SU493984A3 - Photosensitive element - Google Patents

Abstract

1377747 Azido substituted carboxylic acids HOWSON-ALGRAPHY Ltd 17 Oct 1972 [22 Oct 1971] 49297/71 Heading C2C [Also in Divisions C3 and G2] The preparation of the following acids and their acid chlorides is disclosed: 4-azido-α- bromo-#-chlorocinnamylidene acetic acid (I); 4 - azido - 8 - chlorocinnamylidene acetic acid; 4 - azido - α - cyano - 8 - chlorocinnamylidene acetic acid; 4-azido-α-cyano-cinnamylidene acetic acid; 3-azido-benzylidene-α-cyanoacetic acid; 4 - azido - 2 - chlorobenzylidene - α- cyanoacetic acid; 4-azido-3,5-dibromobenzylidene - α - cyanoacetic acid; 3 - azido - 4- methyl - benzylidene - α - cyano acetic acid; 3 - azido - 4 - methoxy - benzylidene - α - cyano acetic acid; and 4 - azido - benzylidene - α- bromo-cyano acetic acid. In an example I is prepared by reacting 4-azido-#-chlorocinnamaldehyde (cf. U.S. Specification 3,598,844) dissolved in glacial acetic acid with cyano acetic acid. The acid chloride is obtained by further reaction with thionyl chloride.

Description

This invention relates to photosensitive materials.

Known photosensitive materials, photopolymers used as resists in photomechanical processes. But, firstly, they do not change in color when exposed, and secondly, they require the addition of an expensive supersensitizer to achieve the required photosensitivity.

To eliminate these drawbacks, a photosensitive element has been proposed, consisting of a substrate and a layer of photosensitive polyester applied onto it, including groups of the general formula

NS-R- (CRi CR2) a (CRi) b-COO- attached to carbon atoms of a polymer compound having several mobile hydrogen atoms,

where a and, or 1; a - {- b at least 1;

R is an aromatic radical with an arbitrary substitution;

Ri, Rz, Rs, R4 may be the same or different and represent either a halogen atom, a hydrogen atom, cyano groups, alkyl groups, aryl, alkoxy, aralkyl, aralkoxy.

The formula provides that at least one of the groups Rj-R4 represents a halogen atom or a cyano group.

In the proposed photosensitive polyesters in one case, they include groups of the general formula.

L3-R- (CR,) a () b-COO-,

attached to carbon atoms

where, 1;

R - R4 - groups defined above;

RI is a halogen atom or cyano group.

For example, in this formula, a and b can both be 1;

R is a phenyl group;

RI is a chlorine atom;

R2 and R3 are hydrogen, bromine, chlorine or cyano groups.

In another case, photosensitive polyesters may include groups of the general formula

L3-R- (CRi CR2) a - () b-COO-,

attached to carbon atoms, where a and b (or 1; a + & at least 1;

R is a substituted aromatic radical;

RI-R4 may be the same or different and represent a halogen atom, hydrogen, cyano groups, alkyl, aryl, alkoxy, aryloxy, aralkyl or aralkoxy groups, with the proviso that at least one RI-R4 group represents a halogen atom or a cyano group.

For example, in this formula, a may be 0;

b - 1; Rs is hydrogen; - a bromine atom, chlorine or cyano group.

In accordance with the present invention, polymeric substances, to which ether groups are attached, have several mobile hydrogen atoms capable of substitution. These are predominantly epoxy resins, but substances such as phenoxy resins, polyvinyl alcohol, cellulose, cellulose ethers or novolac resins can be used.

Esters of the present invention can be prepared by the reaction of an acid chloride of the general formula

N3-R - () a - () - SOS1,

in which a, b, R, Ri-R4 have the values indicated above, with the listed polymeric compounds. .O VC- / VO-CH-CHCHHg-CH-CH The reaction takes place in the presence of a base, a tertiary amine, which simultaneously serves as a solvent.

Other solvents may be dioxane, dimethylformamide, methylene chloride or methyl ethyl ketone. Suitable tertiary amines can be triethylamine, N-methylpiperidine, pyridine, quinoline, dimethylaniline, or a mixture thereof. The reaction is carried out at 20-70 ° C.

Details of the esterification methods are discussed in the examples. As polymeric compounds containing mobile hydrogen atoms, epoxy resins obtained by condensation of bisphenol A and epichlorohydrin were suitable.

Their general formula is Vo-CH -CH-sn

/ h

L N V N with N 2

 V-o-CH -CH-CH in which p have values from 9 to 12 preferably. It has been found that Epikote 1007 and Epikote 1009 are suitable epoxy resins of the type indicated above. These products manufactured by Shell Chemical Co. are available and have the following characteristics: Resin grade p 1007 1009 1700-2050 2400-3400 Equivalent weight of epoxide 40-110 Viscosity 40% solution in butyl (Diaital), 25 ° C, poise Specific gravity at 20 ° C Average molecular weight Equivalent esterification weight Melting point 120-130 140-155 none, ° C (Durrans) Can be used for these purposes and other condensation products of epichlorohydrin with aromatic hydroxy compounds, such as: dioxy diphenylmethane, -dioxydiphenyl ether, -dioxydiphenylsulfone. acid chlorides; those obtained from the following substituted acids. K -, - / V H CH-C-C ° I C 1 H // II b. And 1 1 0 L - CH CH-s. // D 0, - / 5 1 C

Chlorine anhydrides can be used alone or in a mixture with each other, or in a mixture with acid chlorides that do not contain azido groups, aliphatic or aromatic.

For example, chlorine sulfides of acetic, propionic, caproic, benzoic acids can be used.

The reaction of the acid chloride containing no azido group of an acid with a polymeric compound can take place both simultaneously with the reaction of the acid hydroxide of azido acid, before or after it.

The preferred method for preparing the esters is to dissolve the polymer substance, for example, methyl ethyl ketone (prepare 10-40% solution), add an acid chloride or a mixture of acid chlorides in methyl ethyl ketone or without a solvent, then add a sufficient amount of pyridine to convert the total chlorohydride. the reaction mixture at a temperature between 40-60 ° C from 2 to 4 hours.

The reaction mixture is diluted with a methyl ethyl ketone – toluene solvent mixture (1;), filtered to remove pyridine. After applying the photosensitive ether solution to the substrate and drying it, the photosensitive element is ready.

It is exported over a period of time, depending on the composition of the photosensitive composition, the substrate, the intensity of the light source and the type of product offered.

Exposed areas become insoluble, while unexposed areas are easily removed with the same solvents on which the light-sensitive composition is prepared.

The solvent or mixture of solvents used to develop the image after exposure should be selected with care, since the development should not affect the exposed areas.

Dioxane, ethyl acetate glycol monoethyl ether, ethyl acetate glycol monomethyl ether and tetrahydrofurfuryl acetate can be suitable agents.

Photosensitive elements and substances for their preparation can be used in the production of printing plates, can be used for selective etching on metal.

Photopolymers are also suitable for other cephlorides and slowly drop by drop into the floating alcohol. The resulting esters are yellow-brown powders. Esters are used in the production of printing plates; therefore, the present invention involves the preparation of a photosensitive element containing a substrate on which a film containing ether is applied. The substrate can be glass, paper, resin-embedded paper, synthetic resin foil, metal (aluminum, zinc, magnesium, copper). The photosensitive layer on the substrate is formed as follows: the photosensitive ether is dissolved in a suitable solvent or mixture of solvents such as dioxane, ethyl acetate glycol monomethyl ether, ethyl acetate glycol mono ethyl ether, and the resulting solution is applied to the substrate by any method (by immersing the substrate in solution or centrifuging) whereupon the solvent is removed by drying in air or at elevated temperature. The coating weight per square meter is usually 0.2-2 g. For industrial purposes, the following substances can be added to the esters of the invention, if required, dyes, plasticizers, wetting agents, supersensitizers, stabilizers, non-reactive polymers, photosensitive polymers, as well as substances capable of reaction with photolyzed azido radicals.

for example, for printed circuits, for decorative effects.

The following examples illustrate the present invention.

Example 1

A. Preparation of 4-azidoss-cyano-b-chlorocinnamylidene acetic acid epoxy resin.

2.42 g of 4-azido- | 3-chlorocinnamine aldehyde (prepared by the modified specification of US Patent No. 3598844) was dissolved in 50 ml of glacial acetic acid. 5.4 g of cyanoacetic acid was added and the mixture was heated at 80 ° C for 2 hours, during which time the product was separated as thin needles. After filtration, the product was washed with glacial acetic acid (2x5 ml), then dried over sodium hydroxide to obtain 1.4 g of the desired product. After recrystallization from methanol, dark yellow needles of 4-azido-a-cyano-6-chlorocinnamylidene acetic acid were obtained.

4 g of the acid containing azido group was heated by transferring from 25 ml of distilled thionyl chloride at reflux temperature for 6 hours. One part of thionyl chloride was removed by vacuum distillation, and the cooled solution was purified with petroleum ether (at a boiling point of 40-60 ° C). The acid chloride precipitated as an orange powder.

2.00 g (0.01 g-eq) of Epikote 1007 was dissolved in 30 ml of dioxane and 2.93 g (0.01 M) of chlorine anhydride a was added. After moving over 10 minutes, 1.0 ml of pyridine was added and the mixture was heated at 50 ° C for 4 hours. Pyridine chloride was filtered off, and the solution was added dropwise to 400 ml of ethanol. The precipitated resin was filtered and washed with excess ethanol on the filter. Exit 3.41 g.

A maximum of 375 nm was detected on the UV spectrum.

Extinction at 375,510 (in dioxane).

B. Getting printing plates.

2.5 g of ester of epoxy resin 4-azido-a-cyano-bchlorocinnamylidene acetic acid was dissolved in a mixture of equal volumes of dioxane and 2-methoxy ethyl acetate so as to obtain a 5% solution. The solution was diluted with toluene to 2.5% and then applied to the surface of an electro-crushed aluminum plate using a centrifuge to obtain a coating weighing 0.5 g / m. After drying, the resulting photosensitive plate is exposed to light for 30 seconds in contact with the negative at a distance of 0.65 m from the pulsating 4000 W xenon lamp. In areas irradiated with light, a deep yellow-brown coloring was obtained. The exposed plate was developed, using a mixture of glycol ether and the wetting agent of patent No. 1220808 (United Kingdom), washed with water and covered with oily printing ink.

Example 2. A. Preparation of 4-azido-a-bromo-b-chlorocinnamylidene acetic acid ester epoxy resin. 20.7 g of 4-azido-p-chlorocinnamine aldehyde in

200 ml of methylene chloride was added to a solution of 42.8 g of triphenylcarbethoxy-bromophosphorane in 200 ml of methylene chloride. The resulting solution was then aged for 60 hours. The solvent was removed in vacuo at 25 ° C, and the remaining crystalline mass was extracted with 6x50 ml of n-pentane. After evaporation of the combined extracts in vacuo at a temperature below 20 ° C, 24.0 g of ether was obtained. 3.56 g of ether dissolved in 50 ml of methanol,

treated with 10 ml of 50% sodium hydroxide solution at 25 ° C. After 24 hours, the solvent was removed in vacuum below 25 ° C, and the sodium salt of the product was extracted while washing the solid residue with hot water.

(5X100 ml). After cooling the extracts, a crystalline sodium salt was obtained, from which 4-azido-a-bromo-b-chlorocinnamylidene acetic acid (1) was obtained after exposure to an acid (2NHCI).

4 g of 4-azido-a-bromo-b-chlorocinnamylidene acetic acid was heated with 10 ml of thionyl chloride for 4 hours at 70-75 ° C. 5 ml of thionyl chloride was removed in vacuo, and the acid chloride was isolated while stirring the mixture with petroleum ether (in the boiling range 40-60 ° C;) and filtered.

2.00 g (0.01 g-eq) of Epikote 1007 was dissolved in a mixture of 8 ml of methyl ethyl ketone and 8 ml of dioxane. 3.47 g (0.01 M) of acid chloride added

and the mixture was stirred for 10 minutes, 1.0 ml of pyridine was then added and the mixture was heated at 50 ° C for 2 hours. After filtration, the solution was added dropwise to ethanol, and the precipitate was filtered and washed

excess ethanol. Output 2.23 g.

In the UV spectrum, we found a maximum at 349 nm. The extinction at 349 nm E |, 270 (in dioxane). B. Getting prints (printing plates).

2.5 g of epoxy resin 4-azido-a-bromo-bchlorocinnamylidene acetic acid was dissolved in a mixture of equal volumes of 2-methoxyethyl acetate and dioxane so as to obtain a 5% solution. The solution was diluted with toluene to 2.5%, and then applied using a centrifuge to the surface of a sheet of electro-crushed anodic aluminum so as to obtain a coating weighing 0.5 g / m. The plate was dried, and then exposed and produced according to the method described in example 1, B. The plate was rinsed with water and covered with ink (typographical).

PRI me R 3.

A. Preparation of 3-azido4-methylbenzylidine-a-cyanoacetic acid epoxy resin.

425 ml of concentrated sulfuric acid

and 36 ml of concentrated nitric acid

shifted and cooled in a bath of dry ice and

9

acetone to 0 ° C. 100 ml of 4-toluic aldehyde was slowly added with stirring, while the temperature of the reaction mixture was maintained between -2 and + 2 ° C. The resulting mixture was heated to 40 ° C and then cooled to room temperature. The product was isolated by pouring into crushed ice. The yield of 3-nitro-4-tolualdehyde was 74 g.

50 g of 3-nitro-4-tolualdehyde, dry cyanoacetic acid and glacial acetic acid were heated at 100 ° C for 7 hours. 3-nitro-4-methylbenzylidene-a-cyanoacetic acid was filtered and washed with glacial acetic acid and water. Output 32 g.

25 g of 3-nitro-4-methylbenzylidene - cc-cyanoacetic acid was dissolved in 350 ml of alcohol. 350 ml of water was added and the mixture was heated to boiling. 55 g of sodium dithionite was added (slowly) and the mixture was heated under reflux for 30 minutes, cooled and acidified with hydrochloric acid. The solution was boiled until more significant quantities of sulfur dioxide were detected. 50 ml of concentrated hydrochloric acid was added, and the mixture was cooled from 0 to -5 ° C. A 40% solution of sodium nitrite was added until a slight excess of nitrous acid was established. 20 g of sodium azide in 50 ml of water were added dropwise through a funnel and the precipitated 3-azido-4-methyl: benzylidene-a-cyanoacetic acid (formula IX) was filtered through a pump. After washing with water, 5.78 g of product was obtained.

The acid was converted to the acid chloride by the method described in example 2, A.

1.00 g (0.009 g-eq) of Epikote 1007 was dissolved in 6 ml of methyl ethyl ketone and 0.99 g of chloride (0.004 M) of 3azido-4-methylbenzylidene-a-cyanoacetic acid chloride in 6 ml of methyl ethyl ketone was added to the solution. 0.5 ml of pyridine was added and the mixture was heated at 75 ° C for 2 hours. After diluting with 8 ml of dioxane, ether was isolated by adding dropwise to the solution in water. Output 0.75 g.

The UV spectrum detected a maximum at 298 nm.

The extinction at 298 Ej °, 156 (in dioxane).

B. Getting prints.

The process of Example 2 was repeated, B, except that 2 minutes were required for exposure to obtain the desired image. The coated plate was rinsed in water and covered with a thick layer of printing ink.

Example 4

A. Preparation of β-benzoate epoxy 4-azidobenzylidene-a-cyanoacetate.

6 g (0.03 g-eq) of Epikote 1007 was dissolved in 27 ml of methyl ethyl ketone. 4.9 g (0.021 g-eq) acid chloride 4-azidobenzylidene-a-cyanoacetic acid (formula IV) was added to

ten

the mixture with stirring for 15 minutes Then 1.2 ml of benzoyl chloride and 3.0 ml of pyridine were added and the temperature was raised to 50 ° C. This temperature was maintained for 2 hours. The mixture was then cooled and filtered, and the filtrate was added dropwise to ethanol. The precipitated ether was collected and washed with an excess of ethanol. Output 8.8 g. On the UV spectrum, a maximum was detected at

345 nm.

B. Getting prints. The procedure of Example 2 was repeated, B, except that the exposure time required 1 minute.

Example 5. Getting / g-azidobenzalcyanoacetic acid.

Equal amounts of azidobenzaldehyde and cyanoacetic acid were condensed together, using as catalyst

glacial acetic acid for 4 hours. The acid chloride was isolated by precipitation into gasoline.

Esterification of epoxy resin.

Enoxysmol, known as Epikote 1009,

which is obtained from epichlorohydrin, and Bisphenol A, was dissolved in methyl ethyl ketone and an equivalent amount of acid chloride was added. The mixture was heated in a water bath for five hours in the presence of a small amount of pyridine. The resulting ester was precipitated into industrial methylated alcohol, washed with industrial methylated alcohol, and dried to obtain a pale yellow powder.

Getting prints. A 3% solution of ester, obtained as shown above, in a mixture of 2-methoxy ethyl acetate and toluene (1: 3 by volume), was applied using a centrifuge to the surface of crushed aluminum, serving as its anode in an electrolytic solution of phosphoric acid, to form a coating weighing 0.5 g / cm. After drying, the resulting photosensitive plate was exposed to negative and Kodak 3.

A pulser was used, and a xenon lamp with a power of 2000 watts for 1 min. The depth of staining was obtained from the area fragmented by light. The exposed plate was produced using a mixture of

glycol ether and wetting agent known in patent no. 220808 (U.K.).

The vented plate was washed and covered with printing ink. The image was solid at 9 and had a tail at 14.

Subject invention

60

Claims (10)

1. A photosensitive element consisting of a substrate coated with a layer containing a photosensitive polyester, characterized in that, in order to improve the image quality, as a photosensitive material body polyester, an ester is used containing a group of the general formula M3-R- (CRi CR2) a- (SKZ SK4) С-COO-, attached to carbon atoms of polyhydric; where a and b are zero, or 1 and at least 1; R is an aromatic radical optionally substituted with a group or groups in addition to the azido group, and Ri, Rz, Rs, R4, which may be the same or different, are halogen atoms, hydrogen atoms, cyano groups, alkyl groups, aryl groups , alkoxy groups, aryloxy groups, aralkyl groups or aralkoxy groups, provided that at least one of the Ri-R4 groups is a hydrogen atom or a cyano group. 2. The element according to claim 1, characterized in that in the formula a is 1 b is zero or 1; RI, R2, Rs, R4 are as defined in claim 1, and RI represents a halogen atom or a cyano group. 3. The element according to claim 2, characterized in that in formula a and 6 both are equal to 1; R is a phenyl group; RI is a chlorine atom; R2 and Rs are a hydrogen atom and R4 is a hydrogen atom, a bromine atom, a chlorine atom or a cyano group. 4. The element of claim 1, wherein in the formula R represents an aromatic radical substituted by a group or groups in addition to the azido group, and a and b, have the meanings of claim 1. 5. The element according to claim 4, characterized in that in the formula equal to zero; b is 1; RS is a hydrogen atom; 12 R4 is a bromine atom, a chlorine atom or a cyano group, and R is a phenyl group substituted by a methyl group, a methoxy group, a bromine atom or a chlorine atom. 6. The element according to claim 1, wherein the ether is the product of the interaction of the polyhydric substance and the acid selected from; 4-azido-a-bromo-b-chloro-cyannamylidene acetic acid, 4-azido-b-chlorocinnamylidene acetic acid, 4-azido-a-cyano-b-chlorocinnamylidene acetic acid, 4-azido-1a-cyano-b-shchinnamylidene acetic acid, Z-azido-4-benzylidene-a-cyanoacetic acid, 4-azido-2 - chlorobenzylidene - a - cyanoxy acid, 4-azido-3,5-dibromobenzylidene - a - cyanoacetic acid, Z-azido-4-methylbenzylidene - a - cyanoacetic acid, Z-azido-4-methoxybenzylidene - a - cyanoacetic acid, 4-azidobepylidene - a - bromo cyanoacetic acid. 7. Element no. 1, characterized in that the ester is the product of the interaction of the polyhydric substance and 4-azidobenzylidene-a-cyanoacetic acid. 8.Item on PP. 1-7, characterized in that the polyhydric substance is an epoxy resin. 9. The element according to claim 8, wherein the epoxy resin is a condensation product of bisphenol and epichlorohydrin. 10. Element on PP. 1-9, characterized in that the polyhydric substance is a polyvinyl alcohol, a cellulosic compound or a novolac resin.