DE2302820C3 - Photopolymerizable mixture - Google Patents

Description

It is known that photopolymerizable mixtures containing ethylenically unsaturated monomers, certain add light-absorbing compounds in order to increase the photographic sensitivity of the mixtures. From US Pat. No. 3,427,161 it is also known to be photo-crosslinkable for photoinsolubilization Polymeric Λ-dicarbonyl compounds and combinations to use Λ-dicarbonyl compounds with ultraviolet radiation absorbing ketones, however, cyclic cis-α-dicarbonyl compounds have not yet become generally known as photoinitiators. By US Pat. No. 2,951,758, column 2, line 39, it is demonstrated that these compounds are the Initiate photopolymerization only very weakly.

There are also known photopolymerization systems, in addition to an ethylenically unsaturated compound and a photoinitiator as sensitizers also contain styryl or cyanine dyes. It has, however show that the described combination of mono- or polymethine dyes with photoinitiators on the Basis of organic bromine compounds only to a limited extent to a more favorable spectral Sensitivity leads. It also succeeds to the same extent only an increase in the exposure time required for photopolymerization according to the procedure US Pat. No. 3,099,558, according to which a monomer containing the group CFh = C c is directly attached an electronegative group adhering to

exposed to electromagnetic radiation of a certain spectral range. The photopolymerizable Layer as the only initiator of the photopolymerization an aromatic diazonium compound in addition contain a styryl or a cyanine dye.

A photopolymerizable recording material composed of a support and a photopolymerizable layer is also known which, in addition to a photopolymerization initiator, also contains a cyanine or styryl dye and an antihalation dye (cf. DT-AS 17 97 186). This combination is intended to solve the problem of faithfully reproducing very light or very dark areas of a master copy without having to accept a drop in photographic sensitivity. *, ₅

There are also known photopolymerizable mixtures, which a photoinJiiatorsystem from dicarbonyl compounds whose photographic effectiveness is increased by added sensitizers (cf. DT-OS 17 69 359, 19 52 804 and 15 22 359). These too Photoinitiator systems can, however, be improved considerably with regard to their sensitivity to light.

The object of the invention is to provide a photopolymerizable mixture that contains a dicarbonyl compound and contains a sensitizer as a photoinitiator system which has improved photographic sensitivity and is also characterized by a particularly wide range of spectral sensitivity.

The invention is based on a photopolymerizable, optionally a mixture which can be applied to a layer support

to form a) at least one non-gaseous ethylenically unsaturated compound having a boiling point above 100 ⁰ C which is capable of addition polymerization through photo initiated a high polymer,

b) an α-dicarbonyl compound as a photoinitiator,

c) an actinic radiation with an absorption maximum below 520 nm absorbing, capable of sensitizing deir polymerization-initiating effect of the dicarbonyl compound from the group of
Bis (p-aminophenyl-a ^ -unsaturated) ketones,
Bis (alkylamino) acridine dyes,
Cyanine dyes having two heterocyclic rings linked by a single methine group,

Styryl dye bases,

7-dialkylamino-4-alkylcoumarins with 1 to 4 carbon atoms in the alkyl radicals of the 4- and 7 position,

p-aminophenyl ketones, p-dialkylaminophenyl-unsaturated compounds
or the 6-dialkylamino quinaldine.
It is characteristic that ¹ it contains, as a photopolymerization initiator, a cyclic cis-α-dicarbonyl compound which is intramolecularly unreactive, in which, if the atoms adjacent to the vicinal carbonyl groups are carbon atoms, these are not parts of an unsaturated radical. _h0

From DT-OS 17 69 359 photopolymerizable mixtures are known which, in addition to an ethylenic unsaturated monomers a photoinitiator system from a cyclic dicarbonyl compound (e.g. a phenanthrenequinone) and one to activate the photo initiator- (, 5 contain the bis (alkylamino) acridine dye. In the photoinitiator systems of the invention are phenanthrenequinones not included. The technical progress of the photopolymerizable mixtures compared to the invention the mixtures known from DT-OS 17 69 359 lies in the considerably better light sensitivity

in DT-OS 19 52 804 photopolymerizable mixtures are described which, in addition to the unsaturated Compound contain a photoinitiator system from an o-quinone initiator and at least one thioketone, wherein, according to one embodiment, a p-aminophenyl ketone in addition to the o-quinone initiator in this mixture present Against the mixtures described here are those with the photoinitiator systems photopolymerizable mixtures equipped according to the invention with regard to photosensitivity considerably superior. A disadvantage of the known initiator system composed of o-quinone and thioketone is that that this combination is often accompanied by a color formation, which is suitable for certain areas of application, in which a colorless image or one with a different color is desired, has a disruptive effect In addition, it should be noted that too large a proportion of thioketone reduces the photosensitivity of the photopolymerizable mixture, due to the increased color intensity, which is caused by the Thioketone is evoked. The undesired effects shown do not apply when using the Photoinitiator systems of the invention which are incapable of triggering any coloration.

The DT-OS 15 22 359 are photopolymerizable recording materials with such photopolymerizable mixtures can be found in addition to an ethylenically unsaturated, crosslinkable compound, a photoinitiator system from a «-dicarbonyl compound, z. B. diacetyl, and a photoinitiator sensitizing compound, z. B. Michler's ketone (p-dialkylaminophenyl ketone) may contain. The photoinitiator system of the invention has the significant advantage over this system that the dicarbonyl compounds present according to the invention boil much higher than the low-boiling diacetyl initiator (boiling point 88 ^° C.) of the known system. In the photopolymerizable mixture of the invention, 10O ⁰ C is the lowest boiling point of the ethylenically unsaturated monomer, the lowest temperature above which all the constituents present boil. The dicarbon compounds in the systems of the invention boil or melt with decomposition at temperatures above 180 ^° C. In contrast, the high volatility of this compound due to the low boiling point of the known diacetyl initiator increases the risk of fire and increased risk of poisoning from inhaled vapors during manufacture , Storage and application. The increased volatility leads to poor reproducibility and even insensitivity, depending on the extent of evaporation of the diacetyl initiator from its photopolymerizable mixture. The disadvantages mentioned do not apply to the photoinitiator systems of the invention, due to their high boiling point or melting point.

In the photoinitiator system described from the non-low-boiling benzil and also in the frame Michler's ketone applied to the invention as a sensitizer can be the ones explained above Disadvantages do not occur, but this particular system is the initiator combination of the invention with respect to significantly inferior to photosensitivity.

According to one embodiment of the invention, the photopolymerizable mixture contains from 3 to 100 Parts by weight of the ethylenically unsaturated compound (a) 97 to 0 parts by weight of a macromolecular, organic, polymeric binder (s). Preferably 3 to 95 parts by weight of (a) and 97 to 5 parts by weight of the binder are present.

According to a further embodiment of the invention are both to 0,00t to 10 parts by weight based on 100 parts by weight of the total weight of ethylenically unsaturated compound plus a binder before the cyclic cis-a-Dicarbonylverbi / idungen and the actinic radiation absorbing compound (c) w. It has also been found that the photopolymerizable mixture contains up to 10 parts by weight of a hydrogen or electron donor compound (d) which forms free radicals per 100 parts by weight of the total weight of the ethylenically unsaturated compound plus a binder

A thermal addition polymerization inhibitor is also useful in the photopolymerizable mixture present, optionally in amounts of 0.001 to 4.0 parts by weight, based on 100 Parts by weight of the total weight of the ethylenically unsaturated compound plus a binder, is present.

The photopolymerizable compositions of the invention have utility in imaging Materials have improved photo initiation and increased photographic sensitivity. Such materials can be self-supporting, but they can also consist of a layer carrier on which the photopolymerizable mixture described above has been applied.

Suitable, free radical initiated, chain propagating, addition polymerizable, Ethylenically unsaturated compounds which are suitable for the invention are preferably: an alkylene or polyalkylene glycol diacrylate consisting of an alkylene glycol having 2 to 15 carbon atoms or one Polyalkylene ether glycol with 1 to 10 ether bonds has been produced, as well as the corresponding ones in the US Patent 29 27 022 described compounds, for example those comprising a plurality of Have addition-polymerizable, ethylenic bonds, especially if these are terminal Bonds exist and especially those in which at least one and preferably most of such- ger bonds are conjugated with a doubly bonded carbon atom. That’s included Cases in which a carbon atom is attached twice to carbon and to heteroatoms such as nitrogen, Oxygen and sulfur, bonded Substances that have proven to be extremely effective are those in which the Ethylenically unsaturated groups, especially the vinylidene groups, with ester or amide structures present conjugated. The following compounds of this type are of considerable importance: unsaturated Esters of alcohols, for example polyols and especially those of the α-methylene carboxylic acids, for example

Ethylene glycol diacrylate,

Diethylene glycol diacrylate,

Glycerine diacrylate,

Glycerine triacrylate,

Ethylene glycol dimethacrylate,

1,3-propanediol dimethacrylate,

1,2,4-butanetriol trimethacrylate,

1,4-cyclohexanediol diacrylate,

1,4-benzenediol dimethacrylate,

Pentaerythritol tetramethacrylai,

13-propanediol diacrylate,

1,3-pentanediol dimethacrylate,

the bis-acrylates and -methacrylates of polyethylene glycols a molecular weight of 200 to 500, also unsaturated amides, especially those of the «-Methylene carboxylic acids and especially those of the α-ω-diamines and those interrupted by oxygen atoms ω-diamines, like

Methylene-bis-acrylamide,

Methylene-bis-methacrylamide,

Ethylene-bis-methacrylamide,

l.e-hexamethylene-bis-acrylamide,

Diethylenetriamine-tris-methacrylamide,

Bis (y-methacrylamidopropoxy) -ethane-0-

methacrylamidoethyl methacrylate,

N- (j3-hydroxyethyl) -j9- (methacryIamido) -

ethyl acrylate and
NN-bis-CS-methacryloxyethyl acrylamide;

Vinyl ester, like

Divinyl succinate, divinyl adipate,

Diviny phthalate, divinyl terephthalate,

Divinylbenzene-1,3-disulfonate and

Divinyl butane-1,4-disulfonate;

also styrene and its derivatives and unsaturated aldehydes such as sorbaldehyde (hexadienal). One An important class of these preferred addition-polymerizable constituents are the esters and amides of «-Methylene carboxylic acids and the substituted carboxylic acids with polyols and polyamines, in which the molecular chain between the hydroxyl and amino groups made up only of carbon or through oxygen atoms interrupted carbon atoms. The preferred monomeric compounds are polyfunctional Functionally, however, monofunctional monomers can also be used. In addition, the polymerizable, ethylenically unsaturated polymers of US Patents 30 43 805 and 29 29 710 and Use similar substances, alone or in combination with other substances. Acrylic and methacrylic acid esters of polyhydroxy compounds such as pentaerythritol and methylolpropane, as well as acrylic acid and methacrylic acid esters of adducts of ethylene oxide and polyhydroxy compounds, respectively the details of US Pat. No. 3,380,831 are also useful. The one in US patents 34 18 295 and 34 48 089 explained, photo-crosslinkable polymers can also be used. The amount of added monomer will vary with the particular polymer employed.

In the case of the cyclic cis-a-dicarbonyl compounds are organic compounds that have vicinal carbonyl groups in which the Oxygen atoms of the carbonyl groups must be on one side of the molecule; the remaining portion of the cyclic molecule can contain one or more heteroatoms in addition to the carbon atoms. If the atoms adjacent to the two vicinal carbonyl groups are both carbon atoms, then so they must be saturated, so they cannot be part of an unsaturated radical. The cyclic dicarbonyl compound, which has been excited by radiation absorption or by energy transfer does not have to be in the Be able to react by splitting off hydrogen intramolecularly to form cyclic products. This property is found in those cyclic ones

cis-a-dicarbonyl compounds in which the carbonyl groups be held rigidly in a conformation that precludes such cyclization reactions. the Required rigid molecular conformation can usually be obtained by using cyclic cis-a-dicarbonyl compounds in which the carbonyl groups have been built into a framework consisting of several rings. A preferred such a compound is 2,3-bornanedione, also known as camphorquinone. Others corresponding connections are as follows:

2,2,5,5-tetramethyl-tetrahydro-3,4-furandione,

Parabanic acid, (imidazoltrione),

Indole-2,3-dione (isatin),

1,1, M-tetramethyl-tetralin ^ .S-dione,

3-methyl-1 ^ -cyclopentanedione;

2,3-Dioxo-5,6-diethyloxy-5,6-dicyanopyrazine

and

imid.

The actinic radiation absorbing compounds (component c) of the photopolymerizable mixture, which can be converted into an excited state by absorption of actinic radiation and which, if excited in this way, the cyclic cis-oc-dicarbonyl compound sensitize, are nitrogen-containing, aromatic or heterocyclic compounds with an absorption spectrum below 520 nm. These are nitrogen-containing, aromatic or heterocyclic compounds around bis- (paminophenyl-a, /? - unsaturated) Ketones, bis (alkylamino) acridine dyes, cyanine dyes with two heterocyclic dyes linked by a single methine group Rings, styryl dye bases, 7-dialkylamino-4-alkylcoumarins with 1 to 4 carbon atoms in the 4- and 7-position alkyl, p-aminophenyl ketones, p-Dialkylaminophenyl unsaturated compounds or 6-dialkylamino quinaldines as explained below.

The bis (p-aminophenyl-a, j3-unsaturated) ketones are described in U.S. Patent No. 36 52 275th The bis (alkylamino) acridine dyes correspond to the formula in column 9, lines 31 to 42 of US Pat. No. 3,563,751, they are also explained in column 3, lines 21 to 43, and lines 50 to 71 of this patent. In the case of the cyanine dyes are single cyanines which have two heterocyclic rings which are linked by a single methine group and which correspond to the following formulation:

Heterocyclic ring,
which contains 5 valuable nitrogen

- CH = heterocyclic ring,
which contains trivalent nitrogen

Some examples of such cyanine dyes are shown in column 3, lines 17 to 33 of U.S. Patent No. 3,099,558 listed. The styryl dye bases have a heterocyclic ring and a benzene ring. those about a Vinyl group are linked and correspond to the following formulation:

[Heterocyclic ring with trivalent nitrogen] —CH-CH

wherein R2 is an alkyl radical having 1 to 4 carbon atoms stands. Some compounds of this genus are listed in column 6, line 61, to column 7, Line 9 of this patent specification is reproduced. A preferred styryl dye base is 2- (p-dimethylaminostyryl) benzothiazole.

The 7-dialkylamino-4-alkylcoumarins are coumarins with alkyl substituents in the 4- and 7-positions which contain 1 to 4 carbon atoms. Several examples of such coumarins are listed in column 3, line 71 through column 4, line 4 of US Pat. No. 3,583,797.

In the p-aminophenyl ketones is that of the formula in column 15, line 71, corresponding to column 16, line 4, of U.S. Patent No. 35 52 973 compounds. A further description of these ketones is given in column 3, line 40 to column 4, line 10 of this patent specification. p, p'-bis (dimethylamino) - benzophenone, also known as Michler's ketone, belongs to this genus.

The p-dialkylaminophenyl-unsaturated compounds correspond to the formula

60

N-

R ₁

atoms mean and R2 stands for -CN, -CHO,

O OH

- C - CH

CH = N

HN

I! —C

-CH = CH-C

where R3 is hydrogen, -R, -OR,

wherein R and Ri can be alkyl groups with 1 to 4 carbon, halogen or phenyl.

609 647 277

ίο

The 6-dialkylamino quinaldines are by the formula

characterized in which R and Ri are alkyl groups with 1 to 4 ίο Represent carbon atoms.

Michler's ketone is in his list of the actinic radiation absorbing compounds listed Effectiveness particularly out, as well as its homologues, vinylogues and analogues, cyanine dyes and Styryl bases and mixtures thereof.

The hydrogen donors which provide free radicals and which are useful as component (d) are alkyl and alkoxy alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, amines and amides, ie compounds which have a hydrogen atom to be given off. Suitable active methylene compounds include

5,5-dimethyl-1,3-cyclohexanedione,

1,3-indanedione, 2-phenyl-1,3-indanedione, 1,3-diphenyl-1,3-propanedione and 4,4,4-trifluoro-2,4-hexanedione.

Suitable amines are the monoalkyl, dialkyl and trialkyl amines, in which the alkyl radical has 1 to 6 carbon

(G) Synthetic rubber compounds, for example mixed polymers of butadiene and acrylonitrile, and 2-chloro-1,3-butadiene polymers, (H) cellulose esters, for example cellulose acetate, Cellulose acetate succinate and cellulose acetate butyrate,

(I) polyvinyl esters, for example polyvinyl acetate / acrylate), polyvinyl acetate / methacrylate) and polyvinyl acetate,

(]) Polyacrylate and «-alkyl polyacrylate esters, for example poly (methyl methacrylate) and poly (ethyl methacrylate),
(K) Polyethers, for example the polyethylene oxides

of polyglycols,
(L) poly (vinyl chloride) and its mixed polymers,

for example poly (vinyl chloride / acetate), (M) polyvinyl acetate, e.g. polyvinyl butyral

and polyvinyl formal,
(N) polyformaldehydes,
(O) polyurethanes,
(P) polycarbonates,
(Q) polystyrenes.

The photopolymerizable mixtures can also be inhibitors for thermal polymerization (f) contain, for example: p-methoxyphenol, hydroquinone and alkyl- and aryl-substituted hydroquinones and quinones, tert-butylcatechol, pyrogallol, copper resinate, Naphthylamines, j3-naphthol, copper (I) chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitro

atoms "has, for example triethylamine, dibutylamine 30 benzene and dinitrobenzene, p-toluquinone and chloranil
and trihexylamine, also alkylenediamines with 1 to 4 The polymeric component of the photopolymerizable

Carbon atoms, for example ethylenediamine, and mixtures can be non-thermoplastic or 1,3-propylenediamine; Alkanolamines, for example
Ethanolamine, diethanolamine and triethanolamine; so

other polymeric compounds may have been added to improve certain desirable properties, bii hihä

such as the 35 listed in US Pat. No. 3,026,203, for example, the adhesive strength on the substrate,

Polyamines. Other suitable amines are described in US Pat. No. 3,479,185. Mixtures of two or more of the components corresponding to (d) can be used.

p g

the adhesion strength to the image receiving material during transfer, abrasion resistance and toughness against chemical agents. Polymeric compounds suitable as additives are polyvinyl alcohol Cll lih H

Triphenylphosphine, an electron donor, can be found in cellulose, anhydrous gelatin, phenolic resins

pypp
also use as component (d).

Macromolecular film-forming organic polymeric binders which have proven themselves as component (e), are

, p

and melamine formaldehyde resins. If desired, the photopolymerizable layers can also immiscible polymeric or non-polymeric organic or inorganic fillers or reinforcing agents

(A) Polyesters, for example poly-E-caprolactone and 45, which are used for the exposure of the

Mixed polyesters, for example the wavelengths used by the reaction of polymethylene glycol of the formula HO (CH2) nOH, where π is an integer from 2 to 10 inclusive and (1) hexahydro-photopolymerizable material are essentially transparent. Those SiCh substances come into question here, which in such a way ih id dß with the formation of an organic layer on the surface

Phthalic acid, sebacic acid and terephthalic acid before their SiOi particles have been treated that

re, (2) terephthalic acid, isophthalic acid and sebacic acid, (3) terephthalic acid and sebacic acid, {4} terephthalic and isophthalic acids and (5) Mixtures of mixed polyesters made from these are more dispersible in organic compositions such as the photopolymerizable mixtures of the invention became. The production of such organophilic S1O2 substances is described in US Pat. No. 2,657,149, for example

these glycols and (I) terephthalic acid ^ 55 can be found. Further examples: Bentonite, SiOz isophthalic and sebacic acids as well as (Π) Tereph- powdered glass, colloidal carbon as well as

Thai, isophthalic, sebacic and adipic acids have been produced.

(B) polyamides, for example N-methoxymethyl polyhexamethylene adipamide;

(C) Mixed vinyl chloride polymers, for example those based on vinylidene chloride / acrylonitrile, vinylidene chloride / methacrylate and vinylidene chloride / vinyl acetate,

(D) copolymers of ethylene and vinyl acetate,

(E) cellulose ethers, e.g. methyl cellulose, Ethyl cellulose and benzyl cellulose,

(F) polyethylene,

Different types of dyes and pigments Such substances are used in different amounts, which depend on the desired properties of the photopolymerizable layer. The fillers are useful to improve the strength of the mixtures, to reduce the stickiness and also as colorants , how

shown in example 55, also in a more hydrophilic Colloid such as gelatin.

As free radical initiators of addition polymerisation activated by actinic radiation

02820

bar, generally have their maximum sensitivity in the ultraviolet range, the Radiation sources generally deliver an effective amount of this type of radiation. To such radiation sources include charcoal arc lamps. Mercury vapor lamps, fluorescent lamps with ultraviolet radiation emitting fluorescent substances, argon incandescent lamps, electronic flash lamps and photographic floodlights. This is where the mercury vapor lamps are generally used held at a distance of 3.8 to 50.8 cm from the photopolymerizable layer. Under special Under certain circumstances it can be advantageous to expose with visible light. In these cases the Radiation source deliver a significant amount of visible radiation. Many of the light sources listed deliver the required amount of visible light.

The invention achieves that a photopolymerizable recording material is available, that has expanded sensitivity in the visible regions of the spectrum.

The photopolymerizable compositions and materials of the invention can be applied to metal surfaces

apply to make photosensitive lithographic printing plates or as a photoresist in the Manufacture of etched or plated printed circuit boards or chemical milling processes Way of being applied. The mixtures of the invention can also be used to produce color images, which can be used to improve the color of color separation negatives. Those made with these materials Images can also be used for making copies by means of thermal transfer to a Insert the underlay. Other areas of application are obvious to the person skilled in the art, many possible uses are described in U.S. Patents 2,760,863, 30,60,023 and 3,060,026.

Suitable supports for the photopolymerizable layers are those made of metal and flexible polymeric films. The associated coating processes are in the above-mentioned patents specified.

The invention is illustrated by the following examples

Examples 1 to 44

Several proportions of coating solutions below Compositions were made as follows: cellulose acetate

(Acetyl: 40.0%, ASTM Viscosity: 25) 2.7 g

Cellulose acetate butyrate

(Butyrate: 170/0, ASTM Viscosity: 15) 4.2 g

Trimethylol propane triacrylate 13.5 g

Acetone 116.0 g

The cis-fc-dicarbonyl compounds (initiators) and Sensitizers were added to the solution in such amounts that the concentration of initiator and sensitizer in the coated sample corresponded to the data given in Table I. The Solutions were on 0.025 mm thick film support made of polyethylene terephthalate with adjustment of a thickness applied in the moist state of 0.05 mm, dried to form a photopolymerizable layer and laminated at room temperature with 0.025 mm thick polyethylene terephthalate cover films.

Then the samples were exposed through a gray scale consisting of dispersed in gelatin and in Cellulose acetate included carbon particles. The density graduation corresponded to this table a Keüfakior of Vy 2 for each level of the optical

Density. The exposures were carried out with the aid of a 1000 watt tungsten filament lamp, which worked at 120 volts and a color temperature of 3200 ^° K for one

Panel I.

Distance of 1.12 m from the sample. After the exposure, the cover sheet was removed and the photopolymerizable layer dusted with Jungle Black (Pigment Black I, CI. 50 440) to give a positive image receive. The optical densities of the steps of the image were measured and plotted against the logarithm of the Exposure applied. The logarithm of the exposure that gave an optical density that was around 0.1 was above the optical density of base plus fog was used as the criterion for the sensitivity of the layer viewed. The relative sensitivities of various photopolymerizable compositions are given in Table I. listed, expressed in equivalent exposure time and based on the actual exposure time in Seconds required to obtain an image with an optical density close to 0.1 is above the base value plus veil, multiplied by the percentage of light transmitted by the Step wedge at this point. Accordingly, a lower number characterizes a photographic one more sensitive system. The molar concentrations of the ingredients in the applied and dried Mixtures are attached to each component in brackets. The wavelength of the absorption maximum, Nurse, is given in nanometers. Two or three Values for Amax show an absorption double or a triple absorption, the highest value being required to be below 520 nm

Example cis-ac-dicarbonyl compound Sensitizers

Equivalents Exposure time

1 23 bomandion (0.047) 2 the same (0.047) 3 desgL (0.047) 4th desgL (0.047) 5 the same (0.047) 6th desgL (0.047) 7th desgL (0.047) 8th desgL (0.047)

Michler's Ketone (0.047)
4,4'-bis (diethyiamino) benzophenone (0.047)
4-dimethylaminobenzophenone (0.047)
4-dimethylaminoact-tophenone (0.047)
4-dimethylaminobenzoin (0.047)
4-dimethylaminobenzaldehyde (0.047)
4-dimethylaminobenzonitrile (0.047)
7-diethylarnino-4-methylkurnarin (0.047)

358 2.9 370 13th 350 18.0 325 24.0 343 11.6 323 14.4 312 36.0 370 7.2

Table I (continued)

Example cis-m-dicarbonyl compound

Sensitizers

14th

Aquiviilc Bclichtur

/ L-Il

2,3-Bornanedione (0.094) the same (0.094)

the same

the same
the same

the same

the same
the same
the same
the same

(0.094)

(0.047) (0.047)

(0.047)

(0.094) (0.094) (0.094) (0.094)

19th the same (0.094) 20th
21
22nd 2,2,5,5-tetram
ethyl tetrahydro
3,4-furandione
the same
the same (0.094)
(0.094)
(0.094) 23 the same (0.094) 24 the same (0.094) 25th
26th Parabanic acid
(Imidazoltrione)
23-Bornandione (0.094)
(0.047) 27 the same (0.094) 28
29 1,4,5,6-tetrahydro
5,6-dioxo-23-py-
razin-dicarboximide
23-dioxo-5,6-di-
ethoxy-5,6-di-
cyanopyrazine (0.047)
(0.047)

3,3'-Diethylthiacyanine p -toluenesulfonate 410.430 36.0

^ '- Diethylthiacyanine p-toluenesulfonate 410.430 1.8

Michler's Ketone (0.047)

S.S'-Diethylthiacyanine p -toluenesulfonate 410,430 3.2

7-diethylamino-4-methylcoumarin (0.047)

2- (p-Dimethylaminostyrene) benzothiazole 412.428 18.0

2- (p-Dimethy! Aminostyrene) -benzothiazole 412,428

Michler's ketone (0.047) [3-ethyl-naphthoxazole] - [3'-ethyl-naphthothiazole] -monomethine cyanine p-toluenesulfonate 398.425

Michler's Ketone (0.047)

3,3'-Diethylthiacyanine p-toluenesulfonate 410,430

Triethanolamine (0.02)

S.S'-Diethylthiacyanine p -toluenesulfonate 410.430 9.5

5,5-dimethyl-1,3-cyclohexanedione (0.094)

S.S'-Diethylthiacyanine p -toluenesulfonate 410,430

N-phenylglycine (0.094)

Sweet'-diethylthiacyanine p-toluene sulfonate 410.430 2.9

4-dimethylaminobenzophenone (0.047) 2,5-bis (p-diethylaminobenzilidene) cyclopentanone (0.047) 2,5-bis (p-diethylaminobenzilidene) -cyclopentanone (0.023)

Michler's ketone (0.047) Michler's ketone (0.047) 2,5-bis- (p-diethylaminobenzilidene) -cyclopentanone (0.023) S.S'-diethylthiacyanine-p-toluenesulfonate (0.023) S.S'-diethylthiacyanine-p-toluenesulfonate ( 0.023) Michler's Ketone (0.047) Michler's Ketone (0.047)

Michler's ketone (0.047) triphenylphosphine (0.047) 33'-diethylthiacyanine p-toluenesulfonate (0.023) Michler's ketone (0.047) triphenylphosphine (0.047) Michler's ketone (0.047)

Michler's ketone (0.047) 35g

475 90.0 475 12.0 358 5.8 358 4.7 475 410, 430 140.0 410, 430 4.8 358 358 16.0 358 1.5 410, 430 0.7 358 358 68

Table I (continued)

example cis-a-dicarbony 1 compound (0.007) Sensitizers Λ max Equivalents
Rpliphi ι in PS- 11th time 30th 1,1,4,4-tetra Michler's Ketone (0.047) 358 methyltetralin (0.047) 5.7 2,3-dione (0.094) 15th 31 Indole-23-dione Michler's Ketone (0.047) 358 32 3-methyl- Michler's Ketone (0.047) 358 1,2-cyclopentane (0.188) 5.7 dion - 33 2.3-Bornandione (0.094) 1,3-bis (p-dimethylaminobenzylidene) - 435 12th acetone (0.023) 34 the same (0.047) Auramine O (0.024) [bis- (p-dimethyl- 375, 396, 36 aminophenyl) methylenimine] 440 35 the same (0.094) N- (p-dimethylaminobenzylidene) -p-anisides 314 150 (0.094) (0.047) 90 36 the same (0.094) Acridine Orange (0.023) 490 -400 37 the same 6-dimethylamino quinaldine (0.047) 380 Comparison the same (0.24) - 220 attempt Comparison the same (0.24) > 400 attempt Comparison 2,2,5,5-tetra attempt methyltetrahydro- (0.188) 3.8 3,4-furandione 38 2,2,5,5-tetra 1,3- bis- (p- dimethylaminobenzylidene) - 435 methyltetrahydro- (0.094) acetone (0.023) 115 3,4-furandione 39 2,2,5,5-tetra 2,5-bis (p-dimethylaminocinnamylidene) - 505 methyltatrahydro- (0.094) cyclopentanone (0.047) 9.5 3,4-furandione 40 2,3-bornandione co-p-Dimethylaminobenj: yliden-4-methyl- 410

41 2,2,5,5-tetra- (0.094)

methyltetrahydro-3,4-furandione

acetophenone (0.047)

w-p-Dimethylaminobenzylidene-4-methylacetophenone (0.047)

42 2,3-bornandione (0.094) Diethyl Orange (0.023) 43 the same (0.094) Diethyl Orange (0.023) N-phenylg'.ycin (0.094) 44 2,2,5,5-tetra (0.094) Diethyl Orange (0.023) methyltetrahydro- 3,4-furandione

410

470, 502 470, 502

470, 502

15th

45 1.8

36

All the compounds listed in the table above are known from the literature, with the exception the cis-α-dicarbonyl compounds given in Examples 28 and 29. These are as follows manufactured:

A. 1,4,5,6-Tetrahydro-5,6-dioxo-2,3-pyrazinedicarboximide

A solution of 2,3-dioxo-5,6-dicyano-1,2,3,4-tetrahydropyrazine (14.57 g, 0.09 mol, prepared as described by H. Brederek and G. Sch motzer, ANN. 600, pp. 95 to 108, [1956]) in concentrated sulfuric acid (150 ml) was stirred at room temperature for 1 week and then to 650 g

Poured ice. The deposited precipitate was

twice with 500 ml of water and then with 500 ml

Acetone washed. With a yield of 79%

were 12.9 g of product with a melting point of

408 ° C (with decomposition) obtained, which turns out to be

analytically pure and the following analytical data

6o showed:

Ultra red:

3175cm - '(NH);

1780.1730 cm - '(ImidC = 1700.1680 cm- '(C = O); 1600cm - '(C = C); 1525 cm - '(NH).

O);

609 647 277

Ultraviolet:

; H ₂ o 222 πιμ (extinction coefficient ε

"""301 mμ (ε = 9650),
375 mμ (ε = 960).

Elemental analysis for QH3O4N3:
Calculated: C 39.79. H 1.67. N 23.20%; found: C 39.61. H 139, N 22.99%; C 39.75, H 1.76, N 23.12%.

This implementation can be summarized by the following equation:

NC H O Il H O

\ YJ ^ HN / ^ N ⁷ VH ₁ SO ₄
NC HO _ö

The IAS.e-tetrahydro-S.e-dioxo-W-pyrazine-dicarboximide produced by the process described was used in Example 28.

B. 2,3-Dioxo-5,6-diethoxy-5,6-dicyanopyrazine

A solution of diiminosuccinonitrile (DISN), namely 20 g = 0.188 mol in 250 ml of acetonitrile, which as in of US Pat. No. 3,564,039 indicated, was produced slowly over the course of 1.75 hours at Room temperature registered in a solution of oxalyl chloride (60 g, 0.475 mol) in diethyl ether (150 ml). After stirring for a further 3 hours at room temperature, the solvents and excess oxalyl

18th

chloride removed (oil pump) and then dissolved i "acetonitrile (100 ml) and absolute.n ethanol (100 _m n The mixture was allowed to stand overnight at room temperature and then the filtrate filtered was preabsorbed on silica gel and chromatoprafiert Elution with diethyl ether gave a crude product in the form of a viscous oil which solidified on standing. Recrystallization from a mixture of acetonitrile and carbon tetrachloride gave a pure product. About 2.04 g with a melting point of 205 to 208 were obtained in a yield of 43% ⁰ C. The analytical data for the compound used in Example 29 are shown below:

3340 to 2860 cm- '(wide, NH); 2245cm ^-1 (C = N);

ClCOCOCl 1103 cm- '(COC).
High resolution mass spectrometry:

Molecular ion, measured value: m / e 252 0849; calculates m / e for C10H12O4N4: 252 0859.

Elemental analysis for C10H12O4N4: Calculated: C 47.62, H 4.80, N 22.22%. Found: C 47.91, H 4.88, N 22.32%; C 47.82, H 4.82, N 22.31%.

The conversions can be illustrated by the following equation:

C ₂ H ₅ O

NC
C ₂ H ₅ OH \ J

DISN NC

C ₅ H ₅ O

Examples 45-52

Egg. were several proportions of coating solutions with the following composition:

Poly (methyl methacrylate) 57.9 g

Triethylene glycol dimethacrylate 33.1 g

Victoria Pure Blue B.O. (CI. 42 595) 0.03 g

Trichlorethylene 364.0 g

Certain proportions of cis - «- dicarbonyl compound and of sensitizer were added to the solutions in order to adjust the concentrations of initiator and sensitizer given in Table II in the coated sample. The solutions were applied to a 0.025 mm thick polyethylene terephthalate film with a doctor blade setting a layer thickness in the moist state of 0.075 mm. Was then allowed to dry at room temperature and the coated film on the copper surface of a copper-coated, 0.076 mm thick Polyäthylenterephthalatfilms at 12O ⁰ C and 2.72 atm. laminated on.

The materials obtained in this way were exposed through a silver step wedge, the illuminance of which increased by the factor l / T from step to step. The exposure was carried out with a Xenon arc exposure device that worked at 3750 watts and at a distance of 45.7 cm for 30 seconds Application came. After the exposure, the cover sheet was removed; the image was made by spraying of 1,1,1-trichloroethane at a distance of 12.7 cm below Apply a pressure of 0.34 atm. 45 sec. Developed to remove the unpolymerized parts of the Layer to be removed, after which it was washed out with water. The samples were then placed in a ferric chloride solution (42 ° Baume), which removed the copper in those places that were not through the photopolymerizable Portions of the layer were covered. The one required to produce an etch-resistant film Minimum exposure was chosen as the sensitivity point. Everyone's relative sensitivity to light The sample is given in Table II.

TafeUl

Example cis-α-Dicarbonyl Compound Sensitizer Relative sensitivity to light

2,3-Bornanedione (0.045) Parabanic acid (0.045) 2,3-Bornanedione (0.045)

the same
the same

desgL

the same

(0.045) (0.045)

(0.045)

(0.045)

(0.045)

Comparative like
sample

52 2,2,5,5-tetra- (0.090)

methyltetrahydro-3,4-furandione

Comparative - none -

Michler's Ketone (0.022)

Michler's Kelon (0.022)

S.S'-diethylthiacyanine-p-toluene sulfonate

(0.024)

Michler's ketone (0.022) 7-diethylamino-4-methyl-coumarin (0.022)

S.S'-diethyl thiacyanine p-toluenesulfonate

(0.024) Sweet'-Diethylthiacyanine p -toluenesulfonate

(0.024) triethanolamine (0.078)

33'-diethylthiacyanine p-toluenesulfonate

(0.024) 5,5-dimethyl-1,3-cyclohexanedione (0.055)

2,5-bis- (p-diethylaminobenzilidene) -cyclopentanone (0.023)

Michler's Ketone (0.45)

358 2.8 358 1.4 410, 430 11.0 358 370 1.2 410, 430 0.6

410, 430

475

2.8

410.430 2.0

no playback

0.36 1.0

Example 53

A coating solution was prepared as follows:

Polymethyl methacrylate 2.53 g (Molecular weight: 60,000) 2.17 g Triethylene glycol dimethacrylate S.S'-diethyltniacyanine-p-toluene- 0.08 g sulfonate 0.08 g Michler's ketone 0.10 g 2,3-bornandione 20.0 g Trichlorethylene

35

40

The solution was applied to a 0.19 mm thick polyethylene terephthalate film with a wet thickness of 0.05 mm applied and allowed to dry.

A second coating solution was prepared as follows:

Polymethyl methacrylate 1.27 g (Molecular weight: 60,000) 1.42 g Triethylene glycol dimethacrylate 25% dispersion of carbon black in 6.2 g Isopropanol S.S'-diethylthiacyanine-p-toluoI- 0.05 g sulfonate 0.05 g Michler's ketone 0.08 g 2,3-bornandione 3.9.4 g Trichlorethylene

55 folded and laminated to one another while passing through ^{rollers heated to 100 °} C. at the appropriate pressure.The material obtained in this way was from the clear side through a step wedge, the illuminance of which increased by a factor of \ fl from step to step, with a quartz iodine lamp of 1000 watts exposed, the 30 sec. at a distance of 1.5 m for use kam.Die exposed sample was then delaminated at 100 ⁰ C, to a positive, black image on the 0.10 mm thick layer support and a negative, black picture on the 0.19 mm thick substrate to yeast.

Example 54

A coating solution with the following composition was prepared:

Cellulose acetate

(Acetyl: 40%, ASTM Viscosity: 25) 0.16 g

Cellulose acetate butyrate

(Butyral: 17%, ASTM viscosity: 15) 0.25 g

Trimethylolpropane triacrylate 0.80 g

Acetone 6.9 g

Michler's ketone 0.0128 g

2,3-Bornandione 0.0080 g

The solution was adjusted to a moisture thickness of 0.05 mm with the help of a doctor blade to a 0.10 mm thick polyethylene terephthalate film for photographic Purposes applied with an adhesive layer from that described in US Pat. No. 2,779,684, Example 4 Resin had been overlaid and allowed to dry.

The clear layer and the black layer were made

6o The solution was applied with the aid of a doctor blade to a 0.025 mm thick, not coated with an adhesive layer, polyethylene terephthalate film with a thickness in the wet state of 0.025 mm. The coated material was dried and laminated at room temperature with a 0.025 mm thick, uncoated polyethylene terephthalate cover sheet.

A sample of the material produced in this way was passed through a step wedge, the illuminance of which was from Step by step by a factor of 2, with a rotating diazo copier (average Internet

10

intensity: 3.2 mw / cm ² ) exposed. The cover sheet was then removed and the top layer was sing-dusted with Quindomagenta (CI. Pigment Red 122)

Polymerization had occurred up to and including the 16th stage. No pigment accepted these stages.

A comparative material that is produced in the same way, but without the addition of 2,3-bornanedione polymerized only up to and including the 6th step at the specified exposure.

Example 55

A solution with the following composition was prepared:

Mixed polymer of methyl meth-

acrylate and methacrylic acid

(90/10 molar ratio) 2 g

Diethylene glycol diacrylate 5 g

4,4'-bis (diethylamino) benzophenone 0.05 g

2,3-bornanedione 0.10 g

Ethylene glycol monoethyl ether 8.0 g

This solution was made into a solution of 10 g of gelatin in 40 g of water by mixing in one high-speed mixer for 2 min. dispersed. The dispersion was reduced to 0.10 mm using a doctor blade thick polyethylene terephthalate substrate with adjustment of a thickness in the wet state of 0.076 mm applied and dried. A sample of the material produced in this way was passed through a transparent th template using a light source operating at 3750 watts for 5 seconds at a distance of 45.7 cm exposed The exposed material was immersed in a 2% solution of Basic Violet IO (CI. 45 170) for 2 min. immersed, washed with cold water for 15 min. and dried A positive gastric day

colored picture

The material described above can be used for the production of thick engraving forms. A Process for the production of an engraving printing form consists in that one in any order carries out the following procedural steps:

a) The exposed on the on a layer support, for example a transparent support film, applied layer with actinic light, first through an engraving screen and then with a transparency with continuously running tonal values that is created by photopolymerization provides a modulated resist image, and

b) the surface of the layer is placed on the layer to be imaged and moistened with water to adhere and pulls off the transparent support, after which one

c) the surface with a conventional etching solution, for example iron (III) chloride, etches to a deep create printing surface;

d) the etched surface is washed, for example with hot water, to remove the remaining etching solution and remove the photopolymer resist.

The procedure can also be carried out by cutting the layer with the engraving visor through the transparent substrate through and with the image with continuously running tonal values from the opposite side exposed. In addition, the dispersion can be applied directly to the surface to be etched be applied.

Claims (10)

Patent claims: 1. Photopolymer. ' arable, if necessary Layer base from a mixture that can be applied a) at least one non-gaseous, ethylenically unsaturated compound with a boiling point above 100 ° C, which is capable of photoinitiated addition polymerization To form high polymer, «o b) a Λ-dicarbonyl compound as photoinitiator, c) an actinic radiation with an absorption maximum below 520 nm absorbing, capable of sensitizing the polymerization initiating effect of the dicarbonyl compound from the group of
Bis- (p-aminophenyl) - <x ^ -unsaturated) ketones, Bis (alkylamino) acridine dyes,
Cyanine dyes having two heterocyclic rings linked by a single methine group, Styryl dye bases, 7-dialkyl? Mino-4-alkylcoumarins with 1 to 4 Carbon atoms in the alkyl radicals in the 4- and 7-position, p-Aminophenylkeione, p-Dialkylaminophenylunsaturated links or the 6-dialkylaminochinaldine,
characterized in that it contains, as photopolymerization initiator, a cyclic cis - «- dicarbonyl compound which is intramolecularly unreactive, in which, if the atoms adjacent to the vicinal carbonyl groups are carbon atoms, these are not parts of an unsaturated radical. 2. Photopolymerizable mixture according to claim 1, characterized in that it is as cyclic cis-α-dicarbonyl compound 2,3-Bomandione, WAS-Tetramethyltetrahydro - ^ - furandione,
Imidazolrione,
Indole-2,3-dione (isatin),
l, l, 4,4-tetramethyl-tetralin-2,3-dione,
3-Methyll ^ -cyclopentan-dione, W-Dioxo-S.ö-diethyoxy-S ^ -dicyano-pyrazine
or lAS.b-Tetrahydro-Se-dioxo ^ -pyrazinedicarboximid
contains 3. Photopolymerizable mixture according to claim and 2, characterized in that it is 3 to 100 Parts by weight of the ethylenically unsaturated compound (a) 97 to. 0 parts by weight of a macromolecular, contains organic polymeric binder (s). 4. Photopolymerizable mixture according to claim to 3, characterized in that the cyclic cis-a-dicarbonyl compound and the actinic Radiation absorbing compound (c) both at 0.001 to 10 parts by weight based on 100 Parts by weight of the total weight of the ethylenically unsaturated compound plus a binder, are present. 5. Photopolymerizable mixture according to claim to 4, characterized in that it is up to 10 Parts by weight of a hydrogen or electron donor compound which forms free radicals (d) ICO parts by weight of the total weight from Ethylenic contains unsaturated compound plus a binder b. Photopolymerizable mixture according to Claims 1 to 5, characterized in that it contains up to 4.0 parts by weight of a thermal addition polymerization inhibitor (f), based on 100 parts by weight of the total weight of the ethylenically unsaturated compound plus a binder 7. Photopolymerizable mixture according to claim 1 to 6, characterized in that the cis-α- dicarbonyl compound 23-Bornandione is 8. Photopolymerizable mixture according to claim 1 to 7, characterized in that the actinic Radiation absorbing compound one of the following compounds is applied: Michler's ketone, 4,4'-bis (diethylamino) benzophenone, S ^ '- diethylthiacyanine-p-toluene sulfonate, 2- (p-dimethylaminostyrene) benzothiazole, [3-ethyl-naphthoxazole] [3'-ethyl-naphthol- thiazole] -monomethinecyanine-p-toluenesulfonai, Diethyl orange, 7-diethylamino-4-methylcoumarin or 2,5-bis- (p-diethylaminobenziliden) - cyclopentanone. 9. Photopolymerizable mixture according to claim 1 to 8, characterized in that it is the thermal addition polymerization inhibitor in amounts of 0.001 to 4.0 parts by weight, based to 100 parts by weight of the total weight of the ethylenically unsaturated compound plus one Contains binding agent. 10. Photopolymerizable mixture according to claim 1 to 9, characterized in that it is in dispersed in a hydrophilic colloid.