AU603196B2

AU603196B2 - Polymerizable N-containing acrylates and a radiation-polymerizable mixture containing same

Info

Publication number: AU603196B2
Application number: AU13809/88A
Authority: AU
Inventors: Klaus Rode
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1987-03-28
Filing date: 1988-03-28
Publication date: 1990-11-08
Anticipated expiration: 2008-03-28
Also published as: ZA882204B; DE3710279A1; KR880011211A; EP0287818A2; EP0287818A3; BR8801396A; JPS63277653A; EP0287818B1; DE3881263D1; JP2509288B2; KR960016468B1; AU1380988A

Description

-J

I i i 44371 JGS:GS 1987T/12

AUSTRALIA

PATENTS ACT 1952 COMPLETE SPECIFICATION 7

(ORIGINAL)

FOR OFFICE USE Application Number: Lodged: Complete Specification Lodged: Accepted: Published: This document contains the amendments made under Section 49 and is correct for printing.

Priority: Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: HOECHST AKTIENGESELLSCHAFT 6230 Frankfurt/Main 80, Germany Klaus Rode ARTHUR S. CAVE CO.

Patent Trade Mark Attorneys Level Barrack Street SYDNEY N.S.W. 2000

AUSTRALIA

Complete Specification for the invention entitled POLYMERIZABLE\ -:CMPtUNs AND A RADIATION-POLYMERIZABLE MIXTURE CONTAINING SAME.

The following statement is a full description of this invention including the best method of performing it known to me:- 1

ASC

ARTHUR S. CAVE CO.

PATENT AND TRADE MARK ATTORNEYS

SYDNEY

2071M/gs J MES G. SIELY F.I.P.A .1 1 -i m 1 1 POLYMERIZABLE AOMIMOUNDSW AND A RADIATION-POLYMERIZABLE MIXTURE CONTAINING SAME Background Of The Invention 9999 o 9 4 990 9 9 9 9 99 9 9 a 4* 5 The present invention relates to polymerizable compounds having at least twe\acrylate or alkacrylate group in the molecule, and to a raditationpolymerizable, in particular photopolymerizable, mixture containing these compounds.

Photopolymerizable mixtures which contain acrylates and/or methacrylates as polymerizable compounds are known. For the production of photoresist materials, in particular dry photoresist coatings, mixtures are preferred which contain acrylates or methacrylates having urethane groups in the molecule and which can be developed using aqueous-alkaline solutions. Such mixtures are described, for example, in German Offenlegungsschift No. 2,822,190, German Auslegeschrift No. 2,115,373, German Patent No. 2,361,041 and U.S. Patent No.

3,850,770 and No. 3,960,572.

jn'>j -la- 4_ :1 On the other hand, photopolymerizable mixtures are also known which, in order to increase the photosensitivity, contain certain combinations of photoinitiators and activators, for example, carbonyl-group-containing initiators and tertiary amines. Such mixtures with a synergistic action are described, for example, in German Offenlegungsschriften Nos. 2,602,419 and 2,251,048 and U.S. Patent No. 3,759,807. A disadvantage of these mixtures which contain low-molecular-weight amines is that they have a short shelf life since the r amines can easily bleed out, in particular from thin coatings.

In Japanese Patent Application No. 50/129,214, a photopolymerizable mixture is described which contains a tetra(meth)acrylate of a 1 tetrahydroxyalkylalkylenediamine as the polymerizable I compound. The tetrafunctional compound serves as a r crosslinking agent.

I 20 Summary Of The Invention It is therefore an object of the present j invention to provide polymerizable acrylates or i alkacrylates, which are suitable for use in radiation-polymerizable mixtures, in particular in photopolymerizable mixtures, having high radiation- Ssensitivity, without the addition of low-molecular weight volatile or easy diffusing constituents.

In accordance with this invention, there is provided a compound of the general formula I -2-

F

R

1

R

3 R(m-n)Q (-cH 2 -CO)a-CONH(X1-NHCOO)b-X 2

(-OOC-C=H

2 cn

(I)

R

2 in which D1 .I I I I Q denotes -N N- or n ~D 2 So R denotes an alkyl, hydroxyalkyl or aryl group,

R

1 and R 2 each denote a hydrogen atom, an alkyl group or an alkoxyalkyl group,

R

3 denotes a hydrogen atom, a methyl group or an ethyl group, I X 1 denotes a saturated hydrocarbon group having 2 to 12 carbon atoms,

SX

2 denotes a (c+l)-valent saturated hydrocarbon :o group in which up to 5 methylene groups may be replaced by oxygen atoms,

D

1 and D 2 each denote a saturated hydrocarbon group having 1 to 5 carbon atoms, E denotes a saturated hydrocarbon group having 2 to 12 carbon atoms, a cycloaliphatic group which has 5 to 7 ring members and which may contain up to 2 N, o or S atoms as ring members, an arylene group having 6 to 12 carbon atoms, or a heterocyclic aromatic group having 5 or 6 ring members, a denotes 0 or an integer from 1 to 4, b denotes 0 or 1, c denotes an integer from 1 to 3, m denotes 2, 3 or 4, depending on the valency of Q, and n denotes an integer from 1 to m, it being possible for all radicals of the same definition to be identical to or different from one another.

In accordance with this invention, there is furthermore provided a radiation-polymerizable mixture comprising: 10 a) a polymeric binder b) an acrylate or alkacrylate of a polyvalent, urethane group-containing alcohol, and c) a compound or combination of compounds which under the action of actinic radiation is capable of initiating polymerization of compound b).

The radiation-polymerizable mixture according Sto this invention is characterized in that the acrylate or alkacrylate is a compound of the above formula I.

Description Of Preferred Embodiments The present invention is directed to compounds of Formula I and to radiation-polymerizable mixtures and recording materials prepared therefrom. The recording materials comprise a support coated with a radiation-polymerizable layer, comprising a mixture of the above-described composition.

When, in the compound of the general formula I, more than one R radical or more than one radical of the type mentioned in brackets is bound to the central group Q, these radicals may be different from one another.

Compounds in which all substituents of Q are polymerizable radicals, in which m=n, are generally preferred.

\<1 In general, a=0 &\not more than one radical, and preferably a=l.

If R is an alkyl or hydroxyalkyl group, it generally has from 2 to 8, preferably from 2 to 4, carbon atoms. The aryl radical R can generally be mononuclear or dinuclear, preferably mononuclear, and optionally be substituted by alkyl or alkoxy groups having up to 5 carbon atoms or by halogen atoms.

If R 1 and R 2 are alkyl or alkoxyalkyl groups, they can contain from 1 to 5 carbon atoms.

R

3 is preferably a hydrogen atom or a methyl group, in particular a methyl group.

I t X 1 is preferably a straight-chain or branched aliphatic or cycloaliphatic radical preferably having from 4 to 10 carbon atoms.

X

2 preferably has from 2 to 15 carbon atoms, of which up to 5 may be replaced by oxygen atoms. If these are pure carbon chains, those having from 2 to 12, preferably from 2 to 6, carbon atoms are generally employed. X 2 can also be a cycloaliphatic group having from 5 to 10 carbon atoms, in particular a cyclohexyl group.

D

1 and D 2 may be identical or different and, together with the two nitrogen atoms, form a

A

CD

1 a+n saturated heterocyclic ring having from 5 to preferably 6, ring members.

If E is an alkylene group, it preferably has from 2 to 6 carbon atoms, and as an arylene group it is preferably a phenylene group. As cycloaliphatic groups, cyclohexylene groups are preferred, and as aromatic heterocyclic rings, those containing N or S as heteroatoms and having 5 to 6 ring members are preferred.

The value of c is preferably 1.

The polymerizable compounds of the formula I where Q=N,-and n=m and which contain two urethane groups in each radical are prepared by reacting acrylates or alkylacrylates which contain free hydroxyl groups in a known fashion with the same number of moles of diisocyanates, and reacting the excess isocyanate group with hydroxyalkylamines.

When a=0, a urea group is produced.

The hydroxyalkylamines used as starting materials are known or are prepared by analogy with known compounds. They include, for example, compounds obtained by an addition reaction of ethylene oxide or higher alkylene oxides and ammonia or amines, such as triethanolamine, N-alkyl-N,Ndi(hydroxyalkyl)-amines, diethanolamine, tris-(2hydroxypropyl)amine or tris-(2-hydroxybutyl) amine.

The diisocyanates used as starting materials are known or are prepared by analogy with known compounds. They include, for example, ethylene diisocyanate, propylene diisocyanate, butylene-1,3diisocyanate, hexamethylene diisocyanate, 2,2,4trimethylhexamethylene diisocyanate, 2,4-dimethyl-6ethyl-octamethylene diisocyanate, 1,4-cyclohexylene -6diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4diisocyanato-methylcyclohexane and 1,1,3-trimethyl-3- The hydroxyl group-containing esters used are, in particular, hydroxyethyl methacrylate and hydroxypropyl methacrylate or and furthermore the corresponding acrylates, because they are the simplest representatives of this group.

However, the following compounds can also be used with advantage: 2-hydroxybutyl methacrylate, 4hydroxybutyl methacrylate, 2-hydroxycyclohexyl or t methacrylate and other hydroxyalkyl methacrylates having up to 12, preferably up to 6, carbon atoms in t the alkyl radical, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate t and other polyethylene glycol monomethacrylates having up to 5 oxyethylene units, trimethylolethane S^ dimethacrylate, trimethylolpropane dimethacrylate, Spentaerythritol trimethacrylate and the reaction 20 products of these branched polyvalent esters with up S« to 4 moles of alkylene oxide, in particular ethylene Soxide, known from DE-B 1,267,547, and the I corresponding acrylates.

t The preferred polymerizable compounds of the 25 formula I, where n=3 and b=o, are prepared by reacting the above described hydroxyalkylamines with isocyanate-group containing acrylates or Salkylacrylates.

The isocyanate group-containing ester employed is, in particular, isocyanatoethyl (meth)acrylate, because this is the simplest representative of this group. However, the following compounds can also be used with advantage: 3-isocyanatopropyl -7- 1 3 i--i I-"-Iw"iuw .rmethacrylate, 4-isocyanatobutyl methacrylate, isocyanatoisohexyl methacrylate and other isocyanatoalkyl (meth)acrylates having up to 12, preferably up to 6, carbon atoms in the alkyl radical.

The preferred polymerizable compounds of the formula I where Q= n=4 and b=l or b=O, S: are prepared analogously to the polymerizable compounds where Q=N. The tetrahydroxyalkyli ''alkylenediamines employed as starting materials are known or can be prepared analogously to known compounds.

i Examples of them include compounds obtained by addition reactions between ethylene oxide or higher alkylene oxides and diamino compounds, such as I ethylene diamine and other alkylene diamines having up to 12, preferably up to 6, carbon atoms in their M alkylene groups, p-phenylenediamine, benzidine, diamino pyridines, diamino pyrimidines and diamino purines.

The polymerizable compounds of the formula I where

D

1 Q=-N N- and b=l or b=0

SD

2 are prepared analogously to the above-described polymerizable compounds. The N-hydroxyalkyl heterocyclic compounds used as starting materials are known or can be prepared analogously to known compounds. Examples include reaction products of ethylene oxide with piperazine, 1,4diazocycloheptane, and 1,10-diaza4,7,13,16tetraoxacyclooctadecane. Piperazine is preferably employed, because it is the simplest representative of this group of compounds.

The reaction of isocyanates with the OH-groupcontaining amines and alkylacrylates is expediently carried out in an inert solvent such as toluene, pyridine or methyl ethyl ketone. In order to n' O° thermally stabilize the products, which have a great tendency towards polymerization, quinones, preferably 0* benzoquinone, are added in concentrations of about 0.01 2 by weight.

The compounds of this invention where Q=S are prepared analogously to the general procedures given above, starting from the appropriate bis-hydroxyalkyl o* sulfide.

SAn essential advantage of the compounds according to this invention resides in the fact that I they and in particular those where m=n result in photopolymerizable mixtures which are distinguished by excellent photosensitivity.

It may also be advantageous to add conventional polymerizable compounds, containing two I or more polymerizable acrylate or methacrylate groups, to the compounds of this invention. Care has to be taken that the above-described advantages achieved due to using the novel polymerizable compounds are not curtailed too significantly by the known compounds.

Examples of known compounds are acrylates and methacrylates of dihydric or polyhydric alcohols, -9- ~Lq, I such as ethylene glycol diacrylate, polyethylene glycol dimethacrylate, acrylates and methacrylates of trimethylolethane, trimethylolpropane, pentaerythritol and dipentaerythritol and of polyhydric alicyclic alcohols. The products of the reaction of diisocyanates with partial esters of polyhydric alcohols can also be employed with advantage. Such monomers are described in German Offenlegungsschriften Nos. 2,064,079, 2,361,041 and 2,822,190.

The proportion of monomers in the mixture is generally from about 10 to 80, preferably from about to 60 by weight.

I Binders which can be employed include a large number of soluble organic polymers. Examples which may be mentioned are: polyamides, polyvinyl esters, polyvinyl acetals, polyvinyl ethers, epoxy resins, polyacrylates, polymethacrylates, polyesters, alkyd resins, polyacrylamide, polyvinyl alcohol, 20 polyethylene oxide, polydimethylacrylamide, u-0 polyvinylpyrrolidone, polyvinylmethylformamide, polyvinylmethylacetamide and copolymers of the monomers which form the homopolymers listed.

Further suitable binders are natural substances or converted natural substances, for 1 example gelatin and cellulose ethers.

Binders which are insoluble in water but soluble, or at least swellable, in aqueous-alkaline solutions are used with particular advantage since layers containing such binders can be developed using the preferred aqueous-alkaline developers. Such binders can contain, for example, the following i -4 -7 groups: -COOH, -PO 3

H

2 -So 3 H; -S02NH-, -S0 2

-NH-SO

2 and -S0 2

-NH-CO-.

Examples of these which may be mentioned are: maleic resins, polymers made from (methacryloyloxy)-ethyl N-(p-tolylsulfonyl)carbamate, and copolymers of these and similar monomers with other monomers, and also vinyl acetate/crotonic acid and styrene/maleic anhydride copolymers. Alkyl methacrylate/methacrylic acid copolymers and copolymers made from methacrylic acid, higher alkyl methacrylates and methyl methacrylate and/or styrene, acrylonitrile and the like, as described in German Offenlegungsschriften No.

2,064,080 and 2,363,806, are preferred.

The amount of binder is generally from about to 90, preferably from about 30 to 80 by weight, of the components of the coating.

Depending on the planned use and depending on Sthe desired properties, the photopolymerizable mixtures can contain a wide variety of substances as additives. Examples are: inhibitors for preventing thermal polymerization of the monomers, hydrogen donors, substances modifying the sensitometric properties of the mixtures, dyes, colored and colorless pigments, plasticizers, such as polyglycols or esters of p-bydroxybenzoic acid.

These components are expediently selected so that they absorb as little as possible in the actinic radiation region which is important for the initiation process.

In the context of this description, actinic radiation should be understood as any radiation whose energy corresponds at least to that of short-wave -11-

I

,1

I

visible light. Visible light and long-wave UV radiation, but also short-wave UV radiation, laser radiation, electron radiation and X-ray radiation are suitable.

A large number of substances can be employed as photoinitiators in the mixture according to this invention. Examples include compounds derived from the basic structures of benzophenones, acetophenones, benzoins, benziles, benzilmonoketals, fluorenone, thioxanthone, polynuclear quinones, acridines and quinozalines; also suitable are trichloromethyl-s- ,l triazines, 2-halogenomethyl-5-vinyl-l,3,4-oxadiazole derivatives, halogenoxazoles substituted with trichloromethyl groups or carbonylmethylene heterocyclic compounds containing trihalogenomethyl groups, such as are described in German Offenlegungsschrift No. 3,333,450.

The initiators are usually added in amounts of 0.01 to 10 by weight, preferably of 0.05 to 4 by weight, each time related to the non-volatile constituents of the mixture.

If imaging is performed by means of electron beams, it is also possible to employ photoinitiators whose absorption ranges are in the short-wave region of the electromagnetic spectrum and which hence show little sensitivity to daylight, in addition to the Sknown photoinitiators which are sensitive to visible and nearUV light. This presents the advantage that the recording materials can be handled without having to exclude the access of light and that these materials are imparted a longer shelf life. Examples of this type of starters include tribromomethylphenylsulfone, 2, 4, 6, 6'- -12- *I hexabromodiphenylamine, petabromoethane, 2, 3, 4, tetrachloroaniline, pentearythritol tetrabromide, chloroterphenyl resins and chlorinated paraffins.

t Aliphatic polyethers are mainly employed as hydrogen donors. If the binder used possesses labile hydrogen atoms, it is also possible for the binder to assume this function or, alternatively, the novel monomers according to this invention, may act as the only hydrogen donors.

The photopolymerizable mixture can be used for a very wide variety of applications, for example for the production of paints which are hardened by light, as dental fillings or tooth replacement material and, in particular, as photosensitive recording material in the reproduction field.

The detailed description of the invention is limited to this latter area of application, but the invention is not limited thereto. Possible applications in this area which may be mentioned are: recording layers for photomechanical production of printing forms for letterpress printing, planographic printing, rotogravure printing, screen printing, of relief copies, for example the production of braille texts, of individual copies, tanned images, pigmented images, etc.. In addition, the mixtures can be used for photomechanical production of etch resists, for example for the production of nameplates, of copied circuits and for chemical milling. The mixtures according to the invention have particular importance as copying layers for the photomechanical production of planographic printing plates and for the photoresist technique.

-13- 1 -I The commercial utilization of the mixture for the applications mentioned can take place in the form of a liquid solution or dispersion, for example as a photoresist solution which is applied by the consumer himself to an individual support, for example for chemical milling, for the production of copied circuits, of screen-printing stencils and the like.

The mixture can also be present as a solid, photosensitive layer on a suitable support in the form of a storable, pre-coated, photo-sensitive *copying material, for example, for the production of printing plates. It is likewise suitable for the t I production of dry resist materials.

I It is generally favorable to keep the mixture away from the influence of at-mospheric .xygen during the photopolymerization. When the mixture is used in the form of thin copying layers, it is advisable to 'apply a suitable protective film which is virtually impermeable to oxygen. This can be self-supporting and removed before development of the copying layer.

For this purpose, polyester films, for example, are suitable. The protective film can also comprise a material which dissolves in the developer liquid or can at least be removed during development from the non-hardened areas. Materials which are suitable for this purpose are, for example, waxes, polyvinyl alcohol, polyphosphates, sugars, etc..

Suitable layer supports for copying materials produced using the mixture according to the invention are, for example, aluminum, steel, zinc, copper and plastic films, for example made from polyethylene terephthalate or cellulose acetate, and also screenprinting supports, such as Perlon gauze., In many -14cases, it is favorable to subject the support surface to pre-treatment (chemical or mechanical), the aim of which is to set the adhesion of the layer correctly, to improve the lithographic properties of the support surface or to reduce the reflectivity of the support in the actinic range of the copying layer (antihalation).

The production of the light-sensitive materials using the mixture according to the invention takes place in a known fashion. Thus, this I mixture can be taken up in a solvent, and the solution or dispersion can be applied to the intended support by pouring, spraying, dipping, roll application, etc. and subsequently dried. Thick layers of 250 Am and more) are advantageously produced by extrusion or press molding as a selfj supporting film, the latter then being laminated, if idesired, onto the support. In the case of dry resists, solutions of the mixture are applied to transparent supports and dried. The photosensitive [layers thickness between about 10 and 100 Am are then likewise laminated onto the desired substrate together with the temporary support.

SThe further processing of the materials is carried out in a known fashion. For better crosslinking of the layers, post-heating after exposure can take place. For development, they are treated with a suitable developer solution, for example, with organic solvents, but preferablr with a slightly alkaline aqueous solution, the unrexposed parts of the layer being removed and the exposed areas of the copying layer remaining on the support.

1 Illustrative embodiments of the invention are given below. Firstly, the preparation of a number of new polymerizable compounds is described. The compounds are employed as polymerizable compounds in the examples below in recording materials according to the invention. In the examples, parts by weight S(pbw) and parts by volume (pbv) are in the ratio g to ccm. Percentage and weight ratios are taken to mean weight units, unless otherwise stated.

1. General procedure for the preparation of compounds of general formula I where b=0 (compounds 1 to 5 and 16 to 21 in Table I) The hydroxyalkyl group-containing amino compound and the isocyanatoalkyl (meth)acrylate are refluxed in the desired molar ratio in ten times the amount of the suitable solvent (toluene, butanone or pyridine) with 0.01 by weight of dibutyltin I dilaurate and 0.01 by weight of benzoquinone until the isocyanate band (2275-2250 cm- 1 can no longer be detected in the IR spectrum (generally after 5 to 8 hours). The solvent Sis subsequently removed by distillation in vacuo at 50* C. The unsaturated compound remains in virtually quantitative yield as a viscous residue.

I

-16-

H

I

2. General procedure for the preparation of compounds of the general formula I where b=l (compounds 6 to 15 in Table I).

Hydroxyalkyl (meth)acrylate and diisocyanate are refluxed for 8 hours in the molar ratio 1:1 in ten times the amount of solvent (toluene, butanone or pyridine) with 0.01 by weight of dibutyltindilaurate and 0.01 by weight of benzoquinone, and the desired number of moles of hydroalkylamine is subsequently added and the mixture refluxed further until the isocyanate band has disappeared in the IR spectrum (generally after 5 to 8 hours). The solvent is subsequently removed by distillaion in vacuo at 50'C. The unsaturated compound remains in virtually quantitative yield as a viscous residue.

The unsaturated compounds 1 to 21 prepared in this way are compiled in Table I.

-17- 3 Table I Ca =ounds of the general formula I, with R2H; R 3 i 3 lCor.o Qj R R RI aI X 1 Ibi X 2 ImlnIN IN I No. f_ 1 0 C2H433 9. 8.81 T5I H I1 9 1 2 IC2H4OH 1 3I2110- 9.51 -3 1 L s 221. 1 11.9 4 j-N-CE 2 -4H 2 C- 13I J 10 1 4 4 9. 8.81 I 7 I I I I I I 1 71 t HI1I 11 8.7{1 Ii 8 l-N-'1123'T- I 4j3j1 4II I4I4I 8.1 8.31 1 II I-CH2C L II 1 1C2H4 1414 I1 C3S6 2 2 I1 -NC~z-NI H II IC3HE1441 1 1 12 I 1 I I 3 I 1 I 1 112 I H 1 I1IC3 33I I -I _13 1 C6H12C2H 422 -18- Table I ccnt'd ri 2,2, 4-trinethylhexarrethylene piperidin-1, 4-.diyJ.

R

3

H

-19- Example 1 2 IElectrochemically roughened and anodized aluminum with an oxide layer of 3 g/m which had been pretreated with an aqueous solution of polyvinylphosphonic acid was used as the layer support for printing plates. The support was coated with a solution of the following composition: 5.85 pbw of a 33.4 strength solution, in methylethyl ketone, of a methyl methacrylate/ methacrylic acid copolymer having an acid number of 110 and an average molecular weight of 35,000, pbw of one of compounds 1 to 14, 1.0 pbw of trimethylolethanetriacrylate, 0.035 pbw of 9-phenylacridine, and 0.02 pbw of the azo dyestuff obtained from 2,4-dinitro-6-chlorobenzene diazonium salt and acetylamino-N-cyanoethyl- N-hydroxyethylaniline, in 26 pbw propylene glycol monomethyl ether.

Application took place by spin-coating such that a dry weight of 2.8 to 3 g/m 2 was obtained. The plate was subsequently dried for 2 minutes at 100° C in a circulating air drying cabinet. The plate was then coated with a 15% strength aqueous solution of polyvinyl alcohol (12% of residual acetyl groups, K value After drying, a protective layer having a weight of 4 to 5 g/m 2 was obtained. The printing :fi 0:_i -d i f i' i" i i i i r:1C3S; ~i;L~ plate obtained was exposed for 30 seconds, using a kW metal halide lamp arranged at a distance of 110 cm under a 13 step exposure wedge which contained density increments of 0.15. The plate was subsequently developed in a developer of the following composition: 120 pbw of sodium metasilicate *9H 2 0, 2.13 pbw of strontium chloride, 1.2 pbw of non-ionogenic wetting agent (coconut .0 fatty alcohol polyoxyethylene ether containing about 8 oxyethylene units) and 0.12 pbw of an antifoam agent, in 4000 pbw of demineralized water.

The plate was inked with an oily printing ink.

The following fully crosslinked wedge steps were obtained: i

F

p ritr r isrr i r i r

E

i r Compound No. Wedge Steps Compound No. Wedge Steps 1 4 8 4 2 6 9 4 3 1 10 3 4 4 11 4 4 12 3 6 4 13 4 S 7 3 14 4 -21r- 1 i ir IC

I

I:

A

I ii Example 2 A solution of the following composition was spin-coated onto the layer support specified in Example 1 under the same conditions as in Example 1: 5.85 pbw of the copolymer solution of Example 1, 2.00 pbw of a monomer, 0.035 pbw of 9-phenylacridine, and 0.02 pbw of the azo dyestuff of Example 1, in 26.00 pbw of propylene glycol monomethyl ether.

After application of a protective layer of polyvinyl alcohol, the plates were exposed and further processed in the same way as in Example 1. The following number of fully crosslinked wedge steps was obtained: t. r, Compound No. wedge Steps 1 6 2 7 4 2 2 13 14 16 7 -22- SWhen an acrylate, namely compound No. 22, was employed in lieu of the polymerizable compounds mentioned above, which all are methacrylates, and the other conditions remained unchanged, the layer obtained was less thoroughly hardened.

Example 3 Under the same conditions as specified in Example 1, the support material of Example 1 was spin-coated with a solution of the following composition: 6.1 pbw of 22.3 strength solution, in butunone, of a terpolymer of styrene, n-hexylmethacrylate, and methacrylic acid (10:60:30) having an acid number of 190, 1.4 pbw of compound 1, 0.049 pbw of 9-phenylacridine, 0.007 pbw of an azo dyestuff obtained from 2diazo-6-nitrobenzthiazole and Ncyanoethyl-N-ethyl-3-methylaniline and 0.120 pbw of 2-mercaptobenzimidazole, in 46.0 pbw of propylene glycol monomethyl ether.

The coated plate was dried in a circulating air drying cabinet at 100°C for 2 minutes and provided with a protective layer according to Example 1. The plate was exposed for 40 seconds through a 13-step exposure wedge, on which a silver film of -23uniform optical density (density 1.5) and uniform absorption over the effective spectral range had additionally been mounted. The exposed plate was subjected to a post-heating treatment in the circulating air drying cabinet, at 100C for 1 minute, was then developed as described in Example 1 and evaluated. Four solid wedge steps were obtained.

Example 4 i A 125 apm thick polyethylene terephthalate film was coated by casting with a layer of the following composition, such that a dry layer thickness of mm was obtained: 90.0 pbw of styrene/isoprene/styrene triple block copolymer having a content of 7.5 of polystyrene at each end; molecular weight 100,000, 10.0 pbw of compound 1, pbw of benziledimethylketal and 0.3 pbw of di-tert.-butylcresol, in 100.0 pbw of toluene.

f The rear surface of the plate was exposed i without an original for 50 minutes, and the front Ssurface of the plate was exposed through an original I for 80 minutes, using a flat-bed exposure apparatus equipped with UVA fluorescent lamps. Then development was performed with a mixture comprising 4 pbv of perchloroethylene and 1 pbv of n-butanol. A flexible printing form with a crisp, 1 mm deep relief pattern was obtained.

-24-

~I

Example The layer support material described in Example 1 was spin-coated with a solution ca: the following composition, such that a dry layer weight of 3 g/m 2 was obtained: 5.85 pbw of the copolymer solution of Example 1, pbw of compound 1, 10 0.035 pbw of 9-phenylacridine, t 0.02 pbw of the azo dyestuff of Example 1,and 0.035 pbw of 4-dimethylamino-4'methoxydibenzalacetone, in 26.0 pbw of propylene glycol monomethyl 15 ether.

The plate was dried, coated with a protective coating as described in Example 1 and exposed for seconds. Two solid steps were obtained on the exposure test wedge after development in accordance with Example 1.

Example 6 This Example was performed to compare the monomer compound No. 1 and trimethylolethanetriacrylate: Solution A 2.8 pbw of the copolymer solution of Example 3, i-ii 1.4 pbw 0.05 pbw 22.0 pbw of compound 1 and of 1,1-dimethoxy-l-phenylacetone, in of propylene glycol monomethyl ether.

Solution B 2.8 pbw 1.4 pbw 0.05 pbw 22.0 pbw of the copolymer solution of Example 3, of trimethylolethanetriacrylate, and of 1,1-dimethoxy-l-phenylacetone,, in of propylene glycol monomethyl ether.

Employing the same support material and conditions as in Example 1, the -wo solutions were spin-coated onto their supports and provided with protective layers,, Exposure, development and evaluation were also performed in accordance with Example 1. After an exposure time of 40 seconds, the printing plates were heat treated at 100°C in the circulating air drying cabinet for 1 minute. The number of solid wedge steps was 8 for solution A and for solution B.

-26- Example 7 A coating solution was prepared from 18.7 pbw of the terpolymer solution of Example 3, 9.3 pbw of compound 1, 0.163 pbw of 9-phenylacridine, and 0.033 pbw of Methyl Violet 42,535), in 36.7 pbw of propylene glycol monomethyl ether, 10 and spin-coated onto a biaxially oriented, 35 pm thick polyethylene terephthalate film, such that a S* dry layer weight of 5 g/m 2 resulted. The layer was post-heated at 100*C in a circulating air drying Scabinet for 3 minutes. At a temperature of 115°C and 15 an advance speed of 1.5 m/s, it was then laminated onto a cleaned support comprised of an insulating material provided with a 35 pm thick copper coating.

The layer was exposed for 30 seconds using a S, kW metal halide lamp (distance 140 cm) as described in Example 1, under a step wedge, and developed for seconds in a spray processor after removing the film, using 0.8 strength soda solution. Five fully crosslinked wedge steps were obtained. The J crosslinked layer was resistant to the iron(III)- Scc 25 chloride solution which is customary in printed circuit board technology. The etch resistance was good.

-27-

I

C

Example 8 In this Example, the monomer compound 1 was compared to a monomer containing urethane groups, which had been obtained by reacting 2,4,4-trimethylhexamethylene diisocyanate with hydroxyethyl methacrylate, in a molar ratio of 1:2.

Solution A 6.27 pbw of the terpolymer solution of Example 3, 10 1.4 pbw of compound 1, 0.058 pbw of 9-phenylacridine, 0.04 pbw of 2,4-bis-trichloromethyl-6-(4styrylphenyl-s-triazine, 0.0043 pbw of the azo dyestuff of Example 3, and 0.0085 pbw of the azo dyestuff of Example 1, in 30.0 pbw of propylene glycol monomethyl ether.

Solution B 6.27 pbw of the terpolymer solution of Example 3, 2.7 pbw of a 51.5 strength solution, in butanone, of the reaction product of 2,4,4-trimethylhexamethylene diisocyanate and hydroxyethyl methacrylate 0.058 pbw of 9-phenylacridine, -28- 0.04 pbw of 2,4-bis-trichloromethyl-6-(4styryl-phenyl)-s-triazine, 0.0043 pbw of the azo dyestuff of Example 3, and 0.0085 pbw of the azo dyestuff of Example 1, in 30.0 pbw of propylene glycol monomethyl ether.

Under identical conditions, the two solutions were spin-coated to the support material described in Example 1, and protective layers were applied in accordance with Example 1. The plates were exposed for 40 seconds according to Example 1, except that a grey filter having an optical density of d 1.57 and a uniform absorption over the whole spectral range was additionally mounted on top of the exposure wedge.

The exposed plate was post-heated at 100°C in a circulating air drying cabinet for 1 minute and then developed and evaluated in accordance with Example 1.

The number of solid wedge steps was 6 for solution A and 4 for solution B.

Example 9 In this solution, the monomer compound 1 (solution A of Example 8) was compared to another nitrogen-containing monomer, namely tetrakis-(2-hydroxy-3methacryloyloxy-propyl)ethylene-diamine according to Japanese Patent Publication No. 50/129,214.

-29rr i A coating solution B comprised of 6.27 pbw of terpolymer solution of Example 3, 1.4 pbw of tetrakis-(2-hydroxy-3methacryloyloxypropyl)-ethylenediamine, 0.058 pbw of 9-phenylacridine, 0.04 pbw of the triazine specified in Example 8, 0.0043 pbw of the azo dyestuff of Example 3, and 0.0085 pbw of the azo dyestuff of Example 1, in 30.0 pbw of propylene glycol monomethyl ether.

was spin-coated onto the support material described in Example 1 under the same conditions as coating solution A of Example 8 and provided with a protective coating according to Example 1. Exposure, post-heating and development were performed as described in Example 8.

No fully crosslinked wedge step was obtained on sample B after an exposure time of 40 seconds.

Sample A gave the same result as in Example 8.

Claims

1. A compound of the formula I R 1 R 3 R(m-n)Q((-CH 2 -CO)a-CONH(X' NHCOO)b-X 2 (-OOC-C=CH 2 )n (I) R 2 in which 10 D Q denotes -N N- or D 2 R denotes an alkyl, hydroxyalkyl or aryl group, R 1 and R 2 each denote a hydrogen atom, an alkyl group or an alkoxyalkyl group, R 3 denotes a hydrogen atom, a methyl group or an ethyl group, X1 denotes a saturated hydrocarbon group having 2 to 12 carbon atoms, X 2 denotes a (c+l)-valent saturated hydrocarbon group in which up to 5 methylene groups may be replaced by oxygen atoms, D 1 and D 2 each denote a saturated hydrocarbon group having 1 to 5 carbon atoms, E denotes a saturated hydrocarbon group having 2 to 12 carbon atoms, a cycloaliphatic group which has 5 to 7 ring members and which contains up to 2 N, O or S atoms as ring members, an arylene group having 6 to 12 -31- carbon atoms, or a heterocyclic aromatic group having 5 or 6 ring members, a denotes 0 or an integer from 1 to 4, b denotes 0 or 1, c denotes an integer from 1 to 3, m denotes 2, 3 or 4, depending on the valency of Q, and n denotes an integer from 1 to m, it being possible for all radicals of the same definition to be identical to or different from one o another. o 0 o 2. A compound as claimed in claim 1, wherein n=m. r t•

3. A compound as claimed in claim 1, wherein E is a saturated alkylene group having 2 to 4 carbon atoms.

4. A compound as claimed in claim 1, wherein R 3 =CH3 A compound as claimed in claim 1, wherein a+b=l or 2.

6. A radiation-polymerizable mixture comprising: a) a polymeric binder, b) an acrylate or alkacrylate of a polyvalent, urethane-group- containing alcohol, and -32- Ii c) a compound or combination of compounds which under the action of actinic radiation is capable of initiating polymerization of compound b), wherein said acrylate or alkacrylate is a compound of formula I as claimed in claim 1.

7. A radiation-polymerizable mixture as claimed in claim 6, wherein the binder is insoluble in water and soluble in an aqueous-alkaline solution.

8. A radiation-polymerizable mixture as 0 r claimed in claim 6, comprising about 10 to 80% by O* weight of acrylate or alkacrylate, about 20 to 90% by Sweight of polymeric binder and about 0.01 to 10% by 5 weight of radiation-activatable polymerization initiator, in each case said amounts being in reference to non-volatile constituents of the S°t mixture.

9. A radiation-polymerizable recording to t, material comprising a layer support and a radiation- polymerizable layer, wherein the radiation- polymerizable layer comprises a mixture as claimed in claim 6. A eempeud as claimed in claim 6, consisting essentially of the recited components.

11. A eemp~eud as claimed in claim 6, comprising an amount of acrylate or alkacrylate of polyvalent, urethane-group-containing alcohol and A AL\ -33- polymerization initiator sufficient to render exposed areas inso~luble in developer soiltion.

12. A G4pwa .1*4as claimed in claim 6, comprising an amount of polymeric binder sufficient to produce a uniform film. 1.3. Any nevel cmo4s~44-ee~ro any novel mixture or material or E Qgip rrt hereof set forth herein, thonmixture, material or DATED this 25th day of March, 1988. 4 0 a HOECHST AKTIENGESELLSCHAFT By Its Patent Attorneys, ARTHUR S. CAVE CO. 4 4 0 4-34-