DE2448821A1 - METHOD OF APPLYING A COPY LAYER - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT

KALLE branch of Hoechst AG K 2343

Wiesbaden-Biebrich October 9, 1974

WLK-Dr.N.-ur

Method for applying a copy layer

The invention relates to a method for applying a photopolymerizable copying layer to a Layer support made of copper or a copper alloy. The application can either be done by spreading a solution of the copy layer components and drying the Layer or by dry transfer of a prefabricated, located on a temporary flexible carrier Copy layer done.

It is known to use light-sensitive layers, in particular Layers of photoresist on wet or dry Paths to a permanent metal substrate, in particular made of copper, to apply the layer to expose and develop imagewise and the exposed areas of the carrier by removal or application of metal to modify. The procedure is mainly used

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especially for the production of printed or copied circuits, but also for photomechanical production of gravure or multi-metal printing plates, which through image-wise etching of supports containing copper can be produced.

A major problem in the processing of photoresist layers, especially photopolymerizable ones Layers on copper carriers consist in the often inadequate adhesion of the layer to the carrier. That makes is especially noticeable when the layer is a photoresist with very fine isolated layer parts has been processed, and then serves as an etching or electroplating reserve. This easily results in fine layer parts infiltrated by the treatment solutions and possibly even separated from the carrier.

One has to remedy this defect in various ways suggested using adhesion-improving additives. For example, U.S. Patent 3,622,334 a dry transferable photopolymerizable layer described, which improves the adhesion to metal carriers containing certain N-heterocycles.

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In U.S. Patent 3,645,772, a method to improve the adhesion of a photoresist layer on copper carriers, in which the carrier is coated with a thin intermediate layer before the layer is applied an organic nitrogen compound that too May contain mercapto groups is coated.

In the German Offen! Zungsschrift 2 028 773 Mercapto compounds as adhesion promoters between photocurable Copy layers and copper carriers described. The adhesion promoters can be in the copy layer or as Interlayer present. As a bonding agent especially heterocycles with mercapto groups »z. B. mercaptobenzothiazole, but also mercaptoacetic acid-2-naphthylamide, described. The latter connection is the only representative of its class on page 6 of the DT-OS called, no further details are given about their effect and application.

The laid-open specification only describes the application of layers from a solution, in particular of photo-curable diazo layers. It has now been shown that Adhesion problems especially with the dry method Layer transfer occur because of such applied

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Layers apparently do not achieve the same level of adhesion to the support as layers that come from solution have been applied. It has also been shown that in particular photopolymerizable layers after the exposure have adhesion problems because they are in the polymerized, hardened state are always more brittle than in the unexposed state. The stronger brittleness can have the consequence that the parts of the picture pass through more easily Etching or electroplating solutions are infiltrated and break out if necessary. On the other hand, the dry-transfer photoresist layer that too as a dry resist layer is called, in the unexposed state it should not be too soft, otherwise it will appear especially in greater layer thicknesses, when storing one shows disturbing cold flow.

The previously known adhesion promoters are both as Layer components as well as in the form of intermediate layers their effect is not yet sufficient to ensure that photopolymerizable layers on copper substrates are so secure anchor that the photoresist produced from it is sufficiently resistant to aggressive etching and electroplating baths is.

The object of the invention was to find new adhesion promoters for to propose the stated purpose in their Effect surpass the previously known.

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The invention is based on a method for applying a photopolymerizable copying layer, which as essential components a polymeric binder, a polymerizable compound that is non-volatile below 100 ° C and has at least one vinyl or vinylidene group and contains a photopolymerization initiator, to a Layer carrier made of copper or a copper alloy to which an aromatic amide of a mercaptoalkanoic acid is added as an adhesion promoter of the copying layer or as Intermediate layer between the copying layer and the substrate is applied.

The method according to the invention is characterized in that

that an amide of the general formula is used as the adhesion promoter

[HS- (CH _{2) n} -C0-NH

used where

m 1 or 2

η 1 or 2

R, H, halogen, an alkyl R ₂ H, halogen, an alkyl

or alkoxy group and or alkoxy group

mean.

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According to the invention is also a photopolymerizable Layer transfer material made from a flexible carrier, a thermoplastic photopolymerizable one Copy layer and optionally a removable cover sheet on the side facing away from the layer support Proposed copy layer, which is characterized is that the photopolymerizable layer has an adhesion promoter of the general formula

[HS- (CHp) _n -CO-NH

l'x \

where m, n, R, and R _? have the meaning given above, distributed uniformly in the layer or as a coating layer on the surface facing away from the support.

As substituents R, and R ^ come halogen atoms, d. H. Fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, are possible. As alkyl and alkoxy groups those with 1-4 carbon atoms are preferred.

The new adhesion promoters show good effect both at Layers that are applied to the copper carrier from liquid solution, as well as those that are through

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dry transmission can be laminated with copper. Her Effect comes in comparison to the well-known adhesion promoters particularly advantageous in the latter process, since the adhesion problems are greater per se

The adhesion promoters can, as already mentioned, both the photopolymerizable copying layer are incorporated as well as in the form of a separate layer between the copper carrier and the copy layer. which The option chosen depends to a large extent on the expediency in the individual case. The application in the Layer saves one work step, but the effect of the same amount per surface unit is greater if it is concentrated at the boundary layer. So you will use the application in the case of relatively expensive adhesion promoters prefer as a separate layer. This can easily be done after the usual pre-cleaning of the copper surface carry out. It is also possible to use the adhesion promoter layer during the production of the dry resist on the surface the photopolymerizable layer, e.g. B. by coating the cover film normally used and lamination of the coated side with the photopolymerizable layer, to open up.

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If the copying layer is applied to the copper carrier from a solution, one proceeds in the same way as it is described in DT-OS 2 028 773, pages 4-5.

When the copy layer is applied to the the carrier to be modified is applied, the procedure is as follows: as described in U.S. Patents 3,622,334 and 3,645,772. These are used as layer transfer materials Laminates are used, which consist of a dimensionally stable carrier film, the dry resist layer and preferably consist of a cover film, as described in US Pat. No. 3,469,982 or DT-OS 2,123,702 are described.

As a carrier to be coated and modified Plates or foils made of copper or copper-containing alloys, e.g. B. made of brass, tombac, bronze, aluminum bronze, German silver or Monel metal 1 is used. The plate or foil can be on a base of a other material, e.g. B. on an aluminum, steel or plastic film or on an insulating plate, z. B. from a synthetic resin molding compound are located. By imagewise modification of the carrier, in particular by

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Etching or electroplating, obtained products are used z. B. for the production of letterpress, gravure or planographic printing plates, for the production of printed circuits, of integrated circuits and for molding.

The photopolymerizable ones used in the process of the invention Layers essentially consist of a high molecular weight binder, polymerizable unsaturated compounds and photoinitiators.

Suitable polymerizable compounds are known and z. In U.S. Patents 2,760,863 and 3,060,023 described. Acrylic and methacrylic acid esters, such as diglycerol diacrylate, guaiacol glycerol ether diacrylate, are preferred, Neopentylglycol diacrylate, 2,2-dimethyl-oil-butanol- (3) -diacrytate and acrylates or methacrylates of hydroxyl-containing polyesters of the desmophent type. In general, connections preferred that contain two or more polymerizable groups. Acrylic and in particular methacrylic acid esters which contain urethane groups. Such monomers are described in German Offenlegungsschriften 2,064,079 and 2,361,041.

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The photopolymer layer also contains at least a photoinitiator. Suitable initiators are z. B. Hydrazones, five-membered nitrogenous Heterocycles, mercapto compounds, pyrylium or thiopyrylium salts, polynuclear quinones, synergistic mixtures of different ketones, dye / Redox systems and certain acridine, phenazine and quinoxaline compounds.

As binders, for. B. polyamides, polyvinyl esters, Polyacrylic, polymethacrylic acid esters, polyvinyl acetals and unsaturated polyesters are suitable.

It is preferred to use binders which are soluble or at least swellable in aqueous alkaline solutions, since layers with such binders can be developed with the preferred aqueous alkaline developers. Such binders can, for. B, contain the following groups: -COOH, -PO ₃ H ₂ , -SO ₃ H, -SO ₂ NH ₂ , -SO ₂ -NH-CO- and the like. Examples include: maleinate resins, polymers of N- (p-Tolylsulfonyl) carbamic acid (ß-methacryloyloxy-ethyl) ester and copolymers of these and similar monomers with other monomers, styrene-maleic anhydride copolymers and methyl methacrylate-methacrylic acid copolymers. Preferably, however

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Copolymers of methacrylic acid, alkyl methacrylates and methyl methacrylate and / or styrene, acrylonitrile and others. as described in OT-OSes 2 064 080 and 2 363 806 are used.

Dyes, pigments, Polymerization inhibitors, color formers and hydrogen donors can be added.

If the adhesion promoter as part of the copy layer are used, they are generally used in amounts of 0.05 to 5 wt .-%, based on non-volatile layer components, added. The preferred range is between about 0.1 and 2% by weight, in particular between 0.4 and 1.5 wt%.

If the adhesion promoter as a separate layer on the copper carrier or on the surface of the copy layer are applied, they are generally used as 0.1 to 5% solutions in organic solvents or in mixtures of organic solvents with Water applied and dried. It is essential that so much adhesion promoter is deposited that a homogeneous, coherent layer is formed.

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The preferred concentration range is between about 0.15 and 2% by weight. As a solvent z. B. lower alkenols and ketones proven.

The inventive method is carried out by the copper-containing support in the usual way cleaned, degreased and, if necessary, mechanically or is roughened by etching. Then, according to one embodiment, the adhesion promoter is in the form of a diluted solution applied and dried. Thereupon the photopolymerizable layer is either made of one Solution or applied by dry lamination under pressure and heating. During further processing, the layer is exposed imagewise in a known manner, and the unexposed layer areas are with a Developer, preferably an aqueous-alkaline solution, the optionally small amounts of organic solvents may contain, extracted. Around the exposed areas of the copper carrier, possibly from layer residues or others Getting rid of impurities is often done with one more Oxidizing agents, e.g. B. an aqueous solution of ammonium peroxydisulfate, after-treated. Then the copper gets in usually etched, or it becomes currentless or galvanic

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metal is deposited at the exposed areas. The cured photoresist layer is then known in the art Way with organic solvents and / or aqueous alkalis removed.

According to another embodiment of the method the adhesion promoter is applied together with the copying layer. It can either be uniformly applied in the coating solution or in the prefabricated dry resist layer be distributed or be present as a separate layer on the surface of the dry resist layer. Further processing takes place in the same way as described above.

The adhesion promoters used according to the invention cause excellent adhesion between the hardened photopolymer layer and the copper substrate. The liability exceeds the one that achieved with the well-known adhesion promoters becomes, considerably. It is so good that it can be etched and galvanized even in strongly acidic baths, without parts of the reserve being infiltrated or separated at the interface. This advantage is particularly evident when using strongly acidic galvanic gold baths and when using very energetic conditions, z. B. a current density twice as high as usual.

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Surprisingly, however, after the etching or Electroplating the reserve with the usual solvents can be removed more easily and quickly than one comparable reserve without using the new one Adhesion promoter has been produced.

The aromatic mercaptoalkanoic acid amides used as adhesion promoters are partly new and partly in the literature described. The new compounds are obtained analogously to the preparation of the known compounds.

The preparation is carried out in such a way that the -2-mercaptoacetic acid or the 3-mercapto-propionic acid with the equivalent Amount of the corresponding aniline mixed and heated under nitrogen for several hours at temperatures of about 130-170 C, until the water formed is driven off. The reaction mixture is dissolved in a suitable solvent and the anilide precipitated by stirring into water.

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The following table shows examples of suitable adhesion promoters with melting points.

T a b e 1 1 e

Compound name melting point,

No. ° ^C

1 2-mercapto-acetic acid ani1ide 110

2 3-mercapto-propionic acid anilides 84-85

3 2-mercapto-acetic acid-2,4-108-110

dichlorani1 id

4- 2-mercapto-acetic acid-3,4-106-108

dimethylani1i d

5 2-mercapto-acetic acid-2- 84-85

methoxy-5. -chlorani 1 i d

6 3-mercapto-propionic acid-2,4-104-106

dichloroanilide

7th 3 - Mercapto-propionic acid 4- 66-67

f1uorani1i d

8 3-mercapto-propionic acid-3- ^ ₁ 10

methylanilide

9 3-mercapto-propionic acid-4- 75-76

methoxyani1i d

10 N, N ¹ -Bis- (3-mercapto-propionyl) - 107-108

1,3-phenylenediamine

11 N, N'-bis (3-mercapto-propionyl) - 278 (dec.)

1,4-phenylenediamine

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The following examples illustrate preferred embodiments of the method and material according to the invention. This includes parts by weight (pbv) and parts by volume (pbv) in the ratio of g to ecm. Unless otherwise stated, percentages are percentages by weight. the Fraction by weight of the monomer units in the polymers are the amounts used in the polymerization.

Examples 1-11
A solution from

5.6 Gt. of the conversion product

from 1 mole of 2,2,4-trimethyl-hexamethylene

di i soeyanat

and 2 moles of 2-hydroxyethyl methacrylate, 6.5 Gt. of a terpolymer made of styrene, n-hexyl methacrylate and methacrylic acid (10:60:30) with an acid number of approx. 182, 0.2 Gt. 9-phenyl-acridine,

0.015 Gt. 4,4'-bis-dimethylamino-benzophenone, 0.15 Gt. Triethylene glycol dimethacrylate and 0.025 Gt. of a blue azo dye obtained by Coupling of 2,4-dinitro-6-chloro-benzene diazonium salt with 2-methoxy-5-acetylamino-N-cyanoethyl-N-hydroxyethyl-aniline, in 28 Gt. Butanone-2

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is spun onto a 25 .mu.m thick polyethylene terephthalate film, so that a 25 .mu.m (30 g / m ² ) thick layer is obtained. It is then dried for 2 minutes at 100 ° C. in a drying cabinet.

In order to protect the layer obtained from contamination by dust and damage, it is covered with a 20-25 µm thick cover film, which adheres less strongly to the layer than the polyester carrier film, is covered. It can thus be stored for a longer period of time.

The copper surface of a 35 µm thick copper foil laminated phenolic laminate board is mechanical cleaned with pumice flour or with a brushing machine and after intensive rinsing with water with oil-free air blow dry.

Samples of the cleaned plate are immersed in an adhesion promoter bath for about 30 seconds, each containing 1 g of the compounds 1-11 in 99 Gt. Contains dissolved ethanol.

After immersion, the plates are dried with a hair dryer and then in a drying cabinet at 100 ° C. for 5 minutes stored.

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In the case of liquid adhesion promoters, e.g. B. Compound no. 8, a wafer-thin, oily film that is not rinsed off with water can be. In the case of compounds which are crystalline at room temperature, forms after immersion and drying A tightly adhering gray to white, fine-grained coating on the Cu surface, which cannot be rinsed off with water either.

The dry resist is applied to the Cu plates pretreated in this way - after the cover film has been peeled off - with the aid of a Laminators, e.g. B. with the laminator type 25 from Dynachem Corp., Santa Fe Springs, USA, with the highest pressure and aminated at a temperature of 115 - 125 ° C at a speed of 0.8 m / minute.

All 11 samples of the laminated to the copper surface Resists are then passed through the carrier film under a negative template with a xenon lamp from the company Klimsch & Co., model Bikop, 8 KW, lamp distance 80 cm, exposed for 17 seconds.

After the carrier film has been peeled off, the hardened layer areas are washed out with 0.4% soda solution. The development time averages 90 seconds.

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The developed plate is then sequentially with the covered the following solutions:

a) Immerse in 15% aqueous ammonium persulfate solution until a uniform Cu surface is achieved, ie no more veils can be observed. The times are given in the table.
Rinse with water for 30 seconds.

b) "30 seconds immersion in 10% sulfuric acid, Rinse with water for 30 seconds.

The cleaned exposed parts of the copper surface are galvanized as follows:

c) Fine-grain copper plastic bath, Schlötter, temp. 20 - 25 C,

pH <l; 30 minutes at 2 A / dm, based on the area to be copper-plated,
30 seconds rinse with water,

d) "Norma" nickel bath, Schlötter, temperature 50-55 ° C., pH 3.5-4.5; 10 minutes at 4 A / dm ² , 30 seconds rinsing with water,

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e) "Autronex-N" gold bath, Blasberg company, temperature 20-25 ° C., pH 3.5-4.0; 15 minutes at 0.6 A / dm ² , rinsing with water for 30 seconds, then drying.

In all galvanic baths it is also possible to work with twice the current density.

For removing the hardened resist area (stripping) the plate can be dipped one after the other in 5% sodium hydroxide solution and methylene chloride.

A sample not treated with adhesion promoter cannot can be stripped as quickly as the one with adhesion promoter pretreated sample.

The decoated samples are then placed in a Etching machine or in a rocking bath at approx. 42 to 55 ° C Etched with an iron-111-chloride solution of 42 Be, with Rinsed with water and blown dry with compressed air. Included the copper surfaces originally covered with resist are etched away.

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Tabel

Example connection etching time with adhesion No. No. 15 % (NH ₄ J ₂ S ₂ Og,

Seconds

1 1 160 2 2 55 3 3 55 4th 4th 160 5 5 95 6th 6th 60 7th 7th 130 8th 8th 90 9 9 160 10 10 125 11 11 60

++ = good adhesion +++ = very good adhesion

Examples 12-22

The coating solution described in Example 1 for Production of the photopolymerizable layer will be 0.15 g ^ 1.2% each (based on solids) of one of the

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Compounds 1-11 added, the acid amide in a part of the solvent used can be dissolved can.

The photopolymer layers are on polyester films in the manner described in Example 1 applied.

The copper plates are pretreated as in Example 1, however, no adhesion promoter layer is applied. That Lamination, exposure and development are carried out as described in Example 1. In the gold bath can just as in Example 1, single and double current densities can be used without impairing the gold bath resistance becomes, which is the case without the use of an adhesion promoter.

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The table shows how the mercapto fatty acid anilides the adhesion at the copper / resist interface improve in acid electroplating baths.

Tabel

Example connection Etching time in adhesion No. No. 15% (NH ₄ ) ^ ₂ O ₈

Seconds

12th 1 13th 2 14th 3 15th 4th 16 5 17th 6th 18th 7th 19th 8th 20th 9 21 10 22nd 11

45 +

45 ++

45 ++

45 +++

30 ++

45 +++

60 +

50 ++

60 +++

50 ++

60 +++

+ - ' satisfactory adhesion + + good adhesion + + + = very good adhesion

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Example 23:
A solution from

5.6 Gt. of the conversion product

from 1 mole of 2, 2, 4-trimethyl-hexamethylene

diisocyanate

and 2 moles of 2-hydroxyethyl methacrylate, 10.0 Gt. a terpolymer made of styrene, n-butyl

methacrylate and methacrylic acid (11.3: 68.7: 20) with an acid number of approx. 125, 0.05 by weight. 9-phenyl-acridine,
0.15 Gt. Triethylene glycol dimethacrylate, 0.025 pbw. the blue indicated in Examples 1 to 11

Azo dye and
0.31 Gt. 3-mercapto-propionic acid ani1 id (compound no.2)

in
30.0 Gt. Butanone-2

is prepared, the acid amide being expedient beforehand is dissolved in part of the butanone.

The solution is down to a thick polyester film so 25.um

2 spun to obtain a 38 µm (45 g / m) thick layer

will. This is followed by 3 minutes at 100 ° C. in a drying cabinet post-dried.

The procedure is continued as described in Examples 12 to 22, but due to the thicker layer 40 to 45 seconds

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announce long exposure. The layer will take about 2 minutes with a solution of

30 Gt. Na ₂ SiO ₃ . 9 H ₂ O and

0.53 Gt. SrCl ₂ . 8 H ₂ O in
970 Vt. water

developed.

The adhesion of the resist provided with adhesion promoter is extraordinary good. It can be simple in all electroplating baths and double current densities are driven.

Example 24:

A copper-phenoplast laminate cleaned with pumice powder ■ plate becomes oil-free after intensive rinsing with water Air blown dry.

Then this plate is put into a pretreatment bath

1 Gt. S-mercapto-propionic acid-Z ^ -dichloro-ani 1 id

(Compound no. 6) and
99 Gt. Ethanol

Immersed for 30 seconds; the pretreatment solution is allowed to drain off and dry it with a hair dryer. This plate is then placed in a drying cabinet at 100 ° C. for 5 minutes stored.

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A dry resist layer is aminated on the Cu surface pretreated in this way at about 115-12O ⁰ C by means of the laminator 1 used in Examples 1 to 11.

The dry resist layer is produced by a Solution of

a) 5.6 Gt. a mixed polymer

175 Gt. 2-ethyl-hexyl methacrylate, 30 Gt. Acrylonitrile, 20 pbw Ethyl methacrylate and 95 Gt. Methacrylic acid,

5.6 Gt. a monomer obtained by reacting 1 mole of 2,2,4-trimethyl-hexamethylene diisocyanate with 2 moles of hydroxyethyl methacrylate, 0.15% by weight. Triethylene glycol dimethyl acrylate, 0.2 pbw. 9-phenyl-acridine,
0.015 Gt. Michler's ketone,
0.04 Gt. of a blue azo dye accordingly

Example 1 in

20 Gt. Ethylene glycol monoethyl ether and 12.5 Gt. Methyl ethyl ketone

is spun onto a 25 µm thick polyester film.

After drying for 2 minutes at IQO ⁰ C, a layer weight becomes

2
of 30 g / m.

The laminated layer is exposed for 20 seconds and made with a solution

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1000 Gt. Water,

15.0 parts by weight of Na ₂ SiO ₃ . 9 H ₂ O,

3 Gt. Polygl-ykol 6000,

0.6 Gt. Levulinic acid and

0.3 Gt. Sr (OH) ₂ . 8 H ₂ O

Wiped for 1 to 2 minutes. Then it is rinsed off with water.

The electroplating is carried out as described in Examples 1 to 11.

The application of the described adhesion promoter causes; greater certainty in the gold bath resistance.

The hardened image areas are then removed with acetone and the exposed Cu tracks are ^{etched in an etching machine with ferric chloride solution at 42 °} C., rinsed with water and blown dry with compressed air.

Example 25:
A solution

5.6 Gt. of the conversion product

from 1 mole of hexamethylene diisocyanate and 2 moles of hydroxypropyl methacrylate,

6.5 Gt. of a terpolymer made of styrene, n-hexyl methacrylate and methacrylic acid (10:60:30) with an acid number of approx. 185,

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2U8821

0.2 Gt. 9-phenyl-acridine,

0.15 Gt. Triethylene glycol dimethacrylate,

0.015 Gt. 4,4'-bisdimethylamino-benzophenone,

0.024 Gt. that given in Examples 1-11

blue azo dye,

0.15 Gt. 3-mercapto-propionic anilide and

30 Gt. Butanone-2

is spun onto a 25 .mu.m thick polyester film

2 changes that a 25 µm = 30 g / m thick layer is obtained will. It is then dried in a drying cabinet ^{at 100 ° C. for 2 minutes.}

Proceed as described in Examples 1 to 11. In the gold bath there can be single and double current densities be driven without the gold bath resistance is impaired. The stripping of the hardened layer areas with acetone or 5% sodium hydroxide solution and methylene chloride is made easier by the addition of adhesion promoter.

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Claims (5)

244882 Claims lA method for applying a photopolymerizable copying layer, which contains as essential components a polymeric binder, a polymerizable, below 100 ⁰ C non-volatile compound with at least one terminal vinyl or vinylidene group and a photopolymerization initiator, on a support made of copper or a copper alloy, in which an aromatic amide of a mercaptoalkanoic acid is added as an adhesion promoter to the copying layer or applied as an intermediate layer between the copying layer and the substrate, characterized in that an amide of the general formula is used R ₁ [H "S- (CH ₉ ) _n -CO-NH-H | 1
■ - 2 'η Uc ⁰¹ JJ R ₂ used where
m 1 or 2,
η 1 or 2, R _{1 is} H, halogen, an alkyl or alkoxy group and Rp is H, halogen, an alkyl or alkoxy group mean. 2. The method according to claim 1, characterized in that a copying layer is applied which contains a polymeric binder which is in aqueous-alkaline solutions is soluble or swellable. 609817/0600 - 29 - 3. The method according to claim 1, characterized in that the copying layer is used as a dry prefabricated layer applies to the substrate. 4. The method according to claim 2, characterized in that you can get the adhesion promoter as a separate layer either applied to the surface of the substrate or to the surface of the copy layer to be laminated thereon. 5. Photopolymerizable layer transfer material for Implementation of the method according to claim 3, consisting of a flexible layer support, a thermoplastic one photopolymerizable copier layer and optionally a peelable cover sheet on the side of the copy layer facing away from the layer support, characterized in that that the photopolymerizable layer one Adhesion promoter of the general formula R. QTs- (CH ₂ ) _n -CO-NH wori η m 1 or 2, η 1 or 2, R, H, halogen, an alkyl or alkoxy group and R ₂ H, halogen, an alkyl or alkoxy group mean evenly distributed in the layer or as holds. Remove the layer on the surface facing away from the carrier 609817/0 600 - 30 -