DE102004022137B3 - Radiation-sensitive composition useful for making lithographic printing plates includes a polyfunctional oxazole, thiazole or selenazole sensitizer and a coinitiator - Google Patents

Abstract

Radiation-sensitive composition comprises an ethylenically unsaturated monomer, oligomer or polymer capable of radical polymerization; a polyfunctional oxazole, thiazole or selenazole sensitizer; and a selected coinitiator that forms radicals with the sensitizer. Radiation-sensitive composition comprises an ethylenically unsaturated monomer, oligomer or polymer capable of radical polymerization; a polyfunctional oxazole, thiazole or selenazole sensitizer of formula (I); and a coinitiator that forms radicals with the sensitizer and is selected from metallocenes, 1,3,5-triazine derivatives with 1-3 trichloromethyl or tribromomethyl groups, peroxides, hexaarylbiimidazoles, oxime ethers, oxime esters, N-arylglycines and their derivatives, thiols, N-aryl, S-aryl and O-aryl polycarboxylic acids, onium salts, alkyl triaryl borates, benzoin ethers, benzoin esters, trihalomethyl aryl sulfones, amines, Dialkylaminobenzoate esters, aromatic sulfonyl halides, imides, diazo sulfonates, 9,10-dihydroanthracene derivatives, acylphosphine oxides, diacylphosphine oxides and alpha-hydroxy or alpha-amino acetophenones. X : O, S or Se; m, n, p, q : 0 or positive integers; pi 1, pi 2, pi 3unsaturated units with conjugated pi-electron systems forming a conjugated pi-electron system with the oxazole, thiazole or selenazole rings; R 1>-R 3>H, halo, alkyl, aralkyl, NR 4>R 5> or OR 6>; R 4>-R 6>alkyl, aryl or aralkyl. Independent claims are also included for: (1) radiation-sensitive element comprising a support coated with a composition as above; (2) forming an image on a radiation-sensitive element as above by irradiating the element imagewise with UV radiation of wavelength greater than 300 nm and removing unirradiated regions of the coating with an aqueous alkaline developer; (3) image-bearing element produced as above; (4) producing a radiation-sensitive element by applying a composition as above onto a pretreated supporf and drying the product. [Image].

Description

The This invention relates to radiation-sensitive compositions, in particular radiation-sensitive compositions containing the π-branched compounds as Sensitiser included. The invention also relates to this based imageable elements, a method of preparation of such elements, a method of imaging such elements and an imaged element, such as. B. a lithographic printing plate.

The The field of lithographic printing is based on immiscibility of oil and water, being the oily one Material or ink preferably from the image area and the Water or dampening agent preferably adopted from the non-image area becomes. If a properly prepared surface is moistened with water and then applied a printing ink, the background or the takes Non-image area the water and rejects the ink while the Image area takes the ink and repels the water. The printing ink on the image area is then applied to the surface of a material, such as paper, Tissue and the like, transferred, on which the picture should be created. In general, the But first transfer ink to an intermediate material called a blanket which then transfers the ink to the surface of the material which the image should be created; This is called offset lithography.

A often used type of lithographic printing plate precursor has one on a carrier aluminum-based, photosensitive coating on. The coating can react to radiation by exposing the exposed one Part so soluble will be removed in the development process. Such a plate is called positive working. Conversely, a plate referred to as negative working when the exposed part of the coating cured by the radiation becomes. In both cases The remaining image area absorbs ink or is oleophilic and the non-image area (background) absorbs water or is hydrophilic. The differentiation between image and non-image areas takes place when exposing, with a film on the plate precursor - to ensure a good contact with vacuum - is applied. The plate is then exposed to a radiation source. Alternatively, you can the plate also digitally without film, z. B. with a UV laser exposed become. If a positive plate is used, that is the image on the plate corresponding area on the film so opaque that Light does not reach the plate while the non-image area appropriate area on the film is clear and the light transmission on the coating, which is then more soluble is allowed. In the case of a negative plate, the reverse is true to: The area corresponding to the image area on the film is clear while the non-image area is opaque. The coating under the clear film area is hardened by the action of light, while the The area not reached by the light is removed during development. The photohardened surface a negative plate is therefore oleophilic and takes printing ink on, while the non-image area which is affected by the action of a developer removed coating, desensitized and therefore is hydrophilic.

Photosensitive Mixtures have been used for years in photopolymerizable compositions for the production of photosensitive materials, such. B. printing plate precursors used. Specially for however, newer applications (eg laser exposure) are becoming more common improved sensitivity, especially in the near UV and visible Spectral range needed, so that the shutter speed is shortened can be. For economic reasons View is interesting, radiation sources with lower photon output instead to use high-power lasers, since these at the present time cost-effective are. It is therefore being tried for some time, the sensitivity of photosensitive mixtures in photopolymerizable Compositions should be used to increase.

DE 30 21 599 A1 discloses radiation-sensitive compositions containing ethylenically unsaturated monomers and a 2- (halomethyl-phenyl) -4-halo-oxazole derivative as a photoinitiator. However, the efficiency of the photoinitiator is insufficient.

US 3,912,606 describes UV curable compositions for films and coatings containing, in addition to ethylenically unsaturated monomers, a photoinitiator selected from haloalkylbenzoxazoles, benzimidazoles and benzothiazoles. Even with these compositions, the efficiency of the photoinitiator is insufficient.

EP 0 741 333 A1 describes photopolymerizable compositions which, in addition to ethylenically unsaturated monomers and organic binders, a combination of an optical brightener and a photoinitiator selected from acyl and diacylphosphine oxides. As optical brighteners, those are mentioned which contain a stilbene, triazine, thiazole, benzoxazole, coumarin, xanthene, triazole, oxazole, thiophene or pyrazoline unit. However, these photopolymerizable compositions do not show sufficient sensitivity by today's standards.

US 3,647,467 describes "photoactivatable" compositions comprising a hexaarylbiimidazole and a heterocyclic compound Ar ¹ -G-Ar ² (wherein Ar ^{1 is} an aryl radical having 6 to 12 ring carbon atoms, Ar ^{2 is} either Ar ¹ or an arylene G-Ar ¹ radical, and G is a divalent furan, oxazole or oxadiazole ring). However, the radiation sensitivity of these compositions is not sufficient for today's requirements.

In US 3,652,275 2-mercaptobenzoxazoles are used as chain transfer agents in "photoactivatable" compositions. However, these compounds do not act as a radiation absorber (sensitizer) in the context of the present invention.

In EP 1 349 006 A1 describes photopolymerizable compositions comprising a binder, a polymerizable compound, an optical brightener as a sensitizer and a photoinitiator. For the irradiation, a wavelength in the range of 300 to 450 nm is used.

In US 6,267,913 B1 and WO 02/079691 A1 describes compounds which are suitable for simultaneous 2-photon absorption.

WHERE 01/96962 A2 and US 2001/0003032 A1 disclose irradiation methods for wide Areas of photopolymers with short-pulse lasers, where a 2-photon-initiated Polymerization occurs.

In DE 11 20 875 B and EP 0 129 059 A1 describes the synthesis of triaryloxazoles and their use as photoconductive substances in electrophotographic elements. None of these documents describes the use of such substances for radical photopolymerization.

It The object of the invention is radiation-sensitive compositions to disposal to provide radiation-sensitive elements with high photosensitivity at the same time good storage stability and yellow light resistance and in Trap of printing plates - high Edition performance on the press, lead.

• (a) ein oder mehrere Arten Monomere und/oder Oligomere und/oder Polymere mit jeweils mindestens einer ethylenisch ungesättigten Gruppe, die einer radikalischen Polymerisation zugänglich ist,
• (b) mindestens einen Sensibilisator,
• (c) mindestens einen Co-Initiator, der zusammen mit dem Sensibilisator (b) Radikale bilden kann und ausgewählt wird aus folgenden Verbindungsklassen: Metallocenen; 1,3,5-Triazinderivaten mit ein bis drei CX₃-Gruppen, wobei X Chlor oder Brom ist; Peroxiden; Hexaarylbiimidazolen; Oximethern; Oximestern; N-Arylglycinen und Derivaten davon; Thiolverbindungen; N-Aryl-, S-Aryl- und O-Aryl-Polycarbonsäuren mit mindestens 2 Carboxylgruppen, von denen mindestens eine an das N-, S- oder O- Atom der Aryleinheit gebunden ist; Oniumsalzen; Alkyltriarylboraten; Benzoinethern; Benzoinestern; Trihalogenmethylarylsulfonen; Aminen; N,N-Dialkylaminobenzoesäureestern; aromatischen Sulfonylhalogeniden; Imiden; Diazosulfonaten; Acylphosphinoxiden, Diacylphosphinoxiden, 9,10-Dihydroanthracenderivaten; α-Hydroxy- und α-Amino-Acetophenonen; und
• (d) gegebenenfalls ein oder mehrere Komponenten ausgewählt aus alkali-löslichen Bindemitteln, Farbmitteln, Belichtungsindikatoren, Weichmachern, Kettenübertragungsmitteln, Leucofarbstoffen, oberflächenaktiven Mitteln, anorganischen Füllstoffen und Thermopolymerisationsinhibitoren,

dadurch gekennzeichnet, dass es sich bei dem mindestens einen Sensibilisator um eine Verbindung der Formel (I) handelt

wobei
X ausgewählt wird aus O, S und Se;
n für 0 oder eine ganze positive Zahl steht;
m, p und q unabhängig voneinander 0 oder eine ganze positive Zahl sind;
die π-Einheiten

unabhängig voneinander ungesättigte Einheiten mit jeweils konjugiertem π-Elektronensystem sind, die kovalent an die heterocyclische Einheit

gebunden sind und zusammen mit dieser wiederum ein konjugiertes π-Elektronensystem bilden und
jeder Rest R¹, R² und R³ unabhängig voneinander aus einem Wasserstoffatom, einem Halogenatom, einem Alkylrest, einem Aralkylrest, einem Rest -NR⁴R⁵ und einem Rest -OR⁶ ausgewählt wird,
wobei
R⁴, R⁵ und R⁶ unabhängig voneinander aus einem Alkylrest, Arylrest und Aralkylrest ausgewählt werden,
und wobei bei jedem der Substituenten von

R², R³, p und q unabhängig ausgewählt wird.The object of the invention is achieved by a radiation-sensitive composition comprising

• (a) one or more types of monomers and / or oligomers and / or polymers each having at least one ethylenically unsaturated group which is amenable to free-radical polymerization,
• (b) at least one sensitizer,
• (C) at least one co-initiator which can form radicals together with the sensitizer (b) and is selected from the following classes of compounds: metallocenes; 1,3,5-triazine derivatives having one to three CX ₃ groups, wherein X is chloro or bromo; peroxides; hexaarylbiimidazoles; oxime ethers; oxime esters; N-arylglycines and derivatives thereof; thiol compounds; N-aryl, S-aryl and O-aryl polycarboxylic acids having at least 2 carboxyl groups, at least one of which is bonded to the N, S or O atom of the aryl moiety; onium salts; Alkyltriarylboraten; benzoin ethers; Benzoinestern; Trihalogenmethylarylsulfonen; amines; N, N-Dialkylaminobenzoesäureestern; aromatic sulfonyl halides; imides; Diazosulfonaten; Acylphosphine oxides, diacylphosphine oxides, 9,10-dihydroanthracene derivatives; α-hydroxy and α-amino-acetophenones; and
• (d) optionally one or more components selected from alkali-soluble binders, colorants, exposure indicators, plasticizers, chain transfer agents, leuco dyes, surfactants, inorganic fillers and thermopolymerization inhibitors,

characterized in that the at least one sensitizer is a compound of the formula (I)

in which
X is selected from O, S and Se;
n is 0 or a whole positive number;
m, p and q are independently 0 or a whole positive number;
the π units

are each independently unsaturated units each having a conjugated π-electron system covalently attached to the heterocyclic moiety

are bound and together with this in turn form a conjugated π-electron system and
each R ¹ , R ² and R ^{3 is} independently selected from hydrogen, halogen, alkyl, aralkyl, -NR ⁴ R ⁵ and -OR ⁶ ;
in which
R ⁴ , R ⁵ and R ^{6 are} independently selected from an alkyl group, aryl group and aralkyl group,
and wherein each of the substituents of

R ² , R ³ , p and q are independently selected.

1 schematically shows the experimental setup used in Examples 20 to 25 for a 2-photon irradiation.

Unless defined otherwise, in the context of this invention an alkyl radical is understood to mean a straight-chain, branched or cyclic saturated hydrocarbon radical which preferably has 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The alkyl radical may optionally have one or more substituents (preferably 0 or 1 substituent), for example selected from halogen atoms (fluorine, chlorine, bromine, iodine), CN, NO ₂ , NR ⁷ ₂ , COOR ⁷ and OR ⁷ (R ⁷ independently represents a hydrogen atom, an alkyl radical or an aryl radical). The above Definition also applies to the alkyl moiety of an aralkyl radical and an alkoxy radical.

Unless defined otherwise, an aryl radical in the context of this invention is understood as meaning an aromatic carbocyclic radical having one or more fused rings, which preferably has 5 to 14 carbon atoms. The aryl radical may optionally have one or more substituents (preferably 0 to 3), for example selected from halogen atoms, alkyl radicals, alkoxy radicals, CN, NO ₂ , NR ⁷ ₂ , COOR ⁷ and OR ⁷ (where each R ^{7 is} independently hydrogen, Alkyl and aryl is selected). The above definition also applies to an arylene radical and the aryl moiety of an aralkyl radical. Preferred examples are a phenyl group and a naphthyl group, which may be optionally substituted.

in the This invention is under a fused ring or Ring system understood a ring connected to the ring to which it condenses is, has two carbon atoms in common.

Unless defined otherwise, in the context of this invention a heterocyclic radical is understood as meaning a 5- to 7-membered (preferably 5- or 6-membered) saturated, unsaturated (non-aromatic) or aromatic ring in which one or more ring carbon atoms is interrupted Heteroatoms selected from N, NR ⁸ , S and O, are replaced (preferably N or NR ⁸ ). The heterocyclic ring may optionally have one or more substituents, for example, selected from alkyl radicals, aryl radicals, aralkyl radicals, halogen atoms, -OR ⁸ , -NR ⁸ ₂ , -C (O) OR ⁸ , C (O) NR ⁸ _2, and CN (wherein each R ^{8 is} independently selected from hydrogen, alkyl, aryl and aralkyl).

When ethylenically unsaturated Monomers, oligomers and polymers can all monomers, oligomers and polymers Polymers can be used which are radically polymerizable and having at least one C-C double bond. It can too Monomers / oligomers / polymers with C-C triple bonds are used, but they are not preferred. Suitable compounds are those skilled in the art well known and can without special limitations are used in the present invention. Preferred are esters of acrylic or methacrylic acid, itaconic acid, the Crotonic and isocrotonic acid, maleic acid and the fumaric acid with one or more unsaturated Groups in the form of monomers, oligomers or prepolymers. You can in solid or liquid Form are present, with solid and viscous forms are preferred. Examples of compounds which are useful as monomers include Trimethylolpropane triacrylate and methacrylate, pentaerythritol triacrylate and methacrylate, dipentaerythritol monohydroxypentaacrylate and methacrylate, dipentaerythritol hexaacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, di (trimethylolpropane) tetraacrylate and methacrylate, diethylene glycol diacrylate and methacrylate, triethylene glycol diacrylate and methacrylate or tetraethylene glycol diacrylate and methacrylate. Suitable oligomers or prepolymers are, for example, urethane acrylates and methacrylates, epoxy acrylates and methacrylates, polyester acrylates and methacrylates, polyether acrylates and methacrylates or unsaturated polyester resins.

In addition to monomers and / or oligomers, it is also possible to use polymers which contain free-radically polymerizable CC double bonds in the main or side chain. Examples of these are reaction products of maleic anhydride copolymers with hydroxyalkyl (meth) acrylates (see, for example, US Pat. DE 4 311 738 C1 ); (Meth) acrylic acid polymers, partially or completely esterified with allyl alcohol (see eg. DE 3 332 640 A1 ); Reaction products of polymeric polyhydric alcohols with isocyanatoalkyl (meth) acrylates; unsaturated polyesters; (meth) acrylate-terminated polystyrenes; Poly (meth) acrylate; Poly (meth) acrylic acids; Poly (meth) acrylamides; (Meth) acrylic acid polymers partially or completely esterified with epoxides containing radically polymerizable groups; and polymers with allyl side groups, which can be prepared, for example, by polymerization of allyl (meth) acrylate, optionally with further comonomers.

Radically polymerizable compounds employable in the present invention are also those having a molecular weight of 3,000 or less, which are reaction products obtained when a diisocyanate is reacted simultaneously with (i) an ethylenically unsaturated compound containing a hydroxy group and (ii) a saturated organic compound with an NH group and an OH group is reacted, wherein the following conditions apply to the amounts of reactants used:
number of moles of isocyanate groups used ≤ number of moles of OH plus NH groups used.

Examples of diisocyanates can be represented by the following formula: O = C = N- (CR ⁹ ₂ ) _a -D- (CR ⁹ ₂ ) _b -N = C = O (III) wherein a and b are independently 0 or an integer from 1 to 3, each R ^{9 is} independently selected from H and C ₁ -C ₃ alkyl, and D is a saturated or unsaturated spacer, optionally in addition to the two isocyanate groups may have further substituents. D may be a chain unit, or an annular unit. In the context of this invention, a diisocyanate is understood as meaning an organic compound which contains 2 isocyanate groups but has neither OH nor secondary and primary amino groups.

R ⁹ is preferably H or CH ₃ .

a and b are preferably independent from each other 0 or 1.

D can z. B. an alkanediyl radical (CH ₂ ) _w , where w is an integer from 1 to 12, preferably 1 to 6 and optionally one or more hydrogen atoms by substituents, such as. B. alkyl radicals (preferably C ₁ -C ₆ ) are replaced, a Cycloalkandiylrest, arylene radical, saturated or unsaturated heterocyclic radical.

As suitable diisocyanates may be mentioned, for example:
trimethyl
1,6-bis- [isocyanate] -hexane
5-isocyanate-3- (isocyanatomethyl) -1,1,3-trimethylcyclohexane
1,3-bis- [5-isocyanate-1,1,3-trimethyl-phenyl] -2,4-dioxo-1,3-diazetidine
3,6-bis- [9-isocyanatnonyl] -4,5-di- (1-heptenyl) cyclohexene
Bis- [4-isocyanate-cyclohexyl] -methane
trans-1,4-bis- [isocyanate] -cyclohexane
1,3-bis- [isocyanatomethyl] -benzene
1,3-bis- [1-isocyanate-1-methyl-ethyl] benzene
1,4-bis- [2-isocyanatoethyl] -cyclohexane
1,3-bis- [isocyanatomethyl] cyclohexane
1,4-bis- [1-isocyanate-1-methyl-ethyl] benzene
Bis [isocyanate] -isododecyl-benzene
1,4-bis- [isocyanate] -benzene
2,4-bis- [isocyanate] -toluene
2,6-bis [isocyanate] toluene
N, N'-bis- [3-isocyanate-4-methyl-phenyl] -urea
1,3-bis- [3-isocyanate-4-methyl-phenyl] -2,4-dioxo-1,3-diazetidine
Bis- [2-isocyanate-phenyl] -methane
(2-isocyanate-phenyl) - (4-isocyanate-phenyl) -methane
Bis- [4-isocyanate-phenyl] -methane
1,5-bis- [isocyanate] -naphthalene
4,4'-bis- [isocyanate] -3,3'-dimethyl-biphenyl

at the ethylenically unsaturated Compound (i) containing a hydroxy group is at least one non-aromatic C-C double bond present, which is preferably terminal. The hydroxy group is preferably not double bonded Bonded carbon atom; the hydroxy group is not a constituent of a carboxyl group. The ethylenic unsaturated Contains compound (i) besides the one OH group no further functional groups, such as NH, which can react with the isocyanate.

Examples of the ethylenically unsaturated compound (i) are
Hydroxy (C ₁ -C ₁₂ ) alkyl (meth) acrylates (eg 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxy-propyl (meth) acrylate, 2-, 3- or 4-hydroxybutyl (meth ) acrylate), hydroxy (C ₁ -C ₁₂ ) alkyl (meth) acrylamides (eg 2-hydroxyethyl (meth) acrylamide, 2- or 3-hydroxypropyl (meth) acrylamide, 2-, 3- or 4-hydroxybutyl (meth) acrylamide), mono (meth) acrylates of oligomeric or polymeric ethylene glycols or propylene glycols (for example, polyethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate), allyl alcohol, pentaerythritol tri (meth) acrylate, 4-hydroxy (C ₁ -C ₁₂ ) alkylstyrene (e.g., 4-hydroxymethylstyrene), 4-hydroxystyrene, hydroxycyclohexyl (meth) acrylate.

With the notation "(meth) acrylate" is within the scope of this Invention meant both methacrylate and acrylate.

at the saturated one Organic compound (ii) is a compound with an OH and an NH group.

wobei R¹⁰ ein geradkettiger (vorzugsweise C₁-C₁₂, besonders bevorzugt C₁-C₄), verzweigter (vorzugsweise C₃-C₁₂, besonders bevorzugt C₃-C₆) oder cyclischer (vorzugsweise C₃-C₈, besonders bevorzugt C₅-C₆) Alkylrest ist,
E ein geradkettiger (vorzugsweise C₁-C₆, besonders bevorzugt C₁-C₂), verzweigter (vorzugsweise C₃-C₁₂, besonders bevorzugt C₃-C₆) oder cyclischer (vorzugsweise C₃-C₈, besonders bevorzugt C₅-C₆) Alkandiylrest ist,

für einen gesättigten heterocyclischen Ring steht, der 5-7 Ringatome aufweist und gegebenenfalls neben dem gezeigten N-Atom noch ein weiteres Heteroatom ausgewählt aus S, O und NR¹² aufweist, wobei R¹² ein Alkylrest ist, der gegebenenfalls mit einer OH-Gruppe substituiert ist,
R¹¹ OH oder ein geradkettiger, verzweigter oder cyclischer Alkylrest ist, der mit einer OH-Gruppe substituiert ist, und
z = 0 gilt, wenn der heterocyclische Ring NR¹² aufweist und R¹² ein mit OH substituierter Alkylrest ist und
z = 1 ist, wenn der gesättigte heterocyclische Ring kein NR¹² aufweist oder der gesättigte heterocyclische Ring ein NR¹² aufweist und R¹² ein unsubstituierter Alkylrest ist.The saturated organic compound (ii) may, for. As represented by the following formula (IV) or (V)

where R ^{10 is} a straight-chain (preferably C ₁ -C ₁₂ , particularly preferably C ₁ -C ₄ ), branched (preferably C ₃ -C ₁₂ , particularly preferably C ₃ -C ₆ ) or cyclic (preferably C ₃ -C ₈ , especially preferably C ₅ -C ₆ ) is alkyl radical,
E is a straight-chain (preferably C ₁ -C ₆ , particularly preferably C ₁ -C ₂ ), branched (preferably C ₃ -C ₁₂ , particularly preferably C ₃ -C ₆ ) or cyclic (preferably C ₃ -C ₈ , particularly preferably C ₅ -C ₆ ) alkanediyl radical,

is a saturated heterocyclic ring having 5-7 ring atoms and optionally in addition to the N atom shown yet another heteroatom selected from S, O and NR ¹² , wherein R ^{12 is} an alkyl radical optionally substituted with an OH group is
R ^{11 is} OH or a straight-chain, branched or cyclic alkyl radical which is substituted by an OH group, and
z = 0 when the heterocyclic ring has NR ¹² and R ^{12 is} an alkyl substituted with OH and
z = 1 when the saturated heterocyclic ring does not have NR ¹² or the saturated heterocyclic ring has NR ¹² and R ^{12 is} unsubstituted alkyl.

For compounds of the formula (IV), preference is given to those in which E is -CH ₂ CH ₂ - and R ^{10 is} a straight-chain C ₁ -C ₁₂ (preferably C ₁ -C ₄ ) alkyl radical.

Preferred compounds of formula (V) are those in which either no further heteroatom is present in the ring and R ^{11 is} an alkyl substituted with OH (ie, hydroxyalkyl substituted piperidines) or an NR ^{12 is present} in the ring and R ^{12 is} with OH is substituted alkyl (ie N-hydroxyalkyl substituted piperazines).

In particular, the following are to be mentioned as compound (ii):
2- or 3- (2-hydroxyethyl) piperidine,
2- or 3-hydroxymethylpiperidine,
N- (2-hydroxyethyl) piperazine and
N- (2-hydroxymethyl) piperazine.

The used molar number of isocyanate groups may be at most as large as the number of moles of OH and NH groups used together, since in the Product no free isocyanate groups should be present.

The Reaction of the diisocyanate with the ethylenically unsaturated Compound (i) and the saturated compound (ii) is usually done in an aprotic solvent, such as a ketone (e.g., acetone, methyl ethyl ketone, diethyl ketone, cyclopentanone and cyclohexanone), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, Dioxane and 1,2-dioxolane) and esters (e.g., ethyl acetate, methyl acetate, Butyl acetate, ethylene glycol diacetate, methyl lactate and ethyl lactate) or in a technical solvent, such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Etc.

It is preferable to use a catalyst for condensation reactions. It can all be knew catalysts suitable for condensation reactions. Examples which may be mentioned here tertiary amines, such as triethylamine, pyridine, etc., and tin compounds, such as dibutyltin dilaurate.

Prefers is running? Reaction at 10 to 120 ° C, more preferably at 30 to 70 ° C from.

at optimized synthesis conditions can obtain a uniform product become. In general, however, it can be assumed that a product mixture arises. The molecular weight of the product should be 3000 or less be. If it is a product mixture is under Molecular weight means the weight average. In the present The invention can be used as a radically polymerizable compound a uniform reaction product as well as a product mixture be used.

Further suitable CC-unsaturated free-radically polymerizable compounds are, for example, in EP 1 176 007 A2 described.

It is natural possible, various types of monomers or oligomers or polymers in mixture, as are mixtures of monomers and oligomers and / or polymers can be used according to the invention, and mixtures of oligomers and polymers. The proportion by weight of free-radically polymerizable Monomers / oligomers / polymers preferably 5 to 95 wt .-%, when using monomers / oligomers particularly preferably from 20 to 85% by weight, based on the dry layer weight of a radiation-sensitive coating prepared from the radiation-sensitive composition according to the invention. The term "dry layer weight the radiation-sensitive coating "is thus within the scope of this invention synonymous with "solids the radiation-sensitive composition ".

in the A compound of this invention is a sensitizer understood, which can absorb radiation during exposure, but alone, d. H. without the addition of coinitiators, can not form radicals.

In The present invention may be a sensitizer or a mixture be used from two or more.

wobei
X ausgewählt wird aus O, S und Se;
n für 0 oder eine ganze positive Zahl steht;
m, p und q unabhängig voneinander 0 oder eine ganze positive Zahl sind;
die π-Einheiten

unabhängig voneinander ungesättigte Einheiten mit jeweils konjugiertem π-Elektronensystem sind, die kovalent an die heterocyclische Einheit

gebunden sind und zusammen mit dieser wiederum ein konjugiertes π-Elektronensystem bilden und
jeder Rest R¹, R² und R³ unabhängig voneinander aus einem Wasserstoffatom, einem Halogenatom, einem Alkylrest, einem Aralkylrest, einem Rest -NR⁴R⁵ und einem Rest OR⁶ ausgewählt wird,
wobei R⁴, R⁵ und R⁶ unabhängig voneinander aus einem Alkylrest, Arylrest und Aralkylrest ausgewählt werden.According to the invention, the sensitizer used is a compound of the formula (I):

in which
X is selected from O, S and Se;
n is 0 or a whole positive number;
m, p and q are independently 0 or a whole positive number;
the π units

are each independently unsaturated units each having a conjugated π-electron system covalently attached to the heterocyclic moiety

are bound and together with this in turn form a conjugated π-electron system and
each R ¹ , R ² and R ^{3 is} independently selected from hydrogen, halogen, alkyl, aralkyl, -NR ⁴ R ⁵ and OR ⁶ ;
wherein R ⁴ , R ⁵ and R ^{6 are} independently selected from an alkyl group, aryl group and aralkyl group.

zur Verfügung stehenden Bindungsstellen beschränkt ist; das Gleiche gilt natürlich für die maximale Anzahl (2 + n) der an

gebundenen heterocyclischen Einheiten.It will be understood by those skilled in the art that the maximum number of substituents R ¹ , R ^2, and R ³ (ie, m, p, and q) will be limited by those at the π units

is limited to available binding sites; The same applies of course to the maximum number (2 + n) of the

bonded heterocyclic units.

When X = O, 2,4,5-substituted oxazoles result,
at X = S corresponding to 2,4,5-substituted thiazoles and
when X = Se corresponding to 2,4,5-substituted selenazoles; Of these, oxazoles and thiazoles are preferred, and oxazoles are particularly preferred.

n is preferably 0, 1 or 2, more preferably 0 or 1.

ist mindestens zweimal (n = 0) an

gebunden; es ist nicht erforderlich, dass diese Substituenten von

alle gleich sind, das heißt, bei jedem dieser Substituenten von

wird jedes X,

R², R³, p und q unabhängig ausgewählt.The substituted heterocyclic unit

is at least twice (n = 0) on

bound; it is not necessary for these substituents to be of

all are the same, that is, for each of these substituents of

every X,

R ² , R ³ , p and q are independently selected.

wird vorzugsweise ausgewählt aus:
einem Polyenrest SUS-1 mit alternierenden Doppelbindungen:

wobei z₁ eine ganze positive Zahl (vorzugsweise 1 bis 3, besonders bevorzugt 1 oder 2) ist, und
R^a und R^b unabhängig voneinander ausgewählt werden aus H, Alkyl, Aryl, Halogen, -CN, -COOH und -COO-Alkyl (bevorzugt H, -CN und CH₃),
einem Polyinrest SUS-2 mit alternierenden Dreifachbindungen:

wobei z₂ eine ganze positive Zahl (vorzugsweise 1 oder 2, besonders bevorzugt 1) ist,
einem Rest SUS-3, bei dem es sich um eine π-verzweigte aromatische Einheit mit (4n + 2) π-Elektronen handelt, vorzugsweise eine der Strukturen SUS-3-a, SUS-3-b und SUS-3-c:

einem Rest SUS-4, bei dem es sich um eine π-verzweigte elektronenarme heteroaromatische Einheit handelt, vorzugsweise einen Rest SUS-4-a, SUS-4-b, SUS-4-c, SUS-4-d und SUS-4-e

einem Rest SUS-5, bei dem es sich um eine π-verzweigte elektronenreiche heteroaromatische Einheit handelt, vorzugsweise einen Rest SUS-5-a, SUS-5-b oder SUS-5-c

wobei X ausgewählt wird aus O, S und Se und
einem Rest SUS-6, bei dem es sich um eine π-verzweigte elektronenreiche heteroaromatische Einheit mit zwei ankondensierten Benzolringen handelt,

wobei X¹ für ein Heteroatom steht, vorzugsweise für O, S, Se, NH oder N-Alkyl (wobei der Alkylrest vorzugsweise 1 bis 5 Kohlenstoffatome aufweist), besonders bevorzugt für O oder S;
als Einheit

können auch Kombinationen der vorstehenden Reste SUS-1 bis SUS-6 verwendet werden, solange dabei die π-Konjugation in der Einheit

und des gesamten Systems (I) nicht verloren geht.The unsaturated unit

is preferably selected from:
a polyene radical SUS-1 with alternating double bonds:

wherein z _{1 is} a whole positive number (preferably 1 to 3, more preferably 1 or 2), and
R ^a and R ^{b are} independently selected from H, alkyl, aryl, halo, -CN, -COOH and -COO-alkyl (preferably H, -CN and CH ₃ ),
a polyunsist SUS-2 with alternating triple bonds:

where z _{2 is} a whole positive number (preferably 1 or 2, more preferably 1),
a residue SUS-3 which is a π-branched aromatic moiety with (4n + 2) π-electrons, preferably one of the structures SUS-3-a, SUS-3-b and SUS-3-c:

a residue SUS-4, which is a π-branched, electron-deficient heteroaromatic unit, preferably a residue SUS-4-a, SUS-4-b, SUS-4-c, SUS-4-d and SUS-4 -e

a residue SUS-5, which is a π-branched electron-rich heteroaromatic moiety, preferably a residue SUS-5-a, SUS-5-b or SUS-5-c

where X is selected from O, S and Se and
a residue SUS-6, which is a π-branched electron-rich heteroaromatic unit with two fused benzene rings,

wherein X ^{1 is} a heteroatom, preferably O, S, Se, NH or N-alkyl (wherein the alkyl group preferably has 1 to 5 carbon atoms), more preferably O or S;
as a unit

It is also possible to use combinations of the above radicals SUS-1 to SUS-6, as long as the π-conjugation in the unit

and the entire system (I) is not lost.

The optional substituents R ¹ are not shown in the residues SUS-1 to SUS-6.

stellen vorzugsweise ebenfalls Strukturen SUS-1 bis SUS-6 dar; die optionalen Substituenten R² und R³ sind nicht gezeigt. Besonders bevorzugt stehen

jeweils für gegebenenfalls substituierte Arylreste, insbesondere für Phenylgruppen, die gegebenenfalls ein- oder mehrfach mit einem Halogenatom oder einem Rest NR⁷ ₂ (jedes R⁷ ist dabei vorzugsweise unabhängig ausgewählt aus Alkyl und Aryl) substituiert sind.The units

also preferably represent structures SUS-1 to SUS-6; the optional substituents R ² and R ³ are not shown. Particularly preferred stand

in each case optionally substituted aryl radicals, in particular phenyl, which are optionally mono- or polysubstituted by a halogen atom or a radical NR ⁷ ₂ (each R ⁷ is preferably independently selected from alkyl and aryl).

gemäß

sind keine erfindungsgemäßen Sensibilisatoren; die Weschselwirkung zwischen

resultiert in Chromophoren, die nicht zu einem hochempfindlichen Photosystem führen.Compounds with a covalent bond between

according to

are not sensitisers according to the invention; the Weschsel effect between

results in chromophores that do not result in a highly sensitive photosystem.

The optional substituents R ¹ , R ² and R ³ are independently selected from hydrogen, halogen, alkyl (preferably C ₁ -C ₈ ), aralkyl, -NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ independently selected from alkyl (preferably C ₁ -C ₈ ), aryl and aralkyl) and a radical -OR ⁶ (wherein R ^{6 is} selected from alkyl (preferably C ₁ -C ₈ ), aryl and aralkyl).

Especially preferred compounds of formula (I) are the following:

Sensitizer 1: 4- (5- (2-chlorophenyl) -2- (4- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) phenyl) oxazole-4- yl) -N, N-diethylbenzenamin

Sensitizer 2: 4- (2- (4- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) phenyl) -5-phenyloxazol-4-yl) -N, N -dimethylbenzenamine

Sensitizer 3: 4- (5- (2-Chlorophenyl) -2- (4- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) -2,3,5 , 6-tetrafluorophenyl) oxazole-4-yl) -N, N-diethylbenzenamin

Sensitizer 4: 4- (5- (2-chlorophenyl) -2- (9- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) anthracen-10-yl) oxazol-4-yl) -N, N-diethylbenzenamin

Sensitizer 5: 4- (2- (2 - ((1E, 13 E) -4 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) styryl ) phenyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

Sensitizer 6: 4- (2- (4 - ((1E, 13E) -4 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) -styryl ) phenyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

Sensitizer 7: 4- (5- (2-chlorophenyl) - (2- (2- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) -3.4, 5,6-tetrafluorophenyl) oxazole-4-yl) -N, N-diethylbenzenamin

Sensitizer 8: 4- (2 - ((1E, 28E) -4 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) vinyl) styryl) -5 -phenyloxazol-4-yl) -N, N-dimethylbenzenamine

Sensitizer 9: (E) -4- (2- (4- (4- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) -phenyl) -5-phenyloxazol-4-yl ) -N, N-dimethylbenzenamine

Sensitizer 10: 4- (2- (4 - ((1E, 26E) -4 - ((E) -4- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) -styryl ) phenyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

Sensitizer 11: 4- (2 - ((E) -2- (5 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) vinyl) thiophene-2 -yl) vinyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

Sensitizer 12: N- (4- (2- (4- (4- (4- (Diphenylamino) phenyl) -5- (perfluorophenyl) oxazol-2-yl) phenyl) -5- (perfluorophenyl) oxazol-4-yl ) phenyl) -N-phenylbenzenamin

Sensitizer 13: 4- (5- (2-chlorophenyl) -2- (6- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) pyridin-2-yl) oxazol-4-yl) -N, N-diethylbenzenamin

Sensitizer 14: 4- (2- (3,5-bis (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) phenyl) -5- (2-chlorophenyl) oxazole -4-yl) -N, N-diethylbenzenamin

Sensitizer 15: 4- (2 - ((1E, 9E, 11E) -3,5-bis ((E) -2- (4- (4- (dimethylamino) phenyl) -5-phenyloxazol-2-yl) vinyl ) styryl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

Sensitizer 16: (E) -4- (5- (2-chlorophenyl) -2- (2- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) vinyl) oxazol-4-yl) -N, N-diethylbenzenamin

Sensitizer 17: 4- (5- (2-chlorophenyl) -2 - ((1E, 3E) -4- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) buta-1,3-dienyl) oxazol-4-yl) -N, N-diethylbenzenamin

The used according to the invention Sensitizers of formula (I) show a yellow to greenish strong Fluorescence.

The compounds of the formula (I) used according to the invention can be prepared by processes which are well known to the person skilled in the art, for example analogously to that described in US Pat EP 0129059 A1 and US 3,257,203 described method; the methods indicated therein can also be used for the synthesis of compounds not explicitly described there by appropriate variation of the starting materials used.

mit Oxazolderivaten, Thiazolderivaten und/oder Selenazolderivaten bewirkt eine wesentlich verbesserte Effizienz der Anregung, was durch eine wesentlich verbesserte Empfindlichkeit der strahlungsempfindlichen Beschichtung dokumentiert wird. Die in (I) angegebenen Substitutionsvariationen ermöglichen eine Variation der Lage der symmetrischen (z. B. A_g) und unsymmetrischen (z. B. B_u) angeregten Zustände in ihrer energetischen Lage. Dadurch wird die elektronische Kopplung dieser symmetrisch verschiedenen angeregten Zustände untereinander verstärkt. Dieses ist von Vorteil für Ein- und Zweiphotonenanregung.The multiple substitution of the unsaturated moiety

with oxazole derivatives, thiazole derivatives and / or Selenazolderivaten causes a significantly improved efficiency of the excitation, which is documented by a significantly improved sensitivity of the radiation-sensitive coating. The substitution variations given in (I) make it possible to vary the position of the symmetric (eg A _g ) and unsymmetrical (eg B _u ) excited states in their energetic position. This enhances the electronic coupling between these symmetrically different excited states. This is beneficial for one and two-photon excitation.

The Sensitizers are used in combination with one or more coinitiators used.

The Amount of sensitiser (s) is not particularly limited but preferably in the range of 0.2 to 25 wt .-%, based on the solids content or dry layer weight of one of the composition prepared coating, more preferably at 0.5 to 15 wt .-%.

In the context of this invention, a coinitiator is understood as meaning a compound which, upon irradiation, can not substantially absorb itself, but forms radicals together with the radiation-absorbing sensitisers used according to the invention. According to the invention, the coinitiators are selected from onium compounds, such as. Ammonium, diazonium, sulfonium, iodonium and N-alkoxypyridinium salts; N-arylglycines and derivatives thereof (e.g., N-phenylglycine); aromatic sulfonyl halides; Trihalogenmethylarylsulfonen; Imides such as N-benzoyloxyphthalimide; Diazosulfonaten; 9,10-Dihydroanthracenderivaten; N-aryl, S-aryl or O-aryl polycarboxylic acids having at least 2 carboxyl groups, at least one of which is bonded to the nitrogen, oxygen or sulfur atom of the aryl moiety (eg, anilinodiacetic acid and derivatives thereof, and others in U.S. Patent Nos. 4,648,755; US 5629354 A described coinitiators); hexaarylbiimidazoles; Thiol compounds (e.g., mercaptobenzothiazole, mercaptobenzimidazole and mercaptotriazole); 1,3,5-triazine derivatives having 1 to 3 CX ₃ groups (wherein each X is independently selected from a chlorine and a bromine atom, preferably a chlorine atom), such as. 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine , 2- (Styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho -1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine and 2- [4 - (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis (trichloromethyl) -s-triazine; oxime ethers and oxime esters, such as those derived from benzoin; metallocenes (preferably titanozene, and more preferably those having 2 five-membered cyclodienyl groups such as cyclopentadienyl groups and one or two six-membered aromatic groups having at least one ortho-fluorine atom and optionally also a pyrryl group such as bis (cyclopentadienyl) bis- [2,6-difluoro-3- (pyrr -1-yl) -phenyl] titanium and dicyclopentadiene bis-2,4,6-trifluoro phenyl-titanium or zirconium); Acylphosphine oxides, diacylphosphine oxides and peroxides (e.g. EP 1 035 435 A1 listed as an organic peroxide type activator).

preferred Co-initiators are hexaarylbiimidazoles and onium compounds as well Mixtures thereof.

wobei A¹-A⁶ substituierte oder unsubstituierte C₅-C₂₀ Arylreste sind, die gleich oder verschieden sind und bei denen im Ring ein oder mehrere C-Atome gegebenenfalls durch Heteroatome, ausgewählt aus O, N und S, ersetzt sein können. Als Substituenten der Arylreste sind solche möglich, die die lichtinduzierte Dissoziation zu Triarylimidazolyl-Radikalen nicht behindern, z. B. Halogenatome (Fluor, Chlor, Brom, Jod), -CN, C₁-C₆ Alkylreste (gegebenenfalls mit ein oder mehreren Substituenten, ausgewählt aus Halogenatomen, -CN und -OH), C₁-C₆ Alkoxy, C₁-C₆ Alkylthio, (C₁-C₆ Alkyl)sulfonyl.Suitable hexaarylbiimidazoles can be represented, for example, by the following formula (II):

where A ¹ -A ^{6 are} substituted or unsubstituted C ₅ -C ₂₀ aryl radicals which are identical or different and in which one or more C atoms in the ring may optionally be replaced by heteroatoms selected from O, N and S. As substituents of the aryl radicals are those which do not hinder the light-induced dissociation to Triarylimidazolyl radicals, z. B. halogen atoms (fluorine, chlorine, bromine, iodine), -CN, C ₁ -C ₆ alkyl radicals (optionally with one or more substituents selected from halogen atoms, -CN and -OH), C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, (C ₁ -C ₆ alkyl) sulfonyl.

preferred Aryl radicals are substituted and unsubstituted phenyl, biphenyl, Naphthyl, pyridyl, furyl and thienyl radicals. Especially preferred are substituted and unsubstituted phenyl radicals; especially preferred are halogen-substituted phenyl radicals.

Examples are:
2,2'-Bis (bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (p-carboxyphenyl) -4,4 ', 5,5''- tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetrakis (p-methoxyphenyl) biimidazole,
2,2'-bis (p-chlorophenyl) -4,4 ', 5,5'-tetrakis (p-methoxyphenyl) biimidazole,
2,2'-bis (p-cyanophenyl) -4,4 ', 5,5'-tetrakis (p-methoxyphenyl) biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4-dimethoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-ethoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (m-fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (p-fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-hexoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-hexylphenyl) -4,4 ', 5,5'-tetrakis (p-methoxyphenyl) biimidazole,
2,2'-bis (3,4-methylenedioxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetrakis (m-methoxyphenyl) biimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetrakis [m- (betaphenoxy-ethoxyphenyl)] - biimidazole,
2,2'-bis (2,6-dichloro-phenyl) -4,4 ', 5,5'-tetraphenyl,
2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (p-methoxyphenyl) -4,4'-bis (o-methoxyphenyl) -5,5'-diphenylbiimidazol,
2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (p-phenylsulfonylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (p-sulfamoylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,5-trimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-4-biphenylyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-1-naphthyl-4,4 ', 5,5'-tetrakis (p-methoxyphenyl) biimidazole,
2,2'-di-9-phenanthryl-4,4 ', 5,5'-tetrakis (p-methoxyphenyl) biimidazole,
2,2'-diphenyl-4,4 ', 5,5'-tetra-4-biphenylylbiimidazol,
2,2'-diphenyl-4,4 ', 5,5'-tetra-2,4-xylylbiimidazol,
2,2'-di-3-pyridyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-3-thienyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-o-tolyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-di-p-tolyl-4,4'-di-o-tolyl-5,5'-diphenylbiimidazol,
2,2'-di-2,4-xylyl-4,4 ', 5,5'-tetraphenylbiimidazole,
2,2 ', 4,4', 5,5'-hexakis (p-benylthiophenyl) biimidazole,
2,2 ', 4,4', 5,5'-hexa-1-naphthylbiimidazol,
2,2 ', 4,4', 5,5'-Hexaphenylbiimidazol,
2,2'-bis (2-nitro-5-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetrakis (m-methoxyphenyl) biimidazole,
2,2'-bis (2-chloro-5-sulfophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2 ', 5-tris (2-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4,5'diphenylbiimidazol,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) biimidazole,
2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chlorophenyl) biimidazole,
2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-p-methoxyphenyl) biimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole,
2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) -biimidazole or
2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5', - tetra (o, p-dichlorophenyl) biimidazole.

Suitable hexaarylbiimidazoles are, for. In US 4,565,769 and US 3,445,232 described and can be prepared by known methods, such as. As the oxidative dimerization of triarylimidazoles.

Suitable onium salts are, for. In US 5,086,086 A described. Preferred onium salts are those in which the onium cation is selected from iodonium, sulfonium, phosphonium, oxysulfoxonium, oxysulfonium, sulfoxonium, ammonium, diazonium, selenonium, arsenonium and N-substituted N-heterocyclic onium cations in which N is an optionally substituted alkyl, alkenyl , Alkynyl or aryl substituted.

The Anion of the onium salt may, for. B. be chloride or a non-nucleophilic Anion, such as tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, Hexafluoroantimonate, triflate, tetrakis (pentafluorophenyl) borate, pentafluoroethylsulfonate, p-methylbenzylsulfonate, ethylsulfonate, trifluoromethylacetate and Pentafluoroethyl.

typical Onium salts that can be used as coinitiators are for example, diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, Diphenyliodonium hexafluorophosphate, Diphenyliodonium hexafluoroantimonate, 4,4'-dicumyliodonium chloride, 4,4'-dicumyliodonium hexafluorophosphate, N-methoxy-α-picolinium-p-toluene sulfonate, 4-methoxybenzene-diazonium-tetrafluoroborate, 4,4'-bis-dodecylphenyl-iodonium-hexafluorophosphate, 2-cyanoethyl-triphenylphosphonium chloride, bis [4-diphenylsulfoniumphenyl] sulfide-bis-hexafluorophosphate, Bis-4-dodecylphenyliodonium hexafluoroantimonate and triphenylsulfonium hexafluoroantimonate.

In The present invention may be any of the above coinitiators or a mixture thereof.

The Amount of the coinitiator (s) is not particularly limited but preferably at 0.2 to 25 wt .-%, based on the dry layer weight, particularly preferably from 0.5 to 15% by weight.

Possibly may be the radiation-sensitive coating of the present invention as well alkali-soluble Contain binder or binder mixture. The binder will preferably selected from polyvinyl acetals, acrylic polymers, polyurethanes and their copolymers. It is preferred that the binder contains acid groups, especially preferably carboxyl groups. Most preferred are acrylic polymers. Binders with acid groups preferably have an acid number in the range of 20 to 180 mg KOH / g polymer. If necessary, can the binder contain groupings that are capable of one Cycloaddition (eg 2 + 2 photocycloaddition). The Amount of the binder is not particularly limited and is preferably in the range of 0 to 90 wt .-%, more preferably 5 to 60% by weight.

The radiation-sensitive coating may also contain small amounts of a thermopolymerization inhibitor. Suitable examples of inhibitors of undesired thermopolymerization are, for. Hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrrogalol, t-butylcatechol, benzoquinone, 4,4'-thio-bis (3-methyl-6-t-butylphenol), 2,2 'Methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxylamine salts. The amount of the non-absorbable polymerization inhibitor in the radiation-sensitive coating is preferably 0% by weight to 5% by weight, based on the dry layer weight, particularly preferably 0.01% to 2% by weight. In many cases, such inhibitors enter the radiation-sensitive coating via commercial monomers or oligomers and are therefore not expressly identified.

In addition, can the radiation-sensitive invention Coating dyes or pigments for coloring the layer included (Contrast dyes and pigments). Examples of the colorant are z. Phthalocyanine pigments, azo pigments, carbon black and titanium dioxide, triarylmethane dyes, such as ethyl violet and crystal violet, azo dyes, anthraquinone dyes and cyanine dyes. The amount of the colorant is preferably 0 to 20 wt .-%, based on the dry layer weight, especially preferably 0.5 to 10 wt .-%.

To improve the physical properties of the cured layer, the radiation-sensitive coating may also contain other additives such as plasticizers or inorganic fillers. Suitable plasticizers include, for. Dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, dioctyl adipate, dibutyl sebacate, triacetylglycerol and tricresyl phosphate. The amount of the plasticizer is not particularly limited, but is preferably 0 to 10% by weight, based on the dry layer weight, more preferably 0.25 to 5% by weight. Suitable inorganic fillers are, for. B. Al ₂ O ₃ and SiO ₂ ; they are preferably in an amount of 0 to 20 wt .-%, based on the dry layer weight, before, particularly preferably 0.1 to 5 wt .-%.

The radiation sensitive coating may also include known chain transfer agents contain. They are preferably in an amount of 0 to 15 wt .-%, based on the dry layer weight, used, particularly preferred 0.5 to 5 wt .-%.

In addition, can contain the radiation-sensitive coating leuco dyes, such as B. leucocrystal violet and leucomalachite green. Your Amount is preferably 0 to 10% by weight, based on the dry layer weight, particularly preferably 0.5 to 5 wt .-%.

Of Furthermore, the radiation-sensitive coating can be surface-active Agents (flow aids) included. Suitable examples are siloxane-containing polymers, fluorine-containing polymers and polymers with ethylene oxide and / or propylene oxide groups. Their amount is preferably 0 to 10% by weight, based on the dry layer weight, more preferably 0.2 to 5% by weight.

Exposure indicators, such as As 4-phenylazodiphenylamine, may also be optional Components of the radiation-sensitive coating available be; their amount is preferably 0 to 5% by weight, particularly preferably 0 to 2% by weight, based on the dry layer weight.

The radiation-sensitive according to the invention Elements can z. B. printing form precursor (especially precursor of lithographic printing plates), printed circuit boards for integrated circuits or Be photomasks.

Especially in the preparation of printing form precursors is preferred as the carrier a dimensionally stable plate-shaped or foil-shaped Material used. As such a dimensionally stable plate or film material is preferably used that already previously as a carrier used for printed matter has been. Examples of such a carrier belong Paper, paper made with plastics (such as polyethylene, polypropylene or polystyrene), a metal plate or foil, such as As aluminum (including Aluminum alloys), zinc and copper plates, plastic films from, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, Cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, Polyethylene, polystyrene, polypropylene, polycarbonate and polyvinyl acetate, and a laminate of paper or plastic film and one of above-mentioned metals or a paper / plastic film by Vaporizing has been metallized. Among these carriers is an aluminum plate or foil is particularly preferable because it is remarkable dimensionally stable and is cheap and besides shows excellent adhesion of the coating. In addition, can a composite foil used in which an aluminum foil is laminated to a polyethylene terephthalate film.

A metal support, especially an aluminum support, is preferably selected from at least one treatment of roughening (eg, by dry-brushing or abrasive-brushing ions or by electrochemical means, eg. With a hydrochloric acid electrolyte), anodization (e.g., in sulfuric acid or phosphoric acid), and hydrophilization.

to Improvement of the hydrophilic properties of the surface of the roughened and optionally anodized in sulfuric or phosphoric acid metal support this can be a post-treatment with an aqueous solution of sodium silicate, calcium zirconium fluoride, polyvinyl or phosphoric acid be subjected. In the context of this invention, the term "carrier" also includes an optional one pretreated supports, the z. B. has a hydrophilizing layer on the surface.

The Details of o. G. Substrate pretreatment are well known to those skilled in the art.

The radiation-sensitive composition according to the present invention is used to prepare a radiation-sensitive element with conventional Coating process (eg spin coating, spray coating, Dip coating, coating by knife) on the surface of the Carrier applied. It is also possible, the radiation-sensitive composition on both sides of the Apply carrier; however, it is preferred that in the elements of the invention only on one side of the carrier a radiation-sensitive coating is applied.

In Usually, the radiation-sensitive composition of a organic solvents or solvent mixture applied.

When solvent are lower alcohols (eg methanol, ethanol, propanol and butanol), Glycol ether derivatives (eg ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, Propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether), ketones (eg diacetone alcohol, acetylacetone, Acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone), Esters (e.g., methyl lactate, ethyl lactate, ethyl acetate, 3-methoxypropyl acetate and butyl acetate), Aromatics (eg toluene and xylene), cycloexane, 3-methoxy-2-propanol, 1-methoxy-2-propanol, methoxymethoxyethanol, γ-butyrolactone and dipolar aprotic solvent (e.g., THF, dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone) and Mixtures suitable. The solids content of the applied radiation-sensitive mixture depends on the coating method used off and amounts to preferably 1 to 50% by weight.

The dry layer weight of the radiation-sensitive layer is preferably 0.5 to 4 g / m ² , more preferably 0.8 to 3 g / m ² .

The additional application of a water-soluble oxygen barrier layer on the radiation-sensitive layer may be advantageous. Suitable polymers for the topcoat include polyvinyl alcohol, polyvinyl alcohol / polyvinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl pyrrolidone / polyvinyl acetate copolymers, polyvinyl methyl ethers, ring-opened copolymers of maleic anhydride and a comonomer such as methyl vinyl ether, polyacrylic acid, cellulose ether, gelatin, etc .; preferred is polyvinyl alcohol. Preferably, the oxygen barrier topcoat composition is applied in the form of a solution in water or a water miscible solvent; In any case, the solvent is selected so that the already existing radiation-sensitive coating does not substantially dissolve when the topcoat composition is applied. The coating weight of the cover layer may, for. B. 0.1 to 6 g / m ² , and more preferably 0.5 to 4 g / m ² . However, the printing plate precursors according to the invention have excellent properties even without a cover layer. The topcoat may also contain matting agents (ie, organic or inorganic particles of 2 to 20 microns particle size) which, upon contact exposure, facilitate the flatness of the film. In order to improve the adhesion of the cover layer on the radiation-sensitive layer, the cover layer adhesion promoter, such. Poly (vinylpyrrolidone) -poly (ethyleneimine) and poly (vinylimidazole).

suitable Cover layers are z. As described in WO 99/06890 A1.

The radiation-sensitive elements produced in this way are imagewise exposed in the manner known to those skilled in the art with radiation having a wavelength of> 300 nm (preferably 350-450 nm) and then developed with a commercially available aqueous alkaline developer. Of particular interest as the radiation source are UV laser diodes which emit UV radiation in the region around 405 nm (eg 405 ± 10 nm). After the imagewise exposure, ie, before developing, a heat treatment at 50 to 180 ° C, preferably 90-150 ° C, be made. The developed elements can be used in the usual way Preservative ("gum") treated. The preservatives are aqueous solutions of hydrophilic polymers, wetting agents and other additives.

It is furthermore favorable, for certain applications (for example in the case of printing plates), for the mechanical strength of the coating parts remaining after the development by a heat treatment (so-called "burn-in") and / or combination of burn-in and flood exposure (eg with UV light). For this purpose, prior to this treatment, the developed element is first treated with a solution which protects the non-image areas in such a way that the heat treatment does not cause color acceptance of these areas US 4,355,096 described. The baking is carried out at a temperature in the range of 150-250 ° C. However, elements such as printing plates made from radiation-sensitive elements of the present invention exhibit excellent properties even without heat treatment. If both burned and flood-exposed, the two treatment steps can be carried out simultaneously or in succession.

The radiation-sensitive elements according to the present invention are characterized by excellent stability in yellow light conditions, high photosensitivity and excellent resolving power at the same time good storage stability out. In the case of printing plate precursors, the developed Printing plates excellent abrasion resistance, ensuring high print runs possible are.

The The invention will be explained in more detail with reference to the following examples.

Examples

manufacturing sensitizers

The synthesis of oxazoles is carried out according to the following reaction equation:

To this end, a × 100 g of sulfuric acid (conc.) Are heated to 60 ° C. (a ≥ 2). To this solution is added a mixture of acyloin A ₁ (a x 0.03 mol) and nitrile A ₂ (a x 0.015 mol). The temperature should not exceed 65 ° C when added. After completion of this process is stirred for a further 1.5 h at 60 ° C and then poured onto ice. Possible rainfall is filtered off. The filtrate is then neutralized with 3N NaOH, the temperature during this process should not exceed 10-15 ° C. Subsequently, the resulting mixture is rendered weakly basic, the final pH of 10 should not be exceeded. The precipitate formed in the neutralization is filtered off, washed neutral, dried and recrystallized from a suitable solvent.

Examples 1 to 18 and Comparative Examples 1 to 4

An aluminum foil roughened electrochemically (in HCl) and anodized was treated with an aqueous solution of polyvinylphosphonic acid (PVPA) and, after drying, coated with a solution composed as follows and then dried: 1.02 g of a terpolymer prepared by polymerization of 470 parts by weight of styrene, 336 parts by weight of methyl methacrylate and 193 parts by weight of methacrylic acid, 30% solution in propylene glycol monomethyl ether 0.1 g Kayamer PM-2 (1 mol phosphoric acid esterified with 1.5 mol hydroxyethyl methacrylate from Coa Corp. Ltd., Japan) 0.2 g Mercapto-3-triazole 3.92 g of a 80% methyl ethyl ketone solution of a urethane acrylate prepared by reacting Desmodur N 100 ^® (available from Bayer) with hydroxyethyl acrylate and pentaerythritol triacrylate; Double bond content: 0.5 double bonds per 100 g, if all isocyanate groups have reacted completely with acrylates containing hydroxyl groups 0.45 g Di (trimethylolpropane) tetraacrylate 1.25 g a dispersion in propylene glycol monomethyl ether containing 7.25% by weight of copper phthalocyanine and 7.25% by weight of a polyvinyl acetal binder containing 39.9 mol% vinyl alcohol groups, 1.2 mol% vinyl acetate groups, 15.4 mol% acetal groups derived from acetaldehyde, 36.1 mol% acetal groups derived from butyraldehyde and 7.4 mol% acetal groups derived from 4-formylbenzoic acid Y g Co-initiator according to Table 1 X g Sensitizer according to Table 1 20 ml Propylene glycol monomethyl ether 16 ml methanol 25 ml methyl ethyl ketone

The solution was filtered, applied to the lithographic support and the coating dried at 90 ° C for 4 minutes. The dry layer weight of the photopolymer layer was about 1.5 g / m ² .

The obtained samples were provided by coating with an aqueous solution of poly (vinyl alcohol) (Airvol ^® 203, with a degree of hydrolysis of 88%) with a covering layer; the topcoat after drying at 90 ° C for 4 minutes had a dry film weight of about 3 g / m ² .

Of the Printing plate precursor was done with a tungsten lamp with a 405 nm metal interference filter exposed a UGRA gray wedge, with the aim of at least one gray wedge to obtain. Immediately after exposure, the plate was left for 2 minutes in an oven at 90 ° C heated.

Subsequently, the exposed plate was treated for 30 seconds with a developing solution containing:
3.4 parts by weight Rewopol NLS 28 ^®
1.1 parts by weight of diethanolamine
1.0 parts by weight Texapon 842 ^®
0.6 parts by weight Nekal BX Paste ^®
0.2 parts by weight of 4-toluenesulfonic acid and
93.7 parts by weight of water

Subsequently was the developer solution rubbed for another 30 seconds with a tampon on the surface and then rinse the entire plate with water. After this treatment the exposed parts remained on the plate. For evaluation the photosensitivity was the plate in the wet state with a Ink blackened.

to Assessment of storage stability The plates became the unexposed printing plate precursors for 60 minutes at 90 ° C stored in an oven, then exposed and as described above developed (storage life test).

To prepare a lithographic printing plate, an imaging layer was applied to an aluminum foil as described above, exposed, heated, developed, and after rinsing with water, the developed plate was abraded and gummed with an aqueous solution of 0.5% phosphoric acid and 6% gum arabic. The thus prepared plate was loaded in a sheet-fed offset printing machine and an abrasive printing ink (Offset S 7184 ^®, containing 10% potassium carbonate) was used.

The Results are summarized in Table 1.

2. 4-(2-(4-(4-(4-(Dimethylamino)phenyl)-5-phenyloxazol-2-yl)phenyl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

3. 4-(5-(2-Chlorphenyl)-2-(4-(5-(2-chlorphenyl)-4-(4-(diethylamino)phenyl)oxazol-2-yl)-2,3,5,6-tetrafluorphenyl)oxazol-4-yl)-N,N-diethylbenzenamin

4. 4-(5-(2-Chlorphenyl)-2-(9-(5-(2-chlorphenyl)-4-(4-(diethylamino)phenyl)oxazol-2-yl)anthracen-10-yl)oxazol-4-yl)-N,N-diethylbenzenamin

5. 4-(2-(2-((1E,13E)-4-((E)-2-(4-(4-(Dimethylamino)phenyl)-5-phenyloxazol-2-yl)styryl)styryl)phenyl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

6. 4-(2-(4-((1E,13E)-4-((E)-2-(4-(4-(Dimethylamino)phenyl)-5-phenyloxazol-2-yl)styryl)styryl)phenyl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

7. 4-(5-(2-Chlorphenyl)-(2-(2-(5-(2-chlorphenyl)-4-(4-(diethylamino)phenyl)oxazol-2-yl)-3,4,5,6-tetrafluorphenyl)oxazol-4-yl)-N,N-diethylbenzenamin

8. 4-(2-((1E,28E)-4-((E)-2-(4-(4-(Dimethylamino)phenyl)-5-phenyloxazol-2-yl)vinyl)styryl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

9. (E)-4-(2-(4-(4-(4-(4-(Dimethylamino)phenyl)-5-phenyloxazol-2-yl)styryl)phenyl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

10. 4-(2-(4-((1E,26E)-4-((E)-4-(4-(4-(Dimethylamino)phenyl)-5-phenyloxazol-2-yl)styryl)styryl)phenyl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

11. 4-(2-((E)-2-(5-((E)-2-(4-(4-(Dimethylamino)phenyl)-5-phenyloxazol-2-yl)vinyl)thiophen-2-yl)vinyl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

12. N-(4-(2-(4-(4-(4-(Diphenylamino)phenyl)-5-(perfluorphenyl)oxazol-2-yl)phenyl)-5-(perfluorphenyl)oxazol-4-yl)phenyl)-N-phenylbenzenamin

13. 4-(5-(2-Chlorphenyl)-2-(6-(5-(2-chlorphenyl)-4-(4-(diethylamino)phenyl)oxazol-2-yl)pyridin-2-yl)oxazol-4-yl)-N,N-diethylbenzenamin

14. 4-(2-(3,5-bis(5-(2-chlorophenyl)-4-(4-(diethylamino)phenyl)oxazol-2-yl)phenyl)-5-(2-chlorophenyl)oxazol-4-yl)-N,N-diethylbenzenamin

15. 4-(2-((1E,9E,11E)-3,5-Bis((E)-2-(4-(4-(dimethylamino)phenyl)-5-phenyloxazol-2-yl)vinyl)styryl)-5-phenyloxazol-4-yl)-N,N-dimethylbenzenamin

16. (E)-4-(5-(2-Chlorphenyl)-2-(2-(5-(2-chlorphenyl)-4-(4-(diethylamino)phenyl)oxazol-2-yl)vinyl)oxazol-4-yl)-N,N-diethylbenzenamin

17. 4-(5-(2-Chlorphenyl)-2-((1E,3E)-4-(5-(2-chlorphenyl)-4-(4-(diethylamino) phenyl)oxazol-2-yl)buta-1,3-dienyl)oxazol-4-yl)-N,N-diethylbenzenamin

Sensitizers used in the examples: 1. 4- (5- (2-Chlorophenyl) -2- (4- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) phenyl) oxazol-4-yl ) -N, N-diethylbenzenamin

2. 4- (2- (4- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) phenyl) -5-phenyloxazol-4-yl) -N, N -dimethylbenzenamine

3. 4- (5- (2-chlorophenyl) -2- (4- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) -2,3,5, 6-tetrafluorophenyl) oxazole-4-yl) -N, N-diethylbenzenamin

4. 4- (5- (2-Chlorophenyl) -2- (9- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) anthracen-10-yl) oxazole -4-yl) -N, N-diethylbenzenamin

5. 4- (2- (2 - ((1E, 13E) -4 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) -styryl) phenyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

6. 4- (2- (4 - ((1E, 13E) -4 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) -styryl) phenyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

7. 4- (5- (2-Chlorophenyl) - (2- (2- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) -3,4,5 , 6-tetrafluorophenyl) oxazole-4-yl) -N, N-diethylbenzenamin

8. 4- (2 - ((1E, 28E) -4 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) vinyl) styryl) -5- phenyloxazol-4-yl) -N, N-dimethylbenzenamine

9. (E) -4- (2- (4- (4- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) -phenyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

10. 4- (2- (4 - ((1E, 26E) -4 - ((E) -4- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) -styryl) -styryl) phenyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

11. 4- (2 - ((E) -2- (5 - ((E) -2- (4- (4- (Dimethylamino) phenyl) -5-phenyloxazol-2-yl) vinyl) thiophene-2 yl) vinyl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

12. N - (4- (2- (4- (4- (4- (Diphenylamino) phenyl) -5- (perfluorophenyl) oxazol-2-yl) phenyl) -5- (perfluorophenyl) oxazol-4-yl) phenyl) -N-phenylbenzenamin

13. 4- (5- (2-Chlorophenyl) -2- (6- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) pyridin-2-yl) oxazole -4-yl) -N, N-diethylbenzenamin

14. 4- (2- (3,5-bis (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) phenyl) -5- (2-chlorophenyl) oxazole 4-yl) -N, N-diethylbenzenamin

15. 4- (2 - ((1E, 9E, 11E) -3,5-bis ((E) -2- (4- (4- (dimethylamino) phenyl) -5-phenyloxazol-2-yl) vinyl) styryl) -5-phenyloxazol-4-yl) -N, N-dimethylbenzenamine

16. (E) -4- (5- (2-Chlorophenyl) -2- (2- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) vinyl) oxazole -4-yl) -N, N-diethylbenzenamin

17. 4- (5- (2-Chlorophenyl) -2 - ((1E, 3E) -4- (5- (2-chlorophenyl) -4- (4- (diethylamino) phenyl) oxazol-2-yl) buta -1,3-dienyl) oxazol-4-yl) -N, N-diethylbenzenamin

It Table 1 shows that by using a combination a sensitizer of the formula (I) and a co-initiator printing plate precursor with high sensitivity and storage stability are obtained lead to printing forms, which allow high circulation.

to Examination of the yellow light safety became the layers of the examples 1 to 19 and Comparative Examples 1 to 2 with a yellow light tube G10 Encapsulite irradiated with an intensity of 100 lux * min and subsequently at 90 ° C heated. While Examples 1 to 19 and Comparative Example 1 residue let develop, remained in Comparative Example 2 after development layer residues, what a Sign of insufficient yellow light stability.

Examples 20 to 25 and Comparative Examples 3 and 4

It Coatings were prepared as in Examples 1 to 19 described. The sensitizers and coinitiators used and their amounts are shown in Table 2.

Subsequently, a 2-photon irradiation with the in 1 shown experimental setup carried out. In 1 are a sapphire laser 1 , the rays emitted 2 , a condensing lens 3 , the focus 4 and the coated plate 5 shown, with the plate 5 is moved in the x direction. This simplified structure was chosen to show that the sensitizers used in the present invention are capable of generating images on lithographic printing plate precursors.

It For example, a Spectra-Physics Ti-sapphire laser was used in Table 2 indicated wavelength emitted and with a pulse width of 80 to 130 fs, a repetition rate of 80.2 MHz and an average power of 250 mW. The condenser lens focused the laser beam on the coated one Plate, which at a speed of 100 microns / s in the x direction was moved. The procedure was repeated several times, being always at a different height (y-direction) was started.

The thus irradiated plate was then as in the examples 1 to 19 described. A cured coating is through not remove the developer; therefore, the remaining of coating parts after developing an indication that a 2-photon-initiated Polymerization has taken place.

Claims (18)

A radiation-sensitive composition comprising (a) one or more types of monomers and / or oligomers and / or polymers each having at least one ethylenically unsaturated group which is amenable to free-radical polymerization, (b) at least one sensitizer, and (c) at least one co-polymerizer. Initiator which together with the sensitizer (b) forms radicals and is selected from the following classes of compounds: metallocenes; 1,3,5-triazine derivatives having one to three CX ₃ groups, wherein X is chloro or bromo; peroxides; hexaarylbiimidazoles; oxime ethers; oxime esters; N-arylglycines and derivatives thereof; thiol compounds; N-aryl, S-aryl and O-aryl polycarboxylic acids having at least 2 carboxyl groups, at least one of which is bonded to the N, S or O atom of the aryl moiety; onium salts; Alkyltriarylboraten; benzoin ethers; Benzoinestern; Trihalogenmethylarylsulfonen; amines; N, N-Dialkylaminobenzoesäureestern; aromatic sulfonyl halides; imides; Diazosulfonaten; 9,10-Dihydroanthracenderivaten; acylphosphineoxides; diacylphosphine; α-hydroxy and α-amino-acetophenones; characterized in that the at least one sensitizer is a compound of the formula (I)

where X is selected from O, S and Se; n is 0 or a whole positive number; m, p and q are independently 0 or a whole positive number; the π units

are each independently unsaturated units each having a conjugated π-electron system covalently attached to the heterocyclic moiety

and together with this in turn form a conjugated π-electron system and each R ¹ , R ² and R ^{3 are} independently selected from hydrogen, halogen, alkyl, aralkyl, -NR ⁴ R ⁵ and a radical - OR ^{6 is} selected, wherein R ⁴ , R ⁵ and R ^{6 are} independently selected from an alkyl radical, aryl radical and aralkyl radical, and wherein each of the substituents of

R ² , R ³ , p and q are independently selected. A radiation-sensitive composition according to claim 1, in addition comprising one or more additives selected from alkali-soluble Binders, thermopolymerization inhibitors, contrasting dyes and pigments, plasticizers, inorganic fillers, chain transfer agents, Leuco dyes, surface-active Means, exposure indicators and leveling agents. A radiation-sensitive composition according to claim 1 or 2, wherein

is selected from a polyene radical SUS-1 with alternating double bonds

wherein z _{1 is} a whole positive number and R ^a and R ^{b are} independently selected from H, alkyl, aryl, halo, -CN, -COOH and -COO-alkyl, a polyunrest SUS-2 having alternating triple bonds,

wherein z _{2 is} a whole positive number, a residue SUS-3 which is a π-branched aromatic moiety with (4n + 2) n electrons selected from the structures SUS-3-a, SUS-3 -b and SUS-3-c:

a residue SUS-4, which is a π-branched electron-deficient heteroaromatic unit selected from SUS-4-a, SUS-4-b, SUS-4-c, SUS-4-d, and SUS-4. e

a residue SUS-5, which is a π-branched electron-rich heteroaromatic unit, selected from SUS-5-a, SUS-5-b and SUS-5-c

wherein X is selected from O, S and Se and a residue SUS-6, which is a π-branched electron-rich heteroaromatic unit having two fused benzene rings,

where X ^{1 is} a heteroatom. A radiation-sensitive composition according to claim 3, wherein the sensitizer is selected from

Radiation-sensitive composition according to a the claims 1 to 4, wherein the co-initiator (c) of hexaarylbiimidazoles, onium compounds and mixtures thereof becomes. Radiation-sensitive element comprising (A) a carrier and (b) one on the carrier applied radiation-sensitive coating of a like in one of the claims 1 to 5 defined composition. Radiation-sensitive element according to claim 6, where it is the carrier is an aluminum foil or plate. Radiation-sensitive element according to claim 7, wherein the aluminum plate or foil before coating at least a treatment selected from roughening, anodizing and hydrophilizing. Radiation-sensitive element according to one of claims 6 to 8, wherein the element also having an oxygen barrier cover layer. Process for imaging a radiation-sensitive Elements comprising (a) Provide one as in one of claims 6 to 9 defined radiation-sensitive element; (b) imagewise Irradiation of the element with UV radiation of> 300 nm; (c) removing the unirradiated Areas of coating with an aqueous alkaline developer. Method according to claim 10, wherein the irradiated element obtained in step (b) before step (c) heated becomes. Method according to claim 10 or 11, wherein the developed element obtained in step (c) subsequently subjected to at least one treatment selected from heating and flooding becomes. Method according to one the claims 10 to 12, wherein the imagewise irradiation with UV radiation of a wavelength from the range of 350-450 nm is made. Illustrated element obtainable by the method of one of the claims 10 to 13. The imaged element of claim 14, wherein is a lithographic printing plate. A process for preparing a radiation-sensitive element comprising (a) providing a pretreated support, (b) providing a radiation-sensitive composition comprising (i) one or more types of monomers and / or oligomers and / or polymers each having at least one ethylenically unsaturated group (ii) at least one sensitizer, (iii) at least one co-initiator which together with the sensitizer (b) forms free radicals and is selected from the following classes of compounds: metallocenes; 1,3,5-triazine derivatives having one to three CX ₃ groups, wherein X is chloro or bromo; peroxides; hexaarylbiimidazoles; oxime ethers; oxime esters; N-arylglycines and derivatives thereof; thiol compounds; N-aryl, S-aryl and O-aryl polycarboxylic acids having at least 2 carboxyl groups, at least one of which is bonded to the N, S or O atom of the aryl moiety; onium salts; Alkyltriarylboraten; benzoin ethers; Benzoinestern; Trihalogenmethylarylsulfonen; amines; N, N-Dialkylaminobenzoesäureestern; aromatic sulfonyl halides; imides; Diazosulfonaten; 9,10-Dihydroanthracenderivaten; acylphosphineoxides; diacylphosphine; α-hydroxy and α-amino-acetophenones; and (iv) at least one solvent, characterized in that the sensitizer is a compound of formula (I): l

where X is selected from O, S and Se; n is 0 or a whole positive number; m, p and q are independently 0 or a whole positive number; and the π units

are each independently unsaturated units each having a conjugated π-electron system covalently attached to the heterocyclic moiety

and together with this in turn form a conjugated π-electron system and each R ¹ , R ² and R ^{3 are} independently selected from hydrogen, halogen, alkyl, aralkyl, -NR ⁴ R ⁵ and a radical - OR ^{6 is} selected, wherein R ⁴ , R ⁵ and R ^{6 are} independently selected from an alkyl group, aryl group and aralkyl group, and wherein in each of the substituents of

R ² , R ³ , p and q are independently selected. c) applying the radiation-sensitive composition provided in step (b) to the support provided in step (a); d) drying. The method of claim 16, wherein the in step (a) provided carrier is an aluminum carrier, the at least one treatment selected from roughening, anodizing and hydrophilizing. Use of one as in any of claims 1 to 5 defined radiation-sensitive composition for the preparation a lithographic printing plate precursor.