DE3539035A1 - COMPOSITION FOR FORMING A LAYER OF THE LITHOGRAPHICALLY APPLICABLE CARRIER PLATE - Google Patents

Description

The invention relates to a composition for forming a layer (A) which can be used in lithography

-jO carrier plate (B), in particular a composition which by applying to the surface of a substrate plate (C) the layer (A) with sufficient hydrophilicity and having sufficient adhesiveness to a photosensitive resin layer, as well as

-J ₅ the method for preparing the composition.

Lithography is one of the printing processes that the Makes use of repulsion between water and oil on the surface of a printing plate. The presensitized lithographic The plate consists mainly of the carrier plate (B) containing the layer (A) and the substrate plate (C) as well as the layer (A) on the surface. applied photosensitive resin layer.

As the substrate plate (C), aluminum plates have already been used on a large scale, the various types of processing and subjected to treatments to meet the requirements of a printing plate. For example to strengthen the adhesion between the aluminum plate and the photosensitive, image-bearing layer, one of the surfaces of the aluminum plate was chemically or mechanically ground, creating tiny Unevenness (unevenness) formed on the treated surface. Then this surface was used to harden anodically oxidized and then with an aqueous

Treated silicate solution or the like to improve their hydrophilicity.

When performing these various treatments, there were problems with maintaining quality of the carrier plate (B) and the need arose for an improvement in the quality control, this being the case necessary facilities and the maintenance of the same to the enormous increase in costs of the so produced Printing plates led.

Furthermore, it is not an exaggeration to say that when using plastic films, plastic sheets or Sheets of paper as substrate plate (C) has no methods, a carrier plate suitable for lithographic purposes (B).

The object of the invention is therefore to make available a carrier plate (B) which has the disadvantages of the known Does not have carrier plate and fully meets the requirements placed on it, in particular, by a treatment process only one layer on the upper surface of the substrate plate (C), regardless of the material the same to apply.

It has now been found that a new composition that

(I) an aqueous solution containing (1) methylolmelamines and (2-1) polyvinyl alcohol, zirconium nitrate and a curing catalyst for methylol melamine or (2-2) an epoxy compound, and (II) one in the aqueous solution comprises dispersed water-insoluble inorganic powdery material attached to the support plate (B) Application for lithographic purposes fully met requirements.

- Q -

A composition suitable for forming a layer (A) of a carrier plate (B) is therefore used to achieve the object proposed, which is characterized by a content of (I) an aqueous solution of (1) methylolmelamines and (2-1) Polyvinyl alcohol, zirconium nitrate and a curing catalyst for the methylol melamines or (2-2) an epoxy compound, and (II) a water-insoluble inorganic powdery material dispersed in the aqueous solution excels.

To achieve the object, a method for producing a composition is also proposed which is suitable for forming a layer (A) of a lithographically applicable carrier plate (B), which is characterized by (i) dispersing a water-insoluble inorganic powdery material in an aqueous mixture, obtained by mixing an aqueous solution of polyvinyl alcohol and zirconium nitrate with an aqueous solution of methylol melamines and a curing catalyst for the methylol melamines or by mixing an aqueous solution of an epoxy compound with an aqueous solution of methylol melamine,
(ii) adding an optional ingredient such as a metal chelating substance, one or more pigments, one or more dyes, a viscosity-increasing substance to the resulting aqueous dispersion,

(iii) vigorously stirring the aqueous mixture and
(iv) removing bubbles from the stirred mixture containing air bubbles.

In particular, the invention relates to a composition for forming a layer (A) of a lithographically applicable one Carrier plate (B) with a content of (I) a

aqueous solution containing (1) methylolmelamines and (2-1) polyvinyl alcohol, Zirconium nitrate and a curing catalyst for methylolmelamines or (2-2) an epoxy compound, and on (II) a water-insoluble inorganic powdery material dispersed in the aqueous solution, and a method for preparing the composition (hereinafter referred to as "composition of the invention" referred to as).

ΊΟ As Methlolmelamine according to the invention are preferred Dimethylolmelamine, Tr! Methylolmelamine and a mixture same used.

As the curing catalyst for Methylomelamine ammonium ^ be mentioned ₅ salts such as ammonium chloride, diammonium hydrogen phosphate, ammonium sulfamate, etc., hydrochlorides or sulfamates of an amino alcohol, amine salts, such as dimethylaniline, pyridine, Picolinmonochloracetat, etc., guanidine sulfamate, inorganic metal salts such as magnesium chloride, zinc chloride, zinc sulfate, etc. . Of these compounds, amine salts are preferred.

According to the invention, the polyvinyl alcohol used is preferably a polyvinyl alcohol which is soluble in water and has a degree of saponification above 85%.

The epoxy compounds according to the invention are water-soluble epoxy compounds having more than two 1,2-epoxy groups (2TC - CC) and 8 to 50 carbon atoms preferred,

for example ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Glycerin polyglycidyl ether, phenol polyethylene glycol diglycidyl ether (commercially available from NAGASE Sangyo Co., Ltd. under the names DENACOL and the

Number designations EX-810 and 811, EX-851, 830 and 832, EX-911, EX-941, 920 and 921, EX-313 and 314 and EX-145).

The water-insoluble inorganic powdery material according to the invention is powdery material which is hydrophilic and is insoluble or hardly soluble in water or an aqueous alkaline solution. For example, can Metal oxides such as zinc oxide, aluminum oxide, antimony oxide, calcium oxide, chromium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, Lead oxide, bismuth oxide, magnesium oxide, manganese oxide, salts such as calcium carbonate, calcium sulfate, etc., silicon compounds like colloidal silica, natural pigments like kaolin, bentonite, clay etc. and powdered metals such as aluminum powder, iron powder, zinc powder, etc. can be applied. Of the above-mentioned water-insoluble inorganic ones powdered materials is colloidal silica particularly suitable for the purposes of the invention.

In addition, it is preferred to use the water-insoluble inorganic powdery material in a size which goes through a sieve of the sieve number 325 Tylor sieve row (Diameter of the powder particles less than 43 µm). Finer Material is even more preferred.

The preparation of the composition of the invention can be carried out, for example, by '.
(i-1) An aqueous solution of polyvinyl alcohol and zirconium nitrate is mixed or mixed with an aqueous solution of the methylol melamines and a curing catalyst for the latter

(i-2) an aqueous solution of an epoxy compound with mixed with an aqueous solution of methylolmelamines,

(ii) Subsequently to the mixed aqueous solution, a water-insoluble inorganic powdery one Material and optionally a metal chelating compound, one or more pigments, one or more dyes, a substance for

Add viscosity increase, etc.
(iii) vigorously stir the entire mixture and
(iv) air bubbles are then removed from the dispersion thus obtained.

In addition, the epoxy component of the layer (A) gives the carrier plate (B) not only hydrophilic properties but Also acts as a hardener for the methylolmelamines, which is why it is not necessary to add one to the system

- \ 5 to add hardening catalyst. However, ammonium chloride, an amino alcohol, etc. can be added as a curing catalyst.

In the composition of the invention, the polyvinyl alcohol contains, the weight ratio of the ingredients is 2 to 10, preferably 4 to 7 parts of zirconium nitrate, 50 up to 200, preferably 80 to 180 parts of methylolmelamines, 50 to 200, preferably 70 to 150 parts of water-insoluble inorganic powdery material and 0.5-10 parts curing catalyst for methylolmelamines for each 100 Share polyvinyl alcohol.

If the amount of zirconium nitrate is less than 2 parts by weight per 100 parts by weight of polyvinyl alcohol, after the thermal treatment, the insolubilization of the polyvinyl alcohol against water is incomplete; if on the other hand more than 10 parts by weight per 100 parts by weight of polyvinyl alcohol tend to be used the non-image-bearing parts due to insufficient hydrophilicity of the surface of layer (A) the printing ink

hold on to what is known as the basic vagueness (ground blur) on the printing plate surface.

If the amount of methylol melamines is less than 50 parts by weight per 100 parts by weight of polyvinyl alcohol, there is a tendency to lower the adhesion between the substrate plate (C) and the layer (A); if on the other hand If more than 200 parts by weight per 100 parts by weight of polyvinyl alcohol are present, it is insufficient Hydrophilicity of the layer (A) easily leads to a so-called basic fuzziness of the printing plate surfaces.

When the amount of the water-insoluble inorganic powdery material is less than 50 parts by weight per 100 Parts by weight of polyvinyl alcohol, there is a great tendency that there is an irregular distribution of the "Unevenness." or "grain" (unevenness) occurs on the surface of the layer (A), resulting in defective Reproducibility of the network points of the image-bearing parts leads; on the other hand, if more than 200 parts by weight per 100 Parts by weight of polyvinyl alcohol are present, the amount of the solution which has permeated into layer (A) increases photosensitive resin, which leads to an increase in the amount of the photosensitive resin solution applied, therefore the use of more than 200 parts is uneconomical.

In the composition according to the invention, which the epoxy bond contains, the weight ratio of the ingredients is 25 to 50, preferably 30 to 40 parts of the epoxy compound and 50 to 200, preferably 70 to 150 parts of the water-insoluble inorganic powdery material each per 100 parts of the methylolmelamines.

If the amount of water-insoluble inorganic powdery material is less than 50 parts by weight per 100 parts by weight of methylolmelamine, there is a great tendency that there is an irregular distribution of the unevenness 5 or grain (uneveness) of the surface of the layer (A) comes, which leads to poor reproducibility of the network points of the image-bearing parts.

On the other hand, if more than 200 parts by weight per 100 parts by weight of methylolmelamines are used, the permeates Solution of the photosensitive resin in the layer (A), resulting in an increase in the amount of the Photosensitive resin applied to the printing plate, so the use of more than 200 parts is uneconomical

15 is borrowed.

For the substrate plate (C) of the carrier plate (B), on the surface of which the composition according to the invention is applied any inexpensive material that meets the requirements for the lithographic plate can be used, such as for example foils or plates of a metal such as aluminum, iron, copper, tin, zinc, lead, etc. or Alloys of the same, plastic films or foils made of polyester, polypropylene, polyimide, polyacrylonitrile, polycarbonate, Polyamide, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyethylene, etc., synthetic papers, art papers, coated papers, cardboard, thin papers, etc. Of the metals are aluminum, zinc, iron, etc. suitable, and from the plastics those with a relatively high dimensional stability such as polyester, polyimide and Polycarbonate.

Of the paper materials are synthetic paper, art paper, coated paper, cardboard, etc. are suitable.

When the composition of the invention on the surface is applied to a metal plate used as the substrate plate (C), it can contain a metal chelate-forming compound like 5-sulf © salicylic acid. Ethylenediaminetetraacetic acid, trans-cyclohexane-1,2, diamine tetraacetic acid, etc. added in order to strengthen the adhesion of the layer (A) formed from the composition according to the invention to the substrate plate (C).

It is not necessary to have the substrate plate (C) before applying the composition according to the invention a special Subject to treatment so long as the surface is not contaminated by an oily substance.

-15 However, the surface of the substrate plate (C) can be one subject to physical treatment such as wet or dry honing, ball grinding, and brush grinding and / or a chemical treatment by acidic or alkali (s) to the specific surface

20 of the same to enlarge.

The lithographic printing plate can be prepared using the composition of the present invention as follows will:

For example, the composition according to the invention is applied to the surface of the substrate plate (C) with a Order bar, etc. applied. The plate treated in this way is then 0.5 to 6 minutes at a temperature of 120 exposed to a thermal treatment to 250 ° C, in which the applied composition according to the invention on the Plate (thickness 2 to 5 / µm) hardens.

When using the polyvinyl alcohol-containing composition, both during the thermal treatment the polyvinyl alcohol as well as the methylol melamines through the action of zirconium nitrate or the curing catalyst cured to form a membrane which is firmly adhered to the surface of the substrate plate (C). In particular, will Polyvinyl alcohol made water-insoluble and at the same time fixes a substance that makes the remaining (s) hydrophilic. Group (s) possesses, on the surface of the membrane thus formed, whereby it is ensured that the for the Layer (A) of the support plate (B) required hydrophilicity is maintained over a long time. on the other hand the water-insoluble inorganic powdery material apparently forms an adequate grain size on the Surface of the layer (A) of the carrier plate (B), which leads to the fact that the layer (A) through the physical Adhesion of the grain firmly adheres to the layer of photosensitive resin applied thereon.

When using the composition containing the epoxy compound the epoxy compound acts as a crosslinking agent for the methylolmelamines during the heat treatment the result of a membrane firmly adhering to the surface of the substrate plate (C). It also fixes the epoxy bond one having the remaining hydrophilic group (s) Substance on the surface of the membrane thus formed, thereby maintaining the for the layer (A) of the Carrier plate (B) required hydrophilicity is guaranteed in the long term. On the other hand, it forms water-insoluble inorganic powdery material on the surface of the layer (A) of the carrier plate (B) is a suitable Grain or unevenness, with the result that the layer (A) by the physical adhesion of the grain firmly attached to the layer of photosensitive

35 borrowed resin adheres.

- 17 - 3B39035

After applying a solution of a photosensitive Resin on the surface of the layer (A) of the carrier plate (B) in a known manner, the carrier plate (B) dried to obtain a presensitized plate having a layer of the photosensitive resin thereon and hereinafter referred to as "PS plate" is obtained.

A lithographically usable printing plate is obtained by exposing the PS plate produced in this way and developing the exposed PS plate.

As indicated above, the invention provides a composition which adheres to the lithographic support plate

(B) meets the requirements, with only one step, namely the step of applying the composition on the surface of the substrate plate (C) is required and the steps for surface treatment such as Surface grinding, anodic oxidation, hydrophilization, etc., all of which have so far been carried out, are unnecessary had to give the carrier plate (B) the desired properties.

The following examples are intended to illustrate the invention.

Examples T until 7th

In an aqueous solution, which can be obtained by dissolving methylolmelamine (available from Nippon Carbide Ind. Co., Ltd. under the trade name NICARESIN) in water guanidine sulfamate in a weight ratio shown in Table 1 was added as a curing catalyst. In these Solution was added to a previously prepared aqueous solution containing 5% by weight of polyvinyl alcohol (from SHINETSU Chem. Ind. Co., Ltd., C-17 grade) and 0.05 to 0.5 wt.% Zirconium nitrate

contained. After adding colloidal silica (manufactured by NIPPON EAROJIL Ind. Co., Ltd., COK 84 quality) to the aqueous mixture was stirred for 2 hours, whereby the colloidal silica was dispersed. After removal of the air bubbles formed in the dispersion, compositions with the weight ratios of the components were obtained as shown in Table 1.

Table 1

Examples
No. Polyvinyl
alcohol
Weight
share i
Zircon
nitrate
Weight;
share ifethylol-
nelamin
Weight. ■ ·
share Colloidal
Silica
Weight
share Guanidine-
sulfamate
Weight /
share : 1 100 6th 50 100 0.5 2 100 6th 100 100 1.0 3 100 6th 150 100 1.5 4th 100 6th 180 100 l, ⁸ 5 100 3 150 50 1.5 6th 100 4th 150 75 1.5 7th 100 10 150 150 1.5

CO CD CO

Examples 8-11

The compositions were made by the same procedure as produced in example 1. The weight ratio of the ingredients of these compositions is shown in Table 2 reproduced.

Examples 12-17

An aqueous solution of 5 g of methylolmelamine in 30 g of water was mixed with another aqueous solution containing 0.5 to 3.5 g of an epoxy compound (available from NAGASE Sangyo Co., Ltd. as DENACOL EX-313). To the so The aqueous mixture prepared was 1.25 to 5 g of colloidal silica (manufactured by Nippon EAROJiI Ind. -15 Co., Ltd., COK 84 grade) and 1.25 to 5 G titanium oxide (manufactured by TEIKOKU Chem. Ind. Co., Ltd., MT-600B Quality) added. This gave compositions having a weight ratio of the given in Table 3 Components.

Examples 18 until 21

Compositions were made by the same procedure as in Example 1 except that the Ingredients in the weight ratio shown in Table 4 were used.

Examples 22 and 23

Two kinds of the composition were prepared by the same procedure as in Example 12 except that the ingredients in the weight ratio given in Table 5 were used.

Table 2

Examples
No. Components of the composition (1) B. C. D. Titanium oxide Weight ratio of (1) 8th A. Zircon
nitrate Methylol- ■
melamine ■ Ammonium-
chloride volume A: B: C: D: E 9 Polyvinyl
alcohol. Zircon
nitrate Methylol
melamine ammonium
sulfamate ¹ barium sulfate l: 0 "05: l, 3: 0, 01: 0, 7 10 Polyvinyl
alcohol Zircon
nitrate Methylol
melamine Dime thy I-
aniline kaolin 1: 0.05: 1.4: 0.02: 0.5 11th Polyvinyl
alcohol Zirconium.
nitrate fethylol-
nelamin magnesium
chloride l: 0.04: V 5: 0 _r 03: 0 ,. 4th Polyvinyl
alcohol 1: 0, 07: ^ 6: 0, 04: 0, 6

Ol CO CO CD OO

Table 3

Examples
Numbers Components of the composition
(Parts by weight) Methylol
melamine Epoxy
link Colloidal
Silica Titanium oxide 12th 100 25th 37.5 37r5 13th 100 25th 50 50 14th 100 25th 75 75 * 15th 100 50 37.5 37.5. 16 100 50 50 50 17th 100 50 75 75

Table 4

^ ~~ "-> ^^ __ ^ examples
- ~~> ^ Nunn) ern
Components "" --- ^^^ 18th 19th 20th 21 Itolyvinyl alcohol
(Parts by weight) 5 7th 6th 8th Zirconium nitrate
(Parts by weight) 0.5 0.5 0.12 0.3 Methylol melamine
(Parts by weight) 8th 10 6th 5 Guanidine sulfanate
(Parts by weight) 0.07 0.05 0, 06 0.05 Water-insoluble inorganic
powdery material
(Parts by weight) colloidal
Pebble 5
acid Kaolin 3
colloidal
Silica 1 Calcium
sulfate 2
Titanium oxide 2 Calcium carbonate - ^
Alumina ²
colloidal silica * ■ water
(Parts by weight) 100 100 100 100

CO CD CO

Tabel

\ Examples
N _ ^ _ ^ Nurtmern
Component ^ ~~~~~~ -— ^ _ ^ 22nd 150 23 Methylol melamine
(Parts by weight) 10 10 Guanidine sulfamate
(Parts by weight) 0.05 - EJxjxy connection
(Parts by weight) 5.0 2.5 ι Colloidal silica
! (Parts by weight) 4.0 4.0 Alumina
(Parts by weight) ". - 5.0 kaolin
(Parts by weight) 3.0 - Ammonia cerebrospinal fluid (10%)
(Parts by weight) - • 0.2 water
(Parts by weight) 150

* E ^ xDxy connection in example 22:

Propylene glycol diglycidyl ether (DENACOL EX-911)

Epoxy compound in Example 23:

Polyethylene glycol diglycidyl ether (DENACOL EX-832)

Test examples 1 until 11th

Tests with the using the invention Composition made printing plates

One of the inventive compositions of the examples was used to produce lithographic carrier plates 1 to 11 on a surface each one degreased thin Aluminum plate (Japanese industrial grade A-1100) one

• Apply a length of 200 mm (200 m / m), a width of 300 mm (300 m / m) and a thickness of 0.15 mm (0.15 m / m) using a No. 6 bar applicator. The composition layered in this way was cured in a hot blast dryer by heating to a temperature of 180 ^{° C. for 3 minutes.} After applying a solution of a photosensitive resin of the negative type on the surface of each carrier plate, the coated plate in a hot blast drier for 1 minute at 120 ⁰ C was dried to (PS plate) gave the presensitized plate.

After placing a negative film (test pattern of 175 lines, network point area 3 to 97%) on the surface of the photosensitive resin layer of each PS plate, and setting the PS plate thus treated in a vacuum printing frame In a manner known per se, the PS plate was exposed to ultraviolet light from a mercury overpressure lamp or High pressure mercury lamp (from OOKU Works, 4kW) irradiated at a distance of 1 m for 30 seconds. After developing the irradiated PS plate with the help of a liquid developer

30 lers, lithographic printing plates were obtained.

After washing the printing plates with water and removing the The printing plate was colored by using water with the help of a squeegee or a rubber roller

a sponge, a protective paint was poured onto the treated surface thereof. The degree of adhesion of the paint to the picture-image parts was then observed.
5

After washing the printing plates again with water, remove the water on them with the aid of the With the rubber roller or the squeegee and drying, the printing plates were subjected to the following tests.

The adhesion of the image-bearing parts to the carrier plate was determined on the basis of the degree of peeling of the network points Judged 1,000 times abrasion using a Taber rotary abrasion device (Wheel of the device (truck wheel) type CS-17,

-15 load 1000 g) was used.

The reproducibility of the image was increased by the reproduc- assessability of the test pattern (175 lines, area of the network points 3 to 97%).

The sensitivity was judged by the number of the step chart (manufactured by Kodak Co., No. 2, of 21 steps).

The hydrophilicity of the non-image-bearing parts was determined (1) according to the degree of soiling by the Protective color after it has been colored and (2) according to whether the offset color goes off or not when you go after Applying the offset color directly to the non-image-bearing

Poured 30 parts of water.

The results of the tests are shown in Table 6.

Test examples 12 to 17

All the printing plates were prepared in the same manner as in Test Example 1 except that in each case the composition of Examples 12 to 17 and applied the layered composition was cured by one-minute heating at a temperature of 30 ⁰ C 2.

Each of these printing plates was subjected to the same tests as in Subjected to Test Example 1, the results are also shown in Table 6.

-15 Comparative test example:

In the same manner as in Test Example 1 except that a composition was used which 100 parts by weight of methylol melamine and 100 parts by weight of colloidal silica instead of the composition according to the invention of Test Example 1, a printing plate was prepared and the same tests as in Test Example 1 subject. The results are also given in Table 6.

Table 6

test
examples Specific Properties of the printing plate Reproduce
availability of
Image ... Hydrophilic
licity _:
the not
image
load-bearing
Parts Numbers
I.
j Liability of
Color on picture
load-bearing
share Liability of
image
load-bearing
Parts A. Is
opportunity A. 1 A. A. A. A. A. 2 A. A. A. A. A. 3 A. A. A. A. A. 4th A. A. A. A. • A 5 A. B. . A. A. A. 6th A. A. A. A. A. 7th A. A. A. A. A. 8th A. A. A. A. A. 9 A. A. A. A. A. 10 A. A. A. A. A. 11th A. A. A. A. A. 12th A. A. A. A. A. 13th A. A. A. A. A. 14th A. A. A. A. 15th A. A. A. A. A. 16 j
A j A. A. A. A. 17th A. A. A. A. C. Comparison
test-
game A. A.

The assessment was made according to the following criteria: A: excellent, B: good, C: poor.

Pressure test example 1

To produce a lithographically applicable carrier plate (B), the composition from Example 3 was applied continuously with a reverse coater and at a speed of 30 m / min onto a degreased surface of a ΊΟ aluminum foil (Japanese industrial standard A-1100) of 500 mm (m / m ) Width and 0.15 mm (m / m) thickness and cured ^{at 230 0 C.}

By applying a solution of a negative type photosensitive resin to the surface of the thus hardened Layering in a manner known per se and drying the same, a presensitized plate (PS plate) was obtained.

After cutting off a piece of this PS plate, a Negative film (negative image bearing film) placed on the photosensitive resin layer of the piece and treated with ultraviolet Light from a 4kW mercury pressure lamp irradiated from a distance of 1 m for 40 seconds. After developing the irradiated PS plate with a developing liquid (Nippaku PS Developer NN-221) and washing with Water, the washed PS plate was dried to obtain a lithographic printing plate.

Using the printing plate thus obtained and a

Printing machine (Heidel KORD) became higher on sheets of paper

Quality printed. More than 50,000 sheets could be printed without difficulty.

Pressure test example 2 ;

A printing test was carried out in the same manner as in Printing Test Example 1, except that the in Example 15 was used in place of the composition of Example 3. The result was, that more than 50,000 sheets could be printed without difficulty.

10 pressure test example 3 ;

A positive-type photosensitive resin solution was applied to the surface to prepare a PS plate the hardened layer of the carrier plate (B), which is in the

-I5 was made in the same way as in Pressure Test Example 1, applied and the coated carrier plate (B) dried. After placing a positive film (a positive Image-bearing film) on the PS plate, this PS plate was exposed to ultraviolet light from a 4 kW mercury pressure lamp irradiated from a distance of 1 m for 50 seconds. For making a lithographic printing plate the exposed PS plate was provided with a positive developer (manufactured by OHKA Ind. Co., Ltd. under the designation PL-101) developed, washed with water and dried

₂₅ net.

using this printing plate was made in the same Way as printed in print test example 1. More than 50,000 sheets could be printed without difficulty.

Pressure test example 4;

Using the support plate (B) obtained in the same manner as in Printing Test Example 2, a Printing plate made and it was made in the same way as

in pressure test example 3, a pressure test was carried out. It it was found that more than 50,000 sheets could be printed without difficulty.

5 pressure test example 5 ;

A printing plate was prepared in the same manner as in Printing Test Example 1 using the compositions of Example 8. As a result, more than 50,000 sheets of paper could be printed without difficulty.

Pressure test example 6 ;

To produce a carrier plate, the composition of Example 19 was applied to the surface of a polyester film with a thickness of 100 μm, the surface of which had previously been blasted by air honing, and the composition thus layered
cured for 1 minute.

layered composition by heating to 2 3 0 ⁰ C

Using this support plate, a printing plate was prepared in the same manner as in Printing Test Example 1 and used for printing. More than 50,000 sheets of paper could be made with this printing plate without difficulty

25 can be printed.

Pressure test example 7 :

Printing was carried out in the same manner as in Printing Test Example 6 except that the composition of Example 22 was applied and the layered composition was cured ^{by heating at 140 ° C. for 10 minutes.} More than 50,000 sheets could be printed without any difficulty.

Pressure test example 8 ;

The composition obtained according to Example 18 was applied to the surface of a previously degreased 25 μm thick aluminum foil which was attached to a 0.2 mm (m / m) thick synthetic paper. To produce a carrier plate, the composition layered in this way was cured ^{by heating to 230 ° C. for 1 minute.}

- | ο Using the carrier plate obtained in this way, a Printing plate prepared in the same manner as in Printing Test Example 1 and used for printing. It could more than 50,000 sheets can be printed without difficulty.

15 pressure test examples 9 and 10:

The carrier plates were layered curing the composition prepared by applying the compositions of Examples 20 and 23 to the surface of a 50 m thick iron foil, whose surface was degreased in advance, and by 1-minute heating at 200 ⁰ C.

Two printing plates were prepared, each of the carrier plates obtained in the same manner as in Pressure test example 1 was used. The printing plates produced were used for printing.

In both cases, more than 50,000 sheets of paper could be printed on without difficulty.

Pressure test example 11;

The composition of Example 21 was applied to the surface to produce a lithographic carrier plate a substrate plate applied by attaching

a 25 µm thick polycarbonate film was made on both surfaces of a degreased 50 µm thick iron foil. The thus layered composition was gehitzt for curing for 3 minutes at 170 ⁰ C.

By using the support plate thus obtained in the same manner as in Printing Test Example 1, a lithographic Printing plate made and used for printing. More than 50,000 sheets of paper could be printed without difficulty

ο be.

Claims (22)

UEXKÜLL S: STCLBERG PATENTANWÄLTE BESELERSTRASSE 4 D-2000 HAMBURG 52 EUROPEAN PATENT ATTORNEYS DR. J.-D. FRHR. by UEXKULL DR. ULRICH GRAF STOLBERG DIPL.-ING. JÜRGEN SUCHANTKE DIPL.-ING. ARNULF HUBER DR. ALLARD from KAMEKE Nippon Foil Mfg. Co., Ltd. 5-13-9 Nishinakajima, Yodogawa-ku, Osaka-shi, Osaka-fu, Japan Prio .: Nov. 5, 1984 JP 233845/84 June 24, 1985 JP 138817/85 22362 / UE / leC / wo November 1985 composition for the formation of a layer of the lithographically applicable carrier plate claims 1. Composition for forming a layer (A) of a lithographically applicable carrier plate (B), characterized by a content
(I) in an aqueous solution
(1) methylol melamines and (2-1) polyvinyl alcohol, zirconium nitrate and a curing catalyst for the methylolmelamines or
(2-2) an epoxy compound and (II) a water-insoluble, powdery inorganic powder dispersed in the aqueous solution Material. 2. Composition according to claim 1, characterized in that the methylol melamines are dimethylol melamine, trimethylol melamine or a mixture thereof. 3. Composition according to claim 1, characterized in that the epoxy compound is one of the water-soluble epoxy compounds having 8 to 50 carbon atoms and two 1,2-epoxy groups (^ C - CC). 4. Composition according to claim 3, characterized in that the epoxy compound is a glycidyl ether of the group consisting of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether and phenol polyethylene glycol. 5. The composition according to claim 1, characterized in that the polyvinyl alcohol is a water-soluble polyvinyl alcohol with a degree of saponification above 85%. 6. The composition according to claim 1, characterized in that the curing catalyst for the methylolmelamines is a salt from the group consisting of ammonium salts, hydrochlorides or sulfamates of an amino alcohol, salts of inorganic and organic acids of an amine and inorganic metal salts. 7. The composition according to claim 6, characterized in that the curing catalyst for the methylol melamine is a compound of the group consisting of ammonium chloride, diammonium hydrogen phosphate, ammonium sulfamate, dim thy 1-aniline hydrochloride, pyridxnhydrochlorid, picolin monochloroacetate, guanidine sulfamate, magnesium chloride, zinc chloride and zinc sulfate. 8. Composition according to claim 1, characterized in that the water-insoluble inorganic powdery material is selected from the group consisting of zinc oxide, aluminum oxide, antimony oxide, calcium oxide, chromium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, lead oxide, bismuth oxide, magnesium oxide, manganese oxide, calcium carbonate , Calcium sulfate, colloidal silica, kaolin, bentonite, clay, aluminum, iron and zinc. 9. Composition according to claim T , characterized in that the amounts of methylolmelamines, zirconium nitrate, water-insoluble inorganic powdery material and curing catalyst in the composition are 50 to 200, 2 to 10, 50 to 200 and 0.5 to 10 parts by weight per 100 parts by weight Polyvinyl alcohol. 10. The composition according to claim 1, characterized in that the amounts of epoxy compound and water-insoluble inorganic powdery material are 25 to 50 and 50 to 200 parts by weight per 100 parts by weight of methylolmelamines, respectively. 11. A method for producing a composition for forming a layer (A) of a lithographically applicable carrier plate (B), characterized by (i) dispersing a water-insoluble inorganic powdery material in an aqueous one Mixture obtained by mixing an aqueous solution of polyvinyl alcohol and zirconium nitrate with an aqueous solution of methylol melamines and a curing catalyst for the methylol melamines or by mixing an aqueous solution of an epoxy compound with an aqueous solution of Receives methylolmelamines, (ii) optionally adding a metal chelating agent Substance, one or more pigments, one or more dyes or a viscosity-increasing one Substance to the aqueous dispersion obtained, (iii) vigorously stirring the resulting aqueous mixture and (iv) removing bubbles from the stirred mixture containing air bubbles. 12. The method according to claim 11, characterized in: that, as methylol melamine, dimethylol melamine, trimethylol melamine or a mixture of these. 13. The method according to claim 11, characterized in that one of the water-soluble epoxy compounds having 8 to 50 carbon atoms and two 1,2-epoxy groups (^ C - CC) is used as the epoxy compound. 14. The method according to claim 11, characterized in that a diglycidyl ether from the group consisting of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether and phenol polyethylene glycol is used as the epoxy compound. 15. The method according to claim 1 1, characterized in that a water-soluble polyvinyl alcohol with a degree of saponification above 85% is used as the polyvinyl alcohol. 16. The method according to claim 11, characterized in that a salt from the group consisting of ammonium salts, hydrochlorides or sulfamates of an amino alcohol, salts of inorganic or organic acids of an amine and inorganic metal salts is used as the curing catalyst for the methylol melamines. 17. The method according to claim 16, characterized in that that a compound of the group consisting of ammonium chloride is used as a curing catalyst for the methylolmelamines, Diammonium hydrogen phosphate, ammonium sulfamate, dimethylaniline hydrochloride, Pyridine hydrochloride, picolin monochloroacetate, Applies guanidine sulfamate, magnesium chloride, zinc chloride and zinc sulfate. 18. The method according to claim 11, characterized in that a material from the group consisting of zinc oxide, aluminum oxide, antimony oxide, calcium oxide, chromium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, lead oxide, bismuth oxide, magnesium oxide, manganese oxide, CaI is used as the water-insoluble inorganic powdery material calcium carbonate, calcium sulfate, colloidal silica, kaolin, bentonite, clay, aluminum, iron and zinc. 19. The method according to claim 11 , characterized in , that one amounts of methylolmelamines, zirconium nitrate, water-insoluble inorganic powdery material and curing catalyst of 50 to 200, 2 to 10, 50 to 200 and 0.5 to 10 parts by weight, respectively 100 parts by weight of polyvinyl alcohol applies. 20. The method according to claim 11, characterized in that the epoxy compound and the water-insoluble inorganic powdery material are used in amounts of 25 to 50 and 50 to 200 parts by weight per 100 parts by weight of methylolmelamines. 21. A lithographically applicable presensitized plate, characterized in that it has been prepared by applying a composition according to claim 1 to the surface of a substrate plate (C), curing the composition coated on the substrate plate and applying a photosensitive resin to the surface of the hardened layer. 22. Presensitized plate according to claim 21, characterized in that the composition according to the method of Example 11 has been prepared.