DE3207827A1 - PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

Henkel, Kern, Feiler for Hänzel Patent attorneys

Registered Representatives

before the

European Patent Office

KONISHIROKU PHOTO INDUSTRY CO., LTD. Tokyo, Japan

Möhlstrasse 37 D-8000 Munich 80

Tel .: 089 / 982085-87 Telex: 0529802 hnkld Telegrams: ellipsoid

FP-1237-3 Dr. F / from

March 4th 1982

Photographic recording material

description

The invention relates to a silver-free photographic recording material for the production of image copies high contrast, especially a highly sensitive and in aqueous systems to high density and image copies high contrast developable photographic recording material, in particular for the production of lithographic Templates.

For producing high-contrast images, for example of lithographic templates, there are already the most diverse silver-free recording materials. However, these have numerous disadvantages. According to In JP-OS 1624/1972 and 2520/1977, a recording material containing dyes or pigments is used photosensitive resin layer. However, since the one contained in the photosensitive resin layer Dye or pigment, which absorbs active radiation responsible for the formation of an image, can be used with such recording materials at most an image high density but drastically reduced sensitivity.

From JP-OS 22929/1974 and 22930/1974 it is known, simultaneously with or after the formation of a portrait in the photosensitive resin layer to color them. The disadvantage here is that not only one special dye-containing Dye bath is required, rather the dyeing conditions must also be carefully controlled,

to achieve an acceptable (image) density. 5

According to JP-OS 65927/1973 and 139720/1975, a metallic masking layer is first applied (on a layer substrate) and a photosensitive resin layer is formed thereon. Here, however, you need special acids or alkalis for etching the metallic layer and the photosensitive resin layer. Causes difficulties here the stability of the treatment solution. In addition, when using such a recording material there is also the risk of workplace or environmental pollution.

From JP-OS 16124/1972 and 89916/1977 it is known, on a by mixing or dispersing a dye or a pigment in a binder and applying a masking layer applied to a layer support to form a photosensitive resin layer. Required for developing the photosensitive layer However, special organic solvents or alkalis are used, which for reasons of possible workplace or pollution is undesirable.

The invention was based on the object of providing a highly sensitive and high resolution having, silver-free photographic recording material

create that for reasons of workplace hygiene and environmental protection without difficulty in aqueous Systems can be developed and with which in each case, for example, lithographic originals of high image density and

high image contrast can be produced. 35

The subject matter of the invention is set out in claims 5

described.

According to a preferred embodiment of the invention, it contains that present in the photosensitive layer

photocurable diazo resin the monomer units with 10

Diazo groups in a larger molar ratio than monomer units of the polymer with a quaternary nitrogen or phosphorus atom are present. If a recording material according to the invention image-compatible

exposed and then in an aqueous solvent 15th

developed, is obtained by removing the unexposed parts of the photosensitive layer and the underlying colored masking layer a high-contrast image.

The invention is explained in more detail below.

Usable in the photosensitive layer in the present invention Photohardenable diazo resins consist of, for example

“_ Wise from the reaction products of diazonium salts with organic condensing agents with reactive carbonyl groups, e.g. aldols or acetals (See. US-PS 2 O63 631 and 2,667,415) and halogenated Lewis acid salts, which by substituting these water

3Q soluble compounds with anion components such as BF. ~, PF,, SiF, SbF, or BeF, according to the teachings of Japanese Patent Laid-Open No. 98613/1979. Particularly preferred Polycondensation products of p-diazodiphenylamine with formaldehyde. These contain polycondensation products presumably monomer units of the following formula:

where X ^ is an anion, for example a halide, sulfate, fluoroborate or hexafluorophosphate _f .

As polymers with quaternary nitrogen or phosphorus atom in the light-sensitive layer according to the invention Recording material the so-called. Cationic polymer electrolytes according to M.F. Hoover in "J. Macromole, Sci-Chem A-4", 1327 (1970) can be used. The quaternary nitrogen or phosphorus atom can either be contained in the main chain or in a side chain of the polymer.

A polymer with a quaternary nitrogen atom in the The main chain contains, for example, what are known as ion-like monomer units the general formula:

! R.

) 2 η

in which mean

X ^ - 'an anion

R is an alkyl group or a group in the form of a carbon ring and

4 *

η is an integer.

A polymer with a quaternary nitrogen atom in the Side chain contains, for example, methacryloxyalkylammonium monomer units the general formula:

X tj

L COO (CH ₂ ) _n -N

where X ~ is an anion

R is an alkyl group or a group in the form of a 20th

Carbon rings and

η is an integer.

Such a polymer can also contain vinylbenzylammonium monomer units the general formula:

III 30

y 11

in which mean

X is an anion

R is an alkyl group or a group in the form of a carbon ring

contain.

Polymers in which these contain benzylammonium are also suitable Monomer units are bound via an amide group (to the main chain) (cf. JP-OS 22766/1980). Such monomer units then correspond to the general formula

in which mean

IV

X is an anion

R is an alkyl group or a group in the form of a carbon ring

Polymers with a quaternary phosphorus atom in the main chain contain, for example, monomer units the general formula:

in which mean

C.

V =.

X is an anion

R, R 'each represent an alkyl group or a group in Shape of a carbon ring

Polymers with a quaternary phosphorus atom in the Side chains contain, for example, monomer units of the general formula:

CH, O

OH , X ^

in which mean

X is an anion and

R is an alkyl group or a group in the form of a

Carbon rings.

Homopolymers which can be used according to the invention can be formed from the monomer units represented by the formula. However, copolymers with 35

other polymerizable units in order to

solubility or the film-forming properties of the ° polymer to be used according to the invention to adjust. Copolymerizable units are, for example, acrylic acid, methacrylic acid or their esters, Styrene, olefins, ethers, vinyl acetate or acrylonitrile.

* In all formulas I to VI, the anions X ^ for example from halogen, sulfuric acid, phosphoric acid, sulfonic acid or hydrogen-containing acid ions exist. Examples of alkyl groups which can be represented by R or R 'are methyl, ethyl, propyl, iso-

butyl, pentyl, hexyl, heptyl or decyl groups. Examples of groups in the form of carbon rings are Aryl, aralkyl or cycloalkyl groups, e.g. benzyl, phenyl, p-methylbenzyl, cyclohexyl or cyclopentyl groups

groups. The in the formulas I to VI at N ⁺ or P ⁺

bonded alkyl groups or groups in the form of carbon rings can be the same or different from one another be.

The are particularly well suited for the purpose of the invention from US-PS 3,709,690 and JP-OS 22766/1980 known or similar compounds. The contents of this Copolymers of monomer units with quaternary However, nitrogen atom does not need within the

a.a.O. specified ranges, one achieves -30

even better results if the contents of the monomer units in question are below the specified lower limits lie.

For example, if that's the quaternary nitrogen atom containing copolymer according to the teachings of US

PS 3,709,690 is said to be water-soluble, it is said that the monomer units with the quaternary nitrogen atom make up at least a third. Achieved according to the invention you get good results when the content of these monomer units is at least one thirtieth. In particular when using such a copolymer as the main component of the light-sensitive layer in addition to the diazo resin should contain the quaternary nitrogen atom containing monomer units are at most one third in view of optimal results. If it is according to JP-OS 22766/1980 to act as a water-dispersible polymer with a quaternary nitrogen atom should, the monomer units containing the quaternary nitrogen atom in the copolymer should at least be a fifth. With the sole use of corresponding copolymers, however, one already achieves Good results at concentrations below 7/10. This is based on the fact that the used in the invention Polymerizaten containing monomer units with the quaternary nitrogen atom not because of their pickling effect on anionic dyes, but because of their water-soluble

* ° and its reactivity with the diazo resin can be used in the exposed areas with the formation of a water-insoluble substance.

Although the reaction mechanism of the reaction of the monomer

units with the quaternary nitrogen atom or the Quaternary phosphorus atom with monomer units of the diazo resin are not yet fully clarified, presumably react the former in the exposed areas somehow with the decomposition product of the latter. If the former is larger

Molar ratio are present than the latter, the decrease

3207327

Water insolubility or the water impermeability of the exposed Districts, so that the exposed districts are right 5

can be well colored by the anionic dye.

On the other hand, when the former are present in a lower molar ratio than the latter, the exposed areas show one
strong water repellency, hence the dyeability

with the anionic dye is quite bad. FoIg-10

Should borrow the monomer units with the quaternary

According to the invention, nitrogen atom or the quaternary phosphorus atom can be present in a 0.1 to 30-fold molar ratio compared to the diazo monomer units, and in particular in the case of a recording material in one
15th

aqueous system developable masking layer under the photosensitive layer to ensure an acceptable image reproduction. The photosensitive layer of a recording material according to the invention can of course contain a polymer with a high content of monomer units with a quaternary nitrogen or phosphorus atom. However, if in such a case the
Increasing the amount of diazo resin decreases the sensitivity. Consequently, the third component (in the light-sensitive

", _ Borrowed layer) a relatively water-insoluble organic filler or a latex without quaternary nitrogen or phosphorus atom. An example for
the former filler is found in JP-OS 13775/1980, an example of the latter is found in JP

OS 2520/1977.

It should preferably be so in the photosensitive layer a lot of diazo resin to be contained that the diazo monomer units contained therein 1/30 to ten times the

Monomer units with quaternary nitrogen or

2
Phosphorus atom. Per m support area is the

Amount of diazo resin is preferably 0.01 to 2 g. If the If the amount of the diazo resin exceeds this range, the sensitivity will decrease. On the other hand, when the amount of diazo resin is below the specified lower limit, the resistance of the photosensitive layer becomes inadequate.

The amount of monomer units with the quaternary nitrogen or phosphorus atom is preferably in Range of thirty times to 1/10 of that in the photosensitive Layer existing diazomonomer units. Appropriately, the amount should not exceed 50, preferably 2 to 25 percent by weight, based on the total weight of the photosensitive layer. If the crowd the exceeds the specified upper limit, the resistance of the photosensitive layer becomes inadequate. When the crowd falls below the specified lower limit, one does not achieve an adequate development speed.

The weight of the photosensitive layer is per

m support surface expediently 0.1 to 20, preferably 0.5 to 5 g. When the strength of the photosensitive Layer falls below the specified lower limit, the durability deteriorates. If the strength is the specified Exceeds the upper limit, the sensitivity and the resolution decrease.

The colored masking layer provided according to the invention is explained in more detail below. The colored masking layer is a layer which, when removed by abrasion or by dissolving away, in the same area and with the same solvent as the light-sensitive layer _{f originally above it, but then dissolved away and removed by the solvent}

Capable of forming a colored image. They are obtained by dispersing, mixing or dissolving a dye or pigments as a colorant in a binder and applying the dispersion, mixture or solution to one Support. As UV absorbers or other dyes according to the invention, for example, the compounds known from JP-OS 16124/1972 are suitable. As pigments organic or inorganic pigments are suitable (cf. Ganryo Binran (Manual of Pigments), published from Nippon Ganryo Gijutsu Kyokai (Japan Pigments Technology Association) and JP-OS 16124/1947).

In the event that the recording material according to the invention is used to produce a lithographic master, carbon black in particular should be used as the coloring agent will. The reason for this lies in the high opacity of soot. When using it, the same density make the masking layer thin, which benefits the image reproduction.

A wide variety of polymers are suitable as binders for the colored masking layer. In particular when the masking layer is to be developable in an aqueous system, water-soluble or slightly water-soluble polymers are suitable as binders. Examples include acrylic resins, vinyl acetate or vinyl alcohol resins, 3® halogen-containing resins, nitrogen-containing vinyl resins, diene polymers, polyoxymethylenes, polyethers, polyethyleneimines, polyester resins, polyamide resins, cellulose derivatives, protein resins and / or copolymers of the same.

The ratio of colorant to binder is familiar to the person skilled in the art, whereby the desired optical density, the solvent

ability and swellability of the masking layer in the developer and the like are to be considered.

The amount of application of the colored masking layer when used of the recording material according to the invention containing them for the production of a lithographic master lies on the one hand in a range that gives a transparency density of at least 2.0 and on the other hand provides the smallest possible thickness (of the masking layer).

If, for example, carbon black is used as a coloring agent,

2 the application rate is preferably 0.2 to 2 g / m 2 Support surface.

As a support for recording materials according to the invention For example, foils made of metal, such as aluminum, iron, steel or their alloys, paper backing, are suitable, in particular art paper, e.g. paper laminated with polypropylene or polyethylene, or plastic Supports, e.g. supports made of cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene or polyvinylidene chloride. Such support should expediently to improve the adhesion of a electrical, chemical or mechanical pretreatment. To control curling or the smoothness of the surface should have an anti-curling layer or a roughening layer on top of the surface Masking layer can be provided on the opposite side.

A recording material according to the invention is obtained for example by applying the respective coating

liquid by fluidized coating, brush coating, coating by means of a doctor blade or coating by means of

ZO

Coating funnel, and then drying the applied layer. The coating liquid for Manufacture of the masking layer and the photosensitive Layer is usually a solution of the various components in water, acetone, methanol, ethanol, methyl glycol, halogenated hydrocarbons or ethyl acetate. To control the surface properties of the recording material, a protective layer or a rough layer, which is soluble in the developer or can be penetrated by this, can be provided. The colored masking layer and / or the light-sensitive

^A wide variety of additives can be incorporated in the same layer of a recording material according to the invention, provided that these do not impair the desired success.

A recording material according to the invention of the described Art is first exposed image-appropriately with active radiation. With the active radiation used it can be any radiation as long as it sensitizes the diazo resin. Preferred

Light sources are mercury lamps and xenon lamps that emit light that is rich in UV. Through this light that becomes Diazo resin mainly sensitized. The image-appropriate exposure usually takes place in contact with the original.

After exposure, the recording according to the invention is

The application material is immersed in a suitable aqueous developer for development. Here the unexposed Districts of the photosensitive layer and the corresponding Areas of the underlying masking layer removed. Development can be done by rubbing the surface

the recording material with a suitable material, e.g. with a sponge. The strenght

of rubbing and the duration of development may vary depending on

the type of recording material used and ver-5

applied developer can be appropriately selected.

Furthermore, these conditions can also be controlled via the temperature of the developer. For the sake of one Environmental protection and workplace hygiene should be considered

Developer preferably water can be used. For the 10th

However, weak alkalis, such as sodium carbonate, or surfactants can also be used to control penetration Funds are also used.

A recording material according to the invention cannot 5

can only be used for the production of lithographic templates, it is also suitable for supporting documents when used a reflective support, e.g. a white translucent support, or for on a print negatives (subjected to a hydrophilization treatment) on a metal plate.

The following examples are intended to illustrate the invention in more detail. Unless otherwise stated, all statements mean “parts” - “parts by weight”.

example 1

On a 100 μm thick polyethylene terephthalate film support is made by applying a coating liquid of the following composition:

Hydroxypropyl methyl cellulose phthalate 10 parts

Soot 5 parts

Methyl glycol 50 parts

Zl

_ a masking layer 2.0 μm thick after drying

carried. A coating liquid is then applied to the masking layer.

ability of the following composition:

Styrene / NiN / N-trimethyl-N-vinylbenzyl-

ammonium chloride (9: 1) copolymer 10% water / ethanol = 3/1 solution 80 parts Commercially available diazo resin

10% aqueous solution 20 parts

applied and dried in such a way that a photosensitive 1.0 µm thick diazo layer is obtained.

The test specimen obtained is left at a temperature of 55 ^° C. for 12 hours. Then a negative film, a Kodak step wedge No. 2, a point card with points from 3 to 97% (150 lines / 2.54 cm) and a card for determining the resolution is placed on the test specimen, whereupon the sandwich is placed for 30 seconds using a commercial metal halide lamp is exposed.

Finally, the test piece 2 is dipped in warm minutes 2O ⁰ C water and weakly rubbed with a sponge to the unexposed areas of the photosensitive layer and the corresponding locations of the darunterliegen- * ® the masking layer to remove. This results in a black image of high density and high contrast as well as good reproduction of the points from 3 to 97%. The surface of the copy image obtained is water-repellent and hardly prone to scratches. The resolution is 80 lines / mm. The recording material is thus a high quality recording material.

Example 2

By applying a coating liquid of the following Composition:

Polymeric latex with a quaternary nitrogen atom

(x: y: z = 4:84:12)

Latex with a solids content of 10% diazo resin according to Example 1 10% aqueous solution

80 parts 20 parts

on the masking layer formed according to Example 1 is a 1.5μπι strong light-sensitive after drying Diazo layer formed.

35 The test specimen obtained is exposed and developed according to Example 1, with a black image being higher

Density and high contrast as well as good reproduction of the Points from 3 to 97% is obtained. The surface of the image copy obtained is hardly susceptible to scratches. The strength the image copy obtained is large. The resolution is 100 lines / mm.

Example 3

A coating liquid of the following composition is applied to the support of Example 1:

Commercial polyvinyl alcohol 100 parts

Soot 5 parts

Glyoxal

0.5% aqueous solution 5 parts

a masking layer with a thickness (after drying) of 2.0 μm is formed.

A light-sensitive layer is applied to the masking layer obtained Coating liquid of the following composition :

The solids content of the latex of

Example 2 is reo ü in methyl glycol

dispersed

10% aqueous dispersion 80 parts

Diazo resin according to Example 1 with a hexafluorophosphate anion

10% solution in meth / lglycol 20 parts

ta ■ 3 2 Ü 7 8 2 V

applied and dried, so that a 1, Ο μκι thick photosensitive Diazo layer is obtained. 5

The test specimen obtained in this way is exposed and developed in accordance with Example 1, with a black image being higher Density and high resolution and good reproduction of the points from 3 to 97% is obtained. The resolving power is 100 lines / mm.

Example 4

A test specimen is produced as in Example 1, but instead of that in the light-sensitive layer contained polymer with quaternary nitrogen atoms 80 parts

Styrene / PjPjP-trioctyl-P-vinylbenzyl-

phosphonium chloride (9: 1) copolymer (10% water / ethanol = 3/1 solution)

be used.

With this specimen, too, an image of high density, high contrast, good reproduction of the points and higher is obtained Film strength. The image has a resolution of 80 lines / mm.

Example 5
5

A test specimen is produced as in Example 1, except that a coating liquid of the following composition is used to form the photosensitive layer:
10

Styrene / NjNjN-trimethyl-N-vinylbenzylammonium chloride (1: 1) copolymer 10% strength aqueous solution 20 parts

Styrene / butyl acrylate (7: 3) latex

10% solids content 60 parts

Diazo resin according to Example 1
10% aqueous solution 20 parts

is used.
20th

With this specimen, too, an image of high density, high contrast, good dot reproduction and high film strength is obtained. The resolution is 100 lines / mm.

Example 6

A test specimen is produced according to Example 2, but as a polymer latex with a quaternary nitrogen atom one with an x: y: z ratio of 4:48:48 is used. Here you get an almost black picture as good as in example 2, but the sensitivity is somewhat lower.

Claims (10)

3 2 ü 7 8 2 claims 1. Photographic recording material in which on the support (a) a colored masking layer and (b) a photo-curable diazo resin and a Polymer with a light-sensitive layer containing quaternary nitrogen or phosphorus atoms are. - ^ - 2. Recording material according to claim 1, characterized in that that in the photosensitive layer the monomer units of the photo-curable diazo resin are contained with diazo groups in a larger molar ratio than the monomer units of the polymer with " quaternary nitrogen or phosphorus atom. 3. Recording material according to claim 1, characterized in that that in the case of the polymer with quaternary Nitrogen or phosphorus atom of the quaternary stick-25 substance or phosphorus atom is contained in the main chain of the polymer. 4. Recording material according to claim 1, characterized in that that in the case of the polymer with a quaternary nitrogen or phosphorus atom, the quaternary nitrogen or phosphorus atom is contained in the side chain of the polymer. 5. Recording material according to claim 1, characterized in that it is 35 draws that it as a polymer with quaternary Nitrogen atom with "monomer units" formula ^(CH 2> n- where mean: X ^ an anion R is an alkyl group or the remainder of a ring-15 shaped hydrocarbon and η an integer contains. 20th 6. Recording material according to claim 1, characterized in that that there is a polymer with a quaternary nitrogen atom with monomer units of the Formula 2b , R COO (CH ₂ ) _n -N ^^ - R where: x ^ »mean an anion R is an alkyl group or the residue of a cyclic hydrocarbon and η is an integer 35 contains. 7. Recording material according to claim 1, characterized in that that there is a polymer with a quaternary nitrogen atom with monomer units the formula where mean: X is an anion R is an alkyl group contains. 8. Recording material according to claim 1, characterized in that that there is a polymer with a quaternary nitrogen atom with monomer units the formula CH. where mean 5 Ώ X ^ an anion R is an alkyl group or the residue of a cyclic hydrocarbon jQ contains. 9. Recording material according to claim 1, characterized in that that there is a polymer with a quaternary phosphorus atom with monomer units Formula 15 x ^v in which mean - (CH ₂ ) an anion 25 R / R 'alkyl groups contains, 10. Recording material according to claim 1, characterized in that that there is a polymer with a quaternary phosphorus atom with monomer units 30 formula O OCH, -CHCH, P® / -R ³⁵ * U ~ \ r in which mean X is an anion R contains an alkyl group ¹⁰ .