FR2609189A1 - PROCESS FOR THE PREPARATION OF PHOTOPOLYMERIZABLE PRODUCTS - Google Patents

Abstract

THE INVENTION RELATES TO A PROCESS FOR OBTAINING PHOTOPOLYMERISABLE PRODUCTS, WHICH ARE USED FOR THE RECORDING OF INFORMATION. THESE PHOTOPOLYMERISABLE PRODUCTS ARE A LIGHT-CURING SYSTEM, WHICH CAN BE DEPOSITED ON A SUPPORT IN THE FORM OF AN AQUEOUS SOLUTION, COMPOSED OF: A) A POLYELECTROLYTE OF FORMULA: (CF DRAWING IN BOPI) B) AN EMULSIONED INITIATOR OR A SYSTEM EMULSIFIED INITIATOR AND C) A DISSOLVED CO-INITIATOR. M IS A MONOMER COPOLYMERISABLE WITH AM (CF DRAWING IN BOPI) Y IS O OR NR R, R ARE AN ALKYL GROUP IN CC OR -ZYC-CRCH R IS H OR CH R IS H OR AN ALKYL GROUP IN CC Z IS AN ALKYLENE GROUP IN CC OR HYDROXYALKYLENE N IS A NUMBER OF 1000 TO 80,000 R IS AN ALKYL GROUP IN CC.

Description

The invention relates to a process for preparing products

  photopolymerizable materials suitable for recording information,

  especially for reprography, for imme-

  prizes, plates, printing plates or for the preparation of layers of surfaoes coating exposed to give an image.

  A multitude of methods for the preparation of

  photopolymerizable products, according to which the light-sensitive layer

  is made from organic solvents.

  The intake from organic solvents is due to the fact that

  many binders used in photopolymerization, for example poly-

  acrylates (various acrylate-based copolymers in DE-A-2,757,932, 2,084,080, 2,205,146, US-A-3,961,961), polyamides (DE-A-2,914,619; 447,592, JP-A-56,067,846), polyurethanes (DE-A-2,818,455,2,917,483, 2,405,714), copolymers of AM (maleic anhydride) (DE-A-1,925,551, US-A-3 873 319), formaldehyde-based resins (DE-A-2 936 904,

  EP-A-10 749, many monomers used, for example acrylic esters,

  (DE-A-2,434,912, US-A-4,115,232, 3,551,148), urea acrylates,

  thanne (DE-A-2,358,948, 2,064,079, US-A-4,072,770), epoxyacrylates

  (DE-A-2,841,880, 2,830,143, US-A-3,832,188), acrylamides (US Pat.

  3,081,168, DE-A-2,361,041, DE-A-2,207,209, and many systems ini-

  used, eg benzoin and ketone ether (DE-A-

  1,769,168, 2,232,365), halogenated carbonyl compounds (US Pat.

  4,001,098), benzophenone and kenzophenone derivatives (DE-A-

  1,949,010), anthraquinone (US-A-2,951,758, 4,046,127), mixtures of benzophenone and Michler's ketone (DE-A-2,216,154), redox dye systems (US-A No. 3,092,096), aromatic diazonium salts in combination with donors (US Pat. No. 3,615,452), ketones and coinitiators (DD-A-158,281) and benzophenone / Michler ketone / compound combinations. Onium (DD-WP G 03 C /

  262 604.1) are soluble only in organic medium.

  The choice of solvents used is carried out

  depending on the binder / monomer / initiator system used. They must

  be compatible with all components and form

homogeneous mixtures.

  The following solvents and solvent mixtures are usual: Alcohols, for example methanol, ethanol, propanol, butanol;

  Ketones, for example acetone, methyl ethyl ketone, cyclohexyl

hexanone;

  Ethers, for example dioxane, tetrahydrofuran, diethyl

  ether; Esters, for example ethyl acetate, butyl acetate

and mixtures of these solvents.

  Similarly, for obtaining photopolymer products

  riseable on the basis of the formation of complex polyelec-

  trolyte, which have significant advantages over

  conventional methods, for example the lack of sensiti-

  oxygen (DE-A-2 816 774, DD-WP G 03 C / 261 567.4) and self-testing (DD-WP G 03 C / 261 567.4, DD-WP G 03 C /

  266 887.7) only one model has been proposed or

  for solvents or mixtures of organic solvents. In addition we know a layer

  photosensitive material, which contains as binder polyvinyl alcohol

  only soluble in water. Here is also introduced a water-soluble monomer (tetradecethylene glycol dimethylacrylate), a monomeric unit (acrylate).

  2-hydroxyethyl), soluble only in organic solvents

  picnics. The initiator used is of the same soluble only

  in organic medium (US-A-3,630,746, 3,801,328, 3,877,939).

  The preparation of the photopolymerizable products by coating

  a carrier with organic solvents requires

  however, that protective

  explosions and imposes hard health conditions. The objective of the invention is to obtain a

  photopolymerizable product, which can be developed in half

  This is a watery place, characterized by a good fixation on the support, high edge sharpness and lack of veil and which is suitable for obtaining opaque and transparent images. The object of the invention is to provide a process for obtaining photopolymerizable products using a light-curing system, which may be

  deposited in the form of an aqueous solution on a support.

  This object will be achieved according to the invention by using

  photopolymerizable products by depositing a solution

  Feeding solution of a light-curing system on a support, an aqueous feed solution of a water-curing light-curing system consisting of a) a polyelectrolyte of the general formula t M- CH-CH.,

C = O C = O

Y 0

He ED

R X

  wherein M is a copolymerizable monomer with AM Xe is R2, R3, -H-Z-Y-C-CR 4 = CH

0

  Y is 0 or NR5 R is a C1-C8 alkyl group R2 R3, which may be identical or different, are each a C1-C4 alkyl group or -Z-Y-C-CR = CH2 group

0

  R is H or CH3 R is H or a C1-C4 alkyl group Z is a C1-C6 alkylene group or hydroxyalkylene n is a number of 1000 to 80,000 b) an emulsified initiator or an emulsified initiator system and

c) a dissolved co-initiator.

  For the aqueous feed solution, use is

  according to the invention, preferably a polyelectrolyte of modified maleic acid copolymers, all the

  ethylenically unsaturated compounds which form copoly-

  mothers with maleic acid that can be

  for example, olefins, α-methylstyrene,

  methyl methacrylate and alkylvinyl ethers.

  Modification of maleic acid copolymers

  is carried out respectively by partial hydrolysis or

  and / or reaction with an aliphatic alcohol, preferably

  C1-C8 alcohol, to give a half-ester, or with an aliphatic amine, preferably a C1-C8 amine, by

  example ammonia, to give a hemiamine. The modification

  of the polyelectrolyte can be carried out in a similar way.

different.

  Complementary node X 0 for polyelectronics

  lyte, one or more unsaturated compounds

  ethylenic compounds which can be addition polymerized, which

  take a primary, secondary or tertiary amino group,

  for example N, N-dimethylaminopropylacrylamide, N, N-

  diethylaminoethylacrylamide, N, N-diethylaminopropylacryl-

  amine, N, N-dimethylaminoethyl acrylate, methacrylate

  diethylaminopropyl-ol-2 late, tris (2-acryloyloxy)

  ethyl) amine, N, N-dimethylaminopropylmethacrylamide,

  N, N-diethylaminoethylmethacrylamine and tris (2-methacryl-

  oyloxyéthyl) amine. The aqueous feed solution comprises in

  in addition to an emulsified initiator system, preferably

  Michler's tone as an H donor and benzophenone as

  acceptor of H, the relationship between the donor of H and the acceptor

  H to be in the range of 1: 3 to 1:10.

  The dispersion is preferably carried out by means of

  a boiler for high temperature. The donor of H and the acceptor

  of H will then be dispersed separately or together. A

  additional component of the feed solution a-

  It is a co-initiator, preferably substituted aromatic diazonium salts and bisdiazonium salts, group V onium compounds such as, for example, phosphonium salts, onium compounds of group VI, for example sulphonium salts and selenium salts and onium salts of group VII, for example salts

of iodonium that can be used.

  This aqueous feed solution will be

  on the various natural or synthetic supports, such as

  for example, copper, aluminum "sandblasted" with alumina, a pastil-

  silicon, oriented polyester films, cellulose triacetate sheets, glass or lined papers using various deposition systems, for example the doctor blade,

  hand pourer, centrifugal jet, cylinder sprinkler

  pressure casting or casting by a slit of

casting.

  The layer thicknesses used will be chosen according to the uses. They are nonetheless between

1 and 0.15 m.

  The great advantage of the process according to the invention is that, in order to obtain photopolymerizable products, no provision for protection against explosions is possible.

  necessary and therefore no special requirements

  safety conditions are not necessary.

  The exposure of the layers prepared according to the invention

  This is done by means of the light sources used in the reprographic technique, such as

  Xenon lamps, arc lamps, flashlights

  fear of mercury; however, the sun's light is also

  appropriate for this exhibition.

  The exposure according to the invention can be carried out

  killed not only through the support but also from the face of the photopolymer layer. For protection

  against mechanical deterioration and inhibitory oxygen

  it is possible to apply one or more layers of protection

  on the photopolymer layer. As layers of protection

  products such as those based on polyvinyl alcohol

  and polyvinylpyrrolidone are particularly suitable.

  A special protective layer against oxygen is,

  for the polyelectrolytes used, however not necessary.

  After exposure of the photopolymerizable layers prepared according to the invention, the development is carried out with

  the water. The development time required depends on the time

  the thickness of the layer and the polysalt used.

  It is nevertheless generally understood between 1 s and 60 s.

  The photopolymerizable layers prepared according to

  the invention have excellent sensitivity to light.

  Mière. This means that already after exposure times

  very short time, the mechanical properties of

  to give an image fulfill all the conditions

  a development with a high quality.

Example 1

  A mixture of 510 parts of methyl

  polystyrene-maleic acid hemiester, 371 parts of

  thylaminoethylacrylamide and 37 parts of diphenyl

  in a mixture of 1900 parts of ethanol and 3800 parts of water.

  This solution was introduced by means of a

  dispersion apparatus the solution of the initiating system,

  90 parts of tricresyl phosphate, 37 parts

  of benzophenone, 15 parts of Michler's ketone and 310 parts

methanol.

  The layers were cast on the triacet leaf

  cellulose (Cellite leaf) using a doctor blade

  0.25 mm and then dried. The thickness of the

che was 10 / um.

  The image was exposed through the Cellite sheet with a mercury vapor lamp (HBO

  500) 2 s at a distance of 60 cm. Development is taking place

  kills in the water. We got a very good image in relief.

Example 2

  A mixture of 510 parts of hemies was dissolved

  maleic acid polystyrene ethyl ester, 371 parts diethylaminoethylacrylamide, 25 parts gelatin and 37

  parts of diphenyliodonium chloride in a mixture of

  laid with 1900 parts of ethanol and 3800 parts of water. The initiator system consisting of 37 parts of benzophenone and 15 parts of Michler's ketone, which was dissolved in 90 parts of tricresyl phosphate and 310 parts of methanol, was introduced into this solution by means of a dispersion apparatus. The layers were deposited with spin casting apparatus on a Cellite sheet and then dried. The thickness of the dry layer was 8 μm. Exposed with a mercury vapor lamp (HBO

  500) 3 s at a distance of 60 cm to form the image. Of the-

development is done with water.

Example 3

  A mixture of 500 parts of hemies was

  Butyl ter of poly-o (methylmethyl styrene), 247

  parts of dimethylaminoethyl acrylate, 37 parts of

  fate of diphenyliodonium acid and 25 parts of gelatin in a mixture consisting of 1800 parts ethanol and 3900 parts

  of water. The system was mechanically dispersed in this solution.

  initiator composed of 37 parts of benzophenone,

  parts of Michler's ketone, which was dissolved in 90 parts

  tricresyl phosphate and 310 parts of methanol.

  The layers were deposited on the Cellite sheet with a manual pourer and then dried. The thickness

of the layer was 9 μm.

  The sun was exposed to 15 s.

is done with water.

Example 4

  A mixture of 510 parts of methyl

  maleic acid polystyrene hemiester, 340 parts of dimethylaminopropylacrylamide, 100 parts of gelatin and 75 parts of diphenyliodonium acid sulfate in a mixture

  composed of 1900 parts of ethanol and 3800 parts of water.

  The system was introduced into this solution

  initiator consisting of 75 parts benzophenone and 15 parts

  of Michler's ketone, which was dissolved in 90 parts

  of tricresyl phosphate and 310 parts of methanol

yen of a dispersion apparatus.

  The layers were cast on aluminum sandblasted with a-

  1 lumen by applying a 0.25 mm squeegee and then dried.

  The thickness of the dry layer was 6 μm. Exposed with a mercury vapor lamp (HBO 200) 8 s at a distance of 60 cm to form

1 picture.

  The development is done with water. We get a

good image in relief.

Example 5

  A mixture of 500 parts of polystyrene-maleic acid was dissolved, which was reacted at 50% with butylamine to give a hemibutylamide and 50% with butanol to give a butylhemiester,

  309 parts of diethylaminoethylacrylamide and 40 parts of tetrafluoroboro

  spleen of p-Mfe-benzenediazonium in a mixture of 1900 parts of ethanol

and 3800) parts of water.

  This solution has introduced the system initiator com-

  75 parts of benzophenone and 15 parts of Michler's ketone,

  that was mechanically dissolved in 90 parts of

  and 310 parts of methanol in a dispersion apparatus.

  The layers were poured on a sheet of

  Cellite with centrifugal casting apparatus and

  dried. The thickness of the dry layer was 8 μm.

  Exposed with a mercury vapor lamp

  (HBO 500) 4 s at a distance of 60 cm to form the image.

  Development is done with water.

Example 6

  A mixture of 510 parts of methyl

  polystyrene-maleic acid hemiester, 340 parts of

  methylaminopropylacrylamide and 37 parts of

  phenyliodonium in a mixture consisting of 1900 parts

of ethanol and 3800 parts of water.

  The solution of the initiator system was introduced into this solution by means of a dispersing apparatus.

  90 parts of tricresyl phosphate, 37 parts

  of benzophenone, 15 parts of Michler's ketone and 310

parts of methanol.

  The layers were deposited on the Cellite sheet

  by hand pourer and then dried.

  The thickness of the dry layer was 9 μm.

  Exposed with a mercury vapor lamp (HBO 500) 3 s at a distance of 60 cm to give the image through the Cellite sheet. Development is carried out

in water.

  We got a good image in relief.

Claims (3)

  1. Process for the preparation of photopoly   by depositing a feed solution of a light-curing system on a support, characterized in that an aqueous feed solution of a light-curing system, which can be provided by water, consisting of a) a polyelectrolyte of the general formula & M-CH-CH n \ - n C = O C = O   o R X   wherein M is a copolymerizable monomer with maleic anhydride X e is R2R3 eH-Z-Y-C-CR4 = CH I 2   where Y is O or NR R 1 is C 1 -C 3 alkyl, R, R, which may be identical or different, are each a C 1 -C 4 alkyl group or -ZY-CCR 4 = CH 2 Or R 4 is H or CH 3 R is a C1-C4 alkyl group Z is a C1-C6 alkylene or hydroxyalkylene group n is a number from 1,000 to 80,000.   b) an emulsified initiator or an emulsified initiator system and c) a dissolved co-initiator.   2. Process for the preparation of photopoly   merisables according to claim 1 characterized in that an aqueous feed solution is used consisting of: 11- a) a maleic acid styrene hemiester polyelectrolyte with aminoalkylacryl- or tertiary methacrylamides, b) an emulsified initiator system constituted by an H donor and an H acceptor in the ratio of 1: 3 to 1:10 and   c) a diphenyliodonium salt as initiator.   3. Process for the preparation of photopolymers   compositions according to claim 2, characterized in that an aqueous feed solution is used which contains Michler's ketone as an emulsified initiator system.   as a donor of H and as an acceptor of H benzo benzophenone.