FI57183C - LJUSKAENSLIG POLYMER LAEMPLIG ATT ANVAENDAS FOER FRAMSTAELLNING AV TRYCKPLATTOR - 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

Γ, ··· ^ - · -Ι rft1 Μ ADVERTISEMENT r Π A ft T

^ (11) UTLÄGGININCSSKRIFT ^ / 183

C - «Patent ayönr.dty 10 ~ 6 10PO

tfcvM '' Patent meddelat ^ v ^ (51) K ».lk.3 / lnt.CI.3 G 03 C 1/70 FINLAND —FINLAND (21) Pw * ntt« »lMimi · - temtaraeknlnt 2886/72 (22) H »k # ml * ptlYl — Antdkninpdtf 18.10.72 '' (23) AJkuptlvt — GlMghttadtg l8.10.72 (41) Tullut JulklMkO - Bltvlt off« ntlig 23 QU 73

Patent. And registrarlhallltu. NlhtiväJuip ™, „moonLtallotoun date.-

Patent- oeh registeratyrelsan AmSJun utUgd odi utl.tkrifc «n publkarad 29.02.80 (32) (33) (31) Requested« ueiktui — tegird prtorit «t 22.lO.7i English-England (GB) U9297 / 71 (71) Howson-Algraphy Ltd., Vickers House, Millbank Tower, Millbank,

London SW1, England-England (GB) (72) Allen Peter Gates, Knaresborough, Yorkshire, England-England (GB) (7 * 0 Kolster Ab (5M) Photosensitive polymer suitable for use in the manufacture of printing plates - Ljuskänslig polymer hotplate for the purpose of the triccplate

Photosensitive materials, known as photopolymers, are well known and are used, e.g., as resists in photomechanical treatments, such as in the manufacture of nameplates and printed circuits and in the manufacture of printing plates in which exposed, light-cured areas form a printed image. Such materials have two detrimental features. Discoloration does not occur during exposure and the addition of an expensive "hypersensitizer" is usually required to improve spectral sensitivity so as to provide a reasonable exposure time for a light source conventionally used in industry, e.g., 3 minutes, using a carbon arc lamp or pulsating xenon lamp. Examples of previously known products include (i) a product known under the trademark "Kodak Photo Resist" (RTM) which is believed to be polyvinyl cinnamate, which is described, inter alia, in British Patent No. 695 197 and in which suitable hypersensitizers are described in British Patent No. : 7 ^ 3 U55 (e.g., the addition of 3-methyl-2-benzoylmethylidene-γ-naphthothiazoline as a hypersensitizer increases the rate 700-fold), (ii) Kodak Ortho Resist (RTM), which is assumed to be 2,571,83 polyvinylcinnamylidene acetate ( which has been hypersensitized with a pyrylium salt and is described in British Patent Publication Nos. 9 ^ 9 919) »and (iii) the polymeric cinnamoylated epoxy resins described in British Patent Publication Nos. 19 ^ 572, 913 76 U and 921 530, which use a sensitized , I + '- bis (dimethylamino) benzophenone. As mentioned above, the layers of these materials do not change color during exposure, and yet this is a highly desirable feature, e.g., in phase and repeat processing or when using several different negative "masters" when exposing different areas. Recent attempts to add photochromic agents to visualize areas that have been exposed to light have failed because, if the addition has been sufficient to produce a color change that can be seen in the treatment pin-actinic light, change the exposed area of the additive to affect its developability. or print properties. This is presumably due to the dissolution of the photochromic material in either the developer or the etchant or the printing ink, as the case may be, which makes the photoresist porous. The same effect has been observed in a few cases when the hypersensitizer has been extracted from the image area.

It has now been found that certain polymeric esters have the desired properties in providing a good color change upon exposure and in themselves are so rapid that they do not require any hypersensitizers for use under normal conditions, although such a sensitizer may be added if desired to provide a "camera speed" printing plate. Made from these esters. 11a Photoresists do not have degraded properties in the sense that they would not withstand the action of corrosive substances and have a long service life in the printing press.

The present invention relates to a photosensitive polymer suitable for use in the manufacture of printing plates and containing a plurality of azido-substituted ester groups attached to carbon atoms of a polymeric polyhydric substance, characterized in that the groups have the general formula N3-R- (CR1 = CR2) & - (CR -CR 1 -COO- wherein a and b are zero or 1 and a + b is at least 1, R is a phenylene radical optionally substituted by one or more halogen atoms, an alkyl group or an alkoxy group, and R 1, R 2 R 1 and R 2, which may be the same or different, are halogen atoms, hydrogen atoms or cyano groups, provided that at least one of the groups R 1 -R 2 is a halogen atom or a cyano group.

3 57183

Photosensitive resin esters of azido-substituted aromatic acids have been described in the literature »e.g. epoxy resin azido-benzoates in British Patent 1,118,213» and similar azido-cinnamates are needed in Czech Patent 1,35,029, but only these known esters provide added sensitizers to provide adequate exposure. As a result, it was not expected that the products of the invention would provide the desired properties, nor could it be expected that this could be achieved without affecting their lightfastness.

In one embodiment, the photosensitive polymeric ester of the invention contains groups of the general formula N3-R- (CR = CE2) a- (CR3 = CRu) b-C00- attached to carbon atoms, wherein a is 1, b is 0 or 1, R 1, R 2, R 3 and R 2 are as defined above and R 1 is a halogen atom or a cyano group. For example, in this formula, a and b may both be 1, R may be a phenyl group, R 1 may be a chlorine atom, R 8 and R 3 may be hydrogen atoms, and may be a hydrogen atom, a bromine atom, a chlorine atom or a cyano group.

According to the present invention, ester groups are attached to carbon atoms of a polyhydric material. This polyhydric material is preferably an epoxy resin. However, other polyhydric materials such as phenoxy resins, poly (vinyl alcohol), cellulose and cellulose ester or novolak resin made from phenol and formaldehyde can also be used.

The esters of the invention may be prepared by reacting at least 57183 one acid chloride of the formula N -R- (CR = CR n) - (CR * CR, L-COCl, wherein a, b, R, R and Rjj are as defined above to react with such a polyhydric material, the reaction may be in the presence of a base which may be a tertiary amine which may also act as a solvent, or in the presence of other solvents such as dioxane, dimethylformamide, methylene chloride or methyl ethyl ketone. triethylamine, N-methylpiperidine, pyridine, quinoline, dimethylaniline, and mixtures thereof The reaction is preferably carried out at a temperature of 20 to 70. Other esterification methods are known to those skilled in the art.

As the polyhydric substance, epoxy resins derived from the condensation of bisphenol A and epichlorohydrin and having the formula T-C \ H H 0 / ° \ f 3 I / \

ch3 I

Jn ch3 is Λ Γ *, 0H Ί ^ s / \ I / -vU Λ CH - CH-CHg - 0 — Λ /) - 0- /. N-O-CH 2 -CH-CH 2 -O-C 2 O 3 CH 2 -CH-CH 2 ch 3 ch 3 L -n in which n is preferably 9 ~ 12. Epoxy resins of this type which have been found to be useful are "Epikote 1007" and "Epikote 1009". · Such products are manufactured by Shell Chemical Company and have the following properties: 5 57183

Properties of Epicote resin 1007 1009

Epoxide equivalent weight 1700-2050 21 * 00-3 ^ 00 UO weight - / ?: viscosity of its solution in "butyl-dioxitol" at 25 ° C, 16-26 UO-110 poise

Specific gravity 20 ° C 1.19 1 * 19

Average molecular weight 2900 2750

Esterification equivalent weight 200 220

Melting point ° C, Durrana 120-130 lUO-155

Condensation products of epichlorohydrin with other aromatic hydroxy compounds can be used as the polyhydric material. Examples of other aromatic hydroxy compounds that can be used are bisphenols: U * -dihydroxy-diphenylmethane h, 1 * '- dihydroxy-diphenyl ether U, U'-dihydroxy-diphenylsulfone.

Suitable acid chlorides are those derived from the following azido-substituted acids:

Cl Br '^ 0 (i) N -— V' S— C = CH-CH = C-C ^ _

3 \ - / OH

Cl H

I I

(ii) N - (f 'S-C * CH-CH = C-C

3 \ - / ^ OH

Cl CN ^ o

(iii) —C * CH-CH »C-C

CN ^ 0

/ 7 ~ \ I

(iv) / —CH “C'C

CN - 1 ^ (v) N - s '' V-CH »CH-CH» C-C ^

^^ 0H

571 83 t (▼ i) CH-c-q 2

N- 'OH

MD * 3-O "~ ch -? '0 \

-S.C1 CH OH

Br 0

(▼ lii) H 2 - / - CH-C-C

CH 2 OH

f / °

(ix) CH 2 - (N - CH-C-C

\ τ = ^ ..- Cl OH

3

(x) CH 2 O - CH - C - C

is oh 3 _ __o (XI) H5-f3-0H.C-0 ^

'-' Br OH

The acid chlorides can be used alone or in combination with each other and / or in admixture with acid chlorides without azido groups of aliphatic and aromatic carboxylic acids. When acid chloride-free acid chlorides are also used, the ester also contains ester rithane derived from such acid chlorides. For example, if acetic acid, propionic acid, 2-ethylhexanoic acid or benzoic acid is used, the ester obtained also contains acetate, propionate, 2-ethylhexanoate or benzoate groups. The reaction of a non-self-acidic acid chloride with a polyhydric agent can take place not only simultaneously with the acid chloride of the above-mentioned general formula, but also before or after it.

As will be apparent from the following examples, the esters of the present invention may contain non-esterified hydroxyl groups.

In a very preferred process for the preparation of the esters according to the invention, a polyhydric substance, preferably an epoxy resin, is first dissolved in methyl ethyl ketone or dioxane to give a 10-UO solution, acid chloride or a mixture of acid chlorides or acid chloride-containing acid chloride either as such or dissolved in methyl ethyl ketone or dioxane. Sufficient pyridine is then added to convert all the acid chloride and the mixture is heated at U0-60 ° C for 2 h. The reaction mixture is diluted 1: 1 with methyl ethyl ketone-toluene, filtered to remove pyridinium chloride and slowly added dropwise to the stirred alcohol. The esters are obtained as a tan powder.

As already mentioned above, the esters of the invention are of great value in the manufacture of photographic plates, etc. Using these esters, a radiation-sensitive product can be prepared containing (i) a carrier to which the film containing the ester of the invention is attached, such as glass, paper, resin-impregnated paper , a plastic film or e.g. aluminum, zinc, magnesium or copper block board, and (ii) a layer formed by the supported ester of the invention.

When a layer of a photosensitive material is to be formed on a support, the photosensitive material is dissolved in a suitable solvent or solvent mixture such as dioxane, ethylene glycol monomethyl ether acetate or ethylene glycol monomethyl ether acetate. by drying or heating. The weight of the coating per square meter is generally 0.2-2 g.

For coating purposes in industry, it may be desirable to add to the polymer of the invention one or more of the following: colorants, plasticizers, wetting agents, hypersensitizers (as mentioned above), stabilizers, unreacted polymers, and also agents capable of reacting with photols.

After the carrier is coated with a film of an ester-containing photosensitive solution, it is dried to form a photosensitive product. When using the product, the photosensitive coating is exposed below the pattern for a period of time which depends on the composition of the coating, the thickness of the coating, the carrier, the intensity of the light source and the quality of the desired product. Exposed areas remain soluble, allowing image development using a suitable solvent or solvent emulsion developer.

8 57183

The solvent or solvent mixture used to develop the patterned product must be carefully selected because it should have a good solubilizing effect in unexposed areas, but little effect on cured areas. Suitable solvents include dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and tetrahydrofuryl acetate.

By adding solvents to the developer that dissolve poorly or not at all unexposed sites, such as propylene glycol or ethylene glycol monoethyl ether, it is possible to reduce the dissolution rate of the unexposed material and thus promote controlled development.

Preferred objects in which the photosensitive substances and products according to the invention can be used are the production of printing plates and etching products. Photopolymers are suitable for other purposes in addition to printing purposes, e.g. in the manufacture of printed circuits and the like, in chemical milling and in the manufacture of ornamental products.

The following examples illustrate the invention.

Example 1 (a) Preparation of U-azido-cis-cyano-d-chlorocinnamylideneacetic acid epoxy resin ester.

2.1 * 2 g of 1 * -azido-γ-chlorocinnamaldehyde (prepared by modifying the method disclosed in U.S. Patent No. 3,598,81 *) was dissolved in 50 ml of glacial acetic acid. To this was added 5 Λ g of cyanoacetic acid, and the mixture was heated at 00 ° C for 2 hours, during which time the product separated as fine needles. After filtration, the product was washed with glacial acetic acid (2 x 5 mL) and then dried over sodium hydroxide to give 1.0 g of product. Recrystallization from ethanol gave U-azido-non-cyano- () -chlorocinnanylideneacetic acid (iii) as dark yellow needles.

The acid containing 1 g of the azido group was heated with stirring with 25 ml of redistilled thionyl chloride at reflux for 6 hours. Half of the thionyl chloride was removed by distillation in vacuo and the cooled solution was poured into petroleum ether (boiling range U0-60 ° C). The acid chloride precipitated as an orange powder.

2.00 g (0.01 g equivalent) of "Epicote 1007" was dissolved in 30 ml of dioxane a and 2.93 g (0.01-m) of acid chloride were added. After stirring for 10 minutes, 1.0 ml of pyridine was added and the mixture was heated at 50 ° C for 1 * hour. The pyridinium chloride was filtered off and the solution was added dropwise to 1 x 00 ml of ethanol. The blended resin was separated by filtration and washed with ethanol as a filter. Yield 3.1 * 1 g. The UV spectrum had a maximum at 375 nm, an extinction at 375 nm, = 510 (dioxane).

l cm (b) Manufacture of pressure plate.

2.5 g of epoxy resin-1-azido-o-cyano-β-chlorocinnamylidene acetic acid ester was dissolved in a mixture of equal volumes of dioxane and 2-methoxyethyl acetate to give a solution of 5. This solution was diluted with toluene to 2.5 l and then applied to the surface of the electrostructured alum sheet using a rotary apparatus so that the weight of the coating was 0.5 g / m 2. After drying, the resulting photosensitive plate was exposed for 30 seconds in contact with the negative using a U000 watt pulsating xenon lamp at a distance of 0.65 m. A deep tan color formed on the exposed area. The exposed plate was developed using a mixture of glycol ester and wetting agent as described in Example 8 of British Patent No. 1,220,88, rinsed with water and greasy ink was added.

Example 2 (a) Preparation of k-azido-f-bromo-4-chlorocinnamylidene-acetic acid epoxyharte ester.

20.7 g of 1 + -azido-4-chlorocinnamaldehyde in 200 ml of methylene chloride were added to a solution of 1 + 2.8 g of triphenylcarbethoxybromophosphorane in 200 ml of methylene chloride. The resulting solution was then allowed to stand for 60 hours. The solvent was removed in vacuo at 25 ° C and the resulting crystalline mass was extracted with 6 x 50 ml portions of n-pentane. Evaporation of the combined extracts in vacuo below 25 ° C gave 2 l + .0 g of ester. 3.56 g of ester dissolved in 50 ml of methanol were treated with 10 ml of 50% sodium hydroxide solution at 25 ° C. After 2 h, the solvent was removed in vacuo at less than 25 ° C and the sodium salt of the product was extracted by washing the solid residue with hot water (5 x 100 mL). Upon cooling, the extracts gave a crystalline sodium salt which was converted by acidification (2-HCl) to U-azido-β-bromo-β-chlorocinnanylidene acetic acid (formula i).

U g of U-azido-γ-bromo-β-chlorocinnamylidene acetic acid was heated with 10 ml of thionyl chloride for 1+ hours at 70-75 ° C. 5 ml of thionyl chloride were removed in vacuo and the acid chloride was isolated by stirring the mixture with petroleum ether (boiling range 1 + 0-60 ° C) and filtering.

a 2.00 g (0.01 g equivalent) of "Epikote 1007" was dissolved in a mixture of 011 8 ml of methyl ethyl ketone and 8 ml of dioxane. 3.1 * 7 g (0.01-m) of acid chloride a was then added and the mixture was stirred for 10 minutes. Then 10 571 83 1.0 ml of pyridine were 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 off and washed with ethanol.

Yield: 2.23 g in the UV spectrum has a maximum at a wavelength of 3 ^ 9 nm 1¾

Extinction at 3 ^ 9 nm E, = 270 (dioxane).

1 cm (b) Manufacture of printing plates.

2 to 5 g of epoxy resin-1-azido-β-bromo-β-chlorocinnamylidene acetic acid ester were dissolved in a mixture of equal volumes of 2-methoxyethyl acetate and dioxane to give a 5 L solution. This solution was diluted to 2.5 with toluene and then rotatably applied to the surface of the electrically granulated anodized aluminum sheet so that the weight of the coating was 0.5 g / m 2. The sheet was dried and then exposed and developed as described in Example 1 (b). The sheet was rinsed with water and treated with ink.

Example 3 (a) Preparation of 1 * -azidobenzylidene-4-cyanoacetic acid epoxy resin ester.

U-aminobenzaldehyde (Organic Syntheses, Collected Volume IV, page 31, 1963) was diazotized and then reacted with sodium azide to give U-azido-benzaldehyde. 15 ml of U-azidobenzaldehyde were added while shaking to a solution of 11 g of cyanoacetic acid dissolved in 78 ml of 7 to 5? Aqueous sodium hydroxide solution at 25-30 ° C. After 2 hours, the yellow solid was filtered off, redispersed in 700 ml of water and acidified with hydrochloric acid. U-azidobenzylidene-β-cyanoacetic acid (formula iv) was isolated by filtration, washed with water, dried and recrystallized from ethanol.

The acid chloride was prepared by the method described in Example 2.

2.00 g (0.01 g equivalent) of "Epikote 1007" was dissolved in 9 ml of methyl ethyl ketone, and 1.6 U g (0.007 m) of U-azidobenzylidene-β-cyanoacetic acid chloride was added thereto. ml of pyridine was added dropwise and the mixture was heated at 50 ° C for 2 hours, the solution was filtered and passed dropwise into ethanol, and the precipitate was filtered off and washed with ethanol.

Yield: 2.70 g in the UV spectrum has a maximum at a wavelength of 3 ^ 5 nm

Extinction at 3 ^ 5 nm E, - k 2 O (dioxane).

± cm (b) Manufacture of printing plates.

2.5 g of epoxy resin-U-azidobenzylidene-β-cyanoacetic acid ether were dissolved in 23 ml of 2-methoxyethyl acetate and the volume was adjusted to 100 ml with toluene. Then, 0.125 g of Neozapon Blue Fle (BASF), phthalic cyanine blue, was added, and the mixture was stirred for 10 minutes. After filtration, the solution was coated on an electrically granulated anodized aluminum sheet in a rotating device to remove insoluble color particles. The plate was dried and then exposed for 1 minute as described in Example 1 (b). The change in color in the exposed areas occurred from blue to green on the plate, this green color resulting from the combination of blue and azide resin photo-lysis product. The plate was developed as described in Example 1 (b), rinsed and treated with greasy ink.

The presence of color in the coating promoted the development of those areas of the plate which were not in contact with the developer and a clearly visible pattern was obtained.

Example h (a) Preparation of 1 * -azidobenzylidene - * / r? -Anoic acetic acid epoxy resin ester.

2.00 g (0.009 g equivalent) of "Epicote 1009" was dissolved in 9 ml of methyl ethyl ketone and then 0.58 g of (0.0025-o) -azidobenzylidene-β-cyanoacetic acid chloride (formula iv) was added. and 1.0 ml of pyridine. The mixture was heated at 50 ° C for 2 hours, filtered and added dropwise to ethanol.

The precipitated ester was collected and washed with ethanol. Yield 2.31 g. UV-spectral ...,. . , 1% has a maximum wavelength of 3 * »5 nm. The extraction at wavelength 3 ** 5 is E, -1 cm = 133 (dioxane).

(b) Manufacture of printed circuit boards.

5 g of epoxy resin ester product was dissolved in U5 ml of 2-methoxyethyl acetate and made up to 100 ml with toluene. The solution was applied to the copper surface of a plastic sheet laminated with copper foil using a vortex coater with a rotation speed of 80 rpm, and the coating was dried by heating at 100 ° C for 2 minutes.

The plate was exposed for 3 minutes in contact with a negative printed circuit, developed by immersion in 2-methoxyethyl acetate, dried and etched by immersion in Uo JS in ferric chloride solution until the copper had completely removed from the areas not covered by the etchant. A printed circuit was obtained.

Example 5 (a) Preparation of U-azidobenzylidene-andbromoacetic acid epoxy resin ester.

U 1, 1 g of U-azidobenzaldehyde in 100 ml of methylene chloride was added to 12.8 U of triphenylcarbethoxy bromomethylene phosphorane in 100 ml of methylene chloride 57183, and the resulting solution was allowed to stand at room temperature for 6 hours. The solvent was removed in vacuo at room temperature to give a crystalline mixture of ester and triphenylphosphine oxide, from which the ester was extracted by repeated washing with n-pentane. Removal of the solvent in vacuo from the combined extracts at room temperature gave 7.86 g of a pale yellow crystalline product. Sp. 59-6l ° C.

3 g of the ester dissolved in methanol were treated with 10 ml of 50 # sodium hydroxide solution at room temperature and allowed to stand for 2 hours. The solvent was removed in vacuo at 25 ° C, the residue was dissolved in water and the product (formula xi) was stirred by the addition of 2N hydrochloric acid.

The acid chloride was prepared as described in Example 2.

2.00 g (0.01 g equivalent) of "Epicote 1007" was dissolved in 18 ml of dioxane and then 2.51 g (0.01-m) of U-azidobenzylidene-tert-bromoacetic acid chloride and 1.0 g of ml of pyridine. The temperature was raised to 50 ° C and maintained at this value for h hours. Pyridinium chloride was filtered off and the solution was added dropwise to ethanol. The doped ester was collected and washed with additional ethanol. Yield: 2.10 g.

The UV spectrum has a maximum at 319 nm.

1¾

Extinction at 319 nm E, = * 198 (dioxane).

1 cm (b) Manufacture of printing plates.

2.5 g of epoxy whey-N-azidobenzylidene-β-bromoacetic acid ester was dissolved in 23 ml of 2-methoxyethyl acetate and made up to 100 ml with toluene. The solution was added in a rotary apparatus to the surface of an electrically granulated anodized aluminum sheet. The treatment of Example 2 (b) to prepare a printing plate was repeated except that an exposure time of 2 minutes was used.

Example 6 (a) Preparation of U-azido-2-chlorobenzylidene-trichloroacetic acid epoxy resin ester.

2-Chloro-U-aminobenzaldehyde prepared by the above method for the preparation of U-aminobenzaldehyde was diazotized and reacted with sodium azide to give U-azido-2-chlorobenzaldehyde as a yellow solid. 7.35 g of U-azido-2-chlorobenzaldehyde, 2.50 ml of glacial acetic acid and 2.86 g of cyanoacetic acid were stirred together at 50 ° C for 1 hour, after which U-azido-2-chlorobenzylidene-N-cyanoacetic acid (formula vii) separated as a pale yellow solid. The product was filtered off, washed with glacial acetic acid and water and recrystallized from methanol. Yield 6.9 g.

The acid chloride was prepared by the method described in Example 2.

2.00 g (0.01 g equivalent) of "Epicote 1007" was dissolved in 9 ml of methyl ethyl ketone, and then 2.68 g (0.01 g) of U-azido-2-chlorobenzylidene-N-cyanoacetic acid chloride were added. and 1.0 ml of pyridine. The temperature was raised to 50 ° C and maintained at this value for U hours. After filtration, the solution was added dropwise to ethanol, and the doped resin was collected and washed with fresh ethanol. Yield 2, U0 g.

The UV spectrum has a maximum at 3 ^ 2 nm.

l £

Extinction at 3h2 nm ΕΓ * 110 (dioxane).

1 cm (b) Manufacture of printing plates.

The treatment of Example 2 (b) was repeated except that an exposure time of 2 minutes was required.

Example 7 (a) Preparation of U-azido-3,5-dibromobenzylidene-β-cyanoacetic acid epoxy resin ester.

10.30 g of U-aminobenzaldehyde was dissolved in a solution of 2.75 g of HCl in 660 ml of water by heating the mixture to boiling point. 8.50 ml of bromine dissolved in the minimum amount of water was added slowly and the mixture was stirred for 30 minutes. U-amino-3,5-dibromobenzaldehyde separated as a light brown precipitate. Yield 7.01 g.

U-azido-3,5 ′ dibromobenzaldehyde was prepared by diazotizing the amine followed by reaction of the product with sodium azide.

6.5 g of 1 * -azido-3,5-dibromobenzaldehyde were mixed with 6.0 ml of glacial acetic acid and 2.02 g of cyanoacetic acid and heated at 50 ° C for 1 hour. After cooling and allowing the mixture to stand at room temperature for 2 hours, a crystalline mass of U-azido-3,5 "dibromobenzylidene-o-cyanoacetic acid (formula viii) separated. These crystals were washed with a small amount of glacial acetic acid and then with a larger amount of water. again from ethanol Yield 5.5 g ·

The acid chloride was prepared by the method described in Example 2 (a).

2.00 g (0.01 g equivalent) of "Epikote 1007" was dissolved in 9 ml of methyl ethyl ketone and then 3.38 g (0.01-m) of 1 * -azido-3,5 "dibromobenzylidene-x cyanoacetic acid chloride and 1.0 ml of pyridine, respectively, The patient was raised to 50 ° C and kept at 50 [deg.] C. After filtration, the resin was separated by passing the solution dropwise to ethanol in a yield of 3.39 g.

The UV spectrum had a maximum at 33b nm.

1¾

Extinction at 33b nm, ET - 3b0 (dioxane).

1 cm (b) Manufacture of pressure plate.

The treatment according to Example 1 (b) was repeated except that a spherical granulated aluminum plate was used as a support and a 2 minute exposure sieve was used. After development and rinsing with water, greasy ink was added to the plate.

Example δ (a) Preparation of 3-ateidobenzylidene-β-cyanoacetic acid epoxy resin ester.

The 3-aminobenzaldehyde was diazotized and the product was reacted with sodium azide to give 3-azidobenzaldehyde. This was condensed with cyanoacetic acid using the method described in Example 3 (a) and the product (formula vi) was converted to the acid chloride using the method described in Example 2 (a).

2.00 g (0.01 g equivalent) of "Epicote 1007" was dissolved in 9 ml of methyl ethyl ketone, then 2.10 g (0.009 m) of 3-azidobenzylidene-cyanoacetic acid chloride were added and the mixture was stirred. Then 1.0 ml of pyridine was added and the temperature was raised to 50 ° C and maintained at this value for 2 hours The resin was separated by passing the filtered solution into ethanol Yield 3, ib g The UA spectrum has a maximum at 300 nm Extinction at 300 nm, E ^ »370 (dioxane).

1 cm (b) Manufacture of printing plates.

2.5 g of epoxy resin-3-azidobenzylidene-β-cyanoacetic acid ester were dissolved in 23 ml of 2-methoxyethyl acetate. The solution was made up to 100 ml with toluene and 0.25 g of 1,2-benzanthraquinone was added. After filtration, to remove insoluble particles of the hypersensitizer, the solution was added in a rotating device to the surface of the electrically granulated anodized aluminum sheet so that the weight of the coating 2 was 0.5 g / m 2. The dried plate was exposed for 1 minute and developed as described in Example 1 (b). The plate was rinsed and treated with greasy ink.

Example 9 (a) Preparation of 3-azido-U-methylbenzylidene-o-cyanoacetic acid epoxy resin ester.

U25 ml of concentrated sulfuric acid and 36 ml of concentrated nitric acid were mixed in the middle and cooled in a dry ice-acetone bath at 0 ° C. 100 ml of 1 + toluene aldehyde were then slowly added with stirring, keeping the temperature of the reaction mixture between -2 and + 2 ° C. The resulting mixture was warmed to 100 ° C and then allowed to cool to room temperature. The product was isolated by pouring it as a thin stream into fine ice. The yield of 3-nitro-U-tolualdehyde was 7 g · 50 g of 3-nitro-U-tolualdehyde, dry cyanoacetic acid and glacial acetic acid were heated at 100 ° C for 7 hours. 3-Nitro-U-methylbenzylidene-β-cyanoacetic acid was filtered off and washed with glacial acetic acid and water.

Yield 32 g.

25 g of 3-nitro-U-methylbenzylidene-4-cyanoacetic acid were dissolved in 350 ml of alcohol. 350 ml of water were then added and the mixture was heated to boiling point. 55 g of sodium dithionite were then slowly added, the mixture was heated under reflux for 30 minutes, cooled and acidified with hydrochloric acid. The solution was therefore boiled until the odor of sulfur dioxide could no longer be detected. Then, 50 ml of concentrated hydrochloric acid was added, and the mixture was cooled to a temperature between 0 and -5 ° C. A solution of sodium nitrite in U0E was then added until a persistent slight excess of nitric acid remained.

Then 20 g of sodium azide in 50 ml of water from a dropping funnel were added dropwise and the precipitated 3-azido-U-methylbenzylidene-4-cyanoacetic acid (formula ix) was filtered off at the pump. After washing with water, 5> 78 g of product were obtained.

The acid was converted to the acid chloride using the procedure described in Example 2 (a).

1.00 g (0.009 g equivalent) of "Epicote 1007" was dissolved in 6 ml of methyl ethyl ketone and added to a solution of 0.99 g of (O.OOU-m) 3-azido-U-methylbenzylidene-o N-cyanoacetic acid chloride in 6 ml of methyl ethyl ketone, 0.5 ml of pyridine were then added and the mixture was heated at 75 [deg.] C. for 2 hours. nm Extinction at 298 E * 156 (dioxane).

(b) Manufacture of printing plates.

The procedure of Example 2 (b) was repeated except that an exposure time of 2 minutes was required to obtain the desired image. The developed plate was rinsed with water and greasy ink was added.

57183 16

Example 10 (a) Preparation of 3-azido-U-methoxybenzylidene- * 4-cyanoacetic acid epoxy resin ester.

56.3 g of U-anisaldehyde were added very slowly to a dry ice-cooled mixture of 18.3 ml of concentrated nitric acid and 366 ml of concentrated sulfuric acid. After stirring for 1 hour, the mixture was poured into a large volume of ice water, to which dry ice was added occasionally. 3-nitro-U-anisaldehyde hydride precipitated as a pale yellow solid. Recrystallization from methyl alcohol gave a yield of 30.3 g.

10.5 g of 3-nitro-U-anisaldehyde, dry cyanoacetic acid and glacial acetic acid, each, were heated at 105 ° C for 6 hours and at 120 ° C for a further 2 hours. After cooling and standing overnight, 6.0 g of 3-nitro-U-methoxybenzylidene-α-cyanoacetic acid were obtained. Reduction and conversion to 3-azido-U-methoxybenzylidene-β-cyanoacetic acid (Formula X) was accomplished using the procedure described in Example 9 (a) described for the preparation of U-methyl-substituted acid. The acid chloride was prepared by the method described in Example 2 (2).

1.6 g (0.008 g equivalent) of "Epicote 1007" was dissolved in 15 ml of methyl ethyl ketone and added to 1.58 g of (0.006-m) 3-azido-U-methoxybenzylidene-β-cyanoacetic acid chloride in 5 ml: methyl ethyl ketone. 1.0 ml of pyridine was then added and the mixture was heated at 75 ° C for 2 hours. After filtration, the solution was added dropwise to 100 ml of alcohol and the precipitate was filtered off and washed with alcohol. Yield 1.96 g. The UV spectrum had a maximum at 1¾ at 323 nm. Extinction at 323 nm, λmax = 228 (dioxane).

(b) Manufacture of printing plates.

The procedure of Example 2 (b) was repeated except that the plate was exposed for 2 minutes and then developed with an emulsion of 2 parts of a 10 ° C rubber solution containing 1% phosphoric acid and 1 part of 3-methoxybutyl acetate.

Example 11 U-Azido-cyanocinnamylidene acetic acid (Formula V).

1 * -Azidocinnamaldehyde (used crude and prepared according to U.S. Patent 3,598,8UU) was dissolved in 10 ml of dry pyridine and 2.8 g of cyanoacetic acid was added. K drops of piperidine 17 571 83 were then added and the solution was allowed to stand for U hours. The red solution was poured into ice water containing 30 ml of concentrated hydrochloric acid, and then U-HCl was added dropwise with stirring to pH 5. The reddish brown solid was removed by filtration and dissolved in ether and then dried over magnesium sulfate. 0.1 g of charcoal was then added and the solution was filtered. The filtrate was concentrated to give 1.3 g of product, which was recrystallized from ethyl acetate-petroleum ether. Sp. 17 ^ -175 ° C. The UV spectrum had a maximum at 355 nm. Mbla extinction coefficient at 355 nm: 3 ^ 700 in methanol.

The epoxy resin ester of the acid was prepared by an analogous method to that described above and used in the preparation of satisfactory printing plates.

Example 12

It-ateido-β-chlorocinnamylidene acetic acid (formula ii).

20.7 g of U-azido-γ3-chlorocinnamaldehyde was reacted with 3.5 g of triphenylcarbethoxymethylene phosphorane in methylene chloride as described in Example 2 (a). In this case, no ester was separated and the residue remaining after removal of the solvent was dissolved in 10 ml of methanol and treated with 50 ml. 50 # of sodium hydroxide solution. After standing at room temperature for 18 hours, the methanol was removed in vacuo at a temperature below 30 ° C and the sodium salt of the product was removed by extraction with 5 x 100 ml portions of warm water. Oxidation of the cooled extracts with 2-hydrochloric acid gave 8.0 g of carboxylic acid. Recrystallization from methanol gave yellow microcrystals which decomposed at temperatures above 160 ° C. The UV spectrum had a maximum at 325 nm. The molar extinction coefficient at 325 nm = 37> 150 in methanol.

The epoxy resin ester was prepared analogously to that described above and used in the preparation of satisfactory printing plates.

Example 13 (a) Preparation of U-azidobenzylidene-oC-cyanoacetate of polyvinyl alcohol.

A mixture of 7.3 g of "Moviol NS0-88", a polyvinyl alcohol manufactured by Hoechst, and 79 ml of pyridine was heated at 90 ° C for 1 hour. An additional 79 mL of pyridine was then added and the mixture was cooled to room temperature. 3 * 8 g of 3-ateidobenzylidene-o <-cyanoacetic acid (formula iv) chloride were then added so that the temperature of the reaction mixture did not exceed 50 ° C. After stirring for 1.5 hours at this temperature, the mixture was diluted with 160 ml of dimethylformamide and then added dropwise to 1 * liter of water. The precipitate was collected on a filter, redispersed in 1500 ml of ethanol and the mixture was stirred for 30 minutes. After filtration, the solid was washed with water as a filter and then dried at room temperature. The UV spectrum had a maximum at a wavelength of 3 ^ 5 nm.

(b) Manufacture of printing plates.

2.5 g of the above product were stirred with 100 ml of dimethylformamide at 100 ° C for 3 hours. After filtration, the solution was added to the surface of an electrically granulated anodized aluminum sheet in a device having a rotation speed of 80 rpm. The dried plate was exposed for 2 minutes in contact with the negative using a 1 * 000 watt pulsating xenon lamp at a distance of 0.65 m. The plate was developed with a mixture of 1100 ml of dimethylformamide, 250 g of Texafor D.1, 2 g of glyceride oil polyoxyethylene condensate and 10 ml of concentrated sulfuric acid supplemented with 10% water.

Example lU

(a) Preparation of epoxy resin benzoate-U-azidobenzylidene-o-cyanoacetate.

6 g (0.03 g equivalent) of "Epikote 1007" was dissolved in 27 ml of methyl ethyl ketone. To this was added 0.9 g (0.021 g equivalent) of 1 * -azidobenzylidene-β-cyanoacetic acid (Formula iv) and the mixture was stirred 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 cooled and then filtered and the filtrate was passed dropwise into ethanol. The doped ester was collected and washed with ethanol. Yield 8.8 g. The UV spectrum had a maximum at 3 ^ 5 nm.

(b) Manufacture of printing plates.

The treatment of Example 2 (b) was repeated with the difference that an exposure time of 1 minute was used.

Example 15 Preparation of p-azidobenzylidenecyanoacetic acid.

Equal amounts of azidobenzaldehyde and cyanoacetic acid were condensed together, using glacial acetic acid as catalyst, for 1 hour at 55 ° C. The reaction mixture was cooled and the yellow solid was filtered off, washed with cold water and recrystallized from ethanol.

Preparation of p-azidobenzylidene cyanoacetyl chloride.

The acid prepared above was heated to reflux with excess thionyl chloride used for H hours. The acid chloride was separated by addition to petroleum ether.

19,571 83

Esterification with epoxy resin.

An epoxy resin known under the trademark "Epikote 1009" derived from epichlorohydrin and bisphenol A having a molecular weight of about 3750 was dissolved in methyl ethyl ketone, and an equal weight of acid chloride prepared as described above was added thereto. The mixture was heated on a water bath for 5 hours in the presence of a small amount of pyridine. The resulting ester was blended in methylated industrial spirit, washed with such alcohol and dried to give a pale yellow powder.

Manufacture of printing plates.

A 3 solution of the above ester in a mixture of 2-methoxyethyl acetate and toluene (1: 3 by volume) was added by means of a stirrer to the surface of a granulated aluminum sheet anodized in a phosphoric acid electrolyte to give a coating weight of 0.5 g / l. m. After drying, the photosensitive plate was exposed below the negative ("Kodak No. 3 Step Wedge") using a 2,000-watt pulsating xenon lamp for 1 minute to produce a deep crystalline color on the light-exposed areas. 1,220 8θ8 and marketed by IIovson-Algraphy Limited under the trademark "Marathon Developer".

The developed plate was washed and treated with ink. The ink easily adhered to the pattern. The pattern corresponding to the stepped wedge was clear at 9 with its peak at 1U.

Claims (9)

20 57183 Not claimed A photosensitive polymer suitable for use in the manufacture of printing plates and containing a plurality of azido-substituted ester groups attached to carbon tones of a polymeric polybydric substance, characterized in that the groups have the general formula in river a and h are zero or 1 and a -fb is at least 1, R is a phenylene radical optionally substituted by one or more halogen atoms, an alkyl group or an alkoxy group, and R 1, R 8 * R 2 and R 2, which may be the same or different, are halogen atoms, hydrogen atoms or cyano groups, provided that at least one of R R 1 is a halogen atom or a cyano group. A photosensitive polymeric ester according to claim 1, characterized in that in formula a is 1, b is zero or 1, R, R 9, R 1 and R 2 have the same meaning as in claim 1 and R 1 is a halogen atom or a cyano group. A photosensitive polymeric ester according to claim 2, characterized in that in formula a and b are both 1, R is a phenylene group, R 1 is a chlorine atom, R 8 and R 2 are hydrogen atoms and R 1 is a hydrogen atom, a bromine atom, a chlorine atom or a cyano group. A photosensitive polymeric ester according to claim 1, characterized in that in formula a is zero, b is 1, R 1 is hydrogen, R 1 is a bromine atom, a chlorine atom or a cyano group and R is a phenylene group substituted by a methyl group, a methoxyoxy group, a bromine atom or a chlorine atom. The photosensitive polymeric ester according to claim 1, characterized in that it is an ester of a polyhydric substance and an acid selected from the group consisting of: 4-azido-α-bromo-β-chlorocinnamylideneacetic acid 4-azido-d-chlorocinnamylidene acetic acid, 4-azido -. -Dibromobenzylidene-ε-cyanoacetic acid, 571 83 21 3-Azido-4-methyl-benzylidene-β-cyanoethylacetic acid, 3-azido-4-methoxybenzylidene-α-8-cyanoacetic acid and 4-aza-bantylamide ayanoatikkahappo. A photosensitive polymeric ether according to claim 1, characterized in that ae is an ester of a polyhydric substance and 4-azido-benzylidene-β-cyanoacetic acid. A photosensitive polymeric ester according to any one of claims 1 to 6, characterized in that ae further contains ester groups derived from an acid chloride-free acid chloride. A photosensitive polymeric ester according to claim 1, characterized in that the acid chloride without an atido group is an acid chloride of acetic acid or benzoic acid. Photosensitive polymeric ester according to one of the preceding claims, characterized in that ae contains free hydroxyl groups derived from a polyhydric substance. 22____ 57183