GB2083832A - Photopolymerization initiator compositions containing N-oxy-N- heterocyclic activator compounds - Google Patents

Photopolymerization initiator compositions containing N-oxy-N- heterocyclic activator compounds Download PDF

Info

Publication number
GB2083832A
GB2083832A GB8127386A GB8127386A GB2083832A GB 2083832 A GB2083832 A GB 2083832A GB 8127386 A GB8127386 A GB 8127386A GB 8127386 A GB8127386 A GB 8127386A GB 2083832 A GB2083832 A GB 2083832A
Authority
GB
Grant status
Application
Patent type
Prior art keywords
gt
lt
composition
sep
substituted
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.)
Granted
Application number
GB8127386A
Other versions
GB2083832B (en )
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultra-violet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultra-violet or visible light with sensitising agents

Abstract

Co-initiator compositions for photo-polymerization contain N-oxy- N-heterocyclic compounds having from 5 to 14 nuclear atoms and free of nitro groups as activators and amino-substituted photosensitizers. Preferred activators are N- alkoxypyridinium salts and preferred photosensitizers include amino-substituted 3-ketocoumarins.

Description

SPECIFICATION Photopolymerization co-initiators containing N-oxy-N-heterocyclic activator compounds This invention relates to compositions used to photoinitiate the polymerization of additionpolymerizable compounds containing ethylenic unsaturation.

Mixed photoinitiators, hereinafter referred to as "co-initiators", are known for use with addition-polymerizable monomers. Co-initiators usually comprise two compounds, a lightsensitive compound usually identified as a photosensitizer, and an activator compound. The activator is substantially insensitive to activating radiation for the co-initiator composition; but, in the presence of the excited photosensitizer, the activator is believed to contribute to the formation of a free radical. The known classes of activators include amines, sulphinic acid and sulphinic acid esters, sulphones, oc- and ss-dicarbonyls such as bornanedione and acetylacetone, phosphines, phosphites, stannates, and hexaarylbi-imidazoles.

An early example of an effective co-initiator composition is Michler's ketone as the photosensitizer, in combination with benzophenone as the activator, e.g., as described in U.S. Patent No.

3,682,641. This composition has long been considered an industry standard. More recently, a number of aromatic carbonyl compounds have been disclosed as useful photosensitizers with amine activators to form co-initiators. Such compositions are described in Ledwith, J. Oil Col.

Chem. Assoc., 59, p. 1 57 and especially pp. 162-164 (1976). The carbonyl compounds, specifically identified are phenones, including cyclic ketones, such as benzophenone, fluorenones, anthraquinones and anthrones; Although such co-initiators have been highly effective, most of them are not responsive to visible light, thus requiring ultra-violet radiation. Some co-initiators have been found to have a spectral response in the visible wavelengths, but their speed has been so much less than the speed of Michler's ketone and benzophenone that they have not been acceptable.

Thus there has been a long-existing need for the development of a co-initiator composition that not only is responsive to visible light but also has a speed comparable to or better than the speed of conventional ultra-violet responsive co-initiators.

According to the preSent invention there is provided a co-initiator composition for the photopolymerization of addition-polymerizable compounds comprising an amino-substituted photosensitizer and an N-oxy-N-heterocyclic compound having from 5 to 14 nuclear atoms, other than nitro-substituted N-oxy-N-heterocyclic compounds as an activator.

The activator compound is responsive in the presence of the photo-excited amino-substituted photosensitizer to form a free radical.

The term "addition-polymerizable" or "addition 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, in contrast with crosslinking wherein a single photon general creates only one crosslink between polymer molecules. Without being limited to specific mechanisms, addition polymerization achievable with this invention preferably involves the production of free radicals.

The term "photosensitizer" broadly includes both materials which are operable to sensitize crosslinking of polymers as well as those, such as the present "co-initiator compositions", which sensitize only addition polymerization of simple compounds or polymers.

As used herein, with regard to the amino-substituted photosensitizers, "carbocyclic", "aryl", "aromatic", "heterocyclic", "alkyl", and "alkoxy" include substituted as well as unsubstituted carbocyclic, aryl, aromatic, heterocyclic, alkyl and alkoxy, respectively, unless otherwise specified. Suitable substituents include alkoxy groups containing up to 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, isobutoxy and pentoxy; sulphonates, such as fluerosulpho- nate; cyano goups; dialkylamino groups such as dimethylamino, diethylamino and dipropylamino; halogen atoms, such as chlorine and bromine; nitrol groups; hydroxyl groups; and alkyl groups having up to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl and pentyl.

Also, alkenyl includes aryl- or alkyl-substituted alkenyl, for example, styryl, cinnamylidenemethyl, and 2-(2-thienyl)vinyl.

This invention is based upon the discovery that the N-oxy-N-heterocyclic compounds hereinafter described will function as activators in a co-initiator composition. Furthermore, it has been discovered that when used with amino-substituted photosensitizers, these compounds produce unexpectedly high speeds compared to speeds achieved when they are used with non-amino substituted photosensitizers. Thus, a useful photopolymerizable composition comprises an addition-polymerizable compound containing ethylenic unsaturation, and a co-initiator composition comprising a mixture of an amino-substituted photosensitizer, such as an amino-substituted 3-ketocoumarin, and photo-polymerization activator as set forth above.

Any compound containing ethylenic unsaturation which is addition-polymerizable is useful with the co-initiators of this invention. Preferred are simple monomeric compounds containing ethylenic unsaturation as well as polymers containing end groups or pendant groups terminating in ethylenic unsaturation. For example, the phrase "addition-polymerizable compounds" in cludes polymers having recurring units with the structure <img class="EMIRef" id="027056964-00020001" />

in which R is any group capable of forming the backbone of a polymer and T is a hydrogen atom or methyl group.

Examples of useful addition-polymerizable compounds containing ethylenic unsaturation include monomeric acrylates, acrylamides, methacrylates, methacrylamides, acrylonitriles, ally compounds, vinyl ethers, vinyl esters, N-vinyl compounds, styrenes and crotonates. Many examples of each of these classes are well known, e.g., as disclosed in United Kingdom Patent Specification No. 1,534,137 and U.S. Patent No. 3,759,807.

Highly preferred addition-polymerizable compounds are the acrylate compounds as a class.

For years they have been used in photopolymerization and a wide variety have been identified in the literature. Particularly useful examples include alkyl acrylates containing up to 10 and most preferably up to 5 carbon atoms in the alkyl portion, such as methyl acrylate, ethyl methacrylate and butyl acrylate; pentaerythritol tri- and tetraacrylates and methacrylates; esters of polyols including glycol diacrylates and dimethacrylates, such as tripropylene glycol diacrylates, tetaethylene glycol diacrylate, triethylene glycol dimethacrylate, and hexanediol diacrylates; polyether diacrylates such as that obtainable from UCB, a division of Chimique Chaussee de Charleroi, Brussels, Belgium under the trade name ''Ebecryl 210"; and mixtures of the above.Particularly preferred are diacrylates and mixtures of tetraacrylates and tetramethacrylates.

Of the two components of the co-initiator composition, the photosensitizer preferably predominates as the light-absorbing component. That is, all or at least more than 50% of the activating radiation, is absorbed by the photosensitizer. Examples of useful amino-substituted photosensitizers include those having an aromatic or heterocyclic ring having an aminosubstituent such as a dialkylamino group containing up to 5 carbon atoms per alkyl group for example, dimethylamino, diethylamino, dipropylamino containing from 1 to 5 carbon atoms per alkyl for example, dimethylamino, diethylamino, dipropylamino and dibutylamino; piperidinyl; Npyrrolidinyl; morpholino; or substituents that together form a fused hydroquinolizine ring on said aromatic or heterocyclic ring, e.g., <img class="EMIRef" id="027056964-00020002" />

Preferred amino-substituted photosensitizers are carbonyl-containing compounds with significant electron-donating substituents, and a high extinction coefficient.

For example, useful sensitizers include amino-substituted thiazoline and selenazoline sensitizers as described in U.S. Patent 4,062,686 and amino-substituted indanediones, benzophenones, benzylideneacetophenones, and bis(benzylidine) cyclopentanones. Most preferred are keto-coumarins having the formula <img class="EMIRef" id="027056964-00020003" />

in which R1 is an alkyl or alkenyl group having up to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, and 1-butenyl; or a carbocyclic or heterocyclic group having from 5 to 20 nuclear carbon and hetero atoms; and R2, R3 and R4 are each independently a hydrogen atom, a dialkylamino group containing up to 5 carbon atoms in each alkyl portion, such as dimethylamino, diethylamino and dibutylamino; a cycloalkylamino group, such as N-pyrrolodinyl, piperidinyl and morpholinyl; or the groups R2, R3 and R4, when taken together, represent the non-metallic atoms necessary to complete a fused nitrogen-containing ring, such as a fused hydroquinolizine ring; provided that at least one of the groups R2, R3 and R4 is an amino group. As used herein, an amino group includes any N-heterocyclic group containing an uncharged nitrogen atom attached to three separate carbon atoms and does not include aromatic heterocyclic groups such as pyridine or pyridinium. Examples of heterocyclic groups for R' include, 3-coumarinyl, benzofuryl, thienyl, furyl, and pyridyl groups. 3-Coumarinyl groups are preferred examples of such heterocyclic groups.

Also highly preferred are amino-substituted 3-keto-coumarins having polar moieties or substituents, such as ionic moieties, and especially those containing water-soluble and/or alcohol-soluble portions. Useful examples include, attached to the keto group in the 3-position, heterocyclic onium salt group, e.g., pyridinium salt and imidazolium salts, and groups containing solubilizing substituents such as a carboxylate salt, sulphonate salt, quaternized N,N,N-trisubstituted amino, e.g., an N-phenylene-N,N,N-trimethylammonium chloride.Examples of such substituents attached to the coumarin rings include groups containing substituents such as carboxy, carboxyalkyl, carboxyaryl, sulpho, sulphoalkyl, sulphoaryl and the monovalent metal or ammonium (including tetraorganoammonium) salts of said carboxy and sulpho substitutents, and quaternary ammoniurn salt groups such as are noted above.

The amino-substituted 3-ketocoumarins are particularly useful with broad spectrum light sources such as xenon and halogen lamps, or with limited wavelength sources such as mercury lamps having emission spectra at 366, 405, 436 and 547 nm, or lasers emitting at 457 nm, 488 nm or 515 nm.

The following is a partial list of amino-substituted photosensitizers that are highly useful in coinitiator compositions of the invention: Table 1 3-(2-benzofuroyl)-7-diethylaminocoumarin; 3-(2-benzofuroyl)-7-( 1 -pyrrolidinyl)coumarin; 7-dimethylamino-3-(2-thenoylcoumarin; 3-(4-dimethylaminobenzoyl)-7-diethylaminocoumarin; 3, 3'-carbonylbis(7-diethylaminocoumarin); 7-diethylamino-3-[3-(2-thienyl)acryloyl]coumarin; 3-(2-furoyl)-7-diethylaminocoumarin; 3-(4-diethylaminocinnamoyl)-7-diethylaminocoumarin; 3-(4-morpholinocinnamoyl)-7-diethylaminocou marin; 9-(7-diethylamino-3-coumarinoyl)- 1 2,4, 5-tetrahydro-3 H ,6 H, 1 0H[1 Jbenzopyrano[6, 7' 8-i,j]qui- nolizine-1 0-one; which has the structure:: <img class="EMIRef" id="027056964-00030001" />

9-(7-di-n-propylamino-3-coumarinoyl)- 1,2,4, 5-tetrahydro-3 H, 6 H, 1 OH[ 1 ]benzopyrano[6,7, 7,8-i,- jquinolizine-1 0-one; 9-(4-diethylaminocinnamoyl)-1,2,4,5-tetrahydro-3H, 6H, 10H[1]benzopyrano[6,7,8-i,j]quinoliz ine-1 0-one; 7-dimethylamino-3-[3-(2-thienyl)acryloyljcoumarin; 9-[3-(2-thienyl)acryloyl]-1 ,2,4, 5-tetrahydro-3H 6 H, 1 OH[1]-benzopyrano[6,7,8-i,j]quinolizine- 10-one; 7-diethylamino-3-(4-dimethylaminocinnamylideneacetyl)coumarin; 9-[3-(9-julolidyl)acryloyl]-l ,2,4, 5-tetrahydro-3H,GH, 10H[1 ]benzopyranoCG, 7,8-i,jlquinolizine- 10-one; 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)acryloyljcoumarin; 7-diethylamino-3-cinnamylideneacetylcoumarin; 9-[3-(2-thienyl)acryloyl]-1,2,4,5--tetrahydro-3H, 6H, 10H[1]benzopyrano[6,7,8-i,j]quinolize10-one; 7-diethylamino-3-(3-fluorosulphonylbenzoyl)coumarin; 3-(4-cyanobenzoyl)-7-diethylaminocou marin; 3-benzoyl-7-dimethylaminocoumari n; 3-benzoyl-7-diethylaminocou marin; 3-benzoyl-7-pyrrolid inylcoumarin; 3-(4-iodobenzoyl)-7-d i methylaminocoumarin; 3-(4-iodobenzoyl)-7-diethylaminocoumarin; 7-dimethylamino-3-(4-dimethylaminobenzoyl)coumarin; 7-diethylamino-3-(4-nitrobenzoyl)coumarin; 7-diethylamino-3-(2-thenoyl)coumarin; 7-pyrrol idi nyl-3-(2-thenoyl)cou marin; 7-diethylamino-3-(2-furoyl)coumarin; 7-diethylamino-3-(2-methoxybenzoyl)cou marin;; 2-(4-pyrrolidinylbenzylidene)- 1,3-indanedione; 4,4'-bis(dimethylamino) benzophenone (Michler's ketone); 2-[bis(2-furoyl)methylene]-1-methylnaphtho[1,2-d]thiazoline; 2-[(2-furoyl)methylene]-1-methylnaphtho[1,2-d]thiazoline; 2-benzoylmethylene-1-ethylnaphtho[1,2-d]thiazoline; 2-[bis(2-furoyl)methylene]-2-methylbenzothiazoline; 2, 5-bis(4diethylaminobenzylidene)cyclopentanone; 4'-dimethylaminochalcone; and 2-(2-thenoylmethylene)-3-methylnaphtho[1,2-d]thiazoline; A mixture of two or more of any of the above photosensitizers is also useful.

Conventional methods are used to prepare these photosensitizers. For example, useful preparations of ketocoumarins are disclosed in the aforesaid U.S. Patent No. 4,147,552.

The free-radical generating photopolymerization activators which may be used with the photosensitizer described above are N-oxy-N-heterocyclic compounds. Useful examples include those having one of the following formulae: <img class="EMIRef" id="027056964-00040001" />

in which R5 is an alkyl group having up to 3 carbon atoms, such as methyl, ethyl and propyl; or aryl of from 6 to 10 carbon atoms, such as phenyl and naphthyl; R6 is an alkyl group having up to 3 carbon atoms, such as methyl, ethyl, propyl and isopropyl, X- is an anion such as fluoroborate.

Useful activators include the N-alkoxy-N-heterocyclic compounds described in U.S. Patents 3,615,586 and Re 27,925, (Table I) such as: 2-P-anilinovinyl-l -methoxypyridinium p-toluene-sulphonate; 1-methoxy-2-methylpyridinium p-toluene-sulphonate; 1-methoxy-4-methylpyridinium p-toluenesulphonate; anhydro-2-methyl- 1 -(3-sulphopropoxy)pyridinium hydroxide; 1-ethoxy-2-methylpyridinium tetrafluoroborate; 1-methoxy-4-phenylpyridinium tetrafluoroborate; 1-methoxy-4-methylpyridinium tetrafluoroborate; 1 -benzyloxy-2-methylpyridiniu m bromide; 1-ethoxy-2-methylquinolinium tetrafluoroborate; 1,1 '-ethylenedioxybispyridinium dibromide; 1-acetoxy-2-(4-dimethylaminostyryl)pyridinium perchlorate; 1 -benzyloxy-2-(4-dimethylaminostyryl)pyridinium perchlorate;; 1 ,3- i methyl-5-[(l -methoxy-2( 1 H)-pyridylidene)ethylidene]-2-thiobarbituric acid; 3-ethyl-5-[( 1 -methoxy-2(1 H)-pyridylidene)ethylidenel-rhodanine; 1, 3-diethyl-5-[( 1 -methoxy-2( 1 H)-pyridylidene)ethylidene]barbituric acid; 2-(3, 3-dicyanoalkylidene)- 1 -methoxy- 1 , 2-dihydropyridine; 2-[(1-methoxy-2(1 H)-pyridylidene)-ethylidene]benzo[b]-thiophen-3(2H)-one-1,1-dioxide; 3-cyano-5-[( 1 -methoxy-2( 1 H)-pyridyl i dene)ethyl idenel-4-phenyl-2(5 H )-fu ra none; N-ethoxy-2-picolinium iodide; N-ethoxy-2-picolinium hexafluorophosphate; and N-methoxy-2-anilinovinylpyridinium paratoluenesulphonate.

1-methoxy-2-methylpyridinium p-toluenesulphonate; anhydro-2-methyl- 1 -(3-sulphopropoxy)pyridinium hydroxide; 1-benzyloxy-2-methylpyridinium bromide borate; 1-ethoxy-2-methylquinolinium tetrafluoroborate; 1,1 '-ethylenedioxybispyridinium dibromide; 1,1 '-trimethylenedioxybispyridinium dibromide; 1,1'-tetramethylenedioxybis(2-methylpyridium)dibromide; 1,1'-tetramethylenedioxybis(4-methylpyridium)dibromide; 1,1 '-tetramethylenedioxybispyridinium dibromide; 1,1 '-pentamethylenedioxybispyridinium dibromide; 1 -acetoxy-2-(4-dimethylaminostyryl)pyridinium perchlorate; and 1 -benzyloxy-2-(4-dimethylaminostyryl)pyridinium perchlorate.

Still other useful activators include N,N.0-triacylhydroxylamines containing an imide ring, for example, the compounds disclosed in Column 5 of U.S. Patent 3,359,109 and particularly Nbenzoyloxyphthalimides such as: N-(2, 4-dichlorobenoyloxy)phthalimide; N-(cyanobenzoyloxy)phthalimide; N-thenoyloxyphthalimide; and N-benzenesulphonyloxyphthalimide; and substituted equivalents such as: N-(4-chlorobenzenesulphonyloxy)- 1 , 8-naphthalimide.

As used herein with regard to the N,N,0-triacylhydroxylamines, the term ''acryl" is exclusive of nitro-substituted acyl.

The amount of photosensitizer used does not appear to be critical. Preferably it is present in the range of from 0.0002 to 0.2 mmole per gram of dry solids, and preferably in the range of from 0.005 to 0.015 mmole per gram.

Of course, a sufficient amount of the activator must be present to allow interaction between the excited photosensitizer and the activator. Thus the activator is generally present in amounts between 0.005 and 2.0 mmole per gram of dry solids, and preferably between 0.05 and 0.2.

Most preferably, it is present in an amount by weight that is ten times the amount of the photosensitizer.

The unexpected speed produced by the activators of this invention is best understood by comparing their performance, when used with an amino-substituted photosensitizer, to their performance when used with a comparable non-amino-substituted photosensitizer. In fact, in many instances the speeds produced in the latter case are so slow that it might be questioned whether the N-heterocyclic compounds of this invention can even be considered to be useful activators when used with non-amino-substituted photosensitizers. Yet, the speeds obtained with amino-substituted photosensitizers have been found in many cases to be much superior to the speeds produced in the same composition when using the co-initiator Michler's ketone and benzophenone.This behaviour of the N-oxy-N-heterocyclic compounds, when used with amino substituted photosensitizers, is even more striking when it is realized that some other classes of activators useful in co-initiator compositions tend to give better speed results when used with non-amino-substituted photosensitizers.

In certain applications, a binder can be added to the photopolymerizable composition. The addition-polymerizable compound is generally present from 5 to 100 weight percent of the mixture of that compound and the binder.

The dry thickness of the composition may be varied over a wide range. When applied to a support, the dry thickness is generally between 1 micrometer and 1 mm, and is preferably between 20 and 1 20 micrometres. The photopolymerizable composition may be applied to a support by a wide variety of techniques such as spray-coating, whirl-coating, curtain-coating or roll-coating, all of which are conventional.

Any suitable solvent can be selected for preparing a solution of the composition to be coated on a support. Useful examples include dichloromethane, acetone, benzene, alcohols, ethers, and toluene. The choice will depend, of course, upon the addition-polymerizable compound and the co-initiator-composition as well as upon other components that might be included, e.g., polymeric binders.

The photopolymerizable composition can be coated on a variety of known supports, including photographic supports. Typical useful supports include polymeric film, wood fibre e.g., paper, metallic sheet and foil, glass and ceramic supports. Such supports are often provided with one or more subbing layers to enhance the adhesive, antistatic, dimensional, abrasive, hardness, frictional, and/or other properties of the support surface as desired.

Typical polymeric film supports are films of cellulose nitrate and cellulose esters such as cellulose triacetate and diacetate, polystyrene, polyamide, homo- and copolymers of vinyl chloride, poly(vinyl acetal), polycarbonate, homo- and copolymers of olefins, such as polyethylene and polypropylene, and polyesters of dibasic aromatic carboxylic acids with divalent alcohols, such as poly(ethylene terephthalate).

Typical paper supports are those which are partially acetylated or coated with baryta and/or a polyolefin, particularly a poly-a-olefin containing 2 to 10 carbon atoms, such as polyethylene, polypropylene, as well as copolymers, e.g., of ethylene and propylene.

Further details of useful supports are to be found in Research Disclosure, Vol. 176, Publication No. 17643, Para. XVII (Dec. 1978), published by Industrial Opportunities Ltd., Homewell, Havant, Hampshire, PO9 1 EF, United Kingdom.

The compositions of the invention have utility in a wide variety of applications. For example, one preferred use is in an element comprising a support bearing a layer of a photopolymerizable composition, preferably along with a polymeric binder. Particularly preferred supports include copper foil or a silicon chip. Such an element is useful in microelectronics and photofabrication, wherein the foil is etched into desired configurations. In such uses the photopolymerizable composition, together with a compatible binder, acts, as a negative resist that is exposed and developed to form a resist image. As used herein, a binder is "compatible" if it forms a singlephase coating with the co-initiator composition, when dried, and does not interfere with its photopolymerization.

When binders are desired as an additional component, they may be selected from addition polymers, e.g., homopolymers, copolymers and terpolymers of vinyl, especially acrylic monomers; or condensation polymers, e.g., polyesters, polyamides and polysulfonamides and mixtures of the above. Such binders are not needed, however, even in resist applications, when the polymerizable compound and co-initiator composition are film-forming in and of themselves, e.g., when the polymerizable compound is of a relatively high molecular weight such as an oligomer or a polymer.

Plasticizers are optionally included in the photopolymerizable compositions for specific purposes or applications. However, in some cases better speeds are obtained by omitting them.

Additionally, the photopolymerizable compositions are useful to provide polymeric coatings and other articles of manufacture that are uniformly, rather than imagewise, exposed to activating radiation.

In the following examples the photopolymerization speeds obtained with various co-initiator compositions of this invention are reported relative to the speed obtained with the well known co-initiator containing Michler's ketone and benzophenone, which speed is arbitrarily set at 1.

However, because of the difficulty of comparison when relative speeds are widely separated, the speeds of all test compositions were determined relative to an intermediate control B' which consists of 0.08 millimoles of the sensitizer 3,3'-carbonylbis(5,7-di-n-propoxycoumarin) and 0.8 millimoles of the activator ethyl p-dimethylaminobenzoate (DMAB) added to 1 3 millilitres of the photopolymerizable composition. Through many repeated comparisons, the speed of control B' relative to that of the co-initiator containing Michler's ketone and benzophenone was determined to be 3.5.

The effectiveness of co-initiator compositions containing the N-oxy-N-heterocyclic activators of this invention with various amino-substituted photosensitizers is demonstrated in the following examples.

Examples 1-3 Coating compositions were prepared containing 0.08 millimoles of photosensitizer (designated in Table I) and 0.8 millimoles of activator (designated in Table I) in 1 3 millilitre portions of the following solution of an addition-polymerizable composition: Pentaerythritol tetraacrylate 45.0 g Pentaerythritol tetramethacrylate 60.0 g Poly(methyl methacrylate-co-butyl methacrylate-co-acrylic acid) (34:63::3)% available from Rohm 8 Haas Co. under the Trademark "Acryloid B48N" (binder) 120.0 g Poly(methyl methacrylate) available from Rohm s Haas Co. under the Trademark "Acryloid A 11" (binder) 120.0 g t-Butyl 4-hydroxy-5-methylphenyl sulphide (stabilizer) 1.05 g Dibutyl phthalate (plasticizer) 50.4 g Dichloromethane (solvent) 535.2 g Each coating solution was coated at a wet thickness of 300 micrometres on a copper support on a coating block maintained at 18"C. After 5 minutes, the temperature of the block was raised to 66"C for 10 minutes. The strips were then heated in an oven at 90"C for 10 minutes.Test strips were exposed for 1 80 seconds through a KODAK T-1 4 step tablet having optical density increments of 0.15, and a polypropylene cover sheet using a "COLIGHT EXPOSER" device which uses a 400 W medium pressure mercury vapour lamp. The exposed test strips were developed for 55 seconds in a processing bath containing 1 , 1 , 1 -trichloroethane, rinsed for 5 seconds with fresh 1,1,1 -trichloroethane, rinsed with water and dried.

Speeds of co-initiator compositions containing activators not of this invention are reported in Table I for comparison purposes. Such activators include ethyl p-diethylaminobenzoate (DMAB), N-phenylglycine (N PG), 4-methylphenoxyacetic acetic acid and N-methylindole-3-ylacetic acid.

The N-phenylglycine used in the examples was purified by recrystallization from toluene solution.

Thus, in contrast for example to DMAB that performs best with an alkoxy-substituted photositizer (compare Control A and Example 1), the activators of this invention perform best when used with amine photosensitizers. This behaviour is totally unexpected in light of the fact that the speed obtained when used with alkoxy-substituted photosensitizers would hardly suggest that these N-oxy-N-heterocyclic compounds will function as significant activators in any combination.

Table I Relative Speed with the Activators 4-Me-Phenoxy* or Me-Indole** N-methoxy-4 Ac,,,,,etic Phenylpyridin E,xample Photosensitizer DMAB NPG Acid ium fluoroborate Control A 3-benzoyl-7-methoxy- 2.6 2.3 1.5* 0.16 ,coumarin Control B 3,3'-carbonylbis- 3.5 5.0 3.3** 0.6 (5,7-di-n-propoxycoumarin) Example 1 3-benzoyl-7-di- 0.4 2.8 N.A. (not avail- 2.0 ethylaminocoumarin able) Example 2 3,3'-carbonylbis- 0.5 5.9 3.5** 3.2 (7-diethylaminocoumarin) Control C 3-(2-thenoyl)-5,7- 2.1 1.9 N.A. 0.1-0.2 dimethoxycoumarin Example 3 3-(2-thenoyl)-7-di- N.A. N.A. 1.2* 4.0 methylaminocoumarin Examples 4-20 The procedure of Example 1 was repeated, except that the photosensitizer and the activator were selected as indicated in Table II, at 0.08 mM and 0.8 mM, respectively.

Table II <img class="EMIRef" id="027056964-00100001" />

<tb> Example <SEP> Photosensitizer <SEP> Activator <SEP> Relative <SEP> Speed <tb> <SEP> 4 <SEP> 3-(p-dimethylamino- <SEP> N-methoxy-4- <SEP> 1.5 <tb> <SEP> benzoyl)-7-diethyl- <SEP> phenylpyridinium <tb> <SEP> aminocoumarin <SEP> fluoroborate <tb> <SEP> 5 <SEP> 3,3'-carbonylbis- <SEP> N-methoxy-4- <SEP> 0.8 <tb> <SEP> (7-diethylamino- <SEP> methylpyridinium <tb> <SEP> coumarin) <SEP> fluoroborate <tb> <SEP> r <tb> <SEP> 6 <SEP> R <SEP> = <SEP> C2HS <SEP> N-methoxy-4- <SEP> 1.6 <tb> <SEP> Ar <SEP> = <SEP> phenyl <SEP> phenylpyridinium <tb> <SEP> fluoroborate <tb> <SEP> 7 <SEP> R=CH3, <SEP> N-methyoxy-4- <SEP> 1.7 <tb> <SEP> Ar <SEP> = <SEP> 2-benzofuryl <SEP> phenylpyridinium <tb> <SEP> fluoroborate <tb> <SEP> 8 <SEP> R=C2H5 <SEP> " <SEP> 2.1 <tb> <SEP> Ar <SEP> = <SEP> 2-thienyl <tb> <SEP> 9 <SEP> R=CH3 <SEP> ,, <SEP> 1.6 <tb> <SEP> Ar <SEP> = <SEP> p-methoxy <tb> <SEP> phenyl <tb> 10 <SEP> R <SEP> = <SEP> C2H5, <SEP> Ar <SEP> = <SEP> 1.6 <tb> <SEP> p-thiomethoxyphenyl <tb> 11 <SEP> R <SEP> =C2H5, <SEP> Ar= <SEP> " <SEP> 1.6 <tb> <SEP> 1 <SEP> -naphthyl <tb> 12 <SEP> 2-(2-thenoyl- <SEP> ,, <SEP> 1.8 <tb> <SEP> methylene) <SEP> 1-methyl <tb> <SEP> naphtho-2, <SEP> 1 <SEP> -d <tb> <SEP> thiazoline <tb> 13 <SEP> 4-dimethylamino- <SEP> ,, <SEP> 0.38 <tb> <SEP> chalcone <tb> 14 <SEP> 3-(2-benzofuroyl)- <SEP> ,, <SEP> 3.7 <tb> <SEP> 7-diethylamino <tb> <SEP> coumarin <tb> 15 <SEP> 3-(2-benzofuroyl)-7- <SEP> " <SEP> 4.7 <tb> <SEP> (1 <SEP> -pyrrolidinyl) <tb> <SEP> coumarin <tb> 16 <SEP> 7-diethylamino-3- <SEP> " <SEP> 2.6 <tb> <SEP> (4-diethylamino <tb> <SEP> cinnamoyl)coumarin <tb> 1 <SEP> 7 <SEP> Michler's <SEP> ketone <SEP> ,, <SEP> 1.2 <tb> 18 <SEP> 2-tbis(2-furoyl)- <SEP> ,, <SEP> 1.9 <tb> <SEP> methylenej- <SEP> 1 <SEP> methyl <tb> <SEP> naphtho1 <SEP> ,2-d] <tb> <SEP> thiazoline <tb> 1 <SEP> 9 <SEP> 2-(p-pyrrolidinyl- <SEP> ,, <SEP> 0.77 <tb> <SEP> benzylidene)-1 <SEP> 3 <tb> <SEP> indanedione <tb> 20 <SEP> 2,5-bis(4-diethyl- <SEP> ,, <SEP> 1.3 <tb> <SEP> aminobenzylidene) <tb> <SEP> cyclopentanone <tb> Control <SEP> 2,5-(bis(4-ethoxy- <SEP> N-methaxy-4- <SEP> 0.15 <tb> D <SEP> benzylidene)cyclo- <SEP> phenylpyridinium <tb> <SEP> pentanone <SEP> fluoroborate <tb> A comparison of Example 20 against Control D indicates again the importance of the photosensitizer being an amino-substituted photosensitizer.

Examples 21-23-Other Activators The procedure of Example 1 was repeated, except that the photosensitizer and the activator were selected as indicated in Table ill, at 0.08 mM and 0.8 mM, respectively.

Table Ill Relative Example Photosensitizer Activator Speed Control 3-(2-benzofuroyl)-7- N-(4-nitrobenzoyl E diethylaminocoumarin oxy)phthalimide none 21 3-(2-benzofuroyl)-7- N-(2,4-dichloro diethylaminocoumarin benzoyloxy)phthal imide 0.45 22 3-(2-benzofuroyl)-7- N-(p-cyanobenzoyl diethylaminocoumarin oxy)phthalimide 0.45 23 ,, N-thenoyloxy phthalimide 0.45 Control E demonstrated that N-benzoyloxyphthalimide activators in which the benzoyl group is nitro-substituted will not respond to an excited amino-substituted photosensitizer to produce a free radical or aid in the photopolymerization of an addition-polymerizable composition.

Claims (21)

1. A co-initiator composition for the photopolymerization of addition-polymerizable compounds comprising an amino-substituted photosensitizer and an N-oxy-N-heterocyclic compound having from 5 to 14 nuclear atoms, other than nitro-substituted N-oxy-N-heterocyclic compounds as an activator.
2. A composition as claimed in Claim 1, in which the activator is an N-alkoxy-substituted pyridinium salt.
3. A composition as claimed in Claim 2, in which the N-alkoxy-substituted pyridinium salt is an N-methoxy-4-phenylpyridinium salt.
4. A composition as claimed in Claim 2, in which the N-alkoxy-substituted pyridinium salt is an N-methoxy-4-methylpyridinium salt.
5. A composition as claimed in Claim 1, in which the activator is an N-benzoyloxyphthalimide.
6. A composition as claimed in Claim 5, in which the N-benzoyloxyphthalimide is N-(2,4dichlorobenzoyloxy)phthalimide.
7. A composition as claimed in Claim 5, in which the N-benzoyloxyphthalimide is N-4cyanobenzoyloxyphthalimide.
8. A composition as claimed in Claim 1, in which the activator is N-(2-thenoyl)oxyphthalimide.
9. A composition as claimed in Claim 1, in which the activator is an N-benzoyloxynaphthalimide.
1 0. A composition as claimed in Claim 9, in which the N-benzoyloxynaphthalimide is N-4 chlorobenzenesulphonyloxy-1 ,8-naphthalimide.
11. A composition as claimed in the preceding claims in which the amino-substituted photosensitizer is an amino-substituted 3-ketocoumarin having a maximum absorption from 350 to 550 nm and represented by the formula: <img class="EMIRef" id="027056965-00110001" />
in which: R' represents an alkyl or alkenyl group having up to
1 2 carbon atoms, or a carbocyclic or heterocyclic group having from 5 to 20 nuclear atoms; and R2, R3 and R4 each individually represents a hydrogen atom, a dialkylamino group containing up to 5 carbon atoms in each alkyl portion, N-pyrrolidinyl, N-piperidinyl, or N-morpholino, or when taken together R', R2 and R3 represent the non-metallic atoms necessary to complete a fused hydroquinolizine ring; provided that at least one of the groups R2, R3 or R4 represents an amino group.
1 2. A composition as claimed in any of the Claims 1 to 10 in which the amino-substituted photosensitizer is one of those set out in Table I herein.
1 3. A co-initiator composition as claimed in any of the preceding claims in which the activator is present in an amount by weight that is ten times that of the photosensitizer.
14. A photopolymerizable composition comprising an addition-polymerizable compound and a co-initiator composition as claimed in any of the Claims 1 to 1 3.
1 5. A photopolymerisable composition as claimed in Claim 14 in which the photosensitizer comprises from 0.0002 to 0.2 millimoles per gram of dry solids.
16. A photopolymerisable composition as claimed in Claim 1 5 in which the photosensitizer comprises from 0.005 to 0.015 millimoles per gram of dry solids.
1 7. A photopolymerisable composition as claimed in any of the Claims 14 to 1 6 in which the activator comprises from 0.005 to 2.0 millimoles per gram of dry solids.
1 8. A photopolymerisable composition as claimed in Claim 1 7 in which the activator comprises from 0.05 to 0.2 millimoles per gram of dry solids.
1 9. A photopolymerisable composition as claimed in any the Claims 1 4 to 1 8 in which the addition-polymerizable compound comprises one or more acrylate compounds.
20. A photopolymerizable composition as claimed in any of the Claims 14 to 1 8 which includes a binder.
21. A photosensitive material comprising a support carrying a layer of a photopolymerizable composition as claimed in any of the Claims 14 to 20.
GB8127386A 1980-09-10 1981-09-10 Photopolymerization initiators compositions containing n-oxy-n-heterocyclic activator compounds Expired GB2083832B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18585480 true 1980-09-10 1980-09-10

Publications (2)

Publication Number Publication Date
GB2083832A true true GB2083832A (en) 1982-03-31
GB2083832B GB2083832B (en) 1984-07-25

Family

ID=22682702

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8127386A Expired GB2083832B (en) 1980-09-10 1981-09-10 Photopolymerization initiators compositions containing n-oxy-n-heterocyclic activator compounds

Country Status (5)

Country Link
JP (1) JPS5783501A (en)
CA (1) CA1216998A (en)
DE (1) DE3135399A1 (en)
FR (1) FR2489982B1 (en)
GB (1) GB2083832B (en)

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743528A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Enhanced imaging composition containing an azinium activator
US4743530A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Negative working photoresists responsive to longer wavelengths and novel coated articles
US4743531A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Dye sensitized photographic imaging system
US4743529A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Negative working photoresists responsive to shorter visible wavelengths and novel coated articles
EP0269397A2 (en) * 1986-11-21 1988-06-01 EASTMAN KODAK COMPANY (a New Jersey corporation) Dye sensitized photographic imaging system
EP0297871A2 (en) * 1987-06-30 1989-01-04 EASTMAN KODAK COMPANY (a New Jersey corporation) Novel polymethine dyes and UV absorbers and imaging materials for their use
US4839260A (en) * 1987-06-30 1989-06-13 Eastman Kodak Company Novel polymethine dyes and UV absorbers and imaging materials for their use
US4855213A (en) * 1987-06-30 1989-08-08 Eastman Kodak Company Novel polymethine dyes and imaging compositions
US4859572A (en) * 1988-05-02 1989-08-22 Eastman Kodak Company Dye sensitized photographic imaging system
US4886735A (en) * 1987-05-21 1989-12-12 Basf Aktiengesellschaft Photopolymerizable recording materials and photoresist layers and lithographic printing plates based thereon
US4935330A (en) * 1986-02-26 1990-06-19 Basf Aktiengesellschaft Photopolymerizable mixture, photosensitive recording element containing this mixture, and the production of lithographic printing plate using this photosensitive recording element
US4973694A (en) * 1988-05-09 1990-11-27 Eastman Kodak Company Benzofuran dyes containing a coumarin nucleus
EP0441232A2 (en) * 1990-02-09 1991-08-14 BASF Aktiengesellschaft Cationic photopolymerisation process
US5262278A (en) * 1991-01-25 1993-11-16 Basf Aktiengesellschaft Storage-stable solution of a carboxyl-containing copolymer and production of photosensitive coatings and offset printing plates
WO1997042227A1 (en) * 1996-05-04 1997-11-13 Ciba Specialty Chemicals Holding Inc. Polymerisable composition
US6096794A (en) * 1997-11-03 2000-08-01 Ciba Specialty Chemicals Corporation Quinolinium dyes and borates in photopolymerizable compositions
EP1134613A1 (en) * 2000-02-22 2001-09-19 Eastman Kodak Company Photobleachable composition, photographic element containing the composition and photobleach method
WO2004041544A1 (en) 2002-10-30 2004-05-21 Kodak Polychrome Graphics Llc Hetero-substituted aryl acetic acid co-initiators for ir-sensitive compositions
US7056639B2 (en) 2001-08-21 2006-06-06 Eastman Kodak Company Imageable composition containing an infrared absorber with counter anion derived from a non-volatile acid
US7365104B2 (en) 2005-03-31 2008-04-29 Eastman Kodak Company Light curable articles containing azinium salts
EP2236488A1 (en) 2001-03-30 2010-10-06 The Arizona Board of Regents on behalf of the University of Arizona Materials, methods and uses for photochemical generation of acids and/or radical species
WO2012067806A1 (en) 2010-11-15 2012-05-24 Eastman Kodak Company Photoinitiator compositions
WO2012112381A1 (en) 2011-02-14 2012-08-23 Eastman Kodak Company Photoinitiator compositions and uses
WO2012112294A1 (en) 2011-02-14 2012-08-23 Eastman Kodak Company Photocurable and photocured compositions
WO2012112371A1 (en) 2011-02-14 2012-08-23 Eastman Kodak Company Photocurable inks and methods of use
US8399533B2 (en) 2010-11-15 2013-03-19 Eastman Kodak Company Photocurable compositions containing N-oxyazinium salt photoinitiators
US9365658B2 (en) 2010-11-15 2016-06-14 Eastman Kodak Company Method of photocuring acrylate compositions
WO2016106062A1 (en) 2014-12-23 2016-06-30 Bridgestone Americas Tire Operations, Llc Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes
US9475889B2 (en) 2011-05-16 2016-10-25 Eastman Kodak Company Photoinitiator and photocurable compositions and uses

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0466503B2 (en) * 1985-07-09 1992-10-23 Hitachi Chemical Co Ltd

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3359109A (en) * 1964-04-29 1967-12-19 Du Pont Leuco dye-n, n. o-triacylhydroxylamine light-sensitive dye former compositions
US3574622A (en) * 1968-10-09 1971-04-13 Eastman Kodak Co Photopolymerization using n-alkoxy heterocyclic initiators
US4147552A (en) * 1976-05-21 1979-04-03 Eastman Kodak Company Light-sensitive compositions with 3-substituted coumarin compounds as spectral sensitizers
GB2029423A (en) * 1978-08-25 1980-03-19 Agfa Gevaert Nv Photo-polymerisable materials and recording method
JPS626223B2 (en) * 1979-03-06 1987-02-09 Fuji Photo Film Co Ltd

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4935330A (en) * 1986-02-26 1990-06-19 Basf Aktiengesellschaft Photopolymerizable mixture, photosensitive recording element containing this mixture, and the production of lithographic printing plate using this photosensitive recording element
US4743530A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Negative working photoresists responsive to longer wavelengths and novel coated articles
US4743531A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Dye sensitized photographic imaging system
US4743529A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Negative working photoresists responsive to shorter visible wavelengths and novel coated articles
EP0269397A2 (en) * 1986-11-21 1988-06-01 EASTMAN KODAK COMPANY (a New Jersey corporation) Dye sensitized photographic imaging system
EP0269398A2 (en) * 1986-11-21 1988-06-01 EASTMAN KODAK COMPANY (a New Jersey corporation) Enhanced imaging composition containing an azinium activator
EP0269397A3 (en) * 1986-11-21 1988-12-07 EASTMAN KODAK COMPANY (a New Jersey corporation) Dye sensitized photographic imaging system
EP0269398A3 (en) * 1986-11-21 1988-12-14 EASTMAN KODAK COMPANY (a New Jersey corporation) Enhanced imaging composition containing an azinium activator
US4743528A (en) * 1986-11-21 1988-05-10 Eastman Kodak Company Enhanced imaging composition containing an azinium activator
US4886735A (en) * 1987-05-21 1989-12-12 Basf Aktiengesellschaft Photopolymerizable recording materials and photoresist layers and lithographic printing plates based thereon
US4839274A (en) * 1987-06-30 1989-06-13 Eastman Kodak Company Novel polymethine dyes and UV absorbers containing a triarylborylisocyano group and imaging compositions containing these dyes
US4855213A (en) * 1987-06-30 1989-08-08 Eastman Kodak Company Novel polymethine dyes and imaging compositions
US4839260A (en) * 1987-06-30 1989-06-13 Eastman Kodak Company Novel polymethine dyes and UV absorbers and imaging materials for their use
EP0297871A2 (en) * 1987-06-30 1989-01-04 EASTMAN KODAK COMPANY (a New Jersey corporation) Novel polymethine dyes and UV absorbers and imaging materials for their use
EP0297871A3 (en) * 1987-06-30 1990-02-21 EASTMAN KODAK COMPANY (a New Jersey corporation) Novel polymethine dyes and uv absorbers and imaging materials for their use
US4859572A (en) * 1988-05-02 1989-08-22 Eastman Kodak Company Dye sensitized photographic imaging system
US4973694A (en) * 1988-05-09 1990-11-27 Eastman Kodak Company Benzofuran dyes containing a coumarin nucleus
EP0441232A2 (en) * 1990-02-09 1991-08-14 BASF Aktiengesellschaft Cationic photopolymerisation process
EP0441232A3 (en) * 1990-02-09 1992-10-14 Basf Aktiengesellschaft Cationic photopolymerisation process
US5262278A (en) * 1991-01-25 1993-11-16 Basf Aktiengesellschaft Storage-stable solution of a carboxyl-containing copolymer and production of photosensitive coatings and offset printing plates
WO1997042227A1 (en) * 1996-05-04 1997-11-13 Ciba Specialty Chemicals Holding Inc. Polymerisable composition
US6090865A (en) * 1996-05-04 2000-07-18 Ciba Specialty Chemicals Corporation Polymerizable composition
US6096794A (en) * 1997-11-03 2000-08-01 Ciba Specialty Chemicals Corporation Quinolinium dyes and borates in photopolymerizable compositions
EP1134613A1 (en) * 2000-02-22 2001-09-19 Eastman Kodak Company Photobleachable composition, photographic element containing the composition and photobleach method
US6376163B1 (en) 2000-02-22 2002-04-23 Eastman Kodak Company Photobleachable composition, photographic element containing the composition and photobleachable method
EP2236488A1 (en) 2001-03-30 2010-10-06 The Arizona Board of Regents on behalf of the University of Arizona Materials, methods and uses for photochemical generation of acids and/or radical species
US7056639B2 (en) 2001-08-21 2006-06-06 Eastman Kodak Company Imageable composition containing an infrared absorber with counter anion derived from a non-volatile acid
WO2004041544A1 (en) 2002-10-30 2004-05-21 Kodak Polychrome Graphics Llc Hetero-substituted aryl acetic acid co-initiators for ir-sensitive compositions
US7365104B2 (en) 2005-03-31 2008-04-29 Eastman Kodak Company Light curable articles containing azinium salts
WO2012067806A1 (en) 2010-11-15 2012-05-24 Eastman Kodak Company Photoinitiator compositions
US8399533B2 (en) 2010-11-15 2013-03-19 Eastman Kodak Company Photocurable compositions containing N-oxyazinium salt photoinitiators
US9365658B2 (en) 2010-11-15 2016-06-14 Eastman Kodak Company Method of photocuring acrylate compositions
WO2012112381A1 (en) 2011-02-14 2012-08-23 Eastman Kodak Company Photoinitiator compositions and uses
WO2012112294A1 (en) 2011-02-14 2012-08-23 Eastman Kodak Company Photocurable and photocured compositions
WO2012112371A1 (en) 2011-02-14 2012-08-23 Eastman Kodak Company Photocurable inks and methods of use
US9475889B2 (en) 2011-05-16 2016-10-25 Eastman Kodak Company Photoinitiator and photocurable compositions and uses
WO2016106062A1 (en) 2014-12-23 2016-06-30 Bridgestone Americas Tire Operations, Llc Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes

Also Published As

Publication number Publication date Type
FR2489982A1 (en) 1982-03-12 application
FR2489982B1 (en) 1986-02-21 grant
CA1216998A (en) 1987-01-20 grant
CA1216998A1 (en) grant
DE3135399A1 (en) 1982-07-22 application
JPS5783501A (en) 1982-05-25 application
GB2083832B (en) 1984-07-25 grant

Similar Documents

Publication Publication Date Title
US5229253A (en) Photopolymerizable mixture and recording material produced therefrom
US5235015A (en) High speed aqueous solvent developable photopolymer compositions
US6218076B1 (en) Stabilizer for organic borate salts and photosensitive composition containing the same
US5274060A (en) Copolymers crosslinkable by acid catalysis
US3844790A (en) Photopolymerizable compositions with improved resistance to oxygen inhibition
US4743531A (en) Dye sensitized photographic imaging system
US4367280A (en) Photopolymerizable composition
US4351893A (en) Derivatives of aryl ketones as visible sensitizers of photopolymerizable compositions
US6051366A (en) Visible radiation sensitive composition and recording material producible therefrom
US5055579A (en) Heterocyclic compounds containing 4,6-bis-trichloromethyl-s-triazin-2-ly groups
US3479185A (en) Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers
US5153105A (en) Thermally developable light sensitive imageable layers containing photobleachable dyes
US4743530A (en) Negative working photoresists responsive to longer wavelengths and novel coated articles
US3808006A (en) Photosensitive material containing a diaryliodium compound, a sensitizer and a color former
US5723512A (en) Dimeric bisacylphosphines, oxides and sulfides
US6034150A (en) Polymerization processes using aliphatic maleimides
US6048660A (en) Non-volatile phenylglyoxalic esters
US5055372A (en) Photohardenable composition containing borate salts and ketone initiators
US5573889A (en) Process for adjusting the sensitivity to radiation of photopolymerizable compositions
US4587200A (en) Photopolymerizable composition comprising an acridine and a heterocyclic thiol compound as a photopolymerization initiator and a photographic process using said photopolymerizable composition
US5034526A (en) Halomethyl-1,3,5-triazines containing a sensitizer moiety
US5230982A (en) Photoinitiator compositions containing disulfides and photohardenable compositions containing the same
US4162162A (en) Derivatives of aryl ketones and p-dialkyl-aminoarylaldehydes as visible sensitizers of photopolymerizable compositions
US6057380A (en) Photogeneration of amines from α-aminoacetophenones
US5451343A (en) Fluorone and pyronin y derivatives

Legal Events

Date Code Title Description
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19990910