DE3604581A1 - 4-Acylbenzylsulphonium salts, their preparation, and photocurable mixtures and recording materials containing these compounds - Google Patents
4-Acylbenzylsulphonium salts, their preparation, and photocurable mixtures and recording materials containing these compoundsInfo
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- DE3604581A1 DE3604581A1 DE19863604581 DE3604581A DE3604581A1 DE 3604581 A1 DE3604581 A1 DE 3604581A1 DE 19863604581 DE19863604581 DE 19863604581 DE 3604581 A DE3604581 A DE 3604581A DE 3604581 A1 DE3604581 A1 DE 3604581A1
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- formula
- alkyl
- acylbenzylsulfonium
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
Abstract
Description
Die Erfindung betrifft 4-Acylbenzylsulfoniumsalze, ihre Herstellung und Verwendung als Photoinitiatoren für kationisch härtbare Gemische, sie enthalten photohärtbare Gemische sowie photoempfindliche Aufzeichnungsmaterialien zur Herstellung von Reliefbildern und Restistmustern.The invention relates to 4-acylbenzylsulfonium salts, their preparation and Use as photoinitiators for cationically curable mixtures contain photo-curable mixtures as well as photosensitive recording materials for the production of relief images and patterns.
Es ist bekannt, kationische Härtungs- und insbesondere Polymerisationsreaktionen mit Hilfe von Photoinitiatoren zu starten, die bei Bestrahlung Lewis-Säuren freisetzen. Für diese Zwecke wurden Initiatoren beschrieben, unter denen vor allem die Diazoniumsalze der US-A 32 05 157 und 37 08 296 sowie die Oniumsalze von Elementen der V. (vgl. DE-A 25 18 656), VI. (vgl. De-A 25 18 652 und DE-A-29 04 626) und VII. (vgl. DE-A 25 18 639) Hauptgruppe des Periodensystems der Elemente sowie die in den EP-A 22 081, 35 969 und 44 274 beschriebenen Sulfoxoniumsalze hervorzuheben sind. Alle diese Verbindungen sind jedoch in ihren Eigenschaften nicht befriedigend. Diazoniumsalze setzen bei Bestrahlung Stickstoff frei, was zu Blasenbildung in mit Diazoniumsalzen hergestellten Beschichtungen führen kann. Die Jodoniumsalze der DE-A 25 18 639 sind sehr toxisch, ebenso wie die Omniumsalze der DE-A 25 18 652 und 29 04 626 absorbieren sie im Wellenlängenbereich zwischen 300-400 nm nur schwach, so daß den photopolymerisierbaren Gemischen meist ein Sensibilisator zugesetzt werden muß. Die Sulfoxoniumsalze der EP-A 22 081, 33 969 und 44 274 sind nur sehr umständlich unter Verwendung metallorganischer Reagenzien zugänglich, was ihre Herstellung in technischen Mengen sehr erschwert. Ein Nachteil der in US-A-43 058 401 beschriebenen Phenacylsulfoniumsalze ist, daß sie die Härtung bzw. Polymerisation kationisch härtbaren Massen nur während der Bestrahlung auslösen und die erwünschte Nachhärtung nach Bestrahlungsende unterbleibt.It is known to use cationic curing and especially polymerization reactions with the help of photoinitiators to start when irradiated Release Lewis acids. For this purpose, initiators have been described including, in particular, the diazonium salts of US Pat. Nos. 32 05 157 and 37 08 296 as well as the onium salts of elements of V. (cf. DE-A 25 18 656), VI. (see De-A 25 18 652 and DE-A-29 04 626) and VII. (see DE-A 25 18 639) Main group of the periodic table of the elements as well as those in the EP-A 22 081, 35 969 and 44 274 highlight the sulfoxonium salts described are. However, all of these compounds are in their properties not satisfying. Diazonium salts set nitrogen when irradiated free, causing blistering in coatings made with diazonium salts can lead. The iodonium salts of DE-A 25 18 639 are very toxic, absorb as well as the omnium salts of DE-A 25 18 652 and 29 04 626 they are only weak in the wavelength range between 300-400 nm, so that a sensitizer is usually added to the photopolymerizable mixtures must become. The sulfoxonium salts of EP-A 22 081, 33 969 and 44 274 are very cumbersome when using organometallic Reagents accessible, which makes their production in very technical quantities difficult. A disadvantage of the phenacyl sulfonium salts described in US-A-43 058 401 is that the curing or polymerization is cationic trigger curable masses only during irradiation and the desired Post-curing does not occur after the end of radiation.
Gegenstand der vorliegenden Erfindung sind 4-Acylbenzylsulfoniumsalze der
Formel I
worin
R1 einen tertiären Alkylrest oder einen Cycloalkylrest mit 4 bis
8 C-Atomen oder einen gegebenenfalls durch Chlor- oder Bromatome,
C1-C6-Alkyl-, C1-C6-Alkoxy-, C1-C6-Alkylthio-der durch eine Phenylgruppe
substituierten Phenyl-, Furyl-, Thienyl-, Naphthyl- oder
Pyrrolylrest darstellt,
R2 und R3 gleich oder ungleich sind und einen verzweigten oder unverzweigten
C1-C8-Alkyl-, einen C5-C8-Cycloalkyl- oder einen gegebenenfalls
durch einen oder mehrere C1-C6-Alkyl-, C1-C6-Alkoxy- oder
C1-C6-Alkylthiogruppen oder Chlor- oder Bromatome oder Phenylgruppen
substituierten Phenylrest, oder R2 und R3 zusammen -(CH2) p - mit p = 4
bis 5 darstellen,
Ar einen gegebenenfalls durch Chlor- oder Bromatome, C1-C6-Alkyl-,
C1-C6-Alkoxy- oder C1-C6-Alkylthiogruppen substituierten
p-Phenylenrest darstellt,
n die Zahlen 0 oder 1 und
m die Zahlen 1 oder 2 mit der Maßgabe sind, daß m + n = 2, und
X ein nicht-nucleophiles Anion darstellt.The present invention relates to 4-acylbenzylsulfonium salts of the formula I. wherein
R 1 is a tertiary alkyl radical or a cycloalkyl radical having 4 to 8 C atoms or one which may be chlorine or bromine, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio represents the phenyl, furyl, thienyl, naphthyl or pyrrolyl radical substituted by a phenyl group,
R 2 and R 3 are the same or different and are a branched or unbranched C 1 -C 8 alkyl-, a C 5 -C 8 cycloalkyl- or one optionally by one or more C 1 -C 6 alkyl-, C 1 -C 6 alkoxy or C 1 -C 6 alkylthio groups or chlorine or bromine atoms or phenyl groups substituted phenyl radical, or R 2 and R 3 together represent - (CH 2 ) p - with p = 4 to 5,
Ar represents a p-phenylene radical optionally substituted by chlorine or bromine atoms, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or C 1 -C 6 alkylthio groups,
n the numbers 0 or 1 and
m are the numbers 1 or 2 with the proviso that m + n = 2, and
X represents a non-nucleophilic anion.
Weitere Gegenstände der Erfindung sind ein Verfahren zur Herstellung dieser Verbindungen, die Verwendung der Verbindungen als Photoinitiatoren für kationisch härtbare und kationisch polymerisierbare Gemische, damit hergestellte photohärtbare Gemische sowie photoempfindliche Aufzeichnungsmaterialien zur Herstellung von Reliefbildern und Resistmustern.Further objects of the invention are a method for the production of these compounds, the use of the compounds as photoinitiators for cationically curable and cationically polymerizable mixtures manufactured photocurable mixtures and photosensitive recording materials for the production of relief images and resist patterns.
Geeignete erfindungsgemäße Verbindungen der Formel (I) sind vor allem
solche, in denen
R1 einen tert. Butyl-, einen 1,1,2,2-Tetramethylbutyl-, einen 1-Methyl-1-
ethyl-2,2-dimethylpropyl-, einen 1-Methylcyclohexyl-, einen 1-Methylcyclopentyl-,
einen Phenyl-, Methylphenyl-, Ethylphenyl-, Dimethylphenyl-,
Isopropylphenyl-, tert.-Butylphenyl-, Trimethylphenyl-, Chlorphenyl-,
Methoxyphenyl-, Ethoxyphenyl, einen Furyl-, Methylfuryl-,
Thienyl-, Ethylthienyl-, Naphthyl- oder Methylnapthylrest darstellt,
R2 und R3 Methyl-, Ethyl-, Propyl-, i-propyl-, n-Butyl-, tert. Butyl-,
i-Amyl-, n-Hexyl-, n-Octyl-, 2-Ethylhexyl-, i-Nonyl-, Methylheptyl-,
Cyclopentyl-, Cyclohexyl-, Phenyl-, Methylphenyl-, Dimethylphenyl-,
Trimethylphenyl-, tert. Butylphenyl-, Isopropylphenyl-, Methoxyphenyl-,
Ethoxyphenyl-, Isopropylphenyl- oder Dimethoxyphenylreste
darstellen, wobei R2 gleich oder verschieden von R3 sein kann, und
Ar insbesondere p-Phenylen, 2,3,5,6-Tetramethyl- oder Tetrachlor-p-
phenylen, 2,5-Dichlor- oder Dimethyl-p-phenylen bedeutet.Suitable compounds of the formula (I) according to the invention are, above all, those in which
R 1 is a tert. Butyl, a 1,1,2,2-tetramethylbutyl, a 1-methyl-1-ethyl-2,2-dimethylpropyl, a 1-methylcyclohexyl, a 1-methylcyclopentyl, a phenyl, methylphenyl, Represents ethylphenyl, dimethylphenyl, isopropylphenyl, tert.-butylphenyl, trimethylphenyl, chlorophenyl, methoxyphenyl, ethoxyphenyl, a furyl, methylfuryl, thienyl, ethylthienyl, naphthyl or methylnaphthyl radical,
R 2 and R 3 are methyl, ethyl, propyl, i-propyl, n-butyl, tert. Butyl, i-amyl, n-hexyl, n-octyl, 2-ethylhexyl, i-nonyl, methylheptyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tert . Butylphenyl, isopropylphenyl, methoxyphenyl, ethoxyphenyl, isopropylphenyl or dimethoxyphenyl radicals, where R 2 can be identical or different from R 3 , and
Ar in particular means p-phenylene, 2,3,5,6-tetramethyl- or tetrachloro-p-phenylene, 2,5-dichloro- or dimethyl-p-phenylene.
Als nicht nucleophile Anionen X⊖ kommen insbesondere Perchlorat-Anionen und Anionen der Formel (II)Perchlorate anions in particular come as non-nucleophilic anions X⊖ and anions of the formula (II)
[MY q ]⊖ (II)[MY q ] ⊖ (II)
in Betracht, in denen M für ein Bor-, Wismut-, Antimon-, Arsen- oder Phosphoratom steht, Y Fluor- und/oder Chloratome darstellen, ein Y aber auch ein OH-Gruppe sein kann, und q für die Zahlen 4 bis 6 steht und die Zahl von q jeweils um eins höher ist als die Wertigkeit von M. Beispiel geeigneter nucleophiler Anionen [MY q ]⊖ sind Tetrafluoroborat-, Hexafluorophosphat-, Hexafluoroarsenat-, Hexachlorarsenat-, Hexachlorantimonat-, Hexafluorantimonat-, Pentachlorohydroxyantimonat-, Hexafluoroantimonat-, Pentachlorohydroxyantimonat- und Pentafluorhydroxyantimonat-Anionen.into consideration, in which M stands for a boron, bismuth, antimony, arsenic or phosphorus atom, Y represents fluorine and / or chlorine atoms, but a Y can also be an OH group, and q for the numbers 4 to 6 stands and the number of q is in each case one higher than the valency of M. Examples of suitable nucleophilic anions [MY q ] ⊖ are tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroarsenate, hexachloroantimonate, hexafluoroantimonate, pentachlorohydroxyantoroate, hexaf -, Pentachlorohydroxyantimonat- and Pentafluorhydroxyantimonat anions.
Als Beispiele besonders geeigneter erfindungsgemäßer Verbindungen seien genannt die Tetrafluoroborate, Hexafluorophosphate, Hexafluoroarsenate, Hexafluoroantimonate, Hexachloroantimonate des p-Benzoylbenzyldimethylsulfonium-, p-Benzoylbenzyldiethylsulfonium-, p-Benzoylbenzylmethylphenylsulfonium-, p-Benzoylbenzyldiphenylsulfonium-, p-Pivaloylbenzyldimethylsulfonium-, p-Pivaloylbenzylmethylphenylsulfonium-, p-(4-Methylbenzoyl)benzyldimethylsulfonium-, p-(2-Methylbenzoyl)benzyldimethylsulfonium- oder p-Benzoylbenzyltetramethylensulfonium-Kations.Examples are particularly suitable compounds according to the invention called the tetrafluoroborates, hexafluorophosphates, hexafluoroarsenates, Hexafluoroantimonate, hexachloroantimonate of p-benzoylbenzyldimethylsulfonium, p-benzoylbenzyldiethylsulfonium-, p-benzoylbenzylmethylphenylsulfonium-, p-benzoylbenzyldiphenylsulfonium-, p-pivaloylbenzyldimethylsulfonium-, p-pivaloylbenzylmethylphenylsulfonium-, p- (4-methylbenzoyl) benzyldimethylsulfonium-, p- (2-methylbenzoyl) benzyldimethylsulfonium or p-Benzoylbenzyltetramethylene sulfonium cations.
Die erfindungsgemäßen Verbindungen können hergestellt werden, indem man z. B. p-Acylbenzylsulfoniumhalogenide der Formel (III) worin Hal = Halogenid-, insbesondere Bromid- und/oder Chlorid-Anionen darstellt, die nach dem von I. G. Tschitschenko, L. W. Schubina und G. W. Sudnik in Vestn. Belorus. Un-Ta, Ser. 2, 1979, S. 3 (CA 93, 1 49 925), beschriebenen Verfahren aus p-Acylbenzylhalogeniden und Sulfiden in einfacher Weise zugänglich sind, in einem protischen oder aprotischen Lösungsmittel oder Lösungsmittelgemisch bei Temperaturen zwischen -10 und +50°C mit einem Salz der Formel (IV)The compounds of the invention can be prepared by e.g. B. p-acylbenzylsulfonium halides of the formula (III) where Hal = halide, in particular bromide and / or chloride anions, which according to that of IG Tschitschenko, LW Schubina and GW Sudnik in Vestn. Belorus. Un-Ta, Ser. 2, 1979, p. 3 (CA 93, 1 49 925), described processes from p-acylbenzyl halides and sulfides are easily accessible in a protic or aprotic solvent or solvent mixture at temperatures between -10 and + 50 ° C with a Salt of formula (IV)
A⊕X⊖ (IV)A⊕X⊖ (IV)
umsetzt wobei X⊖ die obengegebene Bedeutung hat und A⊕ für ein Proton, ein Ammoniumkation oder ein anderes Kation eines Elements der 1. Hauptgruppe des Periodensystems der Elemente steht. Die erfindungsgemäßen Verbindungen fallen dabei in der Regel als schwerlösliche Salze an. Die Art oder Zusammensetzung und Menge des Lösungsmittels oder Lösungsmittelgemisches sollte so beschaffen sein, daß es das Salz der Formel (IV) nahezu vollständig löst. Geeignet sind zum Beispiel Wasser, Methanol, Ethanol, Propanol, Isopropanol, Dimethylformamid, Dioxan, Tetrahydrofuran, Dimethylsulfoxid oder Aceton sowie Mischungen dieser Lösungsmittel untereinander. In der Regel wird das Salz (IV) in einem Überschuß von 5 und 100% der Verbindung (III) eingesetzt. Die Herstellung einer erfindungsgemäßen Verbindung ist in folgender Gleichung beispielhaft beschrieben: where X⊖ has the meaning given above and A⊕ stands for a proton, an ammonium cation or another cation of an element of the 1st main group of the Periodic Table of the Elements. The compounds according to the invention are generally obtained as poorly soluble salts. The type or composition and amount of the solvent or solvent mixture should be such that it almost completely dissolves the salt of the formula (IV). For example, water, methanol, ethanol, propanol, isopropanol, dimethylformamide, dioxane, tetrahydrofuran, dimethyl sulfoxide or acetone and mixtures of these solvents with one another are suitable. As a rule, the salt (IV) is used in an excess of 5 and 100% of the compound (III). The preparation of a compound according to the invention is described by way of example in the following equation:
Aus dem angegebenen Herstellverfahren geht hervor, daß die p-Acylbenzylverbindungen in sehr einfacher Weise aus gut zugänglichen Ausgangsverbindungen herstellbar sind. Die erfindungsgemäßen Verbindungen zeigen eine sehr gute Reaktivität als Photoinitiatoren in kationisch härtbaren und kationisch polymerisierbaren Massen.It can be seen from the preparation process given that the p-acylbenzyl compounds in a very simple way from easily accessible starting compounds are producible. The compounds of the invention show a very good reactivity as photoinitiators in cationically curable and cationically polymerizable compositions.
p-Acylbenzylsulfoniumsalze der Formel (I) enthaltende photohärtbare Massen enthalten neben einer wirksamen Menge dieser Photoinitiatoren eine Verbindung a) bzw. ein Gemisch von Verbindungen a), die unter dem Einfluß von kationischen Katalysatoren in eine höhermolekulare Verbindung überführbar sind. Verbindungen a) können beispielsweise Oxetane, Thiirane oder Tetrahydrofuran sein. Vorzugsweise ist Verbindung a) ein 1,2-Epoxid, ein Vinylmonomer oder -präpolymer, ein Aminoplast oder ein Phenoplast.Photocurable containing p-acylbenzylsulfonium salts of formula (I) In addition to an effective amount of these photoinitiators, compositions contain one Compound a) or a mixture of compounds a) under the influence convertible from cationic catalysts into a higher molecular compound are. Compounds a) can, for example, oxetanes, thiiranes or tetrahydrofuran. Compound a) is preferably a 1,2-epoxide, a vinyl monomer or prepolymer, an aminoplast or a phenoplast.
Beispiele geeigneter 1,2-Epoxide sind Epichlorhydrin, Propylenoxid oder Glycidylether sowie einwertigen Alkohols oder Phenols, wie n-Butylglycidylether oder Phenylglycidylether, Glycidylester wie Glycidylacrylat oder Glycidylmethacrylat. Vorzugsweise ist Komponente a) ein Epoxidharz und insbesondere ein solches, das mindestens eine direkte an ein Sauerstoffatom gebundene Gruppe der Formel (VI) enthält, worin entweder R4 und R6 je ein Wasserstoffatom darstellen, in welchem Fall R5 ein Wasserstoffatom oder eine Methylgruppe bedeutet, oder R4 und R6 gemeinsam -CH2CH2- darstellen, in welchem Fall R5 ein Wasserstoffatom bedeutet.Examples of suitable 1,2-epoxides are epichlorohydrin, propylene oxide or glycidyl ether and monohydric alcohol or phenol, such as n-butyl glycidyl ether or phenyl glycidyl ether, glycidyl esters such as glycidyl acrylate or glycidyl methacrylate. Component a) is preferably an epoxy resin and in particular one which has at least one group of the formula (VI) bonded directly to an oxygen atom contains, in which either R 4 and R 6 each represent a hydrogen atom, in which case R 5 represents a hydrogen atom or a methyl group, or R 4 and R 6 together represent -CH 2 CH 2 -, in which case R 5 represents a hydrogen atom.
Beispiele solcher Harze sind Polyglycidyl- und Poly(β-methylglycidyl)- ester, die man durch Umsetzung einer zwei oder mehr Carbonsäuregruppen enthaltenden Verbindung mit Epichlorhydrin, Glycerindichlorhydrin oder β-Methylepichlorhydrin in Gegenwart von Alkali erhalten kann. Solche Polyglycidylester können sich von aliphatischen Polycarbonsäuren, wie Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure oder dimerisierter oder trimerisierter Linolsäure, von cycloaliphatischen Polycarbonsäuren wie Tetrahydrophthalsäure, 4-Methyltetrahydrophthalsäure, Hexahydrophthalsäure und 4-Methylhexahydrophthalsäure und aromatischen Polycarbonsäuren wie Phthalsäure, Isophthalsäure und Terephthalsäure ableiten. Weitere geeignete Polyglycidylester sind durch Polymerisation der Glycidylester von olefinisch ungesättigten Säuren, insbesondere von Glycidylacrylat und Glycidylmethacrylat, erhältlich.Examples of such resins are polyglycidyl and poly (β-methylglycidyl) esters obtained by reacting two or more carboxylic acid groups containing compound with epichlorohydrin, glycerol or β-methylpichlorohydrin can be obtained in the presence of alkali. Such Polyglycidyl esters can differ from aliphatic polycarboxylic acids such as Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, of cycloaliphatic polycarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid and aromatic polycarboxylic acids such as phthalic acid, Derive isophthalic acid and terephthalic acid. Other suitable polyglycidyl esters are olefinic by polymerizing the glycidyl esters unsaturated acids, especially glycidyl acrylate and glycidyl methacrylate, available.
Ferner geeignet sind Polyglycidyl- und Poly(β-methylglycidyl)-ether, wie sie durch Umsetzung einer mindestens zwei freie alkoholische und/oder phenolische Hydroxylgruppen pro Molekül enthaltenden Verbindung mit dem entsprechenden Epichlorhydrin unter alkalischen Bedingungen, oder auch in Gegenwart eines sauren Katalysators mit nachfolgender Alkalibehandlung erhältlich sind. Beispiele von Alkoholen und Phenolen für eine solche Umsetzung sind Ethylenglykol, Propandiol, Diethylenglykol, Poly(oxyethylen)glykole, Poly(oxypropylen)glykole, Poly(oxytetramethylen)glykole, Glycerin, 1,1,1-Trimethylolpropan, Pentaerythrit, Sorbit, Bis(4-hydrodycyclohexyl)methan, 2,2-Bis(4-hydroxycyclohexyl)propan, N,N-Bis(2-hydroxyethyl)anilin, p,p′-Bis(2-hydroxyethylamino)diphenylmethan, Bis(4-hydroxyphenyl)methan, Bis(4-hydroxyphenyl)sulfon, 2,2-Bis(4-hydroxyphenyl)propan, sowie Novolake, wie sie durch Umsetzung von Aldehyden, wie Formaldehyd oder Acetaldehyd, mit Phenolen hergestellt werden können.Also suitable are polyglycidyl and poly (β-methylglycidyl) ethers, such as them by implementing at least two free alcoholic and / or phenolic hydroxyl groups per molecule containing compound with the corresponding epichlorohydrin under alkaline conditions, or in Presence of an acid catalyst followed by alkali treatment are available. Examples of alcohols and phenols for such Implementation are ethylene glycol, propanediol, diethylene glycol, poly (oxyethylene) glycols, Poly (oxypropylene) glycols, poly (oxytetramethylene) glycols, Glycerin, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, bis (4-hydrodycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane, N, N-bis (2-hydroxyethyl) aniline, p, p′-bis (2-hydroxyethylamino) diphenylmethane, bis (4-hydroxyphenyl) methane, Bis (4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxyphenyl) propane, and novolaks, such as those obtained by reacting aldehydes, such as formaldehyde or acetaldehyde, can be prepared with phenols.
Beispiele für Epoxidharze mit Gruppen der Formel (VI), worin R4 und R6 zusammen eine -CH2CH2-Gruppe bedeuten, sind Bis(2,3-epoxycyclopentyl)- ether oder 2,3-Epoxycyclopentyl-glycidylether. Examples of epoxy resins with groups of the formula (VI) in which R 4 and R 6 together denote a —CH 2 CH 2 group are bis (2,3-epoxycyclopentyl) ether or 2,3-epoxycyclopentyl glycidyl ether.
Verwendbar sind auch Epoxidharze, in denen einige oder sämtliche Epoxidgruppen mittelständig sind, wie Vinylcyclohexendioxid, Dicyclopentadiendioxid, sowie epoxidierte Polybutadiene oder epoxidierte Copolymere des Butadiens mit Vinylmonomeren. Natürlich sind auch Epoxidharzgemische verwendbar.Epoxy resins containing some or all of the epoxy groups can also be used are medium-sized, such as vinylcyclohexene dioxide, dicyclopentadiene dioxide, and epoxidized polybutadienes or epoxidized copolymers of Butadiene with vinyl monomers. Of course there are also epoxy resin mixtures usable.
Besonders bevorzugt verwendete Epoxidharze sind die Diglycidylether von zweiwertigen Phenolen und von zweiwertigen aliphatischen Alkoholen.Epoxy resins which are particularly preferably used are the diglycidyl ethers of dihydric phenols and dihydric aliphatic alcohols.
Gewünschtenfalls kann man das Epoxidharz auch in an sich bekannter Art einer Mischhärtung mit einem mehrwertigen Alkohol, insbesondere mit einem Molekulargewicht von über 1000 unterwerfen. Geeignete Alkohole dafür sind beispielsweise Poly(oxyethylen)glykole, Polyvinylalkohole, Hydroxypropylcellulose und Teilester der Cellulose.If desired, the epoxy resin can also be made in a manner known per se mixed curing with a polyhydric alcohol, especially with a Submit molecular weight of over 1000. Suitable alcohols for this are for example poly (oxyethylene) glycols, polyvinyl alcohols, hydroxypropyl cellulose and partial esters of cellulose.
Olefinisch ungesättigte Monomere a), die kationisch mit den erfindungsgemäßen Photoinitiatoren polymerisiert werden können, sind z. B. Styrol, α-Methylstyrol, Divinylbenzol, Vinylcyclohexan, 4-Vinylcyclohexan-1, N-Vinylcarbazol, Isopren, Butadien, sowie bevorzugte Vinylether wie Methylvinylether, Isobutylvinylether, 1,1,1-Trimethylolpropan-trivinylether, Glycerintrivinylether, die Vinylether von Ethylenglykol und Polyethylenglykolen sowie cyclische Vinylether.Olefinically unsaturated monomers a) which are cationic with the invention Photoinitiators can be polymerized, for. B. styrene, α-methylstyrene, divinylbenzene, vinylcyclohexane, 4-vinylcyclohexane-1, N-vinyl carbazole, isoprene, butadiene, and preferred vinyl ethers such as Methyl vinyl ether, isobutyl vinyl ether, 1,1,1-trimethylolpropane trivinyl ether, Glycerin trivinyl ether, the vinyl ether of ethylene glycol and polyethylene glycols as well as cyclic vinyl ethers.
Die als Komponente a) bevorzugten Aminoplaste enthalten pro Molekül mindestens zwei an ein Amid- oder Thioamidstickstoffatom bzw. -atome gebundene Methylgruppen, die auch verethert oder verestert sein können. Beispiele solcher Aminoplaste sind die N-Hydroxymethyl-, N-Methoxymethyl-, N-Butoxymethyl- und N-Acetoxymethylderivate von Harnstoff, Thioharnstoff oder cyclischen Harnstoffen, von Carbamaten und Dicarbamaten aliphatischer einwertiger und zweiwertiger Alkohole, sowie von Melamin wie teilveretherte Hexamethylolamin oder von weiteren Polyamino-1,3- triazinen. Bevorzugte Aminoplaste sind die Kondensationsprodukte des Harnstoffs, Hydantoins oder Melamins mit Formaldehyd, z. B. ein Kondensationsprodukt aus Harnstoff mit 1,8 Mol Formaldehyd, sowie teilweise oder völlig veretherte Produkte solcher Kondensationsprodukte mit einem aliphatischen einwertigen Alkohol mit 1 bis 4 Kohlenstoffatomen.The aminoplasts preferred as component a) contain per molecule at least two to an amide or thioamide nitrogen atom or atoms bound methyl groups, which can also be etherified or esterified. Examples of such aminoplasts are the N-hydroxymethyl, N-methoxymethyl, N-butoxymethyl and N-acetoxymethyl derivatives of urea, thiourea or cyclic ureas, of carbamates and dicarbamates aliphatic monohydric and dihydric alcohols, as well as melamine such as partially etherified hexamethylolamine or of other polyamino-1,3- triazines. Preferred aminoplasts are the condensation products of Urea, hydantoins or melamines with formaldehyde, e.g. B. a condensation product from urea with 1.8 mol of formaldehyde, and partly or completely etherified products of such condensation products with an aliphatic monohydric alcohol with 1 to 4 carbon atoms.
Als Phenoplaste werden die bekannten aus einem ein- oder mehrwertigen Phenol und einem Aldehyd wie Formaldehyd hergestellten Resole bevorzugt.The known phenoplasts are made from a mono- or polyvalent Phenol and an aldehyde such as formaldehyde produced resols preferred.
Zur Auslösung des Photopolymerisationsvorgangs verwendet man vorzugsweise aktinische Strahlung einer Wellenlänge von 200 bis 600 nm. Als aktinische Strahlungsquellen eignen sich die bekannten wie Kohlelichtbögen, Quecksilberdampflampen, ultraviolettes Licht ausstrahlende Leuchtröhren und photographische Flutlampen. Die Belichtungszeit hängt unter anderem vom verwendeten polymerisierbaren Substrat, der Art der Lichtquelle und deren Abstand vom bestrahlten Material ab und ist in einem Vorversuch leicht bestimmbar.It is preferred to use to initiate the photopolymerization process actinic radiation with a wavelength of 200 to 600 nm. As actinic Well-known radiation sources such as carbon arcs, mercury vapor lamps, fluorescent tubes emitting ultraviolet light and photographic floodlights. The exposure time depends on, among other things used polymerizable substrate, the type of light source and its Distance from the irradiated material and is easy in a preliminary test determinable.
Die erfindungsgemäßen Zusammensetzungen sind z. B. für Oberflächenbelichtungen verwendbar und als Schicht auf einem Substrat bestrahlbar und härtbar. Bestrahlt man durch eine Maske, so kann man dann die unbelichteten Schichtanteile durch Auswaschen entfernen. Die erfindungsgemäßen Gemische sind so besonders für die Herstellung von Druckplatten und gedruckten Schaltungen verwendbar, wobei die bekannten Methoden zur Herstellung von Druckplatten und gedruckten Schaltungen aus photopolymersierbaren Zusammensetzungen angewandt werden können.The compositions according to the invention are e.g. B. for surface exposures usable and irradiable as a layer on a substrate and curable. If you irradiate through a mask, you can then see the unexposed Remove parts of the layer by washing. The invention Mixtures are so special for the production of printing plates and printed ones Circuits can be used, the known methods of manufacture of printing plates and printed circuits from photopolymerizable Compositions can be applied.
Die erfindungsgemäßen Mischungen sind auch als Klebstoffe, bei der Herstellung von faserverstärkten Verbundstoffen, einschließlich Plattenpreßmassen, zur Herstellung von Kitten und Spachtelmassen oder für Tauchbeschichtungen verwendbar.The mixtures according to the invention are also used as adhesives in the manufacture of fiber-reinforced composites, including sheet molding compounds, for the production of putties and fillers or for dip coatings usable.
Ein erfindungsgemäßes Gemisch mit z. B. einem Epoxidharz oder Phenoplast und einer zur Polymerisation dieses Epoxidharzes oder Phenoplastes bei Belichtung mit aktinischer Strahlung wirksamen Mengen eines 4-Acylbenzylsulfoniumsalzes der Formel I kann auch eine härtende Menge eines latenten Heißhärters für das Epoxidharz oder Phenoplast enthalten, wie Polycarbonsäureanhydride, Komplexe von Aminen, insbesondere primären oder tertiären aliphatischen Aminen wie Trimethylamin und n-Octyldimethylamin mit Bortrifluorid oder Bortrichlorid und latente Bortrifluoridchelate. Geeignete hitzeaktivierbare Vernetzungsmittel für Resole sind z. B. Hexamethylentetramin und Paraformaldehyd. Die für die Heißhärtung erforderliche Temperatur und Erhitzungsdauer sowie die Anteile an hitzeaktivierbarem Härter lassen sich leicht durch Vorversuche in bekannter Weise ermitteln. Erfindungsgemäße Mischungen mit einem Gehalt an Heißhärter und der Möglichkeit einer zweistufigen Härtung zeichnen sich für manche Verwendungen wie Imprägnierungen oder die Herstellung von Formkörpern besonders aus.An inventive mixture with z. B. an epoxy or phenolic and one for the polymerization of this epoxy resin or phenoplast Exposure to actinic radiation effective amounts of a 4-acylbenzylsulfonium salt Formula I can also contain a curing amount of a latent Contain thermosetting agents for the epoxy resin or phenoplast, such as polycarboxylic anhydrides, Complexes of amines, especially primary or tertiary aliphatic amines such as trimethylamine and n-octyldimethylamine with boron trifluoride or boron trichloride and latent boron trifluoride chelates. Suitable Heat-activated crosslinking agents for resols are e.g. B. hexamethylenetetramine and paraformaldehyde. The temperature required for hot curing and heating duration as well as the proportions of heat-activated Hardeners can easily be determined by preliminary tests in a known manner. Mixtures according to the invention with a content of hot hardener and the possibility A two-stage hardening stand out for some uses such as impregnation or the production of moldings.
Eine besondere Anwendungsform der 4-Acylbenzylsulfoniumsalze ist in lichtempfindlichen Aufzeichnungsmaterialien für die Herstellung von Reliefbildern oder Resistmustern mit einer auf einem dimensionsstabilen Träger aufgebrachten lichtempfindlichen härtbaren Schicht.A particular application of the 4-acylbenzylsulfonium salts is in photosensitive recording materials for the production of Relief images or resist patterns with one on a dimensionally stable Carrier applied photosensitive curable layer.
In der DE-A 33 26 036 ist ein photoempfindliches Aufzeichnungsmaterial mit einer auf einen dimensionsstabilen Träger aufgebrachten festen, photoempfindlichen, härtbaren Schicht (S) beschrieben, dieDE-A 33 26 036 describes a photosensitive recording material with a solid, photosensitive, curable layer ( S ) applied to a dimensionally stable support, the
- (i) eine Verbindung mit mindestens zwei aromatischen und/oder heteroaromatischen o-Nitrocarbinolestergruppen der Formel (V) worin A den Rest eines aromatischen oder heteroaromatischen, gegebenenfalls substituierten Ringsystems mit 5 bis 14 Ringgliedern und Z ein Wasserstoffatom, einen Alkylrest mit 1 bis 8 Kohlenstoffatomen oder einen gegebenenfalls subsituierten Aryl- oder Aralkylrest bedeuten,(i) a compound having at least two aromatic and / or heteroaromatic o-nitrocarbinol ester groups of the formula (V) in which A is the radical of an aromatic or heteroaromatic, optionally substituted ring system with 5 to 14 ring members and Z is a hydrogen atom, an alkyl radical with 1 to 8 carbon atoms or an optionally substituted aryl or aralkyl radical,
- (ii) eine vernetzend wirkende Verbindung mit mindestens zwei reaktiven Gruppen, die unter dem Einfluß von Wärme mit -COOH-Gruppen unter Bildung einer kovalenten chemischen Bindung zu reagieren vermögen, wobei (ii) auch als Gruppierung(en), z. B. Amin-, Imin-, Amid-, Epoxid- oder Hydroxy-Gruppierungen in den Verbindungen (i) enthalten sein können, sowie(ii) a crosslinking compound with at least two reactive Groups under the influence of heat with -COOH groups react to form a covalent chemical bond assets, whereby (ii) also as grouping (s), e.g. B. amine, Imine, amide, epoxy or hydroxy groups in the compounds (i) may be included, as well
- (iii) einen Katalysator für die Reaktion der vernetzend wirkenden Verbindung (ii) mit -COOH-Gruppen enthaltenden Verbindungen enthält, der in verkappter, nicht aktiver Form vorliegt, aber photochemisch und/oder thermisch aktivierbar ist.(iii) a catalyst for the reaction of the crosslinking Compound (ii) with compounds containing -COOH groups contains, which is in capped, inactive form, but can be activated photochemically and / or thermally.
Es hat sich nun gezeigt, daß sich die erfindungsgemäßen Verbindungen der Formel (I) hervorragend als photochemisch aktivierbare Katalysatoren (iii) für die Reaktion der vernetzend wirkenden Verbindungen (ii) mit den -COOH-gruppen eignen. Bezüglich weiterer Angaben zu dieser Verwendung der erfindungsgemäßen Katalysatoren in solchen Aufzeichnungsmaterialien sei auf die DE-A-33 26 036, DE-A-32 31 147 und DE-A-32 31 145 verwiesen. Der Einsatz von z. B. Benzoylbenzylsulfoniumverbindungen der Formel (I) verleiht solchen Aufzeichnungsmassen eine gute Lagerstabilität. So können sie mehrere Wochen bei 50°C gelagert werden, ohne daß sich dadurch die sehr guten Eigenschaften der Aufzeichnungsmaterialien und die hohe Qualität der hieraus hergestellten Reliefbilder oder Resistmuster verschlechtern. It has now been shown that the compounds of the invention Formula (I) excellently as photochemically activatable catalysts (iii) for the reaction of the crosslinking compounds (ii) with the -COOH groups. For more information on this use of the catalysts of the invention in such recording materials please refer to DE-A-33 26 036, DE-A-32 31 147 and DE-A-32 31 145. The use of e.g. B. Benzoylbenzylsulfonium Compounds of Formula (I) gives such recording compositions good storage stability. So can they are stored for several weeks at 50 ° C without the very good properties of the recording materials and the high quality the relief images or resist patterns produced therefrom deteriorate.
Erfindungsgemäße lichtempfindliche Aufzeichnungsmaterialien eignen sich für die Herstellung von Hoch-, Tief-, Offset- oder Siebdruckformen, Photoresist- oder Lötstoppmasken. Sie eignen sich auch für Schichtübertragungsmaterialien bei der Herstellung von Leiterplatten, gedruckten Schaltungen, integrierten Schaltungen etc. Die Herstellung von Reliefbildern oder Resistmuster mit die erfindungsgemäßen Katalysatoren enthaltenden Aufzeichnungsmaterialien kann wahlweise nach negativ arbeitenden oder positiv arbeitenden Verfahren erfolgen, wie sie an sich bekannt und beispielsweise in der DE-B-23 09 062 sowie den DE-A-32 31 144, DE-A-32 31 145 und DE-A-32 41 147 beschrieben sind. Hierzu wird zunächst die lichtempfindliche härtbare Schicht (S) der erfindungsgemäßen Aufzeichnungsmaterialien bildmäßig mit aktinischem Licht belichtet. Die bildmäßige Belichtung erfolgt dabei je nach Verfahrensführung entweder durch ein Bildpositiv oder Bildnegativ oder bei der Herstellung von Tiefdruckformen oder durch ein Raster oder Rasterpositiv bzw. ein Raster oder Rasternegativ, wobei letzteres auch zusammen mit einem Halbtonnennegativ angewandt werden kann. Die bildmäßige Belichtung der lichtempfindlichen härtbaren Strahlen (S) kann auch mit einem bildbmäßig modulierten aktinischem Laserstrahl, z. B. einem UV-Laser, erfolgen.Photosensitive recording materials according to the invention are suitable for the production of high, low, offset or screen printing forms, photoresist or solder mask. They are also suitable for layer transfer materials in the production of printed circuit boards, printed circuits, integrated circuits etc. The production of relief images or resist patterns with the recording materials containing the catalysts according to the invention can optionally be carried out using negative-working or positive-working methods, as is known per se and, for example, in DE-B-23 09 062 and DE-A-32 31 144, DE-A-32 31 145 and DE-A-32 41 147 are described. For this purpose, the photosensitive curable layer ( S ) of the recording materials according to the invention is first exposed imagewise with actinic light. Depending on the process, the image-wise exposure takes place either by means of an image positive or image negative or in the production of gravure printing forms or by means of a screen or screen positive or a screen or screen negative, the latter also being able to be used together with a half-ton negative. The imagewise exposure of the photosensitive curable rays ( S ) can also with an imagewise modulated actinic laser beam, e.g. B. a UV laser.
Bei den positiv arbeitenden Verfahren zur Herstellung der Reliefbilder oder Resistmuster werden nach der bildmäßigen Belichtung der lichtempfindlichen härtbaren Schicht (S) die belichteten Schichtanteile, in denen die photoempfindlichen Substanzen wie die o-Nitrocarbinolestergruppierungen unter Bildung von freien Carboxylgruppen gespalten worden sind, mit einem wäßrigen Entwicklerlösungsmittel in üblicher Weise, beispielsweise durch Besprühen, Ausreiben oder Ausbürsten entfernt. Der Vorgang der bildmäßigen Belichtung und des Auswaschens der lichtempfindlichen Schicht (S) kann bei den positiv arbeitenden Verfahren auch mehrmals wiederholt werden. Nach der letzten bildmäßigen Belichtung sowie dem Entfernen der belichteten Schichtanteile wird der auf dem Träger verbliebene Teil der lichtempfindlichen Schicht (S), der nunmehr bereits ein positives Abbild der bildmäßigen Vorlage darstellt, vollflächig mit aktinischem Licht nachbelichtet. Für diese vollflächige Nachbelichtung können die gleichen Lichtquellen herangezogen werden, wie für die vorerwähnte bildmäßige Belichtung, wobei die Dauer für die vollflächige Nachbelichtung im allgemeinen im Bereich von 0,05 bis 50 Min. liegt. Im Anschluß an die vollflächige Nachbelichtung wird die Schicht (S) thermisch vernetzt und gehärtet.In the positive working methods for producing the relief images or resist patterns, after the imagewise exposure of the photosensitive curable layer ( S ), the exposed layer portions in which the photosensitive substances such as the o-nitrocarbinol ester groups have been cleaved to form free carboxyl groups are treated with an aqueous developer solvent removed in the usual way, for example by spraying, rubbing or brushing. The process of imagewise exposure and washing out of the photosensitive layer ( S ) can also be repeated several times in the case of the positive working methods. After the last imagewise exposure and the removal of the exposed layer portions, the part of the light-sensitive layer ( S ) which remains on the support and which now already represents a positive image of the imagewise template, is exposed over its entire area with actinic light. The same light sources can be used for this full-area post-exposure as for the aforementioned imagewise exposure, the duration for the full-surface post-exposure generally being in the range from 0.05 to 50 minutes. Following the full-area post-exposure, the layer ( S ) is thermally crosslinked and hardened.
In den negativ arbeitenden Verfahren werden nach der bildmäßigen Belichtung der Schicht (S) die belichteten Bereiche zunächst selektiv thermisch gehärtet und vernetzt. Die nichtvernetzten Bereiche der Schicht (S) können danach direkt mit einem geeigneten Entwicklerlösungsmittel ausgewaschen werden. Vorteilhafterweise wird jedoch die Schicht (S) zunächst noch einmal vollflächig mit aktinischem Licht nachbelichtet und dann mit einem wäßrigen Entwicklerlösungsmittel ausgewaschen. Nach dem Auswaschen der Schicht (S) kann diese noch einmal kthermisch nachgehärtet und nachvernetzt werden. Erfolgt das Auswaschen der Schicht (S) unmittelbar nach der bildmäßigen Belichtung, so ist für eine solche thermische Nachvernetzung und Nachhärtung der Schicht (S) nach dem Auswaschen noch einmal vollflächig mit aktinischem Licht zu belichten.In the negative working processes, after the imagewise exposure of the layer ( S ), the exposed areas are first selectively thermally hardened and crosslinked. The non-crosslinked areas of the layer ( S ) can then be washed out directly with a suitable developer solvent. Advantageously, however, the layer ( S ) is first exposed again over the entire area with actinic light and then washed out with an aqueous developer solvent. After the layer ( S ) has been washed out, it can be thermally hardened and crosslinked again. If the layer ( S ) is washed out immediately after the image-wise exposure, then for such thermal post-crosslinking and post-hardening of the layer ( S ) it is again necessary to expose the entire area to actinic light after the washout.
Als Entwickler-Lösungsmittel können in den negativ arbeitenden Verfahren geeignete Lösungsmittel verwendet werden; vorzugsweise sowohl in den positiv arbeitenden als auch in den negativ arbeitenden Verfahren wäßrige Entwickler-Lösungsmittel. Hierbei kann es sich um Wasser oder auch um Mischungen von Wasser mit wasserlöslichen organischen Lösungsmitteln handeln, denen gegebenenfalls zur Einstellung eines optimalen pH-Wertes geringe Mengen an Alkalien oder organischen Basen zugesetzt werden können.As a developer solvent can be used in the negative working process suitable solvents are used; preferably both in the positive working as well as aqueous working in the negative working processes Developer solvent. This can be water or Mixtures of water with water-soluble organic solvents act, where appropriate for setting an optimal pH small amounts of alkalis or organic bases are added can.
Die Bedingungen für die thermische Härtung und Vernetzung der Schicht (S) hängen von der als Katalysator (Komponente iii) eingesetzte p-Acylbenzylsulfoniumverbindung ab. Vorteilhaft wird die Härtung und Vernetzung bei erhöhten Temperaturen durchgeführt. Im allgemeinen können mit den erfindungsgemäßen Katalysatoren in den Aufzeichnungsmaterialien die Temperaturen für die thermische Härtung und Vernetzung der Schicht (S) unter 150°C gehalten werden, so daß auch thermisch empfindliche Untergründe, wie sie z. B. in der Dünnschichttechnologie und bei der Herstellung von Leiterbahnen zur Anwendung kommen können, als Trägermaterialien eingesetzt werden können. Im allgemeinen liegen die Temperaturen für die thermische Härtung und Vernetzung der die erfindungsgemäßen Katalysatoren enthaltenden Schicht (S) im Bereich von 30 bis 150°C, vorzugsweise im Bereich von 50 bis 130°C. Die Dauer für die thermische Härtung und Vernetzung der Schicht (S) liegt üblicherweise im Bereich von 10 Minuten bis einigen Stunden, beispielsweise 5 Stunden. Dabei werden die Bedingungen für die thermische Härtung der Schicht (S) so gewählt, daß die gehärteten und vernetzten Reliefbilder oder Resistmuster die gewünschten mechanischen, physikalischen und chemischen Eigenschaften besitzen.The conditions for the thermal curing and crosslinking of the layer ( S ) depend on the p-acylbenzylsulfonium compound used as the catalyst (component iii). The curing and crosslinking is advantageously carried out at elevated temperatures. In general, the temperatures for the thermal curing and crosslinking of the layer ( S ) can be kept below 150 ° C with the catalysts of the invention in the recording materials, so that thermally sensitive substrates, such as z. B. in thin-film technology and in the production of conductor tracks can be used as carrier materials. In general, the temperatures for the thermal curing and crosslinking of the layer ( S ) containing the catalysts according to the invention are in the range from 30 to 150 ° C., preferably in the range from 50 to 130 ° C. The duration for the thermal curing and crosslinking of the layer ( S ) is usually in the range from 10 minutes to a few hours, for example 5 hours. The conditions for the thermal hardening of the layer ( S ) are chosen so that the hardened and crosslinked relief images or resist patterns have the desired mechanical, physical and chemical properties.
Die Erfindung wird durch die nachfolgenden Beispiele näher erläutert. Die in den Beispielen genannten Teile und Prozente beziehen sich, sofern nicht anders angegeben, auf das Gewicht. Volumenteile verhalten sich zu Teilen wie Liter zu Kilogramm.The invention is illustrated by the following examples. The Parts and percentages given in the examples relate, if not otherwise specified, by weight. Volumes behave too Divide like liters to kilograms.
Herstellung von p-Benzoylbenzyldimethylsulfonium-hexafluorphosphatPreparation of p-benzoylbenzyldimethylsulfonium hexafluorophosphate
19,9 g p-Benzoylbenzyldimethylsulfoniumbromid wurden in 420 g Wasser suspendiert, und eine Lösung von 11,8 g Kaliumhexafluorophosphat in 110 ml Wasser wurde zugegeben. Es wurde 12 Stunden bei 20°C nachgerührt, das Produkt abgesaugt, mit Wasser gewaschen und bei 50°C im Vakuum getrocknet. Es wurden 19,9 g (83,9% der Theorie) p-Benzoylbenzyldimethylsulfonium- hexafluorophosphat erhalten. Tabelle 1 gibt Struktur, Analyse und Eigenschaften wieder.19.9 g of p-benzoylbenzyldimethylsulfonium bromide was added to 420 g of water suspended, and a solution of 11.8 g of potassium hexafluorophosphate in 110 ml of water was added. The mixture was stirred at 20 ° C for 12 hours, the product is suctioned off, washed with water and dried at 50 ° C. in vacuo. 19.9 g (83.9% of theory) of p-benzoylbenzyldimethylsulfonium Obtained hexafluorophosphate. Table 1 gives structure, analysis and properties again.
In ähnlicher Weise wie in Beispiel 1 angegeben, wurden die anderen in Tabelle 1 beschriebenen p-Acylbenzylsulfoniumsalze erhalten. In a manner similar to that given in Example 1, the others in Table 1 described p-acylbenzylsulfonium salts obtained.
In 5 Ansätzen wurden jeweils 72 Teile eines Methylmethacrylat-Copolymerisats, welches 35% o-Nitrobenzylacrylat einpolymerisiert enthielt, 27 Teile eines Bisphenol-A-diglycidylethers (Epicote® 828 der Firma Shell), 0,7 Teile Benzildimethylketal, 0,1 Teile eines schwarzen Farbstoffes, 0,2 Teile des Polymethinfarbstoffes der Formel sowie 4 Teile der in Tabelle 2 zusammengestellten Onium-Salze in 160 Volumenteilen Essigsäuremethylester gelöst. Aus den jeweiligen Lösungen wurden auf Polyesterfolien lichtempfindliche härtbare Schichten (S) so aufgegossen, daß nach Entfernen des Lösungsmittels und Trocknung Schichtstärken von jeweils ca. 10 µm resultieren. Die so hergestellten Aufzeichnungsmaterialien wurden über 6 Wochen bei 50°C gelagert.In 5 batches, 72 parts of a methyl methacrylate copolymer which contained 35% o-nitrobenzyl acrylate in copolymerized form, 27 parts of a bisphenol A diglycidyl ether (Epicote® 828 from Shell), 0.7 part of benzil dimethyl ketal, 0.1 part of a black Dye, 0.2 parts of the polymethine dye of the formula and 4 parts of the onium salts listed in Table 2 dissolved in 160 parts by volume of methyl acetate. Photosensitive curable layers ( S ) were poured from the respective solutions onto polyester films in such a way that after removal of the solvent and drying, layer thicknesses of approximately 10 μm each resulted. The recording materials thus produced were stored at 50 ° C. for 6 weeks.
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Beispiel 7: p-Benzoylbenzyl-dimethylsulfonium-hexafluorophosphat
Beispiel 8: p-Benzoylbenzyl-dimethylsulfonium-hexafluoroarsenat
Beispiel 9: p-Benzoylbenzyl-tetramethylensulfonium-hexafluorophosphat
Beispiel 10: p-Benzoylbenzyl-tetramethylensulfonium-hexafluoroarsenat
Vergleichsversuch 1: Diphenyliodonium-hexafluoroarsenat.Example 7: p-Benzoylbenzyldimethylsulfonium hexafluorophosphate
Example 8: p-Benzoylbenzyldimethylsulfonium hexafluoroarsenate
Example 9: p-benzoylbenzyl tetramethylene sulfonium hexafluorophosphate
Example 10: p-Benzoylbenzyl tetramethylene sulfonium hexafluoroarsenate
Comparative experiment 1: Diphenyliodonium hexafluoroarsenate.
Zur Herstellung von Resistmustern wurden die freien Oberflächen der Schichten (S) 90 sec. vollflächig mit einer 500 Watt Höchstdruck-Quecksilberlampe vorbelichtet und auf ein mit Palladium bedampftes Glas auflaminiert. Die lichtempfindlichen Schichten (S) wurden dann mittels einer photographischen Positiv-Vorlage durch die Polyesterfolien hindurch mit einer 500 W Höchstdruck-Quecksilberlampe 3 Minuten lang bildmäßig belichtet. Anschließend wurden die Polyesterfolien von den Schichten (S) abgezogen und die belichteten Anteile der Schichten (S) mit einem wäßrigen Entwicklerlösungsmittel (81 Teile Wasser, 16 Teile 2-Butoxyethanol, 3 Teile Triethanolamin) in t Minuten (vgl. Tab. 3) ausgewaschen. Die so erhaltenen vorlagengetreuen Resistmuster wurden mit der gleichen Lampe wie oben nochmals vollflächig, d. h. ohne bildmäßige Vorlage, für eine Dauer von 15 Minuten nachbelichtet und dann je insgesamt 120 Minuten in steigenden Temperaturschritten von je 20°C im Temperaturbereich von 60°C bis 120°C thermisch gehärtet und vernetzt. Die erhaltenen Resists waren hervorragend als Ätzrestiste geeignet, wiesen sauber ausgebildete scharfkantige Flanken auf und waren gegen die konzentrierte Salpetersäure (65%ig) des Palladiumätzbades stabil. Nach dem Ätzen und Strippen der Resiste mit heißem Dimethylformamid wurden so Palladiumbahnen erhalten, die eine getreue Wiedergabe der Bildvorlage darstellten. Die in Tabelle 3 wiedergegebenen Ergebnisse zeigen, daß mit den erfindungsgemäßen Sulfoniumsalzen gemäß Beispielen 7 bis 10 ähnliche Ergebnisse erzielt wurden wie mit dem toxischen Iodoniumsalz (vgl. DE-A-25 18 639) gemäß Vergleichsversuch 1.To produce resist patterns, the entire surface of the layers ( S ) was pre-exposed for 90 seconds with a 500 watt high-pressure mercury lamp and laminated onto a palladium-vapor-coated glass. The photosensitive layers ( S ) were then imagewise exposed through the polyester films using a positive photographic original with a 500 W high-pressure mercury lamp for 3 minutes. The polyester films were then removed from the layers ( S ) and the exposed portions of the layers ( S ) were washed out with an aqueous developer solvent (81 parts of water, 16 parts of 2-butoxyethanol, 3 parts of triethanolamine) in t minutes (cf. Table 3) . The resist patterns obtained in this way were subsequently exposed again over the entire area, that is to say without a pictorial template, for a period of 15 minutes using the same lamp as above, and then for a total of 120 minutes each in increasing temperature steps of 20 ° C. in the temperature range from 60 ° C. to 120 ° C thermally hardened and cross-linked. The resists obtained were outstandingly suitable as etching resists, had clean, sharp-edged flanks and were stable against the concentrated nitric acid (65%) of the palladium etching bath. After etching and stripping the resists with hot dimethylformamide, palladium webs were thus obtained which represented a faithful reproduction of the original image. The results shown in Table 3 show that similar results were obtained with the sulfonium salts according to the invention according to Examples 7 to 10 as with the toxic iodonium salt (cf. DE-A-25 18 639) according to comparative experiment 1.
In vier verschiedenen Ansätzen wurden je 10 bzw. 15%ige acetonische Lösungen von p-Benzoylbenzyl-tetramethylensulfonium-hexafluorophosphat (Beispiel 11, 10%ig), p-Benzoylbenzyl-tetramethylen-sulfonium-hexafluoroarsenat (Beispiel 12, 15%ig), p-Benzoylbenzyl-tetramethylen- sulfonium-hexafluoroantimonat (Beispiel 13, 15%ig), N-Phenyl-carbamoyl- methyldimethyl-sulfoxonium-hexafluorophosphat (Vergleichsversuch 2 nach EP-A-44 274, 15%ig) dem Bisphenol-A-diglycidylether (Epikote® 828 der Firma Shell) in einer Menge zugesetzt, daß der Initiatorsalz-Anteil, bezogen auf Epoxid, jeweils 3% betrug. Die ohne Erwärmung hergestellten photoempfindlichen Mischungen wurden mit einem 80 µm Rakel auf Glasplatten aufgezogen (effektive Schichtdicken ca. 50 µm), vor der Belichtung 5 Min. zur Entfernung des Acetons abgelüftet und unter Luft im Abstand von ca. 10 cm fünfmal mit einer Bandgeschwindigkeit von 15 m/min. an 2 Lampen mit je 80 W/cm Leistung vorgeführt. Die Beurteilung der belichteten Schichten erfolgte sofort nach der Belichtung, nach 2 Stunden und nach 1 Tag. Wie die Ergebnisse in Tabelle 4 zeigen, härten die erfindungsgemäßen Sulfoniumsalze deutlich besser als das im Vergleichsversuch 2 getestete angegebene Sulfoxoniumsalz nach EP-A-44 274. In four different batches, 10% and 15% acetone were used Solutions of p-benzoylbenzyl tetramethylene sulfonium hexafluorophosphate (Example 11, 10%), p-benzoylbenzyl-tetramethylene-sulfonium-hexafluoroarsenate (Example 12, 15%), p-benzoylbenzyl-tetramethylene- sulfonium hexafluoroantimonate (Example 13, 15%), N-phenyl-carbamoyl- methyldimethylsulfoxonium hexafluorophosphate (comparative experiment 2 after EP-A-44 274, 15% strength) the bisphenol A diglycidyl ether (Epikote® 828 der Shell) added in an amount such that the initiator salt portion, based on epoxy, was 3% in each case. The made without heating Photosensitive mixtures were applied to glass plates using an 80 μm doctor blade applied (effective layer thicknesses approx. 50 µm), before exposure 5 minutes to remove the acetone and ventilated in air at a distance of approx. 10 cm five times with a belt speed of 15 m / min. demonstrated on 2 lamps with 80 W / cm power each. Assessing the exposed layers took place immediately after exposure, after 2 hours and after 1 day. As the results in Table 4 show, those according to the invention harden Sulfonium salts significantly better than that in comparative experiment 2 specified sulfoxonium salt tested according to EP-A-44 274.
Claims (10)
R1 einen tertiären Alkylrest oder Cycloalkylrest mit 4 bis 8 C-Atomen oder einen gegebenenfalls durch Chlor- oder Bromatome, C1-C6-Alkyl-, C1-C6-Alkoxy, C1-C6-Alkylthio- oder durch eine Phenylgruppe substituierten Phenyl-, Furyl-, Thienyl-, Naphthyl- oder Pyrrolylrest darstellt,
R2 und R3 gleich oder ungleich sind und einen C1-C8-Alkyl-, einen C5-C8-Cycloalkyl- oder einen gegebenenfalls durch einen oder mehrere C1-C6-Alkyl-, C1-C6-Alkoxy- oder C1-C6-Alkylthiogruppen oder Chlor- oder Bromatome oder Phenylgruppen substituierten Phenylrest, oder R2 und R3 zusammen -(CH2) p - mit p= 4 bis 6 darstellen,
Ar einen gegebenenfalls durch Chlor- oder Bromatome, C1-C6-Alkyl-, C1-C6-Alkoxy- oder C1-C6-Alkylthiogruppen substituierten p-Phenylenrest darstellt,
n für die Zahlen 0 oder 1 und
m für die Zahlen 1 oder 2 mit der Maßgabe stehen, daß m + n = 2, und
X⊖ ein nicht-nucleophiles Anion darstellt.1. 4-acylbenzylsulfonium salts of the formula I. wherein
R 1 is a tertiary alkyl radical or cycloalkyl radical having 4 to 8 carbon atoms or one optionally by chlorine or bromine atoms, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio or by represents a phenyl group substituted phenyl, furyl, thienyl, naphthyl or pyrrolyl radical,
R 2 and R 3 are the same or different and are a C 1 -C 8 alkyl, a C 5 -C 8 cycloalkyl or one optionally by one or more C 1 -C 6 alkyl, C 1 -C 6 Alkoxy or C 1 -C 6 alkylthio groups or chlorine or bromine atoms or phenyl groups substituted phenyl radical, or R 2 and R 3 together represent - (CH 2 ) p - with p = 4 to 6,
Ar represents a p-phenylene radical optionally substituted by chlorine or bromine atoms, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or C 1 -C 6 alkylthio groups,
n for the numbers 0 or 1 and
m stand for the numbers 1 or 2 with the proviso that m + n = 2, and
X⊖ represents a non-nucleophilic anion.
R1 Phenyl oder tert. Alkyl, R2 und R2 gleich oder verschieden, C1-C4-Alkyl- und/oder Phenylreste oder R2 und R3 zusammen C4-C8-Alkylenreste und X⊖ MHal6⊖- oder [MHal5(OH)]⊖-Anionen mit M = P, As oder Sb und Hal = Cl und/oder F darstellen.3. 4-acylbenzylsulfonium salts according to claim 1 having the formula wherein
R 1 is phenyl or tert. Alkyl, R 2 and R 2 identical or different, C 1 -C 4 alkyl and / or phenyl radicals or R 2 and R 3 together C 4 -C 8 alkylene radicals and X⊖ MHal 6 ⊖- or [MHal 5 (OH )] Represent ⊖ anions with M = P, As or Sb and Hal = Cl and / or F.
- a) mindestens eine Verbindung, die unter dem Einfluß von kationischen Katalysatoren in eine höhermolekulare Verbindung überführbar ist und
- b) eine wirksame Menge mindestens eines 4-Acylbenzylsulfoniumsalzes der in Anspruch 1 angegebenen Formel (I) als Photoinitiator.
- a) at least one compound which can be converted into a higher molecular weight compound under the influence of cationic catalysts and
- b) an effective amount of at least one 4-acylbenzylsulfonium salt of the formula (I) given in claim 1 as a photoinitiator.
- (i) mindestens eine Verbindung mit mindestens zwei aromatischen und/oder heteroaromatischen o-Nitrocarbinolestergruppierungen der Formel worin A den Rest eines aromatischen oder heteroaromatischen, gegebenenfalls substituierten Ringsystems mit 5 bis 15 Ringgliedern und Z ein Wasserstoffatom, einen Alkylrest mit 1 bis 8 Kohlenstoffatomen oder einen gegebenenfalls substituierten Aryl- oder Aralkylrest bedeuten,
- (ii) mindestens eine vernetzend wirkende Verbindung mit mindestens zwei reaktiven Gruppen, die unter dem Einfluß von Wärme mit -COOH-Gruppen unter Bildung einer kovalenten chemischen Bindung zu reagieren vermögen, wobei (ii) auch als Gruppierung(en) in den Verbindungen (i) enthalten sein kann,
- (iii) mindestens ein 4-Acylbenzylsulfoniumsalz der in Anspruch 1 angegebenen Formel.
- (i) at least one compound with at least two aromatic and / or heteroaromatic o-nitrocarbinol ester groups of the formula in which A is the radical of an aromatic or heteroaromatic, optionally substituted ring system with 5 to 15 ring members and Z is a hydrogen atom, an alkyl radical with 1 to 8 carbon atoms or an optionally substituted aryl or aralkyl radical,
- (ii) at least one crosslinking compound with at least two reactive groups which are able to react under the influence of heat with -COOH groups to form a covalent chemical bond, with (ii) also as group (s) in the compounds (i ) can be included
- (iii) at least one 4-acylbenzylsulfonium salt of the formula given in claim 1.
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