DE2706575A1 - REINFORCED COMPOSITES - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Kocnigsberg ^ r Dipl.-Fhys. R. Holzbauer - Dipl.-Ing. F. Klint-sois-fcn - Dr. F. Zumstein jun.

PATENT LAWYERS

TELEPON: SAMMISL NO. 22 53-41

TELEX r, 2U979 TELEGRAMS: ZUMPAT

POST SCHLCKKONTO: MUNICH 91139 809. Hl 7. 70O10O8O BANK ACCOUNT: BANKIIALJG H AUFHÄUSER KTO. NR 397997.13LZ 70O3O600.

8 MUNICH 2.

BRÄUHAUSSTRASSE 4

■ 270657b

Case 3-10536 / AHL 250+

CIBA-GEIGY AG, CH-4-002 Basel / Switzerland

Reinforced composites

7098-U / 0898

3 27ü6b7b

The present invention provides a method of making reinforced photopolymerizable composites and thermosetting compositions and reinforcing materials, as well as those obtained in this way by this process Composites.

Composite structures are generally produced by using fibrous materials such as paper, glass and carbon fibers, with the solution of a solid thermosetting Resin and a heat-activated hardener for the resin impregnated, the resin itself through evaporation of the Solvent solidifies and, if desired, the resin composition hardens by the action of heat. Composite structure can also be produced from foils of a thermosetting resin composition by applying a foil of the resin composition lays a fibrous reinforcement and applies heat and pressure to it so that the resin mass flows around the fibers, However, it remains curable, and then further heated, if desired, so that the resin mass through the heat-activatable Is hardened harder. Both of these methods have certain disadvantages.

When using a solvent it is not always possible to remove all traces of it before final curing to eliminate. The finished composite may therefore have voids caused by evaporation of this residual solvent contain. The use of solvents can also be used due to their toxicity or flammability, odor also environmental pollution, lead to difficulties.

_ ₂ _ 7 Π υ,. . ι, I 0 8 9 6

If an adhesive film is used, it must first be removed a liquid thermosetting resin and is then extended to the solid state. Through such a Processes add significantly to the cost of the composite. Both procedures also require a substantial one Energy expenditure, either for solvent evaporation or for advancing the resin.

A process has now been found which can be used without the disadvantages of the prior art processes Impregnate reinforcement materials with a liquid, solvent-free resin compound and quickly turn this compound into one can transfer solid, but still heat-hardenable state. In this novel process, one is made of a hot-curable Phenolic resin and a photopolymerizable resin consisting of liquid resin composition after being used for impregnation of the reinforcement material was used, photopolymerized by exposure to actinic radiation, optionally in the presence of a photosensitizer, but not heat-crosslinked, and the resulting prepreg is desired to be obtained cured by heating to form the composite.

The subject matter of the present invention is accordingly a process for the production of preprogs, which is characterized in that one

i) a fair Π'ππι / res reinforcing material with a liquid Masr.eia ^ ri ¹ ;; ·· i ert both a heat-hardenable phenol / aldehyde resin and at least a photopolyir.erisbareno

7 0 'j; W 0 8 9 R - 3 -

Component (except the phenol / aldehyde resin) and, if required, a thermosetting agent for the phenol / aldehyde resin contains, and

ii) the material impregnated with actinic radiation as follows exposed that said mass solidifies by photopolymerization of said photopolymerizable component, while the phenol / aldehyde resin remains essentially in the thermosetting state.

The invention also relates to prepregs produced by this process.

The invention also relates to a method for producing a reinforced composite which is characterized in that a photopolymerized, but still heat-curable according to the invention Hot-cured prepreg, as well as reinforced composites made using this process.

The compositions used to produce the prepregs according to the invention must be less than those used to form the prepregs conditions used be liquid, but are preferably solvent-free.

As the photopolymerizable component used in the compositions of the present invention, any known can be used use chemical type polymerizing under the action of actinic radiation. Such substances are for example by Kosar in "Light-sensitive systems: Chemistry and Applications of Non-Silver Halide Photographic Processes [Photosensitive Systems: Chemistry and

Use of photographic processes without silver halide] ", Wiley, New York, 1965, 473 pp.

As is well known, such components belong to two main classes:

(a) those that are polymerized by a radical chain reaction (light-induced polymerization), as well as

(b) those in which the polymerization occurs through the reaction of an excited monomer molectile with another monomer molecule is effected.

The first type requires only one photopolymerizable group per molecule in order to polymerize long To form chains, while the second type must have at least two photopolymerizable groups per molecule, since they would dimerize on irradiation, but would not polymerize if there was only one such group per molecule template.

Preferred photopolymerizable substances of the first type used according to the invention have one or if they are unconjugated, have more than one ethylene bond. Such substances are, for example, acrylic esters with at least one group of the general formulas I, II or

CH ₂ = C (R) COO- I

CH ₂ = C (R) CONH -LcHCOO- II

CH ₂ = C (R) CONHCH (OH) CH ₂ COO- III

709834/0898 - 5 -

wherein R is a hydrogen, chlorine or bromatora or a Alkyl hydrocarbon group with 1 to 4 carbon atoms, especially a methyl group. Other examples are styrene and crotonic acid.

The photopolymerizable materials of the second type include those having at least two, and preferably three or more, azido, coumarin, stilbene, maleimide, pyridinone, chalcone, propenone or pentadienone groups or in their 3-position by groups which are in conjugation with the ethylene double bond of the acrylic group or ethylenic are aromatically unsaturated, have substituted acrylic acid groups.

Suitable azides are, for example, those with at least two groups of the formula

N ₃ -Ar- IV

wherein Ar is a mono- or binuclear aromatic radical with 6 to 14 carbon atoms, in particular a phenylene or naphthylene group.

Suitable coumarins are, for example, those with at least two groups of the formula

wherein R stands for an oxygen atom, a carbonyloxy group (-COO-). a sulfonyl group or a sulfonyloxy group stands.

7 0 9 c ' Z Ul 0 8 9 6 - 6 -

270657b

Substances containing stilbene groups are, for example, those with at least two groups of the formula

-Dl = CH f ^^ \

L ΊΓ " ^VI

wherein R represents the total containing up to 10 carbon atoms Radical, a five- or six-membered nitrogen-containing heterocyclic ring, which with a benzene or Naphthalene nucleus condenses and via a carbon atom adjacent to a nitrogen atom therein of said heterocyclic Ringes is linked to the specified benzene nucleus, such as a benzimidazolyl or naphthotriazolyl group.

Substances containing maleimide units are for example those with at least two groups of the formula

R ³

f VII

wherein the R ^ each represent an alkyl group having 1 to 4 carbon atoms, a chlorine or bromine atom or a phenyl group, in particular for a methyl group.

Substances containing pyridinone units are, for example, those with at least two groups of the formula

VIII

wherein R is aliphatic or cycloaliphatic

70983 A / 0896 .. 7 _

JT

A radical having 1 to 8 carbon atoms and a is zero or an integer from 1 to 4.

Containing chalcone, propenone and pentadienone groups Compounds are, for example, those with at least two groups of the formula

IX

or

wherein the R each stands for a halogen atom, an alkyl, cycloalkyl, Alkenyl, cycloalkenyl, alkoxy, cycloalkoxy, alkenoxy, cycloalkenoxy, carbalkoxy, carbocycloalkoxy, carbalkenoxy or carbocycloalkenoxy group, such organic groups containing 1 to 9 carbon atoms, or for a nitro group or a carboxyl, sulfonic acid or phosphonic acid group in salt form, a has the meaning given above has, R represents a valence bond or a hydrogen atom, Y is a carbon atom chain that is a grouping in itself the formula

R ⁷
--CH "= C

i!

XI

C «CH - -

¹⁰

XII

OR ¹⁰

a .. ^. U Wf XXII ■ J * Λ. J- X.

7 R

where R and R independently of one another each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group, preferably a mononuclear group

7 R v / ie a phenyl group, or R and R together are one Polymethylene chain with 2 to 4 methylene groups mean R and R each represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl group, preferably a mononuclear group such as a phenyl group, and e and f each represent zero, 1 or 2, provided that they are not both zero, contains, represents and Z represents represents an oxygen or sulfur atom.

Suitable 3-substituted acrylates are those with at least two groups of the general formula

R ¹¹ CH = C (R) COO-XIV

where R is an aliphatic or mononuclear aromatic, araliphatic or heterocyclic group, preferably with up to 12 carbon atoms, in conjugation with the specified Ethylenically or aromatically unsaturated double bond, such as prop-2-enyl, phenyl, 2-furyl, 2- or 3-pyridyl or styryl group and R has the meaning given above.

Specific examples are the sorbic acid diesters of poly (oxyethylene) glycols and poly (oxypropylene)

709034/0896 - 9 -

glycols.

If desired, you can use a mixture of photopolymerizable Use connections.

Used as particularly preferred photopolymerizable components used in the process according to the invention acrylic and methacrylic acid esters, such as 1-acryloxy-2-hydroxy-3-phenoxypropane and in particular diacrylates and dimethacrylates of di- and trihydric alcohols, in particular aliphatic alcohols with 2 to 10 carbon atoms, such as 1,2-bis- (acryloxy) -ethane, 1,3-bis- (acryloxy) -propane, 1,4-bis- (acryloxy) -butane, 1,3-bis (acryloxy) -2,2-diinethy! propane, 1,2-Bi s- (3-acryloxy-2-hydroxypropoxy) -ethane, 1,3-Bi s- (3-acryloxy-2-hydroxypropoxy) -propane, 1,4-bis (3-acryloxy-2-hydroxypropoxy) butane and 1,3-bis (3-acryloxy-2-hydroxypropoxy) -2,2-dimethylpropane and the corresponding methacrylates.

As the phenolic resins in the present invention, there can be used any of a phenol and an aldehyde among acidic and alkaline ones Use prepared resole or novolak. Suitable phenols include phenol itself, Resorcinol, alkyl-substituted phenols such as cresols, xylenols and tertiary-butylphenols as well as aryl-substituted phenols, especially p-phenylphenol. The one condensed with the phenol Aldehyde is preferably formaldehyde, but other aldehydes such as acetaldehyde and furfural can also be used. Novolaks are preferred as phenolic resins, in particular those made from phenol itself and formaldehyde.

7 Ü υ u ό UI 0 8 9 6 - 10 -

2Vübb7b

The molar ratio between the pho-copolymerizable Component and phenol / aldehyde resin in the masses is generally 1:10 to 10: 1, with ratios between 1: 5 and 5: 1 preferred v / earth.

The photopolymerizable component is preferred irradiated therefor in the presence of a photopolymerization catalyst.

Photopolymerization catalysts suitable for use in accordance with the invention are well known and are described, for example, in the book by Kosar cited above. The catalysts fall into two main classes,

(a) those that give an excited state on irradiation, which leads to the formation of free radicals, which then initiate the polymerization of the monomer (photoinitiators), and

(b) those which produce an excited state on irradiation, which in turn transfers its energy to a monomer molectile transmits, so that an excited molecule is created, which then crosslinks with another monomer molecule (photosensitizers).

The first class includes organic peroxides and hydroperoxides, oc-halogen-substituted acetophenones such as 2,2,2-trichloro-4'-tert.butylacetophenone, benzoin and its Alkyl ethers, e.g. the n-butyl ether, benzophenones, O-alkoxycarbonyl derivatives the oximes of benzil or 1-phenylpropane-1,2-dione, such as benzil- (0-ethoxycarbonyl) -a-monoxime and l-phenylpropane-l, 2-dione-2- (0-ethoxycarbonyl) -oxime, benzil-

709034/0896

2706bV5

acetals, e.g. its dimethyl acetal, and also Geraische of phenothiazine dyes (e.g. methylene blue) or quinoxalines (e.g. metal salts of 2- (m- or p-methoxyphenyl) -quinoxaline-6 ¹ - or -7'-sulfonic acids) with electron donors such as sodium benzene sulfinate or another Sulphinic acid or its salt, an arsine, a phosphine or thiourea (photoredox systems), these initiators being used for unsaturated esters, in particular acrylates and methacrylates, and also acrylamides.

The photosensitizers include 5-nitroacenaphthene, 4-nitroaniline, 2,4,7-trinitro-9-fluorenone, 3-methyl-1,3-diaza-1,9-benzanthrone as well as bis- (dialkylamino) -benzophenones, especially Michler's ketone, i.e. bis- (p ~ dimethylamino) benzophenone.

Generally 0.1 to 20%, and preferably 0.5 to 15 % by weight, of photopolymerization catalyst is incorporated, based on the weight of the photopolymerizable component.

The reinforcement can be in the form of woven or unwoven sheets, straight lengths or chopped strands and can consist of natural or synthetic fibers, in particular glass, boron, stainless steel, tungsten, silicon carbide, asbestos, an aromatic polyamide or carbon.

Actinic radiation with a wavelength of 200-600 is preferably used in the photopolymerization process nm. Suitable actinic radiation sources are below

- 12 -

270657b

other charcoal arcs, mercury vapor arcs, fluorescent tubes with fluorescent materials emitting ultraviolet light, argon and xenon glow lamps, tungsten lamps and photographic flood lamps. Underneath are mercury vapor arcs, Sunbeams, fluorescent sunsets and metal halide lamps are particularly suitable for testing. The time required to expose the photopolymerizable component will depend on several factors, including, for example, the individual substance used, the amount of that substance in the reinforcement, the Type of light source and its distance from the impregnated material. The one familiar with photopolymerization methods A person skilled in the art can easily determine the appropriate times, but the product photopolymerized in this way must still be heat-curable be. The irradiation takes place naturally at

a temperature below that at which extensive hot curing would occur.

Phenol / aldehyde novolaks are used together with a substance that releases formaldehyde under the action of heat, like Paraform, but usually hexamethylenetetramine, as a heat curing agent. Resole can be used if desired apply with a latent acid catalyst. The hot curing agent is usually before the impregnation of the Reinforcement dissolved or suspended in the liquid mass. The temperatures required for hot curing and the amounts of formaldehyde releasers or latent acid catalysts can easily be determined by series tests

709S34 / 0896

determine and can readily be determined by a person skilled in the art from those already existing relating to the hot-curing of phenolic resins Knowledge can be derived.

The photopolymerizable, thermosetting compositions, including any thermosetting agent for the phenol / aldehyde resin and any photopolymerization catalyst for the photopolymerizable component, are preferably applied to the reinforcement material in such a way that the prepreg 20 to 80 wt .-% of the mass mentioned and accordingly contains 80 to 20% by weight reinforcement. 30 to 50% by weight of the mass and 70 are particularly preferred up to 50% by weight reinforcement is used.

Products produced according to the invention can be used in

In the form of flat sheets or shaped bodies. If a hollow molded body is required, it is special convenient to impregnate a continuous cable of fibrous reinforcing material and the cable under at the same time Exposure to actinic radiation to wind a bobbin. Such windings still have a certain Degree of flexibility which allows the winder to be removed more easily than one formed in one step the rigid winding would be possible. If necessary the winding can be heated to complete the hardening process.

The following examples illustrate the invention. The temperatures are degrees Celsius and the parts are parts by weight unless otherwise stated. The epoxy content is

- 14 -

by titration against Ο, ΐη-perchloric acid solution in glacial acetic acid determined in the presence of excess tetraethylammonium chloride, v / whether crystal violet is used as an indicator.

All stated interlaminar shear strengths represent the average of three results and were determined by ASTM method D 2344-72. "Resin-forming content" means the percent residue which is left after heating a 1 gram sample of the material for 3 hours remains in a dish of 5 cm diameter in the drying cabinet at atmospheric pressure and 120 °.

EXAMPLE 1

Benzoin n-butyl ether (2 parts) and hexamethylenetetramine are added (4 parts) to a mixture of 2,2-dimethyl-1,3-propanediol bisacrylic acid ester (50 parts) and a solid phenol / formaldehyde novolak resin of molecular weight of 420 in number average and a phenol / formaldehyde molar ratio of 1: 0.72 (50 parts). This liquid mass becomes used to impregnate a glass cloth (rectangular fabric). The impregnated glass cloth is exposed on both sides for 60 seconds with a 500 W medium-pressure mercury vapor lamp at a distance of 15 cm. The mass solidifies as the photopolymerization progresses.

A 6-fold glass cloth laminate is placed on top by placing six 15 cm square pieces of prepreg for 1 hour at 170 ° under a pressure of 2.1 MN / m verpres.yt. This laminated body, consisting of 25.4% resin and 74.6% glass, has an interlaminar shear strength

709Ö.U / 089R - 15 -

speed of 15.5 MN / m. After immersing the Layered body in boiling water is its interlami-

Nare shear strength still 8.6 MN / m.

EXAMPLE 2

First, the photopolymerizable component 1,4-bis (3-methacryloxy-2-hydroxypropoxy) butane is placed in situ here. Methacrylic acid (3137.3 g), triethylamine (21.1 g) and hydroquinone (7.8 g) are stirred at 120 ° and added over 2 1/4 hours with 4,000 g butane-1,4-di-diglycidyl filter (with an epoxide content of 9.12 eq / kg), which contains 6.4 g of hydroquinone. The mixture is then at 120 ° further stirred for 3/4 hour, after which its epoxy content is negligible.

Hexamethylenetetramine (4 parts) and benzoin butyl ether (2 parts) are added to a 3: 1 mixture (100 parts) of the above dimethacrylate and the phenol / formaldehyde novolak resin used in Example 1. As described in Example 1, the liquid mass is used to produce a prepreg, except that the impregnated glass cloth is only irradiated for 5 seconds. A six-layer body is produced as described in Example 1. This laminated body, consisting of 32.996 resin and 67.2% glass,

has an interlaminar shear strength of 19.5 MN / m.

EXAMPLE 3

One coated from poly (p-phenylene terephthalamide) fibers existing tissue with a mass of 70 parts phenol / formaldehyde resol, 30 parts l-acryloxy-2-

709834/0896 - 16 -

hydroxy-3-phenoxypropane (according to British patent specification No. 1 407 813) and 1 part benzil dimethylacetal. The resin former content of the resol is 78tf and the molar ratio Phenol: formaldehyde 1: 1.6. A prepreg thus obtained is exposed to a high pressure metal halide quartz lamp for 30 seconds irradiated. A good laminate is obtained by taking six 15 × 15 cm pieces of this prepreg pressed at 150 under a pressure of 2.1 MM / m, releasing the pressure after every 2 and 4 minutes. to allow volatile substances to escape.

EXAMPLE 4

As described in Example 3, using unidirectional carbon fibers instead of Polyamide fibers and with one-minute irradiation one

ι.

good six-shift corps.

EXAMPLE 5

A polyoxyethylene disorbic acid ester is prepared as follows:

A stirred mixture of 100 g of polyoxyethylene glycol with an average molecular weight of 200, 110 g of triethylamine and 50 ml of toluene is added at room temperature in the course of 30 minutes with 130.5 g of Sorblneiureohlorid. The mixture is stirred for 1 hour at 80 °, cooled to room temperature, then filtered and the reading medium is distilled off at reduced pressure, leaving the usual Dieorbineaure ester behind.

One produces a carbon * toffaeerprepreg, whereby one

70983470898

- 17 -

the fibers with a mass of 30 parts of the disorbic acid ester, 70 parts of the phenol / formaldehyde novolak used in Example 1, 4 parts of hexamethylenetetramine and 1 part of Michler's ketone coated. "The prepreg is double-sided Irradiated for 15 minutes with a 400 W high-pressure metal halide quartz arc lamp and pressed for 1 hour 170 ° under a pressure of 2.1 MN / m a six-layer body generated.

EXAMPLE 6

In the same way as described in Example 5, poly (p-phenylene terephthalamide) fibers are used a six-layer body. Instead of such fibers, one could also use poly (m-phenylene-isophthalamide) fibers insert.

709834/0896

- 18 -ORIGfNAL INSPECTED

Claims (15)

PATENT CLAIM 1. A process for the production of prepregs, characterized in that that he i) a fibrous reinforcing material with a liquid Impregnated mass, which contains both a thermosetting phenol / aldehyde resin and at least one photopolymerizable Component (apart from the phenol / aldehyde resin) and preferably a heat curing agent for the phenol / aldehyde resin and a photopolymerization catalyst for the photopolymerizable Component contains, and ii) the material impregnated with actinic radiation as follows exposed that said mass solidifies by photopolymerization of said photopolymerizable component, while the phenol / aldehyde resin remains essentially in the heat-curable state. 2. The method according to claim 1, characterized in that the molar ratio of the photopolymerizable component to the phenol / aldehyde resin in the mass in the range 1:10 to 10: 1. 3. Method according to claim 1 or 2, characterized in that that the fibrous reinforcement material made of glass, boron, stainless steel, tungsten, silicon carbide, asbestos, aromatic polyamide or carbon. 4. The method according to any one of the preceding claims, characterized in that the phenol / aldehyde resin is a novolak in the presence of formaldehyde under the action of heat separating substance as a heat curing agent for it 709834/0896 - 19 - ORIGINAL INSPECTED 2706b7b begins. 5. The method according to any one of the preceding claims, characterized in that the weight of the photopolymerization catalyst 0.1 to 20% based on the weight of the photopolymerizable component is. 6. The method according to any one of the preceding claims, characterized in that the phenol / aldehyde resin and the photopolymerizable substance together with any Heisshärtungsmittel of the phenol / aldehyde resin and any photopolymerizable component 20 to 80 wt -.% Make the prepreg. 7. The method according to any one of the preceding claims, characterized in that the photopolymerizable Component photopolymerized by radical chain reaction. 8. The method according to any one of claims 1 to 6, characterized characterized in that the photopolymerizable component by reaction of an excited monomer molectile with a photopolymerized another monomer molecule. 9. The method according to claim 7, characterized in that the photopolymerizable component is one or, if they are unconjugated, have more than one ethylene bond and preferably an acrylic ester with at least one Group of formula CH ₂ = C (R) COO- I CH ₂ = C (R) CONH -Λ CHCOO- LJ ₂ 709834/0896 - 20 - 2706b7b C (R) CONHCH (OH) CH COO- wherein R is a hydrogen, chlorine or bromine atom or is an alkyl hydrocarbon group having 1 to 4 carbon atoms, in particular a diacrylate or dimethacrylate represents a di- or trihydric aliphatic alcohol having 2 to 10 carbon atoms. 10. The method according to claim 8, characterized in that the photopolymerizable component is at least two Azido, coumarin, stilbene, maleimide, pyridinone, chalcone, Propenone or pentadienone groups or acrylic acid groups, those in their 3-position by groups that are in conjugation with the ethylene double bond of the acrylic group are ethylenically or aromatically unsaturated, are substituted, having. 11. The method according to claim 10, characterized in that the phoxopolymerizable component is at least two Groups of the formula N ₃ -Ar- wherein Ar is a mono- or binuclear aromatic radical with 6 to 14 carbon atoms, or at least two groups of the formula wherein R represents an oxygen atom, a carbonyloxy group (-C00-), a sulfonyl group or a sulfonyloxy group stands, or at least two groups of the formula 70983W0896 - 21 - , -CH - ^CH - Γ where R stands for the total containing up to 10 carbon atoms Remainder of a five- or six-membered nitrogen-containing heterocyclic ring, which with a benzene or Naphthalene nucleus condenses and via a carbon atom adjacent to a nitrogen atom therein of said heterocyclic Ring is linked to the specified benzene nucleus, in particular a benzimidazolyl or naphthotriazolyl group, or at least two groups of the formula ^R V ^ ^ ^co wherein the R ^ each represent an alkyl group with 1 to A carbon atoms, in particular a methyl group, a chlorine or Bromine atom or a phenyl group, or at least two groups of the formula '■ -Ο- • I where R * stands for an aliphatic or cycloaliphatic A radical having 1 to 8 carbon atoms and a is zero or an integer from 1 to 4, or at least two groups the formula 709834/0896 - 22 - 2VOBb ¹ Zb or 5
wherein the R each for a halogen atom, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, cycloalkoxy, alkenoxy, cycloalkenoxy, carbalkoxy, carbocycloalkoxy, carbalkenoxy or carbocycioalkenoxy group, such organic groups 1 to 9 carbon atoms, or represent a nitro group or a carboxyl, sulfonic acid or phosphonic acid group in salt form, a has the meaning given above, R represents a valence bond or a hydrogen atom, Y represents a carbon atom chain which is a grouping of the formula CH » C C = CH -CH R » O ο E ¹⁰ CH - i- c- ■ Ä- J. < V- Λ VR
where R and R independently of one another represent a hydrogen atom or an alkyl or aryl group or R and R together are a polymethylene chain with 2 to 4 methylene groups 70983 A / 0896 ^ς 2 V Ü bb 7 b Q IQ mean, R and R each for a hydrogen atom or a Are alkyl or aryl, and e and f are each zero, 1 or 2, provided that they are not both zero are, contains, represents and Z represents an oxygen or sulfur atom, or at least two groups of the formula R ¹¹ CH = C (Fc ⁵ ) COO- where R is an aliphatic or mononuclear aromatic, araliphatic or heterocyclic group with up to 12 Carbon atoms which are ethylenically or aromatically unsaturated in conjugation with the specified double bond, preferably a phenyl, 2-puryl, 2- or 3-pyridyl, styryl or prop-2-enyl group and R is the one given above Has meaning, contains. 12. The method according to claim 7 or 9, characterized in that the photopolymerization catalyst for the photopolymerizable component uses one which, upon irradiation, results in an excited state that leads to Formation of free radicals leads, which then initiate the polymerization of the photopoiymerisbaren component. 13. The method according to claim 12, characterized in that the photopolymerization catalyst is an organic Peroxide or hydroperoxide, an oc-halogen-substituted one Acetophenone, benzoin or an alkyl ether thereof, a benzophenone, a benzil acetal, a mixture of a phenothiazine dye or a quinoxaline with an electron donor or an O-alkoxycarbonyl derivative of a benzil or 1-phenyl _ 24 - 709G3 4/0896 * 27Q6b7b propane-1,2-dionoxiras is. 14. The method according to any one of claims 8, 10 and 11, characterized in that the photopolymerization catalyst for the photopolymerizable component uses one which has an excited state upon irradiation which in turn transfers its energy to a monomer molecule transmits, whereby an excited molecule is formed, which then crosslinks with another monomer molecule. 15. The method according to claim 14, characterized in that the photopolymerization catalyst is 5-nitroacenaphthene, 4-nitroaniline, 2,4.7-trinitro-9-fluorenone, 3-methyl-1,3-diaza-1,9-benzanthrone or a bis (dialkylamino) benzophenone 709334/0896 - 25 -