FR2489982A1 - COMPOSITION FOR PRIMING PHOTOPOLYMERIZATION CONTAINING N-OXY-N-HETEROCYCLIC COMPOUNDS AS ACTIVATORS - Google Patents

Abstract

THE PRESENT INVENTION CONCERNS A COMPOSITION FOR INITIATING THE POLYMERIZATION OF POLYMERIZABLE MONOMERS BY ADDITION. THIS COMPOSITION CONTAINS N-OXY-N-HETEROCYCLIC COMPOUNDS HAVING 5 TO 14 INTRACYCLIC ATOMS AS ACTIVATORS AND PHOTOSENSITIZERS SUBSTITUTED BY AN AMINO GROUP. THE ADVANTAGEOUS ACTIVATORS ARE N-ALKOXYPYRIDINIUM SALTS AND THE ADVANTAGEOUS PHOTOSENSITIZERS ARE AMINO 3-CETOCOUMARINS. APPLICATION TO MICROELECTRONICS AND TO THE MANUFACTURING OF OBJECTS BY PHOTOGRAPHIC MEANS.

Description

The present invention relates to compositions for priming by

  radiation of the polymerization of the compounds

  with addition-polymerizable ethylenic unsaturation.

  In order to polymerize polymeric monomers,

  addition sands, radiation initiator compositions

  ment, hereinafter referred to as co-initiators or co-initiators

  primers, which usually comprise two compounds, a light-sensitive compound called a photosensitizer, and

  an activator compound. The activator is practically insensitive

  to the activation radiation of the co-initiator, but

  think that in the presence of the photosensitizer excites, it con-

  tribute to the formation of a free radical. Known classes of activators include amines, sulfinic acid and

  its esters, sulphones, alpha and beta dicarboxylic

  such as bornanedione and acetylacetone,

  phosphines, phosphites, stannates, and hexaarylbis

  imidazole. An effective co-initiator known for a long time is

  the combination of a Michler's ketone as photosensitization

  It has been considered for a long time to have been regarded as an industrial reference by a benzophenone activator, as described, for example, in U.S. Patent No. 3,682,641. More recently, there have been described a number of aromatic carbonyl compounds useful as photosensitizers with amine activators to form co-initiators. These compositions are described by Ledwith in J. Oil Col. Chem. Assoc., 59, p. 157 and particularly pp. 162-164 (1976). The carbonyl compounds specifically mentioned are phenones, including cyclic ketones such as benzophenone, fluorenones,

anthraquinones and anthrones.

  Although these co-initiators are very effective, most

  part of them do not give an answer to the light

  thus requiring the use of ultra-violet radiation

  purple. We found some co-initiators that have an answer

  in visible wavelengths, but their sensi-

  is so inferior to the association of ketone

  of Michler and benzophenone that they are not acceptable

tables.

  This is why the need has been felt for a long time.

  time to find a co-initiator who not only feels

  visible radiation, but has a similar sensitivity

  at or better than conventional co-initiators sensitive to UV radiation. The subject of the present invention is a co-initiator for

  the photopolymerization of the polymerizable compounds by

  said composition containing a photosensitizer

  substituted with an amino group and an activator compound,

  characterized in that said activator compound is a heterocyclic compound

  clique containing a nitrogen atom substituted by a radical

  oxy and having from 5 to 14 intra-cyclic atoms.

  The compound forms a free radical in the presence of

photo-excited sensitizer.

  The terms "addition polymerizable" or "poly-

  addition-based "refers to the chain reaction that occurs when a single photon causes the addition of more than one pattern to a growing polymer, as opposed to crosslinking where a single photon typically creates a Only crosslinking bond between the polymer molecules Without being limited to specific mechanisms, the addition polymerization which can be obtained with the co-initiator according to the invention preferably involves the production of free radicals. photosensitizer "understands in a way

  both substances which act in

  the cross-linking of polymers, as those which, as in

  case of the present invention, only sensitize the poly-

  merit by addition of simple compounds or polymers.

  With regard to the amino-substituted photosensitizers, the terms "carbocyclic", "aryl", "aromatic", "heterocyclic", "alkyl" and "alkoxy" as used hereinafter include the same. groups both substituted and unsubstituted, unless otherwise specified. Suitable substituents include alkoxy groups of 1 to 5 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, isobutoxy and pentoxy; sulfonate groups, such as fluorosulfonate; cyano; dialkylamino such as dimethylamino, diethylamino and dipropylamino; halogens such as chloro and bromo; nitro; hydroxy; and alkyl of 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl and pentyl. Alkenyl groups include aryl or substituted alkyl alkenyls, e.g.

  styryl, cinnamylidenemethyl and 2- (2-thienyl) vinyl.

  The present invention is based on the discovery that the N-oxyN-heterocyclic compounds described hereinafter act as activators in a coinitiator. In addition, we discovered

  that when using these compounds with photosensitization

  With amino-substituted resins, they unexpectedly exhibit high sensitivities, compared to those obtained when used with non-amino substituted photosensitizers. Thus, a photopolymerizable composition

  useful comprises a polymeric ethylenically unsaturated compound

  risible by addition and a co-initiator comprising a mixture of an amino-substituted photosensitizer, such as a

  3-ketocoumarin substituted with an amino group, and an

  light-curing unit as described above.

  Any compound containing ethyl unsaturation

  enic and addition polymerizable can be used with the coamins according to the invention. Advantageous compounds are simple ethylenically unsaturated monomers, as well as polymers whose ends or side chains terminate in ethylenic unsaturation. For example,

  the term "addition polymerizable" includes poly-

  mothers with structural motifs: * R

OC-CT = CH2

  It o R represents any group capable of forming the polymer backbone and T is a hydrogen atom or a

methyl group.

  Examples of ethyl-unsaturated monomeric compounds are

  enantially polymerizable additives include acrylates, acrylamides, methacrylates, methacrylamides, acrylonitriles, allylic compounds, vinyl ethers, vinyl esters, N-vinyl compounds, styrenes and crotonates. Many of the compounds belonging to each of these classes are well known, and are described, for example, in British Patent 1,534,137 and the United States Patent.

of America 3,759,807.

  Acrylates are a particularly advantageous class of addition polymerizable compounds. They have been used for years for photopolymerization, and many have been cited in the literature. Particularly useful examples include alkyl acrylates containing from 1 to 10 and more preferably from 1 to 5 carbon atoms in the alkyl part, such as methyl acrylate, ethyl methacrylate and butyl acrylate;

  tri- and tetraacrylates and tri- and tetra-

  pentaerythritol methacrylates; polyol esters

  taking glycol diacrylates and dimethacrylates, such as tripropylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol dimethacrylate, and hexanediol diacrylate; polyether diacrylates such as that sold by the firm UCB, Chemique Chaussée de Charleroi division, Brussels, Belgium under the trade name "Ebecryl 210"; and mixtures of the above compounds. Particularly preferred compounds are diacrylates and mixtures of tetraacrylates and tetramethacrylates.

  Of the two constituents of the co-initiator, it is advantageous

  photosensitizer which predominates as an absorbing

  light, i.e., all or at least 50% of the activating radiation is absorbed by the photosensitizer. Examples of useful amino-substituted photosensitizers include those having an aromatic or heterocyclic ring with an amino substituent such as a dialkylamino group containing from 1 to 5 carbon atoms in each alkyl radical, for example, dimethylamino, diethylamino, dipropylamino and dibutylamino. ; piperidinyl N-pyrrolidinyl; morpholino; or substituents which together form a hydroquinolizine ring fused with said aromatic or heterocyclic ring, for example according to the formula: U) Preferred amino-substituted photosensitizers are

  compounds containing a carbonyl group with substituents

  strong electron donors and an extinction coefficient

high level.

  For example, useful sensitizers include

  amino-thiazolines and the amino-selenazolines described in

  of the United States of America 4,062,686 and the Indanediones,

  benzophenones, benzylideneacetophenones and bisphenol

  (benzilidine) cyclopentanones substituted with an amino group.

  The most advantageous compounds are cetocoumarines of formula: ## STR2 ##

R3 / C-R

R4

  R1 is an alkyl or alkenyl group of 1 to 12 carbon atoms;

  Bone such as methyl, ethyl, propyl, isopropyl and 1-butene

  nyl, or a carbocyclic or heterocyclic group of 5 to 20 intracyclic atoms (carbon and heteroatoms); R2, R and R are each, independently, a hydrogen atom, a dialkylamino group containing from 1 to 5 carbon atoms in each of the alkyl radicals, such as dimethylamino, diethylamino, and

  dibutylamino; a cyclic alkylamino group such as N-pyrrolidone

  lidinyl, piperidinyl and morpholinyl; or R, R3 and R taken together represent the nonmetallic atoms necessary to complete a nitrogen atom containing fused ring, such as a hydroquinolizine ring; provided that at least one of

2 3 4

  R, R and R groups is an amino group. As used herein, the term "amino group" includes any N-heterocyclic group containing an uncharged nitrogen atom, bound to 3 different carbon atoms and does not include aromatic heterocyclic groups such as pyridine or pyridinium salts. Examples of heterocyclic groups for R 1 include 3-coumarinyl, benzofuryl, thienyl, furyl and pyridyl. 3-coumarinyl groups are examples

  advantageous of such heterocyclic groups.

  Also highly preferred compounds are 3-keto-marine amines having polar groups or substituents, such as ionic groups, and particularly those containing water-soluble and / or alcohols groups. Useful examples include heterocyclic onium salts, linked to the 3-position keto ring, for example.

  examples of pyridinium salts, imidazolium etc., and groups

  containing a solubilising substituent such as a carboxylate, a sulfonate, a N, N, N-trisubstituted quaternized amine group,

  for example, N-phenylene-N, N, N-trimethylammonium chloride.

  These substituents linked to the coumarin nucleus contain, for example,

  carboxy, carboxyalkyl, carboxyaryl, sulfo, sulfoalkyl, sulfoaryl and monovalent metal or ammonium salts (including tetraorganoammonium) of said carboxy and sulfo groups, and quaternary ammonium salts such as

than mentioned above.

  3-Cetocoumarin amines are particularly useful with broad spectrum light sources such as xenon and ialogen lamps or with narrow spectrum sources such as mercury lamps having a spectral emission at 366, 405, 436 and 547 nm. , or lasers emitting at 457, 488 or

515 nm.

  The following is a partial list of photosensitivity

  are substituted by a very useful amino group in the

co-initiators according to the invention.

  3- (2-benzofuroyl) -7-diethylaminocoumarin; 3- (2-benzofuroyl) -7- (1pyrrolidinyl) coumarin; 7-dimethylamino-3- (2-thenoyl) coumarin; 3- (4diméthylaminobenzoyl) -7-diethylaminocoumarin; 3,3'-carbonylbis (7diéthylaminccoumarin>); 7-diethylamino-3-Z3- (2-thienyl) acryloyl / coumarin; 3- (2-furoyl) -7-diethylaminocoumarin; 3- (4-diethylaminocinnamoyl) -7dithylaminocoumarin; 3- (4-morpdiethylaminocinnamoyl) -7diethylaminocoumarine; 3- (4-morpholinocinnamoyl) -7diethylaminocoumarihe;

  9- (7-diethylamino-3-coumarinoyl) -1,2,4,5-tetrahydro

  3H, 6H, 1OH / 17benzopyranoZ6,7,8-i, j / quinolizine-LO

one, of structure:

N (C2H5) 2

  9- (7-di-n-propylamino-3-coumarinoyl) -l, 2,4,5-tetrahydro

  3H, 6H, 1OH1 / benzopyranoZ6,7,8-i, j / quinolizine-lO-one; 9- (4-diethylaminocinnamoyl) -1,2,4,5-tetrahydro-3H, 6H, 10HZL; benzopyranoZ6,7,8I, quinolizin-10-one; 7-dimethylamino-3-3- (2-thienyl) acryloyl / coumarin;

  9-Z3- (2-thienyl) acryloyl7-1,2,4,5-tetrahydro-3H, 6H, -

  1OHZI / benzopyranoZ6,7,8-i, juinolizine-lO-one;

  7-diethylamino-3- (4-dimethylaminocinnamylidèneacetyl) -

coumarin;

  9-Z3- (9-julolidyl) acryloyl / -l, 2,4,5-tetrahydro

  3H, 6H, lOHZl / benzopyranoZ6,7,8-i, uinolizine-lO-one; 3-cinnamoyl-7-diethylaminocoumarin; 7-diethylamino-3- (4-morpholinocinnamoy) coumarin; 7-diethylamino-3- (4-ethoxycinnamoyl) coumarin; 3- (4-bromocinnamoyl) -7diethylaminocoumarine;

  7-diethylamino-3-Z3- (4-methoxy-l-naphthyl) acryloyl / -

  coumarin; 7-diethylamino-3-cinnamylidèneacetylcoumarine;

  9-Z3- (2-thienyl) acryloyl / -1,2,4,5-tetrahydro-3H, 6H, 10H

  Z1 / benzopyranoZ6,7,8-i, j / quinolizine-lO-one; 7-diethylamino-3- (3-fluorosulfonylbenzoyl) coumarin; 3- (4-cyanobenzoyl) -7diéthylaminocoumarine; 3-benzoyl-7-diméthylaminocoumarine; 3-benzoyl-7diéthylaminocoumarine; 3-benzoyl-7-pyrrolidinylcoumarine; 3- (4iodobenzoyl) -7-diméthylaminocoumarine; 3- (4-iodobenzoyl) -7diéthylaminocoumarine; 7-dimethylamino-3- (4-dimethylaminobenzoyl) coumarin; 7-diethylamino-3- (4-nitrobenzoyl) coumarin; 7-diethylamino-3- (2-thenoyl) coumarin; 7-pyrrolidinyl-3- (2-thenoyl) coumarin; 7diéthylamino-3- (2-furoyl) coumarin; 7-diethylamino-3- (2-methoxybenzoyl) coumarin; 2- (4-pyrrolidinylbenzylidène) -1,3-indandione; 4,4'bis (dimethylamino) benzophenone (Michler's ketone) 2-Lbis (2-furoyl) methylene-11-methylnaphtho-2,4-diazothiazoline; 2-Z (2-thenoyl) methylene / -1méthylnaphtoZl, 2-d / thazoline; 2-benzoylmethylene-1-ethylnaphtho / 1,2d / thiazoline; 2- / bis (2-furoyl) methylene / -2-méthylbenzothiazoline; 2,5bis (4-diethylaminobenzylidène) cyclopentanone; 4'-diméthylaminochalcone; 2 (2-thénoylméthylène) -3-méthylnaphto / 2,1-d / thiazoline. One can also use a mixture of two or more of

photosensitizers above.

  Conventional methods are used to prepare these

  tosensibilisateurs. For example, US Patent 4,147,552

  cited above, describes a process for preparing ketocoumarian

nes.

  Light-curing activators, generating a radical

  free call, which can be used with the described photosensitizer

  above, are N-oxy-N-heterocyclic compounds. Examples

  Useful compounds include compounds having one of the following formulas:

R5 R5

a) X b) XX

OR6 OR6

  c) R5 d) oex OR6 x o G OR o R5 is an alkyl group of 1 to 3 carbon atoms, such as methyl, ethyl or propyl; or aryl of 6 to 10 carbon atoms such as phenyl and naphthyl; R6 is an alkyl group of 1 to 3 carbon atoms such as methyl, ethyl, propyl and isopropyl; and X is an anion such as a fluoroborate.

  Useful activators include the N-alkoxy compounds

  N-heterocyclics described in U.S. Patent 3,615,586 and in U.S. Patent Publication No. 27925 (Table I) such as:

  2- p -anilinovinyl-1-methoxypyridine p-toluenesulfonate

  minium; p-toluenesulfonate of 1-methoxy-2-methylpyridinium; 1-methoxy-4-methylpyridinium 4-toluenesulphonate; anhydro-2-methyl-1- (3-sulfopropoxy) pyridinium hydroxide; 1-ethoxy-2-methylpyridinium tetrafluoroborate; 1-methoxy-4-phenylpyridinium tetrafluoroborate; 1-methoxy-4-methylpyridinium tetrafluoroborate; 1-benzyloxy-2-methylpyridinium bromide; 1-ethoxy-2-methylquinolinium tetrafluoroborate; 1,1'-ethylenedioxybispyridinium dibromide;

  1-acetoxy-2- (4-dimethylaminostyryl) pyridine perchlorate

minium;

  1-Benzyloxy-2- (4-dimethylaminostyryl) pyridine perchlorate

minium;

  1,3-dimethyl-5- (t-1-methoxy-2 (1H) -pyridylidene) ethyl acid

dène7-2-thiobarbituric;

  3-ethyl-5 - [[1-methoxy-2 (1H) -pyridylidene) ethylidene] rhodium;

Danine;

  1,3-diethyl-5 - [(1-methoxy-2 (1H) -pyridylidene) ethyl]

  dène7barbiturique; 2- (3,3-dicyanoalkylidene) -1,1-methoxy-1,2-dihydropyridine;

  2 - [(1-methoxy-2 (1H) -pyridylidene) -ethylidene] benzo [b] -7-

thiophen-3 (2H) -one-1,1-dioxide;

  3-cyano-5 - [(1-methoxy-2 (1H) -pyridylidene) ethylidene / -4-

  phenyl-2 (5H) -furanone; N-ethoxy-2-picolinium iodide, N-ethoxy-2-picolinium hexafluorophosphate; N-methoxy-2-anilinovinylpyridinium paratoluenesulfonate; 2 methoxy-2-methylpyridinium 2-toluenesulfonate;

Z489981

  anhydro-2-methyl-1- (3-sulfopropoxy) pyridinium hydroxide; 1-benzyloxy-2-methylpyridinium borate bromide; ethoxy-2-methylquinolinium tetrafluoroborate; 1,1-ethylenedioxybispyridinium dibromide; 1,1'-trimethylenedioxybispyridinium dibromide; 1,1'tetramethylenedioxybis (2-methylpyridinium) dibromide; 1,1'tetramethylenedioxybis (4-methylpyridinium) dibromide; 1,1'tetramethylenedioxybispyridinium dibromide; 1,1'pentamethylenedioxybispyridinium dibromide;

  1-acetoxy-2- (4-dimethylaminostyryl) pyridine perchlorate

minium;

  1-Benzyloxy-2- (4-dimethylaminostyryl) pyridine perchlorate

minium.

  Other useful activators include N, N, O-triacylhy-

  hydroxylamines containing an imide ring, for example the compounds described in column 5 of US Pat. No. 3,359,109, and particularly N-benzoyloxyphthalimides such as: N- (2,4-dichlorobenzoyloxy) phthalimide; N- (cyanobenzoyloxy) phthalimide; Nthenoyloxyphthalimide; N-benzenesulfonyloxyphthalimide; and substituted equivalents such as:

  N- (4-chlorobenzenesulfonyloxy) 1,8-naphthalimide.

  As used herein for N, N, O-triacylhydroxyl-

  amines, the term "acyl" does not include acyl groups

substituted by a nitro radical.

  The amount of photosensitizer to use is not critical. Advantageously, it is between 0.0002 and 0.2 mmol / g of dry solid, and advantageously between 0.005 and 0.015 mmol / g. It is obvious that a sufficient amount of activator

  must be present to allow the interaction between the

  excited sensitizer and activator. The quantities of

  The amount of the tivater is generally 0.005 to 2.0 mmol / g dry solid, and preferably 0.05 to 0.2. Most advantageously, the amount of activator represents 10 times

that of the photosensitizer.

  We will better understand the unexpected nature of sensiti-

  obtained with the activators according to the invention in

  the sensitivities obtained when using these activators with an amino-substituted photosensitizer and when used with a comparable non-amino-substituted photosensitizer. In fact, in the latter case, the sensitivities obtained with most of the examples of N-heterocyclic compounds according to the invention are so low that

  might wonder whether these compounds can even be considered

  as activators when used with non-amino substituted photosensitizers. Despite this,

  the sensitivities obtained with the photosensitizers

  of an amino group and an activator according to the invention are in most cases much higher than those

  we obtain when we use for the same composition photo-

  polymerizable mixture of Michler's ketone and

  phenone as co-initiator. This behavior of the N-oxy compounds

  N-heterocyclics used with photosensitizers

  substituted by an amino group, is even more remarkable

  if we recall that certain other classes of

  useful in co-initiators tend to be better

  their sensitivities when used with photosensitive

bilisers without amino substituents.

  In some applications, a binder may be added to the photopolymerizable composition. The addition-polymerizable compound is generally present at a content of between 5 and 100/100 by weight of the mixture of this compound and the binder. The thickness of the composition in the dry state can vary within wide limits. When the composition is applied to a support, the thickness in the dry state is generally included

  between 1 mm and 1 mm, and advantageously between 20 Nm and 120 Nm.

  The photopolymerizable composition can be applied to a support by a variety of techniques such as spray coating, spin coating, curtain coating,

  roll, which are all classic.

  Any suitable solvent may be selected to prepare a solution of the bed composition, for example, dichloromethane, acetone, benzene, alcohols, ethers and toluene. The choice obviously depends on the addition polymerizable compound and co-initiator, as well as other constituents that must be incorporated, such as for example polymeric binders. The photopolymerizable composition can be applied to

  various known media, including photographic media.

  Conventional carriers include polymeric films, wood fibers, for example, paper,

  metal plates, glass and ceramic supports.

  These supports are often provided with one or more layers

  to improve the adhesive properties, anti-static,

  characteristics of abrasiveness, hardness, friction and / or other properties desired for

surface of the support.

  The conventional polymeric film supports are cellulose nitrate, and cellulose ester films such as cellulose triacetate and cellulose diacetate, polystyrene, polyamides, vinyl chloride homo- and copolymers, polyacetal vinyl polycarbonates, olefin homo- and copolymers, such as polyethylene and polypropylene, and dibasic aromatic carboxylic acid polyesters with divalent alcohols, such as

  polyethylene glycol terephthalate.

  Classic paper stands are partially

  acetylated or barium-coated and / or polyolefin-coated, in particular

  bind, a polymer of a c-olefin containing from 2 to 10 carbon atoms, such as polyethylene, polypropylene, and

  copolymers, for example of ethylene and propylene.

  Further details on the media can be found in Research Disclosureir, Vol 176, publication

  17, 643, paragraph 17 (December 1978).

  The priming compositions according to the invention are useful in various applications. For example, as

  advantageous application, a product comprising a support

  as a layer of a photopolymerizable composition, preferably

  with a polymeric binder. The supports particularly

  advantageous are a copper foil or silicone pellet

  cium. These products are used in microelectronics and in the manufacture of objects by photographic means, applications in which a sheet is engraved according to a configuration

  desired. In such uses, the photo composition

  polymerisable, with a compatible binder, act as a

  negative reserve exposed and developed to form an image.

  In the context of the present invention, the binder is said to be compatible if it forms on drying a layer with a single phase

  with the co-initiator, and does not interfere with the photopolymer-

  tion. When it is desired to add a binder, it may be chosen from addition polymers, for example homopolymers, copolymers and vinyl terpolymers, particularly of acrylic monomers, or condensation polymers.

  for example, polyesters, polyamides, polysulfon-

  amides and mixtures of these compounds. However, such binders are not necessary, even for a resist, when the polymerizable compound and co-initiator form a film by themselves, for example when the polymerizable compound is of relatively high molecular weight, such as an oligomer,

or a polymer.

  Plasticizers may optionally be incorporated into

  polymerizable compositions for specific applications

  cific. However, in some cases, better

sensibilities by not putting any.

  The photopolymerizable compositions are also useful for obtaining polymeric coatings and other articles, which are exposed to activation radiation in a uniform manner,

and not according to an image.

  In the following examples, the sensitivities obtained with the various co-initiators according to the invention are given with respect to a reference sensitivity obtained with the composition containing Michler's ketone and benzophenone.

  and arbitrarily given a value of 1.

  However, because of the difficulty of comparing

  related issues when they are very different,

  the sensitivities of all compositions tried by

  to an intermediate control test B1 which is formed of

  0.08 mmol of the sensitizer 3,3'-carbonylbis (5,7-di-n-propoxy)

  coumarin) and 0.8 mmol of the activator Q-dimethylamino-

  ethyl benzoate (DMAB), added to 13 ml of the photopolymerizable composition. Using a large number of comparative tests, it was determined that the sensitivity of control test B1 compared to that of co-initiator containing the

  Michler's ketone and benzophenone was 3.5.

  The following examples show the effectiveness of co-initiators containing N-oxy-N-heterocyclic compounds as

  activators according to the invention with various photosensibilisa-

  substituted by an amino group.

EXAMPLES 1 to 3

  Coating compositions containing 0.08 mmol of the photosensitizer shown in Table I and 0.8 mmol of the activator shown in Table I are prepared in 13 ml of the

  following solution of an additive-polymerizable composition

  Pentaerythritol tetraacrylate 45.0 g Pentaerythritol tetramethacrylate 60.0 g Copolymer of methyl methacrylate, butyl methacrylate and acrylic acid (34: 63: 3)% sold by Rohm & Haas Co. under trade name "Acryloid B 48 N" (binder) 120.0 g Methyl polymethacrylate, sold by Rohm & Haas Co. under the tradename "Acryloid A 11" (binder) 120.0 g

4-hydroxy-5- t-butyl sulphide

  methylphenyl (stabilizer) 1.05 g dibutyl phthalate (plasticizer) 50.4 g Dichloromethane (solvent) 535.2 g Each solution is coated in layers of 300 gm wet thickness on a copper support placed on a sleeping block maintained at 18 ° C. After 5 minutes, the temperature of the block is raised to 66 ° C. for 10 minutes. The resulting strips are then heated in an oven at 900 ° C. for 10 minutes. They are exposed for 180 s under a KODAK T-14 sensitometric scale with an optical density increment of 0.15, and

  a propylene supplement sheet, using a

  positive "COLIGHT EXPOSURE" equipped with a sea lamp

  medium pressure cure of 400 W. The exposed strips are developed for 5 seconds with clean 1,1,1-trichloroethane,

* Rinse with water and dry.

  The sensitivities of co-initiators containing

  other than the invention are reported in Table I

  for comparison. Such activators include p-dimethyl

  ethyl aminobenzoate (DMAB), N-phenylglycine (NPG),

  4-methylphenoxyacetic acid and N-methylindole-3- acid

  ylacetic. N-phenylglycine used in Examples

  was purified by recrystallization from toluene.

  Comparing the control test A with Example 1, it can be seen, for example, that, unlike DMAB, which gives better results with an alkoxy-substituted photosensitizer, the activators according to the invention give better results.

  results with the amino photosensitizers. This behavior

  is totally unexpected, because the sensitivity obtained in

  using N-oxy-N-heterocyclic compounds with

  sensitizers substituted by an alkoxy group suggests

  that these N-oxy-N-heterocyclic compounds will not be able to

  no case act as a strong activator.

TABLE I

  Relative sensitivity with activators Photosensitizer DMAB NPG Fluoroborate

  4-Me-Phenoxyacetic acid * N-methoxy-4-

  or Me-Indole acetic ** Phenylpyridinium Witness A Witness B

Example 1

Example 2

Witness C

Example 3

3-benzoyl-7-methoxy

coumarin

3,3'-carbonylbis-

(5,7-di-n-propoxy

coumarin)

3-benzoyl-7-di-

éthylaminocoumarine

3,3'-carbonylbis-

(7-diethylamino

coumarin)

3- (2-thenoyl) -5,7

dimethoxycoumarin

3- (2-thenoyl) -7-di-

  methylaminocoumarin 2,6 3,5 0,4 0,5 2,1 2,3, 0 2,8, 9 1,9 no not available available 1,5 * not available not available 1,2X

Example

0.16 0.6 3.2 3.2

0.1-0.2

4.0 * 4 oe O6 oe N "

EXAMPLES 4 to 20 -

  The procedure of Example 1 is repeated except that the photosensitizers and activators shown in Table II are used, respectively, of 0.08 mmol and 0.8 mmol. Photosensitizer Example

3- (p-dimethylamino)

benzoyl) -7-diethyl-

aminocoumarin

3,3'-carbonylbis-

(7-diéthylamr.ino-

coumarin)

R = C2H5

Ar = phenyl

R = CH3,

Ar = 2-benzofuryl

R = C 2H5

  Ar = 2-thienyl R = CH3 Ar = p-methoxyphenyl R = C2H5, Ar pthiomethoxyphenyl R = C2H5, Ar 1-naphthyl

2- (2-thénoyl-

methylene) 1-methyl-

naphtho-2,1-d-

  thiazoline Activator Relative sensitivity Fluoroborate

N-methoxy-4-

Phenylpyridinium Fluoroborate

N-methoxy-4-

  Methylpyridinium 1.5 0.8 Fluoroborate 1.6

N-methoxy-4-phenyl

Pyridinium Fluoroborate 1.7

N-méthoxr4-

  phenylpyridinium 2.1 1.6 1.6 1.6 1.8 7 9 1 1 24899and Example Photosensitizer Activator Sensitivity 13 4-dimethylamino- "0.38 chalcone 14 3- (2-benzofuroyl) -" 3.7 7 Diethylamino-coumarin 3- (2-benzofuroyl) -7- "4,7 (1-pyrrolidinyl) coumarin 16 7-diethylamino-3-" 2,6

(4-diethylamino

  cinnamoyl) coumarin 17 Michler's ketone "1,2 18 2- / Sis (2-furoyl) -" 1,9

méthylène7-1-methyl

naphtho / T, 2-d7 / -

  thiazoline 19 2- (p-pyrrolidinyl- "0.77

benzylidene) -1,3

  indanedione 2,5-bis (4-diethyl-1,3-aminobenzylidene) cyclopentanone Control D 2,5- (bis (4-ethoxy-Fluoroborate) 0.15

benzylidene) cyclo- N-methoxy-4-

  Phenylpyrinium pentanone The comparison of Example 20 with Control D further indicates the importance of the amino substituent for the photosensitizer. EXAMPLES 21 to 23 - Other activators The procedure of Example 1 is repeated, except that the photosensitizer and the activator are those indicated in Table III, respectively, of 0.08 mmol and

0.8 mmol.

TABLE III

  Example Photosensitizer Witness E 21 23

3- (2-benzofuroyl) -7-

diethylaminocoumarin

3- (2-benzofuroyl) -7-

diethylaminocoumarin

3- (2-benzofuroyl) -7-

  Diethylaminocoumarin II Activator Relative Sensitivity N- (4-nitrobenzoyl) No oxy) phthalimide N- (2,4-dichloro-0.45)

benzoyloxy) phtal-

  imide N- (p-cyanobenzoyl-0.45 oxy) phthalimide N-thenoyloxy-0.45 phthalimide

  The control test E shows that an N-benzoyloxyphthalate

  imide in which the benzoyl group is substituted with a

  nitro radical does not respond to a substituted photosensitizer

  killed by an excited amino group to produce a free radical or to contribute to the photopolymerization of a composition

addition polymerizable.

Claims (8)

  1 - Composition for the co-priming of the photopolymerization of addition-polymerizable compounds, containing an amino-substituted photosensitizer and an activator, characterized in that the activator is an N-oxy-N-heterocyclic compound having from 5 to 14 atoms   intracyclics) with the exception of N-oxy-N-hetero-   cyclic groups substituted by a nitro group.   2 - Composition according to claim 1, characterized in that the activator is a pyridinium salt substituted on nitrogen with an alkoxy radical.   3 - Composition according to claim 2, characterized in that the activator is a salt of N-methoxy-4-phenylpyridinium   or a salt of N-methoxy-4-methylpyridinium.   4 - Composition according to claim 1, characterized in that   that the activator is N-benzoyloxyphthalimide.   - Composition according to claim 4, characterized in that   that the activator is N- (2,4-dichlorobenzoyloxy) phthalate   imide or N-4-cyanobenzoyloxyphthalimide.   6 - Composition according to claim 1, characterized in that   that the activator is N- (2-thenoyl) oxyphthalimide.   7 - Composition according to claim 1, characterized in that   that the activator is N-benzoyloxynaphthalimide.   8 - Composition according to claim 7, characterized in that   that the activator is N-4-chlorobenzensulfonyloxy-1,8- naphthalimide.   9 - Composition according to any one of claims 1 to   8, further characterized in that the photosensitizer   substituted by an amino group is an amino-3-ketocouma-   having a maximum wavelength of absorption of   between 350 nm and 550 nm and represented by the formula: R 2 R 3 R o R 1 represents an alkyl or alkenyl group of 1 to 12   carbon atoms or a carbocyclic or heterocyclic group   clicks from 5 to 20 intracyclic atoms; and R2, R3 and R each independently represent a hydrogen atom, a dialkylamino group containing from 1 to 5 carbon atoms in each alkyl radical, an N-pyrrolidinyl, N-piperidinyl, or N-morpholino group, or R1, R2 and R3 taken together, represent non-atoms   necessary to complete a hydro-   quinolizine, at least one of R, R or R4 represents an amino group.