10 rlng atoms, for examplel pyridyl, pyrrollnyl, pyrrolidyl and the liXe; or R2 and R3 or R2-R4, when taken together, comprise the number o~ non-metallic atoms that 20 complete with the coumarin moiety an aryl ring or one or two fused saturated or unsaturated heterocyclic rlngs contalnlng ~rom about 5 to 10 ring atoms. Useful examples lllustrative of such latter fused heterocyclic rings include the struc-ture:
c_Rl ~ ~
~J . O
, ~
`:
Examples Or heterocyclic gr~ups ~or ~1 lnclude benzo~uryl, thienyl, thenyl, ~uryl~ pyridyl and the 11ke. 3,3 carb~yl-bis(coumarlns~ are addltional prererre~ ~ampl~ o~ ~uch heterocycllc groups.
3-ketocoumarlns substltuted ln the benzo portlon ,~
o~ the coumarln structure by dn amlne group wlll produce~
when adml~ed wlth certaln a~t~Yators, excellen~ ~peed ~or photopolymerlzed monomers. As ~e~cribed and cl~med ~n commonly owned U.S. Patent Nc. 4,27~,751, issued July 14, 1g81, 10 bY SPecht et al, entitled '~Photopolymerization Co-lnitiator Composltions Comprlsln~ Amlne-Substl~uted Ketocoumar~n5 an~
Acet~c Acid Derl~ative ~ctlvators", such ket~cou~arln~ are particularly errec~lve co-photolnltlators ~hen co~blned wlth indole-3-ylacetic acld or N-phenylglycine. They also 1~ pro~ide the adYan~age Or slgn1ricant absorptlon ~t the spectral lines 366, 4Q5, ~36 ~nd ~47 nm, whicb ~llow~ the use of broad spectral llght s~urces such ~ ~eD~n, mercury, or halogen lamps, as well as strong ab30rpt~0n at 4BB nm whlch allows the use of argon laser E~po~ure~
The ~ollowlng ls a llstlng Or coumarins hl~hly userul as one o~ the components o~ the co-~nttlator ~omposl-tion Or the inventlon:
3-(~-nltrobenzoyl~-5,7-dl-n-propoxycoumarln;
3-(2-benzo~uroyl2-7-diethylam~noc~umarln;
25 3-(2-benzo~uroyl~-7-(1-pyrr~lldln,yl)~oumarln;
7~dimethylamlno-3 thenoylcoumarin;
3-ben~oyl-7-diethylamin~coumar~n;
3-~o-methoxybenzoyl~-7-diethylaminocoumarln;
3-(p-dimethylam~n~benzoyl~-7-diethylamlnocDumarin;
30 3,3'-carbonylbls~5,7 dl n-propoxycou~ar~n);
393'-carbonyl~is~7-diethylaminoeoumarin) 9 3-benzoyl-7-methoxyco~marin;
7dlethylamino-3-~3-(2-th~enyl)~cryl~yl3coumarln;
3-(2~uroyl)-7-dlethyl~mlnw oumarin, 35 3-(p-dlethylamlnocinnamoyl~-7-Blethylam1noc~u~arin;
7-methoxy-3-~3-pyrldylcarbonyl)coumarin;
3 ~4-morpholinocinna~oyl~-7-diethylamlnocoumarin;
.~
76~5 9-(7-diethylamino-3-coumarinoyl)-1,2~4,5-tetrahydro-3H,6H,lOHtl]benzopyrano[9,9a,1-gh]quinolazlne-10-one; which has the structure:
o I
~,J N(C2H5)2 5 9-(7-n-propylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H, 6H,lOH[l]benzopyrano[9,9a,1-gh]quinolazine-10-Qne;
9-(4-diethylaminoclnnamoyl)-1,2,4,5-tetrahydro-3H,6H, lOH[l]benzopyrano[9,9a91-gh~quinolazlne-10-one~
3-b~nzoyl-5~7-dl-n-propoxycoumarin;
10 7-dimethylamino-3-[3-(2-thienyl)acryloyl]coumarin;
9-t3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,lOH[l]-benzopyrano[9,9a,1-gh]quinolazine-10-one;
7-diethylamino-3-(4-dlmethylamlnocinnamylideneacetyl)coumarin;
9-L3-(9-~ulolidyl)acryloyl]-1~2,4,5-tetrahydro-3H,6HglOH[l]
benzopyrano[9,9a,1-gh~quinolazine-10-one;
3-(p-cyanobenzoyl)-5,7-di-n-propoxycoumarin;
3,3'-carbonylbis(5,7-dibutoxycoumarln);
3,3'-carbonylbis(7-acetoxycoumarin~;
5,7,7'-trimethoxy-3,3'-carbonylbiscoumarin;
2~ 3-cinnamoyl-7-diethylamlnocoumarin, 7-diethylamino-3-(4-morpholinocinrlamoyl)coumarin;
7-diethylamino-3-(4-ethoxycinnamoyl)coumarin;
3-(4-bromocinnamoyl~-7-diethylaminocoumarin, ~, 7-dlethylamino-3-[3-(4-methoxy-1-naphthyl)~cryloyl]coumarin;
l125 7-diethylamino-3-cinnamylideneacetylCoUmarin;
!;9-[3-(2-thienyl)acryloyl]-192,4,5-tetrahydro-3H,6H,lOH-:[l~benzopyrano~9a,1-gh]quinolazine-10-one;
7-diethylamino-3-(3-~luorosulfonylbenzoyl)coumarin;
;3 (4-methoxybenzoyl)-5,7-di-n-propoxycoumarin;
30 3-(4-nitrobenzoyl)-5,7-di-n-propoxycoumarin;
3-(3-trifluoromethylbenzoyl)-5,7-di-n-propoxycoumarin;
3-(4-cyanobenzoyl)-7-dlethylaminocoumarin;
3-benzoyl-5,7-dimethoxycoumarin, . ~
~7695 3-benzoyl-5,7-diethoxycoumarin;
3-benzoyl-6-methoxycoumarln;
3 benzoyl-8-ethoxycoumarin;
3-benzoylbenzoLf~coumarin;
5 5,7-diethoxy-3-(2-thenoyl~coumarin; ~_ 3-(2-benzofuroyl~-5,7-dlethoxycoumarin;
3-ben7oyl-7-hydroxycoumarin;
7-aceto~y-3-benzoylcoumarln3 7-methoxy-3-(4-methoxybenzoyl3coumarin;
10 3-(4-fluorosulfonylbenzoyl~-7-methoxycoumarin, 3-(4-ethoxyclnnamoyl~-7-methoxycoumarin;
3-benzoyl-7-dimethylaminocoumarln;
3-benzoyl-7-diethylaminocoumarin;
3-benzoy]-7-pyrrolidinylcoumarln;
15 3-(4-iodobenzoyl~-7-dimethylaminocoumarin;
3-(4-iodobenzoyl)-7-diethylamlnocoumarin;
7-dimethylamino-3-~4-dlmethylaminobenzoyl)coumarin;
7-diethylamino-3 (4-nitroben oyl)coumarin;
7-diethylamino-3-(2-thenoyl)coumarln;
20 7-pyrrolidinyl-3-(2-thenoyl~coumarin;
7-diethylamino-3-(2-furoyl2coumarln;
7-diethylamino-3-~2-methoxybenzoyl)coumarin;
3,3'-carbonylbiscoumarin;
3,3'-carbonylbis(7-methoxycoumarin);
25 3,3'-carbonylbis(6-methoxycoumarin);
3,3'-carbonylbis(5,7-dimethoxycoumarin), 3,3l-carbonylbis~5,7-diethoxycoumarin; and 3,3'~carbonylbis(5~7-di-iso-propoxycoumarin).
A mixture of two or more o~ any o~ the above 30 coumarins can also be used.
Conventional methods can be used to prepare these coumarins. ~or e~ample, prepar~tlons are disclosed in the - aforesaid U.S. Patent No. 4,147,552.
The free-radical photopolymerization activator 35 used in the composition of this invention is selected from the group consisting of amines, acetlc acid derivatives, phosphines, phosphites, bismuthines, arsenes, stibenes, sulfinic acid and sulfinic acid esters, sulfones, ~ and ~-dicarbonyls, such as 2,3-bornanedlone and acetylacetone, ~:~3~
--10~-ketones such as fluorenone, bi-imidazoles, and stannates.
or this list, most are known activators for use wlth other sensitizers. Representatlve patents detalllng numerous examples of such known activators include U.S. Patent Nos.
5 3,488,269; 3,573,922; 3,650,927, 3J729~404; and 3,933,682.
In addition, Michler's ketone~ hereto~ore known to be a photosensitizer only, is believed to function ln this ln-vention as an actlvator at least ln some lnstances, when used with the coumarin sensltizers o~ this lnventlon. Also, 10 it is believed that the nitrogen-free acetic acld derivative actlvators herein described have not been recognized hereto-fore as activators for use wlth any sensltlzer.
Preferred actlvators are those that produce a speed equal to or better than that of Michler's ketone and 15 benzophenone used as the co-initlator. Thus, many amlne activators are preferred, and particularly the followlng, when used with selective coumarins Or the inventlon:
Dl / ~ 2 (II) D3 I D5 i D7 (III) ~ CH2 C
T' D N D
(IV~ D8 C - D10 `.,: Dll wherein D and Dl are the same or different and are each alkyl containing ~rom 1 to about 12 carbon atoms, such as methyl, ethyl, propyl and the like; or together they are the necessary atoms to ~orm wlth the nltrogen atom one or more . 5 heterocyclic rings having about 5 to 10 nuclear atoms;
D2 is the group -CooD5; the group -C~D6; hydroxy alkyl such as hydroxymethyl~ hydroxyethyl and the like;
alkyl containing ~rom 1 to 3 carbon atoms, such as methyl~
ethyl, propyl and the like; hydrogen; X; or aldehyde;
D3 is hydrogen; alkyl containing from 1 ~o about 12 carbon atomsS such as methyl 9 ethyl, propyl and the like;
or aralkyl containing from 1 to 3 carbon atoms in the alkyl portion and 6 to 10 carbon atoms in the aryl portion, such as benzyl and the like, : 15 D is alkyl or aralkyl containing ~rom 1 to about 12 carbon atoms in the alkyl portion and 6 to 10 carbon atoms in the aryl portion, such as benzyl and the like;
D5 is aryl of from 6 to 10 nuclear carbon atoms or alkyl containing from 1 to about 15 carbon atoms, such as 20 me~hyl, propyl, isopropyl, butyl3 octyl, and the like, including alkyl substituted with aryl such as phenyl, or substituted with 2-phthalimido or with -OOC-C=CH2; or is the group -Q-OOC ~ wherein D and Dl are as described above and Q is a linking group such as alkylene, 25 unsaturated alkylene, phenylenebisalkylene and the like;
D is alkyl containing from 1 to about 3 carbon atoms, such as methyl, ethyl, propyl and the like; aryl of from 6 to 10 nuclear carbon atomsg e.g., p-dialkylamino-phenyl; or is the group -CH2C02D;
3o D7 is hydrogen or alkyl containing from 1 to about 3 carbon atoms, such as methyl, ethyl, propyl and the like;
D8~D10 are each independently aryl~ at least two of which are dialkylaminoaryl;
Dll is hydrogen, or alkyl or alkenyl Or ~rom 1 to 35 8 carbon atoms;
~37695 X is hydrogen or halogen such as chlorlne, bromine and the like;
T' is a linking group connecting the amine molety to the backbone of the polymer recurring unit 3 such as an 5 alkylene ester containing 1 to about 5 carbon atoms. ,_ Represen~ative use~ul amines falling withln structures (I) through (IV) above include ethyl p-dimethyl-aminobenzoate; other esters Or p-dimethylamlnobenzoic acid, e.g., n-butyl p-dimethylamlnobenzoate, phenethyl p-dimethyl-lO aminobenzoate, 2-phthalimidoethyl p-dimethylaminobenzoate, 2-methacryloyloxyethyl p-dimethylaminobenzoate, pentamethyl-enebis(p-dimethylamino)ben20ate; 4,4'-bis(dimethylamino)-benzophenone; phenethyl and pentamethylene esters of m-dimethylaminobenzoic acid; p-dimethylamlnobenzaldehyde;-2-15 chloro-4-dlmethylaminobenzaldehyde; p-dimethylamlnoaceto-phenone; p-dimethylaminobenzyl alcohol; ethyl (p-dlmethyl- ~`
amino)benzoyl acetate; p-N-plperldlnoacetophenone; 4 di-methylaminobenzoin, N,N-dimethyl-p-toluidine; N,N-diethyl-m-phenetidine, tribenzylamlne; dibenzylphenylamlne; N-methyl-20 N-phenylbenzylamine; p-bromo-N,N-dimethylaniline; tridodecyl-amine; and 4,4',4"-methylidynetris(N,N-dimethylaniline) (crystal violet~ leuco base).
Still other amines whlch are useful as activators include those described in U.S. Patent No. 4,1339909, e.g., 25 dimethylaminoethyl acrylate.
In the case of amines of the structure (IV) above 3 a particularly useful class are latex polymerlc particles prepared as described in Research Disclosure, Publication No. 15930, July 1977, except that the polymer is modlfied to 3 include pendant amines. When using such a latex, hydro-phoblc coumarins can be loaded into the l~tex to provide a water-dispersible composition for coating.
The following preparation can be used to synthe-size such latex polymer partlcles having pendant amines:
35 Preparation o~ Poly(methyl methacrylate--co-N~N-dimethylamino-ethyl methacrylate-co-2-hydroxyethyl methacrylate-co-2-acrylamido-2-methylpropanesulphonic acid) .
;, , `::
~3~7695 In a dropping funnel was placed:
Methyl methacrylate 20 ml N,N-dimethylaminoethyl meth-acrylate 31 ml 2-hydroxyethyl methacrylate lO ml j 2-acrylamido-2-methylpropane~
sulphonic acid ~as 10% w/v aqueous solution ad~usted to pH 5) lO ml Sodium metabisulphite l.0 g Poly(acrylamide-co-carbowax 550 acrylate) (8:1~ 0.5 g Distilled water 40 ml In the reaction flask was placed:
Potassium persulphate 4.8 g Sodium metabisulphite 1.8 g Poly(acrylamide-co-carbowa~
550 acrylate2 (8:1) o.8 g Distilled water lO0 ml The polymerization was carried out at 80C in a reaction vessel equipped with stirrer~ dropping funnel and nltrogen inlet. Nitrogen blanketing was one of three measures taken against inhibition by oxygen. In addition, the distilled water solvent was boiled and purged with nitrogen before use, and 25 there was a scavenging period o~ 15 mlnutes where the contents of the reaction vessel were stirred at 800C, generating a radical flux from the initiators, before monomer addition started.
The contents of the dropping funnel were added over 3 a period of one hour and the reaction mixture was then stirred ~' for a further four hours. The crude late~ was filtered through muslin to remove coagulum before being dialysed against water for 24 hours. The latex was then flltered once more before storage.
.~ 35 Another pre~erred class of activators are acetic acid derivatives having a structure ~ D12 (V~ D13 or _ _ _ _ (VI~ J- ~ -TZ-CH2COOH
wherein D12 is hydrogen or alkyl o~ from 1 to 4 carbon atoms, e.g., methyl, ethyl or the like; D13 is carboxylated alkyl o rrom 1 to 4 carbon atoms, e.g., methyl, ethyl or 7 the like; Z is the number of atoms necessary to complete one or more substituted or unsubstituted heterocyclic rings havlng from about 5 to about 9 nuclear atoms; T2 is -0-, -NH-, -S-, or a carbon-to-carbon bond; Jl, J2 and J3 are the sam~ or different and are each hydrogen or an electron-10 donating group such as alkyl, alkoxy, dialkylamino containing from 1 to about 4 carbon atoms; or thioalkyl ether containing f:rom 1 to about 5 carbon atoms in the alkyl portion; e.g., methyl, isobutyl, methoxy, propoxy~ dimethyl-amino, dieth;ylamlno, methylthio, ethylthio and the like; and 15 hydroxy. Examples include phenylacetic acids, phenoxyacetic acids and (phenylthio)acetic acids.
Highly preferred activators of the above formulas ~I) through (VI) are coumarin-free activators such as N-phenylglycine; 3-indoleacetic acid; N-methyl-3-indoleacetic 20 acid; ethyl ~nd butyl dimethylaminobenzoate; N-methyl-N-benzylaniline; N,N-dimethylamino-p-toluidine; p-hydroxy-methyl~N~N-dimethylaniline and N,N-dibenzylaniline; and those in which T is oxygen, e.g., 4-methoxyphenoxyacetic acid and 2-(4-methoxyphenylthio)acetic acid.
With respect to phosphines as the activator, such phosphines can have the structure R6 _ p _ R8 wherein R6, R7 and R8 are the same or different and are each alkyl or alkoxy Or ~rom 1 to about 20 carbon atoms, for 30 example, methyl, ethyl, isooctyl, dodecyl, methoxy, ethoxy, propoxy, and the like; or aryl or alkaryl of from about 6 to 10 carbon atoms, e.g., phenyl, tolyl, naphthyl, and substi-~' ~L3~ 5 -1~
kuted aryl as described above~ ~epresentatlye ~mples Or such phosphlnes are ll~ted ln ~.S. ~tent No. 3~729~404, i~sued ~n April 24 r 1973 .
With respect to pho~phltes ~s ~he ac~Y~or~ ~uc~,~
5 ph~sphltes can have the ~ruc~ure RlD
o R90-P-ORll wherein R9, R10 and Rll are the same or dlf~ercnt and ~re each alkyl containlng ~rom 1 to about 12 carbon fitoms 9 ~r example, methyl, ethyl~ lscoctyl, dodecyl, and the llke; or ~0 aryl or alkaryl containin~ rrom 6 to 10 earb~n atoms, e.g., phenyl, tolyl, naphthyl~ and substituted aryl as descrlb~d above. Representative examples Or ~u~h phosphlte~ are al~G
listed in the above-noted V.S. P~tent No. 3~729~04.
Wlth respect ~o the ~- and ~-dlc~r~nyl~ aæ t~e 1~ activator, userul partlcular examples lnclude 2g3-bornane-dione and acetylacetone.
A mixture o~ Swo or m~re actl~ators o~ the types described above can also be used with the ket~coumarin sensitlzers described.
2~ Not all free-radical photop~lymerlzatl~n actl-~ators will work with the ~oumarins ~ thls invent~n to produce a speed that is at least 1/5 that achleved when uslng Michler's ketone and benzophenone as the ~o-init~ators (a~d the pre~lously ~tated light source). For comparison 25 purposes, some comblnations whlch have been ~ound to ~all to provlde the above-noted mlnlm~m ~peed areS when ~Qd with ~
mi~ure o~ pentaerythr~t~l tetraacrylate snd pentaerythrltol ~etramethacrylate as the poly~eri~able compound, p-dlmethyl-aminobenæoate admlxed with elther 7-diethyl~lno 3-(4- ~
30dlmethylamlnobenzoyl)coumarln, 9-(7-~ipropyla~lno-3-coumarln-oy 1 ) 1 3 2,4,~-tctr~hydr~ 3H,6~,10HCl]benzopyrano r ~, 9a,1-ghJqulnolazlne-10-Dne~ or 7-diethylamlno-3-(4~dlethylamino~
clnnamoyl)c~umarin.
3~ 6~ ~
~16-Although preferably the actlvator absorbs less than 50% o~ the activating radiatlon, it is contemplated that actlvators that absorb more than 50% can also be used, provided at least some radiation ls still absorbed by the 1 5 coumarin.
1 The amount of coumarin used does not appear to be critical. Thus, the coumarin can be present in the range of about .0002 to about 0.2 mmoles per gram of dry solids content. Actual preferred examples tested were in the range 10 of from about 0.005 to about 0.015 mmoles per gram.
Of course, sufficient activator needs to be present to allow the free-radical reaction to take place between the excited coumarin and the activator. ~hus the activator can be present in amounts between about 0.005 and 15 about 2.0 mmoles per gram of dry sollds, and preferably between about 0.05 and about 0.2.
The polymerizable compound is generally present from about 5 to about lQ0 weight percent of the mlxture o~
that compound and the blnder.
The dry thickness of the composition when coated can be between about 1 micron and about 1 mm, and is pre-ferably between about 20 and about 120 microns.
Any suitable solvent can be selected ~or preparlng a dope o~ the composltlon to be coated on a support.
25 Typical examples include dichloromethane, acetone, benzene, alcohols, ethers, toluene and the like. The choice will depend, of course, upon the polymerizable compound and the activator selected as well as upon other components that might be included, eOg., polymeric binders.
The support ~or the composition can be a variety of known supports, includlng photographic supports. Typical t useful supports include polymeric ~ilm, wood fiber--e.g., ,- paper~ metallic sheet and foil, glass and ceramic supporting elements provided with one or more subbing layers to enhance 35 the adhesive, antistatic9 dimensional, abrasive, hardness, ~rlctional, and/or other propertles of the support surface which might be desired.
Typical o~ userul polymeric film supports are films of cellulose nitrate and cellulose esters such as . ~ 376 cellulose trlaceta~e and dl~cetate, polystyre~e~ polyaml~s, homo- and copolymers Or ~inyl chlorlde, poly~vlnyl ace~al)~
polycarbonate, homo- and copoly~ers Or olerlns, ~uch as polyethylene and polypropylene, ~d polyester~ o~ ~lba~le aromatic carboxylic ac~ds w~th dlvalent alcQhols, ~uch ~8 poly(ethylene terephthalate).
Typical of useful paper ~upports are tho~e whlch are partlally acetylated or coated wlth bary~a and/or a polyole~in, particularly a polymer Or an ~-ole~ln containlng 10 2 to 10 carbon atoms, such as polyethylene, polypropylene, copolymers of ethylene and propylene and the like.
~ urther deta~ls Or userul ~upp~rts ~an be round ln ~esearch Dlsclosure, Vol. 176, ~ublic~tlon No. 17643~ Para.
XVII (Dec. 1978), publ~shed by Industrlal Opportunities 15 Ltd.~ Homewell, Havant~ H~mPshlre. P09 lEF, Unltefl Kinedom.
The composltlon o~ the lnvention ~n be ~pplled to a support for a variety Or uses 9 by a wlde ~arlety b~
techniques such as spray-coatlng, whlrler-coat~ng, cur~aln-coatlng, roll~coating, and the llke, all o~ which are 20 conventlonal.
A highly pre~erred embodlment Or the lnventlon is an element comprising a metallic support bearlng the compo-sltlon of the lnventlon, preferably along wl~h a polymeric binder. Partlcularly preSerred metallic supports ~re copper 25 foll. Such an element ls use~ul ~n mlcroelectrDnlcs and photo~abr~catlon, wherein the roil ls etched into deslred conrlgurations. In such a use, the photopvlymerlzable composition of the ln~en~ion, together wlth a blnder, ac~s as a negatlve resist that ls exposed and developed to form, 30 ror example, annular-shaped spacers ~or beam leads that are etched out of the metal ~oil usln~ a positlve-work~ng re~lst ~or the beam lead portions o~ the metal~ Certain ex~mples Or .uch a use hre ~escri~ed in U.S. Patent No. 3~795,043, lssued o~ March 5, 1974, and more ~peci~lcally in co~monlv 35 owned V.S. Patent No. 4,247,623, issued January 27, 1981, by John Gulld, ent1tled ~Blank and Process ~or the ~ormation Or Beam ~eads ror IC Chlp Bondin~".
,~
1~37~5 When binders are desired as an additional com-ponent, they can be selected from, e~g., homopolymers, copolymers and terpolymers of polyacrylates, polyesters, poly(acrylic acid2, mixtures of the same, and the like.
5 Such binders are not needed, however, even in resist appli-cationsg when the polymerizable compound and co-initiator composition are sufficiently film-forming in and of them-selvesS e.g., when the polymeriæable compound is of a relatively high molecular weight such as an oligomer or a 10 polymer.
Additionally, the composition can be used to manu-facture non~imaged polymeric coatings and other articles of manufacture.
Examples The following e~amples further illustrate the nature of the invention.
Examples lA and lB
To demonstrate the marked lncrease ln speed obtaln-able by the invention compared to the speed available from 20 the conventional co-initiator of Michler's ketone and benzo-phenone, the two coatings were prepared ~rom the following dope comprised of:
Ketocoumarin Table I
Pentaerythritol tetraacrylate 45.0 g 25 Pentaerythritol tetramethacrylate60.0 g t-Butyl 4-hydroxy-5-methylphenyl sulfide 1.05 g Poly(methyl methacrylate,co-butyl methacrylate-co-acrylic acid) (34:63:3) available from Rohm & Haas under the trademark "Acryloid B48N" 120 g i Poly(methyl methacrylate~ available from Rohm & Haas under the trademark "Acryloid A-lltt 120 g Dibutyl phthalate Cstabilizer2 50-4 g 35 Dichloromethane solvent 535.2 g Activator Table I
:~:ll37~i~5 TABLE I
Amounts Example lA Example lB
3-benzoyl-5,7-di-n-5 propoxycoumarin 0.0~ mmole 3-(2-benzofuroyl)-7-(l-pyrrolidinyl)coumarin ---- 0.5 mmole ethyl p-dimethylaminobenzoate o.8 mmole N-phenylglycine -~-- 0.8 mmole in 2 ml of ethanol The dopes were coated at a wet thickness of 300 microns on a copper support on a coating block malntained at 18C. After ~ minutes9 the temperature o~ the block was raised to 66C for 10 minutes. The coating was then placed - 15 in an oven at ~QC for 10 minutes. Test strips were exposed ~or 180 seconds through a Kodak T-14 step tablet having optical density increments of 0.15 and a polypropylene cover sheet using a "COLIGHT XPOSER I" device, which uses a 400W
medium pressure mercury lamp. The exposed test strips were 20 deyeloped for 55 sec in a processing tank containing 1,1,1-trichloroethane, rinsed ~or 5 seconds with fresh 1,1,1-trichloroethane, rinsed with water and dried. As a control, an identical element was prepared and exposed identically, except that the co-initiator was 0.1 millimole o~ Michler's 25 ketone and o.8 millimole of benzophenone.
The results were that Example lA had a speed, observed as the last solid step produced, that was over three* times as fast as the speed of the control, and Example lB had a speed that was seven times the speed of the ! 30 control.
Examples ?-34 , To demonstrate the e~fectiveness of various cou-marins when used with various amines9 the procedure o~
Example 1 was repeated, except that the co-initiator was the 35 coumarin and the amine indicated in Table II. ~In some cases 0.04 millimole o~ the coumarin was used, it being found that no di~ference in speed resulted in varying the amount o~ coumarin from 0. o8 to 0. 04 . ) In these and in all "
~ *The accuracy o~ all the speeds herein reported is about +20%.
. 1~L37~i9~;
subsequent examples, to determlne relative speeds the last solid step produced was compared to that produced when using the co-initiator 3,3'-carbonylbis(5,7-di-n-propoxycoumarin) plus ethyl p-dimethylaminobenzoate. A~ter a number of 5 repeated tests, this co-inltiator composltion was ~ound to , give an average speed o~ 3.5 times the speed of Michler's ketone and benzophenone. This result is given in Example 5.
The comparison of relative speeds is more readily made against a fast "control" than it ls against the much slower 10 speed achieved by the actual control of Michler's ketone and benzophenone. However, since the actual state of the art control is Michler's ketone and benzophenone rather than Example 5~ all relatlve speeds were recalculated to be exprèssed compared to a relative speed of 1.0 for the 15 example that used Mlchlerls ketone and benzophenone.
The examples have been arranged in Table II
according to their resulting speed, as is explained here-ina~ter.
TABLE II
20 Example Coumarin Amine _ Part A
2 3-(p-diethylaminocinnamoyl)- N-phenylglycine 7-diethylaminocoumarin 3 3-~2-ben ofuroyl~-7-diethyl- N-phenylglycine 2~ aminocoumarin
Chi~lque Chaus3ee de Charlerol, Bru~elæ, ~elglum under the 35 ~rade nsme "Ebecryl 210"; and mixtures Or the abo~e.
~3~69 Of the two components of the co-initiator composi-tion, the one which preferably predominates as the light-absorbing component is the coumarin. That ls, preferably greater than about 50% of the actlvatlng radiation, and ln 5 some cases, all of that radiation, is absorbed by the ~_ coumarin. In accordance with one aspect of the inventlon, the coumarin is a 3-ketocoumarln bearlng a variety o~
substituents ad~acent to the carbonyl group. A prêferred group of such coumarlns are those having the ~ormula R c_ R3 ~
wherein Rl is as defined above, and R2, R3 and R4 are the same or di~ferent and are each hydrogen; dialkylamlno or alkoxy containing from 1 to about 5 carbon atoms in the alkyl portion, such as dimethylamlno, diethylamino, methoxy, 15 ethoxy, n-propoxy and the llke; a heterocyclic group of one or more saturated or unsaturated rlngs containlng from about 5 to 10 rlng atoms, for examplel pyridyl, pyrrollnyl, pyrrolidyl and the liXe; or R2 and R3 or R2-R4, when taken together, comprise the number o~ non-metallic atoms that 20 complete with the coumarin moiety an aryl ring or one or two fused saturated or unsaturated heterocyclic rlngs contalnlng ~rom about 5 to 10 ring atoms. Useful examples lllustrative of such latter fused heterocyclic rings include the struc-ture:
c_Rl ~ ~
~J . O
, ~
`:
Examples Or heterocyclic gr~ups ~or ~1 lnclude benzo~uryl, thienyl, thenyl, ~uryl~ pyridyl and the 11ke. 3,3 carb~yl-bis(coumarlns~ are addltional prererre~ ~ampl~ o~ ~uch heterocycllc groups.
3-ketocoumarlns substltuted ln the benzo portlon ,~
o~ the coumarln structure by dn amlne group wlll produce~
when adml~ed wlth certaln a~t~Yators, excellen~ ~peed ~or photopolymerlzed monomers. As ~e~cribed and cl~med ~n commonly owned U.S. Patent Nc. 4,27~,751, issued July 14, 1g81, 10 bY SPecht et al, entitled '~Photopolymerization Co-lnitiator Composltions Comprlsln~ Amlne-Substl~uted Ketocoumar~n5 an~
Acet~c Acid Derl~ative ~ctlvators", such ket~cou~arln~ are particularly errec~lve co-photolnltlators ~hen co~blned wlth indole-3-ylacetic acld or N-phenylglycine. They also 1~ pro~ide the adYan~age Or slgn1ricant absorptlon ~t the spectral lines 366, 4Q5, ~36 ~nd ~47 nm, whicb ~llow~ the use of broad spectral llght s~urces such ~ ~eD~n, mercury, or halogen lamps, as well as strong ab30rpt~0n at 4BB nm whlch allows the use of argon laser E~po~ure~
The ~ollowlng ls a llstlng Or coumarins hl~hly userul as one o~ the components o~ the co-~nttlator ~omposl-tion Or the inventlon:
3-(~-nltrobenzoyl~-5,7-dl-n-propoxycoumarln;
3-(2-benzo~uroyl2-7-diethylam~noc~umarln;
25 3-(2-benzo~uroyl~-7-(1-pyrr~lldln,yl)~oumarln;
7~dimethylamlno-3 thenoylcoumarin;
3-ben~oyl-7-diethylamin~coumar~n;
3-~o-methoxybenzoyl~-7-diethylaminocoumarln;
3-(p-dimethylam~n~benzoyl~-7-diethylamlnocDumarin;
30 3,3'-carbonylbls~5,7 dl n-propoxycou~ar~n);
393'-carbonyl~is~7-diethylaminoeoumarin) 9 3-benzoyl-7-methoxyco~marin;
7dlethylamino-3-~3-(2-th~enyl)~cryl~yl3coumarln;
3-(2~uroyl)-7-dlethyl~mlnw oumarin, 35 3-(p-dlethylamlnocinnamoyl~-7-Blethylam1noc~u~arin;
7-methoxy-3-~3-pyrldylcarbonyl)coumarin;
3 ~4-morpholinocinna~oyl~-7-diethylamlnocoumarin;
.~
76~5 9-(7-diethylamino-3-coumarinoyl)-1,2~4,5-tetrahydro-3H,6H,lOHtl]benzopyrano[9,9a,1-gh]quinolazlne-10-one; which has the structure:
o I
~,J N(C2H5)2 5 9-(7-n-propylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H, 6H,lOH[l]benzopyrano[9,9a,1-gh]quinolazine-10-Qne;
9-(4-diethylaminoclnnamoyl)-1,2,4,5-tetrahydro-3H,6H, lOH[l]benzopyrano[9,9a91-gh~quinolazlne-10-one~
3-b~nzoyl-5~7-dl-n-propoxycoumarin;
10 7-dimethylamino-3-[3-(2-thienyl)acryloyl]coumarin;
9-t3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,lOH[l]-benzopyrano[9,9a,1-gh]quinolazine-10-one;
7-diethylamino-3-(4-dlmethylamlnocinnamylideneacetyl)coumarin;
9-L3-(9-~ulolidyl)acryloyl]-1~2,4,5-tetrahydro-3H,6HglOH[l]
benzopyrano[9,9a,1-gh~quinolazine-10-one;
3-(p-cyanobenzoyl)-5,7-di-n-propoxycoumarin;
3,3'-carbonylbis(5,7-dibutoxycoumarln);
3,3'-carbonylbis(7-acetoxycoumarin~;
5,7,7'-trimethoxy-3,3'-carbonylbiscoumarin;
2~ 3-cinnamoyl-7-diethylamlnocoumarin, 7-diethylamino-3-(4-morpholinocinrlamoyl)coumarin;
7-diethylamino-3-(4-ethoxycinnamoyl)coumarin;
3-(4-bromocinnamoyl~-7-diethylaminocoumarin, ~, 7-dlethylamino-3-[3-(4-methoxy-1-naphthyl)~cryloyl]coumarin;
l125 7-diethylamino-3-cinnamylideneacetylCoUmarin;
!;9-[3-(2-thienyl)acryloyl]-192,4,5-tetrahydro-3H,6H,lOH-:[l~benzopyrano~9a,1-gh]quinolazine-10-one;
7-diethylamino-3-(3-~luorosulfonylbenzoyl)coumarin;
;3 (4-methoxybenzoyl)-5,7-di-n-propoxycoumarin;
30 3-(4-nitrobenzoyl)-5,7-di-n-propoxycoumarin;
3-(3-trifluoromethylbenzoyl)-5,7-di-n-propoxycoumarin;
3-(4-cyanobenzoyl)-7-dlethylaminocoumarin;
3-benzoyl-5,7-dimethoxycoumarin, . ~
~7695 3-benzoyl-5,7-diethoxycoumarin;
3-benzoyl-6-methoxycoumarln;
3 benzoyl-8-ethoxycoumarin;
3-benzoylbenzoLf~coumarin;
5 5,7-diethoxy-3-(2-thenoyl~coumarin; ~_ 3-(2-benzofuroyl~-5,7-dlethoxycoumarin;
3-ben7oyl-7-hydroxycoumarin;
7-aceto~y-3-benzoylcoumarln3 7-methoxy-3-(4-methoxybenzoyl3coumarin;
10 3-(4-fluorosulfonylbenzoyl~-7-methoxycoumarin, 3-(4-ethoxyclnnamoyl~-7-methoxycoumarin;
3-benzoyl-7-dimethylaminocoumarln;
3-benzoyl-7-diethylaminocoumarin;
3-benzoy]-7-pyrrolidinylcoumarln;
15 3-(4-iodobenzoyl~-7-dimethylaminocoumarin;
3-(4-iodobenzoyl)-7-diethylamlnocoumarin;
7-dimethylamino-3-~4-dlmethylaminobenzoyl)coumarin;
7-diethylamino-3 (4-nitroben oyl)coumarin;
7-diethylamino-3-(2-thenoyl)coumarln;
20 7-pyrrolidinyl-3-(2-thenoyl~coumarin;
7-diethylamino-3-(2-furoyl2coumarln;
7-diethylamino-3-~2-methoxybenzoyl)coumarin;
3,3'-carbonylbiscoumarin;
3,3'-carbonylbis(7-methoxycoumarin);
25 3,3'-carbonylbis(6-methoxycoumarin);
3,3'-carbonylbis(5,7-dimethoxycoumarin), 3,3l-carbonylbis~5,7-diethoxycoumarin; and 3,3'~carbonylbis(5~7-di-iso-propoxycoumarin).
A mixture of two or more o~ any o~ the above 30 coumarins can also be used.
Conventional methods can be used to prepare these coumarins. ~or e~ample, prepar~tlons are disclosed in the - aforesaid U.S. Patent No. 4,147,552.
The free-radical photopolymerization activator 35 used in the composition of this invention is selected from the group consisting of amines, acetlc acid derivatives, phosphines, phosphites, bismuthines, arsenes, stibenes, sulfinic acid and sulfinic acid esters, sulfones, ~ and ~-dicarbonyls, such as 2,3-bornanedlone and acetylacetone, ~:~3~
--10~-ketones such as fluorenone, bi-imidazoles, and stannates.
or this list, most are known activators for use wlth other sensitizers. Representatlve patents detalllng numerous examples of such known activators include U.S. Patent Nos.
5 3,488,269; 3,573,922; 3,650,927, 3J729~404; and 3,933,682.
In addition, Michler's ketone~ hereto~ore known to be a photosensitizer only, is believed to function ln this ln-vention as an actlvator at least ln some lnstances, when used with the coumarin sensltizers o~ this lnventlon. Also, 10 it is believed that the nitrogen-free acetic acld derivative actlvators herein described have not been recognized hereto-fore as activators for use wlth any sensltlzer.
Preferred actlvators are those that produce a speed equal to or better than that of Michler's ketone and 15 benzophenone used as the co-initlator. Thus, many amlne activators are preferred, and particularly the followlng, when used with selective coumarins Or the inventlon:
Dl / ~ 2 (II) D3 I D5 i D7 (III) ~ CH2 C
T' D N D
(IV~ D8 C - D10 `.,: Dll wherein D and Dl are the same or different and are each alkyl containing ~rom 1 to about 12 carbon atoms, such as methyl, ethyl, propyl and the like; or together they are the necessary atoms to ~orm wlth the nltrogen atom one or more . 5 heterocyclic rings having about 5 to 10 nuclear atoms;
D2 is the group -CooD5; the group -C~D6; hydroxy alkyl such as hydroxymethyl~ hydroxyethyl and the like;
alkyl containing ~rom 1 to 3 carbon atoms, such as methyl~
ethyl, propyl and the like; hydrogen; X; or aldehyde;
D3 is hydrogen; alkyl containing from 1 ~o about 12 carbon atomsS such as methyl 9 ethyl, propyl and the like;
or aralkyl containing from 1 to 3 carbon atoms in the alkyl portion and 6 to 10 carbon atoms in the aryl portion, such as benzyl and the like, : 15 D is alkyl or aralkyl containing ~rom 1 to about 12 carbon atoms in the alkyl portion and 6 to 10 carbon atoms in the aryl portion, such as benzyl and the like;
D5 is aryl of from 6 to 10 nuclear carbon atoms or alkyl containing from 1 to about 15 carbon atoms, such as 20 me~hyl, propyl, isopropyl, butyl3 octyl, and the like, including alkyl substituted with aryl such as phenyl, or substituted with 2-phthalimido or with -OOC-C=CH2; or is the group -Q-OOC ~ wherein D and Dl are as described above and Q is a linking group such as alkylene, 25 unsaturated alkylene, phenylenebisalkylene and the like;
D is alkyl containing from 1 to about 3 carbon atoms, such as methyl, ethyl, propyl and the like; aryl of from 6 to 10 nuclear carbon atomsg e.g., p-dialkylamino-phenyl; or is the group -CH2C02D;
3o D7 is hydrogen or alkyl containing from 1 to about 3 carbon atoms, such as methyl, ethyl, propyl and the like;
D8~D10 are each independently aryl~ at least two of which are dialkylaminoaryl;
Dll is hydrogen, or alkyl or alkenyl Or ~rom 1 to 35 8 carbon atoms;
~37695 X is hydrogen or halogen such as chlorlne, bromine and the like;
T' is a linking group connecting the amine molety to the backbone of the polymer recurring unit 3 such as an 5 alkylene ester containing 1 to about 5 carbon atoms. ,_ Represen~ative use~ul amines falling withln structures (I) through (IV) above include ethyl p-dimethyl-aminobenzoate; other esters Or p-dimethylamlnobenzoic acid, e.g., n-butyl p-dimethylamlnobenzoate, phenethyl p-dimethyl-lO aminobenzoate, 2-phthalimidoethyl p-dimethylaminobenzoate, 2-methacryloyloxyethyl p-dimethylaminobenzoate, pentamethyl-enebis(p-dimethylamino)ben20ate; 4,4'-bis(dimethylamino)-benzophenone; phenethyl and pentamethylene esters of m-dimethylaminobenzoic acid; p-dimethylamlnobenzaldehyde;-2-15 chloro-4-dlmethylaminobenzaldehyde; p-dimethylamlnoaceto-phenone; p-dimethylaminobenzyl alcohol; ethyl (p-dlmethyl- ~`
amino)benzoyl acetate; p-N-plperldlnoacetophenone; 4 di-methylaminobenzoin, N,N-dimethyl-p-toluidine; N,N-diethyl-m-phenetidine, tribenzylamlne; dibenzylphenylamlne; N-methyl-20 N-phenylbenzylamine; p-bromo-N,N-dimethylaniline; tridodecyl-amine; and 4,4',4"-methylidynetris(N,N-dimethylaniline) (crystal violet~ leuco base).
Still other amines whlch are useful as activators include those described in U.S. Patent No. 4,1339909, e.g., 25 dimethylaminoethyl acrylate.
In the case of amines of the structure (IV) above 3 a particularly useful class are latex polymerlc particles prepared as described in Research Disclosure, Publication No. 15930, July 1977, except that the polymer is modlfied to 3 include pendant amines. When using such a latex, hydro-phoblc coumarins can be loaded into the l~tex to provide a water-dispersible composition for coating.
The following preparation can be used to synthe-size such latex polymer partlcles having pendant amines:
35 Preparation o~ Poly(methyl methacrylate--co-N~N-dimethylamino-ethyl methacrylate-co-2-hydroxyethyl methacrylate-co-2-acrylamido-2-methylpropanesulphonic acid) .
;, , `::
~3~7695 In a dropping funnel was placed:
Methyl methacrylate 20 ml N,N-dimethylaminoethyl meth-acrylate 31 ml 2-hydroxyethyl methacrylate lO ml j 2-acrylamido-2-methylpropane~
sulphonic acid ~as 10% w/v aqueous solution ad~usted to pH 5) lO ml Sodium metabisulphite l.0 g Poly(acrylamide-co-carbowax 550 acrylate) (8:1~ 0.5 g Distilled water 40 ml In the reaction flask was placed:
Potassium persulphate 4.8 g Sodium metabisulphite 1.8 g Poly(acrylamide-co-carbowa~
550 acrylate2 (8:1) o.8 g Distilled water lO0 ml The polymerization was carried out at 80C in a reaction vessel equipped with stirrer~ dropping funnel and nltrogen inlet. Nitrogen blanketing was one of three measures taken against inhibition by oxygen. In addition, the distilled water solvent was boiled and purged with nitrogen before use, and 25 there was a scavenging period o~ 15 mlnutes where the contents of the reaction vessel were stirred at 800C, generating a radical flux from the initiators, before monomer addition started.
The contents of the dropping funnel were added over 3 a period of one hour and the reaction mixture was then stirred ~' for a further four hours. The crude late~ was filtered through muslin to remove coagulum before being dialysed against water for 24 hours. The latex was then flltered once more before storage.
.~ 35 Another pre~erred class of activators are acetic acid derivatives having a structure ~ D12 (V~ D13 or _ _ _ _ (VI~ J- ~ -TZ-CH2COOH
wherein D12 is hydrogen or alkyl o~ from 1 to 4 carbon atoms, e.g., methyl, ethyl or the like; D13 is carboxylated alkyl o rrom 1 to 4 carbon atoms, e.g., methyl, ethyl or 7 the like; Z is the number of atoms necessary to complete one or more substituted or unsubstituted heterocyclic rings havlng from about 5 to about 9 nuclear atoms; T2 is -0-, -NH-, -S-, or a carbon-to-carbon bond; Jl, J2 and J3 are the sam~ or different and are each hydrogen or an electron-10 donating group such as alkyl, alkoxy, dialkylamino containing from 1 to about 4 carbon atoms; or thioalkyl ether containing f:rom 1 to about 5 carbon atoms in the alkyl portion; e.g., methyl, isobutyl, methoxy, propoxy~ dimethyl-amino, dieth;ylamlno, methylthio, ethylthio and the like; and 15 hydroxy. Examples include phenylacetic acids, phenoxyacetic acids and (phenylthio)acetic acids.
Highly preferred activators of the above formulas ~I) through (VI) are coumarin-free activators such as N-phenylglycine; 3-indoleacetic acid; N-methyl-3-indoleacetic 20 acid; ethyl ~nd butyl dimethylaminobenzoate; N-methyl-N-benzylaniline; N,N-dimethylamino-p-toluidine; p-hydroxy-methyl~N~N-dimethylaniline and N,N-dibenzylaniline; and those in which T is oxygen, e.g., 4-methoxyphenoxyacetic acid and 2-(4-methoxyphenylthio)acetic acid.
With respect to phosphines as the activator, such phosphines can have the structure R6 _ p _ R8 wherein R6, R7 and R8 are the same or different and are each alkyl or alkoxy Or ~rom 1 to about 20 carbon atoms, for 30 example, methyl, ethyl, isooctyl, dodecyl, methoxy, ethoxy, propoxy, and the like; or aryl or alkaryl of from about 6 to 10 carbon atoms, e.g., phenyl, tolyl, naphthyl, and substi-~' ~L3~ 5 -1~
kuted aryl as described above~ ~epresentatlye ~mples Or such phosphlnes are ll~ted ln ~.S. ~tent No. 3~729~404, i~sued ~n April 24 r 1973 .
With respect to pho~phltes ~s ~he ac~Y~or~ ~uc~,~
5 ph~sphltes can have the ~ruc~ure RlD
o R90-P-ORll wherein R9, R10 and Rll are the same or dlf~ercnt and ~re each alkyl containlng ~rom 1 to about 12 carbon fitoms 9 ~r example, methyl, ethyl~ lscoctyl, dodecyl, and the llke; or ~0 aryl or alkaryl containin~ rrom 6 to 10 earb~n atoms, e.g., phenyl, tolyl, naphthyl~ and substituted aryl as descrlb~d above. Representative examples Or ~u~h phosphlte~ are al~G
listed in the above-noted V.S. P~tent No. 3~729~04.
Wlth respect ~o the ~- and ~-dlc~r~nyl~ aæ t~e 1~ activator, userul partlcular examples lnclude 2g3-bornane-dione and acetylacetone.
A mixture o~ Swo or m~re actl~ators o~ the types described above can also be used with the ket~coumarin sensitlzers described.
2~ Not all free-radical photop~lymerlzatl~n actl-~ators will work with the ~oumarins ~ thls invent~n to produce a speed that is at least 1/5 that achleved when uslng Michler's ketone and benzophenone as the ~o-init~ators (a~d the pre~lously ~tated light source). For comparison 25 purposes, some comblnations whlch have been ~ound to ~all to provlde the above-noted mlnlm~m ~peed areS when ~Qd with ~
mi~ure o~ pentaerythr~t~l tetraacrylate snd pentaerythrltol ~etramethacrylate as the poly~eri~able compound, p-dlmethyl-aminobenæoate admlxed with elther 7-diethyl~lno 3-(4- ~
30dlmethylamlnobenzoyl)coumarln, 9-(7-~ipropyla~lno-3-coumarln-oy 1 ) 1 3 2,4,~-tctr~hydr~ 3H,6~,10HCl]benzopyrano r ~, 9a,1-ghJqulnolazlne-10-Dne~ or 7-diethylamlno-3-(4~dlethylamino~
clnnamoyl)c~umarin.
3~ 6~ ~
~16-Although preferably the actlvator absorbs less than 50% o~ the activating radiatlon, it is contemplated that actlvators that absorb more than 50% can also be used, provided at least some radiation ls still absorbed by the 1 5 coumarin.
1 The amount of coumarin used does not appear to be critical. Thus, the coumarin can be present in the range of about .0002 to about 0.2 mmoles per gram of dry solids content. Actual preferred examples tested were in the range 10 of from about 0.005 to about 0.015 mmoles per gram.
Of course, sufficient activator needs to be present to allow the free-radical reaction to take place between the excited coumarin and the activator. ~hus the activator can be present in amounts between about 0.005 and 15 about 2.0 mmoles per gram of dry sollds, and preferably between about 0.05 and about 0.2.
The polymerizable compound is generally present from about 5 to about lQ0 weight percent of the mlxture o~
that compound and the blnder.
The dry thickness of the composition when coated can be between about 1 micron and about 1 mm, and is pre-ferably between about 20 and about 120 microns.
Any suitable solvent can be selected ~or preparlng a dope o~ the composltlon to be coated on a support.
25 Typical examples include dichloromethane, acetone, benzene, alcohols, ethers, toluene and the like. The choice will depend, of course, upon the polymerizable compound and the activator selected as well as upon other components that might be included, eOg., polymeric binders.
The support ~or the composition can be a variety of known supports, includlng photographic supports. Typical t useful supports include polymeric ~ilm, wood fiber--e.g., ,- paper~ metallic sheet and foil, glass and ceramic supporting elements provided with one or more subbing layers to enhance 35 the adhesive, antistatic9 dimensional, abrasive, hardness, ~rlctional, and/or other propertles of the support surface which might be desired.
Typical o~ userul polymeric film supports are films of cellulose nitrate and cellulose esters such as . ~ 376 cellulose trlaceta~e and dl~cetate, polystyre~e~ polyaml~s, homo- and copolymers Or ~inyl chlorlde, poly~vlnyl ace~al)~
polycarbonate, homo- and copoly~ers Or olerlns, ~uch as polyethylene and polypropylene, ~d polyester~ o~ ~lba~le aromatic carboxylic ac~ds w~th dlvalent alcQhols, ~uch ~8 poly(ethylene terephthalate).
Typical of useful paper ~upports are tho~e whlch are partlally acetylated or coated wlth bary~a and/or a polyole~in, particularly a polymer Or an ~-ole~ln containlng 10 2 to 10 carbon atoms, such as polyethylene, polypropylene, copolymers of ethylene and propylene and the like.
~ urther deta~ls Or userul ~upp~rts ~an be round ln ~esearch Dlsclosure, Vol. 176, ~ublic~tlon No. 17643~ Para.
XVII (Dec. 1978), publ~shed by Industrlal Opportunities 15 Ltd.~ Homewell, Havant~ H~mPshlre. P09 lEF, Unltefl Kinedom.
The composltlon o~ the lnvention ~n be ~pplled to a support for a variety Or uses 9 by a wlde ~arlety b~
techniques such as spray-coatlng, whlrler-coat~ng, cur~aln-coatlng, roll~coating, and the llke, all o~ which are 20 conventlonal.
A highly pre~erred embodlment Or the lnventlon is an element comprising a metallic support bearlng the compo-sltlon of the lnventlon, preferably along wl~h a polymeric binder. Partlcularly preSerred metallic supports ~re copper 25 foll. Such an element ls use~ul ~n mlcroelectrDnlcs and photo~abr~catlon, wherein the roil ls etched into deslred conrlgurations. In such a use, the photopvlymerlzable composition of the ln~en~ion, together wlth a blnder, ac~s as a negatlve resist that ls exposed and developed to form, 30 ror example, annular-shaped spacers ~or beam leads that are etched out of the metal ~oil usln~ a positlve-work~ng re~lst ~or the beam lead portions o~ the metal~ Certain ex~mples Or .uch a use hre ~escri~ed in U.S. Patent No. 3~795,043, lssued o~ March 5, 1974, and more ~peci~lcally in co~monlv 35 owned V.S. Patent No. 4,247,623, issued January 27, 1981, by John Gulld, ent1tled ~Blank and Process ~or the ~ormation Or Beam ~eads ror IC Chlp Bondin~".
,~
1~37~5 When binders are desired as an additional com-ponent, they can be selected from, e~g., homopolymers, copolymers and terpolymers of polyacrylates, polyesters, poly(acrylic acid2, mixtures of the same, and the like.
5 Such binders are not needed, however, even in resist appli-cationsg when the polymerizable compound and co-initiator composition are sufficiently film-forming in and of them-selvesS e.g., when the polymeriæable compound is of a relatively high molecular weight such as an oligomer or a 10 polymer.
Additionally, the composition can be used to manu-facture non~imaged polymeric coatings and other articles of manufacture.
Examples The following e~amples further illustrate the nature of the invention.
Examples lA and lB
To demonstrate the marked lncrease ln speed obtaln-able by the invention compared to the speed available from 20 the conventional co-initiator of Michler's ketone and benzo-phenone, the two coatings were prepared ~rom the following dope comprised of:
Ketocoumarin Table I
Pentaerythritol tetraacrylate 45.0 g 25 Pentaerythritol tetramethacrylate60.0 g t-Butyl 4-hydroxy-5-methylphenyl sulfide 1.05 g Poly(methyl methacrylate,co-butyl methacrylate-co-acrylic acid) (34:63:3) available from Rohm & Haas under the trademark "Acryloid B48N" 120 g i Poly(methyl methacrylate~ available from Rohm & Haas under the trademark "Acryloid A-lltt 120 g Dibutyl phthalate Cstabilizer2 50-4 g 35 Dichloromethane solvent 535.2 g Activator Table I
:~:ll37~i~5 TABLE I
Amounts Example lA Example lB
3-benzoyl-5,7-di-n-5 propoxycoumarin 0.0~ mmole 3-(2-benzofuroyl)-7-(l-pyrrolidinyl)coumarin ---- 0.5 mmole ethyl p-dimethylaminobenzoate o.8 mmole N-phenylglycine -~-- 0.8 mmole in 2 ml of ethanol The dopes were coated at a wet thickness of 300 microns on a copper support on a coating block malntained at 18C. After ~ minutes9 the temperature o~ the block was raised to 66C for 10 minutes. The coating was then placed - 15 in an oven at ~QC for 10 minutes. Test strips were exposed ~or 180 seconds through a Kodak T-14 step tablet having optical density increments of 0.15 and a polypropylene cover sheet using a "COLIGHT XPOSER I" device, which uses a 400W
medium pressure mercury lamp. The exposed test strips were 20 deyeloped for 55 sec in a processing tank containing 1,1,1-trichloroethane, rinsed ~or 5 seconds with fresh 1,1,1-trichloroethane, rinsed with water and dried. As a control, an identical element was prepared and exposed identically, except that the co-initiator was 0.1 millimole o~ Michler's 25 ketone and o.8 millimole of benzophenone.
The results were that Example lA had a speed, observed as the last solid step produced, that was over three* times as fast as the speed of the control, and Example lB had a speed that was seven times the speed of the ! 30 control.
Examples ?-34 , To demonstrate the e~fectiveness of various cou-marins when used with various amines9 the procedure o~
Example 1 was repeated, except that the co-initiator was the 35 coumarin and the amine indicated in Table II. ~In some cases 0.04 millimole o~ the coumarin was used, it being found that no di~ference in speed resulted in varying the amount o~ coumarin from 0. o8 to 0. 04 . ) In these and in all "
~ *The accuracy o~ all the speeds herein reported is about +20%.
. 1~L37~i9~;
subsequent examples, to determlne relative speeds the last solid step produced was compared to that produced when using the co-initiator 3,3'-carbonylbis(5,7-di-n-propoxycoumarin) plus ethyl p-dimethylaminobenzoate. A~ter a number of 5 repeated tests, this co-inltiator composltion was ~ound to , give an average speed o~ 3.5 times the speed of Michler's ketone and benzophenone. This result is given in Example 5.
The comparison of relative speeds is more readily made against a fast "control" than it ls against the much slower 10 speed achieved by the actual control of Michler's ketone and benzophenone. However, since the actual state of the art control is Michler's ketone and benzophenone rather than Example 5~ all relatlve speeds were recalculated to be exprèssed compared to a relative speed of 1.0 for the 15 example that used Mlchlerls ketone and benzophenone.
The examples have been arranged in Table II
according to their resulting speed, as is explained here-ina~ter.
TABLE II
20 Example Coumarin Amine _ Part A
2 3-(p-diethylaminocinnamoyl)- N-phenylglycine 7-diethylaminocoumarin 3 3-~2-ben ofuroyl~-7-diethyl- N-phenylglycine 2~ aminocoumarin
4 3,3'-carbonylbis(7-diethyl- N-phenylglycine aminocoumarin) Part B ~ooD5 N(CH3)2 D
3,3'-carbonylbis(5,7-di-n- -C2H5 propoxycoumarin) 6 3,3'-carbonylbis(5,7-di-n- -C4H9 propoxycoumarin) 7 3,3'-carbonylbis(5,7-di-n- C8H17 propoxycoumarin) 8 3,3'-carbonylbis(5,7-di-n- -C12H25 propoxycoumarin) 1~37'~9S
Table II (Contlnued) Example Coumarin Amlne 9 3,3~ carbonylbis(5,7-di-n- -CH2CH2C6H5 propxycoumarin~
10 3,3'-carbonylbis(5,7-di-n- -CH2CH2~00C-C=CH2 ~-propoxycoumarin) _________________ ___________ ____________________________ 11 3,3'-carbonylbis(5,7-di-n- N-phenylglycine propoxycoumarin) 12 3-benzoyl-7-methoxycoumarin p-dlmethylamino-benzaldehyde 13 3-benzoyl-7-diethylamino-N-phenylglycine coumarin 14 3 (p-morpholinostyryl~N-phenylglycine carbonyl 7-diethylamino-coumarin 9--(7-diethylamino~3-coumar- N-phenylglycine inoyl)-1,2,4,5-tetrahydro-3H,6H,lOH[l]benzopyrano-[9,9a,1-gh]quinolazine-10 one Part C
16 3,3t-carbonylbis(5,7-di-n- ethyl p-(dimethyl-propoxycoumarin)amino)benzo-ylacetate 25 17 3,3'-carbonylbis(5,7-di-n- p-bromo-N,N-di-propoxycoumarin)methylaminoanillne 18 3,3'-carbonylbis(5,7-di-n~ 2-chloro-4-dimethyl propoxycoumarin)aminobenzaldehyde 19 3,3'-carbonylbis(~97-di-n- p-piperidinoaceto-propoxycoumarin)phenone 3,3'-carbonylbis(5,7-di-n- 2-phenylethyl m-di-propoxycoumarin)methylaminobenzoate 21 3,3'-carbonylbis(5,7-di-n- pentamethylene bis-propoxycoumarin)(p-dimethylamino-benzoate) 22 3,3'-carbonylbis(5,7-di-n- N-methyl-N-phenyl-propoxycoumarin)benzylamine Part D
23 3,3'-carbonylbis(5,7-di-n- 2-phthalimidoethyl propoxycoumarin)p-dimethylamino-benzoate 24 3,3'-carbonylbis(5,7-di-n- 2-phthalimidoethyl propoxycoumarin)m-dimethylamin benzoate 3~ S
TABLE II (concluded?
Example Coumarin Amine 3'3' carbonylbis~5,7-di-n pentamethylene bis-propoxycoumarin) (m-dimethylamino-benzoate) 26 3,3'~carbonylbis(5J7-di-n- p-dlethylaminobenz- ~.
propoxycoumarin) aldehyde 27 3,3'-carbonylbis(5,7-di-n- dibenzylphenylamine propoxycoumarin) 10 28 3-benzoyl-7-methoxycoumarin pentamethylene bis-(p-dimethylamino-benzoate) Part E
29 3,3'-carbonylbis(5,7-di-n- 3-ethoxy-N,N-diethyl-propoxycoumarin) aniline 3,3'-carbonylbis(5,7-di-n- N,N-bis(2-hydroxy-propoxycoumarin) ethyl)anillne 31 3-benzoyl-7-methoxycoumarin 4,4',4" methylldyne-(N,N~dimethylaniline) 20 32 3-benzoyl-7-methoxycoumarin tridodecylamlne 33 3-ben7~oyl-7-methoxycoumarin tribenzylamine 34 3,3'-carbonylbis(7-dlethyl- indole-3-ylacetic aminocoumarin) acid Part F
25 Control 3-benzoyl-7-methoxycoumarin 3,3'-carbonylbis(7-diethylamino-coumarin) All those examples listed in Part A of Table II were found to have a relative speed of between about 4 and about 30 6 and Part B a speed of between about 3 and about 3.5.
Those of Part C had a speed of between about 2 and about 3, those of Part D between about 1.25 and about 2, and those of ~.~ Part E between about 0.25 and about 0.8. Part F, a co-initiator described in the aforesaid U.S. Patent No. 4,147,552, 35 and different from Mlchler's ketone admixed with benzo-phenone, produced a speed of about 0. o8 .
Examples 35-41 To further demonstrate the effectiveness of various amino-coumarins when used with various amlne acti-40 vators, the co~tings and exposure of Example 1 were repeatedusing the coumarins and amines of Table III as a co lnitlator.
The speedsg stated as in the previous examples relative to a speed of 1 for Michler's ketone and benzophenone, are given ln Table III.
3~ ~ ~5 ~23-Table III
Relative Speed Example Coumarin For the Noted Amine COOC2Hs ~ .
CH3)2 C~3 CH2 3~,2-benzofuroyl 7-diethylamino-coumarin 3.5 2.5 36 3-benzoyl-7-diethyl-aminocoumarin 0.4 0.5 37 7-dimethylamino-3-thenoylcoumarin 1.2 0.9 38 7-diethylamino-3-(,o-methoxybenzoyl~-coumarin 0.5 o.6 39 7-diethylamino-3-(m-fluorosulfonyl-benzoyl~coumarin 0.4 0.6 7-diethylamino-3-(p-dimethylaminobenzoyl2-coumarin 0. o8 o. 2 41 3-(2-benzofuroyl~-7-(l~pyrrolidinyl~
coumarin 3.5 2.5 25 Examples 42-60 To demonstrate the use of the invention wlth additional acetic acid derivatives as the actlvator~ Example 1 was repeated except that the coumarin and the activator~
selected were those indicated in the following table. All 30 speeds are stated relative to an arbitrary speed of 1.0 for the results obtained when using, as a control co-lnitiator, Michler's ketone and benæophenone.
~i37G95;
--24_ a~
a)
3,3'-carbonylbis(5,7-di-n- -C2H5 propoxycoumarin) 6 3,3'-carbonylbis(5,7-di-n- -C4H9 propoxycoumarin) 7 3,3'-carbonylbis(5,7-di-n- C8H17 propoxycoumarin) 8 3,3'-carbonylbis(5,7-di-n- -C12H25 propoxycoumarin) 1~37'~9S
Table II (Contlnued) Example Coumarin Amlne 9 3,3~ carbonylbis(5,7-di-n- -CH2CH2C6H5 propxycoumarin~
10 3,3'-carbonylbis(5,7-di-n- -CH2CH2~00C-C=CH2 ~-propoxycoumarin) _________________ ___________ ____________________________ 11 3,3'-carbonylbis(5,7-di-n- N-phenylglycine propoxycoumarin) 12 3-benzoyl-7-methoxycoumarin p-dlmethylamino-benzaldehyde 13 3-benzoyl-7-diethylamino-N-phenylglycine coumarin 14 3 (p-morpholinostyryl~N-phenylglycine carbonyl 7-diethylamino-coumarin 9--(7-diethylamino~3-coumar- N-phenylglycine inoyl)-1,2,4,5-tetrahydro-3H,6H,lOH[l]benzopyrano-[9,9a,1-gh]quinolazine-10 one Part C
16 3,3t-carbonylbis(5,7-di-n- ethyl p-(dimethyl-propoxycoumarin)amino)benzo-ylacetate 25 17 3,3'-carbonylbis(5,7-di-n- p-bromo-N,N-di-propoxycoumarin)methylaminoanillne 18 3,3'-carbonylbis(5,7-di-n~ 2-chloro-4-dimethyl propoxycoumarin)aminobenzaldehyde 19 3,3'-carbonylbis(~97-di-n- p-piperidinoaceto-propoxycoumarin)phenone 3,3'-carbonylbis(5,7-di-n- 2-phenylethyl m-di-propoxycoumarin)methylaminobenzoate 21 3,3'-carbonylbis(5,7-di-n- pentamethylene bis-propoxycoumarin)(p-dimethylamino-benzoate) 22 3,3'-carbonylbis(5,7-di-n- N-methyl-N-phenyl-propoxycoumarin)benzylamine Part D
23 3,3'-carbonylbis(5,7-di-n- 2-phthalimidoethyl propoxycoumarin)p-dimethylamino-benzoate 24 3,3'-carbonylbis(5,7-di-n- 2-phthalimidoethyl propoxycoumarin)m-dimethylamin benzoate 3~ S
TABLE II (concluded?
Example Coumarin Amine 3'3' carbonylbis~5,7-di-n pentamethylene bis-propoxycoumarin) (m-dimethylamino-benzoate) 26 3,3'~carbonylbis(5J7-di-n- p-dlethylaminobenz- ~.
propoxycoumarin) aldehyde 27 3,3'-carbonylbis(5,7-di-n- dibenzylphenylamine propoxycoumarin) 10 28 3-benzoyl-7-methoxycoumarin pentamethylene bis-(p-dimethylamino-benzoate) Part E
29 3,3'-carbonylbis(5,7-di-n- 3-ethoxy-N,N-diethyl-propoxycoumarin) aniline 3,3'-carbonylbis(5,7-di-n- N,N-bis(2-hydroxy-propoxycoumarin) ethyl)anillne 31 3-benzoyl-7-methoxycoumarin 4,4',4" methylldyne-(N,N~dimethylaniline) 20 32 3-benzoyl-7-methoxycoumarin tridodecylamlne 33 3-ben7~oyl-7-methoxycoumarin tribenzylamine 34 3,3'-carbonylbis(7-dlethyl- indole-3-ylacetic aminocoumarin) acid Part F
25 Control 3-benzoyl-7-methoxycoumarin 3,3'-carbonylbis(7-diethylamino-coumarin) All those examples listed in Part A of Table II were found to have a relative speed of between about 4 and about 30 6 and Part B a speed of between about 3 and about 3.5.
Those of Part C had a speed of between about 2 and about 3, those of Part D between about 1.25 and about 2, and those of ~.~ Part E between about 0.25 and about 0.8. Part F, a co-initiator described in the aforesaid U.S. Patent No. 4,147,552, 35 and different from Mlchler's ketone admixed with benzo-phenone, produced a speed of about 0. o8 .
Examples 35-41 To further demonstrate the effectiveness of various amino-coumarins when used with various amlne acti-40 vators, the co~tings and exposure of Example 1 were repeatedusing the coumarins and amines of Table III as a co lnitlator.
The speedsg stated as in the previous examples relative to a speed of 1 for Michler's ketone and benzophenone, are given ln Table III.
3~ ~ ~5 ~23-Table III
Relative Speed Example Coumarin For the Noted Amine COOC2Hs ~ .
CH3)2 C~3 CH2 3~,2-benzofuroyl 7-diethylamino-coumarin 3.5 2.5 36 3-benzoyl-7-diethyl-aminocoumarin 0.4 0.5 37 7-dimethylamino-3-thenoylcoumarin 1.2 0.9 38 7-diethylamino-3-(,o-methoxybenzoyl~-coumarin 0.5 o.6 39 7-diethylamino-3-(m-fluorosulfonyl-benzoyl~coumarin 0.4 0.6 7-diethylamino-3-(p-dimethylaminobenzoyl2-coumarin 0. o8 o. 2 41 3-(2-benzofuroyl~-7-(l~pyrrolidinyl~
coumarin 3.5 2.5 25 Examples 42-60 To demonstrate the use of the invention wlth additional acetic acid derivatives as the actlvator~ Example 1 was repeated except that the coumarin and the activator~
selected were those indicated in the following table. All 30 speeds are stated relative to an arbitrary speed of 1.0 for the results obtained when using, as a control co-lnitiator, Michler's ketone and benæophenone.
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Example 63 To demonstrate the use of the lnvention with 2,3-bornanedione as the activator, Example 1 was repeated using a dope containing 0.1 mmole of 2,3-bornanedione and 0.1 5 mmole of 3-(2-benzofuroyl)-7-diethylamlnocoumarln. The ,_ relative speed result, compared to a speed o~ 1 ~or the s~me dope using however Michler's ketone and benzophenone, was o.78.
By way of contrast, when this example was repeated 10 but with 0.1 mmole of 7-diethylamino-4-methylcoumarln as the photosensitizer in the manner taught by U.S. Patent Reissue No. 283789, reissued on Aprll 27, 1976, the speed result was only 0.32 compared to a speed of 1.0 for Michler7s ketone and benzophenone.
15 Examples 64 and 65 To demonstrate the e~fectiveness o~ phosphines as the activator, the coatings and exposure Or Example 1 were repeated except that 3,3'-carbonylbis(5,7-di-n-propoxy-coumarin) and equimolar amounts of triphenylphosphine, 20 Example 64, and tritolylphosphine, Example 65, were used as the ketocoumarin and the activators. The speed of Example 64 was 0.56 and that Or Example 65 was 0.34, compared to a speed of 1.0 for Michler's ketone and benzophenone.
Example 66 To demons~rate the effectiveness of stibenes as the activator, the coatings and exposure of Example 65 were repeated except that an equimolar amount of triphenylstibene was tested as the activator. The relative speed was 0.29.
Exam~le 67 3 To demonstrate the effectiveness of a ketone as the activator9 the coatings and exposure of Example 1 were repeated except that an equimolar amount of fluorenone was tested along with 3,3'-carbonylbis(7-diethylaminocoumarin) as the co-initiator. The relative speed was found to be 35 about 0.o5 that of the speed available from Michler's ketone and benzophenone as the co~initiator.
ExampleS 68-7?
To demonstrate the invention for use with different monomers, a stock solution was prepared as ~ollows:
, 3~ ~ 5 "Acryloid A-ll" 60 g "Acrylold B-48N" 60 g 3,3'-carbonylbis(5,7-di-n-propoxycoumarin~ 1.5 g Ethyl p-dimethylaminobenzoate 1.5 g t.
t-Butyl pyrocatechol 0.525 g Dichloromethane 278.6 g To 39.11 g of the stock solution 5.25 g of the following monomers were added:
Example Monomer 68 tetraethylene glycol diacrylate
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Example 63 To demonstrate the use of the lnvention with 2,3-bornanedione as the activator, Example 1 was repeated using a dope containing 0.1 mmole of 2,3-bornanedione and 0.1 5 mmole of 3-(2-benzofuroyl)-7-diethylamlnocoumarln. The ,_ relative speed result, compared to a speed o~ 1 ~or the s~me dope using however Michler's ketone and benzophenone, was o.78.
By way of contrast, when this example was repeated 10 but with 0.1 mmole of 7-diethylamino-4-methylcoumarln as the photosensitizer in the manner taught by U.S. Patent Reissue No. 283789, reissued on Aprll 27, 1976, the speed result was only 0.32 compared to a speed of 1.0 for Michler7s ketone and benzophenone.
15 Examples 64 and 65 To demonstrate the e~fectiveness o~ phosphines as the activator, the coatings and exposure Or Example 1 were repeated except that 3,3'-carbonylbis(5,7-di-n-propoxy-coumarin) and equimolar amounts of triphenylphosphine, 20 Example 64, and tritolylphosphine, Example 65, were used as the ketocoumarin and the activators. The speed of Example 64 was 0.56 and that Or Example 65 was 0.34, compared to a speed of 1.0 for Michler's ketone and benzophenone.
Example 66 To demons~rate the effectiveness of stibenes as the activator, the coatings and exposure of Example 65 were repeated except that an equimolar amount of triphenylstibene was tested as the activator. The relative speed was 0.29.
Exam~le 67 3 To demonstrate the effectiveness of a ketone as the activator9 the coatings and exposure of Example 1 were repeated except that an equimolar amount of fluorenone was tested along with 3,3'-carbonylbis(7-diethylaminocoumarin) as the co-initiator. The relative speed was found to be 35 about 0.o5 that of the speed available from Michler's ketone and benzophenone as the co~initiator.
ExampleS 68-7?
To demonstrate the invention for use with different monomers, a stock solution was prepared as ~ollows:
, 3~ ~ 5 "Acryloid A-ll" 60 g "Acrylold B-48N" 60 g 3,3'-carbonylbis(5,7-di-n-propoxycoumarin~ 1.5 g Ethyl p-dimethylaminobenzoate 1.5 g t.
t-Butyl pyrocatechol 0.525 g Dichloromethane 278.6 g To 39.11 g of the stock solution 5.25 g of the following monomers were added:
Example Monomer 68 tetraethylene glycol diacrylate
6~ 1,6-hexanediol diacrylate triethylene glycol dimethacrylate 71 tetraethylene glycol dimethacrylate 72 diethylene glycol dimethacrylate Each example was then coated onto 35 mlcrons copper foil at a wet thickness of 300 microns. The dry coating was approxi-mately 75 mlcrons thick.
All coatings were exposed to a Colight I exposing 20 unit equi~ped with a 400W medium pressure lamp, for two minutes through a T-14 step tablet having lncrements of 0.15 density, followed by a one-minute spray development in l~l,l-trichloroethane and a water rinse. The speeds of the coated resist were measured as the last observed solid 25 step a~ter development and were as ~ollows:
Example Speed 68 12+
6~ 10 Example 73 As an example of the extremely fast speeds that can be obtained, a composition similar to that tested in 35 Example 1, but wlthout the plasticizer dibutyl phthalate, was prepared and shown to have a speed as ~ollows:
. . .
. ~ 3~ ~ 9 Relative Ketoc~umarinAckivator Speed*
0.08 mmole of 3~2-benzo 0.8 mmole of N-methyl ~uroyl)-7-diethylamln~ -3-indole acetlc acid 5 coumarin ~.6 ~C~mpared t~ a speed ~f 1.~ for Mlchler's ketone and benzD-~~
-phenone .
The ~n~ent~on has been described in detail wlth particular reference to cer~ain prererred embodiments ~here-1~ of, but ~t will be understood that variatlons and modi~ic~-tions can be e~ected within the spirit and scope o~ the inventlon.
All coatings were exposed to a Colight I exposing 20 unit equi~ped with a 400W medium pressure lamp, for two minutes through a T-14 step tablet having lncrements of 0.15 density, followed by a one-minute spray development in l~l,l-trichloroethane and a water rinse. The speeds of the coated resist were measured as the last observed solid 25 step a~ter development and were as ~ollows:
Example Speed 68 12+
6~ 10 Example 73 As an example of the extremely fast speeds that can be obtained, a composition similar to that tested in 35 Example 1, but wlthout the plasticizer dibutyl phthalate, was prepared and shown to have a speed as ~ollows:
. . .
. ~ 3~ ~ 9 Relative Ketoc~umarinAckivator Speed*
0.08 mmole of 3~2-benzo 0.8 mmole of N-methyl ~uroyl)-7-diethylamln~ -3-indole acetlc acid 5 coumarin ~.6 ~C~mpared t~ a speed ~f 1.~ for Mlchler's ketone and benzD-~~
-phenone .
The ~n~ent~on has been described in detail wlth particular reference to cer~ain prererred embodiments ~here-1~ of, but ~t will be understood that variatlons and modi~ic~-tions can be e~ected within the spirit and scope o~ the inventlon.
Claims (15)
1. In a photopolymerizable composition comprising an addition polymerizable compound containing ethylenic unsaturation, and a co-initiator composition comprising a carbonyl compound and a photopolymerization activator re-sponsive in the presence of the photo-excited form of said carbonyl compound to form a free radical, said activator being selected from the group consisting of an amine, an acetic acid derivative, a phosphine, a phosphite, a bis-muthine, an arsene, a stibene, a sulfinic acid, a sulfinic acid ester, a sulfone, an .alpha.- or .beta.-dlcarbonyl, a ketone, a bi-imidazole, and a stannate;
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
2. In a photopolymerizable composition comprising an addition polymerizable compound containing ethylenic unsaturation and a co-initiator composition comprising an amine capable of forming a free radical in the presence of a photo-excited carbonyl compound, and a carbonyl compound;
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position, wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms/ or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position, wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms/ or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
3. In a photopolymerizable composition comprising an addition polymerizable acrylate and a co-initiator composition comprising an amine capable of forming a free radical in the presence of a photo-excited carbonyl com-pound, and a carbonyl compound;
the improvement wherein said carbonyl compound is 3-(2-benzofuroyl)-7-diethylaminocoumarin.
the improvement wherein said carbonyl compound is 3-(2-benzofuroyl)-7-diethylaminocoumarin.
4. In a photopolymerizable composition comprising an addition polymerizable acrylate and a co-initiator composition comprising an amine capable of forming a free radical in the presence of a photo-excited carbonyl com-pound, and a carbonyl compound;
the improvement wherein said carbonyl compound is 3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin.
the improvement wherein said carbonyl compound is 3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin.
5. A composition as defined in claims 3 or 4, wherein said amine is ethyl p-dimethylaminobenzoate.
6. A composition as defined in claims 3 or 4, wherein said amine is N-methyl-N-benzylaniline.
7. A composition as defined in claims 3 or 4, wherein said amine is a polymer.
8. In a photopolymerizable composition comprising an addition polymerizable acrylate and a co-initiator composition comprising an amine capable of forming a free radical in the presence of a photo-excited carbonyl com-pound, and a carbonyl compound;
the improvement wherein said carbonyl compound is 3-(p-diethylaminocinnamoyl)-7-diethylaminocoumarin.
the improvement wherein said carbonyl compound is 3-(p-diethylaminocinnamoyl)-7-diethylaminocoumarin.
9. In a photopolymerizable composition comprising an addition polymerizable acrylate and a co-initiator composition comprising an amine capable of forming a free radical in the presence of a photo-excited carbonyl com-pound, and a carbonyl compound;
the improvement wherein said carbonyl compound is 3,3'-carbonylbis(7-diethylaminocoumarin).
the improvement wherein said carbonyl compound is 3,3'-carbonylbis(7-diethylaminocoumarin).
10. In a photopolymerizable composition comprising an addition polymerizable acrylate and a co-initiator composition comprising an amine capable of forming a free radical in the presence of a photo-excited carbonyl com-pound, and a carbonyl compound;
the improvement wherein said carbonyl compound is 3,3'-carbonylbis(5,7-di-n-propoxycoumarin).
the improvement wherein said carbonyl compound is 3,3'-carbonylbis(5,7-di-n-propoxycoumarin).
11. In a photopolymerizable composition com-prising an addition polymerizable compound containing ethylenic unsaturation, and a co-initiator composition comprising a carbonyl compound and an activator capable of forming a free radical in the presence of the photo-excited form of said carbonyl compound, said activator having the structure wherein R6, R7 and R8 are the same or different, and are each alkyl or alkoxy containing from 1 to about 20 carbon atoms, or aryl or alkaryl containing from 6 to 10 carbon atoms;
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position, wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position, wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
12. In a photopolymerizable composition comprising an addition polymerizable compound containing ethylenic unsaturation, and a co-initiator composition comprising a carbonyl compound and an activator capable of forming a free radical in the presence of the photo-excited form of said carbonyl compound, said activator having the structure wherein R9, R10 and R11 are the same or different and are each alkyl containing from 1 to about 12 carbon atoms, or aryl or alkaryl containing from 6 to 10 carbon atoms, the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
13. In a photopolymerizable composition com-prising an addition polymerizable compound containing ethylenic unsaturation, and a co-initiator composition comprising a carbonyl compound and a photopolymerization activator responsive in the presence of the photo-excited form of said carbonyl compound to form a free radical, said activator being selected from the group consisting of an amine, an acetic acid derivative, a phosphine, a phosphite, a bismuthine, an arsene, a stibene, a sulfinic acid or a sulfinic acid ester, a sulfone, an .alpha.- or .beta.-dicarbonyl, a ketone, a bi-imidazole, and a stannate;
the improvement wherein said carbonyl compound is selected from the group consisting of 3-(p-nitrobenzoyl)-5,7-di-n-propoxycoumarin 3-(2 benzofuroyl)-7-diethylamlnocoumarin 3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin 7-dimethylamino-3-thenoylcoumarin 3-benzoyl-7-diethylaminocoumarin 3-(o-methoxybenzoyl)-7-diethylaminocoumarin 3-(p-dimethylaminobenzoyl)-7-diethylaminocoumarin 3,3'-carbonylbis(5,7-di-n-propoxycoumarin) 3,3'-carbonylbis(7-diethylaminocoumarin) 3-benzoyl-7-methoxycoumarin 7-diethylamino-3-[3-(2-thienyl)acryloyl]coumarin 3-(2-furoyl)-7-diethylaminocoumarin 3-(p-diethylaminocinnamoyl)-7-diethylaminocoumarin 7-methoxy-3-(3-pyridylcarbonyl)coumarin 3-(4-morpholinocinnamoyl)-7-diethylamlnocoumarin 3-benzoyl-5,7-di-n-propoxycoumarin 7-dimethylamino-3-[3-(2-thienyl)acryloyl]coumarin 9-(7-diethylamino-3 coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 3-(p-cyanobenzoyl)-5,7-di-n-propoxycoumarin 9-(7-n-propylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 9-(4-diethylaminocinnamoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 9-[3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 7-diethylamino-3-(4-dimethylaminocinnamylidene-acetyl)coumarin 9-[3-(9-julolidyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]qulnolazine-10-one 3,3'-carbonylbis(5,7-dibutoxycoumarin) 3,3'-carbonylbis(7-acetoxycoumarin) 5,7,7'-trimethoxy-3,3'-carbonylbiscoumarin 3-cinnamoyl-7-diethylaminocoumarin 7-diethylamino-3-(4-morpholinocinnamoyl)coumarin 7-diethylamino-3-(4-ethoxycinnamoyl)coumarin 3-(4-bromocinnamoyl)-7-diethylaminocoumarin 7-diethylamino-3-[3-(4-methoxy-1-naphthyl)acryoyl]-coumarin 7-diethylamino-3-cinnamylideneacetylcoumarin 9-[3-(2 thienyl)acryloyl]-1,2,4,5-tetrahydro-3H, 6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 7-diethylamino-3-(3-fluorosulfonylbenzoyl)coumarin 3-(4-methoxybenzoyl)-5,7-di-n-propoxycoumarin 3-(4-nitrobenzoyl)-5,7-di-n-propoxycoumarin 3-(3-trifluoromethylbenzoyl)-5,7-di-n-propoxycoumarin 3-(4-cyanobenzoyl)-7-diethylamlnocoumarin 3-benzoyl-5,7-dimethoxycoumarin 3-benzoyl-5,7-diethoxycoumarin 3-benzoyl-6-methoxycoumarin 3-benzoyl-8-ethoxycoumarin 3-benzoylbenzo[f]coumarin 5,7-diethoxy-3-(2-thenoyl)coumarin 3-(2-benzofuroyl)-5,7-diethoxycoumarin 3-benzoyl-7-hydroxycoumarin 7-acetoxy-3-benzoylcoumarin 7-methoxy-3-(4-methoxybenzoyl)coumarin 3-(4-fluorosulfonylbenzoyl)-7-methoxycoumarin 3-(4-ethoxycinnamoyl)-7-methoxycoumarin 3-benzoyl-7-dimethylamlnocoumarin 3-benzoyl-7-diethylaminocoumarln 3-benzoyl-7-pyrrolidinylcoumarin 3-(4-iodobenzoyl)-7-dimethylaminocoumarin 3-(4-iodobenzoyl)-7-diethylaminocoumarin 7-dimethylamino-3-(4-dimethylamlnobenzoyl)coumarin 7-diethylamino-3-(4-nitrol)enzoyl)coumarin 7-diethylamino-3-(2-thenoyl)coumarin 7-pyrrolidinyl-3-(2-thenoyl)coumarin 7-diethylamlno-3-(2-furoyl)coumarin 7-diethylamino-3-(2-methoxybenzoyl)coumarln 3,3'-carbonylbiscoumarin 3,3'-carbonylbis(7 methoxycoumarin) 3,3'-carbonylbis(6-methoxycoumarin) 3,3'-carbonylbis(5,7 dimethoxycoumarin) 333'-carbonylbis(5,7-diethoxycoumarin) 3,3'-carbonylbis(5,7-diiso-propoxycoumarin);
said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
the improvement wherein said carbonyl compound is selected from the group consisting of 3-(p-nitrobenzoyl)-5,7-di-n-propoxycoumarin 3-(2 benzofuroyl)-7-diethylamlnocoumarin 3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin 7-dimethylamino-3-thenoylcoumarin 3-benzoyl-7-diethylaminocoumarin 3-(o-methoxybenzoyl)-7-diethylaminocoumarin 3-(p-dimethylaminobenzoyl)-7-diethylaminocoumarin 3,3'-carbonylbis(5,7-di-n-propoxycoumarin) 3,3'-carbonylbis(7-diethylaminocoumarin) 3-benzoyl-7-methoxycoumarin 7-diethylamino-3-[3-(2-thienyl)acryloyl]coumarin 3-(2-furoyl)-7-diethylaminocoumarin 3-(p-diethylaminocinnamoyl)-7-diethylaminocoumarin 7-methoxy-3-(3-pyridylcarbonyl)coumarin 3-(4-morpholinocinnamoyl)-7-diethylamlnocoumarin 3-benzoyl-5,7-di-n-propoxycoumarin 7-dimethylamino-3-[3-(2-thienyl)acryloyl]coumarin 9-(7-diethylamino-3 coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 3-(p-cyanobenzoyl)-5,7-di-n-propoxycoumarin 9-(7-n-propylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 9-(4-diethylaminocinnamoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 9-[3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 7-diethylamino-3-(4-dimethylaminocinnamylidene-acetyl)coumarin 9-[3-(9-julolidyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]qulnolazine-10-one 3,3'-carbonylbis(5,7-dibutoxycoumarin) 3,3'-carbonylbis(7-acetoxycoumarin) 5,7,7'-trimethoxy-3,3'-carbonylbiscoumarin 3-cinnamoyl-7-diethylaminocoumarin 7-diethylamino-3-(4-morpholinocinnamoyl)coumarin 7-diethylamino-3-(4-ethoxycinnamoyl)coumarin 3-(4-bromocinnamoyl)-7-diethylaminocoumarin 7-diethylamino-3-[3-(4-methoxy-1-naphthyl)acryoyl]-coumarin 7-diethylamino-3-cinnamylideneacetylcoumarin 9-[3-(2 thienyl)acryloyl]-1,2,4,5-tetrahydro-3H, 6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one 7-diethylamino-3-(3-fluorosulfonylbenzoyl)coumarin 3-(4-methoxybenzoyl)-5,7-di-n-propoxycoumarin 3-(4-nitrobenzoyl)-5,7-di-n-propoxycoumarin 3-(3-trifluoromethylbenzoyl)-5,7-di-n-propoxycoumarin 3-(4-cyanobenzoyl)-7-diethylamlnocoumarin 3-benzoyl-5,7-dimethoxycoumarin 3-benzoyl-5,7-diethoxycoumarin 3-benzoyl-6-methoxycoumarin 3-benzoyl-8-ethoxycoumarin 3-benzoylbenzo[f]coumarin 5,7-diethoxy-3-(2-thenoyl)coumarin 3-(2-benzofuroyl)-5,7-diethoxycoumarin 3-benzoyl-7-hydroxycoumarin 7-acetoxy-3-benzoylcoumarin 7-methoxy-3-(4-methoxybenzoyl)coumarin 3-(4-fluorosulfonylbenzoyl)-7-methoxycoumarin 3-(4-ethoxycinnamoyl)-7-methoxycoumarin 3-benzoyl-7-dimethylamlnocoumarin 3-benzoyl-7-diethylaminocoumarln 3-benzoyl-7-pyrrolidinylcoumarin 3-(4-iodobenzoyl)-7-dimethylaminocoumarin 3-(4-iodobenzoyl)-7-diethylaminocoumarin 7-dimethylamino-3-(4-dimethylamlnobenzoyl)coumarin 7-diethylamino-3-(4-nitrol)enzoyl)coumarin 7-diethylamino-3-(2-thenoyl)coumarin 7-pyrrolidinyl-3-(2-thenoyl)coumarin 7-diethylamlno-3-(2-furoyl)coumarin 7-diethylamino-3-(2-methoxybenzoyl)coumarln 3,3'-carbonylbiscoumarin 3,3'-carbonylbis(7 methoxycoumarin) 3,3'-carbonylbis(6-methoxycoumarin) 3,3'-carbonylbis(5,7 dimethoxycoumarin) 333'-carbonylbis(5,7-diethoxycoumarin) 3,3'-carbonylbis(5,7-diiso-propoxycoumarin);
said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
14. In a photopolymerizable element comprising a support and on the support a layer comprising an addition polymerizable compound containing ethylenic unsaturation, and a co-initiator composition comprising a carbonyl com-pound and a photopolymerization activator responsive in the, presence of the photo-excited form of said carbonyl compound to form a free radical, said activator being selected from the group consisting of an amine, an acetic acid derivative, a phosphine, a phosphite, a bismuthine, an arsene, a sti-bene, a sulfinic acid, a sulfinic acid ester, a sulfone, an .alpha.- or .beta.-dicarbonyl, a ketone, a bi-imidazole, and a stannate;
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source, a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
15. In a method of photopolymerizing a composition by exposing it to activating radiation, the composition com-prising an addition polymerizable compound containing ethyl-enic unsaturation and a co-initiator composition including a carbonyl compound and a photopolymerization activator re-sponsive in the presence of the photo-excited form of said carbonyl compound to form a free radical, said activator being selected from the group consisting of an amine, an acetic acid derivative, a phosphine, a phosphite, a bis-muthine, an arsene, a stibene, a sulfinic acid, a sulfinic acid ester, a solfone, an .alpha.- or .beta.-dicarbonyl, a ketone, a bi-imidazole, and a stannate;
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source 3 a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
the improvement wherein said carbonyl compound is a coumarin having an absorption maximum between about 250 and about 550 nm and a substituent in the 3-position wherein R1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 nuclear carbon and hetero atoms, said coumarin and said activator being present in an amount sufficient to provide, when the composition is coated, dried and exposed to a medium pressure mercury light source 3 a speed that is at least about one-fifth that of the same composition coated, dried and exposed identically except with a co-initiator consisting of Michler's ketone and benzophenone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4966179A | 1979-06-18 | 1979-06-18 | |
| US49,661 | 1979-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1137695A true CA1137695A (en) | 1982-12-14 |
Family
ID=21961008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000336005A Expired CA1137695A (en) | 1979-06-18 | 1979-09-20 | Photopolymerizable compositions featuring novel co-initiators |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS564604A (en) |
| CA (1) | CA1137695A (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6016958A (en) * | 1983-07-07 | 1985-01-28 | Asahi Chem Ind Co Ltd | Novel functional monomer and photo-polymerizable composition containing the same |
| GB2189496B (en) * | 1986-04-23 | 1989-11-29 | Hitachi Chemical Co Ltd | Photopolymerizable composition |
| JPH06689B2 (en) * | 1986-09-05 | 1994-01-05 | 宇部興産株式会社 | Photopolymerizable dental material |
| JPS6454440A (en) * | 1987-08-24 | 1989-03-01 | Toyo Boseki | Photopolymerizable composition |
| DE3918105A1 (en) * | 1988-06-02 | 1989-12-14 | Toyo Boseki | PHOTOPOLYMERIZABLE COMPOSITION |
| JP2801007B2 (en) * | 1988-07-19 | 1998-09-21 | キヤノン株式会社 | recoding media |
| JPH02114266A (en) * | 1988-10-24 | 1990-04-26 | Toyobo Co Ltd | Photopolymerizable composition |
| JP2003002861A (en) * | 2001-06-20 | 2003-01-08 | Hayashibara Biochem Lab Inc | Enone compound |
| JP4658512B2 (en) * | 2004-04-27 | 2011-03-23 | 日本臓器製薬株式会社 | Coumarin derivative and Maillard reaction inhibitor containing the derivative |
| JP2006273848A (en) * | 2005-03-02 | 2006-10-12 | Sumitomo Chemical Co Ltd | Application of cinnamoyl compound |
| US20090143368A1 (en) * | 2005-03-02 | 2009-06-04 | Hiroaki Shiraki | Use of Cinnamoyl Compound |
| EP2870147B1 (en) * | 2012-07-27 | 2019-02-20 | Sun Chemical Corporation | Ketocoumarins as photoinitiators and photosensitizers in inks |
| ITVA20120041A1 (en) * | 2012-10-22 | 2014-04-23 | Lamberti Spa | 3-CHETOCUMARINE FOR PHOTOPOLYMERIZATIONS THROUGH LED |
| JP7255067B2 (en) * | 2017-08-09 | 2023-04-11 | アイジーエム・グループ・ベスローテン・フェンノートシャップ | Multifunctional polymer photoinitiator |
| WO2020130120A1 (en) * | 2018-12-20 | 2020-06-25 | 学校法人京都薬科大学 | Cancer metastasis inhibitor |
| CN113518805B (en) * | 2018-12-28 | 2023-08-08 | 意大利艾坚蒙树脂有限公司 | Photoinitiator |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3650917A (en) * | 1969-08-25 | 1972-03-21 | Phillips Petroleum Co | Recovery of products from electrochemical fluorination |
| US3682641A (en) * | 1970-03-23 | 1972-08-08 | Du Pont | Photoresist developer extender baths containing polyoxyalkylene ethers and esters and process of use |
| US3729404A (en) * | 1971-09-10 | 1973-04-24 | Grace W R & Co | Photocurable polyene-polythiol polymers using a phosphine plus an additional sensitizer |
| US3933682A (en) * | 1973-01-31 | 1976-01-20 | Sun Chemical Corporation | Photopolymerization co-initiator systems |
-
1979
- 1979-09-20 CA CA000336005A patent/CA1137695A/en not_active Expired
-
1980
- 1980-06-18 JP JP8267080A patent/JPS564604A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS564604A (en) | 1981-01-19 |
| JPH0232285B2 (en) | 1990-07-19 |
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