FR2462733A1 - PROCESS FOR THE PRODUCTION OF TWO-COMPONENT DIAZOIC IMAGE TRAINING MATERIAL - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS A PROCESS FOR THE PRODUCTION OF A MATERIAL WITH TWO DIAZOIC IMAGE FORMING COMPONENTS. THE PROCESS ACCORDING TO THE INVENTION CONSISTS OF APPLYING TO A FACE OF A FLAT SUPPORT A LAYER OF A LIQUID COMPOSITION CONTAINING 1 A COMPOUND CROSS-LINKABLE BY HIGH ENERGY RADIATION AND 2 A COMPOUND OF HIGH MOLECULAR WEIGHT NOT CROSS-LINKABLE BY HIGH RADIATION ENERGY, BUT SUITABLE FOR IMPREGNATION BY A PHOTOSENSITIVE COMPOSITION, TO IRRADIER THE SAID LIQUID COMPOSITION BY HIGH ENERGY RADIATION TO CAUSE CROSSCULATION AND HARDENING OF THE COMPOSITION, THEREFORE FORMING A LAYER SUITABLE FOR IMPREGNATION, THEN LAYER THUS FORMED BEFORE THE SAID PHOTOSENSITIVE COMPOSITION AND TO DRY THE LAYER.

Description

The present invention relates to a method for the production of

  producing a two-component diazo imaging material.

  Two-component diazic image-forming materials, i.e., diazo-like imaging materials, have been widely used comprising a photosensitive layer-carrying medium which contains as its main components a sodium salt.

  diazonium and a coupler capable of reacting with the diazonium salt.

  On the other hand, there is also known a method for

  producing a two-component diazo image-forming material

  to apply to a support (for example a film

  plastic solution) a solution prepared by dissolving a binder of high molecular weight (for example cellulose diacetate, cellulose triacetate, cellulose butyrate, etc.) in a low-boiling organic solvent (for example acetone). methyl acetate, etc.), usually at a thickness of about 50 to 100p, to be dried at elevated temperature (usually

  from about 100 to 200 ° C) for a long time (for example

  several minutes) to form a layer capable of impregnating and impregnating said impregnable layer with a photosensitive composition containing a sensitive diazonium salt

in the light, then to dry.

  Furthermore, in this method, a coupler is incorporated at least in the photosensitive composition and / or in the layer

suitable for impregnation.

  The long time drying at high temperature is carried out in industry by transporting said support coated with

  the solution by means of several precisely adjusted cylinders.

  However, the conventional method described above for forming the impregnable layer has the following defects: (a) it comprises drying for a long time at temperature

  high, which requires a large amount of thermal energy

  nomic; (b) it requires an apparatus for treating a large amount of organic solvent to be evaporated; (c) it requires a large space for the drying installation;

  (d) it requires precise adjustment of the multiple cylinders.

  The subject of the invention is a method for producing a diazo image forming two-component material which

  eliminates the defects of the conventional method described above.

  According to the invention. we propose a process for the pro-

  forming a diazo image forming two-component material, which comprises applying to one side of a planar support a layer of a liquid composition (hereinafter referred to as "liquid solution to be exposed") containing (1) a high energy irradiation crosslinkable compound; and (2) a high energy irradiation non-crosslinkable high molecular weight compound, but suitable for impregnation with a photosensitive diazonium salt photosensitive composition (hereinafter referred to as "weight compound").

  high molecular weight conferring impregnability

  tion "), irradiating said liquid composition with radiation

  high energy to cause crosslinking and hardening.

  composition and then impregnate the layer with the said

  photosensitive composition, and to dry the layer.

  The planar support to be used in the invention may be of the type conventionally used to produce the known diazic imaging materials. For example, it may be a plastic film, synthetic paper, pasting paper, metal, glass, woven or nonwoven fabric, or the like. Of these, the plastic films are excellent in terms of physical strength (especially dimensional stability), flatness properties and transparency, for example polyethylene terephthalate films.

  biaxially oriented polyethylene are particularly preferred.

  The photosensitive diazonium salt may be of the type conventionally used for the production of forming materials

  diazo image. This photosensitive diazonium salt is usually

  used as a double salt with an inorganic halogenated salt. Examples of such double salts include, for example, 4-dimethylaminobenzenediazonium tetrafluoroborate,

  bis (3-methoxy-4-pyrrolidinobenzene) tetrachlorozincate

  diazonium, etc. The type of coupler to be used in the invention is

  also known and chosen according to the desired color of the image.

  Typical couplers are phenolic compounds and

  compounds containing active methylene groups.

  Examples of useful phenolic compounds include

  resorcinol, bisresorcinol sulfide, monohydroxyethyl ether,

  2-hydroxynaphthalene-2-methylanilide

  carboxylic acid, ethanolamide of 2-hydroxynaphthalene-3-

  carboxylic acid, etc. and examples of useful compounds containing

  active methylene groups include acetanilide, N-acetyl-

  glycine, 1,4-bis (acetylacetamido) ethane, etc. In the invention, it is desirable to incorporate an acidic builder in said impregnable layer and / or said photosensitive composition so as to prevent the

  staining due to premature copulation.

  Impregnation of the impregnable layer with the photosensitive composition can be carried out using

  conventional known impregnation apparatus, such as apparatus

  impregnation stage comprising feed cylinders

liquid and a scraper.

  The drying after impregnation of said layer capable of impregnation with said photosensitive composition can

  be carried out under conventional conditions, using

  In the invention, the impregnable layer is formed by irradiation with high energy radiation of a liquid composition containing a high energy radiation curable compound and a compound of the invention. of high molecular weight conferring the property of impregnation ability, which causes the crosslinking and

hardening of the composition.

  As high energy radiation mentioned in

  the invention, ultraviolet radiation is particularly preferred.

  violets or electron beams.

  Examples of radiation sources from an irrational device

  Ultraviolet light that can be used include metal halide-mercury vapor lamps, low pressure, medium pressure, high pressure mercury vapor lamps, etc., which emit ultraviolet radiation from the far ultraviolet to near ultraviolet (ie, about 200 to 450 nm). Examples of electron beam irradiation apparatuses that can be used include those having an acceleration voltage of 100 to 600 keV and an electric current value of 10 to 100 mA. High energy irradiation cross-linkable compounds have already been fully disclosed in the literature, for example in US Pat. Nos. 4,205,018.

  and 3,888,830, and these known compounds can be used in the invention.

tion.

  Of these known compounds, non-oligomeric compounds which are liquid at room temperature (by

  about 20 to 30 ° C) and which contain 1 to 4 ethyl bonds.

  and not more than 10 repeating units and have a molecular weight

  from about 300 to 6,000, or those that are liquid at the

  room temperature and which contain from 2 to 6 epoxy groups.

  Among these preferred compounds, mention will in particular be made of those which have

  a boiling point of at least 100 C.

  Non-oligomeric compounds that are liquid at the

  ambient temperature and which contain from 1 to 4 ethylenic

  Examples of monomers containing a single ethylenic linkage are, for example, methyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate and the corresponding methacrylates. styrene, N-vinylpyrrolidone, etc. Examples of preferred non-oligomeric compounds which contain from 2 to 4 ethylenic linkages and which are liquid at room temperature include, for example, ethylene glycol diacrylate, propylene glycol diacrylate, diacrylate

  of 1,6-hexanediol, trimethylolpropane triacrylate, tetra-

  pentaerythritol acrylate and the corresponding methacrylates.

  Examples of preferred compounds containing from 1 to 6 epoxy groups and liquid at room temperature include, for example, 1,6-hexanediol diglycidyl ether, ether

  glycerol triglycidyl, bis (tetraglycidyl ether)

  resorcinol and epoxidic novolacs (for example, having a

worth of epoxide from 172 to 18]).

  As high molecular weight compounds imparting the property of impregnation ability, cellulose derivatives are particularly preferred. However, we can also use

  vinyl polymers of the copolycondensation resins of

  dehyde, etc. Among these, it is preferred to choose a cellulose derivative

  lose having satisfactory compatibility.

  More particularly, useful cellulosic derivatives include, for example, (a) fatty acid esters obtained by modifying cellulose with a fatty acid such as

  cellulose acetate, cellulose acetate butyrate, acetoisobutyl

  spleen cellulose, cellulose acetopropionate, etc. (b) inorganic esters obtained by modification of the cellulose with nitric acid, such as cellulose nitrate, and (c) alkyl ethers obtained by modification of the cellulose with a sulphate of

  dialkyl or an alkyl halide, such as ethylcellulose,

  pylcellulose, etc. High molecular weight compounds to use

  in the invention to confer the ability of

  are necessary and indispensable to impregnate

  suitable for impregnation with the photosensitive composition

  the photosensitive diazonium salt. In addition, the high molecular weight compounds allow rapid absorption of an alkaline compound such as ammonia gas into the impregnable layer of the diazolic imaging material, which has the practical advantage of enabling perform development

in a short time.

  In the practice of the invention, the ratio of the coupler to be added to the diazonium salt (i.e., the coupler / diazonium salt ratio) is ordinarily in the range of 0.2 / 1 to 8/1 and preferably from 0.5 / 1 to 3.5 / 1. The proportion of the

  sum of the amounts of the diazonium salt and the coupler is preferably

  from 5% to 50% and, more particularly, from 10% to 40%,

  the weight of said layer capable of impregnation.

  When a non-oligomeric liquid compound containing from 1 to 4 ethylenic bonds is incorporated in the liquid composition to be irradiated, the amount (% by weight) of the high molecular weight compound imparting the impregnability property is incorporated into the liquid composition to be irradiated.

  to the crosslinkable compound by high energy irradiation is preferably

  from 20 to 80% 7. and, more particularly, from 35 to 68%. When a liquid compound containing from 2 to 6 epoxy groups is incorporated, the corresponding amount (% by weight) is preferably 10.

  at 90% by weight and, more particularly, from 30 to 70%. in weight.

  In the case where the invention is implemented according to the ultraviolet radiation embodiment of a liquid composition containing a non-oligomeric liquid compound

  having 1 to 4 ethylene bonds, it is preferred to use an

  photocrosslinker capable of producing free radicals

  by ultraviolet irradiation.

  Examples of such photo-crosslinking activators include, for example, benzoin, benzoin methyl ether, benzophenone, benzil, etc. In the case where the invention is implemented according to the irradiation mode of a liquid composition containing a liquid compound having from 2 to 6 epoxy groups, it is advantageous to use an activator of photocrosslinking capable of producing a Lewis acid acting as a hardening agent

  for ordinary epoxy resins.

  Interesting examples of these photo activators

  Preferred crosslinking compounds capable of producing a Lewis acid are described, for example, in U.S. Patent Nos. 3,708,296, 3,721,617 and 3,936,557, Japanese Patent Publications Nos. 14277177, 14278/77 and US Pat. 14279/77, and Japanese Unexamined Patent Publication No. 30402/77, etc.

  A polymer inhibitor is preferably incorporated.

  a small amount of heat in the liquid composition to be irradiated, which contains the non-oligomeric liquid compound containing from 1 to 4 ethylenic bonds, to prevent gelation of the

  liquid composition during storage. Examples of these

  thermal polymerization bitters include, for example,

  hydroquinone, hydroquinone monomethyl ether, 2,6-di-

  tert-butyl-p-cresol, cupferron, etc. However, copper salts generally used as thermal polymerization inhibitors

  can not be used here because they accelerate the decomposition

sition of diazonium salt.

  In the case where the liquid composition to be irradiated which contains a non-oligomeric liquid containing from 1 to 4 ethylenic bonds is used, it is preferred to use together a

  crosslinkable oligomer containing 2 or more ethylenic linkages.

  Crosslinkable oligomers that are compatible with said non-oligomeric liquid compound containing from 1 to 4 ethylenic linkages are preferred. In general, it is advantageous to use

  oligomers having a molecular weight of about 300 to 3000.

  Examples of such crosslinkable oligomers include acrylic or methacrylic polyesters obtained using a

  low molecular weight polyester, epoxyacrylates, epoxymetha-

  crylates, urethanes-acrylates, urethanes-methacrylates, etc. In addition, the two-component diazo image-forming material according to the invention may contain ordinary stabilizers such as 5-sulfosalicylic acid, acidic ingredients, such as succinic acid, inorganic acids, such as

  that zinc chloride, alkaline sulfonates such as 2,7-

  disodium naphthalenedisulfonate, or thioureas such as thiourea or diethylthiourea. In addition, it is also possible to incorporate insoluble powders such as colloidal silica, barium sulfate powder, clay, etc. In the case where a liquid composition to be irradiated which contains a liquid compound containing from 2 to 6 oxygen groups is used, it is preferred to incorporate therein a low molecular weight liquid compound containing an epoxy group as diluent. Examples of such diluents include styrene oxide, phenol glycidyl ether, etc., known as diluents for ordinary epoxy resins, and, in addition, glycidyl methacrylate, allylic alcohol glycidyl ether, etc. that contain a group

epoxy and an ethylenic group.

  The invention described here in detail eliminates

  the defects of the conventional processes mentioned above, in

  forming a two-component diazo imaging material

  with industrial advantages.

  The two-component diazo imaging material can be developed by contacting it after contact exposure through an original, with an alkaline compound capable of reacting with the diazonium salt and the coupler to form an azo dye; we can mention, for example, putting in contact

  with water vapor containing ammonia under atmospheric pressure

  or anhydrous ammonia under high pressure, during

  a short duration, for example several seconds.

  Examples of light sources that can be used for the contact exposure for the two-component diazo imaging material described above include

  those that emit light rich in ultraviolet light, that is,

  have a wavelength of 300 to 450 nm, such as a black light lamp, a medium pressure, high pressure or very high pressure mercury vapor lamp, a halide lamp

  metallic mercury vapor or a carbon arc lamp.

  In the exhibition and development of the material

  two-component diazodine image format, it is advantageous to use

  commercially available apparatus such as SRD-1635 manufactured by the Applicant, Duplifiche Model 562 from Minnesota Mining & Manufacturing Co., etc. The following examples illustrate the invention without, however, limiting its scope. In these examples, the parties and

  volumes are by weight (kg) and liters, respectively.

EXAMPLE 1

  Synthesis Example 1 (polyester acrylate synthesis).

  Isophthalic acid 83 parts Diethylene glycol 106 parts

Adipic acid 146 parts -

  P-toluenesulfonic acid (catalyst) 2.5 parts The above mixture is reacted at 120 ° C. and, when the acid number reaches 130 to 150, 116 parts of 2-hydroxyethyl acrylate and 0, 45 part of hydroquinone monomethyl ether (thermal polymerization inhibitor), then reacted at 120 C for 4 hours by bubbling air therein to

obtain a polyester acrylate.

  Then, according to the following formula, a

liquid composition to be irradiated.

  2-hydroxyethyl acrylate (crosslinking agent) Polyester acrylate described above (crosslinkable oligomer) 1/2 sec cellulose acetate butyrate (composed of

  high molecular weight conferring the

  impregnation ability), CAB 381-2, Eastman Kodak Co., United States of America) 1/2 sec cellulose butyrate (as described above), HSB from Eastman Company Kodak Co., United States of America) Methyl methacrylate-ethyl methacrylate copolymer (as described above), Acryloid B72, Rohm X Haas Co., United States of America Benzodine isopropyl ether The composition described above has a viscosity of 1350 cP (at 25.degree. C., measured by means of a Brookfield viscometer, the same viscometer model being also used in FIG. following examples). It is applied by means of a coating machine to a film of polyethylene terephthalate drawn biaxially from

  75p thick (Merinex # 542 from ICI Co., Inc.)

  Brittany) carrying an underlayer, then it is passed continuously

  through an ultraviolet irradiation apparatus (used

  three mercury vapor metal halide lamps of W / cm, manufactured by Iwasaki Electric Co., Ltd.) at a scroll speed of 20 m / min, to form the layer.

  impregnating agent having a thickness of about 6.5P.

  A solution is then prepared in the following manner

  Two-component diagenic photosensitive composition composition comprising the following ingredients: 2,5-diethoxythiomorpholino-tetrafluoroborate 10 parts benzenediazonium (diazonium salt) Acetylacetanilide (coupler) 6 parts 2'-2-hydroxynaphthalene-18-carboxylic acid 2'-methylanilide ( coupler) Stannic chloride (accelerated metal salt2.5 parts developing) Tartaric acid (copulation inhibitor 3.5 parts premature) Thiourea (reducing agent) 0.8 part Acetone 700 volumes Said layer suitable for impregnation applied

  on the film is impregnated with the solution of photo-composition

  sensing described above, at a scroll speed of 20 m / min, by scraping by means of a "kiss coater" bar and wire and dried by passing through a simple vertical dryer equipped with a plus small number of support cylinders to get

  a two-component diazdic imaging material.

  The two-component diazo image-forming material

  thus obtained is exposed and developed by ammonia and

  developed material is subjected to tests to obtain the results

  States listed in Table I below.

TABLE I

  Sensitivity 2 Maximum Density (Portions of Image) 1.7 Minimum Density (Bottom Portions) 0.06 Pencil Hardness 4-5 HI Fragility 2 Adhesion 100/100 Developmental Ability 2 Resistance to Migration 1 Resistance to efflorescence 2

  For the sensitivities in Table 1, the sensitivities

  Higher, equal, lower and extremely low (unusable material in practice) compared to that of an equal product obtained by the conventional method are denoted 1, 2, 3 and 4.

  respectively. In particular, a sample is

  to a No. 3 step corner of Eastman Kodak Co. and developed by ammonia. Then we examine the number of transparent ranges: a transparent sample up to the fourth range is noted 1, until the third range 2 and

  until the second or the first range 3 or 4.

  The surface hardness of the developed sample is

  indicated according to the scale of hardness of the pencils.

  Adhesion according to Japanese JIS D-0202 was determined by the so-called "cross-cut" adhesion test. According to this test, 100 (10 x 10) squares of 1 mm square are cut with a razor on the surface of the developed sample and cellulosic adhesive tape is pressed onto the drawing. We tear up

  then quickly the ribbon and examine the number of squares

  both on the surface: this number is indicated in the table. So,

  / 100 means that none of the 100 squares were torn off.

  Fragility is determined by strongly crumpling a sample developed with both hands 5 times. A sample is rated 1 if it does not show delamination of the film, 2 if there is

  has a very weak linear delamination, 3, if there is a delamination

  Linearity of 1 cm or more or on a surface of about 4 mm2

  and 4 if there is more delamination.

  The development ability is determined using a commercial ammonia developing apparatus and

  1, 2, 3 and 4, respectively, the corresponding developmental

  laying at development rates of 15 m / min, 12 m / min, 8 n / min and 5 m / min respectively. The ability to develop a product of equal quality obtained by the conventional process is

noted 2.

  Migration is the phenomenon of an azo dye

  in the colored portions that migrate outwards when an

  The developed sample is left for about 1 month under conditions

  where the humidity variation is relatively large. For migration resistance, a sample without exudation, even stored for 1 month under the conditions described above after development is rated 1, a sample with low exudation but only at the same degree. commercially available disazo image forming materials is note 2 and a sample showing a

significant exudation is noted 3.

  Efflorescence is the phenomenon in which,

  when an oily product adheres to portions of the image of a sample

  As the dye is developed, the dye is efflorescent in the portion in contact with the oily substance. For example, an efflorescence in the form of a fingerprint may occur if a sample is touched with the end of a dirty finger. Efflorescence resistance is determined by strongly pressing portions of the image with the ends of the fingers, placing the sample in an oven at 80 ° C and examining the efflorescence after a certain time. The samples showing efflorescence after 5 to 8 h, after 4 to 5 h, after 2 to 3 h and after 1 to 2 h are noted i, 2, 3 and 4, respectively. The resistance to the efflorescence of a

  product of equal quality obtained by the conventional process is noted 2.

  The scoring methods described above are

  also implemented in the following examples, except where

  contrary. As seen in the description above, a

  notation of 2 corresponding to a diazo image-forming material obtained by the conventional method is taken as a reference in the

scoring system.

EXAMPLE 2

  Synthesis Example 2 (sythesis of a modified epoxy-acrylate resin

by a urethane).

  Deoxy-urethane resin (EPU-10 from 68 parts Asahi Electro Chemical Co., Ltd.) Acrylic acid 14.4 parts Triethylbenzylammonium chloride (catalyst) 0.5 part Trimethylolpropane triacrylate (reaction diluent and crosslinking agent ) 55 parts

  Monomethyl ether of hydroquinone (inhibit

  The above mixture is reacted at 100.degree.

  6 hours with sparging with dry air to obtain an acetate solution

  epoxy-urethane resin in trimethylolpropane triacrylate.

  A liquid composition to be irradiated with high energy radiation is then prepared according to the following formula.

  2-hydroxypropyl acrylate (crosslinking agent)

culating)

  Solution in trimethylol triacrylate

  propane (crosslinking agent) of the urethane

  epoxy-acrylate resin obtained in synthesis example 2 (crosslinkable oligomer) Ketone resin (composed of weight

  molecular-high conferring

  impregnation test, Hilac 111 from Hitachi Chemical Co., Ltd. Cellulose Acetobutyrate (high molecular weight compound conferring impregnation ability, CAB 551-0.2 from Eastman Kodak Co., USA. Benzoin ethyl ether (photocrystalline activator) parts 13 parts parts 33 Parts 4 Parts The following additives for the two-component diazo imaging material are added to the resulting liquid-to-irradiation composition to prepare a homogeneous composition.

(viscosity 1750cP at 25C)).

  Finely pulverized 2,7-Naphthalenedisulphonate disodium (development accelerator) Tartaric acid (premature copulation inhibiting agent) Thiourea (reducing agent), 2 parts 4.7 parts 11 parts A film of terephthalate is coated with the composition described above biaxially oriented polyethylene 28 / thick untreated having no undercoat and irradiated with ultraviolet light using the same apparatus as in Example 1 to form a layer suitable for impregnation (about 6p thick). In this case, the composition applied is heated to 60.degree. C. and extruded and the running speed of the

film is 23 m / min.

  A diazo two-component photosensitive composition comprising the following ingredients is then prepared: 2.5 dibutoxymorpholino-10.5 parts benzenediazonium tetrafluoborate (diazonium salt) 2-hydroxynaphthalene-19 parts 3-carboxylic acid 2-methylanilide (coupler) Chloride Zinc (7-part diazodium stabilizer and development accelerator) Acetone 500 volumes 2-methoxyethanol 200 volumes This photosensitive composition is impregnated and dried using the same apparatus as in Example 1 to obtain a material. diazo image formatter

  two-component. In this case, the upper limit of the temperature

  drying rate is adjusted to 120 C and scrolling speed

  of the film is 23 m / min, as above.

  The results of the tests on the two-component diazo imaging material described above are indicated

in Table II below.

TABLE II

  Sensitivity 2 Maximum density density (image portions) 1.6 minimum density (background portions) 0.06 Pencil hardness 3-4H Fragility 1 Adhesion 98/100 * Developability 1-2

* Average values of 12 tests.

  Resistance to migration 1 Resistance to efflorescence 1

EXAMPLE 3

A liquid composition is prepared

the following formula.

  Glycidyl ether of phenol (crosslinking agent) Glycidyl methacrylate (C) Glycerol triglycidyl ether (Cd.) Cellulose acetate butyrate (high molecular weight compound imparting impregnation ability), CAB 551-0.01 Company Eastman Kodak Co., United States of America) Ethylhydroxyethylcellulose (do, "EHEC-Low", from Hercules Inc. United States of America) to irradiate according to 19 parts 52 parts 23 parts parts 13 parts The composition described above (viscosity 860 cP at 25 C) is applied to a film of polyethylene terephthalate or biaxially entrained 75p thick with an undercoat, and cured by irradiation with electron beams, at a voltage of 300 keV acceleration and with a current value of 100 mA, with an absorbed dose of about 1.5 Mrad (1.5 × 10 4 Gy) to form an impregnable layer about 8 thick. A two-component diazo photosensitive composition comprising the following components is then prepared: Bis (3-methyl-4-pyrrolidino-6-benzenediazonium) tetrachlorozincate (diazonium salt) 2-hydroxy-9-hydroxy-3-N-morpholinopropylamide 5 parts naphthalene-3-carboxylic acid (coupler) Citric acid (premature coupling agent 8 parts) Disodium 2,7naphthalenedisulfonate 3 parts (development accelerator) Thiourea (reducing agent) 7,5 parts 2-methoxyethyl acetate 200 volumes Acetonitrile 70 volumes Dioxane 130 volumes The impregnable layer described is impregnated

  above with the resultant photosensitive solution.

  using a rod and wire coater and dried at 80-120 ° C to obtain a two-component imaging material. The results of the material tests are

  shown in Table III below.

TABLE III

  Sensitivity 2 Maximum Density (image portions) 1.8 Minimum Density (Bottom Portions) 0.05 Pencil Hardness 4-5H Fragility 1 100/100 Adhesion Aptitute to Development 1-2 Resistance to Migration 1 Resistance to efflorescence 1

EXAMPLES 4 to 14

  Synthesis Example 3 (urethane-acrylate synthesis) Tolylenediisocyanate (2,4-derivative / 2,6-derivative 174 parts: 20) Triethylene glycol 75 parts 1,6-hexanediol diacrylate 200 parts Hydroquinone monomethyl ether 0.57 part the above mixture is reacted at 60 ° C for 4 hours by bubbling air therein to prepare a prepolymer

  containing isocyanato groups at both ends of the chalne.

  116 parts of 2-hydroxyethyl acrylate are then added and

  reacted at 60 ° C for 6 hours to obtain a urethane acrylate.

In addition, in the above reaction mixture, 1,6-hexanediol diacrylate is used as a diluent for the polyaddition reaction. However, since he can function as an agent

  crosslinking agent, the mixture can be used directly as

  of a composition to form a layer capable of impregnating

  tion. Synthesis Example 4 (synthesis of epoxy acrylate) Epoxy resin (Epikote 828 from Shell International Chemicals Corp. epoxy equivalent: 185: 192) 94.5 parts Acrylic acid 36 parts N, N-dimethylaniline (catalyst) 1.3 The above mixture is reacted at 100.degree.

  bubbling air in to get an epoxy acrylate.

  Liquid compositions to be irradiated according to the formulas given in Table IV below are prepared and applied and cured in the same manner as in Example 1 to form layers capable of impregnating onto 75% thick biaxially oriented polyethylene terephalate carrying an underlayer. Each of the suitable layers

  at the impregnasion is impregnated with the same composition photo-

  sensitive than in Example 2 and the two-component diazo image-forming materials thus obtained are subject to the same

  tests as previously described. In addition, the speed of

  the film to form the impregnable layer and the speed of travel of the film in the impregnation step

  vary in the ranges of 15 to 80 m / mmn and 30 to 80 m / min,

tively.

TABLE IV

  Irradiated liquid composition | Results of the Exem-Agent OligoSensi- Ds tests - maximum maximum pmae density

  full cross-linkability (por-

  at the same time as the * 1. * 2 * 3 the picture) bottom) * 4 * 5 * 6 * 7 * 8 * 9

  4 50C1 15Q1 30P 1 1,5S1 2001 1 1,54 0,06 4H 2 100/100 1-2 1 2

  45C2 25Q2 20P2 2Sl 500i1 2-3 1.86 0.07 3-4H 1-2 100/100 1-2 2 2 6 55C 20QP 3S 5 i2 2 1.72 0.08 3H 1 100/100 2 2 2 7 30C4 40Q3 20P4 3S3 1000i 1- 2 1.51 0.06 2H 1 100/100 2 2 3 4c. 3o 4 3, 2, oo / _ oo _ 8 45C 30Q 15P 35S 550i 1 1.45 0.07 2-3H 2-3 90/100 3-4 2 1-2

  C 15Q1 30P 2.0S3 3001 2 1.73 0.05 4H 2 85/100 1 1 2

  40C7 25Q2 25P5 2.5S5 1000i 2 4 2.10 0.09 2H 1 100/100 2-3 3 4 il 55C 20Q 20P 2S 500i 1-2 1.32 0.06 5H 4 30/100 2 1 2

  12 30C9 30Q2 35P3 4S4 150012 2 1.69 0.07 2H 1 100/100 2-3 3 2

  13 5C2 10Q3 35 5S2 700i2 2 1.61 0.06 3H 1 100/100 2 1-2 1-2 C1. 14 10C7 + 20Q3 35P4 3S5 1250i2 3 1488 0.12 2-3H 1-2 70/100 3 2 3 C8 t- r ', "4 w4 w% The items at the top of the columns of Table IV have the following meanings:

  * 1 high molecular weight compound conferring the ability to

  gnation * 2 Photocure Activator * 3 Thermal Polymerization Inhibitor * 4 Pencil Hardness * 5 Fragility * 6 Adherence * 7 Developmental Ability 8 Resistance to Migration

* 9 Resistance to efflorescence.

  The abbreviations for the various ingredients have the following meanings: Crosslinking agents C1 2-hydroxyethyl acrylate C2 2-hydroxypropyl acrylate C3 Tetrahydrofurfuryl acrylate C4 Ethylene glycol monoacrylate C5 Ethyl crotonate C6 Cyclohexyl acrylate C7 2-Ethylhexyl acrylate C8 Diacrylate 1,6-hexanediol C phenoxydethyl acrylate

C10 N-vinylpyrrolidone.

  Crosslinkable Oligomers Q1 Epoxyacrylate (Synthesis Product of Synthesis Example 4) Q2 Urethane-Acrylate (Synthesis Product of Synthesis Example 3) Q3 Urethane-epoxyacrylate (Synthesis Product of Example of Synthesis 3)

  synthesis 2; trimethylolpropane triacrylate solution).

  High molecular weight compounds imparting the ability to print

  gnation. P Acetobutyrate cellulose 1/2 sec. (CAB 381-2, P1 Eastman Kodak Co., United States of America)

  P2 Copolymer methyl methacrylate-ethyl methacrylate (Acryloid-

  B72, Rohm & Haas Co., USA) P3 Methyl acrylate-methyl methacrylate copolymer (Acryioid-10, Rohm b Haas Go., United States of America) P Resin Xylenic (Nikanriol L, from Mitsubishi Gas P4 Chemical Industries Ltd.) P5 Ketone Resin (Hilac 111, from Hitachi Chemical Co., Ltd.) P Ketone Resin (Kunstharz EFS, Bayer AG, P6 Federal Republic of Germany) Photocure activators S1 Benzyl ethyl ether S2 Benzile S3 Benzoyl isopropyl ether S4 Benzophenone S5 2-tert-butylanthraquinine Thermal polymerization inhibitors i1 Hydroquinyl monomethyl ether

2,6-di-tert-butyl-p-cresol.

  In Table IV, the numbers preceding the abbreviations

  described above indicate parts by weight. For example,

  37C9 means 37 parts of the cross-linking agent C. For the inhibitors

  Thermal polymerisation bitters, the weights are indicated in

parts per million.

EXAMPLES 15 to 19

  The impregnable layers, each formed on a biaxially oriented polyethylene terephthalate film 28f in thickness and containing the adjuvants for the two-component diazo imaging material, prepared in Example 2 are impregnated with different two-component diazo photosensitive compositions in which a plurality of diazonium salts are combined with a plurality of couplers. We try them

  image-forming materials thus obtained and the results obtained

  naked are shown in Table V below. In the preparation of the photosensitive compositions, the amount of zinc chloride and the amount and type of the solvent used are the same as in

  Example 2 for comparison purposes.

TABLE V

  Exem- photosensitive agents Results of the two-component Exemazo tests Results of the tests

pile Coupler coupler Sensitivity Density

diazonium! Maximum color bnsi-

  (Bilit portions of the image) 9d1 19,8a1 Blue 1,5-1,8 1 1 16 l0d2 15,0a2 Brown 1,4-1,6 2 reddish 17 lld1 l, la2 Brown 1,4-1,7 1 reddish 18 15d2 18,0a3 Yellow 1,3-1,4 2 1 6,5dl + 6,5d2 27,3a 1 + 2,21a2 Bluefun 1,4-1,6 1 func1 Abbreviations for Table V have the following characteristics: Diazonium salts mean the respective ingredients in the following. bis (3-methoxy-4-pyrrolidinobenzenediazonium) tetrachlorozincate

  d2 4-N, N-dimethylaminobenzenediazonium tetrafluoborate.

  2-Hydroxynaphthalen-3-carboxylic acid a1 2'-methylanilide a2 bis (2,4-dihydroxyphenyl) sulfide couplers

a3 acetylacetobenzylamide.

  In Table 5 placed before the abbreviations

  feel parts by weight. For example 15a3 means 15 parts

azo coupler a3.

  It is understood that the invention is not limited to

  preferred embodiments described above as illustrative

  and the person skilled in the art may make various modifications and changes thereto without departing from the scope and

the spirit of the invention.

Claims (17)

R E V E N D I C A T I 0 N S CLAIM $   1 - Process for the production of a two-component diazoic image-forming material, characterized in that it consists in applying to a face of a plane support a layer of a liquid composition containing (1) a crosslinkable compound by high energy radiation and (2) a molecular weight compound   non-crosslinkable by high energy radiation, but suitable for   required for the impregnation with a photosensitive composition, irra-   depositing said liquid composition with high energy radiation   to cause the crosslinking and hardening of the composition   tion, thus forming a layer suitable for impregnation, then   impregnating the layer thus formed with said photo-composition sensitive and to dry the layer.   2 - Process according to claim 1, characterized in that said compound crosslinkable by high energy radiation is a liquid compound containing 1 to 4 ethylenic bonds, and is not oligomeric.   3 - Process according to claim 1, characterized in that said compound crosslinkable by high energy radiation   is a liquid compound containing from 2 to 6 epoxy groups.   4 - Process according to claim 1, characterized in that said high molecular weight non-crosslinkable compound by high energy radiation but suitable for impregnation with a photosensitive composition containing a diazoniui salt   photosensitive, is a cellulosic derivative.   Process according to claim 1, 2, 3 or 4, characterized in that a coupler is incorporated in said composition   photosensitive material containing a diazonium salt or in said   liquid to be applied to the surface of a plane support.   6 - Process according to claim 2, characterized in that   that the non-oligomeric liquid compound having 1 to 4 ethylenic bonds   is selected from methyl acrylate, 2-ethyl acrylate and   hexyl, 2-hydroxyethyl acrylate, tetrahydroacrylate   furfuryl, phenoxyethyl acrylate, the corresponding methacrylates   styrene, N-vinylpyrrolidone, ethylene glycol diacrylate, propylene glycol diacrylate, diacrylate   of 1,6-hexanediol, trimethylolpropane triacrylate, tetra-   pentaerythritol acrylate and the corresponding methacrylates.   7 - Process according to claim 3, characterized in that said liquid compound containing from 2 to 6 epoxy groups is chosen from 1,6-hexanediol diglycidyl ether, ether   glycerol triglycidyl ether, tetraglycidyl bis-   cinol and epoxy novolacs having an epoxide equivalent from 172 to 181.   8 - Process according to claim 1, 2, 3, 6 or 7, characterized in that said compound crosslinkable by radiation   at high energy has a boiling point of at least 100 C.   9 - Process according to claim 4, characterized in that said cellulose derivative is chosen from (a) the fatty acid esters obtained by modification of the cellulose with a fatty acid (b) the inorganic esters obtained by modification of the cellulose in nitric acid and (c) alkyl ethers obtained by modification of the cellulose with dialkyl sulphate or an alkyl halide.   10 - Process according to claim 1, characterized in that the high energy radiation is selected from the rays   ultraviolet and electronic beams.   11 - Process according to claim 1, 2 or 3, characterized   in that the molar coupling / diazonium salt ratio is from 0.2 / 1 to 8/1.   12 - Process according to claim 11, characterized   in that the coupler / diazonium salt ratio is 0.5 / 1 to 3.5 / 1.   13 - Process according to claim 1, 2 or 3, characterized   in that the sum of the coupler and diazunium salt amounts is 5 to 50% based on the weight of the impregnable layer. 14 - Process according to claim 13, characterized in that the sum of the amounts of coupler and diazonium salt   is 10 to 40% relative to the weight of the layer capable of gnation.   Method according to claim 2 or 6, characterized   in that the amount of non-oligomeric compound containing from 1 to 4 ethylene bonds is from 20 to 80% by weight   high molecular weight compound conferring the ability to   gnation. 16 - Process according to claim 15, characterized in that the amount of non-oligomeric compound containing from 1 to 4 ethylenic bonds is from 35 to 68% by weight.   high molecular weight compound conferring the ability to gnation.   17 - Process according to claim 3 or 7, characterized   in that the amount of liquid compound containing from 2 to 6 groups   epoxy is 10 to 90% based on the weight of the high-weight compound   molecular imparting impregnation ability.   18 - Process according to claim 17, characterized   in that the amount of liquid compound containing from 2 to 6 groups -   epoxy is 30 to 70% based on the weight of the high-weight compound   molecular imparting impregnation ability.   19 - Process according to claim 2 or 6, characterized in that one incorporates a thermal polymerization inhibitor   in the liquid composition to be irradiated.   - Process according to claim 19, characterized in that the thermal polymerization inhibitor is chosen from   hydroquinone, hydroquinone monomethyl ether, 2,6-di- tert-butyl-cresol and cupferron.   21 - Process according to claim 2 or 6, characterized   in that the liquid composition to be irradiated contains an oligomer   Crosslinkable mother containing two or more ethylenic bonds.   22 - Process according to claim 21, characterized in that said oligomer has a molecular weight of about 300 to 3,000.