CA1269791A - Curable composition and the use thereof - Google Patents
Curable composition and the use thereofInfo
- Publication number
- CA1269791A CA1269791A CA000454404A CA454404A CA1269791A CA 1269791 A CA1269791 A CA 1269791A CA 000454404 A CA000454404 A CA 000454404A CA 454404 A CA454404 A CA 454404A CA 1269791 A CA1269791 A CA 1269791A
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- polymerised
- cations
- arene
- free radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
- C08F4/82—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals pi-Allyl complexes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
Abstract
Curable composition and the use thereof Abstract Iron (II)-aromatic compound complexes mixed with electron acceptors as an oxidising agent are suitable initiators for the polymerised by irradiation of organic material which can be polymerised by cations and/or free radicals. The composition composed of the polymerisable material and of the initiator mixture is suitable for the production of protective coatings and can be used as a photographic recording material.
Description
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Case 6-1/~431/=
Curable composition and the use thereof The present invention relates to a curable composi-tion composed of a) a material which can be polymerised by cations and/or by free radicals, b) an iron(II~-aromatic com-pound complex and c) an oxidising agent, a process for poly-merising such material by the action of radiation, a mate-rial coated with the composition and the use thereof.
It is known from the literature that, for example, iodon;um, sulfonium and diazonium salts are suitable photo-initiators for the radiation-induced polymerisation of orga-nic material which can be polymerised by cations (see, for example~ German Auslegeschrift 2,518~639, J. Polym. Sci., Polymer Chemistry Ed., 17, 1059 t1979)~ Makromol. Chem., Suppl. 3, 348 (1979~ German Offenlegungsschriften 2,520,489,
Case 6-1/~431/=
Curable composition and the use thereof The present invention relates to a curable composi-tion composed of a) a material which can be polymerised by cations and/or by free radicals, b) an iron(II~-aromatic com-pound complex and c) an oxidising agent, a process for poly-merising such material by the action of radiation, a mate-rial coated with the composition and the use thereof.
It is known from the literature that, for example, iodon;um, sulfonium and diazonium salts are suitable photo-initiators for the radiation-induced polymerisation of orga-nic material which can be polymerised by cations (see, for example~ German Auslegeschrift 2,518~639, J. Polym. Sci., Polymer Chemistry Ed., 17, 1059 t1979)~ Makromol. Chem., Suppl. 3, 348 (1979~ German Offenlegungsschriften 2,520,489,
2,854,011 and 3~021,376, U.S. Patent Specification 4,210,449 and British Patent Applicat;on 2,046,269A). Owing to their relatively low-wavelength absorption range (about 190 to 400 nm), these known photoinitiators require the use of sen-sitisers, such as coloured polycyclic hydrocarbons, for ex-ample perylene dyes, aromatic amines~ benzoin alkyl ethers or alkoxyacetophenones, in order to cure, by the ac~ion of light, systems which can be polymerised by cations. The curing by heat of systems containing such photo;nitiators is preferably carried out in the presence of reducing agents, such as copper, tin, iron or cobalt salts, thiophenols, as-corbic acid and the like.
Our own investigations have shown that metallocene complex salts are photoinit;ators for organic materials poly-merisable by cations, and do not require the concomitant use - ~ ~
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o~ sens;tisers. These mater;als can be cured e;ther w;th-out further treatment at high temperatures or, after the act;on of rad;at;on, at temperatures h;gher than the tem-perature of irradiation. It would be more advantageous if the polymer;sation could be carr;ed out at even lower tem-peratures or merely by the act;on o~ irradiation and the heating due to the heat of polymerisation. It is also de-s;rable that it should be possible to polymerise organic materials ~hich can be polymerised simultaneously by cat-;ons or free radicals or by both mechanisms, by means o~ a photo;nitiator and under the action of radiat;on.
The object of the present invention ;s to prov;de a curable composition meeting these requirements.
The present invention relates to a curable composi-t;on contain;ng a) at least one material wh;ch can be poly-merised by free radicals or by cations, or at least one material which can be polymer;sed by free radicals and cat-ions, b) at least one iron compound of the formula I
[(R )(R2FeII) ]+a _ ~LQ ) q ~I), ;n ~hich a is 1 or 2 and q is 1, 2 or 3, L is a d;valent to heptavalent metal or non-metal, Q is a halogen atom, m is an integer corresponding to the sum of the valenc;es of L and q, R1 is a ~-arene and R2 is the anion of a1r-arene, and c~ at least one electron acceptor as an oxidising agent.
Su;table ~-arenes R1 are, ;n particular, aromatic groups having 6 to 24 carbon atoms or hetero-aromatic groups having 3 to 20 carbon atoms, it being possible for these groups to be unsubstituted or monosubstituted or polysubsti~
tuted by identical or different monovalent radicals, such as halogen atoms, preferably chlorine or bromine atoms, or C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8 alkoxy, cyano, C1-C8-alkylthio, alkyl Cz-C6-monocarboxy-late, phenyl, c2-c5-alkanoyl or benzoyl groups. These ~-arene groups can be mononuclear sys~ems, condensed polynuc-lear systems or non-condensed polynuclear systems, it being X
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12~979 poss;ble in the last-mentioned systems for the nuclei to be linked directly or via bridge members, such as -S- or -O-.
As the anion of a ~-arene, R2 can be an anion of a ~-arene of the type ment;oned above, for example the inde-nyl anion and, in particular, the cyclopentadienyl anion, it be;ng also poss;ble for these an;ons to be unsubst;tuted or monosubstituted or polysubstituted by identical or dif-ferent monovalent radicals, such as C1-C8-alkyl, C2-C8-alkenyl, C2-c8-alkynyl~ alkyl ~2-C6-monocarboxylate, cyano, c2-c5-alkanoyl or benzoyl groups.
The alkyl, alkoxy, alkylthio, alkyl monocarboxylate and alkanoyl substituents can be linear or branched. Typi~
cal alkyl, alkoxy, alkylthio, alkyl monocarboxylate or alka-noyl substituents which may be mentioned are methyl, ethyl, n-propyl, ;sopropyl, n-butyl, sec.-butyl, ter.t-butyl, n-pentyl, n-hexyl and n-octyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-hexyloxy and n-octyloxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, n-pen-tylthio and n-hexylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl and n-pentyl carboxylate, and acetyl, propionyl, butyryl and valeroyl, respectively. In this respect, preference attaches to alkyl, alkoxy, alkylthio and alkyl monocarboxylate groups having 1 to 4, and especially 1 or 2, carbon atoms in the alkyl moieties, and to alkanoyl groups having 2 or 3 carbon atoms. Preferred substituted ~-arenes or anions of substituted ~-arenes are those containing one or two o-f the abovementioned substituents, in particular chlorine or bromine atoms or methyl, ethyl, methoxy, ethoxy, cyano, methyl or ethyl carboxylate and acetyl groups.
Suitable hetero-aromatic ~-arenes are systems con-taining S, N and/or O atoms. Hetero-aromatic ~-arenes con-taining S and/or O atoms are preferred~ Examples oi suit-able ~-arenes are benzene, toluene, xylenes, ethylbenzene, methoxybenzene, ethoxybenzene~ dimethoxybenzene, p-chloro-toluene, chlorobenzene, bromobenzene, dichlorobenzene, ace-tylbenzene, trimethylben2ene, trimethoxybenzene, naphtha-:' '' , ~,. ~"' ' .
37<3~
lene, 1,2-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalene, methylnaphthalenes, methoxynaphthalenes, ethoxynaphthalenes, chloronaphthalenes, bromonaphthalenes, b;phenyl, indene, biphenylene, fluorene, phenanthrene, anthracene, 9,10-di-hydroanthracene, tr;phenylene, pyrene, naphthacene, coronene, th;ophene, chromene, xanthene, thioxanthene, ben20th;0phene, naphthoth;ophene, thianthrene, diphenylene oxide, d;phenyl-ene sulf;de, acr;dine and carbazole.
Examples of anions of substituted ~-arenes are the anions of methylcyclopentadiene, ethylcyclopentadiene, n-propylcyclopentadiene and n-butylcyclopentadiene and the anions of d;methylcyclopentad;ene, methyl and ethyl cyclo-pentadiene-carboxylate and acetylcyclopentadiene, prop;onyl-cyclopentad;ene, cyanocyclopentadiene and benzoylcyclopenta-diene Preferred anions are the an;on of unsubstituted in-dene and especially of unsubstituted cyclopentadiene.
Preferably, a has a value of 1 and R1 ;s benzene, toluene, xylene, methoxybenzene, chlorobenzene, p-chloroto-luene, naphthalene, methylnaphthalene, chloronaphthalene, methoxynaphthalene, biphenyl, indene, pyrene, perylene or diphenylene sulfide and R2 is the anion of cyclopentadiene, acetylcyclopentad;ene, methylcyclopentad;ene, phenylcyclo-pentadiene or indene.
Complexes of the formula I wh;ch are part;cularly preferred are those in which a is 1, R1 is ~6-pyrene or -naphthalene and R2 ;s the an;on of ~5-cyclopentad;ene.
Examples of su;table metals or non-metals L are Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn and Cu; lan-thanides, such as Ce, Pr and Nd, or act;n;des, such as Th, Pa, U or Np. Suitable non-metals are, in particular, B, P
and As. L is preferably P, As, B or Sb, P be;ng particu-larly preferred. As the halogen atom, Q is preferably Cl and especially F.
Examples of complex an;ons [LQm] q are BF4 , PF6 , AsF6 , SbF6 , FeCl4 , SnCl62 , SbCl6 and BiCl6 . The particularly preferred complex an;ons are SbF6 , sF4 , AsF6 and PF~ .
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The compounds of the formula I are known or can be prepared by analogous processes.
The electron acceptors used as an oxidising agent are preferably an organic hydroperoxide, an organic per-acid or a qu;none.
The following are examples: tertiary butyl hydroper-oxide, cumene hydroperoxide, triphenylmethyl hydroperoxide, tetralin hydroperoxide, ~-methyltetralin hydroperoxide, de-calin hydroperoxide, perbenzoic acid, m-chloroperbenzoic acid or benzoquinone.
Examples of organic materials which can be polymer-ised by cations and are suitable for the curable composi-tions according to the invention are those of the following types, it being possible to use these on their own or as mixtures of at least two components:
I. Ethylenically unsaturated compounds which can be polymerised by a cationic mechanism. These include 1. mono-olefins and diolefins, for example isobutylene, butadiene, isoprene, styrene, ~-methylstyrene, divinylbenzenes, N-vinylpyrrolidone, N-vinylcarbazole and acroleine~ 2~ Vinyl ethers, for example methyl vinyl ether, isobutyl vinyl ether, trimethylolpropane trivinyl ether and ethylene glycol di-vinyl ether; and cyclic vinyl ethers, for example 3,4-di-hydro-2-formyl-2H-pyrane tdimeric acroleine) and the 3,4-dihydro-2H-pyran-2-carboxylic acid ester of 2-hydroxymethyl-
Our own investigations have shown that metallocene complex salts are photoinit;ators for organic materials poly-merisable by cations, and do not require the concomitant use - ~ ~
~ 2 _ ~2~9'7~
o~ sens;tisers. These mater;als can be cured e;ther w;th-out further treatment at high temperatures or, after the act;on of rad;at;on, at temperatures h;gher than the tem-perature of irradiation. It would be more advantageous if the polymer;sation could be carr;ed out at even lower tem-peratures or merely by the act;on o~ irradiation and the heating due to the heat of polymerisation. It is also de-s;rable that it should be possible to polymerise organic materials ~hich can be polymerised simultaneously by cat-;ons or free radicals or by both mechanisms, by means o~ a photo;nitiator and under the action of radiat;on.
The object of the present invention ;s to prov;de a curable composition meeting these requirements.
The present invention relates to a curable composi-t;on contain;ng a) at least one material wh;ch can be poly-merised by free radicals or by cations, or at least one material which can be polymer;sed by free radicals and cat-ions, b) at least one iron compound of the formula I
[(R )(R2FeII) ]+a _ ~LQ ) q ~I), ;n ~hich a is 1 or 2 and q is 1, 2 or 3, L is a d;valent to heptavalent metal or non-metal, Q is a halogen atom, m is an integer corresponding to the sum of the valenc;es of L and q, R1 is a ~-arene and R2 is the anion of a1r-arene, and c~ at least one electron acceptor as an oxidising agent.
Su;table ~-arenes R1 are, ;n particular, aromatic groups having 6 to 24 carbon atoms or hetero-aromatic groups having 3 to 20 carbon atoms, it being possible for these groups to be unsubstituted or monosubstituted or polysubsti~
tuted by identical or different monovalent radicals, such as halogen atoms, preferably chlorine or bromine atoms, or C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8 alkoxy, cyano, C1-C8-alkylthio, alkyl Cz-C6-monocarboxy-late, phenyl, c2-c5-alkanoyl or benzoyl groups. These ~-arene groups can be mononuclear sys~ems, condensed polynuc-lear systems or non-condensed polynuclear systems, it being X
...... .
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, ~.
12~979 poss;ble in the last-mentioned systems for the nuclei to be linked directly or via bridge members, such as -S- or -O-.
As the anion of a ~-arene, R2 can be an anion of a ~-arene of the type ment;oned above, for example the inde-nyl anion and, in particular, the cyclopentadienyl anion, it be;ng also poss;ble for these an;ons to be unsubst;tuted or monosubstituted or polysubstituted by identical or dif-ferent monovalent radicals, such as C1-C8-alkyl, C2-C8-alkenyl, C2-c8-alkynyl~ alkyl ~2-C6-monocarboxylate, cyano, c2-c5-alkanoyl or benzoyl groups.
The alkyl, alkoxy, alkylthio, alkyl monocarboxylate and alkanoyl substituents can be linear or branched. Typi~
cal alkyl, alkoxy, alkylthio, alkyl monocarboxylate or alka-noyl substituents which may be mentioned are methyl, ethyl, n-propyl, ;sopropyl, n-butyl, sec.-butyl, ter.t-butyl, n-pentyl, n-hexyl and n-octyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-hexyloxy and n-octyloxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, n-pen-tylthio and n-hexylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl and n-pentyl carboxylate, and acetyl, propionyl, butyryl and valeroyl, respectively. In this respect, preference attaches to alkyl, alkoxy, alkylthio and alkyl monocarboxylate groups having 1 to 4, and especially 1 or 2, carbon atoms in the alkyl moieties, and to alkanoyl groups having 2 or 3 carbon atoms. Preferred substituted ~-arenes or anions of substituted ~-arenes are those containing one or two o-f the abovementioned substituents, in particular chlorine or bromine atoms or methyl, ethyl, methoxy, ethoxy, cyano, methyl or ethyl carboxylate and acetyl groups.
Suitable hetero-aromatic ~-arenes are systems con-taining S, N and/or O atoms. Hetero-aromatic ~-arenes con-taining S and/or O atoms are preferred~ Examples oi suit-able ~-arenes are benzene, toluene, xylenes, ethylbenzene, methoxybenzene, ethoxybenzene~ dimethoxybenzene, p-chloro-toluene, chlorobenzene, bromobenzene, dichlorobenzene, ace-tylbenzene, trimethylben2ene, trimethoxybenzene, naphtha-:' '' , ~,. ~"' ' .
37<3~
lene, 1,2-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalene, methylnaphthalenes, methoxynaphthalenes, ethoxynaphthalenes, chloronaphthalenes, bromonaphthalenes, b;phenyl, indene, biphenylene, fluorene, phenanthrene, anthracene, 9,10-di-hydroanthracene, tr;phenylene, pyrene, naphthacene, coronene, th;ophene, chromene, xanthene, thioxanthene, ben20th;0phene, naphthoth;ophene, thianthrene, diphenylene oxide, d;phenyl-ene sulf;de, acr;dine and carbazole.
Examples of anions of substituted ~-arenes are the anions of methylcyclopentadiene, ethylcyclopentadiene, n-propylcyclopentadiene and n-butylcyclopentadiene and the anions of d;methylcyclopentad;ene, methyl and ethyl cyclo-pentadiene-carboxylate and acetylcyclopentadiene, prop;onyl-cyclopentad;ene, cyanocyclopentadiene and benzoylcyclopenta-diene Preferred anions are the an;on of unsubstituted in-dene and especially of unsubstituted cyclopentadiene.
Preferably, a has a value of 1 and R1 ;s benzene, toluene, xylene, methoxybenzene, chlorobenzene, p-chloroto-luene, naphthalene, methylnaphthalene, chloronaphthalene, methoxynaphthalene, biphenyl, indene, pyrene, perylene or diphenylene sulfide and R2 is the anion of cyclopentadiene, acetylcyclopentad;ene, methylcyclopentad;ene, phenylcyclo-pentadiene or indene.
Complexes of the formula I wh;ch are part;cularly preferred are those in which a is 1, R1 is ~6-pyrene or -naphthalene and R2 ;s the an;on of ~5-cyclopentad;ene.
Examples of su;table metals or non-metals L are Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn and Cu; lan-thanides, such as Ce, Pr and Nd, or act;n;des, such as Th, Pa, U or Np. Suitable non-metals are, in particular, B, P
and As. L is preferably P, As, B or Sb, P be;ng particu-larly preferred. As the halogen atom, Q is preferably Cl and especially F.
Examples of complex an;ons [LQm] q are BF4 , PF6 , AsF6 , SbF6 , FeCl4 , SnCl62 , SbCl6 and BiCl6 . The particularly preferred complex an;ons are SbF6 , sF4 , AsF6 and PF~ .
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The compounds of the formula I are known or can be prepared by analogous processes.
The electron acceptors used as an oxidising agent are preferably an organic hydroperoxide, an organic per-acid or a qu;none.
The following are examples: tertiary butyl hydroper-oxide, cumene hydroperoxide, triphenylmethyl hydroperoxide, tetralin hydroperoxide, ~-methyltetralin hydroperoxide, de-calin hydroperoxide, perbenzoic acid, m-chloroperbenzoic acid or benzoquinone.
Examples of organic materials which can be polymer-ised by cations and are suitable for the curable composi-tions according to the invention are those of the following types, it being possible to use these on their own or as mixtures of at least two components:
I. Ethylenically unsaturated compounds which can be polymerised by a cationic mechanism. These include 1. mono-olefins and diolefins, for example isobutylene, butadiene, isoprene, styrene, ~-methylstyrene, divinylbenzenes, N-vinylpyrrolidone, N-vinylcarbazole and acroleine~ 2~ Vinyl ethers, for example methyl vinyl ether, isobutyl vinyl ether, trimethylolpropane trivinyl ether and ethylene glycol di-vinyl ether; and cyclic vinyl ethers, for example 3,4-di-hydro-2-formyl-2H-pyrane tdimeric acroleine) and the 3,4-dihydro-2H-pyran-2-carboxylic acid ester of 2-hydroxymethyl-
3,4-dihydro-2H-pyran. 3. Vinyl esters, for example vinyl acetate and vinyl stearate.
II. Heterocyclic compounds which can by polymerised by cations, for example ethylene oxide, propylene oxide, epichlorohydrin and glycidyl ethers of monohydric alcohols or phenols, for example n-butyl glycidyl ether, n~octyl gly-cidyl ether, phenyl glycidyl ether and cresyl glyc;dyl ether; glycidyl acrylate, glycidyl methacrylate, styrene oxide and cyclohexene oxide; oxetans~ such as 3,3~dimethyl-oxetane and 3,3-di-(chloromethyl)-oxetane; tetrahydrofuran;
dioxolane, trioxane and 1,3,6-trioxacyclooctane; lactones, such as ~-propiolactone, ~-valerolactone and -caProlactone;
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th;;ranes, such as ethylene sulf;de and propylene sulfide;
azet;d;nes, such as N-acylazet;d;nes, for example N-benzoyl-azet;d;ner and the adducts of a~e-t;dine with d;isocyanates, for example toluylene~2,4-d;isocyanate and toluylene-2,6-d;;socyanate and 4,4'-d;am;nod;phenylmethane d;;socyanate;
epoxy res;ns; and l;near and branched polymers hav;ng gly-c;dyl groups ;n the s;de cha;ns, for example homopolymers and copolymers of polyacrylate and polymethacrylate glyc;-dyl esters.
Part;cularly important representatives of these polymer;sable compounds mentioned above are the epox;de re-s;ns and, ;n part;cular, the d;epoxides and polyepoxides and epox;de resin prepolymers of the type used for the prepara-t;on of crossl;nked epoxy res;ns. The d;epoxides and poly-epox;des can be al;phat;c, cycloal;phatic or aromat;c com-pounds. Examples of such compounds are the glycidyl ethers and ~-methyl glycidyl ethers of aliphatic or cyGloaliphat;c d;ols or polyols, for example those of ethylene glycol, pro-pane-1,2-d;ol, propane-1,3-d;ol, butane 1,4-diol, d;ethyl-ene glycol, polyethylene glycol, polypropylene glycol, gly-cerol, tr;methylolpropane or 1,4-d;methylolcyclohexane or those of 2,2-bis-(4-hydroxycyclohexyl)-propane and N,N-bis-(2-hydroxyethyl)-an;l;ne; and the glycidyl ethers of d;phe-nols and polyphenols, for example resorcinol, 4,4'-d;hydroxy-d;phenylmethane, 4,4'-d;hydroxyd;phenyl-2,2-propane, novo-laks and 1,1,2,2-tetrakis-~4-hydroxyphenyl)-ethane. Further examples are N-glycidyl compounds, for example the d;glyc;-dyl compounds of ethyleneurea, 1,3-propyleneurea or 5-d;-methylhydanto;n or of 4,4'-methylene-5,5'-tetramethyld;hy-dantoin or compounds such as tr;glycidyl isocyanurate.
Further glycidyl compounds of industrial importance are the glycidyl esters of carboxylic acids, in particular dicarboxylic and polycarboxylic acids. Examples of these are the glycidyl esters of succinic acid, adipic acid, aze-laic acid, sebacic acid, phthal;c acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid~ isophthalic acid or trimellitic acid or of dimer;sed fatty acids.
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Examples of polyepox;des other than glyc;dyl com-pounds are the diepoxides of vinylcyclohexene and clicyclo-pentadiene, 3-(3l,4'-epoxycyclohexyl)-8,9-epoxy-Z,4~d;oxa-sp;roCS.S]undecane and of 3',4'-epoxycyclohexylmethyl 3,~-epoxycyclohexanecarboxylate, butad;ene d;epox;de or lso-prene d;epox;de, epoxid;sed l;noleic acid derivat;ves or epoxidised polybutad;ene.
Preferred epoxide resins are diglyctdyl ethers, which may be so-called advanced, of dihydric phenols or di-hydric aliphatic alcohols having 2 to 4 carbon atoms. The diglycidyl ethers, which may be so-called advanced, of 2,2-bis-(4-hydroxyphenyl)-propane and of bis-~4-hydroxyphenyl)-methane are particularly preferred.
Further su;table compounds which can be polymerised by cations are the following: III. Methylol compounds:
1. AminopLasts, such as the N-hydroxymethyl, N-methoxymethyl, N-n-butoxymethyl and N-acetoxymethyl derivatives of amides or amide-like compounds, for example cyclic ureas, such as ethyleneurea (imidazolidin-2-one), hydantoin, urone (tetra-hydrooxadiaz;n~4-one), 1,2-propyleneurea (4-methylim;dazol;~
din-2-one), 1,3-propyleneurea (hexahydro-2H-pyrimid-2-one), hydroxypropyleneurea (5-hydroxyhexahydro-2H-pyrimid-2-one), 1,3,5-melamine and further polytriazines, such as acetogu-anam;ne, benzoguanam;ne and adipoguanam;ne.
If des;red it is possible to employ aminoplasts con-ta;ning both N-hydroxymethyl and N-alkoxymethyl groups or both N-hydroxymethyl and N-acetoxymethyl groups (for example a hexamethylolmelamine in wh;ch 1 to 3 of the hydroxyl groups are etherified with methyl groups).
Preferred aminoplasts are the condensation products of urea, urone, hydantoin or melamine with formaldehyde and also partially or completely etherified products of such condensation products with an aliphatic, monohydric alcohol having 1 to 4 carbon atoms.
2, Phenoplasts. Preferred phenoplasts are resols prepared from a phenol and an aldehyde. Suitable phenols include phenol itself, resorcinol, 2,2 bis-(p-hydroxyphenyl)-pro-': "":' :`
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pane, p-chlorophenol, a phenol which is substituted by one or two alkyl groups each of which has 1 ~o 9 carbon atoms, such as o-, m- and p-cresol, the xylenols, p-tert.-butyl-phenol and p-nonylphenol and also phenyl-substituted phe-nols, in particular p-phenylphenol. The aldehyde which is condensed with the phenol is preferably formaldehyde, but other aldehydes, such as acetaldehyde and furfural, are also suitable. If desired, a mixture of such curable phenol/
aldehyde resins can be used~
The preferred resols are condensation products of phenol, p-chlorophenol, resorcinol or o-, m- or p-cresol with formaldehyde.
Suitable organic materials which can be polymerised by free radicals are, in particular, monoethylenically or polyethylenically unsaturated compounds. The follow7ng are examples: styrene, vinylpyr;dine, v;nyl acetate, divinylben-zene, vinyl ethers, acrylamide~ methacrylamide9 bisacryl-amide, bismethacrylamide and unsaturated polyesters, parti-cularly those based on male;c acid. Preferred materials are the esters or amides of acrylic acid and/or methacrylic acid with linear or branched alcohols, polyols or monoamines or polyamines, respectively. The polyols and polyamines can also be in the form of partial esters.
Examples of polyamines are ethylenediamine, propyl-enediamine, butylenediamine, hexylenediamine, phenylenedi-amine, benzylened;am-7ne, naphthylenediamine, d;ethylenetri-amine, triethylenetetramine and diaminoethyl ethers~ Examples of polyols are l;near and branched alkylenediols, such as ethylenediol, propylenediol, butylenediol, pentylenediol, hexylenediol, octylenediol, polyoxaalkylenediols, such as diethylene and triethylene glycol and polyethylene glycols having a molecular weight of ZOO to 500, 1,4-dihydroxycyclo-hexane, 1,4-di-(hydroxymethyl)-cyclohexane, d;hydroxyben-zenes, hydroxymethylphenols, triols, such as 1,2,3-trihy-droxypropane, 1,2,~-trihydroxybutane and trimethylolpropane, pentaerythritol, dipentaerythritol and low-molecular poly-esters contain;ng hydroxyl end groups.
: .... ..
. . :
': .~
7~3~
_ 9 _ Examples of suitable alcohols and monoamines are methanol, ethanol, propanol, butanol~ pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, cyclohexanol, phenol, glyc;dyl, methylam;ne, d;methylam;ne and ethylam;ne.
Examples of organ;c materials wh;ch can be polymer-ised by cations and free radicals are m;xtures of the above-ment;oned mater;als wh;ch can be polymer;sed by cat;ons and free rad;cals, respect;vely. M;xtures conta;n;ng epox;de res;ns are preferred. Part;al esters of epox;de res;ns and acryl;c ac;d, methacryl;c ac;d or a m;xture of these ac;ds are also su;table~
The ;ron compound b) and the ox;d;s;ng agent c) can be present ;n the compos;t;on ;n an amount of 0.1 to 15, preferably 0.5 to 10, % by we;ght, relat;ve to the polymer-;sable organic mater;al~ The rat;o by we;ght of the ;ron compound b) to the ox;d;s;ng agent c) can be between 1:10 and 5:1, preferably between 1:5 and 1:1.
The curable compos;t;ons accord;ng to the ;nvent;on can be obta;ned, for example, ;n the -form of homogeneous l;quid m;xtures or ;n a homogeneous or ;nhomogeneous glass-l;ke form. Homogeneous, glass-l;ke products can be obtained ;n a manner known per se~ for example by l;quefy;ng sol;d, polymer;sable organ;c mater;als, ;f appropr;ate by add;ng suitable solvents, ;n the dark or under red l;ght, heat;ng to temperatures above the;r glass trans;tion po;nt, add;ng the components b) and c) and cooling the result;ng mixtures.
If des;red, the glass-l;ke product thus obtained can subse-quently be comm;nuted. Inhomogeneous, glass-l;ke products can be obta;ned, for example, by m;x;ng glass-l;ke, polymer-;sable materials ;n the form of powder with the components b) and c).
The composit;ons accord;ng to the ;nvention are stable, and thus storable, at room temperature and ;n rela-t;ve darkness, for example ;n red l;ght. They can be cured by heat w;thout further treatment, preferably at tempera-tures near to the melting point or decomposition point of the components b) and c).
: ., , 379~
An essential advantage of the composit;on according to the ;nvent;on ;s that ;t can be cured by -the ac-t;on o-f rad;at;on~ complete cur;ng generally be;ng effected by the heat formed ;n the react;on, and external heat;n~ be;ng un-necessary. However, ;t can somet;mes be preferable to apply external heat;ng after exposure to l;ght, for example ;f fa;rly short reaction t;mes are des;red.
The present invention also relates, therefore, to a process for the polymer;sat;on of an organ;c material which can be polymerised by free radicals or cations, a mixture of these mater;als or a mater;al wh;ch can be polymer;sed by free rad;cals and cations, under the action of rad;ation, in the presence of a photoinitiator and, ;f appropr;ate, by heat, wherein the photoinit;ator ;s a mixture of a) at least one iron compound of the formula I
[ (R ) (R Fe ) a] q (LQm) q ( I ~
in wh;ch a is 1 or 2 and q ;s 1, Z or 3, L ;s a divalent to heptavalent metal or non-metal, Q ;s a halogen atom, m ;s an ;nteger correspond;ng to the sum of the valenc;es of L and q, R1 ;s a ~ -arene and R2 ;s the an;on of a ~l-arene, and b) at least one electron acceptor as an ox;d;s;ng agent, and where;n, ;f des;red, the polymer;sat;on react;on ;s subsequently completed by apply;ng heat~
The ;rrad;at;on of the curable m;xture is preferably effected by means of electron beams or actin;c l;ght, pre-ferably of a wavelength between 200 and 600 nm and an ;nten-s;ty between 150 and 5000 watts. Examples of su;table l;ght sources are xenon lamps, argon lamps, tungsten lamps, car-bon arcs and metal hal;de and metal arc lamps, such as low-pressure, med;um-pressure and h;gh-pressure mercury lamps~
The ;rrad;at;on ;s preferably carr;ed out w;th metal hal;de lamps or h;gh-pressure mercury lamps. The ;rrad;at;on t;me depends on var;ous factors, ;ncluding, for example, the polymerisable organic material, the nature of the light source and the distance of the latter from the irradiated .. ..
'' ' - ~ ~ -~, ~
~L2~9t79~
mater;al~ The irrad;ation t;me is preferably 10 to 60 sec-onds.
The composit;ons which have been exposed to light can be heated in conventional convection ovens. If short heat;ng or react;on t;mes are necessary, the heating can also be effected by exposure to~ for example, IR rad;at;on, IR lasers or m;crowave dev;ces~ The polymer;sat;on tempera-tures are in the range from room temperature to about 80~.
The compos;tions accord;ng to the invention can also conta;n further add;t;ves which are known and are custom-ar;ly employed ;n the art of photopolymer;sable mater;als.
Examples of such add;t;ves are p;gments, dyes, f;llers and re;nforcing agents, glass fibres and other f;bres~ flame-retard;ng substances, ant;static agents, flow control agents, ant;ox;dants and l;ght stab;l;sers, and also conventional photo;n;tiators, such as acetophenones, acylphosph;ne oxides or aromat;c ketones5 In order to improve the final proper-ties of epoxide resins ;t is possible to incorporate poly-funct;onal hydroxy compounds, for example as described in German Offenlegungsschr;ft 2,639,395.
In order to ;ncrease the;r capacity to be stored ;n the dark, the curable compos;t;ons can conta;n weak organ;c bases, such as n;tr;les, am;des, lactones or urea der;va-t;ves. In order to prevent premature react;on caused by unintentional e~xposure, small amounts of UV absorbers and/or organ;c dyes can be added.
The compos;t;on accord;ng to the ;nvent;on can be appl;ed by customary methods to at least one surface of a substrate. The coated material ;s also a subject of the invent;on. Examples of su;table substrates are metals and metallo;ds, such as steel, alum;n;um, copper, cadm;um~ z;nc and s;l;con, and also ceram;cs, glass, plast;cs, paper and wood. The coated mater;al can be used for the product;on of protect;ve layers and pass;vating layers by exposure, wh;ch ;s a further subject of the ;nvent;onO
If only part of the coating is irradiated through a photomask during exposure, the unexposed areas can subse-~ _.
'; ' ~:
~i9~7~
- lZ -quently be removed by means of a suitable solvent. The coated mater;al ;s thus also su;table for use as a photo-graph;c record;ng mater;al, for the production of pr;nting plates and, espec;ally, pr;nted c;rcu;ts, an~ also as a solder resist. Use as a photographic recording material is also a subiect of the present invention~
The compos;tions accord;ng to the invent;on can also be used as adhes;ves or for the product;on of putt;es, f;l-~ers or f;bre-re;nforced compos;te materials and lam;nated substances.
The compos;t;ons accord;ng to the ;nvention have a h;gh sensitivity to light without further sensitisation, which also means short exposure times for curing~ At the same time, initiators which are effective for cat;on;c and free radical polymerisation are produced during exposure, which w;dens the field of application in respect of polymer~
isable materials. It is surprising in this respect that the oxid;s;ng agent only becomes effect;ve after exposure and enables cur;ng to be carried out by irradiat;on. It is very advantageous that curing is generalLy effected by the action of radiation without the applicat;on of external heat.
The following examples illustrate the invention in greater detail.
Examples 1 - 11: 2.5 mg of a solution containing 50/u mole of a compound of the formula I and 250 ~u mole of oxidising agent per g of epoxide resin is irradiated ;n an aluminium crucible at 0C using a 1000-watt high-pressure mercury lamp. The closed cruc;ble ;s transferred to a differential scanning calorimeter ~DSC-30, Mettler) and heated at a heat-up rate of 20C/m;nute. In the course of th;s the follow-ing parameters are determined: the start of the exothermic react;on (TStart)~ the react;on enthalpy liberated (~E) and the~temperature at max;mum reaction enthalpy (Tm The following epoxide resins are employed:
1) A technical bisphenol A d;glyc;dyl ether having an epox-ide content of 5.2 equ;valents/kg.
2) A technical cycloaLiphatic epoxide of the formula .:
3l2$~379~
- ~3 -/~0\ /~\
3) A glyc;dylised cresol-novolak hav;ng an epoxide content of 4.8 equivalents/kg.
The const;tuents and the results are listed in the follow;ng table. It w;ll be seen that the polymerisation starts ;n the region of room temperature and proceeds to complet;on at low temperatures, only slightly above the starting temperature.
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Example 12: A solution of 2 ~ of a techn;cal b;sphenol A
diglycidyl ether (epoxide content: 5.2 equ;valentstkg), 0.1 mmol of ~6-naphthalene)-(~5-cyclopentadienyl)-irontII) hexafluorophosphate and O.S mmol of cumene hydro-peroxide ;s appl;ed to a copper-backed epox;de pl.ate by means of a 25 ~u doctor blade. A tack-free, acetone-resistant film is obtained after 30 seconds exposure ~distance approx. 50 cm) to a 5000-watt metal hal;de lamp.
Example 130 Example 12 is repeated using tert;ary butyl hydro-peroxide instead of cumene hydroperoxide. The same resu lt is obtained.
Example 14: A solution of 2 9 of a mixture of 48 parts of polyester acrylate, 32 parts of butanediol diacrylate and 20 parts of dicyclopentadienyl hydroxyethyl acrylate, 0.1 mmol of ~6-2-propylbenzene~ 5-cyclopentadienyl)-iron(II) hexafluorophosphate and 0.5 mmol of tert;ary butyl hydroperox;de ;s appl;ed to a sheet of glass by means of a 50 ,u doctor blade. A tack-free f;lm is obta;ned after ;rradiation (30 seconds, distance approx. 50 cm) using a 1000-watt halogen lamp.
,, .. . ~:.. . - ., ::
II. Heterocyclic compounds which can by polymerised by cations, for example ethylene oxide, propylene oxide, epichlorohydrin and glycidyl ethers of monohydric alcohols or phenols, for example n-butyl glycidyl ether, n~octyl gly-cidyl ether, phenyl glycidyl ether and cresyl glyc;dyl ether; glycidyl acrylate, glycidyl methacrylate, styrene oxide and cyclohexene oxide; oxetans~ such as 3,3~dimethyl-oxetane and 3,3-di-(chloromethyl)-oxetane; tetrahydrofuran;
dioxolane, trioxane and 1,3,6-trioxacyclooctane; lactones, such as ~-propiolactone, ~-valerolactone and -caProlactone;
:"' ;. "
.. . ..
979~
th;;ranes, such as ethylene sulf;de and propylene sulfide;
azet;d;nes, such as N-acylazet;d;nes, for example N-benzoyl-azet;d;ner and the adducts of a~e-t;dine with d;isocyanates, for example toluylene~2,4-d;isocyanate and toluylene-2,6-d;;socyanate and 4,4'-d;am;nod;phenylmethane d;;socyanate;
epoxy res;ns; and l;near and branched polymers hav;ng gly-c;dyl groups ;n the s;de cha;ns, for example homopolymers and copolymers of polyacrylate and polymethacrylate glyc;-dyl esters.
Part;cularly important representatives of these polymer;sable compounds mentioned above are the epox;de re-s;ns and, ;n part;cular, the d;epoxides and polyepoxides and epox;de resin prepolymers of the type used for the prepara-t;on of crossl;nked epoxy res;ns. The d;epoxides and poly-epox;des can be al;phat;c, cycloal;phatic or aromat;c com-pounds. Examples of such compounds are the glycidyl ethers and ~-methyl glycidyl ethers of aliphatic or cyGloaliphat;c d;ols or polyols, for example those of ethylene glycol, pro-pane-1,2-d;ol, propane-1,3-d;ol, butane 1,4-diol, d;ethyl-ene glycol, polyethylene glycol, polypropylene glycol, gly-cerol, tr;methylolpropane or 1,4-d;methylolcyclohexane or those of 2,2-bis-(4-hydroxycyclohexyl)-propane and N,N-bis-(2-hydroxyethyl)-an;l;ne; and the glycidyl ethers of d;phe-nols and polyphenols, for example resorcinol, 4,4'-d;hydroxy-d;phenylmethane, 4,4'-d;hydroxyd;phenyl-2,2-propane, novo-laks and 1,1,2,2-tetrakis-~4-hydroxyphenyl)-ethane. Further examples are N-glycidyl compounds, for example the d;glyc;-dyl compounds of ethyleneurea, 1,3-propyleneurea or 5-d;-methylhydanto;n or of 4,4'-methylene-5,5'-tetramethyld;hy-dantoin or compounds such as tr;glycidyl isocyanurate.
Further glycidyl compounds of industrial importance are the glycidyl esters of carboxylic acids, in particular dicarboxylic and polycarboxylic acids. Examples of these are the glycidyl esters of succinic acid, adipic acid, aze-laic acid, sebacic acid, phthal;c acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid~ isophthalic acid or trimellitic acid or of dimer;sed fatty acids.
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.
. .
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Examples of polyepox;des other than glyc;dyl com-pounds are the diepoxides of vinylcyclohexene and clicyclo-pentadiene, 3-(3l,4'-epoxycyclohexyl)-8,9-epoxy-Z,4~d;oxa-sp;roCS.S]undecane and of 3',4'-epoxycyclohexylmethyl 3,~-epoxycyclohexanecarboxylate, butad;ene d;epox;de or lso-prene d;epox;de, epoxid;sed l;noleic acid derivat;ves or epoxidised polybutad;ene.
Preferred epoxide resins are diglyctdyl ethers, which may be so-called advanced, of dihydric phenols or di-hydric aliphatic alcohols having 2 to 4 carbon atoms. The diglycidyl ethers, which may be so-called advanced, of 2,2-bis-(4-hydroxyphenyl)-propane and of bis-~4-hydroxyphenyl)-methane are particularly preferred.
Further su;table compounds which can be polymerised by cations are the following: III. Methylol compounds:
1. AminopLasts, such as the N-hydroxymethyl, N-methoxymethyl, N-n-butoxymethyl and N-acetoxymethyl derivatives of amides or amide-like compounds, for example cyclic ureas, such as ethyleneurea (imidazolidin-2-one), hydantoin, urone (tetra-hydrooxadiaz;n~4-one), 1,2-propyleneurea (4-methylim;dazol;~
din-2-one), 1,3-propyleneurea (hexahydro-2H-pyrimid-2-one), hydroxypropyleneurea (5-hydroxyhexahydro-2H-pyrimid-2-one), 1,3,5-melamine and further polytriazines, such as acetogu-anam;ne, benzoguanam;ne and adipoguanam;ne.
If des;red it is possible to employ aminoplasts con-ta;ning both N-hydroxymethyl and N-alkoxymethyl groups or both N-hydroxymethyl and N-acetoxymethyl groups (for example a hexamethylolmelamine in wh;ch 1 to 3 of the hydroxyl groups are etherified with methyl groups).
Preferred aminoplasts are the condensation products of urea, urone, hydantoin or melamine with formaldehyde and also partially or completely etherified products of such condensation products with an aliphatic, monohydric alcohol having 1 to 4 carbon atoms.
2, Phenoplasts. Preferred phenoplasts are resols prepared from a phenol and an aldehyde. Suitable phenols include phenol itself, resorcinol, 2,2 bis-(p-hydroxyphenyl)-pro-': "":' :`
,~
. . :
. ,, .; .
:
,.~ .
379~
pane, p-chlorophenol, a phenol which is substituted by one or two alkyl groups each of which has 1 ~o 9 carbon atoms, such as o-, m- and p-cresol, the xylenols, p-tert.-butyl-phenol and p-nonylphenol and also phenyl-substituted phe-nols, in particular p-phenylphenol. The aldehyde which is condensed with the phenol is preferably formaldehyde, but other aldehydes, such as acetaldehyde and furfural, are also suitable. If desired, a mixture of such curable phenol/
aldehyde resins can be used~
The preferred resols are condensation products of phenol, p-chlorophenol, resorcinol or o-, m- or p-cresol with formaldehyde.
Suitable organic materials which can be polymerised by free radicals are, in particular, monoethylenically or polyethylenically unsaturated compounds. The follow7ng are examples: styrene, vinylpyr;dine, v;nyl acetate, divinylben-zene, vinyl ethers, acrylamide~ methacrylamide9 bisacryl-amide, bismethacrylamide and unsaturated polyesters, parti-cularly those based on male;c acid. Preferred materials are the esters or amides of acrylic acid and/or methacrylic acid with linear or branched alcohols, polyols or monoamines or polyamines, respectively. The polyols and polyamines can also be in the form of partial esters.
Examples of polyamines are ethylenediamine, propyl-enediamine, butylenediamine, hexylenediamine, phenylenedi-amine, benzylened;am-7ne, naphthylenediamine, d;ethylenetri-amine, triethylenetetramine and diaminoethyl ethers~ Examples of polyols are l;near and branched alkylenediols, such as ethylenediol, propylenediol, butylenediol, pentylenediol, hexylenediol, octylenediol, polyoxaalkylenediols, such as diethylene and triethylene glycol and polyethylene glycols having a molecular weight of ZOO to 500, 1,4-dihydroxycyclo-hexane, 1,4-di-(hydroxymethyl)-cyclohexane, d;hydroxyben-zenes, hydroxymethylphenols, triols, such as 1,2,3-trihy-droxypropane, 1,2,~-trihydroxybutane and trimethylolpropane, pentaerythritol, dipentaerythritol and low-molecular poly-esters contain;ng hydroxyl end groups.
: .... ..
. . :
': .~
7~3~
_ 9 _ Examples of suitable alcohols and monoamines are methanol, ethanol, propanol, butanol~ pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, cyclohexanol, phenol, glyc;dyl, methylam;ne, d;methylam;ne and ethylam;ne.
Examples of organ;c materials wh;ch can be polymer-ised by cations and free radicals are m;xtures of the above-ment;oned mater;als wh;ch can be polymer;sed by cat;ons and free rad;cals, respect;vely. M;xtures conta;n;ng epox;de res;ns are preferred. Part;al esters of epox;de res;ns and acryl;c ac;d, methacryl;c ac;d or a m;xture of these ac;ds are also su;table~
The ;ron compound b) and the ox;d;s;ng agent c) can be present ;n the compos;t;on ;n an amount of 0.1 to 15, preferably 0.5 to 10, % by we;ght, relat;ve to the polymer-;sable organic mater;al~ The rat;o by we;ght of the ;ron compound b) to the ox;d;s;ng agent c) can be between 1:10 and 5:1, preferably between 1:5 and 1:1.
The curable compos;t;ons accord;ng to the ;nvent;on can be obta;ned, for example, ;n the -form of homogeneous l;quid m;xtures or ;n a homogeneous or ;nhomogeneous glass-l;ke form. Homogeneous, glass-l;ke products can be obtained ;n a manner known per se~ for example by l;quefy;ng sol;d, polymer;sable organ;c mater;als, ;f appropr;ate by add;ng suitable solvents, ;n the dark or under red l;ght, heat;ng to temperatures above the;r glass trans;tion po;nt, add;ng the components b) and c) and cooling the result;ng mixtures.
If des;red, the glass-l;ke product thus obtained can subse-quently be comm;nuted. Inhomogeneous, glass-l;ke products can be obta;ned, for example, by m;x;ng glass-l;ke, polymer-;sable materials ;n the form of powder with the components b) and c).
The composit;ons accord;ng to the ;nvention are stable, and thus storable, at room temperature and ;n rela-t;ve darkness, for example ;n red l;ght. They can be cured by heat w;thout further treatment, preferably at tempera-tures near to the melting point or decomposition point of the components b) and c).
: ., , 379~
An essential advantage of the composit;on according to the ;nvent;on ;s that ;t can be cured by -the ac-t;on o-f rad;at;on~ complete cur;ng generally be;ng effected by the heat formed ;n the react;on, and external heat;n~ be;ng un-necessary. However, ;t can somet;mes be preferable to apply external heat;ng after exposure to l;ght, for example ;f fa;rly short reaction t;mes are des;red.
The present invention also relates, therefore, to a process for the polymer;sat;on of an organ;c material which can be polymerised by free radicals or cations, a mixture of these mater;als or a mater;al wh;ch can be polymer;sed by free rad;cals and cations, under the action of rad;ation, in the presence of a photoinitiator and, ;f appropr;ate, by heat, wherein the photoinit;ator ;s a mixture of a) at least one iron compound of the formula I
[ (R ) (R Fe ) a] q (LQm) q ( I ~
in wh;ch a is 1 or 2 and q ;s 1, Z or 3, L ;s a divalent to heptavalent metal or non-metal, Q ;s a halogen atom, m ;s an ;nteger correspond;ng to the sum of the valenc;es of L and q, R1 ;s a ~ -arene and R2 ;s the an;on of a ~l-arene, and b) at least one electron acceptor as an ox;d;s;ng agent, and where;n, ;f des;red, the polymer;sat;on react;on ;s subsequently completed by apply;ng heat~
The ;rrad;at;on of the curable m;xture is preferably effected by means of electron beams or actin;c l;ght, pre-ferably of a wavelength between 200 and 600 nm and an ;nten-s;ty between 150 and 5000 watts. Examples of su;table l;ght sources are xenon lamps, argon lamps, tungsten lamps, car-bon arcs and metal hal;de and metal arc lamps, such as low-pressure, med;um-pressure and h;gh-pressure mercury lamps~
The ;rrad;at;on ;s preferably carr;ed out w;th metal hal;de lamps or h;gh-pressure mercury lamps. The ;rrad;at;on t;me depends on var;ous factors, ;ncluding, for example, the polymerisable organic material, the nature of the light source and the distance of the latter from the irradiated .. ..
'' ' - ~ ~ -~, ~
~L2~9t79~
mater;al~ The irrad;ation t;me is preferably 10 to 60 sec-onds.
The composit;ons which have been exposed to light can be heated in conventional convection ovens. If short heat;ng or react;on t;mes are necessary, the heating can also be effected by exposure to~ for example, IR rad;at;on, IR lasers or m;crowave dev;ces~ The polymer;sat;on tempera-tures are in the range from room temperature to about 80~.
The compos;tions accord;ng to the invention can also conta;n further add;t;ves which are known and are custom-ar;ly employed ;n the art of photopolymer;sable mater;als.
Examples of such add;t;ves are p;gments, dyes, f;llers and re;nforcing agents, glass fibres and other f;bres~ flame-retard;ng substances, ant;static agents, flow control agents, ant;ox;dants and l;ght stab;l;sers, and also conventional photo;n;tiators, such as acetophenones, acylphosph;ne oxides or aromat;c ketones5 In order to improve the final proper-ties of epoxide resins ;t is possible to incorporate poly-funct;onal hydroxy compounds, for example as described in German Offenlegungsschr;ft 2,639,395.
In order to ;ncrease the;r capacity to be stored ;n the dark, the curable compos;t;ons can conta;n weak organ;c bases, such as n;tr;les, am;des, lactones or urea der;va-t;ves. In order to prevent premature react;on caused by unintentional e~xposure, small amounts of UV absorbers and/or organ;c dyes can be added.
The compos;t;on accord;ng to the ;nvent;on can be appl;ed by customary methods to at least one surface of a substrate. The coated material ;s also a subject of the invent;on. Examples of su;table substrates are metals and metallo;ds, such as steel, alum;n;um, copper, cadm;um~ z;nc and s;l;con, and also ceram;cs, glass, plast;cs, paper and wood. The coated mater;al can be used for the product;on of protect;ve layers and pass;vating layers by exposure, wh;ch ;s a further subject of the ;nvent;onO
If only part of the coating is irradiated through a photomask during exposure, the unexposed areas can subse-~ _.
'; ' ~:
~i9~7~
- lZ -quently be removed by means of a suitable solvent. The coated mater;al ;s thus also su;table for use as a photo-graph;c record;ng mater;al, for the production of pr;nting plates and, espec;ally, pr;nted c;rcu;ts, an~ also as a solder resist. Use as a photographic recording material is also a subiect of the present invention~
The compos;tions accord;ng to the invent;on can also be used as adhes;ves or for the product;on of putt;es, f;l-~ers or f;bre-re;nforced compos;te materials and lam;nated substances.
The compos;t;ons accord;ng to the ;nvention have a h;gh sensitivity to light without further sensitisation, which also means short exposure times for curing~ At the same time, initiators which are effective for cat;on;c and free radical polymerisation are produced during exposure, which w;dens the field of application in respect of polymer~
isable materials. It is surprising in this respect that the oxid;s;ng agent only becomes effect;ve after exposure and enables cur;ng to be carried out by irradiat;on. It is very advantageous that curing is generalLy effected by the action of radiation without the applicat;on of external heat.
The following examples illustrate the invention in greater detail.
Examples 1 - 11: 2.5 mg of a solution containing 50/u mole of a compound of the formula I and 250 ~u mole of oxidising agent per g of epoxide resin is irradiated ;n an aluminium crucible at 0C using a 1000-watt high-pressure mercury lamp. The closed cruc;ble ;s transferred to a differential scanning calorimeter ~DSC-30, Mettler) and heated at a heat-up rate of 20C/m;nute. In the course of th;s the follow-ing parameters are determined: the start of the exothermic react;on (TStart)~ the react;on enthalpy liberated (~E) and the~temperature at max;mum reaction enthalpy (Tm The following epoxide resins are employed:
1) A technical bisphenol A d;glyc;dyl ether having an epox-ide content of 5.2 equ;valents/kg.
2) A technical cycloaLiphatic epoxide of the formula .:
3l2$~379~
- ~3 -/~0\ /~\
3) A glyc;dylised cresol-novolak hav;ng an epoxide content of 4.8 equivalents/kg.
The const;tuents and the results are listed in the follow;ng table. It w;ll be seen that the polymerisation starts ;n the region of room temperature and proceeds to complet;on at low temperatures, only slightly above the starting temperature.
:',: ':
:, ''~, ..:::
' ~ ' '; ' " , , :~-2~9t~
_ __ ~
~:n ro ~ ~ N
~ o~
N ' t~l N ~1 N
~1 ~--O
X
`O ~ ~ I~ 00 00 O`
e ~ U~ ~ ~ ~ r E ~ . . .
Q O
X
~ O O O ~ O O
t~ ~ ~ N r~
c~ ~) - ~
o GJ
~ l - o o o o o o o o aJ o o o o o o o XQ ~ ~ ~ ~ M 00 00 CO
Ll~ ~
~ ~
X
O ~n D J - ~ _ _ E (~ a.
_ r ~ O ~
O Q a~ E C
-- O -- O _ ~
r ::~ D :~ ~ ~, ' ~J~ Q ~ O ~ ~
~,GJ ~0~,~IJ o~,~J cO ~J O
~J ~ o~ ~ ~ a~ ~ oo 'D O
OJ ~ J C ~ J ~ ~ J ~ J
~ c ~ a~ Q Q Q
~1~ ~ ~ O ~ , _ , ' Q X E EX Ex Q ' Q '-~ Q '-~ LLILLI W
OI I HI I t~ I I t~ .,C .,C
O `O U~ _ `O U~ -- `O U~ -- ~0~--C_~ -- -- I.L -- -- LL V _ . .__ o o oo L ~ c ~ ~ C C _ aJ ~, o ., L ~ 'D L .~ ~ ~ ~ L o , ,C
.,. a~ ~ cll ~ Q 0 C'-- X '' J X'~ J X ~-- X C O ~1) J O O
~ ~~ ~ O ~ >~ O~ :~ O ~ :~ O ~) _ ~ ~ N N
'' a~'-- +' 'L aJL ~ aJ' ~ ~ E -O ~ cl c a, D Q IJ D Q ~ D Q ~ n Q ') ~ O E D Q
. _.. __. . . ... _ aJ
x E ~ ~J ~ ~ 11~ ~0 1' LLI ~0 _ ._ , .. .. _ _ . ___ .__ ...
. , ~, .. : , , ,, ~:
,:,: , '-; .. , .-.. ,. . : .
~`97~
_ ~
v ~ ~ ~" N
d o~
~ E O
E ~
X L
~ ~ O O ~ ~0 _ ,~
O
~ O O O
~ ~_ O O O O
X ~ ~~ ~
111 ~
Ao _ ____ .. _. __ ~
., '~ C
X ~r- ~ N
~il O (I) Q aJ
~, __ _._ O H
v E ~ r L
D O Q ~ O
l_ ~ A J O O J
Q~ C ~ Q t~ 1~
~ ~ o I C:
_ _O C ~ ~H
Q QL a) a A H
~ E EO Q x ~ v E c cQ ~ H Q ~. Q
t~ ~V) g--V~ ~
., V L ~ ~ N L ~ ~ L ~ ~
C L L,L ~, L ~ L ~ L
~ ~ ~ Q Q a~ ~ n Q ~ ~ Q
: .. - .__ x E oO O~ O
uJ ~ ~ ~
-.
79~
Example 12: A solution of 2 ~ of a techn;cal b;sphenol A
diglycidyl ether (epoxide content: 5.2 equ;valentstkg), 0.1 mmol of ~6-naphthalene)-(~5-cyclopentadienyl)-irontII) hexafluorophosphate and O.S mmol of cumene hydro-peroxide ;s appl;ed to a copper-backed epox;de pl.ate by means of a 25 ~u doctor blade. A tack-free, acetone-resistant film is obtained after 30 seconds exposure ~distance approx. 50 cm) to a 5000-watt metal hal;de lamp.
Example 130 Example 12 is repeated using tert;ary butyl hydro-peroxide instead of cumene hydroperoxide. The same resu lt is obtained.
Example 14: A solution of 2 9 of a mixture of 48 parts of polyester acrylate, 32 parts of butanediol diacrylate and 20 parts of dicyclopentadienyl hydroxyethyl acrylate, 0.1 mmol of ~6-2-propylbenzene~ 5-cyclopentadienyl)-iron(II) hexafluorophosphate and 0.5 mmol of tert;ary butyl hydroperox;de ;s appl;ed to a sheet of glass by means of a 50 ,u doctor blade. A tack-free f;lm is obta;ned after ;rradiation (30 seconds, distance approx. 50 cm) using a 1000-watt halogen lamp.
,, .. . ~:.. . - ., ::
Claims (16)
1. A curable composition containing a) at least one material which can be polymerised by free radicals or by cations, or at least one material which can be polymerised by free radicals and cations, b) at least one iron compound of the formula I
[(R1)(R2FeII)a]+a ? (LQm)-q (I) in which a is 1 or 2 and q is 1, 2 or 3, L is a divalent to heptavalent metal or non-metal, Q is a halogen atom, m is an integer corresponding to the sum of the valencies of L and q, R is a .pi.-arene and R2 is the anion of a .pi.-arene, and c) at least one electron acceptor as an oxidising agent.
[(R1)(R2FeII)a]+a ? (LQm)-q (I) in which a is 1 or 2 and q is 1, 2 or 3, L is a divalent to heptavalent metal or non-metal, Q is a halogen atom, m is an integer corresponding to the sum of the valencies of L and q, R is a .pi.-arene and R2 is the anion of a .pi.-arene, and c) at least one electron acceptor as an oxidising agent.
2. A composition according to claim 1, wherein R1 is an aromatic group having 6 to 24 carbon atoms or a hetero-aromatic group having 3 to 20 carbon atoms, these groups being unsubstituted or monosubstituted or polysubstituted by identical or different halogen atoms or C1-8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-8-alkoxy, cyano, C1-8-alkylthio C2-6-monocarboxylic acid ester, phenyl, C2-5-alkanoyl or benzoyl groups.
3. A composition according to claim 1, wherein R is .pi.-arene having 6 to 24 carbon atoms or of a hetero-aromatic .pi.-arene having 3 to 20 carbon atoms, each of these being un-substituted or monosubstituted or polysubstituted by identi-cal or different C1-8-alkyl, C2-8-alkenyl, C2-C8-alkynyl, C2-6-monocarboxylic acid ester, cyano, C2-5-alkanoyl or benzoyl groups.
4. A composition according to claim 1, wherein a is 1 and R is benzene, toluene, xylene, methoxybenzene, chloro-benzene, p-chlorotoluene, cumene, naphthalene, methylnaph-thalene, chloronaphthalene, methoxynaphthalene, biphenyl indene, pyrene, perylene or diphenylene sulfide and R2 is the anion of cyclopentadiene, acetylcyclopentadiene, methyl-cyclopentadiene, phenylcyclopentadiene or indene.
5. A composition according to claim 1, wherein a is 1, R1 is ?6-pyrene or ?6-naphthalene and R2 is the anion of ?5 -cyclopentadiene.
6. A composition according to claim 1, wherein [LQm]-q is SbF6-, Bf4-, AsF6- or PF6-.
7. A composition according to claim 1, wherein the oxid-ising agent is an organic hydroperoxide, an organic per-acid or a quinone.
8. A composition according to claim 7, wherein the oxid-ising agent is tertiary butyl hydroperoxide, cumene hydro-peroxide, triphenylmethyl hydroperoxide, tetralin hydroper-oxide, .alpha.-methyltetralin hydroperoxide, decalin hydroperoxide, perbenzoic acid, m-chloroperbenzoic acid or benzoquinone.
9. A composition according to claim 1, wherein the or-ganic material which can be polymerised by cations is an epoxide resin.
10. A composition according to claim 1, wherein the mate-rial which can be polymerised by free radicals is a mono-ethylenically or polyethylenically unsaturated compound.
11. A composition according to claim 1, wherein the mate-rial which can be polymerised by cations and free radicals is a mixture of an epoxide resin and a monoethylenically or polyethylenically unsaturated compound or a partial ester of an epoxide resin and acrylic acid, methacrylic acid or a mixture of these acids.
12. A composition according to claim 1, which contains the iron compound b) and the oxidising agent c) in an amount of 0.1 to 15% by weight, relative to the polymerisable orga-nic material.
13. A composition according to claim 12, wherein the ratio by weight of the iron compound b) to the oxidising agent c) is between 1:10 and 5:1.
14. A process for the polymerisation of at least one mate-rial which can be polymerised by free radicals or by cations, or of at least one material which can be polymerised by free radicals and cations, by the action of radiation in the pre-sence of a photinitiator and, if appropriate, by heating, wherein the photoinitiator is a mixture of a) at least one iron compound of the formula I
[(R1)(R2FeII)a]+a ?(LQm)-q (I) in which a is 1 or 2 and q is 1, 2 or 3, L is a divalent to heptavalent metal or non-metal, Q is a halogen atom, m is an integer corresponding to the sum of the valencies of L and q, R1 is a .pi.-arene and R2 is the anion of a .pi.-arene, and b) at least one electron acceptor as the oxidising agent and, if desired, polymerisation is completed subsequently by the application of heat.
[(R1)(R2FeII)a]+a ?(LQm)-q (I) in which a is 1 or 2 and q is 1, 2 or 3, L is a divalent to heptavalent metal or non-metal, Q is a halogen atom, m is an integer corresponding to the sum of the valencies of L and q, R1 is a .pi.-arene and R2 is the anion of a .pi.-arene, and b) at least one electron acceptor as the oxidising agent and, if desired, polymerisation is completed subsequently by the application of heat.
15. A coated material wherein a layer of the composition according to claim 1 has been applied to a substrate.
16. A process for the production of photographic relief images, which comprises irradiating a material according to claim 15 through a photomask, if appropriate while heating, and then removing the unexposed portions with a developer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2691/83-1 | 1983-05-18 | ||
| CH269183 | 1983-05-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1269791A true CA1269791A (en) | 1990-05-29 |
Family
ID=4239405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000454404A Expired - Lifetime CA1269791A (en) | 1983-05-18 | 1984-05-16 | Curable composition and the use thereof |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5073476A (en) |
| EP (1) | EP0126712B1 (en) |
| JP (1) | JPH0639483B2 (en) |
| KR (1) | KR920005529B1 (en) |
| AT (1) | ATE24243T1 (en) |
| AU (1) | AU573219B2 (en) |
| BR (1) | BR8402336A (en) |
| CA (1) | CA1269791A (en) |
| DE (1) | DE3461677D1 (en) |
| ES (1) | ES532965A0 (en) |
| ZA (1) | ZA843733B (en) |
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| JP2022183077A (en) | 2021-05-28 | 2022-12-08 | 住友化学株式会社 | Salt, acid generator, resist composition, and method for producing resist pattern |
| JP2022183074A (en) | 2021-05-28 | 2022-12-08 | 住友化学株式会社 | Salt, acid generator, resist composition, and method for producing resist pattern |
| TW202311315A (en) | 2021-08-06 | 2023-03-16 | 日商住友化學股份有限公司 | Resist composition and method for producing resist pattern capable of producing a resist pattern having few defects and good CD uniformity |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3425988A (en) * | 1965-01-27 | 1969-02-04 | Loctite Corp | Polyurethane polyacrylate sealant compositions |
| GB1285284A (en) * | 1969-05-26 | 1972-08-16 | Hitachi Ltd | Epoxy resin composition |
| US3855040A (en) * | 1972-07-03 | 1974-12-17 | Loctite Corp | Anaerobic compositions |
| GB1465200A (en) * | 1973-09-03 | 1977-02-23 | Dainichi Nippon Cables Ltd | Composition for electrical insulation |
| US4273668A (en) * | 1977-09-14 | 1981-06-16 | General Electric Company | Arylsulfonium salt-solvent mixtures |
| US4343885A (en) * | 1978-05-09 | 1982-08-10 | Dynachem Corporation | Phototropic photosensitive compositions containing fluoran colorformer |
| EP0094915B1 (en) * | 1982-05-19 | 1987-01-21 | Ciba-Geigy Ag | Curable compositions containing metallocen complexes, activated primers obtained therefrom and their use |
| IE54465B1 (en) * | 1982-05-26 | 1989-10-25 | Loctite Ltd | Two-part self-indicating adhesive composition |
| US4446246A (en) * | 1982-09-09 | 1984-05-01 | Three Bond Co., Ltd. | Catalyst systems for two-pack acrylic adhesive formulations |
| US4808638A (en) * | 1986-10-14 | 1989-02-28 | Loctite Corporation | Thiolene compositions on based bicyclic 'ene compounds |
| US4857437A (en) * | 1986-12-17 | 1989-08-15 | Ciba-Geigy Corporation | Process for the formation of an image |
| JPH0258528A (en) * | 1988-08-25 | 1990-02-27 | Mitsui Petrochem Ind Ltd | Active energy ray-curable composition and bonding of optical disc substrate to hub using said composition |
-
1984
- 1984-05-10 US US06/608,753 patent/US5073476A/en not_active Expired - Lifetime
- 1984-05-14 AT AT84810232T patent/ATE24243T1/en not_active IP Right Cessation
- 1984-05-14 DE DE8484810232T patent/DE3461677D1/en not_active Expired
- 1984-05-14 EP EP84810232A patent/EP0126712B1/en not_active Expired
- 1984-05-16 CA CA000454404A patent/CA1269791A/en not_active Expired - Lifetime
- 1984-05-17 AU AU28314/84A patent/AU573219B2/en not_active Ceased
- 1984-05-17 ES ES532965A patent/ES532965A0/en active Granted
- 1984-05-17 BR BR8402336A patent/BR8402336A/en not_active IP Right Cessation
- 1984-05-17 ZA ZA843733A patent/ZA843733B/en unknown
- 1984-05-17 KR KR1019840002693A patent/KR920005529B1/en not_active IP Right Cessation
- 1984-05-18 JP JP59098905A patent/JPH0639483B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0126712A1 (en) | 1984-11-28 |
| ZA843733B (en) | 1985-01-30 |
| EP0126712B1 (en) | 1986-12-10 |
| AU573219B2 (en) | 1988-06-02 |
| JPS59219307A (en) | 1984-12-10 |
| JPH0639483B2 (en) | 1994-05-25 |
| BR8402336A (en) | 1984-12-26 |
| AU2831484A (en) | 1984-11-22 |
| DE3461677D1 (en) | 1987-01-22 |
| KR920005529B1 (en) | 1992-07-06 |
| US5073476A (en) | 1991-12-17 |
| ES8602043A1 (en) | 1985-11-16 |
| ATE24243T1 (en) | 1986-12-15 |
| ES532965A0 (en) | 1985-11-16 |
| KR840009315A (en) | 1984-12-26 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |