FR2782560A1 - LIGHT-ACTIVATED COMPOSITION, RESERVES INCLUDED THEREOF AND USES THEREOF - Google Patents

Abstract

The invention relates to a light activatable composition.The composition comprises at least one compound that can be cross-linked by the action of an acid, and / or at least one compound whose solubility changes under the action of an acid. , and as a photoinitiator, at least one acid generating compound by exposure to light of wavelength between 240 and 390 nm and having an epsilon molecular extinction coefficient of less than 10 at the wavelength of the line i (365 nm). These compositions are particularly suitable for the preparation of negative and positive photosensitive resistances, printing plates, image recording materials or color filters. Application to photosensitive materials.

Description

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 The present invention relates to compositions comprising latent acidic compounds, the use of these compounds as photosensitive acid generators, especially in chemically amplified photosensitive resistances, printing plates, color filters or recording materials. images which are developable in an alkaline medium, their use as dissolution inhibitors in a corresponding positive photosensitive resist, and a process for the production of images using these resins, printing plates or image recording materials.

 By a chemically amplified photosensitive resist is meant a resist composition whose photosensitive component, when irradiated, generates only the amount of acid which is necessary to catalyze a chemical reaction of at least one component sensitive to the reaction. This has the effect of starting to develop the final differences in solubility between the irradiated and unirradiated areas of the photoresist.

 U.S. Patent 4,540,598 discloses industrial paint formulations based on a large number of photosensitive oximesulfonates and conventional acid-curable resins. These formulations are first hardened with actinic light, in particular with radiation of wavelength between 250 and 400 nanometers. Oximesulfonates generate an acid, so that a thermal cure during which the material also becomes insoluble in the usual solvents can take place even at very low temperatures. Nothing can be inferred about an exposure in accordance with an image of corresponding resist layers nor the problems associated with it, and nothing about the imaging properties of the many formulations falling within the generic framework of teaching

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 of this patent. Oximesulfonates, which are poorly soluble in aqueous alkaline developing agents, can be converted to the soluble form of the free acid by irradiation. Together with a suitable film-forming resin, they can therefore be used as dissolution inhibitors for the production of positive photosensitive resistances.

 Conventional positive photosensitive resist compositions based on oxime sulfonates and alkali-soluble binders, generally cresol novolacs or hydroxymethylacrylate / acrylic acid copolymers, are also known and are proposed in document EP 0 241 423. According to US Pat. this reference, one can use a radiation of 200 to 600 nm to expose these reserves. The disadvantage of these photosensitive reserves is however that the resolution and the sensitivity are never simultaneously entirely satisfactory. This is particularly the case when the exposure is made with radiation in the mercury line band i which has a wavelength of 365 nanometers and which is often used for exposure according to an image of layers of photoresist, because medium pressure and high pressure mercury lamps are inexpensive sources of radiation to produce radiation having a good intensity in these wavelengths.

 Therefore, there is clearly a need for latent, nonionic, reactive acid generators which are thermally and chemically stable and which, after having been activated by light, in particular by radiation having the wavelength of the line Mercury (365 nm) can be used as catalysts for various acid-catalyzed reactions such as polycondensation reactions, acid catalyzed depolymerization reactions, electrophilic acid-catalyzed substitution reactions or removal of protecting groups. by acid catalysis. In particular, there is a need for acid generators that can be activated

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 by light and with which systems of greater thickness can be exposed so as to maintain both high sensitivity and good shape retention profiles. This large thickness is, for example, advantageous for ion implantation processes in which the constant increase in ion doses requires thicker layers to resist ion bombardment. In addition, there are other fields of application in which thick resin layers are necessary for simple geometrical reasons, for example in the manufacture of magnetic heads for hard disks and storage media. Another desirable property is high thermal stability providing high resistance against ion treatment during ion implantation operations that are commonly performed in the fabrication of semiconductor devices.

 US 5,627,011 teaches the use of oximesulfonates in photosensitive resistances at high resolution and high sensitivity for exposure to the i line. This publication mentions oxime sulphonates which can give rise to aromatic sulphonic acids.

 EP 780 729 and WO 98/10335 provide chemically amplified resist compositions comprising oxime sulfonates having alkylsulfonic acid groups in place of aromatic sulfonic acid groups.

 JP 9-292704 teaches that the properties of a photoresist are further improved if oxime sulfonates having short (C 1 -C 4) alkylsulphonic acid groups having a molecular extinction coefficient e <100 are used. at the wavelength of the line i (365 nm).

 The present invention provides photoresist compositions having excellent resist profiles while at the same time maintaining excellent sensitivity, even in resist layer thicknesses well in excess of the usual 1-2 micron range.

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 These properties are particularly observed when the photoresist compositions are exposed to radiation in the band of the mercury line i having a wavelength of about 365 nanometers.

 Surprisingly, excellent profiles are obtained at the same time as good sensitivity with chemically amplified photosensitive resist compositions which are developable in aqueous alkaline media and with resist layer thicknesses exceeding 2 m using generators. photosensitive acids which have a molecular extinction coefficient of less than 10.

This applies to both negative and positive photosensitive resistances containing an acid-sensitive component that undergoes an acid catalyzed chemical reaction that modifies the solubility of the compositions in the aqueous alkaline developing agents.

 Thus, the present invention relates to light-activatable compositions, comprising (a) at least one compound that can be crosslinked by the action of an acid, and / or (b) at least one compound whose solubility changes under the influence of action of an acid, and (c) as a photoinitiator, at least one acid generating compound by exposure to light of wavelength between 240 and 390 nm and having a molecular extinction coefficient E less than 10 at the wavelength of the line i (365 nm).

 In particular, the compound (c) is a compound generating a sulfonic acid.

 Preferred compositions are those having a thickness greater than 2 m when applied to a substrate.

The invention further relates to a composition as described above, comprising as component (c) a compound having a structural unit of formula I
C = NO-SO2- (I),

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 and wherein the compounds are characterized by a molecular extinction coefficient of less than 10 at 365 nm.

dans laquelle R1, R2' R3, R4 et R5 sont chacun, indépendamment des autres, l'hydrogène, un radical alkyle en C1-C12 substitué par un ou plusieurs atomes d'halogène ou non substitué, ou un atome d'halogène ; R6 est un radical alkyle en C1-C18 substitué par un ou plusieurs atomes d'halogène ou non substitué, phényl- (alkyle en C1-C3), camphoryle, phényle, naphtyle, anthracyle ou phénanthryle, les radicaux phényle, naphtyle, anthracyle et phénanthryle n'étant pas substitués ou étant substitués par un ou plusieurs atomes d'halogène et/ou radicaux halogénoalkyle en
C1-C4, CN, N02, alkyle en C1-C16, phényle, OR , COORg, -0(CO)-alkyle en C-C, S020R9 et/ou NR7R8 ; R7 et R8 sont chacun, indépendamment de l'autre, l'hydro- gène ; un radical alkyle en C1-C12 qui n'est pas subs- titué ou est substitué par un ou plusieurs radicaux OH, alcoxy en C1-C4, alkylsulfonyle en C1-C12, phényl- sulfonyle, (4-méthylphényl)sulfonyle et/ou alcanoyle en
C1-C6 ; un radical alkyle en C2-C12 qui est interrompu par -0- et qui n'est pas substitué ou est substitué par un ou plusieurs radicaux OH, alcoxy en C1-C4' alkyl- sulfonyle en C1-C12, phénylsulfonyle, (4-méthylphényl)- sulfonyle et/ou alcanoyle en C1-C6 ; ou un radical phényle, alcanoyle en C2-C6, benzoyle, alkylsulfonyle Preferred compositions are such compositions which comprise, as component (c), a compound of the formula

wherein R1, R2 'R3, R4 and R5 are each, independently of each other, hydrogen, C1-C12alkyl substituted by one or more halogen or unsubstituted, or halogen; R6 is a C1-C18 alkyl radical substituted with one or more halogen or unsubstituted phenyl- (C1-C3) alkyl, camphoryl, phenyl, naphthyl, anthracyl or phenanthryl, the phenyl, naphthyl, anthracyl and phenanthryl are not substituted or substituted by one or more halogen atoms and / or haloalkyl radicals
C1-C4, CN, NO2, C1-C16 alkyl, phenyl, OR, COORg, -O (CO) -alkyl CC, SO2RR9 and / or NR7R8; R7 and R8 are each, independently of the other, hydrogen; a C1-C12 alkyl radical which is not substituted or is substituted by one or more OH, C1-C4 alkoxy, C1-C12 alkylsulfonyl, phenylsulphonyl, (4-methylphenyl) sulphonyl and / or alkanoyl
C1-C6; a C2-C12 alkyl radical which is interrupted by -O- and which is unsubstituted or substituted by one or more OH, C1-C4 alkoxy, C1-C12 alkylsulfonyl, phenylsulfonyl radicals, methylphenyl) sulfonyl and / or C 1 -C 6 alkanoyl; or phenyl, C 2 -C 6 alkanoyl, benzoyl, alkylsulfonyl

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C 1 -C 6 phenylsulfonyl, (4-methylphenyl) sulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; or R7 and R8 together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered ring which may be interrupted by -O- or -NR11-; R9 is a C1-C2 alkyl radical which is unsubstituted or is substituted by one or more C1-C4 OH and / or alkoxy radicals, or is a C2-C12 alkyl radical which is interrupted by -O- and which is not substituted or is substituted by one or more OH and / or C1-C4 alkoxy radicals; R10 is hydrogen; a C1-C12 alkyl radical which is not substituted or is substituted by one or more phenyl, OH, C1-C12 alkoxy, C1-C12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or alkanoyl radicals; C2-C6; a C2-C12 alkyl radical which is interrupted by -O- and which is unsubstituted or substituted by one or more phenyl radicals,
OH, C 1 -C 12 alkoxy, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; or a phenyl radical; R 11 is hydrogen, a C 1 -C 12 alkyl radical substituted with one or more OH or unsubstituted or a C 2 -C 12 alkyl radical which is interrupted by -O-; and wherein the compounds of formula la are characterized by a molecular extinction coefficient of less than 10 at 365 nm.

 According to the present invention, it is also possible to use mixtures of isomeric forms (cis-trans isomers, E / Z isomers or syn / anti) oximes sulfonates of formula la.

 An alkyl radical Ci-ci, is linear or branched and it is for example an alkyl radical C1-C16, C1-C14, C1-C12, C1-C8, C1-C6 or C, -C4. Examples are the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and hexyl radicals.

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 heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl.

 The terms C 1 -C 16 alkyl, C 1 -C 12 alkyl and C 1 -C 4 alkyl have the same meaning as that given above for a C 1 -C 18 alkyl radical corresponding to the corresponding number of carbon atoms.

 A halogen is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, preferably fluorine or chlorine.

 A C 1 -C 12 alkyl radical substituted with one or more halogen atoms or a C 1 -C 12 alkyl radical substituted with one or more halogen atoms are alkyl radicals as described above, which comprise one or more atoms of the same halogen or different halogens as substituents. There are, for example, 1 to 3 or 1 or 2 substituent halogen atoms on the alkyl radical.

The halogen atoms can be attached to the same carbon atom, but can also be attached to carbon atoms other than the alkyl radicals. Examples are fluoromethyl, chloromethyl, bromomethyl, trifluoromethyl, 1-chloroethyl, 2-chloroethyl, and the like.

 A C 1 -C 4 haloalkyl radical corresponds to a C 1 -C 4 alkyl radical which is substituted with one or more halogen atoms. The same explanations as those given above apply to these radicals, up to the corresponding number of carbon atoms.

 A C2-C12 alkyl radical which is interrupted by -O- is linear or branched and, for example, is interrupted 1 to 6 times, for example 1 to 3 times or 1 or 2 times by -0-.

z = 1 à 5, -(CH2CH20)5CH2CH2-, -CH2-CH(CH3)-0-CH2-CH(CH3)- ou -CH2-CH(CH3)-O-CH2-CH2CH2-. The 0 atoms in the alkyl chain are located at non-consecutive positions. Thus, structural units are produced such as, for example, -CH2-O-CH2-, -CH2CH2-O-CH2CH2- '- [CH2CH2O] y-, - [CH2CH2O] z-CH2-, where y = 1 to 6 and

z = 1 to 5, - (CH 2 CH 2 O) 5 CH 2 CH 2 -, -CH 2 -CH (CH 3) -O-CH 2 -CH (CH 3) - or -CH 2 -CH (CH 3) -O-CH 2 -CH 2 CH 2 -.

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 A C1-C12 alkoxy radical is linear or branched and it is, for example, a C1-C8, C1-C6 or C1-C4 alkoxy radical. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy or dodecyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy or tertbutyloxy, preferably methoxy. The term C 1 -C 4 alkoxy has the same meaning as given above, corresponding to the corresponding number of carbon atoms.

 A C1-C12 alkylsulfonyl radical is a (C1-C12) alkyl-O-SO2- radical, in which the C1-C12 alkyl moiety is as defined above.

 A C1-C6 alkanoyl radical is linear or branched and it is, for example, a C 1 -C 4 alkanoyl radical. Examples are the formyl, acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl or hexanoyl radicals, preferably acetyl.

 A phenyl (C 1 -C 3) alkyl radical is, for example, a benzyl, phenylethyl, α-methylbenzyl or α, α-dimethylbenzyl radical, especially benzyl.

 Substituted phenyl, naphthyl, anthracyl and phenanthryl radicals are substituted 1 to 4 times, for example 1.2 or 3 times, in particular 1 or 2 times. The substituents carried by the phenyl ring are attached to the 2, 2,4, 2,6, 3, 3,5, 4 or 6 positions, in particular at the 2-position, the 3-position, the 4-position or the 6-position of the ring. phenyl.

 If R7 and R8 together with the nitrogen atom to which they are attached form a five-, six- or seven-membered ring which can be interrupted by -O- or -NR-, then saturated rings are formed. or unsaturated, for example aziridine, pyrrole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, piperidine or morpholine.

 The phrase "and / or" used in the present specification and claims is intended to express the fact that not only one of the terms (substituents)

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 defined may be present, but also several of the defined terms (substituents) may be present together, i.e., mixtures of different terms (substituents).

 The expression "at least" means one or more.

 The molecular extinction coefficient E of the acid generating compounds which are suitable for the compositions according to the present invention is less than 10 to 365 nm (mercury line). The coefficient E is a component of the Beer-Lambert equation, which is well known to those skilled in the art. This coefficient is determined from the UV absorption spectra of the compounds, which are measured in common organic solvents such as acetonitrile or tetrahydrofuran (THF). Since the E values move slightly depending on the solvent used to measure the UV spectrum, all the values mentioned in the present invention relate to the use of THF as the solvent.

 In general, any compound generating an acid by irradiation and having a molecular extinction coefficient of less than 10 is suitable for the corresponding compositions or photoresists according to the present invention. For example, Lewis acid generating compounds are suitable as well as Brønsted acid generating compounds, for example, carboxylic acid generating compounds, sulfonic acids, phosphonic acids, PF6, BF4, SbF5-, and the like. Examples of such compounds are sulfonium and iodonium salts, as well as derivatives of nitrobenzylsulfonates and bis-sulfonyldiazomethanes. Preferably, sulfonic acid generating compounds such as oxime sulfonates are used in the present compositions.

 In particular, the oxime sulphonates which are suitable as acid generators in the compositions according to the invention are the compounds of formula la having a molecular extinction coefficient of less than 10, in which

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R1, R2, R3, R4 and R5 are each, independently of the others, hydrogen, a C1-C8 alkyl radical, a halogen atom or a C1-C4 haloalkyl radical; R6 is C1-C18alkyl, phenyl (C1-C3alkyl) camphoryl, C1-C10haloalkyl, phenyl, naphthyl, anthracyl or phenanthryl, wherein the phenyl, naphthyl, anthracyl and phenanthryl radicals are unsubstituted or are substituted by one or more halogen atoms and / or C 1 -C 4 haloalkyl radicals, CN,
N02, C1-C16 alkyl, phenyl and / or OR10; and R10 is as defined above.

 The compositions preferably comprise compounds of formula la having a molecular extinction coefficient of less than 10, wherein R 1, R 2, R 3, R 4 and R 5 are each, independently of the others, hydrogen, a C 1 -C 4 alkyl radical. a halogen atom or a C 1 -C 4 haloalkyl radical provided that at least two of the radicals R 1, R 2, R 3, R 4 and R 5 are hydrogen; R6 is C1-C12 alkyl, phenyl (C1-C3) alkyl, camphoryl, C1-C4 haloalkyl or phenyl, wherein the phenyl radical is unsubstituted or substituted by one or more halogen atoms and / or C1-C4 haloalkyl, NO2, C1-C8 alkyl, phenyl and / or OR10 radicals; and R10 is a C1-C12 alkyl radical.

 Examples of latent sulfonic acids of formula la are methanesulfonates, butanesulfonates, benzenesulfonates, 4-methylphenylsulphonates, 4-methoxybenzenesulfonates and 10-camphorsulphonates of α-hydroxyimino-4-methylbenzyl cyanide, α-hydroxyimino-4-butylbenzyl cyanide, α-hydroxyimino-3-methylbenzyl cyanide, α-hydroxyimino-2-methylbenzyl cyanide, α-hydroxyimino-2,4-dimethylbenzyl cyanide, α-hydroxyimino-3,4-dimethylbenzyl cyanide, α-hydroxyimino cyanide 3,4-dibutylbenzyle,

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 α-hydroxyimino-2,4,6-trimethylbenzyl cyanide, α-hydroxyimino-2-chlorobenzyl cyanide, α-hydroxyimino-2,4-dichlorobenzyl cyanide, α-hydroxyimino-4-chlorobenzyl cyanide, cyanide of a- hydroxyimino-4-fluorobenzyl.

Oximesulfonates of formula I or Ia are prepared by processes described in the literature, for example by reacting the appropriate free oxime of formula 2 with sulfonic acid halides of formula 3 in the presence of a base such as triethylamine, or by reacting the salt of an oxime with a sulfonic acid chloride. These methods have been published, for example in EP 48 615.

NC Nec 0 I C = N-OH + CI-SO 2 -Ra. Where R is R3 and R1, R2, R3, R4, R5 and R6 are as R4 RS as defined above.

 The reaction is conveniently conducted in an inert organic solvent in the presence of a tertiary amine. The sodium salts of the oximes are obtained, for example, by reacting the corresponding oxime with a sodium alkoxide in dimethylformamide (DMF).

 The sulphonates of oximes are obtained in the form of syn (E, cis) or anti (Z, trans) or also in the form of mixtures of the two conformers. According to the present invention, it is possible to use isolated conformers as well as any mixtures of the different conformers. If an isolated conformer is required, it is obtained from the mixture by usual techniques, known to those skilled in the art, for example crystallization, distillation or chromatography.

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 The oximes (2) required for the reaction are prepared by general analogy with known methods, for example by reacting compounds containing reactive methylene groups, such as benzyl cyanide derivatives or phenylacetic acid derivatives, with a alkyl nitrite, for example methyl nitrite or isoamyl nitrite, and sodium alkoxide, for example sodium methanolate. These reactions are described, inter alia, in "The systematic identification of organic compounds", John Wiley and Sons, New York, 1980, page 181, in Die Makromolekulare Chemie, 1967, 108, 170, or in Organic Synthesis, 1979,59 , 95.

 Oximes can also be obtained, for example, by reacting a corresponding carbonyl or thiocarbonyl compound with hydroxylamine. Another method of preparation is the nitrosation of hydroxylated aromatic compounds.

 The preparation of the sulfonic acid halides (3) is known to those skilled in the art and described, for example, in conventional chemistry textbooks.

 An object of the present invention is to provide photosensitive resistances comprising compounds generating an acid by irradiation, these compounds having a molecular extinction coefficient E of less than 10 at 365 nm. Thus, an object of the invention is a chemically amplified photosensitive resist, which is sensitive to wavelength radiation between 340 and 390 nm, comprising a photosensitive acid generator characterized by a lower molecular extinction coefficient. at 10 to 365 nm.

 Another object of the present invention is to provide photosensitive resistances comprising compounds of formula I or la. Thus, an object of the invention is a chemically amplified photosensitive resist, which is sensitive to radiation of wavelength between 340 to 390 nm, comprising a photosensitive acid generator of formula I, as defined above. , characterized

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 by a molecular extinction coefficient of less than 10 at 365 nm, as well as a chemically amplified photosensitive resist, which is sensitive to radiation of wavelength between 340 to 390 nm, comprising a photosensitive acid generator of formula la, as defined above, characterized by a molecular extinction coefficient of less than 10 at 365 nm. These chemically amplified photosensitive resistances preferably have a thickness greater than 2 m. In addition, the compositions according to the invention are preferably applied in a thickness greater than 2 m before the irradiation.

 These reserves include chemically amplified negative photosensitive resistances which are developable in an alkaline medium and have a reserve thickness greater than 2 μm and are sensitive to radiation of wavelength between 340 and 390 nanometers, these reserves being based on a photosensitive acid generator having a molecular extinction coefficient of less than 10 at 365 nm.

 These reserves still include in particular chemically amplified negative photosensitive reserves which are developable in an alkaline medium and have a reserve thickness greater than 2 m and are sensitive to radiation of wavelength between 340 and 390 nanometers, these reserves being base of the oximes sulfonates as defined above as a photosensitive acid generator.

 Another embodiment of the invention relates to chemically amplified positive photosensitive resistances which are developable in an alkaline medium and have a reserve thickness greater than 2 m and are sensitive to radiation with a wavelength of between 340 and 390 nanometers, these reserves being based on oxime sulfonates as defined above as a photosensitive acid generator.

 These two embodiments of the photosensitive resistances of the invention can easily resolve structural motifs having domain dimensions.

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 submicrometer, the radiation used having a wavelength between 340 and 390 nanometers. The reserve structures remaining on the substrate after development have a very good stiffness of the side walls.

Despite the extremely low optical absorption, the reserves also have excellent sensitivity to given radiation.

This characteristic is particularly unexpected, since oxime sulphonates chosen as acid generators absorb radiation of this wavelength only to an extremely low degree. In addition, negative reserves in particular have the added advantage of providing improved thermal resistance that is favorable to ion implantation processes.

 The present invention also relates to the use of compounds of formula I or la, having a molecular extinction coefficient of less than 10, as photosensitive acid generators in compositions comprising compounds which can be crosslinked by the action of an acid or / and as dissolution inhibitors for compounds whose solubility changes under the action of an acid, wherein the irradiation is carried out, for example, in accordance with an image, as well as a process for generating acids wherein a photosensitive acid generator of formula I or 1a, having a molecular extinction coefficient of less than 10, is irradiated with light of wavelength between 340 and 390 nm.

 In photocurable compositions, sulfonic acid oximes esters act as latent curing catalysts: when irradiated with light, they generate an acid that catalyzes the crosslinking reaction. In addition, the acid generated by the irradiation can, for example, catalyze the removal of suitable acid-sensitive protecting groups from a polymer structure, or catalyze the cleavage of polymers containing acid-sensitive groups forming part of the polymer. polymer skeleton. Other applications are, for example, color change systems based on

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 on a change in pH or solubility, for example of a pigment protected by acid-sensitive protecting groups. Compositions using latent pigments or pH-sensitive dyes in combination with oximes sulfonates can be used as light indicators or as simple disposable dosimeters.

These dosimeters are particularly interesting for a light that is invisible to human eyes, such as UV or IR light.

 The oximesulfonates of the present invention may also be used to form polymers which under the effect of an acid undergo a transition to a state where they have the properties required by photolithography techniques. For example, oxime sulfonates can be used to form conjugated emissive polymers as described by ML Renak, C. Bazan, D. Roitman, Advanced Materials, 1997, 9, 392. These shaped emissive polymers can be used to manufacture microscale light emitting diodes (LEDs) that can be used to fabricate display screens and information storage media. Similarly, polyimide precursors (e.g., polyimide precursors having acid-labile protecting groups whose solubility changes during development) can be irradiated to form shaped polyimide layers which can serve as protective coatings. insulating layers and intermediate layers in the production of microchips and printed circuit boards.

 From the literature, it is known that conjugated polymers such as, for example, polyanilines, can be converted from the semiconductor state to the conductive state by proton doping. The oximesulfonates of the present invention can also be used as acid generators to image-image these conjugated polymers to selectively achieve such conversion in the exposed areas.

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 Esters of oximes of sulfonic acids which are poorly soluble in an aqueous alkaline developing agent can be rendered soluble in the developing agent by conversion to the free acid under the action of light, and they can therefore be used as dissolution inhibitors in combination with suitable film-forming resins.

 The resins which can be crosslinked by acid catalysis are, for example, mixtures of polyfunctional alcohols or of polyester or polyester resins containing hydroxyl groups or of partially hydrolysed polyvinyl acetals or of polyvinyl alcohols with polyfunctional acetal derivatives. Under certain conditions, a self-condensation of the functionalized resins with acetal groups is for example also possible.

 In addition, oxime sulfonates are used, for example, as light-activated curing agents for resins containing siloxane groups.

These resins may, for example, undergo acid-catalyzed hydrolysis self-condensation or be crosslinked by a second component of the resin, such as a polyfunctional alcohol, a hydroxyl-containing acrylic or polyester resin, a partially hydrolysed polyvinyl acetal or a polyvinyl alcohol. This type of polycondensation of polysiloxanes is described, for example, by J.J.

Lebrun, H. Pode, Comprehensive Polymer Science, Volume 5, page 593, Pergamon Press, Oxford, 1989.

 It is obvious that the acid-initiated reactions as described above in the context of the present invention can be performed not only with oxime sulfonates as acid generating agents, but also with other compounds. acid generators having a molecular extinction coefficient of less than 10. Examples of these compounds are set forth above.

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 As already mentioned above, the difference in solubility that occurs between the irradiated and non-irradiated areas as a result of the acid-catalyzed reaction of the resist material during or after irradiation of the resist can be of two types, depending on other components that are present in the formulation or the reserve. If the compositions according to the invention comprise components which increase the solubility of the composition in the developer, the resist is positive.

On the other hand, if these components reduce the solubility of the composition, the reserve is negative.

 The acid-sensitive components which produce a negative reserve are in particular compounds which, when catalysed by an acid (for example the acid formed during the irradiation of the compound of formula I or la) are capable of crosslinking reaction with themselves or with one or more other components of the composition. Compounds of this type are, for example, known acid-curable resins such as, for example, acrylic, polyester, alkyd, melamine, urea, epoxy and phenolic resins, or mixtures thereof.

Amino resins, phenolic resins and epoxy resins are very suitable. Acid curable resins of this type are generally known and are described, for example, in Ullmanns Enzyklopadie der technischen Chemie, 4th edition, Vol. 15 (1978), pp. 613-628. The resins are generally present in a concentration of 2 to 40% by weight, preferably 5 to 30% by weight, based on the total dry weight of the negative resist composition.

 Particularly preferred acid-curable resins are amino resins, such as etherified or non-etherified urea, guanidine, biuret or melamine resins, preferably methylated melamine resins or butylated melamine resins, and the like. glycoluriles and corresponding urones. The resins considered in the present context are the mixtures

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common techniques, which usually also include oligomers, as well as pure and high purity compounds. The most preferred acid-curable resins in the context of the present invention are N-methoxymethylmelamine (Formula 7), tetramethoxymethylglycoluril (Formula I) and N, N'-dimethoxymethylurone (Formula 9):

The concentration of the acid generating compound in general, and in particular the concentration of the compound of formula I or Ia in the negative reserves is usually from 0.1 to 30% by weight, preferably 0.1 to 20% by weight, relative to the total dry weight of the composition. A concentration of 1 to 15% by weight is particularly preferred.

 Where appropriate, the negative compositions may further comprise a film-forming polymer binder. This binder is preferably a phenolic resin soluble in alkaline medium. Suitable resins for this purpose are, for example, novolacs derived from an aldehyde, typically acetaldehyde or furfuraldehyde, but especially formaldehyde, and a phenol, for example unsubstituted phenol, a mono- or dichlorophenol such as p-chlorophenol, phenol mono- or disubstituted with C1-C9 alkyl groups such as o-, m- or p-cresol, various xylenols, p-tert-butylphenol, p-nonylphenol , p-phenylphenol, resorcinol, bis (4-hydroxyphenyl) -

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 methane or 2,2-bis (4-hydroxyphenyl) propane. Also suitable resins are homo- and copolymers based on ethylenically unsaturated phenols, for example vinyl or 1-propenyl substituted phenol homopolymers such as p-vinylphenol or p- (1-propenyl) phenol, or copolymers thereof. these phenols with one or more ethylenically unsaturated compounds, for example styrenes.

The amount of binder generally ranges from 30 to 95% by weight, or preferably from 40 to 80% by weight.

 As a special embodiment, the invention includes negative photosensitive resistances having a resist thickness greater than 2 μm which are developable in an alkaline medium, suitable for exposure radiation having a wavelength between 340 and 390 nanometers, comprising an oxime sulfonate of formula la as described above, an alkali-soluble phenolic resin as a binder and a component which, when acid catalyzed, undergoes a crosslinking reaction with itself and / or with the binder.

 Particularly preferred negative photosensitive resistances comprise 1 to 15% by weight of oxime sulfonate as acid generating agent, 40 to 99% by weight of a phenolic resin as binder, for example one of those mentioned above. , and 0.5 to 30% by weight of a melamine resin as crosslinking agent, the percentages being expressed relative to the weight of dry matter of the composition. The use of novolak or, in particular, a polyvinylphenol as binder gives a negative reserve having particularly good properties.

 It is preferable to use a negative resist comprising N-methoxymethylmelamine or tetramethoxymethylglycolurile and N, N'-dimethoxymethylurone of technical or very pure quality as amino resin.

 Oximes sulfonates are also used as acid generators that can be photochemically activated to effect cross-linking catalyzed by

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 an acid of, for example, poly (glycidyl) methacrylates in negative resist systems. These crosslinking reactions are described, inter alia, by Chae et al., In Pollimo, 1993, 17 (3), 292.

 Monomeric or polymeric compounds which are insoluble in an alkaline medium but which are cleaved in the presence of an acid or may undergo an intramolecular rearrangement such that there are still reaction products which are soluble in a conventional alkaline developing agent and / or which render an additional alkaline-insoluble and acid-resistant binder otherwise soluble in the developing agent, also impart a positive characteristic to the novel photosensitive resist compositions according to the invention. Substances of this type are hereinafter referred to as dissolution inhibitors.

 As another special embodiment, the invention therefore includes alkaline-developable positive photosensitive resistances suitable for exposure radiation having a wavelength of 340 to 390 nanometers, comprising a compound of formula I or , having a molecular extinction coefficient of less than 10, and at least one compound which substantially prevents the composition from dissolving in an alkaline developing agent, but which can be cleaved in the presence of an acid such that the reaction products the remaining ones are soluble in the developing agent and / or cause dissolution in the developing agent of an additional acid-resistant binder which would otherwise be substantially insoluble in the developer.

 As dissolution inhibitors, monomeric and polymeric organic compounds having functional groups which are themselves soluble in an alkaline medium, for example aromatic hydroxyl groups, carboxylic acid groups, secondary amino groups and keto groups, may be used. or aldehyde. Before their use as dissolution inhibitors, these compounds

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 Organic monomers and polymers have been chemically modified by reaction with a suitable compound so as to become insoluble in an aqueous alkaline medium, the protecting groups formed in the aforementioned reaction being capable of being acid catalyzed to bring the functional groups back to normal. their initial form.

 Suitable protective species for the protection of hydroxyl groups, carboxylic acid groups or secondary amino groups are, for example, dihydrofuran or 3,4-dihydropyran and their derivatives, benzyl halides, alkyl halides, haloacetic acids, haloacetates, chlorocarbonates, alkylsulfonyl halides, aromatic sulfonyl halides, dialkyl dicarbonates or trialkylsilyl halides. The protecting groups are introduced by usual reactions known to those skilled in the art. A conventional conversion to ketals and acetals is suitable for protecting keto and aldehyde groups. Such chemically amplified positive reserve systems are described, inter alia, by E. Reichmanis, F. M. Houlihan, 0. Nalamasu, T. X. Neenan, Chem. Mater., 1991, 3.344; or C. G. Willson, "Introduction to Microlithography", 2nd edition, edited by L. S. Thompson, C. G. Willson, M. J.

Bowden, Amer. Chem. Soc., Washington DC, 1994, page 139.

 Compounds bearing blocked aromatic hydroxyl groups are particularly preferred, these compounds possibly being monomers or polymers. The aromatic monomers preferably contain one or more aromatic rings, preferably 2 to 6 aromatic rings, containing 6 to 14, preferably 6, ring carbon atoms. In addition to the blocked hydroxyl groups, the aromatic rings may of course have other substituents, preferably C1-C4alkyl, C1-C4alkoxy, or halogen atoms. Particularly preferred monomeric dissolution inhibitors are of the bisphenyl type, for example compounds of formula

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où chaque Y est un groupe sensible aux acides, tel qu'un groupe hydroxyle phénolique, qui est protégé par un radical sensible aux acides approprié, tel qu'un groupe éther, carbonate, silyle, tétrahydropyrannyle ou tétrahydrofurannyle (voir, par exemple, le document EP 475 903), et Z est une liaison simple directe ou est l'un des radicaux -S-, -0-, -SO-, -S02-, -CO-, -C(Ra)(Rb)- où Ra est l'hydrogène ou un radical méthyle ou aryle, et Rb est l'hydrogène ou un radical méthyle. Des radicaux divalents -C(Ra)(Rb)particulièrement préférés sont -CH2-, -C(CH3)2- et -C(CH3)(Ph)-. Les inhibiteurs de dissolution polymères préférés sont dérivés de résines phénoliques usuelles, habituellement de polyvinylphénols, dont les groupes hydroxyle sont également bloqués d'une manière conforme à la description ci-dessus. Des inhibiteurs de dissolution portant des groupes protecteurs des genres indiqués sont connus dans la technologie. Des inhibiteurs portant des groupes carbonate sont décrits, entre autres, par Dennis R. McKean, Scott A. McDonald, Nicholas J. Clecak et C. Grant Willson dans "Novolak based deep-UV resists", SPIE Vol. 920, Advances in Resist Technology and Processing V (1988), pages 60-63, ou par Masamitsu Shirai et Masahiro Tsunooka dans "Photochemistry of Imino Sulfonate Compounds and their Application to Chemically Amplified Resists", Journal of Photopolymer Science and Technology, Vol. 3 (3), 1990, pages 301-304. Les inhibiteurs de dissolution portant des groupes protecteurs peuvent être préparés par des procédés classiques connus, par exemple comme décrit par J.M.J. Frechet, E. Eichler, H. Ito et C.G. Willson, Polymer, 24 (1983), page 995. Des inhibiteurs de dissolution portant des groupes trialkylsilyloxy ou tert-butyloxy sont proposés dans le document EP 0 329 610, des inhibiteurs portant des groupes protecteurs du type tétrahydrofurannyle et tétrahydropyrannyle sont décrits, entre autres, par N. Hayashi, S.M.A.

wherein each Y is an acid-sensitive group, such as a phenolic hydroxyl group, which is protected by a suitable acid-sensitive radical, such as an ether, carbonate, silyl, tetrahydropyranyl or tetrahydrofuranyl group (see, for example, EP 475 903), and Z is a direct single bond or is one of the radicals -S-, -O-, -SO-, -SO2-, -CO-, -C (Ra) (Rb) - where Ra is hydrogen or a methyl or aryl radical, and Rb is hydrogen or a methyl radical. Particularly preferred divalent radicals -C (Ra) (Rb) are -CH2-, -C (CH3) 2- and -C (CH3) (Ph) -. The preferred polymeric dissolution inhibitors are derived from conventional phenolic resins, usually polyvinylphenols, whose hydroxyl groups are also blocked in a manner as described above. Dissolution inhibitors bearing protecting groups of the kinds indicated are known in the art. Inhibitors carrying carbonate groups are described, inter alia, by Dennis R. McKean, Scott A. McDonald, Nicholas J. Clecak and C. Grant Willson in "Novolak based deep-UV resists", SPIE Vol. 920, Advances in Resist Technology and Processing V (1988), pages 60-63, or by Masamitsu Shirai and Masahiro Tsunooka in "Photochemistry of Imino Sulfonate Compounds and their Application to Chemically Amplified Resists", Journal of Photopolymer Science and Technology, Vol. 3 (3), 1990, pages 301-304. Dissolving inhibitors bearing protecting groups can be prepared by known conventional methods, for example as described by JMJ Frechet, E. Eichler, H. Ito and CG Willson, Polymer, 24 (1983), page 995. Inhibitors of dissolution carrying trialkylsilyloxy or tert-butyloxy groups are proposed in EP 0 329 610, inhibitors bearing protective groups of the tetrahydrofuranyl and tetrahydropyranyl type are described, inter alia, by N. Hayashi, SMA

Hesp, T. Ueno, M. Toriumi, T. Iwayanagi and S. Nonogaki

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 in Polym. Mast. Sci. Eng., 61 (1989), pp. 417-421. Aromatic compounds bearing substituted tetrahydropyranyl groups are described in more detail in EP 0 475 903. The protecting groups may be introduced in a manner known to those skilled in the art by addition of 3,4-dihydropyrans or , 4-dihydrofurans under acidic conditions.

 In positive resistances of the type mentioned, a film-forming polymer dissolution inhibitor may be the only binder contained in the photosensitive resist, or may be used in admixture with an acid-inert binder and, where appropriate, an inhibitor of monomeric dissolution.

 Examples of inert binders in the presence of acid are novolaks, especially novolacs based on o-, m- or p-cresol and formaldehyde, as well as poly- (p-hydroxystyrene), poly (p-hydroxy α-methylstyrene) and the copolymers of p-hydroxystyrene, p-hydroxy-α-methylstyrene and acetoxystyrene.

 Examples of polymeric dissolution inhibitors are novolaks, in particular novolacs based on o-, m- or p-cresol and formaldehyde, poly (p-hydroxystyrene), poly (p-hydroxy-α-methylstyrene) copolymers of p-hydroxystyrene or p-hydroxy-α-methylstyrene and acetoxystyrene or acrylic acid and / or methacrylic acid, and also (meth) acrylic acid esters, which are reacted with in a known manner with dihydrofuran, 3,4-dihydropyran, benzyl halides, alkyl halides, haloacetic acids, haloacetates, chlorocarbonates, alkylsulfonyl halides, aromatic sulfonyl halides, sodium dicarbonates, dialkyl or trialkylsilyl halides. Also suitable polymers are copolymers of p- (2-tetrahydropyranyl) oxystyrene or p- (tert-butyloxycarbonyl) oxystyrene with (meth) acrylic acid, (meth) acrylates and / or p-acetoxystyrene and

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 copolymers of p-hydroxystyrene and / or p- (2-tetrahydropyranyl) oxystyrene with 3-hydroxybenzyl (meth) acrylate, which may, if necessary, be further protected by reaction with one of the compounds mentioned above.

 Particularly suitable polymers are transparent in a wavelength range of 180 to 1000 nm and carry groups which, after acid catalyzed deprotection, cause a change in solubility, as well as hydrophobic and hydrophilic groups which improve the dissolution of the generator. of acid and ensure the ability to develop in aqueous alkaline medium.

Examples of these polymers are acrylates and methacrylates prepared by co- or terpolymerization of the corresponding monomers. The monomers may also carry organosilicon radicals in order, for example, to increase the resistance in the case of dry etching processes. Examples of corresponding monomers are: methyl (meth) acrylate, (meth) acrylic acid, tert-butyl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, 3-oxocyclohexyl (meth) acrylate , tetrahydropyranyl (meth) acrylate, adamantyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate.

 The invention therefore also relates to a chemically amplified positive resist comprising, as a photosensitive acid generator, a compound of formula I or Ia having a molecular extinction coefficient e of less than 10, and a photoresist comprising polymers which are transparent to the wavelength region of 180 nm.

 A special embodiment of this positive resist according to the invention comprises 75 to 99.5% by weight of a film-forming polymer which contains protective groups which can be removed by acid catalysis, and 0.5 to 25% by weight of oxime sulfonates of formula I or formula Ia, having a molecular extinction coefficient E of less than 10, the percentages being expressed by weight

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 dry matter compositions. In this context, preference is given to compositions comprising 80 to 99% by weight of the mentioned polymer and 1 to 20% by weight of oxime sulfonate.

 Another embodiment is a positive resist comprising 40 to 90% by weight of an inert film-forming polymer in the presence of acid as a binder, 5 to 40% by weight of a monomeric or polymeric compound having catalytically removable protecting groups acid, and 0.5 to 25% by weight of oximes sulfonates of formula I or la, as described above, the percentages being expressed relative to the weight of dry matter of the compositions. Compositions comprising 50 to 85% by weight of an inert binder in the presence of acid, 10 to 30% by weight of monomer or polymer dissolving inhibitor and 1 to 15% by weight of sulfonates are preferred. oxime.

 Oximes sulfonates can also be used as solubilizers which can be activated by light. In this case, the compounds are added to a film-forming material comprising substantially no components that polymerize with the oxime sulfonate when heated or when irradiated with actinic radiation. However, oximes sulfonates reduce the rate at which the film-forming material dissolves in a suitable developing medium. This inhibitory effect can be canceled by irradiating the mixture with actinic radiation, so that a positive image can be produced. Such an application is described, for example, in EP 241 423.

 Another special embodiment of the invention is a positive resist comprising a compound of formula I or 1a, having a molecular extinction coefficient of less than 10, and a binder which is substantially insoluble in an alkaline developing agent and which becomes soluble in the developing agent in the presence of the photolysis products of the compound of formula I or la.

In this case, the quantity of oxime sulphonate mentioned

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 of formula I or is generally from 5 to 50% by weight relative to the weight of dry matter of the composition.

 The use of the oximesulfonates according to the invention in chemically amplified systems, which operate on the principle of the removal of a protective group from a polymer, generally produces a positive reserve.

Positive reserves are preferred to negative ones in many applications, especially because of their better resolution. However, it is also interesting to produce a negative image using the positive reserve mechanism, in order to combine the advantages of the high resolution of the positive reserve with the properties of the negative reserve. This can be done by introducing a so-called image inversion step as described, for example, in EP 361 906. For this purpose, the image-wise irradiated resist material is processed prior to the development step. for example with a gaseous base to thereby neutralize the acid that has been produced according to the image. Then, a second irradiation, over the entire surface, and a thermal aftertreatment are performed and the negative image is finally developed in the usual manner.

 In addition to the aforementioned components, it is also possible to add compounds that accelerate or enhance acid formation in the photoresist compositions of both negative and positive types containing oxime sulfonate. Such acid enhancers are described, inter alia, by K. Arimitsu et al., J. Photopolym. Sci. Technol., 1995, 8, page 43, K. Kudo et al., J. Photopolym. Sci. Technol., 1995, 8, page 45, or K. Ichimura et al., Chem. Lett., 1995, page 551.

 In addition to the above-mentioned components, the photoresist compositions of both negative and positive types may further comprise one or more of the additives commonly used in photoresists, in amounts well known to those skilled in the art.

Examples of these additives are control agents

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 flow agents, wetting agents, adhesives, thixotropic agents, dyes, pigments, fillers, dissolution accelerators, etc. However, it is not necessary to add substances which further sensitize the compositions for irradiation in the mercury line band, since this would normally result in a decrease in the resolution of the resist.

 For certain applications, resinous mixtures having monomeric or oligomeric constituents containing polymerizable unsaturated groups are used. These surface layers can also be cured using the compounds of formula I or Ia as described above.

In addition to component c), it is possible to use 1. radical polymerization initiators or 2. photoinitiators. The former initiate the polymerization of unsaturated groups by heat treatment, the latter by UV irradiation. Examples of additional photoinitiators for use in the compositions according to the invention are, for example, radical photoinitiators, typically chosen from benzophenones, acetophenone derivatives such as a-hydroxycycloalkylphenylketone, a dialkoxyacetophenone, the α-hydroxyacetophenone or α-aminoacetophenone, 4-aroyl-1,3-dioxolannes, benzoin alkyl ethers and benzil ketals, phenylglyoxalic esters and derivatives thereof, dimeric phenylglyoxalic esters, peresters, for example benzophenone peresters -Tetracarboxylic acids as described for example in EP 126 541, monoacylphosphine oxides, bisacylphosphine oxides or titanocenes. Illustrative examples of particularly suitable additional photoinitiators are the following: 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl- 1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acroyloxyethoxy) benzoyl] -1-hydroxy-1-methylethane, diphenylketone, phenyl-1-hydroxycyclohexyl ketone, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 1- (3,4-dimethoxyphenyl) -2-benzyl-

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 2-dimethylaminobutan-1-one, (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane, benzyl dimethyl ketale, bis (cyclopentadienyl) bis (2,6-difluoro-3-pyrrylphenyl) titanium, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide and bis (2,4,6 -triméthylbenzoyl) phenylphosphine.

Other suitable additional photoinitiators are provided, for example, in US 4,950,581, from column 20, line 35, to column 21, line 35. Other examples are trihalomethyltriazine derivatives or compounds of hexaarylbisimidazolyle.

 Other examples of additional photoinitiators are also cationic photoinitiators, usually peroxides, such as benzoyl peroxide (other suitable peroxides are described in US 4,950,581, column 19, lines 17 to 25). ), aromatic sulfonium or iodonium salts (such as those described, inter alia, in US 4,950,581 from column 18, line 60, to column 19, line 10) or salts of cyclopentadienyl complexes -arene-iron (II), for example (6-isopropylbenzene) - (5-cyclopentadienyl) iron (II) hexafluorophosphate.

 For the application, the compositions generally also comprise a solvent. Examples of suitable solvents are acetone, methyl ethyl ketone, ethyl acetate, methyl 3-methoxypropionate, ethyl pyruvate, 2-herptanone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, ethyl methyl ketone, 2-ethoxyethanol, 2-ethoxyethyl acetate and, in particular, 1-methoxy-2-propyl acetate or propylene methyl ether acetate, -glycol. The solvent may also be added as a mixture, for example of two or more of the aforementioned solvents. The choice of the solvent and its concentration depends, for example, on the nature of the composition and the application technique.

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 The solution is uniformly applied to a substrate by known application techniques, such as spin coating, dipping, doctor blade coating, curtain application techniques, brushing, spraying and reverse roll coating. It is also possible to apply the photosensitive layer to a temporary flexible support and then to coat the final substrate by layer transfer (lamination).

 The amount applied (layer thickness) and the nature of the substrate (application substrate) depend on the field of use in question. The range of layer thicknesses may in principle comprise values from about 0.1 μm to more than 100 μm, but values> 2 μm are preferred particularly in the context of the present invention. Particularly preferred layer thicknesses are from 2 μm to 100 μm, for example from 2.5 μm to 60 μm or 2.5 μm to 20 μm.

 Possible areas of use of the composition of the invention are as follows: photosensitive resistances for electronics, such as etch resistors, electroplating resistors or solder resistors, manufacture of integrated circuits or reserves for thin film transistors (reserves for TFT), manufacture of printing plates such as offset printing plates or screen printing stencils, use in the engraving of castings or in stereolithography techniques, use in color filters or materials image recording and all other types of lithographic imaging processes and, preferably, use as a microreserve in the manufacture of integrated circuits. Application substrates and operating conditions vary by use and are well known in the art.

 When the compositions are used as microreserves for the manufacture of integrated circuits and large-scale integration circuits, like this

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 is preferred, the layer thicknesses are usually 2 to 30 m, preferably 2 to 10 m. The method preferably employs process steps where the relatively large thickness provides certain advantages or is necessary to provide the desired functionality. An example of such use is that of reserves for ion implantation having layer thicknesses usually between 2 and 10 μm, preferably between 2 and 7 μm.

 The compositions according to the invention are also remarkably suitable as coating compositions for all types of substrates, including wood, textiles, paper, ceramics, glass, plastics such as polyesters, polyterephthalate ethylene, polyolefins or cellulose acetate, especially in the form of films, and in particular for coating metals such as Ni, Fe, Zn, Mg, Co or especially Cu and Al and also Si, the oxides or nitrides of silicon, on which an image must be formed by irradiation in accordance with an image. The meaning of the term "imagewise irradiation" is explained below.

 After the application process, the solvent is generally removed by heating to give a layer of the photoresist on the substrate. The drying temperature must obviously be lower than the temperature at which certain components of the reserve could be cooked thermally. Precautions must be taken in this regard, especially in the case of negative photosensitive reserves. In general, the drying temperatures are between 80 and 140 C.

 The resist layer is then irradiated in accordance with an image. This irradiation performed in a predetermined pattern using actinic radiation includes both irradiation through a photomask having a predetermined pattern, for example a slide, that irradiation made using a laser beam

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 which is displaced on the surface of the substrate coated with the layer, for example under the control of a computer, and thus produces an image.

 Suitable radiation sources are those which emit radiation of a wavelength within the sensitivity region of the resist, for example between 340 and 390 nanometers. Point sources and planiform projectors (rows of reflector lamps) are all appropriate. Examples are: carbon electrode arc lamps, xenon arc lamps, medium pressure, high pressure and low pressure mercury vapor lamps, possibly doped with metal halides (metal halogen lamps), microwave excited metal vapor lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flashlamps, photographic lighting lamps, electron beam lamps electrons and X-ray beams generated by means of synchrotrons or laser plasma. Mercury vapor lamps are particularly suitable, especially medium- and high-pressure mercury vapor lamps, whose radiation from emission lines at other wavelengths is filtered off, if necessary. This is particularly the case for shortwave radiation. The distance between the lamp and the substrate to be exposed according to the invention may vary, for example, from 2 cm to 150 cm, depending on the use in question and the type and / or the power of the lamp.

A suitable laser light source is, for example, an argon ion laser that emits radiation at wavelengths of 364 and 388 nanometers. With this type of irradiation, it is not absolutely essential to use a photomask in contact with the photopolymer layer: the controlled laser beam is able to "write" directly on the layer. For this purpose, the high sensitivity of the materials according to the invention is very advantageous, allowing high writing speeds at intensities.

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 relatively low. By irradiation, the oxime sulfonate contained in the composition in the irradiated areas of the surface layer decomposes to form sulfonic acids. If light emitting lamps are used in a wavelength range exceeding 340 to 390 nm, the exposure wavelength is selected using a filtering device.

In general, interference filters are used.

 After the irradiation, and if necessary a heat treatment, the non-irradiated portions (in the case of negative reserves) or the irradiated portions (in the case of positive reserves) of the composition are removed in a manner known per se by using a development agent.

 It is generally necessary to allow a certain period of time before the development stage to allow the reaction of the acid-sensitive components of the resist composition. In order to accelerate this reaction and, therefore, the occurrence of a sufficient difference in solubility between the irradiated and unirradiated areas of the resist layer in the developer, the layer is preferably heated before being developed. Heating can also be done or started during irradiation. Temperatures are preferably from 60 to 160 C. The time period depends on the heating process and, if necessary, the optimum period can be easily determined by those skilled in the art by means of some routine experiments. It is usually a few seconds to several minutes. For example, a very suitable period is 10 to 300 seconds when using a hot plate and 1 to 30 minutes when using a convection oven.

 The resist layer is then developed, the portions of the layer which, after irradiation, are more soluble in the developing agent being removed.

If necessary, this step can be accelerated

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 by gentle agitation of the workpiece, gentle brushing of the resist layer in the developing bath or spraying of the developer. The aqueous alkaline developing agents that are common in stock technology can be used for development. These developing agents include, for example, sodium or potassium hydroxide, carbonates, acidic carbonates, silicates or metasilicates thereof, but preferably non-metallic bases such as ammonia or amines, for example ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamines such as dimethylethanolamine, triethanolamine, quaternary ammonium hydroxides, for example tetramethylammonium hydroxide or tetraethylammonium hydroxide. Development solutions are generally at a concentration of up to 0.5N, but are usually diluted appropriately before use. For example, solutions with a normality of about 0.1 are well suited. The choice of developer depends on the nature of the photoresist, especially the nature of the binder used or the resulting photolysis products. Aqueous developer solutions may also include, if necessary, relatively small amounts of wetting agents and / or organic solvents. Representative examples of organic solvents which may be added to the developing liquids are, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone, isopropanol, as well as mixtures of at least two of these solvents. . A representative aqueous / organic development system is based on Butyl cellosolve / water.

 Thus, the present invention also relates to a method for producing an image, which comprises (a) coating a substrate with a layer of a composition as described above, (b) irradiating the layer with

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 radiation having a wavelength of 340 to 390 nanometers in a desired pattern and, after (c) a heating period at temperatures of 60 to 160 C, (d) removing the most soluble portions of the layer with a aqueous alkaline developing agent.

 In another aspect, the present invention also relates to the use of the compositions described above for the production of printing plates, color filters, resist materials and image recording materials, or image recording materials for holographic images, as well as the use of compounds of formula I or la, having a molecular extinction coefficient E of less than 10, as acid generators sensitive to radiation of a length of d wave less than 390 nm in the production of printing plates, color filters, resist materials or image recording materials, or image recording materials for holographic images.

 In addition to a color change, it is possible that pigment crystals are precipitated during the acid-catalyzed protection removal of the soluble pigment molecules; this phenomenon can be used in the production of color filters.

 The compounds of formula I are normally added to the light-activatable compositions in an amount of from 0.1 to 30% by weight, for example from 0.5 to 20% by weight, preferably from 1 to 10% by weight. .

 An object of the present invention is also a negative photoresist comprising, as the acid generating compound of formula la, α- (methanesulfoniumoxyimino) -3,4-dimethylphenylacetonitrile, α- (methanesulfonium-oxyimino) -4-methylphenylacetonitrile or α- (4-toluenesulfoniumoxyimino) phenylacetonitrile.

 The following Examples illustrate the invention in more detail. As in the remainder of the description, parts and percentages are by weight unless otherwise indicated.

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Example 1
A negative resist composition is prepared by mixing: 70 parts by weight of polyvinylphenol resin (Maruzen Chemical Co., Ltd.), 25 parts by weight of hexamethoxymethylmelamine, Cymel-303 (American Cyanamid), and 150 parts by weight of propylene glycol methyl ether acetate.

 Separately, 5 parts by weight of α- (methanesulfonium-oxyimino) -3,4-dimethylphenylacetonitrile was dissolved as an acid generating agent (having an E of 4.1 in tetrahydrofuran solution at 365 nm) in 10 parts by weight. N, N-dimethylacetamide.

 Both solutions are mixed to form a stock solution.

 A silicon wafer is uniformly spun coated with this prepared resist solution, followed by drying at 110 ° C for 90 seconds to form a dried photoresist layer having a thickness of 5 μm. The resist layer is exposed with a mask aligner (Canon PLA501) using the interference filter to select the 365 nm line, followed by post-exposure firing at 110 ° C for 90 seconds. The resulting formulation is subjected to development treatment in 2.38 wt% aqueous tetramethylammonium hydroxide for 60 seconds, then washed with water and air-dried.

 Photosensitivity for a line pattern and 2 m spaces, expressed as the exposure dose at which the resist layer on the exposed areas can be completely formed at a ratio of 1: 1, 210 mJ / cm 2 (energy) .

 In addition, a resist layer configured in a pattern of lines and gaps having a line width of 2 μm is formed in the same manner as above and examined with a scanning electron microscope to study

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 the cross-sectional profile of the lines. It is found that the cross section has a rectangular shape disposed perpendicularly to the substrate. The relative width of the line formed by varying the exposure dose between 0.8 and 1.2 times the photosensitivity is graphically transcribed as a function of the relative energy applied.

The slope of an adjustment line is 0.28. The tolerance of the examined system is better as the slope is lower.

Example 2
A stock formulation according to Example 1 is prepared. However, as the acid generating agent, 5 parts by weight of α- (methanesulfoniumoxyimino) -4-methylphenylacetonitrile (having a solubility of 0.35 e in tetrahydrofuran) are used. at 365 nm) in place of a- (methanesulfonium-oxyimino) -3,4-dimethylphenylacetonitrile.

 According to the same evaluation conditions as those described in Example 1, the resulting photosensitivity is 300 mJ / cm 2. The cross sectional profile of a 2 m wide line of the resist layer examined with a scanning electron microscope is a rectangular shape disposed perpendicular to the substrate. The slope determined in the same manner as described in Example 1 is 0.31.

Example 3
A stock formulation according to Example 1 is prepared. However, as the acid generating agent, 5 parts by weight of α- (4-toluenesulfoniumoxyimino) phenylacetonitrile (having a # of 0.28 in solution in tetrahydrofuran with 365 nm) in place of a- (methanesulfonium-oxyimino) -3,4-dimethylphenylacetonitrile.

 According to the same evaluation conditions as those described in Example 1, the resulting photosensitivity is 500 mJ / cm 2. The cross sectional profile of a 2 m wide line of the resist layer examined with a scanning electron microscope is a form

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 rectangular disposed perpendicular to the substrate.

The slope is 0.42.

Comparative Example
A stock solution is prepared in substantially the same manner as described in Example 1, but replacing the acid generating agent with 5 parts of a- (methanesulfonium-oxyimino) -2-thiophenylacetonitrile having 58 in solution in tetrahydrofuran at 365 nm. The result of the evaluation is a photosensitivity of 60 mJ / cm2 and a slope of 0.72.

Claims (16)

1. light-activable composition, characterized in that it comprises: (a) at least one compound which may be cross-linked by the action of an acid, and / or (b) at least one compound whose solubility changes under the action of an acid, and (c) as a photoinitiator, at least one acid generating compound by exposure to light of wavelength between 240 and 390 nm and having a molecular extinction coefficient E less than 10 at the wavelength of the line i (365 nm).  2. Composition according to claim 1, characterized in that it comprises, as component (c), a compound comprising a structural unit of formula I

 said compound being characterized by a molecular extinction coefficient of less than 10 at 365 nm.  3. Composition according to claim 1, characterized in that it comprises, as component (c), a compound of formula

 wherein R1, R2, R3, R4 and R5 are each, independently of the others, hydrogen, C1-C12 alkyl substituted by one or more halogen or unsubstituted, or halogen; R 6 is C 1 -C 18 alkyl substituted by one or more halogen or unsubstituted phenyl (C 1 -C 3) alkyl camphoryl, phenyl, naphthyl, <Desc / Clms Page number 39> OH, C1-C12 alkoxy, C1-C12 alkylsulfonyl, phenyl- C1-C6; a C2-C12 alkyl radical which is interrupted by -O- and which is unsubstituted or substituted by one or more OH, C1-C4 alkoxy, C1-C12 alkylsulfonyl, phenylsulfonyl radicals, methylphenyl) sulfonyl and / or C 1 -C 6 alkanoyl; or a phenyl, C 2 -C 6 alkanoyl, benzoyl, C 1 -C 6 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl radical; or R7 and R8 together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered ring which may be interrupted by -O- or NR 1 1 -; Rg is a C1-C12 alkyl radical which is unsubstituted or substituted by one or more OH and / or C1-C4 alkoxy radicals, or is a C2-C12 alkyl radical which is interrupted by -O- and which is not substituted or is substituted by one or more OH and / or C1-C4 alkoxy radicals; R10 is hydrogen; a C1-C12 alkyl radical which is not substituted or is substituted with one or more phenyl, OH, C1-C12 alkoxy, C1-C2 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or alkanoyl radicals; C2-C6; a C2-C12 alkyl radical which is interrupted by -O- and which is unsubstituted or substituted by one or more phenyl radicals, OH, C1-C4 alkoxy, C1-C12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or alkanoyl C1-C4, CN, NO2, C1-C16alkyl, phenyl, OR10, COOR9, -O (CO) -C1-C4alkyl, SO20R9 and / or NR7R8; R7 and R8 are each, independently of the other, hydrogen; a C1-C12 alkyl radical which is unsubstituted or substituted by one or more radicals  anthracyl or phenanthryl, the phenyl, naphthyl, anthracyl and phenanthryl radicals being unsubstituted or substituted by one or more halogen atoms and / or haloalkyl radicals <Desc / Clms Page number 40>  sulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; or a phenyl radical; R 11 is hydrogen, a C 1 -C 12 alkyl radical substituted with one or more OH or unsubstituted or a C 2 -C 12 alkyl radical which is interrupted by -O-; the compounds of formula la being characterized by a molecular extinction coefficient e of less than 10 at 365 nm.  4. chemically amplified photosensitive resist which is sensitive to radiation of wavelength between 340 and 390 nm, characterized in that it comprises a photosensitive acid generator of formula I, as defined in claim 2, characterized by a molecular extinction coefficient of less than 10 at 365 nm.  5. The chemically amplified photosensitive resist as claimed in claim 4, which is sensitive to radiation of wavelength between 340 and 390 nm, characterized in that it comprises a photosensitive acid generator of formula la, as defined in claim 3, characterized by a molecular extinction coefficient E of less than 10 at 365 nm.  6. chemically amplified photosensitive resist according to claim 4 or 5, characterized in that it has a thickness greater than 2 μm.  7. Chemically amplified negative photosensitive resist characterized in that it comprises a compound of formula la having a molecular extinction coefficient E of less than 10, is developable in an alkaline medium, has a reserve thickness greater than 2 μm and is sensitive. at radiation of wavelength between 340 and 390 nanometers.  A negative photoresponsive having a resist thickness greater than 2 μm, which is developable in an alkaline medium and is suitable for exposure radiation having a wavelength between 340 and 390 nanometers, characterized in that it comprises a oxime sulphonate of formula la as described in claim 3, <Desc / Clms Page number 41>  an alkali-soluble phenolic resin as a binder and a component which, when catalyzed by an acid, undergoes a cross-linking reaction with itself and / or with the binder.  9. chemically amplified positive photosensitive resist, characterized in that it comprises a compound of formula la having a molecular extinction coefficient E of less than 10, is developable in an alkaline medium, has a reserve thickness greater than 2 μm and is sensitive. at radiation of wavelength between 340 and 390 nanometers.  10. A positive photosensitive resist characterized in that it comprises a compound of formula la as described in claim 3, and a binder which is substantially insoluble in an alkaline developing agent and which becomes soluble in the developing agent. presence of the photolysis products of the compound of formula la.  Use of a composition according to claim 1 for the preparation of chemically amplified negative photosensitive resistances, positive photosensitive resistances, printing plates, color filters or image recording materials.  A process for the production of chemically amplified negative photosensitive resistances, positive photosensitive resistances, printing plates, color filters or image recording materials, characterized in that a composition according to claim 1 is irradiated. with light having a wavelength of 340 to 390 nm.  13. A process for the production of an image, characterized in that it consists of (a) coating a substrate with a layer of a composition according to claim 1, (b) irradiating the layer with radiation having a length of wave of 340 to 390 nanometers in a desired pattern, (c) heating the layer to temperatures of 60 to 160 C, and (d) removing the most soluble portions of the layer with an aqueous alkaline developer. <Desc / Clms Page number 42>  14. Use of a compound of formula I or Ia, having a molecular extinction coefficient of less than 10, as a photosensitive acid generator in compositions comprising compounds that can be crosslinked by the action of an acid and or as a dissolution inhibitor for compounds whose solubility changes under the action of an acid.  A process for generating sulfonic acids, characterized in that a photosensitive acid generator of formula Ia, having a molecular extinction coefficient of less than 10, is irradiated with light having a wavelength of between 340 and 390 nm.  Negative photosensitive reserve according to claim 8, characterized in that it comprises, as acid generating compound of formula Ia, α- (methanesulfonium-oxyimino) -3,4-dimethylphenylacetonitrile, α- (methanesulfonium-oxyimino) 4-methylphenylacetonitrile or α- (4-toluenesulfoniumoxyimino) phenylacetonitrile.