DE2360350A1 - PROCESS FOR THE PHOTOPOLYMERIZATION OF ETHYLENIC UNSATURED COMPOUNDS - Google Patents

Description

Case 8-8542 / TEL 127 + ■ - D R. B E R G D I P L. - IN G. STAPF

^ a & e ο ö3 ^ z / i £, L · La ι f DlPL-ING. SCHWAB CP. pp. CAHDf.'AIR

_ -. ui j β HONCHEN (30 · MAUERK1RCHEBSTR.45

Germany

Attorney's File 24,500. December 4, 1973

Ethylic photopolymerization process unsaturated compounds *

When photopolymerization is the polymerization process stimulated or initiated by radiation, e.g. in the range of ultraviolet or visible waves. According to the present. Invention can now in an advantageous manner with ethylenically unsaturated compounds Polymerized with the help of a new catalyst system, the system consists of a diazine compound, preferably a quinoxaline, and an electron donor. which act together as a photoredox couple.

409823/1172

In the present process for the photopolymerization of ethylenically unsaturated compounds using at least of a photoredox pair is a redox pair on the one hand a diazine compound with the ring system of the formula

(D

wherein Z is a nitrogen atom or a hydrogen atom or signifies a substituent bonded carbon atom, this diazine compound can also be quaternized and, on the other hand, uses an electron donor. The ones used for photopolymerization applied radiation is in the range from 200 to 450 nm.

r -for the present method suitable non-quaternary diazo bonds are known in. large numbers. These are, for example, quinoxalines, pyrazines or phenazines, including benzophenazines. They can be produced by known methods. Cf., on this ACE Simpson, Condensed Pyridazine and Pyrazine Rings in A. Weissberger, The Chemistry of Heterocyclic Compounds J. Wiley & Sons, New York (1953); '. ·, \

6.A. Swan & DG Felton ^ Phenazines, in A. Weissberger, ibid, 1 (1957); YT Pratt in RC TSlderfield, Heterocyclic Cojnpounds, J. Wiley & Sons, New York 1957, Vol. 6, page 377 ff; ) DE Pearson, ibid. Page 624 ff; JP Horwitz, ibid. 1961, Vol. 7, page 720 ff.) 4Q9823 / 1 1 72 ^ - ^

■ - 3 -

23SD35Ö

In the present processes, diazine compounds of the formulas (2) Ms (13) are preferably used:

It

J k J ■ ι

i E ■ ι I. ■ 1

■ 41

Marg

^U l Nl.

1 R ₂₁

51

n-1

^V 33

«43

U ₉ ^R 22

44

^U 2 ^R 23

409823/1172

R,

(10)

R,

Rc

(12)

^R 32

33

(13) R,

NO

■ Χ

NO.

53

A09823 / 1

When the compounds of the above formulas (2) to (8) are quaternary (n = 2, U = N — Y, see below) can each give two possible isomers of the cation, e.g.

(14.1) 1 l®) ^and p

CH).

In the formulas, the individual symbols have the same meaning throughout, and they mean the following:

η - one of the numbers 1 and 2, Z ₁ - a nitrogen atom or a group C

J- ι

T)

(Rc see below), 5.,

U, U - one U is a nitrogen atom and the other U, if η = 1, also a nitrogen atom, and when η = 2, a group of the composition

N =

Y - an optionally further substituted alkyl radical, U- ,, U, - a U, a nitrogen atom and the other U,, if η = 1, also a nitrogen atom,

409823/1172

and when η is -Z , a

CH,

Group,

- one U _{2 is} a nitrogen atom and the other U _{2 is} one

CHv

Group,

independently of one another, a hydrogen atom, a optionally further substituted alkyl, alkoxy, aroyl, aryloxy or aralkoxy radical (as substituents on alkyl groups there are e.g. halogen atoms, acylamino, acyloxy, hydroxyl, alkoxy, alkylsulfuryl, Alkylthionyl, cyano, carboxymurealkyl 'ester, carboxamide groups and as substituents on aryl residues, preferably benzene residues, methyl groups, Halogen atoms such as chlorine, methoxy groups, acylamino, acyloxy, hydroxyl, trialkylsilyl, Carboxylic acid alkyl ester, carboxamide, alkylsulfuryl-alkylthionyl, Arylsulfuryl, arylsulfonyl, cyano and sulfonic acid groups); or R, and together with two carbon atoms of ring I. a heterocyclic or isocyanic ring (e.g. one of the formulas

409823 / 11'7 2

- a not further substituted or further substituted (see above, R ₁ , ^) benzene radical, a benzoyl group, an optionally further substituted methyl group or a hydrogen atom; or Rj ₁ and ^ ₁ together with two carbon atoms of the ring I form a five- to six-membered heterocyclic or isocyclic ring

R-2 »R99 - a phenyl group, a benzoyl radical, a phenylsulfonic acid group, a hydroxymethyl group or a hydrogen atom

^R 13 '^ 3 ~ both a phenyl group or both a methyl group,

Ro, R /, Rc - independently of each other, a hydrogen atom, an optionally further substituted alkyl, alkoxy, aryloxy, or aralkpxy radical (concerning substituents see above, R ,, Ro)> a halogen atom, a nitro group, a cyano group, a hydroxyl group, a given

A09823 / 1 172

- ■ .- ■ 9 - ■ -

if further substituted amino group (e.g. acylamino group, mono- or dialkylamino group), an alkylammonium group, carboxylic acid group, carboxamide group, carboxylic acid alkyl ester group or sulfonic acid group * or two of R ₀ , R # and Rc together with two adjacent carbon atoms of the ring II an isocyclic, heterocyclic ring

R'o> R '/, R'c any of these three symbols has any of the for Ro, R /, Rc given meanings, the second means a hydrogen atom, a halogen atom, a Amino group, an alkyl or an alkoxy group and the third is a hydrogen atom or an alkoxy group, or two of these symbols are members of a ring of the specified composition and that third means a hydrogen atom or an alkoxy group.

An analogous choice of the substituents R.oi » ^R 4l» ^R 51

is also with the diazo compounds of the formulas (4 ^ to (9) etc. preferred,

Ro j, R / -t , Rc-, - a hydrogen atom, a lower alkyl group, - _ - a lower alkoxy group, a chlorine atom, a nitro group, a primary amino group,

0 9-8 23/1 172

an acylamino group (such as acetyl, propionyl, benzoyl), a trimethylammonium group, a. Carboxamide group optionally further substituted with one to two lower alkyl groups, a carboxylic acid *, carboxylic acid methyl ester or carboxylic acid ethyl ester or sulfonic acid group, or two of R ,,, R, ~ and R ₁ ... together with two adjacent carbon atoms of ring II an isocyclic or heterocyclic ring (lower alkyl groups are those with a maximum of 4 carbon atoms),

4252 hydrogen atom, a methyl, methoxy,

Ethoxy, nitro, amino, acetylamino, trimethylammonium or sulfonic acid group or two of Roo »Ra ^ ^unt ^ ^ o ^{together 111} ^ t two adjacent carbon atoms of the ring II an isocyclic or heterocyclic ring,

R, 3 »Rco - a hydrogen atom, a methyl, methoxy,

Ethoxy, nitro, amino, trimethylammonium or sulfonic acid group or two of L ", R, ο and R" together with two neighboring carbon atoms of the ring II a dioxole, dioxane or pyridine ring

409823/1172

R ₃₄ , R ₄₄ , Rc ₄ - a hydrogen atom, a methyl group or

Methoxy group e ^
X - an anion,

X-. ^ - one of the anions Cl ^, I ^, ClO, ^,

CH ₃ SO ₄ ^Θ , FSO ₃ ^Θ , BF ₄ ®, PF ₆ ® and g X ₂ - one of the anions I ", ClO .; and CHoSO, ^,

Compounds which contain sulfonic acid groups or carboxylic acid groups can be present not only in the form of their free acids, ie with HOOG or HO ₃ S groups, but also as salts. Depending on the conditions of the deposition, for example the selected PjT value or the cation which the salt used for deposition has, the acid _{groups can be present as —SO 3} or —COO cation groups, such as, for example, —SO — Na , -SO ₃ K, COONa, -COOLi, -COONH _4. Thus, apart from the free acids, they are preferably salts of the alkaline earth or, in particular, of the alkali group. In this sense, the terms "carboxylic acid" and "sulfonic acid" are included to understand.

Please also refer to the following publications: where diazine compounds of the composition specified above and processes for their production are described:

DT-OS 2 144 297 (gases 8-TEL 93 / E)

DT-OS 2 144 298 (Case 8-TEL 92 / E)

DT-OS 2 OlO 280 (gases 8-TEL 64 / E.

409823/1172

: As examples of the anions (X ^) are mentioned: Br "", Cl ~, Ι ^Ό , ClO ₄ , CH ₃ SO ₄ , BF ₄ FSO ₃ ^Θ , AlCl ₄ ^θ , FeCl ₄ ^Θ , PFg ^Θ , SbCIg ^Θ ,. _u . p-toluenesulfonate ", p-chlorobenzenesulfonate", oxalate ", SCN ^Θ , acetate ^Θ ,. HSO ₄ ^, AuCl ₄ ^Θ , SnCl ₄ ^{Θ 2} , ZnCl ₄ ^, AsFg ®, AsCIg ®

In general, water-soluble diazine compounds are preferred, especially those with water solubility of at least 0.05% (g diazine in 100 g aqueous solution) at 20 ° C.

Such water-soluble diazines are, for example, the phenylsulfonic acid quinoxalines the formula

^R 5

which can be prepared by treating the corresponding compound free of sulfonic acid groups at low temperature with chlorosulfonic acid and saponifying the sulfonic acid chloride thus obtainable. This gives a mixture of 2-phenylquinoxaline-3 ¹ - and -4 ¹ -sulfonic acids, which if desired '^; broken down into its components or used as such for photopolymerization according to the invention.

409823/1172

The quaternary quinoxaline compounds are also new, e.g. those of the formulas (15) to (18), which also form an object of the present invention:

A.

(15)

Quinoxalinium salts of the formula

Il

R '

Il

wherein R "and R""are hydrogen atoms, alkyl or aryl radicals optionally substituted with halogen atoms, alkyl, hydroxyl, alkoxy, nitro, amino, cyano, carboxylic acid, carboalkoxy or carboxamide groups, R" o, R "^ and R" ₅ > independently of one another, hydrogen atoms, halogen atoms, alkyl, alkoxy or nitro groups, where at least one of the R "~». R ", and R" c is different from hydrogen and R ", and R", or R "and Rr can also together form the addition to a heterocyclic ring fused to the six-membered ring I, and X is an anion.

«0 9 823/1172

(16)

Quinoxalinium salts of the formula

R " ₅ CH ₃

where R '^, r >>_2> r "_3>r" ^, r >> ₅ and X have the meaning given.

(17)

Quinoxalinium salts of the formula

wherein K- ¹¹ OJ R "a and R" _{5 have} the meaning given,

R ".., and R ¹¹ Oi are hydrogen atoms, methyl groups, acetoxymethyl

groups or optionally further substituted phenyl radicals and X ^. "one of the anions Cl ^ü , I, ClO,, CH ₃ SO, ^

FSO ₃ ®, BF,

and

mean.

409823/1 1 72

Quinoxalinium salts of the formula

R ¹

ti

where X ₁ ^ has the meaning given, R ¹ V? ^un d ^ "99 methyl acetoxymethyl or phenyl groups, R" «,, R" ,, and R ¹ '»independently of one another, hydrogen atoms, chlorine atoms, methyl groups, methoxy groups, ethoxy groups, benzyloxy groups or nitro groups, where at least one of the R "qi>R" ai

and R ". is different from hydrogen and R" oi ^{un (} i

Ai

or R ¹¹ Ai ^{un (} i S! ' ₅ i can also together form the additions to a pyridirio-dioxole or dibxane ring condensed with the six-membered ring II.

These and other quaternary diazo compounds can be obtained by quaternizing the corresponding bases will. In particular, compounds of the formula (2) in which Y is an alkyl group and η is 2 can be passed through Prepare alkylation of the corresponding diazines (n = 1). These Alkylation is generally carried out at an elevated temperature and normal or elevated pressure. Suitable alkylating agents are e.g. dialkyl sulfates such as dimethyl sulfate or diethyl sulfate, alkyl halides, especially iodides such as methyl iodide

409823/1172

or ethyl iodide.

A particularly active alkylating agent, for example, eats CHoSO-F as described by MG Ahmed et al. (Chem. Comm. 1968 , 1533).

If for any reason it is desired to use the anion X ^ in a primarily formed quinoxalinium salt exchange, it can easily be done by double reaction of the quinoxalinium salt with a corresponding one Salt can be done in aqueous solution. If the desired salt does not readily precipitate, it can be precipitated by adding it an inactive, water-miscible organic solvent. Suitable solvents are alcohols like methanol or-> ethanol, acetone, acetonitrile, tetrahydrofuran, Dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane.

Particularly suitable electron donors in the present process are sulfine compounds and phosphine compounds and arsine compounds such as those described in DT-OS 1,720,906.

Any of the organic sulfinic acids in their free form or in the form of a salt or organic ester can be used as the organic sulfine compound in the process according to the invention, as described in VN Michailowa et al., Joum. Organ. Chimii, JL, 1621 [1965]; DT-AS 1 145 168; BE-PS 624 071; JD Margerum et. Al., J. Am. Chem. Soc, 93 ,

409823/1172

3066 [1971]. ,

In addition, esters or adducts of sulfinic acids can be used Carbony! Compounds, in particular aldehydes, can be used. Examples of suitable sulfinic acids are p-toluenesulfinic acid, Benzenesulfinic acid, p-bromobenzenesulfinic acid, Naphthalene-1- or -2-sulfinic acid, 4-acetylaminobenzenesulfinic acid, Z-hydroxybenzene-l-carboxylic acid-S-sulfinic acid, aliphatic sulfinic acids such as ethanesulfinic acid, 1,4-butanedisulfinic acid, Phenyl methanesulfinic acid.

All soluble salts come as salts of sulfinic acids Salts that are compatible with the other components of the light-sensitive solution, e.g. the sodium salts, potassium salts, Lithium salts, magnesium salts, calcium salts, barium salts, silver salts, zinc salts, aluminum salts are possible. Suitable. Esters of these acids are especially the methyl esters, Ethyl ester, propyl ester, butyl ester. Aldehyde adducts of sulfinic acids are, for example, those with formaldehyde, acetaldehyde, Isobutyraldehyde, adducts formed by heptaldehyde. Other suitable organic sulfine compounds are those of ' sulfenic acid amides derived from these acids, such as sulfinic acid alkylamides or sulfinic acid arylamides and the sulfinic acid chlorides.

Are phosphines or arsines used as electron donors used, these preferably correspond to the formula

409 823/1 1 7 2

(19) « ⁶

where W is a phosphorus or arsenic atom and R _Ä , R-, and R ₀

O / ο

independently of one another, are alkyl, aryl, aralkyl or alkylaryl, it being advantageous when _s is at least one of these radicals having a water-solubilizing group, eg, .a hydroxyl, carboxylic acid or sulfonic acid group or a group having a quaternary nitrogen atom.

Suitable phosphines are described in Topics in Phosphorus Chemistry, Vol. I ₁ ed. By M. Grayson, EJ Griffith, John Wiley & Sons Inc., page 1 [19641; ibidem, Vol. 3, page 1; HJ Bestmann et al :, Angew. Chemie 75, 475 [1963].

Suitable arsines are described in W.U. Cullen et al., Chem. Ind. 1963, 983; W.R. Cullen et al., Can, J. Chem. 41, 1625 [1963].

As tertiary, organically substituted phosphines in the process according to the invention, for example Tributylphosphine, triphenylphosphine, dibutylphenylphosphine, methyldiphenylphosphine and methylbutylphenylphosphine use Find. Examples of suitable tertiary, organically substituted

4098 23/1172

te arsine compounds are triphenylarsine, methyldiphenylarsine, Trioctylarsine, dibutylphenylarsine, and methylbutylphenylarsine ο

In general, it is convenient in the present process, mixtures of. preferably water soluble. Monomers with one terminal double bond (monofunctional) and those with several terminal double bonds (polyfunctional) to use. With the right ratio, the gel point, i.e. the point where the polymer becomes insoluble will be influenced. In particular, exposure times of the invention are due to the monomer ratio Procedural influences. The polymerization does not take place in the liquid, but in the solid phase, i.e. in a dry one Layer instead, affects the monomer ratio described above the adhesion and flexibility of the polymer formed on its support.

Examples of polyfunctional monomers are: N: N'-alkylenebisacrylamides, secondary acrylamides, tertiary Acrylamides, divalent or trivalent acrylic or methacrylic acid salts Metals.

Suitable examples of monomers for the inventive Procedures are:

Alkylenebisacrylamides of the formula. ;

409823/1172

(20)

R ¹

III

R "

H ₂ C = C — C N-

R ¹

-N-C-G =

Il I

OR ¹

= CH,

secondary acrylamides of the formula

(21)

Il

H ₀ C = C- ^ ι

R ¹

Ν — R ¹

»11

tertiary acrylamides of the formula

(22)

H ₀ C = C- ^ ι

R '

and salts of mono- to trivalent metals of the formula

(23)

40982 3 / 1.1.7

In the formulas (20) to (23) mean.Ä an alkylene group with 2 to 6 carbon atoms, B. ¹ a hydrogen atom or a methyl group, R "and R" ¹ each a hydrogen atom or an alkyl group with a maximum of 4 carbon atoms , Preferably a methyl or ethyl group, M an m-valent metal atom, and m is 1, 2 or 3.

Further examples of monomers are:.

Acrylamide, acrylonitrile, acrylic acid-0-hydroxyethylamide, acrylic acid, Methacrylic acid, the sodium or potassium salts thereof Acids, calcium diacrylate, barium diacrylate, methacrylamide, Methacrylic acid methyl ester, acrylic acid methyl ester, acrylic acid ethyl ester, Hydroxymethyl diacetone acrylamide, diacetone acrylamide, also vinyl pyrrolidone, vinyl methyl ether, vinyl butyl ether, Butyric acid vinyl ester, butadiene, isoprene, vinyl chloride, vinylidene chloride. «'

The radiation to be used in the present method is in the range from 200 to 450 nm. Otherwise, the polymerization can be carried out in a manner known per se, e.g. in a block, in emulsion or in solution. Of course, this method can also use two or more different Monomers are copolymerized.

409823/1 172

The catalyst system to be used according to the invention is suitable to record information, especially under Application of the mentioned acrylic acids and water-soluble Acrylic acid derivatives, where the information is, for example, a reproduction of a top-down or transparent image, initially based on different degrees of polymerization and then easily and in a known manner into visible images, e.g. relief images, can be converted. In such a method of recording information by imagewise exposure of a layered material with at least one layer that

at least one polymerizable, ethylenically unsaturated compound,

at least one pair of photoredoxes and - optionally a macromolecular binder '

contains, is according to the present invention as a photoredox pair on the one hand a diazine compound of the composition specified at the outset and on the other hand an organic one Electron donor applied, the radiation used for exposure being in the range from 200 to 450 nm, the If necessary, the polymerization image is in a relief or Absorption image can be converted.

A water-soluble colloid is preferably used as the binder. This and the rest of the components of the layer. materials are cast in the form of an aqueous solution onto an opaque or transparent substrate to form a layer. the After drying, the layer thickness is advantageously 1 to

409823/1 172

In this way, layers of high transparency are created, which is retained during and after the polymerization. Gelatin, poly-. vinyl alcohols, poly-N-vinylpyrrolidones and various Copolymers of maleic anhydride are considered, including those under the names EMA (Monsanto), GANTREZ (GAF), PA resins (Gulf Oil) and SMA (Sinclair Petroleum Inc.) are commercially available available products. '·

The exposed image can be easily washed off or rubbing with a moist fiber material, the unexposed and therefore not polymerized Parts are removed.

By dipping the material with the fixed image in an aqueous or organic dye bath with a dye, adsorbed by the image substance or in some way otherwise it is fixed on this, the colorless Easily develop a relief image into a color image. Is easier it is, however, necessary to incorporate the color substance into the casting solution. The color substance can be introduced into the casting solution in monomolecular or colloidal form or as a pigment will. '

The carrier of the photographically sensitive monomer '■ layer can be modified by suitable processes in such a way that optimal adhesion of the resulting polymer to it is achieved.

4 0.9823 / 1-1 72 '- ·. ■ ί /

The following are suitable for this:

- Surface substrate with hardened, originally water-soluble colloids (e.g. gelatine).

- Additions of wetting agents to the casting solution,

- surface treatment of the support with wetting agents,

- Surface modifications of the carrier through chemical reactions (e.g. silylations).

The sensitivity of the recording material is below

2
anaerobic conditions at 1 mJ / cm and under aerobic conditions

2 conditions at 0.5 J / cm.

Incidentally, this method offers the following advantages :

1) It turns out that the system is not very sensitive to oxygen compared to other, known methods. This can be due to the formation of quinoxaline anion radicals, which in turn are powerful reducing agents and consume the oxygen present.

2) The redox systems known to date have an effect in many photographic areas of application because of the visible Absorption chromophores of the required dye are negative (US Pat. No. 3,097,096, DT-OS 1,720,906).

These systems are sensitive to daylight and a darkroom is required to operate them. Often a

409823/1 1 72

complicated bleaching process, which reduces the dye used to its colorless leuco form. But the latter is often quite unstable and slowly oxidizes back to the dye (cf. DT-OS 1 720 906). The quinoxalines have an electromagnetic absorption spectrum in the range from 200 to 400 nm and are therefore for the most part colorless compounds the S-S-J ^ band in the region of the maximum UV radiation of many High pressure mercury copier lamps. As a result, no bleaching of the quinoxaline, which acts as part of the redox couple, is necessary after photopolymerization.

3) The use of this highly active initiator (redox couple) makes it possible to work with colored monomer layers, i.e., for example, yellow, magenta and cyan layers can be made without the sensitivity of the material being significantly impaired. The cause lies in the Position of the quinoxaline absorption band, which is able to cover the minimum of the dye absorption band. The with the initiator system according to the present invention, in the presence of the water-soluble colloidal binders Polymers produced are characterized by extremely good physical properties (adhesion to copper, aluminum, triacetate and. polyester).

409823/1 172.

5) The material also works free of organic solvents or from acidic or basic aqueous developer systems. It is therefore much more environmentally friendly as copying materials, which are processed using organic solvents or acidic or basic aqueous developers need (e.g. DT-OS 2 039 861).

6) The polymers produced and colored on a transparent base have excellent properties in relation to each other on the point reproduction. Dots imaged on the photopolymer can be removed without the slightest loss of size and density be copied onto suitable documents. This attribute

is important in halftone reproduction processes.

Production instructions now follow Diazo compounds.

(a) 1,2,3, -trimethyl-6- or -y-methoxyquinoxalinium methosulfate

3.6 g (0.02 mol) of 2,3-dimethyl-6 ^ methoxyquinoxaline are in 12 ml of freshly distilled dimethyl sulfate are dissolved and heated to 60 ° C. for 3 hours in a stream of nitrogen. From the dark colored solution, the desired product precipitates out as yellow-brown crystals on slow cooling, which are filtered off, washed with dry acetone and then dried will. Yield about 2.9 g corresponds to 47% of theory; Melting point: 178 ° C (decomposition)

IR (KBr) and NMR spectra (D _o 0) show that of the structure

'409823 / Τ 172 bands to be expected.

(b) 1,2,3-trimethyl-6- or 7-methoxyquinoxalinium perchlorate

1.35 g (0.0043 moles) of 1,2,3-trimethyl-7-methoxyquinoxalinium methosulfate are dissolved in 5 ml of water. The solution obtained in this way is treated with 1.7 g (0.0086 mol) of sodium perchlorate in 2 ml Water added; the one you want is immediately separated Perchlorate. To complete the reaction, stirring is continued for 15 minutes at room temperature. Then the precipitate is filtered off and washed with a little cold water. For cleaning, the crystals are in 20 ml of water taken up and treated in the heat with activated carbon. To cooling and drying give about 0.6 g (46% of Theory) brownish yellow crystals with a melting point of 193.1 ° C, their IR (KBr) and NMR (acetone -dg) spectrum with the structure is consistent.

(c) 1,2,3-trimethyl-6,7-dimethoxyquinoxalinium iodide

In a 100 ml stirred autoclave, 5.5 g (0.025 mol) 2,3-Dimethyl-6,7-dimethoxyquinoxaline dissolved in 30 ml of methyl iodide. This solution is heated to 100 ° C. for 24 hours while stirring, during which the pressure rises to about 7 atU. To the yellow precipitate is filtered off after cooling to room temperature off, washed, .with a little dry acetone and dried, yield about 6.5 g corresponds to 72% of theory.

■■ ^ uy ^, 409 823/117 2

Melting point 210 to 212 ° C (decomposition). IR (KBr) and NMR (DMSO-dβ) spectrum agree with the postulated structure.

Those listed in the table can be used in an analogous manner Quinoxalinium salts are produced. All compounds show in the IR or NMR spectrum that of theirs Structure of the absorption bands to be expected.

(d) 2-phenylquinoxaline -3'- and -4'-sulfonic acid

In a with RUhrer ,. Thermometer, and drying tube provided KUHLER reaction vessel are added 72 ml of chlorosulfonic acid and cooled to 0 ⁰ C. 20 g of 2-phenylquinoxaline are added in portions, the temperature being kept between 0 and 10 ° C. It is then allowed to warm to room temperature and heated to 90 to 105 ° C. for 8 hours. After cooling, the viscous mass is poured onto 300 g of ice and then refluxed until all of the precipitate has dissolved (hydrolysis of the sulfonic acid chloride ). After cooling, this solution is extracted by shaking with benzene and then continuously concentrated. First 700 mg of pure 2-phenylquinoxaline-4'-sulfonic acid fall (NMR: all aromatic protons on the benzene ring show ortho- and meta-coupling) and ^, finally 1000 mg of pure 2-phenylquinoxaline-3 ^l -sulfonic acid (NMR: one aromatic proton on the benzene ring only shows meta-coupling). A total of about 20 g of a mixture of 2-phenylquinoxaline-3'- and -4 ¹ -sulfonic acid, which is obtained in

270 ° C does not yet melt.

4 0 9 8 2 3/1172

The quinoxalines useful in the present process

and quinoxalinium salts in the table below correspond to the formula

(24)

n-1

Z means C

(No. 1 to 146)

or N

(No. 147 to 151)

"d" means decomposition * means "hydrobromide"

** 'means OeI, which partially solidifies when left standing

In the case of quinoxalinium salads, only one of the two is in each case isomeric forms. Whether the compound is in the specified or its isomeric configuration was determined not examined.

409 823/1172

\ i 205 - 8 d 123-8 d 4th 120 d 218 - 22 d 145 d -α
co
tH
CM 224.8 Τ »
CM
I.
f "
O
ΐ-ί
CM 140 d O
co
CO
Ä
CJ O
CJ O
. r-t
CJ O
co
co
O O
t-1
CJ <»■
O
co
CO
Pd
ο ο
rt
CJ ο
'CO
CO
Pd
O CM CM CM CM CM CM CM CNS. CM CHg CH ₃ CHg CHg CO
Pd
CJ CHg CO
Pd
CJ CHo CHg Pd id Pd CM
O id ' Pd Pd Pd Pd O
CO
id
CJ O
co
CJ O
I.
CM
CJ
I.
__in
¹ ^ VO
CJ O
co
Pd
CJ ό
ι
CM
id
ο
CM
Pd
ο
ο ο
CO
id
ο ο
CO
Pd
CJ ο
CO
Pd
ο Pd Melting point ■ O
co Pd Pd O
CO
O ΡπΡ
VO
CJ Pd Pd CHgO Pd CHg in
Pd
vO
CJ in
Pd ₀
O co
Pd
U «Η
Pd
νθ
CJ ιη
id
VD
O m
Pd
VD CHg VD
υ
ι
O
CO
CJ
I. m
Pd
VD
CJ CHg in
Pd
VD co
Pd
CJ -υ- »" ιη
Pd
VD
CJ m
Pd
VD
CJ CO
Pd
ο I.
Pd ^
VD
O
ι
O
CO
Pd
O
I. in the CM co 2 νθ - ι co I «- 9 8 2 3 / 117 IpT OJ
(A.

- ■ 31 -.

- CXD j r-1 ; ■ * ■ ... Ο . CM Ό co I. Ό ■ On -P 1
t r-l I • in Ii-i VO I. M. i-l CO <} · O -I On CM, <f ON ■ t I. VD VO Ph r-1 CM ON . r-1 CO tsi O in CM H ON r-l OO ω ο O t-J S ο co O _r C7, CO r-l O
CO O P-J O O ' O CO xrx O r-1 O - Pd O CM O ' O O CO O CM O t-1 CO CO CO co CO O ■ JxJ CM co id CO id CM O .CO id co O" id O CO CM Pd O Pd CM O Pd co id O CM O CO CM id O td O CO Pd CO ο O CO X id id O id co Pd co id O td ο -OH O co O id O m • · ■ id CO O w.: W. ο Pd in O O CM Pd O O id co co O Pd co O CM id . id 5mj co ° ■ O - O; - ΙΓΛ
CD CO td U id co id id O U O id id O co co in ■ td co O in td id id id id in Ph ' CO O O VO co U co νθ td in CJ) id co id νθ O co id - in ' ■ O id O Pd νθ id O in · <- O υ CO Pd ^: in U Pd co vO VO id id O Pd O ■ ·; VO r-l VO; co ■ O O pH r-1 O r-l rf ^: CO r-1 CM i-i - in rl _: τ-1

409823/1 1 72

No. CHg ^R 2 XL-, ^E 4 0-CH ₂ -O ^E 5 HC
N CH
X
H H · Y η 1 X - Melting point
⁰ C. 19th ^C 6 ^H 5 CHg 0-CH ₂ -O H • H H CHg 2 CHgSO ₄ 196 d σ 20th ^C 6 ^H 5 CHg 0-CH ₂ -CH ₂ -O H H H CHg 2 ClO ₄ 252 ■ d GO
OO
Ν3
CaJ 21 ^C 6 ^H 5 ' ^C 6 ^H 5 H H H · H CHg 2 CHgSO ₄ 212 - 6 d 1
“S3 22nd CHg ·. ^C 6 ^H 5 ' H H CHg 2 CHgSO ₄ 213-7- d -23 CHg . CH ₃ H - 1 - · 106.5 d 24 C ^ H ₅ -CO
Q 0 CHg ■ H CHg 2 ClO ₄ 199 25th C ₅ H ₅ -CO CH-CO.
O _> H - 1 - . 171 d 26th H - 79.7

CD O CO Ul O

\ ύ 192.2 121.6 205.9 109.4, O
O 213.4 00
t-1 180 -'8 ά ι ι 1 ' CO
K
O ι ι
I. τ-ί CHg. r-l I. '- Y'> - CO
4 η η • • 'Ί OCH ₃ ¹
OCH ₃ W. W.
S>
Ο— W
^: ο
ι
CO
CJ 72 ^w . ' ■■■ .- ■ ί
ο O
ι
CM
-W
U
ι
O CM
§ CO
CO
do
ο
ι W. W. CO
U W. * m
νθ
O CO
W.
υ CO
Pd
ο CO
W.
υ νθ
O CHg ΙΠ
νθ CO
W-
υ CO
W.
Ü CO ΙΠ
do
νθ
Q CH ₃ CM CO
CM
9 f \ ftf t CM
■% * s ^ t / rl CM
CO CO
CO 40 9 323 / -P
ι
H
ω ο
ο
τα. H LPi
Pn ρΓ CM
Ph

300 171.3 177.2 108.9 ■ 250.8 r- <
rl 150.5 180.8 183.7 I. I. ι ■ O
rl
O I. ι ■■ ". ■ i-l r-l CM r-l t-l r-l I. I. I. i CO
id
O I. I. - ! id id CM
G id id X X X id co.
co
G id O
co
id
ο O
I.
in
X
CM
Ü co
X
O V O
co
id
U . O
CM
id
O
CM
id
ο
ι
O O
co
id
U id
* X ο
co
X
O id PO X • ο
CO
X
O id
ο
CM
id
c_>
I. ° cn
-B co
id
U ο
υ
ι
in
id
VO
O co
id
ο CO
id
U in
VO
O co
id
c_> CO
tr!
O id
O
CM
id
U id '^;
O
cm
S. CO
W.
O O
υ
I.
in
id
νθ
O CO
id
ο CO
id
O in
id
VO
CJ co
id.
U in
id
VO
O - r-l id
O
CM
S. Melting point
⁰ C <J "
CO. in
co νθ
CO CO 00
co he*
co O CM rf ΙΓΛ -φ
(A. v \
pi CM H •
U

409823/1 1 72

-P
M.
Ά
N
H
(UO
I °
O 198.5 .145.7 . 194 209.3 181.4 73.3 137.0 252 100.6. · 1 O
τ-Ι
O.... <f
O -
T-4
Ü. <f
O
r-l
O I. I. I. I. I. r-l CNl CN! CNl t-t r-l: r-l r-l I. CO
K
O co
Pd
O co
O ■ 1 -f I. | η: Pd Pd Pd Pd Pd Pd Pd ■ Pd O
CNl
Pd
U
O W. co
α t-J
O ^ ~ \
in
Pd
CNJ
O
O
U in
Pd
CNJ
υ
O
υ ο ■
CO
Pd
O m
Pd
CNl.
O
O
I.
O K
O
CNl
B. Pd id " Pd Pd Pd Pd CNl Pd LTv
Ph H '.
ο
CNl
Ed.
ο in
Pd
VD
ϋ CO
Pd
U in
Pd
VD
O in
VD
O co
■ Pd
O in
■ Pd
VO
O co
Pd
U co
Pd
O P ^ CO in"
VO
CJ) co
Pd
:. £> ■ m
Pd
■ vO
O in
Pd
VD
O - co
Pd
υ: in
Pd -:
VD
CJ CO
B. CO
8th.: <f, "
. <· "'- -
f in
.-st VO st **; O
in r-l
■ m CM
Ph ρΤ •
! ^

409 8 237ΊΤ7 2

No. ■ ^H i E ₂ H CO-OC ₂ H ₅ .V Y - - - η X • - Melting point
V 52 ^C 6 ^H 5 ^C 6 ^H S ■■. H CHgO H - - 1 - - 151.9 40 9 8 53 CH, CHg CHgO CHgO NHCO
CHg - ■ 1 - ■ . 183.9 co 54 ' ° 6 ^H 5 ^C 6 ^H 5 CHgO CHgO H - 1 - 252.4 ro 55 ■ ^CH 3 • ^CH 3 H CHgO H ■ ι - 178.1 • 56 ^C 6 ^H 5 C ₆ H ₅ H CHgO 'Cl 1 - 186.4. : 57 CH ₃ CHg ' H Cl Cl 1 147.3 ^C 6 ^H 5 ■ H CO-OCHg OCHg 1 140.0 " ^C 6 ^H 5 ^C 6 ^H 5 H 1 290.3

No. J ' R ₂ ^R 3 ' ^E 4 ——— Y η 1 1 X Melting point
"'ic 60 ^C 6 ^H 5 C ₆ H ₅ H- CO-OCH ₃ H - 1 290.3 JN
O 61 CH ₃ CH ₃ - H CO-OCH ₃ H - 1 - 262.6 ' (O
00
ro
CJ 62 % C ₆ H ₅ H ■ C ₉ H ₁ -O H - .1 - 154.3 - * 63 C ₆ H ₅ , CH ₃ H " CH ₃ O H 1 - . 88.6 , 64 .CH ₃ ^C 6 ^H 3 H CH ₃ Q "Η- · / , - 1 - 122.0 65 , ^C 6 ^H 5 ^C 6 ^H 5 H CH ₃ O -H . - 1 - ·, ■ 160.8 66 CH ₃ CH ₃ H CH ₃ O H - 1 - -, 100.3 67 C ₆ H ₅ ^C 6 ^H 5 H C ₄ H ₉ O H -. 144.0 68 CH ₃ CH ₃ H . CH ₃ O .NHC = O _
5 - 196.3.

CT> O CP

in

CM

CM

in

CM

in

CM

ο in

ο in

CM.

co

r-l CM

CM
G

CM
G

CM

CM'

co Ed OO O CJ

CM

O O

co

CM

O co

ffi

CO

VO O

vo

co EO O

co O

co O

CO

CO

EU-O

Ed

co

in

Ed

VO O

vo o

CO

co

co

σ *
vo

CM

CO

in

409823/1172 VO

r- »

ι CM ■ - I. - • in CO • r-4 O - I. ■ id CM ■ VD he «■ vO 4 - - ■ ρ-: «Ι ■ ο ·. «· I. in Ο ") oo; : CM ιη · - » I. O- - τ-I I. in . r-l O r-i in CM ' ι ■■ CM in CM CM 1 I. ■: ■: O Oi FV r-l JU. r-l pci CM CM '■■ O U -
I. id H- Ed I. Eleven <D O I ΚΛ O U ' j θ ο 1 CM O - ^: in O id I. CQ te ™ Ed.
vD I. 11 I « O Ed: ■ H. r-I I., I. . I. I. a ■ CO I. - U ⁴ Ed
U vD 1 : I- * ' ■ u; ": 1 * V * -id: ι- CM Ο ! ._ U - CO X id id. id in
id O U ' CM ■ U .id. ■ VD- 1 O W.
CJ) ι · ""; CO o: CM Q I. CM O Ed. ,:
U " Ed. CM
Ed.
U: O ; '-00 · ^:. Ό. > ·. '·. I. I. CJ) • ι cm; CM co O, Ed o: p id r . "■ -. CM in O Ed O 'Ed ..' OO - o; : •. id- in co; P. CO ' id
VD : 5G
O .id ^: id ° * Q. '. . V ©; ^{: U} -; . in co CM ΙΠ _; co. -; vO in
id. ; id vD ' U ^: O \O . u- ! .. · "·;. U ; co- in : "- vO ' C5 tn: ■ * - co ι vO; ;. co *

4 Q ag 2 371 172 ■■ ■

\ j * VO in co •H ■ id OO m r ^ O m rl OO
r-I QJ CM , ■ OO ON 00 CM
r-4 Xi CM
r-I CO
r-1 I \ in 4J if) CM O • X U
β J-I 1 ON CO: Ph ■ I. r-I P- O
- f} ₍ £ _j cO , I. H-
(D Ό r-i r-I I. Q) O
Ό co r-1 • OO T-I '■ I °
c i I. I. te • r-4 - ON
r-i I. r-I I. I. CQ te te CO O te I. "pe; rH I. te "; I. 1" O U. I. O: w! * O O co I. t-l r-l ό co co te te O re 1 tr te S. O te CJ) CM O O te ο I. O IDd O te CO te ·. I j I ' co te pe O O O te O ■ -ο- ■ co co CJ -. te GJ "O - I. G G ^ io ^; σ ffi> CT te I KS te
O te Q ICd U • te
O CM
te CJ * ~> co -1
te CnI I.
CM cj> Fi co
CNj -; ■ S-i
PQ i
CM O ■
I. ° i te
O te
O CM
te. ν CNJ co O te r I W te :.
O
CNJ
te O
CM co
te CO 1 : CnJ
te
O G
CM
s : CNJ te .v
O; ■:
OT
I.
CM
te
U 8th
ι ·:
O
CM
te ON ■ @; CNJ
te ϊ
U O co CO CM ;CM co OO CM: ON co
ON On CO
O
CM
O CO LH te
O;
I: ■ ON O O ON r-1 On

098 23/1172

236Ö350

■ '■ - pi - 187 • 187 - c> r-l "- pi co 165 VO - U vO O O -P ' IO
• OO co
rl co
On FQ L55, IO 85 I. • • PJ CM H
'Φ O
0 O t-l r-l I. I. r-l . pi I. • ι ■ '■ O :, ' t-J i-I υ "■ ' r-t r-l J? Γ , _ ■ " _r 1 I. _ ^: PiV 1 rf PJ. co τ-λ.
P. b O , ____ - ^ O K ^w O
CO co
-.8th S-. co
B. SS- PJ ι CM ■
μ CM O pi
O ■ ·· : ■. ■■■ '■ - , - 'OK O ■ g O
O
O ϋ Pi ■ pi pi
CM CM
pi I.
CM U P.
O O U - ". ■ O
O IT »
pi O I.
O Vo . pi . ■■ ** pi pi pi co P "· - . ι r-] Pi - O O
O
ρ
CM U
PQ
CM
U. P. J-I
FQ
CM
B. • ■ - Pi O FQ
CM
S. J-I
FQ
CM
B. j ^
FQ
CM
O JI
FQ
CM
Pi
U U
PQ
CM
B. ο. KM Ö co 125 U .J-I O H OO. FQ U U U ". O" PQ FQ CM FQ FQ FQ O CM PJ CM CM CM - ■ ι
CM P-! O pi pi pi pi P. U. O ο. O vO O
2 .; CM CO <f ' 99 O O Ö i
r-l ■ s

409823/1172

94.3 71.8 80.3 162.6 > 300 ■ I.
• ν
rl
rl 180.8 • 00
CM
CM
r-l I. • ■ r-l ' I. • I. r-l r-l t-l r-t 1-1 I. ι-1 t-l I. • I. ■ Pd ■ I. I. Pd O
cn
Pd
υ Pd Pd ο
cn
ο B- a W. IO
CM
O
O
O
O CHgO - - ■ COOK Pd CM
S ' O
CM
I.
CM
O
I.
O CM
O
53 K ■ ■ Pd Pd ο
CM
Pd
ρ Pc Pd
ο
CM
Ü PG. cn
δ
ο
U
O
I.
CM cn
-SJ
O
O
CJ
O
I ·
CM
Ed cn
W.
ü
O
O
O
CM
CC
υ pd
ο
CM ο
CM
Pd
ο ο
CM FCl
CM O
CM
ο cn
υ
ο
ο
ο
ι
CM cn
υ
O
O
O
I.
CM
Ü cn
W.
O
O
O
O
I.
CM
tr!
O. . cn
Pd
υ
O
υ
ο
ι
CM
O Pd
ο
CM
O Pd
O
CM
Pd
ρ ■ 111 U
FQ
CM
Pd
υ 113 cn
C)
O
U
O
CM
8th 106 107 108 109 ο
r-l 112 r-l
r-l Melting point " | M I »T tr- | pf ^rt \

409823/1172

κ " H ω ο

ö.- ο

CO

VO

CJv

Cf)

VD

CM, Η r-4

QÖ

tr »

r-t

ro

H Ü

ro

CO

O O O

G O Q

.WHERE

VCS

tJPt

■ «■■

CO

CM

CO

-ο

JO

VD

CM

Op, τ-)

t-4

to

CM

CO I CM

-S

CM

-P in to CO CO O PU m i-l OO, O N T-I H r-l I. t-i "■ r-l Q) O H dd o I. I. I. r-i r-i O i I. I. W. CO IN THE H δ - co ■■ «■ H tr! -W " O O κ *. Ü W.
I. r-l r-l CM υ O O CM CM CM U O .COW jCM £ ß U. co pi U I OCH \ 1 O O to U ^ W CM O U co ι d -CM CnI tr! cm
rc
O co CM i CM * f I. CM CM CM

I. • O U

U (O CM

co

CNf

co

υ ο ο ο

CM

W.
O

CM U

CM O

CO CM

9: 8 2/3 / "-

Ϊ • 174 I. CO -, CO I. Q, or - ■ f I. ν -
CO - ΐ $ 25 ^ · id ο
g-CJ Nile
| C0Cl ! ^: - HI "'., co - * + » I. VOv CO-. CO ,. I. t-l Il co-- in;; : co _t '; N ': CNJ' CM • td
ο CJ
O ? Η rs CM CJ vo. ί * ω .ο = · T-r td ; "I. O : Ο O ΐ -. ; | - < CJ x- \ CNJ f-t :::.,>. 3 ■ I. ; J I. Ü -----
■ 1 ο id S3 id • ro : '· O O co j:
j « ! 'Λ co id
ο co loo: Ιο ο id CNJ
td ■ S3 O
I. (χ id υ CJ CJ CNl j W id iw * O m t-l ΟΙ cm I
<J- td co co o in i-l O CJ
° \ T Iw CM 2 CN
id - .- CD O O ι CV] Iw CJ CNJ tJ ι Γ ¹ ' IW: Ö CO r-i

9823/1172

No. R ₁ R ₂ R ₃ ^R 4 ^R 5 H Y η X Melting point in ⁰ C 134 CH ₃ CH ₃ H CH ₃ -O H CH ₃ 2 ^PF 6 149 - 152 d 135 ^C 6 ^H 5 ^C 6 ^H 5 H H H CH ₃ 2 ^PF 6 124 - 129 d 136 ^C 6 ^H 5 ^C 6 ^H 5 H CH ₃ H CH ₃ 2 ^PF 6 214 - 218 d • ί-
Ο 137 ^C 6 ^H 5 ^C 6 ^H 5 H CH ₃ H CH ₃ 2 238-239. d 9823, 138 ^C 6 ^H 5 ^C 6 ^H 5 H CH ₃ H CH ₃ 2 AsF ₆ 223-229 d. ■ ^,
-j 139 ^C 5 ^H 5 C ₆ H ₅ H CH ₃ -O H CH ₃ 2 ^PF 6 213 -. 2.16 ro 140 ^C 6 ^H 5 ^C 6 ^H 5 H CH ^ -O H CH ₃ 2 - BF ₄ 208-209 141 ^C 6 ^H 5 ^C 6 ^H 5 H CH ₃ -O . H CH ₃ 2 AsF ₆ 215-217 142 ^C 6 ^H 5 ^C 6 ^H 5 H CH ₃ -O H CH ₃ 2 Cl 174 ¹ 'd 143 ^C 6 ^H 5 ^C 6 ^H 5 H Cl H CH ₃ 2 PF ₆ . 209 - 212 d 144 ^C 6 ^H 5
I. C ₆ H ₅ ClUO
j ClU-O . , H ' CH ₃ 2 Cl ■■ - ■ '· 205'"- 209 - ^: "'"d"" 145 C _r llr
6 5 ^C 6 ^H 5 H CH ₃ ClU Cl 224 d

CT) CD

ί,. ι ■ '■ ., '. ■. '■ CH ₂ -P-COCH ₁ - ■■ ■ - , ....— ...... Bt ■ ΤΗ. ....... X ! Ij
., '■. .., ■ ", ■: .. ,, '... -...... ■■ * # ■.. .. ■ Ϊ .. ■ ¹ T "" Melting point in ⁰ C) Br H ; _CH3 FSO V ν, '■:' (ff?
135 - 145 d Γ -C ₆ Hy ::; ν .. ■ H H Z «Μ η ■; '; ³ ':, j
:
■ .; _: C ₆ H ₅ H H ... J. .....
H Ji ..... ". '"; · *: ". ^; , ■. «'■ ^ lLlZZIi: "147 γ / H OH 'N 1 .126-129,, i; 148, ν CH ₀ -O-COCH _n CH ₁ ■, ty - :> ■. ■. ■■ ■. ^; '-, ■. : ■ 143.4 "'; .. ■!,: 149; N 1 • ■ «. ■ ^; 144.4 · ',. ; -ΐ : Μ: N 1
¹ ■ α JlSl ■■ ':,' N Ι. '·' "- : '. '"203» β /,.;, J.
' ■■. ■ ■ · '■ ν-,!} -., · ■ '· ■ ■■ ■■■■■ ^r :,' ■ ~ ΐ · ί --.CH ₃ .;.: - :. ■■ '■ · ■■■ ·' ■ ■ - ■ · · ■ - · .'- - '.. - ■ - · ■■■ '''; t, ■■ -, ■:

■ «si .. I

example 1

A cellulose triacetate coated with hardened gelatin

2 "

Foil of 234 cm is made with 4 ml of the following solution (Casting solution 1), which is 10 mg of the before casting Quinoxaline compound of the formula

in 2 ml of ethanol and 2 ml of a 0.016 molar aqueous sodium p-toluenesulfinate solution have been added, over-? , layered and dried.

Casting solution 1

18Q ·. ml of 1.4 molar aqueous barium diacrylate solution 60 ml of 1.6 molar aqueous acrylamide solution, 30 ml of 6% aqueous gelatin

30 ml of 0.25% aqueous solution of a nonionic polyfluorinated wetting agent (foot 170 of the 3 M)

pie so treated film is under a photographic Step wedge (12 steps) for 30 seconds in the contact process with a 400 Jiatt high-pressure queek silver lamp at a distance from

3/1172

40 cm exposed. The film is then washed with water or rubbed with damp cotton and then during 10 seconds in a 2% aqueous solution of the dye the formula

(26),

, G ₂ H ₅

"CH ₀ -GH ₀ -N

immersed. The film strip is then briefly washed with water washed and dried. All 12 wedge steps are clear recognizable. The maximum color density is about 3.2.

409823/1172

Example 2

You work like in. Example 1 given, but with the Quinoxaline compound of the formula

(27)

HO ₃ S

N .CH _Q

CH

and gets a similar result. This also applies to the quinoxaline compound of the formula

ClO,

Similar results are obtained if another quinoxaline derivative listed in the table is used in suitable amounts begins. · ·.

409823/1172

Example 3

Proceed as in the example. 1 indicated using one of the quinoxaline compounds listed in Example 1 or 2, but with the following Gies solution:

Pouring solution. 2

90 ml uf & 7oige aqueous solution (tt ^ - ^ - QZ

9α ml 2 % aqueous 45 ml β% aqueous

30 ml Θ, 25% aqueous solution of a; Bieh ^ r -! - ioniscfeen

the

After exposure and is used for rubbing; with the result is one that corresponds to the template

* ■

Example 4

The procedure is as indicated in Example 1 with the only difference that 2 ml of a 0.02 molar aqueous solution of sodium diphenylphosphinobenzol-m-sulfonate (see Ahrland et al. J. Chem. Soc, 1958 , 281) are used instead of p-toluenesulfinate is, and also receives an image with 12 differentiated wedge steps. Instead of the sulfinate or the phosphine compound, triphenylarsine can also be used.

Example 5

If, instead of treating the film with the dye solution during the image generation according to Example 1, 1 ml of a 2X aqueous solution of the dye of the formula given is added to the casting solution 1, the dye Any excess can be easily removed by washing or wiping after exposure. Even so, all 12 wedge steps show different color strengths. The maximum color density is 1.5 to 2.

409823 / 117-2

Example 6

One works with one of the following described Casting solutions 3 to 9.

Casting solution 3

ml of 1.4 molar aqueous barium diacrylate solution 60 ml of 1.6 molar acrylamide solution in ethanol 30 ml 6% aqueous gelatin

30 ml of 0.25% aqueous solution of a nonionic. Wetting agent »e.g. an additive of ethylene oxide on nonylphenol, a lauric acid sthanolamide, of a stearic acid alkanolamide or of diglycol stearate.

Casting solution 4 ■

100 ml of 1.4 molar aqueous barium diacrylate solution, 38 g of acrylamide, dissolved therein
6 g gelatin
2 ml 8% aqueous wetting agent solution (non-ionic)

Casting solution 5

4 g of ethylene maleic anhydride resin 3 g of acrylamide

0.6 g methylenebisacrylamide [H ₂ C- (HN-OC-CH = CH ₂ ) ₂ \

45 ml of water. ""

5 ml 0.25% aqueous wetting agent solution (non-ionic)

4098 23/117?

Casting solution 6

4 g of ethylene maleic anhydride resin 3 g of acrylamide

1 g of acrylic acid-ljl-dimethyl-B-oxobutylamide

Ο »6 g methylenebisacrylamide

5 ml 0.25% aqueous solvent solution

Casting solution 7

165 ml of 1.4 molar aqueous barium diacrylate solution

6.23 grams of acrylamide
350 ml 40% aqueous solution of a high molecular weight

Polyvinyl alcohols (degree of saponification 98%) 10 ml 8% aqueous wetting agent solution

Casting solution 8

3.53 g polyacrylamide (MW: 1- to 3-IQ ⁶ )

ml of 1.4 molar aqueous barium diacrylate solution

3.03 grams of acrylamide

5 ml of 8% aqueous wetting agent solution ml of water.

Pouring solution 9 -

3.53 g polyacrylamide (MW: 1 to 3-10 ⁶ ) 0.3 g methylenebisacrylamide

6 g of acrylamide

1 g of a-hydroxymethylated acrylic acid-l, l-dimethyl

3-oxobutylamide

4 0 9 8 2 3/11 72

23603 5Ö "

A solution of 70 mg of the Quinoxaline No. 113 of the table in 14 ml of ethanol with 14 ml of a 0.02 molar aqueous sodium p-toluenesulfinate solution united. 4 ml of this solution are mixed with 5 ml of one of the Casting solutions 3 to 9 added .. The mixture is on a Cast with a hardened gelatin layer made of triacetate or polyester, so that after the Drying results in a layer thickness of 1 to 10 / * m. The dried, transparent layer is placed under a rasterized, twelve step wedge for 30 seconds in the contact process exposed with a 400 watt high pressure mercury lamp. Thereafter, the exposed material is washed with water or rubbed with damp cotton wool. The template is on the slide recognizable as a gridded surface with 12 distinguishable levels. The exposure time allows the Control the height of the surface grid.

The in this way with the help of the casting solutions 3, 4, 7 or 8 produced raster images can be converted into color images by substantive coloring, which are a negative of the original correspond. For this purpose, the film with the raster image is dipped into a 2 bis for 5 to 30 seconds 5% aqueous solution of the dye of the formula (26).

40 9 823/1172

The film is then briefly washed. All from one. Charged polymers existing grid points are colored.

In all cases, one of the following diazine compounds can be used instead of diazine compound No. 113 with a similar result: No. 8, 10, 11, 23, 26, 27, 28, 30, 31, 32, 33, 34, 36, 37, 38, 39, 40, 43, 88, 2-phenylquinoxaline-3'-, -4 ¹ -sulfonic acid mixture (see preparation instruction (d)), 2-phenylquinoxaline-6- or -7-sulfoic acid, 2,3-dimethyl-5 , 8-dimethoxyquinoxaline or 2,3-dimethyl-5,8-dihydroxy-quinoxaline.

Similar results are also obtained if the barium diacrylate is carried out in the casting solutions 3, 4, 7 or 8 Calcium or strontium diacrylate replaced.

You can also, using one of the casting solutions 3 to 9 and one of the above-mentioned diazine compounds, in the manner indicated, the following electron donors instead of p-toluenesulfinate for imaging use:

Sodium diphenyl phosphinobenzene m-sulfonate, Triphenylarsine,

Sodium dipheylphosphine propane sulfonic acid.

409823/1172

23BO350

Example 7

For the casting solution of example 6 (casting solution 3, diazine no. 113) 1 ml of a 3 7o solution of the dye of the formula (26) added. The solution cast in this way gives a transparent one

red layer with the color density of 4. After two-minute exposure A raster wedge is used for a short wash. All grid points of the template are mapped directly. The image has a maximum color density of 2.

Example 8.

For the casting solution of Example 6, 1 ml of a 2% strength Solution of the dye of the formula.

(27)

C-HST =

CoH, -OH

C ₂ H ₅

Cl

added. After four minutes exposure through a grid the resulting blue layer is briefly washed or rubbed off with a damp cloth, with the original on the surface in blue as a negative. '·

409823/1172

Example 9

In the casting solution of Example 1, ultrasound 100 mg of a red pigment dye with an ultrasonic disperser distributed. The completely transparent potted solution gives a clear layer. After four minutes The film is exposed through the twelve-step wedge rubbed off with a damp cotton ball. All twelve grid levels are distinguishable. ■

Notwithstanding the preceding examples, the polymerization even in the absence of a macromolecule such as polyacrylamide, Gelatin, polyvinyl alcohol. The casting solutions 3 to 9 can be used without the macromolecular Substance can be polymerized in solutions containing water and / or ethanol under the action of light. In this Transparent, water-swellable, e.g. flir useful for medical purposes or in other products such as inks, lacquers, paints, coatings, moldings Manufacture polymers.

40982 3/1172

Example 10

30 g of acrylamide and 1 g of methylenhisacrylamide are dissolved in 50 ml of ethanol-water (1: 1). 100 mg of 2-phenylquinoxaline each and triphenylphosphine, dissolved in 10 ml of ethanol, are added. After a short exposure time with a 200 watt high pressure mercury lamp the polymer which forms and is insoluble in ethanol begins to flocculate.

Instead of triphenylphosphine, equal amounts of Triphenylarsine or p-toluenesulphinic acid as electron donors can be used.

Instead of 2-phenylquinoxaline, the following can also be used Quinoxaline can be used:

Quinoxaline, 2-benzoyl-3-methylquinoxaline, 2-benzoyl-3-phenylquinoxaline 2-acetyl-3-methyl-quinoxaline, 2,3-dimethyl-

5,8-dimethoxyquinoxaline, or one of the compounds No. 23, 27, 37 and 113. Similar results are obtained. ._ ■■ -. '·

Example 11

30 g of acrylamide, 1 g of methylenebisacrylamide and 1 g of diacetone acrylamide are dissolved in 50 ml of water. One adds 200 mg each of 2-phenylquinoxaline-3'-, -4'-sulfonic acid and sodium p-toluenesulfinate added. After a short exposure time with a

40 9 823/1172

200 W high pressure mercury lamp at room temperature, the viscosity of the solution begins to rise sharply. One works under a nitrogen or argon atmosphere at 5 ° C, the increase in viscosity takes place even more rapidly.

Instead of the specified phenylquinoxaline sulfonic acid can also use 2-phenylquinoxaline-3 \ -sulfonic acid with a similar result, 2-phenylquinoxaline-4'-sulfonic acid, 2,3-dimethylquinoxaline-6-sulfonic acid or 2 ~ phenylquinoxaline-6,7-sulfonic acid mixture be used.

409823/1 172

Claims (1)

Claims 1. Process for the photopolymerization of ethylenically unsaturated compounds with the aid of at least one photoredox pair, characterized in that on the one hand a diazine compound with the ring system as the redox couple the formula wherein Z is a nitrogen atom or a carbon atom bonded to a hydrogen atom or a substituent means, where this diazine compound can also be quaternized, and on the other hand uses an electron donor and the radiation used for photopolymerization is in the range from 200 to 450 nm, 2. The method according to claim 1, characterized in that that one polymerizes monomers with at least one terminal carbon-carbon double bond. 3. The method according to claim 2, characterized in that that one monomers with at least two terminal carbon-carbon -Double bonds polymerized. 4 0 9 8 2 3/1 172 ...'.- ~ 62 - "4. ' Method according to claim 3, characterized in that. that you have at least one monomer with a single terminal carbon-carbon double bond and at least a monomer with two terminal carbon-carbon double bonds copolymerized. 5. The method according to any one of claims 2 to 4, characterized in that that the monomers contain terminal H “C = groups and are water soluble. 6. The method according to any one of claims 1 to 5, characterized in that that the photopolymerization takes place in a protic medium » 7. The method according to any one of claims 1 to 6, characterized characterized in that the diazine compound of the formula η-l corresponds to what 409823/1 172 η is 1 or 2, Z _{1 is} a nitrogen atom or a group C, R ₅ a U is a nitrogen atom and '"that other U, when η is 1, also a nitrogen atom, and when η is 2, a group of the addition ammens et zung • ι n-1 X is an anion, Y is an optionally further substituted alkyl radical, L and R ₂ ) independently of one another, a hydrogen atom, an optionally further substituted alkoxy, aroyl, aryloxy or aralkoxy radical or R and R together with two carbon atoms of the ring I one heterocyclic or isocyclic ring lind Rn, R, and R ₁ -, independently of one another, a. Hydrogen atom, an optionally further substituted alkyl, alkoxy, aryloxy · ^ · or aralkoxy radical, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an optionally further substituted amino group, an alkylammonium group, carboxylic acid group, carboxamide group, carboxylic acid alkyl ester group or sulfonic acid group Ro j R / and Rt- together with two adjacent carbon atoms of ring II mean an isocyclic or heterocyclic ring. 8. The method according to claim 7, characterized in that the diazine compound of the formula 409823/1172 π-1 corresponds, where η, U, X, R ,, R ~ have the meaning given, one of the symbols R ^r o>R'a and R ¹ j- has the meaning given for R-, R / and R ₅ , the second of these three symbols is a hydrogen atom, a halogen atom, an amino group, an alkyl or an alkoxy group and the third is a hydrogen atom or an alkoxy group or in which two of these symbols are members of a ring of the specified composition and the third is a hydrogen atom or an alkoxy group. 9. The method according to any one of claims 7 and 8, characterized in, that the diazine compound of the formula n-1 4 0 9 8 2 3/117 2 corresponds, in which η, R., R ₂ , Ro, R /, R ₅ and X have the meaning given-, one U. a nitrogen atom and the other U-, if η = 1 is also a nitrogen atom and if η = is a -N = Group means. 10. The method according to claim 9, characterized in that that the diazine compound of the formula n-1 corresponds, in which n, UL, R ₃ , R ₄ and R _{5 have} the meaning given, R., and R ^ -i an optionally further substituted benzene radical, a benzoyl group, an optionally further substituted methyl group or a hydrogen atom, or R, - . and R _n -I together with two carbon atoms of the ring I form a five- to six-membered heterocyclic or isocyclic ring and X .. © one of the anions AsF ClO mean. CH ₃ SO ₄ FSO, BF ₄ PF and 409823/1172 1-1 ... method according to claim 10, characterized in that that the diazine compound of the formula Rc n-1 corresponds, in which n, U,, H. ,, IL ^, and X, have the meaning given and Ro i »Ra-ι and R ₁ -, a hydrogen atom, a lower alkyl group, a chlorine atom, a nitro group, a primary C nino group , an acylamino group, a trimethylammonium group, a carboxamide group optionally further substituted with one or two lower alkyl groups, a carboxylic acid, carboxylic acid methyl ester or carboxylic acid ethyl ester group or sulfonic acid group, or - ^ together with two neighboring ones Carbon atoms of ring II mean an isocyclic or heterocyclic ring. two vron R ^ ₁ , R., - 1 and 12. The method according to claim 11, characterized in that the diazine compound of the formula 409823/1172 2380350 eats-prictit ,. where lL, _f R „t - tmd.X * have the meaning given, one ü ^ a nitrogen atom and the other a j Θ Group and L ", L" and R, "a hydrogen atom, a methyl, methoxy, ethoxy, nitro," amino, acetylamino, trin> ethylammonium or sulfonic acid group, or two of ILj, R, ₉ and Rc2 together with two adjacent carbon atoms of ring II denote an isocyclic or heterocyclic ring. 13 .. The method according to claim 12 ,. characterized, that the diazine compound of the formula X, 40 98237 117 2 . - 68 - corresponds, where UL and X have the meaning given, R, 2 and R22 a phenyl group, an eenzoyl radical, a phenylsulfonic acid group, a hydroxymethyl group or a hydrogen atom and L-, R, ~ and R ₁ -O a hydrogen atom, a methyl -, methoxy, ethoxy, nitro, amino, trimethylatnmonium or sulfonic acid group, or two of Rqο> Rao and R ₁ -O together with two adjacent carbon atoms of ring II represent a dioxole, dioxane or pyridine ring. 14. The method according to claim 13, characterized in that the diazine compound of the formula corresponds, where U _{2 has} the meaning given, R, 2 and R «3 both a phenyl group or both a methyl group, R-oA» Raa and R ₅ , a hydrogen atom, a methyl group or a methoxy group and X ₂ ^ one of the anions, ClO and CH ₃ SO ₄ mean. 15. The method according to claim 11, characterized in that the diazine compound of the formula 409823/1172 corresponds to where L- ,, ^ oι j ^ qi »R-'ι ^{un (} ^ & ci having the meaning given '. 16. Verfaliren according to claim 12, characterized in, that the diazine compound of the formula corresponds, in which R ^ ₁ ^R 22 ' ^R 31' ^R 41 ^{un (} ^ ^R 51 ^d ^ ^{e an} S ^e S ^e ^ ^{ene have} meaning. 17. The method according to claim 16, characterized in that the diazine compound of the formula 409823/1172 ₅₂ corresponds, in which R, _2> R92 ' ^R 32' ^R 42 ^{un <} * have meaning. ^to S ^e S ^e ^ ^ene 18. The method according to claim 17, characterized in that the diazine compound of the formula 22nd R, 53 corresponds to where L «, R90 Have meaning « ^unt * 19. The method according to any one of claims 1 to 18, characterized in that one.eine sulfine compound as Electron donor used. 20. The method according to claim 19, characterized in that a free sulfinic acid is used as the electron donor, 409823/1172 21. Process according to claim 19, characterized in that a salt of a sulfic acid or an ester of a Sulfinic acid which is derived from an organic hydroxyl compound; in particular derived from an aliphatic alcohol, as an electron donor used.- 22. The method according to any one of claims 1 to 18 ", characterized characterized that one has a phosphine or arsine of: Formula ■ , where W is a phosphorus or arsenic atom and R ^, and R ^, independently of one another, alkyl, aryl, aralkyl? - or Mean alkylaryl groups. 24, The method of claim 22, characterized in that at least one of the radicals R ,, R ^ and Rg a water · ^ lb'slichmachende group, preferably a hydroxyl, e.- Carbonsäur or sulfonic acid group or a group having a nitrogen atom quaternäreti, having. 25, application of the method .according to one of the claims 1 to 18 for recording information. 26, method of recording information by Bildnicissige exposure of a layered material with , 409 823/1172 " at least one layer containing at least one polymerizable, ethylenically unsaturated compound, contains at least one photoredox pair and optionally a macromolecular binder, thereby marked. draws that the photoredox pair on the one hand a diazine compound specified in one of claims 1 to 18 Composition and on the other hand an organic electron donor is applied and the one used for exposure Radiation in the range from 200 to 450 nm, the polymerization image optionally in a relief image or Absorption image is converted. 27. The method according to claim 26, characterized in that electron donors in one of claims 19 to 24 applies. 28. The method according to any one of claims 25 to 27, characterized in that the polymerizable, Ethylenically unsaturated compound of at least one monomeric compound of those specified in one of claims 2 to 5 Composition applies. 29. The method according to any one of claims 25 to 28, characterized in that one water-soluble, colloidal Applies binder. 409823/1172 30. The method according to claim 29, characterized in that the binding agent is gelatin, chemically modified Gelatine, a polyvinyl alcohol, copolymers of maleic anhydride, Methyl cellulose, polyacrylamide or polyvinyl-N-pyrrolidone applies. 31. Photopolymerizable mass, preferably in a layered arrangement on a carrier, "the at least one polymerizable, ethylenically unsaturated compound , -_ at least one photoredox pair and a macromolecular binder contains, characterized in that the photoredox pair of a diazine compound in one of claims 1 and 7 to 18 specified composition and an electron donor. 32. Photopolymerizable composition according to claim 31, characterized characterized in that it contains a dye in finely dispersed or colloidal form. Quinoxalinium salts of formula 409823/1172 Il where R "and R""hydrogen atoms, alkyl or aryl radicals optionally substituted with halogen atoms, alkyl, hydroxyl, alkoxy, nitro, amino, cyano, carboxylic acid, carboalkoxy or carboxamide groups, R" ₃ , R "^ and R" ₅ , independently of one another, hydrogen atoms, halogen atoms, alkyl, alkoxy or nitro groups, where at least one of S- ¹¹ O, R "a and R ^M c is different from hydrogen and R" ₃ and R ", or R" ^ and R ₁ - can also together form the addition to a heterocyclic ring fused to the six-membered ring II, and X is an anion. Quinoxalinium salts of the formula 409823/1172 where R ",, R ¹ V
to have. 3 » ^Rf V>R" ₅ and X the meaning given Quinoxalinium salts of the formula wherein R ", R" and R _{5 have} the meaning given, R ¹¹ J ^ and R ¹¹ Oi hydrogen atoms, methyl groups, ethoxymethyl groups or optionally further substituted Phenyl radicals and X- ^{-c /} one of the anions Cl / ^, 1 ClO CH ₃ SO ₄ FSO, BF, and AsF, ^w mean. 36. Quinoxalinium salts of the formula R ¹ 409823/117 where X has the meaning given, R ¹¹ Io ^{and R} "22 are methyl, acetoxyraethyl or phenyl groups, R ¹¹ Oi>R" ai and R ¹¹ C-. , independently of each other. Hydrogen atoms, chlorine atoms, methyl groups, methoxy groups, ethoxy groups, benzyloxy groups or nitro groups, where at least one of K- ¹¹ QI »R ¹¹ Ai and R" ei is different from hydrogen and R "O ₁ and R ¹¹ A ₁ or R ¹¹ and R ^{11 is} C ₁ also along the additions to a condensable with the sechsgliederigen ring II · ,, - th can form pyridine ^ Pioxol- or dioxane. 1172