DE3145406A1 - DIAZONIUM SULPHONATES AND THEIR USE - Google Patents

Description

- 15 description

The invention relates to new photosensitive diazonium compounds, their manufacture and use. The invention particularly relates to diazonium trifluorinethanesulfonates and preparations containing them which are used in diazo-type materials. The diazonium trifluoromethanesulfonates are used as latent polymerization initiators for the photopolymerization of a polymerizable Systems suitable.

Diazo-type photo reproduction is, of course, a standard practice in the graphic arts field. The touchstone the diazography process is the photosensitivity of the aromatic diazo salts and the fact that these salts are two different; Types of reaction suffer: [1] Replacement or decomposition, with the nitrogen atom is lost or a nitrogen gas is formed and another atom or group is attached to the benzene ring instead is bound; and [2] the coupling in which the nitrogen of the diazo function is retained and the salts with certain, couplable, color-forming components, e.g., a "coupler" or an "azo coupling component", react, whereby the formation of azo dye species takes place.

In the case of positive-working diazo processes, one becomes light-sensitive Diazo salt mass, the sensitizing preparation generally containing a diazo compound, a coupling component or a color former and an acidic coupling inhibitor on a carrier or a base material upset. The support or base material can be paper or a transparent film such as cellulose acetate or a base material coated with plastic. You get a positive working ma-

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material. The positive working material is provided with an image by first exposing it through a master transparency or original. In the exposure stage, the light must provide sufficient energy to decompose the diazo compound in the areas that correspond to the clear background of the original. ^;

The photochemical sensitivity of normally, in The compounds used in diazo type photographic reproduction materials is near ultraviolet Area of the spectrum and is centered around 400 nm (nanometers), where 1 nm is a millimicron or 10 ~ "m is equivalent to. Medium pressure metal halide mercury lamps are therefore generally used in carrying out this step used. As a result, the portion of the diazo coating that is exposed to ultraviolet radiation through the Image of the original is not protected, converted into a colorless substance with the "coupling" component cannot couple, which is generally an aromatic amine, phenol or an aliphatic compound which is active Contains methylene groups is. Thereby colored oxyazo or aminoazo compounds, known as azo dyes are formed. The unaffected diazo compound that remains in areas that light does not has taken, however, by reaction with the coupling component, if the medium is made alkaline, to neutralize the acidic inhibitor, form an azo dye. Thus, where an opaque line appears was on the original, a line of dye on the copy. Diazo type positive photoresponsive material is generally made or is made alkaline Adjust the pH, either by impregnating the material with ammonia vapors or by passing it through a alkaline developing solution conducts (see US Pat

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1,444,469; 1,628,279; 2,217,189; 2 286 701, 2 429 249 and

2,694,009; DE-PSs 56 606, 111 416, 487 247 and 515 205; GB-PSs 234 818, 281 604 and 521 492).

The diazo compounds are used in sensitization preparations generally in the form of stabilized compounds of acid salts with zinc chloride, cadmium chloride, tin (IV) chloride and tetrafluoroborate salts as well as hexafluorophosphate salts. These salts are used to stabilize the Diazo compounds are also used to improve the quality or storage stability of the sensitized Diazo-type materials.

It is common practice to provide some means of preventing discoloration and fading of the images to prevent. In order to achieve this, various additives are generally used in the diazo preparations used, such as thiourea, thiourea derivatives and other similar acting compounds.

The use of the various stabilizers and additives in preparations of the diazo type is, however not entirely satisfactory. In particular are the stability or storage stability properties unsatisfactory of diazo-type materials, especially such diazo-type materials, which are sensitized with preparations containing diazo compounds known to be they have high coupling activity and / or instability exhibit.

When preparing a sensitizing composition, the less solvent is generally required to to obtain the desired or predetermined amount of the diazo compound in solution, the greater the solubility of the

Is diazo compound in the solvent system. However, difficulties then arise, such as an appearance known as "bleeding" or "discoloration". Furthermore, the greater the solubility of the diazo compound, the higher their possible charge in the solvent system, which of course gives a denser image. It follows that the greater the solubility of the photosensitive diazo compound, the greater the practical and economic benefits in using it.

The characteristic photodecomposition of certain aromatic diazo salts has also resulted in these Salts can assume the role of a latent polymerization initiator for polymerization systems, as described in U.S. Patents 3,816,279, 3,816,280, 3,816,281, 3,817,845,

3 817 850, 3 835 003, 3 997 344, 4 054 451, 4 054 452,

4,054,732, 4,056,393, 4,076,536, 4,080,274 and 4,091,194 to be discribed. Of course, diazonium salts that have been used with success in photoresponsive systems of the Diazo type can be used and which can also be used as latent polymerization initiators, a higher commercial value, due to their multiple important uses.

Accordingly, the present invention is based on the object of providing new salts of diazo compounds which can be used to make improved light-sensitive diazo formulations.

According to the invention, new diazo salt compositions are to be made available which have improved stability and storage stability and have compatibility with plastic materials used as supports in photo reproduction materials of the diazo type can be used.

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According to the invention, a diazo salt is to be made available which is not only used in positive-working diazography systems, but can also be used in negative-working diazography systems.

According to the invention, a new diazonium compound is intended for Are made available, which have an increased solubility in organic solvents.

According to the invention, new diazonium compounds are to be made available which also contain suitable latent polymerization initiators for the photopolymerization of certain polymerizable systems.

According to the invention, an economical method for Production of a variety of diazo salt compounds are made available, and the technical use These diazo compounds are said to be made practical, which in the past have been viewed as uneconomical or diazo compounds which in the past were believed to be difficult to prepare be.

According to the present invention, improved photo-reproduction materials of the diazo type and methods using them can be used.

The invention relates to new diazonium salts. The invention relates to new photosensitive diazo compounds. These compounds are diazonium trifluoromethanesulfonates, also known as "diazonium triflates", i.e. trifluoromethylsulfonic acid salts of diazo compounds, are designated. The invention also relates to a method for their production.

The invention also relates to preparations or compositions for diazography which contain a diazonium triflate (a diazonium salt trifluoromethylsulfonic acid), a diazo coupling component and contain an acidic coupling inhibitor, wherein the diazographic preparation for the production photosensitive materials of the diazo type, which are a sheet or film material sensitized with the Preparation, have, is suitable.

The invention also relates to compositions for diazography which contain a new diazonium triflate compound and an enolic, preferably phenolic, blocked coupler or a precursor of an azo coupling component, which in the presence of an acid into an active azo coupling component is transferable, included, the mass on a material of the diazo type, which is a film or Sheet material that is sensitized with the mass, contains, can be used. One such material des Diazo type is for negative working photo reproduction of the diazo type.

The invention also relates to the use of diazonium triflates as latent polymerization initiators in masses that contain the triflate and a cyclic ester, e.g., lactone; a monomeric or prepolymeric epoxy; a cyclic ether such as an oxetane; or mixtures thereof, for the subsequent polymerization of the mass Contain masses of higher molecular weight when exposed to radiation.

The new diazonium triflates according to the invention are trifluoromethylsulfonic acid salts a diazo compound represented by the following general formula can:

O Ob) -N = N ^e - ^e OS-CF,

Il ■>

where Q -N = N- is the cation of an organic diazonium compound, for example the cation of any diazonium compound and in particular known diazonium compounds which are used in diazography preparations for the photoproduction of the diazo type, e.g. the diazonium compounds according to US Pat. No. 2,661,291,

2 694 010, 2 727 820, 2 861 065, 2 948 613, 3 082 200,

3 134 675, 3 164 468, 3 203 803, 3 255 011, 3 386 828,

3,407,066 and 3,816,280. Accordingly, can (D) any unsubstituted or substituted, mono- or polycyclic aryl or heterocyclic aromatic group, but is preferably selected from the Group that includes: unsubstituted or substituted phenyl, naphthyl, anthryl, phenanthryl and azoheterocyclic, aromatic groups. Examples of substituents are those selected from the group that includes: for example an alkyl, alkylamino, I) i alkylamino, Arylamino, aralkylamino, phenoxy, phenyl, phenylthioether, Morpholino, piperidino, pyrrolidino, hexamethyleneimine, Halide, alkoxy, cycloalkyl and piperazino groups. The type, position and number of substituents are without limitation, of course with the exception of those that apply generally chemically. You will accordingly the end use of the diazonium triflate. Parasubstituted compounds are generally special useful and suitable for use in diazography. The preferred alkyl and alkoxy groups are lower alkyl and alkoxy groups of 1 to about 8 carbon atoms; the preferred aryl groups are with 6 to about 10 carbon atoms; and the preferred cycloalkyl groups are those having 3 to about 8 carbon

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atoms. Examples of azaheterocyclic, aromatic Groups are pyridyl groups such as an aminopyridine derivative.

The diazonium triflates are the reaction product of trifluoromethylsulfonic acid or one of their salts and a diazonium compound.

The trifluoromethylsulfonic acid or its salt used to manufacture of the diazo salt of the present invention may be in the form of an acid or in the form of any of them Salts are present, and they are preferably in a form that is more soluble than that in the reaction medium Diazo trifluoromethanesulfonate (diazotriflate), which is produced will. The trifluoromethylsulfonic acid used as a reactant can be represented by the formula MOSO ^ CF-, in which M is hydrogen, a metal cation or another cation, e.g. K, Na or ammonium salts, means.

The diazonium compounds according to the invention for the Reaction with the triflate used can be represented by the general formula CD) -N = NX, wherein (ί £ -N = N- have the same meaning as given above, and X represents an anion which can give a stable diazonium compound. Basically any Diazonium compounds and in particular known diazonium compounds used in diazography preparations can be used for photo-reproduction of the diazo type, e.g., those diazonium compounds which in the U.S. patents listed above. Examples of diazonium compounds include those derived from the following list of cations (D, -N = N and anions X, given as examples. This list is not intended to be limiting.

Cations

(1) p-chlorobenzene diazonium;

(2) 2,4-dichlorobenzene diazonium;

(3) 2,5-dichlorobenzene diazonium;

(4) 2,4,6-trichlorobenzene diazonium;

(5) p-methoxybenzenediazonium;

(6) o-methoxybenzenediazonium;

(7) 2-chloro-4- (dimethylamine) -5-methoxybenzenediazonium;

(8) 4-chloro-2,5-dimethoxybenzenediazonium;

(9) 2,4.5-triethoxy-4-biphenyldiazonium [2,5-diethoxy-4- (p-ethoxyphenyl) benzene diazonium];

(10) 2,5-dimethoxy-4'-diethyl-4-biphenyldiazonium [2,5-dimethoxy-4- (p-tolyl) benzene diazonium];

(11) 2,5-diethoxy-4- (phenylthio) benzene diazoniura;

(12) 2,5-diethoxy-4- (p-toylthio) benzene diazonium;

(13) p-morpholinobenzene diazonium;

(14) 2,5-dichloro-4-morpholinobenzene diazonium;

(15) 2,5-dimethoxy-4-morpholinobenzene diazonium;

(16) 4- (dimethylamino) naphthalenediazonium;

(17) 4-N, N-dimethylaminobenzene diazonium;

(18) 4-N, N-diethylaminobenzene diazonium;

(19) 4-N-ethyl-N-hydroxyethylaminobenzene diazonium;

(20) 4-K-methyl-N-hydroxyethylaminobenzene diazonium;

(21) 4-N-ethylaminobenzene diazonium;

(22) 4-N, N-diethylamino-2-methyTbenzenediazonium;

(23) 4-N-ethyl-N-benzylaminobenzene diazonium;

(24) 4-N, N-diethylamino-3-chlorobenzene diazonium;

(25) 4-N-morpholino-2,5-diethoxybenzenediazonium;

(26) 4- (p -tolylthio) -2,5-diethoxybenzenediazonium;

(27) 4- (p-chlorophenoxy) -2,5-diethoxybenzenediazonium;

(28) 4- (p -ethoxyphenyl) -2,5-diethoxybenzenediazonium;

(29) 4-N, N-bis (β-hydroxyethyl) aminobenzene diazonium;

(30) 4-N-pyrrolidino-3-methylbenzenediazonium;

(31) 4-N- (2,6-dimethylmorpholino) benzene diazonium;

(32) 4-N-piperidinobenzenediazonium;

(33) 4-N-pyrrolidinobenzenediazonium;

(34) 4-N-hexamethyleneiminobenzene diazonium;

(35) 4-N-Pip erazinobenzoldiazonium;

(36) 4-N- (N ¹ -methylpiperazino) benzoidiazonium;

(37) 4-N- [N- (3-aza-bicyclo [3.2.2] nonane)] benzene diazonium;

(38) 4-N- [N '- (β-hydroxyethyl) piperazi.no] benzene diazonixime;

(39) 4-N- (N '-acetylpiperazino) -benzoidiazoniiim;

(40) 4-N-morpholino-2,5-diisopropoxybenzenediazonium;

(41) 4-N-Azacycloheptane-2,5-diethoxybenzenediazonium;

(42) 6-dimethylamino-3-pyridinediazonium;

(43) 6-diethylamino-3-pyridindiazoni \ om;

(44) 6-methylamino-3-pyridinediazoniiiin;

(45) 6-ethylamino-3-pyridinediazoniumim;

(46) 6-morpholino-3-pyridinediazoniumim;

(47) 6-piperazino-3-pyridinediazonium;

(48) 6-benzylamino-3-pyridinediazonium;

(49) 6-p-toluidino-3-pyridinediazoniiam;

(50) 6- (p-Dimethylaminoanilino) -3-pyridinediazoniiam;

(51) N, N ^! - (4,4'-biphenylene) -bis- (6-amino-3-pyridinediazonium);

(52) 6-anilino-3-pyridinediazonium;

(53) 6- (2-pyridylamino) -3-pyridinediazonium;

(54) 6,6 '- (p, p'-methylenedianilino) bis (3-pyridinediazonium);

(55) N-methyl-δ-anilino-S-pyridindiazoniijm;

(56) 6-dimethylamino-5-methyl-3-pyridinediazoni ^ αm;

(57) 2-dimethylamino-3-pyridinediazonium;

(58) 4-N, N-diethylamino-2-ethoxybenzenediazonite;

(59) 4-N -ethylamino-2-methylbenzenediazonium;

(60) 4-N, N-bis-hydroxyethylbenzenediazonium;

(61) 4-N-oxazolidinobenzenediazonium;

(62) 4-N-methyloxazolidinobenzene diazonium;

(63) 4-N- (tetrahydro-1,3-oxazino) benzene diazonium;

(64) p-ethoxybenzenediazonium;

(65) 3-chloro-4,6-dimer; hoxybenzenediazonium;

(66) p-acetamidobenzene diazonium;

(67) 4-bromo-2,5-diethoxybenzenediazonium;

(68) 4-N-benzylamino-2-methoxy-5-methylbenzenediazonium;

(69) 4-N-Benzoylamino-2-methoxy-5-III-ethylbenzenediazonium;

(70) 4-N-Phenylthioacetylamino-2,5-diethoxybenzene ~ diazoniuim;

(71) 4'-acetylamino-2,5-diethoxy-4-biphenyldiazonium;

(72) 4-N-PipeΓidino-5-methoxy-2- (p-tolylthio) -benzenediazoniumom;

(73) 4- (p-tolylthio) -5-niethoxy-2-piperidinobenzenediazonium;

(74) 4 ^^ 101 ^ 01 ^ 0-5 ^ 6-010 ^ -2- (p-tolylthlo) benzene diazonium;

(75) 4-N-piperidino-5-methoxy-2-piperidinobenzenediazonium;

(76) 4-N-piperidino-5-butoxy-2- (p-tolylthio) benzene diazonium;

(77) 4-N-piperidino-5-methoxy-2-phenoxybenzoldiazorLiuπl;

(78) o-nitrobenzenediazonivun;

(79) p-nitrobenzenediazonium;

(80) 4-nitro-2-methylbenzenediazonium;

(81) 4-methyl-2-nitrobenzenediazonium;

(82) 2 ^ -dimethyl-δ-nitrobenzenediazonium;

(83) 3-chloro-4-pyrrolidinobenzenediazonium;

(84) 4-morpholino-3-methoxybenzenediazonium;

(85) 4-N-Benzoylpiperidino-2,5-diisopropoxybenzenediazonium.

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The preferred aromatic diazonium cations are those which after combination with the trifluoromethylsulfonate anion,

OSOpCF ,, easily forms a precipitate, i.e., a reaction product which is insoluble in the reaction medium, which is generally water. Examples of Diazonium cations, which for the most part form water-insoluble triflates, are 4- (p-tolylthio) -2,5-diethoxybenzoldiazonium-; 4-N-morpholino-2,5-diisopropoxybenzenediazonium-; and 4-N-azacycloheptane-2,5-diethoxybenzenediazonium cations. Of course, the preference for any aromatic diazonium cation will ultimately depend on how the diazonium triflate is to be used. In fact, if the diazonium triflate have some water solubility should have such cations as 4-N-ethyl-N-hydroxyäthylaminobenzoldiazonium and 4-N, N-diethylamino-2-methylbenzenediazonium, more suitable than the three previously mentioned Cations.

Among the specific cations listed above are those numbered (11), (12), (15), (24), (25), (30), (34), (40) _; (74), (77), (84) and (85) are preferred.

Anions

(1) tetrafluoroborate, BF ^ ";

(2) hexafluorophosphate,

(3) hexafluoroarsenate (V),

(4) hexafluoroantimonate (V),

(5) pentachlorobismutate (IIl),

(6) trichlorostannite, SnCl ^ ";

(7) trichlorozincate, ZnCl-, ";

(8) chloride, Cl ";

(9) sulfate, SO, "²;

—2

(10) tetrachlorozincate, ZnCl ^;

(11) Hexachlorostannate (IV), SnCIg " ²

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(12) Tetrachloro ferrate (III), FeCl / ";

(13) cadmium chloride, CaCl ^;

(14) bisulfate, HSO ₄ ".

The preferred anions are those which produce a stable diazo salt that is "water soluble; for example it was found that diazo compounds as stabilized salts of zinc chloride, cadmium chloride, tin (IV) chloride and boron trifluoride have suitable water solubility. Accordingly, the hexachlorostannate, tetrachlorozincate and trichlorozincate, trichlorostannite, hexachlorostannate, Tetrafluoroborate as well as the chloride, bisulfate and sulfate anions are the particularly preferred anions. The water solubility mediated by the anions results in easier solubilization of the diazo compound in an aqueous reaction medium and thus a better preparation of the diazonium triflate by precipitation from them. The double salts of the cations can also be formed, and they are for reaction with trifluoromethane sulfonic acid or one of its Salts suitable, according to the invention being a diazonium triflate receives.

The preparation of the diazonium triflates according to the invention can be explained by the following equation:

MOSO ₂ CF ₃ + (D) -N = r; NX j- (D) -N = NO - ^ - CF ₃ + MX

The reaction is generally carried out in an aqueous reaction medium carried out whereby the recovery of the diazonium triflate product is made possible by precipitation from the solution. Although the solubility of the different

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common diazotriflates will vary, some are in water less soluble than others, and appropriate measures can be taken, for example the temperature conditions, Volume conditions and the like can be set accordingly, or one can inoculate to be practical to get a precipitate in all cases. Due to the considerable solubility of the diazonium triflates in organic solvents, but the reaction is in an organic solvent such as hexane or ketone, does not make sense if the diazonium triflate is to be obtained from the solution by precipitation. However, it becomes an organic one If the reaction medium is used, the triflate can still be extracted from it using conventional extraction methods, e.g. by evaporating the organic solvent.

The reaction is carried out in an aqueous medium by dissolving the diazo salt, ^ -N = NX, in the aqueous reaction medium. The trifluoromethyl sulfonic acid or the salt, MOSO ₂ CF, is then introduced into the solution. The solution can be stirred to accelerate the dissolution of the trifluoromethyl sulfonic acid. The temperature at which the reaction medium is kept can vary widely, the thermal sensitivity of the diazo compound used determining the choice of a suitable temperature. In general, however, temperatures in the range of ambient or room temperature to 75 ° C can be used, with temperatures in the range of about 25 to about 45 ° C being preferred. However, temperatures outside these ranges can also be used. The amount of MOSO ₂ CF added is preferably somewhat greater than the stoichiometrically required amount which is required for the reaction with the diazo salt; this corresponds to a molar ratio of 1: 1.

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(R

The aromatic diazonium cation (D) - N = N and the trifluoro

Ck

methyl sulfonate anion OSOpCF ^ always combine in a molar ratio of 1: 1, and thus the exact composition of the reaction product (Q -N = NOSO ₂ CF ^ can be precisely predicted and does not differ from reaction to reaction. This stoichiometry also enables an exact Control of the preparations used in the sensitized materials of the diazo type.

The precipitation of the diazonium triflate product generally takes place without further treatment of the solution. In However, in some cases it may be necessary to remove the precipitate initiate by setting the conditions, e.g. by cooling the aqueous reaction solution or by inoculating the solution. After the product has precipitated out of the solution, the diazonium triflate can easily be added methods known per se, such as by filtration, can be obtained.

Furthermore, there is the in situ formation of the diazonium triflate also possible. For example, when preparing the sensitizing compound, you can use the compound first Prepare a suitable diazo salt instead of the diazonium triflate. Then the trifluoromethyl sulfonic acid can can be added in situ to form the diazonium triflate. Such procedures can also be used in the formation of a diazo type photosensitive material can be used. The original solution or suspension that is applied to the base material or the carrier may contain a suitable diazo salt which is used in the Reaction with trifluoromethyl sulfonic acid results in a diazonium triflate. Accordingly, the trifluoromethylsulfonic acid added to the treated base material or carrier to form the diazonium triflate in situ.

The following examples illustrate the invention. They are a number of specific diazonium triflates that are produced by Implementation of a diazonium salt, which is the cation of Contains triflate, and trifluoromethyl sulfonic acid or one of its salts can be produced.

(1) p-N-diethylaminobenzoidiazonium trifluoromethylsulfonate;

(2) 3-chloro-4-N-diethylaminobenzene diazonium trifluo rmethylsulfonate;

(3) ο-chlorobenzene diazonium trifluoromethylsulfonate;

(4) 4-N-diethylamino-2-ethoxybenzenediazonium trifluoromethylsulfonate;

(5) 4-N-diethylamino-2-methylbenzoidiazonium trifluoromethylsulfonate;

(6) p-N-Dimethylaminobenzenediazonium trifluoromethylsulf onat;

(7) 2,5-diisopropoxy-4 ^ morpholinobenzenediazonium trifluoromethylsulfonate;

(8) 4- (3 »5-dimethylmorpholino) benzene diazonium trifluoromethylsulfonate;

(9) o-methoxybenzenediazonium trifluromethylsulfonate;

(10) 3-Chloro-4-N-pyrrolidinobenzenediazonium trifluoromethylsulf onat;

(11) 3-methyl-4-N-pyrrolidinobenzoidiazonium trifluoromethylsulfonate;

(12) 3-methoxy-4-N-pyrrolidinobenzene diazonium trifluoromethylsulfonate;

(13) S-methoxy 1-4 N-pyrrolidinobenzene diazonium trifluoromethylsulfonate;

(14) 2,4-Dimethoxybenzenediazonium trifluoromethylsulf onat;

(15) 2,5-diethoxy-4- (4 ^f -chlorophenoxy) -benzenediazonium trifluoromethylsulfonate;

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(16) 4-benzyloxybenzenediazonium trifluoromethylsulfonate;

(17) 2,5-diethoxy-4-N-benzamidobenzenediazonium trifluoromethylsulfonate;

(18) 2-methoxy-5-methyl-4-N-benzamidobenzenediazonium trifluoromethylsulfonate;

(19) p-ethoxybenzenediazonium trifluoromethylsulfonate;

(20) 4-chloronaphthalenediazonium trifluoromethylsulfonate;

(21) 4-Pyrrolidinonaphthalenediazonium trifluoromethylsulf onat;

(22) p-chlorobenzene diazonium trifluoromethylsulfonate;

(23) 6-Morpholino-3-pyridinediazonium trifluoromethyl sulf onat;

(24) 6-Dimethylamino-3-pyridinediazonium trifluoromethyl sulf onat;

(25) 4-N-methanesulfonamido-2,5-dimethoxybenzenediazonium trifluoromethylsulfonate;

(26) 4- (2,6-dimethylmorpholino) benzene diazonium trifluoromethylsulfonate;

(27) 4-N-dimethylamino-3-chlorobenzene diazonium trifluoromethyl sulfonate;

(28) 4- (p-tolylthio) -2,5-dimethoxybenzenediazonium trifluoromethylsulfonate;

(29) 4-N-diethylamino-3-methylbenzenediazonium trifluoromethylsulfonate;

(30) p-N-methylcyclohexylamino-3-chlorobenzene diazonium trifluoromethylsulfonate;

(31) 4-N-Dimethylamino-3-pyridinediazonium trifluoromethylsulf onat;

(32) 2,5-diethoxy-4- (phenylthio) benzene diazonium trifluoromethyl sulfonate;

(33) 2,5-dimethoxy-4-morpholinobenzenediazonium trifluoromethylsulfonate;

(34) 4-N-morpholino-2,5-diethoxybenzenediazonium trifluoromethylsulfonate;

(35) 4-N-hexamethyleneiminobenzenediazonium trifluoromethylsulfonate;

(36) 4-N-Morpholino-5-methoxy-2- (p-toIyIthio) -benzenediazonium trifluoromethylsulfonate;

(37) 4-N-piperidino-5-methoxy-2-phenoxybenzoldiazonilom-trif luoromethyl sulfonate;

(38) 4-N-Morpholino-3-methoxybenzenediazonium-trifluoromethylsulfonate; vmd

(39) 4-N-Benzoylpiperidino-2,5-diisopropoxybenzenediazonium trifluoromethylsulfonate.

Other examples of diazonium triflates are those of Structural formulas:

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Chemical structure

Chemical name

-A

O-CH.

H ₃ CO

0-CH.

N ₂ OSO ₂ CF ₃ 4-N-IYfethoxycarbonylamino-2,5-dimethoxybemzal-diazonium trifluoro-imethylsulfonate

N ₂ OSO ₂ CF ₃ 4-N-acetylamino-2 , 5-dimethoxybenzene

diazoniuni trifluoromethyl sulfonate

N ₂ OSO ₂ CF ₃ 4-N-methylsulfonylamino-2,5-dimethoxybenzene-diazoniuin-trifluoro- 1-sulfonate

Chemical structure

Chemical name

-CH.

N ₂ OSO ₂ CF ₃ 4-N-phenylamino-2-methoxybenzene-diazonium trifluoromethylsulfonate

N ₂ OSO ₂ CF ₃ 4-N-bhenylaminobenzene- = cliazoniuin trifluoromethylsulfonate

N ₂ OSO ₂ CF ₃ 4-N-phenylamino-2-trifluoro-methylbenzene-diazonium trifluor * methyl sulfonate

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Chemical.structure

N ₂ OSO ₂ CF ₃

N ₂ OSO ₂ CF ₃ Chemical name

4-N- p -henylamine-3-trifluoro- 1-methylbenzene-diazonium trifluoromethylsulfonate

4-N-Phenylamino-3-chloro- ^ benzo-irdiazonium-trifluoro methyl sulfonate

O-CH.

N ₂ OSO ₂ CF ₃

4-N-J Benzoylamino-2,5-dimethoxybenz-oldiazonium trifluoro methyl sulfonate.

3U5406 "-: f.! .. Ί

- 36 Chemical structure Chemical name

4-N-Beηzoylamino-3-chloro-ibenzene-:
diazonium trifluoro · methylsulfonate

N ₂ OSO ₂ GF ₃

O-CH.

N ₂ OSO ₂ CF ₃

Cl

O-CH.

N ₂ OSO ₂ CF ₃ 4-NB anzoylamino-3-methoxybenz / diazonium trifluoromethylsulfonate j

4-N-B, enzoylamino-2-chloro-5-methoxybenzene-t-diazonium trifluoro-methylsulfonate

3U5406

Chemical structure Chemical name

CH ₃ CH ₂ -O

0-CH ₂ CH ₃

N ₂ OSO ₂ CF ₃ 4-N-acetylamino-2,5-diethoxybenzP.l-diazonium-trifluoromethyl sulfonate

^ H

CH ₃ CH ₂ -

-CH ₂ CH ₃ 4- (p-Tolylthio) -2,5-diethoxybenzoldiazonium trifluoro methylsulfonate

4- (p-Tolylthio) -3-chloro-benzene oldiazonium-trifluoro methyl sulfonate

3Ϊ45406

Chemical structure Chemical name

O-CH.

4- (p-Tolylthio) -3-methoxybenzolr diazonium trifluoro ■ methyl sulfonate

4- (p-Tolylthio) -3-N-acetylaminobenzoldiazonium trifluoro methyl sulfonate

N ₂ OSO ₂ CF ₃

Carbazol -2-diazonium trifluoromethylsulfonate

3H5406

Chemical structure

Chemical name

₂ OS0 ₂ CF ₃ 4-N-ethyl-N-hydroxyethylaminobenzene diazonium trifluoromethylsulfonate

CH ₃ CH ₂ -O

0-CH ₂ CH ₃

N ₂ OSO ₂ CF ₃ 4-N-Azacycloheptane'-2,5-diethoxybenz Pl diazonium trifluoromethyl sulfonate

N ₂ OSO ₂ CF ₃ 4-methyl-2-nitrobenzene-rdiazonium meets luor- »methylsulfonate ·

3H5406: ::: 1 -

Chemical structure Chemical name

NO ₂

p-Nitrobenzenediazonium trifluoromethylsulfonate

N ₂ OSO ₂ CF,

Of the specific diazonium triflates mentioned above, the following species are currently particularly preferred.

2, S-diisopropoxy ^ -morpholinobenzene diazonium trifluoromethylsulfonate;

3-chloro-4-N-pyrrolidinobenzenediazonium trifluoromethylsulfonate;

3-methyl-4-N-pyrrolidinobenzenediazonium trifluoromethylsulf onat;

3-methoxy-4-N-pyrrolidinobenzoidiazonium trifluoromethylsulfonate;

2,4-dimethoxybenzenediazonium trifluoromethylsulf onat;

2, S-diethoxy ^ -N-benzamidobenzene diazonium trifluo rmethylsulfο nat;

4- (2,6-dimethylmorpholino) benzene diazonium trifluoromethyl sulfonate;

4- (p-tolylthio) -2,5-dimethoxybenzenediazonium trifluoromethylsulfonate;

4- (p-Tolylthio) -2,5-diethoxybenzoldiazonium trif luoromethyl sulfonate;

4- (p-Tolylthio) -3-methoxybenzenediazonium trifluoromethylsulfonate;

4-N-azacycloheptane-2,5-diethoxybenzenediazonium trifluoromethylsulfonate;

2,5-diethoxy-4- (phenylthio) benzoidiazonium trifluoromethylsulfonate;

2, S-dimethoxy ^ -N-morpholinobenzene diazonium trifluoromethylsulfonate;

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4-N-morpholino-2,5-diethoxybenzenediazonium trifluoromethyl sulfonate;

4-N-hexamethyleneiminobenzene diazonium trifluoromethylsulfonate;

4_N-Morpholino-5-methoxy-2- (p-tolylthio) -benzenediazonium trifluoromethylsulfonate;

4-N-piperidino-5-methoxy-2-phenoxybenzenediazonium trifluoromethyl sulfonate;

4-N-Morpholino-3-methoxybenzenediazonium trifluoromethyl sulfate onat; and

4-N-Benzoylpiperidino-2,5-diisopropoxybenzenediazonium trifluoromethyl sulfonate.

The diazonium triflates according to the invention are photosensitive and undergo the same chemical reactions that are characteristic of aromatic diazo salts. Accordingly the diazonium triflates are useful in diazographic processes. There are great advantages in using the diazonium triflates in diazographic processes.

The OS0 ₂ CF, anion generally gives the aromatic diazonium cations with which it is combined, a lower solubility in water compared to the known stabilized salts of diazo compounds, such as those with zinc chloride, cadmium chloride, tin (II) chloride and the like are stabilized. The lower the solubility in water, the easier it is to produce the stabilized diazonium triflates economically in aqueous media.

It has also been found that the diazonium triflates have a significantly higher solubility in organic solvents compared with the known diazo salts including the diazonium hexafluorophosphates. These increased solubility in organic solvents, such as

3U5406

Ketones, alcohols and the like. For the application of the Diazo preparations on plastic layers or carriers used in the manufacture of diazo-type materials facilitates the loading of the solvent with the diazo preparation and gives a material of the diazo type with improved resistance to "tarnishing". The condition known as "turbidity" is the result poor compatibility of the diazo salt with the plastic layer or the support of the diazo-type material, whereby a veil is formed on the plastic layer and thereby the transparency and the general Appearance will be deteriorated. The increased solubility of diazonium triflates in the solvent used for their Application to the carrier will help keep the haze to a minimum and will continue to be maintained denser images.

There is another advantage of using the diazonium triflates compared with the known inorganic ones Fluoride diazosalts, such as tetrafluoroborates and hexafluorophosphates, give the triflates no corrosive gas, e.g. hydrogen fluoride, during decomposition on exposure to light, as before mentioned salts. Such a gas is very corrosive to glass and can therefore be destroyed quickly cause of the light sources, which can lead to a deteriorated image quality.

Sensitizers containing diazonium triflates useful in diazographic applications, can be easily prepared. Diazonium triflates are dated for positive working photo reproduction systems Diazo type particularly suitable, including a sensitizing compound produces a diazonium triflate as a light-sensitive diazonium compound, a diazo coupling

3U5406

component and contains an acidic coupling inhibitor, such as it is well known in the diazography art and, for example, in U.S. Patents 3,203,803, 2,694,010, 3,255,011 and 2,948,613 is described. The coupling component can be any known diazo coupler normally described in Diazo type materials is used. Examples are: 2,3-dihydroxynaphthalene; 1, O-dihydroxynaphthalene; Phloroglucine; Resorcinol; Octylresorcinol; cc-resorcylamide; 3-methyl-1-phenyl-pyrazalone; Acetoacetanilide; N-benzylacetoacetamide; 2,3-dihydroxynaphthalene-6-sulfonic acid; 2,5-xylenol; 6,7-dihydroxy-2-naphthalenesulfonic acid; 2,3-naphthalenediol; m-hydroxyphenylurea; 4,4'-thiodiresorcinol; 3,5-dihydroxybenzoic acid; ß-oxynaphthoic acid nionoethanolamide; and mixtures thereof. The acidic coupling inhibitor can be any of the common and well known inhibitors commonly used in diazo-type materials, e.g. citric acid, tartaric acid, boric acid and the like ..

In addition to the aforementioned materials, reagents commonly used in photoproduction materials can also be used of the diazo type such as reinforcing agents such as ammonium sulfate, zinc chloride or nickel sulfates; Stabilizers such as thiourea or thiosinamine; Accelerator, e.g. B. 1-Allyl-3-ß-hydroxyethylthiourea or 1-allylthiourea; hygroscopic agents, such as glycol or glycerin; and wetting agents, e.g. saponin, lauryl sulfate, kerylbenzenesulfonate or oleyl-N-methyltaurine, can be used.

Finely divided or colloidal silicon dioxide or aluminum oxide and / or aqueous dispersions can also be used or colloidal solutions of organic, film-forming binders, such as colloidal, water-soluble polyvinyl

3U5A06

alcohol, hydroxyethyl cellulose, methyl cellulose, gelatin or the like, or latex-like dispersions of polyvinyl acetate, polyvinyl chloride, polyvinyl chloride acetate, polyvinylidene chloride, Use polyacrylonitrile or polymethyl methacrylate.

To produce a positive-working, diazo-type photosensitive material, the components of previously described sensitization preparation preferred incorporated into a single solution or suspension and applied to the base material through a single coating step or applied to the carrier. The base material can be paper or a film, such as regenerated cellulose, Cellulose acetate butyrate, cellulose acetate propionate, silicon dioxide / polyvinyl butyral, or be a different plastic film; it is particularly preferably a base material which contains a polyethylene terephthalate (polyester) film. Other known substrates such as textile substrates and nonwoven materials, can also be used (see U.S. Patent 3,976,491).

After applying the diazonium triflate, the sensitizing preparation contains, a light-sensitive material of the diazo type is obtained which is one with the Preparation contains sensitized substrate. This sensitized material can then be exposed to light, e.g., ultraviolet Light, decomposing the diazo compound in the unmasked areas, and then the development can take place with the non-decomposed The diazo compound and the coupler react to form a diazo type compound.

The diazonium triflates according to the invention can also in negative-working photo reproduction systems of the diazo type according to Bennett according to US Pat. No. 4,252,884.

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be det. The sensitization preparation for such a thing System contains a diazoniuratriflate in the dual function of the diazonium compound and a light-sensitive, acidic precursor and at least one acid-labile, enolic, preferably phenolic, blocked coupler, which is designed so that it can be converted into an active azo coupling component in the presence of acid is. Preferably the blocked coupler has a structural formula selected from the groups of the following formulas:

γ - ο - C <

-H
I.
YOC-OR;

■ 4

Y-O-C-ORi

Y-O-C-R

Y-O-C-R.

YO-CH ₂ -O- CH ₂ CH ₂ - OCH ₃ ; and Y - 0 - CH ₂ - 0 - CH ₂ CH ₂ - OCH ₃

- O - CH ₂ - O - CH ₂ CH ₂ - OCH ₃

wherein R _1, R _2, R _3, R _4, R _5, R _6, R _7, R _8, R ₁ ^1, R ₂ 'and R _3' which may be the same or different, are selected from alkyl, preferably straight or branched lower alkyl of 1 to 8 carbon atoms; Alkenyl, preferably lower alkenyl with 2 to about 8 carbon atoms, alkynyl, preferably lower alkynyl with 2 to about 8 carbon atoms, aryl, preferably aryl with 6 to about 10 carbon atoms, cycloalkyl, preferably cycloalkyl with 3 to about 8 carbon atoms, aralkyl, alkaryl, aralkenyl and Alkenylaryl, where the alkyl, aryl and alkenyl groups are preferably as defined above; and where R ^ can also mean hydrogen; Y is aryl, for example phenyl, naphthyl, anthryl, phenanthryl and the like; and A is any suitable linking group, for example an alkylene group or a direct chemical bond. In addition, any two or three substituents R can be bonded together to form a tertiary cyclic, bicyclic or heterocyclic structure.

Examples of suitable, acid-labile, phenolic, blocked couplers for the negative-working Bennett system are the following: 1-naphthyl triphenyl methyl ether; 1-methylcyclop enty 1-1 -naphthyl ether; 1-butoxy-1- (1-naphthoxy) ethane; t-butylphenyl ether; 2- (1-naphthoxy) -3-methylbutane; 1- (1-butoxy) -1- (1-naphthoxy) ethane; 1,2-bis (5-t-butoxy-

3U5A06 - ^'::. -.

1-naphthyl) ethane; Dibenzo (d, f) -2,2-dimethyl-1,3-dioxepin; Dibenzo (d, f) -2-methyl-2-phenyl-1,3-dioxepin; Dibenzo (d, f) -2,2-diphenyl-1,3-dioxepin; 2.2 ^! -Di (2-tetrahydropyranoxy) diphenyl; 2,3-isopropylidenedioxynaphthalene; t-butyl-1-naphthyl ether; 1-naphthyl-2-tetrahydropyranyl ether; Benzo (e) -2-phenyl-1,3-dioxin; 1-t-butoxy-5-benzylnaphthalene; t-butyl (4-bromo-i-naphthyl) ether; Dibenzo (d, f) -? - methyl-1,3-dioxepin; ß-methoxyethoxymethyl-a-naphthyl ether; and 3- (methoxyethoxymethoxy) -N- (2-ethy! phenyl) -2-naphthalamide.

The enolic-blocked coupler can be used with any effective diazonium triflate can be avoided. Examples of the particularly preferred compounds are the diazonium triflates listed above. Although the matchmaker and the Diazonium salt ^ molecules with one or more substituents that do not interfere with acid-catalyzed deblocking chemistry, must contain at least two locations on the blocked coupler for some rearrangement and for subsequent coupling of the unblocked molecule «to form an azo dye.

A negative working photoresponsive material according to the invention of the diazo type can conveniently be prepared by first making a solution in pure, organic Solvents the two essential components, i.e. a solution of the diazonium triflate and the blocked Coupler, manufactures. The preferred solvents are generally ketones and low molecular weight alcohols, since these are, for example, typically good solvents for the diazonium triflates. Diazonium triflates however, are extremely soluble in any organic solvent, and hence the choice need not be made Ketones and alcohols are restricted. In practice it was

3H5406

however, it is generally considered advantageous to use a mixture of ketone and alcohol solvents.

The blocked coupler will generally be in the solvent solution dissolved with moderate mechanical stirring, then the diazonium triflate is added and in a similar manner dissolved, although the components can also be added in the reverse order. Additives known per se, such as reinforcing agents, accelerators, hygroscopic agents or wetting agents, can also be used be added to the mass.

A preferred additive is benzotriazole. It was found, that the inclusion of this compound in negative-working diazography preparations both the contrast as well as the sharpness of lines in the images that are formed is improved when benzotriazole is incorporated in an effective amount will. The amount of benzotriazole found to be generally effective is that where the molar ratio of benzotriazole to diazonium salt in the preparation is in the range from about 1:20 to 1: 100.

Although the amounts of the respective components in the Formulation are not particularly critical, it has been found for a negative working Bennett system that incorporation of the diazonium triflate in amounts up to 7 parts by weight / 100 g G. total mixture is particularly suitable, preferred is not less than 0.5 part by weight in the total mixture. The blocked coupler will typically incorporated in a ratio of 0.1 mol / mol diazonium triflate to 2.0 mol / mol diazonium triflate. Preferably contains the mass an amount of about 1.0 blocked coupler / about 1.0 mole diazonium triflate.

The diazonium triflate composition described immediately above is useful or preparation on a suitable base substrate, e.g. cellulose acetate butyrate, cellulose acetate propionate, Ethyl cellulose, silicon dioxide / polyvinyl butyral, applied and preferably on coatings of the previously mentioned materials, which are based on a transparent or opaque polyethylene terephthalate (polyester) film base material are located, whereby the application takes place by impregnation or grain coating. It is preferred that about 30 g of mixture / 0.836 m (square yard) are applied. This consumption varies according to the specific components used, the type and thickness of the polymer, the pre-coating and the desired image density. Preferred the base material used as the underlayer is covered with a layer of cellulose ester, ether or the like. coated or the coating itself can be a similar matrix resin, in addition to the imaging solution Chemicals. A representative film made in accordance with the present invention contains 23.4 to 177 µm (0.92 to 7 mil) bonded, coated polyester base material, which is covered with, for example, 6.25 µm (0.25 mil) matrix resin (e.g., cellulose acetate propionate) with the cover containing the imaging chemicals. Other suitable substrates are common diazo paper stocks, textile substrates, nonwovens, and the like 3 976 491).

Although the imaging components are all in one Can be applied in a single layer, the components can also be present in separate layers be. For example, the diazonium triflate on a polyester coated with matrix are applied, then an insulated or separating layer can be applied, then a second matrix layer can be applied to it.

and then the second layer can be soaked with the blocked coupler.

The resulting diazo-type photosensitive material which comprises a support material with which the diazonium triflate preparation is coated, can then be provided with an image by applying light to it qualitatively and exposed quantitatively sufficiently so that photochemically catalytic amounts of the acid from the diazonium triflate are released after its decomposition. The reaction of the released acid with the blocked couplers gives unblocking and azo active couplers are obtained. The development of the diazo-type materials under alkaline conditions causes coupling of the active Azo coupler with undecomposed diazonium triflate in the areas that are struck by light, with an azo dye is formed. The diazo-type material can then be heated to a temperature before or during development between about 37.8 and 98.9 ° C (100 and 210 ° F).

The background areas of the developed film are then preferably brightened in a neutral environment by making them exposed to total actinic light for a period of about 60 seconds, decomposing any unreacted salts will. Although this last step is not required, it is generally preferred to practice it.

In a further embodiment of the invention can the diazonium triflates as latent polymerization initiators in the polymerization of epoxides, cyclic Ethers such as oxetanes, cyclic esters such as lactones, and / or their mixtures can be used. The procedure comprises the production of a mixture from a material,

which is polymerizable to a material with higher molecular weights and that is a lactone monomer, an oxetane, a monomeric or prepolymeric epoxide or one of them Mixtures and a radiation-sensitive, aromatic Contains diazonium salt, which decomposes when exposed to energy and releases a product which the Polymerization of the material initiated. Such polymerization processes are described in U.S. Patents 3,816,279, 3 816 280, 3 816 281, 2 817 845, 3 817 850, 3 835 003,

3 997 344, 4 054 451, 4 054 452, 4 054 732, 4 056 393,

4,076,536, 4,080,274 and 4,091,194.

Diazonium triflates decompose in a similar way their irradiation, releasing a product which, when in the presence of a cyclic ether or ester monomer, such as oxetanes, epoxides or lactones, there is a cleavage of the carbon-oxygen bond of the ether or ester, whereby the growth of the polymeric chain or the formation of crosslinks is initiated. A theoretical interpretation is that - whereby it should be emphasized that there is only a theoretical interpretation - that at a triflate aryl ester is formed upon decomposition, which then forms a proton, e.g. from the reaction medium extracted from an acid. This acid is then the active agent that breaks the carbon-oxygen bond to initiate the polymerization or crosslinking cleaves, and also the agent which is blocked with the Couplers of the aforementioned negative working diazography system is working. Thus, like the photosensitive aromatic diazonium salts described in the above mentioned patents are mentioned, the diazonium triflates used as latent polymerization initiators will.

3H5406

A general application of the process to the use of diazonium triflates as latent polymerization initiators consists in mixing the diazonium triflates with or without using a suitable solvent, with a polymerizable monomer or one Mixture of the monomers. A suitable, inert solvent is to be understood as meaning a solvent which with the polymerizable material or aryldiazonium compound prior to exposure to actinic radiation does not respond significantly. Examples of such solvents are the dimethyl ether of diethylene glycol, anisole, acetonitrile, Butyronitrile, toluene, acetone, xylene, methyl ethyl ketone, ethyl ether, ether cellosolve, 1,1,2,2-tetrachloroethane-monochlorobenzene, Tetrachloroethane, o-chlorotoluene, ο-dichlorobenzene, trichlorethylene, propylene carbonate and The like .. Mixtures of these solvents can also be used, especially when mixtures of epoxides can be used. It should be emphasized, however, that the use of these solvents is not mandatory.

The amount of the photosensitive compound used in the mixture need not be precisely determined, but it is related to the amount of the monomer to be polymerized. Quite satisfactory results are obtained when a diazonium triflate is used in catalytic amounts, preferably in amounts of from about 0.5 to about 5 percent catalyst precursor based on the weight of the polymerizable material, provided that about 2 percent or less is sufficiently effective with some of the monomer-catalyst precursor systems.

The polymerizable mixture is then applied to a suitable substrate, such as a metal plate, plastic or paper, applied and the substrate is then irradiated with ultraviolet or electron beam radiation. at

3U5406

the irradiation decomposes. Triflate and causes the Initiation of the polymerization of the monomer (s) by the cleavage of the carbon-oxygen bonds.

The source of irradiation for performing the invention The method can be any suitable source such as ultraviolet, actinic radiation, the generated from mercury, xenon or a carbon arc or it can be the light generated by a cathode ray tube. The only limitation that as to the source of radiation that is used is that it has an energy content in the irradiated Must produce film that is sufficient to be polymerizable en system to impart energy at an intensity high enough to prevent the photosensitive from decomposing Connections to achieve. The wavelength (frequency) range of actinic radiation is generally chosen so that there is sufficient absorption of energy so that the desired decomposition occurs.

Such polymerization systems can also be used in systems the images are used. For example, you can use a mixture of monomers with epoxides, which a contains suitable solvent in substantial proportions, apply to a metal plate, if necessary for removal Dry the existing solvent, and the plate is then exposed to ultraviolet light through a mask or exposed a negative. The light initiates the polymerization, which quickly takes place in the exposed image areas progresses. The resulting polymer is in the exposed areas against many or most solvents and chemicals resistant, while the unexposed areas are washed off with suitable solvents can be, leaving an inverse image of the polymer.

3H5406

If necessary, an inert pigment or a filler can be incorporated into the composition containing the diazonium triflate and the polymerizable material, which may even be present in larger proportions by weight, or small amounts of inert, non-volatile liquids such as mineral oil can be incorporated . The incorporation of such inert ingredients makes it desirable that there be a proportional increase in the optimal amount of catalyst precursor used. Even so, the precursors hardly need to exceed 5% of the total weight of the composition.

It can furthermore be preferred to use stabilizers or gel formation inhibitors incorporated into the mixture of monomers and catalysts. Suitable compounds for such purposes can be sulfoxides, such as methyl sulfoxide, propyl sulfoxide, the 1-oxide of tetrahydrothiophene and the like. U.S. Patent 3,711,391; organic amides and ureas, such as N, N-dimethylacetamide and 1,1,3,3-tetramethyl urea U.S. Patent No. 3,711,390; cyclic amides, such as 1-methyl-2-pyrrolidinone, poly- (1-vinyl-2-pyrrolidinone) and the like in U.S. Patent 3,721,617; and organic nitriles such as acetonitrile disclosed in US Pat. No. 3,721,616. Will, As described in these patents, if inhibitors are used, they should be used in amounts which vary from about 0.5 to 5 percent by weight of polymerizable material present in the bulk, with an amount of Inhibitor of less than about 1% by weight, based on the polymerizable material, is generally sufficient.

The following examples illustrate the invention.

3U5406

example

In this example, the preparation of the diazonium triflate, i.e. 4- (p-tolylthio) -2,5-dimethoxybenzenediazonium trifluoromethylsulfonate, explained. The corresponding equation for the reaction is as follows:

H.

+ F ₃ CSO ₃ H

OCH.

1/2 ZnCl ₂ -Cl

+ HCl +

OCH.

N ₂ OSO ₂ CF ₃

41.3 g of 4- (p-tolylthio) -2,5-dimethoxybenzoldiazonium zinc chloride double salt and 400 ml of water are placed in an 800 ml beaker. The resulting mixture is stirred and ^{heated to 65 °} C. for 30 minutes; a cloudy solution is obtained which contains solids suspended therein. The solution is cleared of the insoluble materials and the filtrate is cooled to about 50 to 55 ° C.

15 g of trifluoromethylsulfonic acid are added dropwise; a yellow, voluminous precipitate forms. The slurry is ^{cooled to about 10 °} C. and filtered; a yellow precipitate is obtained. The solids obtained are then washed with a small amount of water and dried by suction. 33.0 g of product are obtained.

400 ml of water are added to the above insoluble substances obtained at the beginning. The solution is heated to 65 ° C. and then separated from the insolubles as described above. 5.0 g of trifluoromethylsulfonic acid are added to the clarified solution; a yellow precipitate is obtained. The yellow solid is recovered as described above; 7.2 g of purified product are obtained, melting point 106 to 108 ^° C.

Example 2

30.5 g of 3-chloro-4-N-pyrrolidinobenzoldiazonium-zirikchloridsalz are placed in a 500 ml beaker. Water is added with stirring until the diazo salt has completely dissolved. The temperature of the resulting solution is about 35 to 40 ^° C., a total of about 300 ml of water having been added. Two filter aid spatulas and one Nuchar spatula are added to the cloudy mixed solution. The slurry is then clarified by filtration; a clear, light orange solution is obtained.

The orange solution is cooled to about 20 ° C and 15.0 g of trifluoromethyl sulfonic acid are added at such a rate that a temperature is maintained of 20 ⁰ C. The first drop of acid already causes turbidity and precipitation increases during the addition. After the addition is complete, the resulting slurry is ^{stirred for 15 min at a temperature of about 10 to 15 °} C. and then filtered; a yellow-green precipitate is obtained.

The yellow-green solids are washed with a small amount of water and dried by suction. the Solids are also dried over P ^ O, - overnight. 18.5 g of diazonium triflate product are formed.

3U5A06

example

Example 3 shows the production of various diazonium triflates explained according to the following extraction scheme.

1.0 mol of the corresponding diazozinc salt is placed in a beaker equipped with a magnetic stirrer. the Moles of added diazozinc salt are 1: 1 (expressed by volume) methylene chloride: water solution containing 13% of the salt. The solution is in the beaker stirred and 1.05 mol of trifluoromethylsulfonic acid are added dropwise from a dropping funnel. The solution is stirred for about 5 minutes. An amount of salt that is 80% of a saturated, aqueous saline solution is then added to the beaker and stirring is continued until the added salt has dissolved (approx. 15 min). The contents of the beaker are then placed in a separatory funnel and it separates into two layers. The organic layer is collected in an Erlenmeyer flask. The organic Layer is dried over sodium sulfate and diluted to three times its volume with hexane. the The resulting solution is stirred vigorously and cooled, and then it is filtered off by suction, whereby the diazonium triflate solid is removed wins. The solid is protected from light while washing with hexane, and then it is dried or filtered in a vacuum.

In experiment 1, 3-methyl-4- (N-diethylamino) benzene diazonium zinc salt is used reacted with trifluoromethylsulfonic acid according to the method described above. You get 3-methyl-4- (N-diethylamino) benzene diazonium triflate with a melting point of 90 to 93 ° C. in a yield of 52%.

In experiment 2, a 2,5-diethoxy-4- (p-tolylthio) benzene diazonium zinc salt is reacted with trifluoromethylsulfonic acid. Is obtained 2,5-diethoxy-4- (p-tolylthio) -benzoldiazoniumtriflat of mp. 101-104 ⁰ C in a yield of 85%.

In experiment 3, a 3-methyl-4-N-pyrrolidinobenzene diazonium zinc salt is reacted according to the method described above. 3-Methyl-4-N-pyrrolidinobenzene diazonium triflate with a melting point of 119 ° to 122 ° C. is obtained in a yield of 61 %.

In experiment 4, a 3-chloro-4-N-pyrrolidinöbenzoldiazonium zinc salt is used reacted with trifluoromethylsulfonic acid according to the method described above. You get 3-chloro-4-N-pyrrolidinobenzene diazonium triflate with a Mp. From 90 to 93 ° C in a yield of 63%.

Example 4

In Example 4, the preparation of a positive working photosensitive system of the diazo type and their Use in the manufacture of a diazo-type photosensitive material is illustrated. A solution from 2,2'-dihydroxybiphenyl 1.18g

4- (p-Tolylthio) -2,5-diethoxybenzoldiazonium-

trifluoromethyl sulfonate 1.84 g

Methyl alcohol acetone

Methyl cellosolve 5-sulfosalicylic acid zinc chloride
Eastman CAP 482.20

is made using a clear varnish with a viscosity of about 800 cP. receives. The paint comes with a suitable coating device on a

55 cnr 40 cnr 5 cnr 0, 25 g 0, 5 g 12, 35 g

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101.6 µm (4 mil) pre-bonded polyester backing is applied and dried for 3.5 min at 75 to 80 ° C. The coated material is covered with a printed sheet and exposed to an ultraviolet light source from 400 to 420 nm. The exposed material is without passed the original through a standard diazo processor; an orange-yellow image reproduction is obtained of the original.

Example 5

The procedure of Example 4 is repeated except that 4-N-pyrrolidino-3-chlorobenzene diazonium trifluoromethylsulfonate is used as diazonium triflate. During exposure and development of the photosensitive Material a sepia picture reproduction of the original is obtained.

Example 6

In Example 6, the preparation of a negative working photosensitive system of the diazo type and their Use in the manufacture of a diazo-type photosensitive material is illustrated. A solution from

4- (p-Tolylthio) -2,5-dimethoxybenzenediazonium trifluoromethylsulfonate 4.30 g

t-butyl naphthyl ether 2.00 g

Acetone 50 cnr

is applied to a suitably precoated polyester base material using a suitable coating unit and ^{dried at 75 to 80 °} C. for 3 * 5 min. The coated base material is exposed through a printed sheet, heated for 15 seconds on a SCOTT 24 preheater and developed by passing it through a Model 6000 dry developer. Subsequently, unused diazo compound is removed from the background during

- 60 -

Brightened for 60 sec in a SCOTT 716 microscope. Man receives a red-purple image with transparent images that correspond to the image of the original original. That is, the type of image was reversed.

Example 7

Using an appropriate 4-N-phenylamino-2-methoxybenzenediazonium zinc chloride salt in the general procedure of Example 1 or 2, 4-N-phenylamino-2-methoxybenzenediazonium trifluoromethylsulfonate is obtained, M.p. 105-107 ° C.

End of description.

Claims (40)

3Ί45Α06. - ■ - - -: ρ KRAUS & WEIS-ERT "* Ii PATENT LAWYERS DR. WALTER KRAUS DIPLOMA CHEMIST DR.-ING. ANNEKÄTE WEISERT DIPL.-ING. SPECIALIZATION CHEMISTRY IRMGARDSTRASSE 15 D-8OOO MUNICH 71 TELEPHONE 089 / 797077-797078 - TELEX 05-212156 kpatd TELEGRAM CRAUS PATENT 3111 JAMES RIVER-GRAPHICS, Inc. South Hadley, USA Diazonium sulfonates and their uses Claims \ 1.) Diazonium trifluoromethanesulfonate of the structural formula ^v - ~ ~ "ii ~ 3
0 wherein (B) -N = N- denotes the cation of an organic diazonium compound. 2. Compound according to claim 1, characterized in that that (Ö) a substituted or unsubstituted phenyl, Naphthyl, anthryl, phenanthryl or azaheterocyclic, aromatic group. 3. A compound according to claim 2, characterized in that Q th a substituted phenyl, naphthyl, anthryl or phenanthryl ^ with one or more Substituen- Λ, which may be the same or different and \ _ 2 - Alkyl, alkylamino, dialkylamino, arylamino, aralkylamines, Phenoxy, phenyl, phenylthioether, morpholine », piperidino, May be pyrrolidino, hexamethyleneimino, halogen, alkoxy, cycloalkyl or piperazino. 4. Compound according to claim 2, characterized in that that (E £ means a heterocyclic pyridyl group. 5. A compound according to claim 1, namely p-N-diethylaminobenzenediazonium trifluoromethylsulf onat; 3-ChloΓ-4-N-diethylaminobenzoldiazonium trifluoromethylsulfonate; o-chlorobenzene diazonium trifluoromethylsulfonate; 4_N_Diäthylamino-2-ethoxybenzoldiazonium trifluoromethylsulfonate; 4-N-diethylamino-2-methyrbenzenediazonium trifluoromethylsulf onat; p-N-dimethylnininobenzene disazonium-trifluoromethylsulf onat; 2,5-diisopropoxy-4-morpholinobenzoldiazonium trif luoromethyl sulfonate; 4- (2,6-dimethylmorpholino) benzene diazonium trifluoromethyl sulfonate; ο-methoxybenzenediazonium trifluoromethylsulfonate; 3-chloro-4-N-pyrrolidinobenzene diazonium trifluoromethylsulf onat; 3-methyl-4-N-pyrrolidinobenzenediazonium trifluoromethylsulf onat, · 3-methoxy-4-N-pyrrolidinobenzenediazonium trifluoromethylsulfonate; 5-methoxy-2-N-pyrrolidinobenzenediazonium trifluoromethylsulfonate; 2,4-dimethoxybenzoidiazonium trifluoromethyl sulf onat; 3H5406 · ■ 2,5-diethoxy-4- (4'-chlorophenoxy) benzene diazonium trifluoromethyl sulfonate; 4-benzyloxybenzenediazonium trifluoromethylsulfonate; 2,5-diethoxy-4-N- "benzaraidobenzoldiazonium trifluoromethylsulfonate; 2-methoxy-5-methyl-4-N- "benzainidobenzenediazoniuin trifluoromethylsulfonate; p-Ethoxybenzoldiazoniuin-trifluoromethylsulfonate; 4-chloronaphthalenediazonium trifluoromethylsulfonate; 4-pyrrolidinonaphthalenediazonium trifluoromethylsulf onat; p-chlorobenzene diazonium trifluoromethylsulfonate; 6-morpholino-3-pyridinediazonium trifluoromethyl sulf onat; 6-dimethylamino-3-pyridinediazonium trifluoromethyl sulf onat; 4-N-dimethylamino-3-pyridinediazonium trifluoromethyl sulf onat; 4-N-methoxycarbonylamino-2,5-dimethoxybenzenediazonium trifluoromethylsulfonate; 4-N-acetylamino-2,5-dimethoxybenzenedazonium trifluoromethylsulfonate; 4-N-methylsulfonylamino-2,5-dimethoxybenzenediazonium trifluoromethylsulfonate; 4-N-phenylamino-2-methoxybenzenediazonium trifluoromethylsulfonate; 4-N-phenylaminobenzenediazonium trifluoromethylsulf onat; 4-N-phenylamino-2-trifluoromethylbenzenediazonium'-trifluoromethylsulfonate; 4-N-phenylamino-3-trifluoromethyrbenzenediazonium trifluoromethylsulfonate; 4-N-phenylamino-3-chlorobenzene diazonium trifluoromethyl sulf onat; 4-N-benzoylamino-2,5-dimethoxybenzenediazonium trifluoromethylsulfonate; 4-N-Benzoylamino-3-chlorobenzene diazonium trifluoromethyl sulf onat; 4-N-Benzoylamino-3-πlethoxybenzoldiazoni ^ 1m-trifluoromethylsulfonate; 4-N-Benzoylamino-2-chloro-5-niethoxy'benzoidiazonium-trif luoromethyl sulfonate; 4-N-acetylamino-2,5-diethoxybenzenediazonium trifluoromethylsulfonate; 4- (p-tolylthio) -2,5-diethoxybenzenediazonium trifluoromethylsulfonate; 4- (p-Tolylthio) -3-N-acetylaminobenzene diazonium trifluoromethylsulfonate; Carbazol-2-diazonium trifluoromethylsulfonate; 4-N-ethyl-N-hydroxyethylaminobenzene diazonium trifluoromethylsulfonate; 4-N-azacycloheptane-2,5-diethoxybenzenediazonium trifluoromethylsulfonate; 4-methyl-2-nitrobenzenediazonium trifluoromethylsulf onat; ρ-nitrobenzenediazonium trifluoromethylsulfonate; 4_N_Dimethylamino-3-chlorobenzene diazonium trifluoromethylsulfonate; 4- (p-tolylthio) -2,5-dimethoxybenzenediazonium trifluoromethylsulfonate; 4-N-diethylamino-3-methylbenzenediazonium trifluoromethylsulfonate; 4- (3,5-dimethylmorpholino) benzene diazonium trifluoromethyl sulfonate; 4-N-methanesulfonamido-2,5-dimethoxybenzenediazonium trifluoromethylsulfonate; p-N-methylcyclohexylamino-3-chlorobenzene diazonium trifluoromethylsulfonate; 4- (p-Tolylthio) ^ - chlorobenzene diazonium trifluoromethylsulf onat; 4- (p-Tolylthio) -3-methoxybenzenediazonium trifluoromethylsulfonate; 2,5 ~ diethoxy-4- (phenylthio) -benzenediazonium trifluoromethylsulfonate; 2,! ^ - dimethoxy ^ -morpholinobenzene diazonium trifluoromethylsulfonate; 4-N-morpholino-2,5-diethoxybenzenediazonium trifluoromethylsulfonate; 4-N-hexamethyleneiminobenzene diazonium trifluoromethylsulf onat; 4-N ~ morpholino-5-methoxy-2- (p-tolylthio) benzene diazonium trifluoromethyl sulfonate; 4-N-piperidino-5-methoxy-2-phenoxybenzenediazonium trifluoromethylsulfonate; 4-N-Morpholino-3-methoxybenzenediazonium trifluoromethylsulf onat; or 4-N-Benzoylpiperidino-2,5-diisopropoxybenzenediazonium trifluoromethylsulfonate. 6. A compound according to claim 1, namely 4- (p-tolylthio) -2,5-diethoxybenzenediazonium trifluoromethylsulfonate; 4- (p-Tolylthio) -3-methoxybenzenediazonium trifluoromethylsulfonate; 4- (p-tolylthio) -2,5-dimethoxybenzenediazonium trifluoromethylsulfonate; or 2,5-diethoxy-4- (phenylthio) benzene diazonium trifluoromethyl sulfonate. 7 · Connection according to claim 1, namely 2, S-diisopropoxy ^ -morpholinobenzene diazonium trifluoromethylsulfonate; 3H5406-: 2, S-dimethoxy ^ -N-morpholinobenzene diazonium trifluoromethylsulfonate; or 4-N-Morpholino-2,5-diethoxybenzenediazonium trifluoromethylsulfonate. 8. A compound according to claim 1, namely ^ N-Morpholino-S-methoxy-Z- (p-tolylthio) -benzene- diazonium trifluoromethyl sulfonate; 4-N-Morpholino-3-methoxybenzenediazonium trifluoromethylsulf onat; or 4- (2,6-Dimethylmorpholino) benzene diazonium trifluoromethyl sulfonate. 9. A compound according to claim 1, namely 3-chloro-4-N-pyrrolidinobenzo! Diazonium trifluoromethyl sulf onat; 3-methyl-4-N-pyrrolidinobenzo! Diazonium trifluoromethyl sulf onat; or 3-methoxy-4-N-pyrrolidinobenzo! Diazonium trifluoromethyl sulfonate. 10. A compound according to claim 1, namely 4-N-hexamethyleneiminobenzene diazonium trifluoromethylsulf onat; or 4-N-Azacycloheptane-2,5-diethoxybenzenediazonium trifluoromethylsulfonate. 11. A compound according to claim 1, namely 4-N-Benzoylpiperidino-2,5-diisopropoxybenzene- diazonium trifluoromethyl sulfonate; or 4-N-piperidino-5-methoxy-2-phenoxybenzenediazonium trifluoromethylsulfonate. 3H5406 12. The compound of claim 1, namely 2,4-dimethoxybenzoidiazonium trifluoromethylsulfonate. 13. A compound according to claim 1, namely 2,5-diethoxy-4-N-benzamidobenzene diazonium trif luorme thylsulfonate. 14. Photosensitive preparation for diazography, characterized in that it (1) a diazonium trifluoromethanesulfonate, as defined in claim 1, (2) a diazo coupling component and (3) one contains acidic coupling inhibitor. 15. Diazography preparation according to claim 14, characterized in that ^ B) of the diazonium trifluoromethanesulfonate is a substituted phenyl, naphthyl, anthryl or phenanthryl group, the one or contains several substituents, which can be the same or different, and which are selected from Alkyl, alkylamino, dialkylamino, arylamino, aralkylamines, Phenoxy, phenyl, phenylthioether, morpholino, piperidino, Pyrrolidino, hexamethyleneimines, halogen, alkoxy, cycloalkyl or piperazino. 16. Diazography preparation according to claim 14, characterized in that (B) ^{1 of} the diazonium trifluoromethanesulfonate is an azaheterocyclic, aromatic group. 17. Diazo-type photosensitive material, thereby characterized in that it contains a carrier material, which with a preparation for diazography, such as it was defined in one of claims 14, 15 or 16, is sensitized. 18. Photosensitive preparation for diazography, characterized in that it (1) at least a photosensitive diazonium trifluoromethanesulfonate as defined in claim 1 and (2) at least one acidic, labile, enolic, blocked coupler, which coupler is adapted to be in the presence is bound by acid to active azo coupling species. 19. Photosensitive preparation for diazography according to claim 18, characterized in that (δ) of the diazonium trifluoromethanesulfonate a substituted or unsubstituted phenyl, naphthyl, anthryl, phenanthryl or azaheterocyclic aromatic group. 20. Photosensitive preparation for diazography according to claim 18, characterized in that® of the diazonium trifluoromethanesulfonate with a substituted phenyl, naphthyl, anthryl or phenanthryl group one or more substituents that are the same or different can be, means, where the substituents are selected from alkyl, alkylamino, dialkylamino, Arylamino, aralkylamines, phenoxy, phenyl, phenylthioether, Morpholino, piperidino, pyrrolidino, hexamethyleneimines, Halogen, alkoxy, cycloalkyl or piperazines ». 21. Photosensitive preparation for diazography according to claim 18, characterized in that the acidic, labile, blocked coupler has the structural formula YOCR ₂ ^XR 3 3U5A06 wherein each of the substituents R, which can be the same or different, is an alkyl, alkenyl, alkynyl, Aryl, cycloalkyl, cycloalkenyl, aralkyl, alkaryl, aralkenyl or alkenylaryl group and Y is Aryl stands. 22. Preparation for diazography according to claim 18, characterized in that the acidic, labile, blocked Coupler the structural formula H
YOC- OR ₄ «5 has, wherein R ^ and R ^, the same or different can be an alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, aralkyl, alkaryl, aralkenyl or alkenylaryl group, where R, - can also mean hydrogen, and Y stands for aryl. 23. Preparation for diazography according to claim 18, characterized in that the acidic, labile, blocked Coupler the structural formula . «6 YOC- 0R _A i ο «7 wherein Rg, Ry and Rg, which are the same or different can be an alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, aralkyl, alkaryl, aralkenyl or alkenylaryl group and Y is aryl. 24. Preparation for diazography according to claim 18, characterized in that the acidic, labile, blocked Coupler the structural formula 3U5406: comprising: Y-O-C-R, YOCR ₉ '\ where R ₁ ·, R ₂ 'and R,' and ^R 3 'where R ₁ , R ₂ and R ,, which can be the same or different, are each an alkyl, alkenyl, alkynyl, aryl, cycloalkyl, Cycloalkenyl, aralkyl, alkaryl, aralkenyl or alkenylaryl group, Y stands for aryl and A stands for any connecting group. 25. Preparation for diazography according to claim 18, characterized in that the acidic, labile, blocked Coupler the structural formula Y - O - CH ₂ - O - CH ₂ CH ₂ - OCH ₃ , wherein Y is an aryl group. 26. Preparation for diazography according to claim 18, characterized in that the acidic, labile, blocked Coupler the structural formula Y - 0 - CH ₂ - 0 - CH ₂ CH ₂ A YO _{- CH 2} - 0 - CH ₂ CH ₂ - ₃ wherein Y is an aryl group and A is any linking group. 27. Preparation for diazography according to claim 18, characterized in that the acidic, labile, phenolic 3H5A06 blocked couplers 1-naphthyl triphenylmethyl ether; 1-methylcyclopentyl-I-naphthyl ether; 1-butoxy-1- (1-naphthoxy) ethane; t-butylphenyl ether; 2- (i-naphthoxy) -3-methylbutane; 1- (1-butoxy) -1- (i-naphthoxy) ethane; 1,2-bis (5-tert-butoxy-1-naphthyl) ethane; Dibenzo (d, f) -2,2-dimethyl-1,3-dioxepin; Dibenzo (d, f) -2-methyl-2-phenyl-1,3-dioxepin; Dibenzo (d, f) -2,2-diphenyl-1,3-dioxepin; 2,2'-di (2-tetrahydropyranoxy) diphenyl; 2,3-isopropylidenedioxynaphthalene; tert-butyl-1-naphthyl ether; 1-naphthyl-2-tetrahydropyranyl ether; Benzo (e) -2-phenyl-1,3-dioxin; 1-tert-butoxy-5-benzylnaphthalene; tert-butyl (4-bromo-1-naphthyl) ether; Dibenzo (d, f) -2-methyl-1,3-dioxepin; ß-methoxyethoxymethyl naphthyl ether; or 3- (methoxyethoxymethoxy) -N- (2-ethylphenyl) -2-naphthalamide is. 28. Photosensitive photo reproduction material of the diazo type, characterized in that it is a carrier material contains, which is sensitized with a diazography preparation according to any one of claims 18 to 27. 29. Material of the diazo type according to claim 28, characterized in that the carrier material is a film substrate is. 30. Photopolymerizable composition, characterized in that it (1) a material which is photopolymerizable to a higher molecular weight compound, wherein the material is a lactone monomer, a monomeric or a prepolymer Epoxy, an oxetane, or a mixture thereof, and (2) an effective catalytic amount of a diazonium trifluoromethanesulfonate as defined in claim 1, to initiate the polymerization of the photopoly- - Contains 12 merisable material during its irradiation. 31. Composition according to claim 30, characterized in that that the photopolymerizable material contains an oxetane. 32. Composition according to claim 30, characterized in that the photopolymerizable material is a lactone monomer and contains a monomeric or prepolymeric epoxy. 33. A method of polymerizing a polymerizable material which is a lactone monomer, a monomeric or prepolymeric epoxide, oxetane or a mixture thereof, characterized in that a mixture of the material and a radiation-sensitive diazonium trifluoromethanesulfonate as defined in claim 1 was produced and then the resulting mixture was irradiated quantitatively and qualitatively sufficiently, to decompose the diazonium trifluoromethanesulfonate and to form a product that initiates the polymerization of the material. 34. The method according to claim 33, characterized in that the photopolymerizable material contains oxetane. 35. The method according to claim 33, characterized in that the photopolymerizable material is a lactone monomer and contains a monomeric or prepolymeric epoxy. 36. Positive working diazo photography photo reproduction process, characterized in that the diazo-type material defined in claim 17 is imagewise irradiated with light, the light being sufficient qualitatively and quantitatively to convert the diazonium trifluoromethanesulfonate into to decompose the exposed areas photochemically, and then the material of the diazo type in alkaline conditions 3U5A06 conditions developed so that between the azo coupling component and the undecomposed diazonium trifluoromethanesulfonate undergoes coupling. 37. Negative Diazography Photo Reproduction Process, characterized in that the material of the diazo type as defined in claim 28, Sometimes with light qualitatively and quantitatively sufficient exposed, so that photochemically catalytic amounts of acid are released from it and thus the coupler molecules deblocked, and the diazo-type material in alkaline Conditions developed so that the active azo coupling species with the undecomposed diazonium trifluoromethanesulfonate in the areas struck by light couple to form an azo dye. 38. The method of claim 37, characterized in that the material of the diazo type is heated before or during processing to a temperature between about 37.8 and about 98.9 ⁰ C (100 and 210 ⁰ F). 39. The method according to claim 37, characterized in that the developed material of the diazo type is additionally is brightened. 40. Photo reproduction process, characterized in that one has a carrier with the mass, as in Claim 30 has been defined, is coated, exposed imagewise with light qualitatively and quantitatively sufficiently, around a lot of diazonium trifluoromethanesulfonate to photochemically decompose, which is sufficient to the polymerization of the polymerizable material in the with light to initiate the surfaces hit, and then the exposure th. Carrier washes with a solvent to remove the unpolymerized Remove material in the unexposed areas, leaving a reverse image of the polymer in the exposed areas remains.