JPS5924147B2 - Production method of new quinoxalinium salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION When photopolymerization is carried out, the photopolymerization process is excited or initiated, for example, by radiation in the infrared or visible wavelength range.

As a result of research, the inventors have discovered a new catalyst system that allows ethylenically unsaturated compounds to be polymerized in an advantageous manner. The catalyst system consists of a diazine compound, preferably a quinoxaline, and an electron donor which together acts as a photoredox couple. This photoredox couple is a diazine with a ring system represented by the formula α:] ... (in which z is a nitrogen atom or a hydrogen atom or a carbon atom bonding a substituent). It is a pair of a compound (this diazine compound may be quaternized) and an electron donor.

The light beam used for photopolymerization is in the wavelength range of 200 to 450 nm. Among the diazine compounds of the above formula, many non-quaternary diazine compounds are known per se. Examples include quinoxaline, pyrazine or phenazine, and benzophenazine. These compounds can be produced by known methods. Regarding this, see A.
11 The Chemistry by Weissberger
y0fHeter0cyc11cC0mp0unds1
1J. W11ey&SONs,. NewYOrk(19
53) A. C. E. 11C0n by SimpsOn
densePyridazineandPyrazi
neRings1 section: Weissberger's (1975) G. A. Swan and D. G. Fell
17 Phenazines 1 term by tOn; R. C
．． Written by Elderfield 11Heter0cy11c
C0mp0unds11J. Wiley & SOns,.
Y. NewYOrk (1957), Vol. 6, pp. 377 et seq. T. Section by Pratt; -D. E. Section by PearsOn; ibid. (1961
), vol. 7, p. 720 et seq. P. HOrwitz
Please refer to the section by As diazine compounds, diazine compounds represented by the following general formulas (2) to (self) have favorable effects.

] When the compound represented by the general formula (2) H8) is a quaternary compound (n=2, U=)N-Y, see below), two types of isomers are formed for each cation. For example, there are compounds represented by the formula and (in the above two formulas, Z1 is missing CH).

In each of the above formulas, each symbol has the same meaning throughout, but n is the number 1 or 2, Z1 is a nitrogen atom or a group (see below), and one of the two U is a nitrogen atom and the other is n=
When 1, it is also a nitrogen atom, but when n=2, it is a group TN+, Y is an alkyl group that may be further substituted depending on the case, and one of the two U1 is a nitrogen atom. When n=1, the other is also a nitrogen atom, but when n=2, it is a group +N, and two U
One of 2 is a nitrogen atom, the other is a group 100→, R1 and R2 are each independently a hydrogen atom, an optionally further substituted alkyl group, an alkoxy group,
Aroyl group, aryloxy group or aralkoxy group (
Examples of substituents for alkyl groups include halogen atoms, acylamino groups, acyloxy groups, hydroxyl groups, alkoxy groups, alkylsulfuryl groups, alkyltheonyl groups,
Examples include a cyano group, a carboxylic acid alkyl ester group, and a carboxylic acid amide group, and examples of substituents on the aryl group, preferably the benzene group, include a methyl group, a halogen atom, such as a chlorine atom, a methoxy group, an acylamino group, an acyloxy group, a hydroxyl group, and a trioxyl group. or R1 and R2 are may be combined with the two carbon atoms of ring (1) to form a heterocycle or homocycle (see for example the following formula), Rll and R2l being further substituted or unsubstituted (R1 and (see case of R2) a benzene group, a benzoyl group, an optionally further substituted methyl group or a hydrogen atom, or Rll and R2
l may be combined with two carbon atoms of the ring () to form a 5- or 6-membered heterocycle or homocyclic ring, Rl2 and R22 are phenyl group, benzoyl group, phenylsulfonic acid group, It is a hydroxymethyl group or a hydrogen atom, and Rl
3 and R22 are both a phenyl group or a methyl group, and R3, R4 and R5 are each independently a hydrogen atom, an optionally further substituted alkyl group, alkoxy group, aryloxy group or aralkoxy group (for substituents, (see the case of R1 and R2), a halogen atom,
nitro group, cyano group, hydroxyl group, optionally further substituted amino group (e.g. acylamino group, mono- or dialkylamino group), alkylammonium group, carboxylic acid group, carboxylic acid amide group, carboxylic acid alkyl ester group or is a sulfonic acid group, or two groups of R3, R4 and R5 may be taken together with two adjacent carbon atoms of the ring ([[) to form a homocyclic or heterocyclic ring, R /3, R'4 and R'5 are this 3
one of the two groups is any one of the definitions given above for R3, R4 and R5, the second one is a hydrogen atom, a halogen atom, an amino group, an alkyl group or an alkoxy group; , the third one is a hydrogen atom or an alkoxy group, or these two are members of the ring and the third one is a hydrogen atom or an alkoxy group.

Similar selections can be made for substituents R3l, R4l and R5l in the case of diazine compounds represented by general formulas (4) to (9), etc., and R3l, R4l and R5l are hydrogen atoms, lower alkyl groups, etc. , lower alkoxy group, chlorine atom, nitro group, primary amino group, acylamino group (e.g. acetyl group, propionyl group, benzoyl group), trimethylammonium group, optionally further substituted with one or two lower alkyl groups Carboxylic acid amide group, carboxylic acid group, carboxylic acid methyl ester group,
is a carboxylic acid ethyl ester group or a sulfonic acid group, or two of R3l, R4l and R5l together with two adjacent carbon atoms of ring (I[) form a homocyclic or heterocyclic ring. (lower alkyl groups have at most 4 carbon atoms), R32, R4
2 and R52 are a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, a nitro group, an amino group, an acetylamino group, a trimethylammonium group, or a sulfo Δtrun group,
Or two of R32, R42 and R52 are rings (
11) may be taken together with two adjacent carbon atoms to form a homocyclic or heterocyclic ring, R33, R43 and R53
is a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, a nitro group, an amino group, a trimethylammonium group or a sulfonic acid group, or R33, R43 and R53
Two of them may be combined with two adjacent carbon atoms of ring (6) to form a dioxole ring, dioxane ring or pyridine ring, and R34, R44 and R54 are hydrogen atoms, methyl groups or methoxy groups. , X○ is an anion, and XIO is an anion ClO. I○, ClO4O, CH3S
O4O. FSO3○, BF4O. PF6O and AsF
6Of)X, ·, and X2O is an anion 10.
Either C1040 or CH3SO4O.

Compounds containing sulfonic or carboxylic acid groups are present in their free acid form, i.e. HOOC group or HO3S
It can also have one group or be present as a salt.

Depending on the conditions during the separation, for example the selected pH value or the cations of the salt used in the separation, the acid group may be
As O3 cationic group or COO monocationic group, for example -SO3Nal-SO3K, -COONa, COOL
It can exist as i or -COONH4.
Apart from the free acids, preference is therefore given to salts of alkaline earth metals or especially alkali metals. In this specification, carboxylic acid or sulfonic acid should be understood to have the above concept. The diazine compounds and their production methods are also described in the following literature:

German Patent Publication No. 2144297, no. No. 2144298 and No. 2010280.

As the anion X○, for example, BrO. ClOlO. Cl
O4○, CH3SO4e. BF4e. TiF4OFSO
3○, AlCl4○, FeCl4○, PF6○, SbC
l6e. SbF6OP-toluenesulfonate 0,. p
-Chlorbenzene sulfonate 01 oxalate 0. S
CN0J Cetate 0. HS040, AUCl4Olsn
cl4○2, ZnCl4e. ASF6O and AsCl
6O is mentioned.

= generally water-soluble diazine compounds, especially at least 0 at 20°C
．． Those having a water solubility of 0.05% (7 diazines in 1007 aqueous solutions) are preferred.

Such a water-soluble diazine is, for example, phenylsulfonic acid quinoxaline of the general formula, which is obtained by treating the corresponding compound, which does not contain a sulfonic acid group, with chlorosulfonic acid at low temperature. It can be made by saponifying sulfonic acid chloride.

where 2-phenylquinoxaline-3'-1 and -4'
- A mixture of sulfonic acids is obtained, which can optionally be separated into its individual components or used as such in the photopolymerization described above. The present inventors have succeeded in producing novel quaternary quinoxaline compounds, for example, compounds represented by the following general formulas.

These compounds can also be used in the photopolymerization described above. A
．． General formula (in this formula, R''1 and R are each independently an unsubstituted alkyl group or aryl group, and R
', R114 and R are independently hydrogen atoms,...
rogen atom, alkyl group, alkoxy group, benzyloxy group or nitro group, R″3, R and R″5
at least one of them is different from hydrogen, and XO
is an anion).

B. A quinoxalinium salt represented by the general formula (in this formula, R'1, R, R''3, R'14, and XO have the above-mentioned meanings).

C. General formula R (In this formula, R″3, R″4 and R″5 have the above meanings, R111 and R″21 are a methyl group or a phenyl group, and Xle is an anion ClO.lO.C
lO4O. CH3SO4○FSO3O. BF4O. P.F.
6O or AsF6O).

D. - General formula (in this formula, Xle has the above meaning, R7l2
and R″22 is a methyl group or a phenyl group, and R″22 is a methyl group or a phenyl group;
"3, R'41 and R"51 each independently represent a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, an ethoxy group,
benzyloxy group or nitro group, where R″3
1, at least one of R'41 and R''51 is different from a hydrogen atom).

These quaternary diazine compounds can be obtained by quaternizing the corresponding base.

The present invention is based on the general formula (in this formula, R1'1 and R are each independently an unsubstituted alkyl group or an aryl group, and R1'3, R'4 and R''5 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a benzyloxy group, or a nitro group, and R″
3, at least one of R and RI5 is different from hydrogen).
! 2, R73, R1 and RI5 have the meanings given above;
The present invention provides a method for producing a novel quinoxalinium salt represented by (X is an anion).

Other compounds, especially those in general formula (2) in which Y is an alkyl group and n is 2, can be prepared by alkylating the corresponding diazines (n=1).

This alkylation is generally carried out at elevated temperatures and under normal or elevated pressure. Suitable alkylating agents are, for example, dialkyl sulfates such as dimethyl sulfate or diethyl sulfate, alkyl halides, especially iodides such as methyl iodide or ethyl iodide. Particularly active alkylating agents are, for example, M. G. As reported by Ahmed et al. (Ch.
em. COmm. l968, 1533) CH3SO3F
It is. If for some reason it is desired to exchange the anion X of the quinoxalinium salt initially formed, this can be readily achieved by metathesis of the quinoxalinium salt with the corresponding salt in aqueous solution.

If the desired salt does not precipitate immediately, precipitation can be accomplished by adding an inert organic solvent that is miscible with water. Suitable solvents are alcohols such as methanol or ethanol, acetone, acetonitrile, tetrahydrofuran, dioxane, 1,2-dimethoxyethane or 1,2-diethoxyethane. As the electron feeder, for example, German Patent Publication No. 17
The sulfine, phosphine and arsine compounds described in US Pat. No. 20906 are suitable.

Examples of organic sulfine compounds include V. N. Michai
JOurn. by Mr. IOwa et al. Organ. Chim
lll↓, 1621 [1965]; German Patent Publication No. 1145168; Pelkey Patent No. 624071
No. specification: J. D. J by Margerrurl et al.
．． Am. Chem. SOc. , Dan''-, 3066 [19
The respective organic sulfinic acids can be used in free form, salt form or organic ester form, as described in 70 et al.

Furthermore, it is possible to use adducts of sulfuric acid with esters or carbonyl compounds, especially aldehyde adducts. For example, suitable sulfinic acids include p-toluenesulfinic acid, benzenesulfinic acid, p-promobenzenesulfinic acid, naphthalene-1- or -2-sulfinic acid, 4-acetylaminobenzenesulfinic acid, 2-hydroxybenzene-sulfinic acid, 1-carboxylic acid-5-sulfinic acid,
Aliphatic sulfinic acids such as ethanesulfinic acid, 1.
4-butanedisulfinic acid and phenylmethanesulfinic acid. Salts of sulfuric acid include all soluble salts that are compatible with the other components of the photosensitive solution, such as sodium salts, potassium salts, lithium salts, magnesium salts, calcium salts, barium salts, silver salts, zinc salts and Examples include aluminum salts.

Suitable esters of this acid are in particular the methyl, ethyl, propyl or butyl esters. Aldehyde adducts of sulfuric acid are, for example, adducts with formaldehyde, acetaldehyde, isobutyraldehyde or heptaldehyde. Other suitable organic sulfinic compounds are sulfinic acid amides derived from these acids, such as sulfinic acid alkylamides, sulfinic acid arylamides, and sulfinic acid chlorides. When using phosphine or amine as an electron donor, the general formula (in which w is a phosphorus or arsenic atom, R6, R7, and R
8 are each independently an alkyl group, an aryl group, an aralkyl group or an alkylaryl group, in which case at least one of these groups is a water-soluble group, such as a hydroxyl group, a carboxylic acid group or a sulfonic acid group. or a group having a quaternary nitrogen atom) is preferred.

A suitable phosphine is M. GraysOn,. E. J.
Written by Griffith11Ph0sph0r0usChe
mistry. 1 Volume 1 Topics, JOhnWil
ey & SOns Inc. , p. 1 [1964];
Volume 3, page 1; H. J. Angew. by Bestmann et al. Chemie L. Dan, 475 [1963].

A suitable arsine is W. R. Ch by Cullen et al.
em. Ind. l963, 983; W. R. Culle
Can.n et al. J. Chem. 4l, 1625 [
1963]. organically substituted tertiary
As phosphine, for example tributylphosphine, triphenylphosphine, dibutylphenylphosphine, methyldiphenylphosphine and methylbutylphenylphosphine can be used in the process according to the invention.

Suitable organically substituted tertiary arsine compounds include, for example, triphenylarsine, methyldiphenylarsine, trioctylarsine, dibutylphenylarsine and methylbutylphenylarsine. In general, water-soluble monomers having one double bond at the end (monofunctional monomers) and water-soluble monomers having multiple double bonds at the ends (polyfunctional monomers) are generally preferred. ) is preferably used.

By appropriate proportions, the gel point and thus the point at which the polymer becomes insoluble can be controlled. In particular, the proportion of monomers controls the exposure time according to the method of the invention. When the polymerization is carried out in the solid phase rather than in the liquid phase, ie in a dry layer, the proportion of said monomers influences the adhesion and flexibility of the polymer formed on the carrier. Examples of polyfunctional monomers include NN″-alkylenebisacrylamide,
Secondary acrylamides, tertiary acrylamides, or divalent or trivalent metal acrylates or methacrylates are mentioned.

Examples of monomers include alkylenepisacrylamide represented by the general formula, secondary acrylamide represented by the general formula,
These are a tertiary acrylamide represented by the general formula, and a mono- to trivalent metal salt represented by the general formula.

In the general formula C2O) {3), A is an alkylene group having 2 to 6 carbon atoms, R is a hydrogen atom or a methyl group, and R7 and R″2 are each a hydrogen atom or a carbon atom. an alkyl group having at most 4 atoms, preferably a methyl group or an ethyl group, M is an m-valent metal atom, and m is 1, 2 or 3.

Other monomers include, for example, acrylamide, acrylonitrile, acrylic acid-β-hydroxyethylamide, acrylic acid, methacrylic acid, sodium or potassium salts of these acids, calcium diacrylate, barium diacrylate, methacrylamide, methacrylic acid. Examples include methyl ester, acrylic acid methyl ester, acrylic acid ether ester, hydroxymethyl diacetone acrylamide, diacetone acrylamide, as well as vinyl pyrrolidone, vinyl methyl ether, vinyl butyl ether, butyric acid vinyl ester, butadiene, isoprene, vinyl chloride, and vinylidene chloride. . The light beam used is in the wavelength range from 200 to 450 nm.

In addition, polymerization can be carried out by methods known per se, for example, in bulk,
It can be carried out in emulsion or solution. According to this method, two or more different monomers can also be copolymerized. Catalytic systems using the novel quinoxalium salts obtained by the process of the invention are suitable for recording information, in particular using the aforementioned acrylic acids and water-soluble acrylic acid derivatives, in which case the information can be e.g. As image reproductions, they can first be produced with different degrees of polymerization and then easily converted into visible images, for example relief images, by known methods.

imagewise exposing a layer material having at least one layer containing at least one polymerizable ethylenically unsaturated compound and at least one photoredox couple and optionally a macromolecular binder; In such a method of recording information, a diazine compound of the above structure and an organic electron donor are used as a photoredox couple,
In this case, the light beam used for exposure is in the wavelength range of 200 to 450 nm, and the polymerized image can be changed into a relief image or an absorption image as desired. Preference is given to using water-soluble colloids as binders.

The binder and other components of the layer material are poured into a layer in the form of an aqueous solution onto an opaque or transparent carrier. Advantageously, the layer thickness after drying is between 1 and 50 microns. In this way, a layer of high transparency is created, which is preserved during and after polymerization. Examples of water-soluble colloids include gelatin,
polyvinyl alcohol, poly-N-vinylpyrrolidone,
and various copolymers of maleic anhydride, particularly under the trade names EMA (Monsanto), GANTREZ (G
AF Co.), PA resin (Gulf Oil Co.) and SM
Examples include products obtained from A (Sinclair Petroleum Company).

The exposed image can be easily fixed by rinsing or rubbing with a damp textile material, with the less exposed and unpolymerized parts being removed. A colorless relief image can be converted into a colored image by impregnating the material with the fixed image in an aqueous or organic dyebath with dyes which are adsorbed by or in some way fixed onto the image material. can be easily colored.

However, it is simpler if the coloring substance is already added to the casting solution. The colored substance can be applied to the casting solution in monomolecular or colloidal form or as a pigment. The carrier of the photosensitive monomer layer can be modified by suitable methods to provide the best adhesion of the resulting polymer to the carrier. For this purpose, the surface is base-treated with a hardened colloid that is water-soluble in nature (e.g. gelatin), a wetting agent is added to the casting solution, the carrier is surface-treated with the wetting agent,
It is suitable to modify the surface of the support by chemical reactions (for example silylation).

The photosensitivity of the recording material is 1 mJ/Cd under anaerobic conditions and 0.5 J/Cd under aerobic conditions.

The use of the quinoxalinium salt obtained by the method of the present invention further provides the following benefits.

(1) It was found that the system according to the present invention has less reactivity to oxygen compared to other known methods. This is because quinoxaline anionic groups are formed which are strong reducing agents and consume the oxygen present. (2) The redox systems known to date have a disadvantageous effect in many photographic applications due to the visible absorbing chromophores of the required dyes (US Pat. No. 3,097,096 and DE 1,720,906). Specification).

This system is sensitive to sunlight and requires a dark room for its handling. A complex bleaching process is often used, which reduces the dye used to its colorless leuco form. These leuco dyes are often unstable and are gradually oxidized back to dyes (see German Patent Publication No. 1720906).
, quinoxaline has an electromagnetic absorption spectrum in the region of 200-400 nm and is therefore an almost colorless compound,
Furthermore, that S.

-The S1 absorption band lies within the maximum ultraviolet radiation range of many mercury high-pressure copying lamps. Therefore, there is no need to bleach the quinoxaline, which acts as the redox couple, after polymerization.
3) By using such a highly active initiator (redox pair), a colored monomer layer can be treated.

i.e. yellow layer without substantial loss of photosensitivity of the material,
Magenta and cyan layers can be created. The reason for this is the position of the quinoxaline absorption band, which can compensate for the smallest part of the dye absorption band. 4) Polymers made using the initiator system according to the invention in the presence of water-soluble colloidal binders show very good physical properties (adhesion strength on copper, aluminum, triacetate and polyester).

]) The material is processed without organic solvents or without acidic or basic aqueous developer systems.

They are therefore essentially less environmentally harmful than copying materials which require organic solvents or acidic or basic aqueous developers for processing (for example, German Patent Application No. 203,986).
1 specification). 5) Pigmented polymers made on transparent substrates show excellent properties in spot reproduction images.

The point image produced on the photopolymer can be reproduced on a suitable substrate without any loss of size or density. This property is important in mesh screen copying. An example of producing a quinoxalinium salt of the present invention will be described below.

i) 1,2,3-trimethyl-6- or -J■■2
・3-dimethyl-6-methoxyquinoxaline 3.67 (
12 ml of freshly distilled dimethyl sulfate (0.02 mol)
and heat at 60° C. for 3 hours in a nitrogen stream.

Upon gradual cooling, the desired product precipitates from the dark solution as yellow, colored crystals. This is filtered, washed with dry acetone and then dried. The yield was approximately 2.97, corresponding to 47% of the theoretical amount. Melting point: 178°C (decomposes). IR
The spectrum (KBr) and Hatake spectrum (D2O) show absorption bands expected from its chemical structure.

(b) 1,2,3-trimethyl-6- or -Jmethoxyquinoxalinium perchlorate 1,2,3-trimethyl-Jmethoxyquinoxalinium methosulfate 1.35V (0.0043 mol) in 5 me of water.

The solution thus obtained was added with 1 ml of sodium perchlorate in 2 ml of water.
．． 77 (0.0086 mol) is added. At this time, the desired barchlorate is immediately precipitated. Stir for 15 minutes at room temperature to complete the reaction. Then filter the precipitate,
Wash with a small amount of cold water. 1. For purification, the crystals are dissolved in 20 mj of water and treated hot with activated carbon.

After cooling and drying, about 0.6y (46% of theory) of yellow, colored crystals with a melting point of 193.1°C are obtained, whose IR spectrum (KBr) and NMR spectrum (acetone D6
) is consistent with its chemical structure. (c) 1, 2, 3
-Trimethyl-6,7-dimethoxyquinoxalinium iodide 5.5y (0.025 mol) of 2,3-dimethyl-6,7-dimethoxyquinoxalinium iodide was added to 30% of methyl iodide in a stirring autoclave with a capacity of 100 ml.
Dissolve in m1.

When this solution is stirred and heated to 100°C for 24 hours, the pressure increases to about 7 atmospheres. After cooling to room temperature, the yellow precipitate was filtered and washed with a small amount of dry acetone.
dry. The yield was approximately 6.57, corresponding to 72% of theory. Melting point: 210-212°C (decomposes). IR spectrum (KBr) and SO spectrum (DlVSO-D
6) is consistent with the predicted chemical structure.

The quinoxalinium salts listed in the following table can be prepared in a similar manner.

All compounds exhibit absorption bands in the IR and NMR spectra expected from their chemical structure.
The quinoxalinium salts of the present invention listed in the following table are compounds represented by the general formula, and "d" in the table means decomposition.

Reference Example 1 2 ml of ethanol and 2 ml of a 0.016 molar aqueous solution of sodium p-toluenesulfinate were added to a 234C71i cellulose triacetate foil coated with hardened gelatin.
Quinoxaline compound 10T19 represented by the formula in m1
The following solution added before casting (casting solution 1) 4
laminate and dry.

B. Flow Molding Solution 1 The foil thus treated is irradiated for 30 seconds with a 400 Watt mercury high pressure lamp from a distance of 40 inches by the contact method under a photographic step wedge (12 steps).

The foil is then washed with water or rubbed with damp cotton, then styled and dried.

All 12 wedge gradations are clearly visible.

The maximum color density is approximately 3.2. Reference Example When the quinoxaline compound represented by Formula 2 is operated in the same manner as in Reference Example 1, similar results are obtained.

This also applies to the quinoxaline compound represented by the formula.

Similar results are obtained when using appropriate amounts of other quinoxaline derivatives listed in the table. Reference Example 3 Using the quinoxaline compound listed in Reference Example 1 or 2, the procedure is repeated in the same manner as in Reference Example 1 using the following casting solution.

Casting Solution 2 After exposure and rubbing with damp cotton, a polymer core corresponding to the original is obtained.

Reference Example 4 Sodium diphenylphosphinobenzene-m-sulfonate (Ahrla
nd et al., J. Chem. SOc. By using 2 mj of a 0.02 molar aqueous solution of 281) and operating as described in Reference Example 1, an image with 12 distinguishable wedge gradations is obtained.

Triphenylarsine can also be used instead of the sulfinate or phosphine compounds. Reference Example 5 Instead of subsequently treating the foil with a dye solution in the production of the image according to Reference Example 1, 1 ml of a 2% aqueous solution of a dye of the above formula is added.
When added to casting solution 1, excess dye can be easily removed by washing or wiping after exposure.

Furthermore, each of the 12 levels of wedges exhibits different color intensities. The maximum color density is 1.5-2. Reference Example 6 The following operations are performed using flow molding solutions 3 to 9, respectively.

Flow molding solution 3 A solution of quinoxaline of formula (to) 70 ~ in 14 ml of ethanol was mixed with 0.02 ml of sodium p-toluenesulfinate.
Combine with 14 ml of molar aqueous solution.

Pour 5 ml of this solution into one of molding solutions 3 to 9.
Add m1. This mixture is poured onto a triacetate or polyester carrier with a hardened gelatin layer, so that after drying the layer has a thickness of 1 to 10 μm. The dried transparent layer is exposed under a 12-step halftone wedge by the contact method for 30 seconds with a 400 watt mercury high pressure lamp.
After this, the exposed material is washed with water or rubbed with damp cotton. On the foil, an image with 12 different gradations can be seen as a halftone surface. The height of the surface screen can be adjusted by the exposure time. The halftone image produced in this way using casting solutions 3, 4, 7 or 8 can be converted by direct dyeing into a colored image, which corresponds to the negative of said image.

For this purpose, the foil, together with the mesh image, is immersed for 5 to 30 seconds in a 2-5% aqueous solution of a dye of the formula (2). The foil is then briefly washed. All halftone dots made of laminated polymer are dyed. Flow molding solution 3, 4,
Similar results are obtained when barium diacrylate is replaced with calcium or strontium diacrylate in 7 or 8.

Using casting solutions 3-9 and one of the diazine compounds described above, the following electron donors can be used for imaging in place of p-toluenesulfinate in the same manner as above.

Sodium diphenylphosphinepropanesulfonate, triphenylarsine, sodium diphenylphosphinepropanesulfonate.

Reference Example 7 Flow molding solution of Reference Example 6 [Flow molding solution 3,
Add 1 ml of a 3% solution of the dye represented by formula (to) to the diazine compound formula (to)].

A transparent red layer with a color density of 4 is obtained from this cast solution. After a 2 minute exposure through a halftone step wedge, a brief wash is carried out. Image dots are immediately formed. The maximum color density of this image is 2. Reference Example 8 To the casting solution of Reference Example 6, 1 ml of a 2% solution of the dye represented by the formula is added.

After 4 minutes of exposure through a mesh screen, the blue layer thus obtained is briefly washed or wet wiped so that the image appears as a blue negative on the substrate. Reference Example 9 Red pigment 100% was added to the casting solution of Reference Example 1 using an ultrasonic disperser.
Disperse the wa.

A clear layer is obtained from this completely clear pouring solution. After 4 minutes of exposure through a 12-step mesh wedge, the foil is rubbed with damp cotton.

All 12 levels of mesh gradation can be distinguished.

Unlike the above examples, polyacrylamide, gelatin,
Polymerization can also be carried out without the presence of macromolecules such as polyvinyl alcohol.

In the case of H, casting solutions 3 to 9 are water and/or
Polymerization can be carried out under the action of light without using solutions containing macromolecular substances in ethanol. In this way or as mentioned in the examples below, water-swellable, e.g. can be used for medicinal purposes or other products, e.g.
Transparent polymers can be made that can be made into paints, molded products, etc. Reference Example 10 Acrylamide 307 and methylenebisacrylamide 1y are dissolved in 50 mj of ethanol and water (1:1).

100 g each of 2-phenylquinoxaline and triphenylphosphine dissolved in 10 ml of ethanol are added.
After a brief exposure to a 200 watt mercury high pressure lamp, an ethanol-insoluble polymer forms and begins to precipitate.

Instead of triphenylphosphine, the same amount of triphenylarsine or p-toluenesulfuric acid can be used as electron donor. The following quinoxalines can also be used in place of 2-phenylquinoxaline.

Quinoxaline, 2-benzoyl-3-methylquinoxaline, 2-benzoyl-3-phenylquinoxaline, 2-
Acetyl-3-methylquinoxaline, 2,3-dimethyl-5,8-dimethoxyquinoxaline, or formula (25)
A compound represented by

Similar results are obtained using these compounds. Reference Example 11 30y of acrylamide, 1y of methylenebisacrylamide and 1y of diacetone acrylamide, 50y of water
Dissolve in m1.

2-phenylquinoxaline-3'-4'-sulfonic acid and sodium p-toluenesulfinate 200 each
Add soku.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R″_1 and R″_2 are mutually independently unsubstituted alkyl groups or aryl groups,
_3, R″_4 and R″_5 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a benzyloxy group, or a nitro group, and R″_3, R″_
General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R″ consists of quaternizing a quinoxaline compound represented by _1, R″_2, R″_3, R″_4 and R″_5 have the above-mentioned meanings, and X^■ is an anion).