DE2909993A1 - UV curing unsaturated polyester compsns. - contg. acyl phosphine oxide cpds. as UV sensitisers - Google Patents

Abstract

Light curing unsatd. polyester resin compsns. are made comprising (a) an unsatd. polyester resin, (b) a copolymerisable monomer (c) an inhibitor and (d) a UV sensitizer of formula R1R2-PO-CO-R3 (I) in which R1 and R2 (same or different) are 1-6C alkyl, cyclohexyl, cyclopentyl, aryl, halogen, alkyl- or alkoxy substd. aryl, or S- or N- contg. 5- or 6-membered heterocyclic gp.; or R2 may also be 1-6C alkoxy, aryloxy or arylalkoxy; or R1 and R2 together may form a ring; R3 is a 2-18C alkyl, 3-10C cycloaliphatic gp., phenyl, naphthyl, S-, O- or N-contg. 5- or 6-membered heterocyclic gp., which may opt. carry further substituents, or a gp. -X-CO-POR1R2, in which X is phenylene or a 2-6C (cyclo)aliphatic divalent gp. R1, R2 and R3 may be olefinically unsatd. The compsn. may als contain (d) paraffins, thermally decomposing initiators, fillers, reinforcing agents, lubricants, inert solvents, low shrink additives, etc. The acylphosphineoxide sensitizers give rapid curing of the compsn. on exposure to UV with less discolouration (yellowing) than with prior art UV sensitizers. The compsns. can be used for moulding, impregnation, coating etc.

Description

non-hardenable molding, impregnating and coating compositions

The invention relates to light-curable molding, impregnating and coating compositions based on unsaturated polyester resins, urethane-modified unsaturated Polyester resins and unsaturated vinyl ester resins that act as acylphosphine oxide compounds as UV sensitizers of the formula R1 R2PO-CO-R3 (I), in which R3 represents a cycloalkyl, aryl, Naphthyl, an S, N or O containing five or six membered heterocyclic The remainder is at least in the two ortho positions to the carbonyl group Substituents A and B bonded, where A and B are identical or different and an alkyl, cycloalkyl, aryl, alkoxy, thioalkyl, carbalkoxy, cyano group or halogen atom.

For the photopolymerization of unsaturated polyester resins (UP resins) numerous compounds are described as sensitizers. Of them have O-alkylxanthogenic acid esters, which are activated by a double bond in the ß-position to the sulfur atom, or aromatic disulfides (DE-AS 12 33 594) has no technical importance. -With However, acyloins, acyloin esters or acyloin ethers are used as UV sensitizers a relatively fast curing of UP resins possible (DE-AS 22 59 161), but are the molding materials after hardening by high-energy L. radiation (High pressure mercury vapor lamp) yellowish. ' This disadvantageous yellowing, which decreases when the molding materials are stored in the dark, when stored during the day or Artificial light but increases again - makes itself in the coating of lighter woods or noticeable disturbing in the production of light and corrugated sheets. This is presumably also the reason why e.g. the production of corrugated sheets through UV curing, such as it was described in US Pat. No. 2,750,320, has not yet been able to establish itself.

The yellowing of molding materials made from UP resins containing benzoin ether were prepared, according to DE-OS 2 104 972 by compounds of the trivalent Phosphorus can be improved, but not suppressed enough to do the above to develop the mentioned applications for UV curing. The use of benzil ketals, which leads to storable, very reactive UV-curable UP resins, brings with it a cheaper molding material color no improvement.

DE-AS 22 59 161 describes a process iur production of moldings, Impregnations and coatings made from UV-curable compounds that contain a combination of sensitizers from naphthalenesulfonyl chloride and compounds of divalent tin. The hardening products are characterized by a reduced yellowing after the Curing under high pressure mercury vapor lamps.

In the German patent application P 28 30 928.6 are light-curable Molding, impregnating and coating compositions are also described as UV sensitizers Acylphosphine oxide - contain compounds of the formula R1R2PO-CO-R3, where R3 is a Alkyl radical with 2 to 18 carbon atoms, a cycloaliphatic radical with 3 to id carbon atoms, an alkyl, alkoxy thioalkoxy substituted phenyl 'or Naphthyl radical and an S- or N-containing five- or six-membered heterocyclic Rest means. However, those radicals for R3 that are at least have bound substituents in the two ortho positions to the carbonyl group. Molding, impregnating and coating compounds according to P 28 30 928.6 are characterized by a high Reactivity when irradiated with longer-wave UV light, which in most Cases that of UV-curable molding compounds based on naphthalenesulfonyl chloride and tin-II - compounds, advantageous over molding compounds with a The content of acyloin derivatives or benzil ketals as sensitizers are essential lower tendency to yellowing of the hardened molding materials and faster curing thick-walled, glass fiber-containing molding compounds.

The object of the present invention was to provide light-curable form, impregnation and to develop coating compositions that use the known processes for the production of Moldings, impregnations and coatings by UV irradiation of UP resin compounds, in particular UP resin compositions according to patent application P 28 30 928.6, in two respects improve: 1. The W-hardening activity of the molding, impregnating and drawing masses should are significantly increased with a comparable color of the moldings obtained.

2. The shelf life of the sensitized molding, impregnating and coating compounds should be decisively improved so that one-component systems can be produced which have a constant hardening activity over the entire storage time.

This object is surprisingly achieved by light-curable molding, impregnating and coating compositions which contain a mixture of a) at least one ethylenically unsaturated copolymerizable polyester, b) at least one ethylenically unsaturated copolymerizable monomeric compound, c) an inhibitor, d) UV sensitizer and optionally e) paraffins, thermally decomposing initiators, metal or amine accelerators, fillers, reinforcing agents, lubricants, UV absorbers, inert solvents, shrinkage-reducing additives and / or other auxiliaries that can be used with unsaturated polyester materials, and are characterized in that the W- Sensitizer consists of at least one acylphosphine oxide compound of the formula where R1 is a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, a cyclohexyl, cyclopentyl, aryl, halogen, alkyl or alkoxyl-substituted aryl, an S- or N-containing five- or six-membered heterocyclic radical; R2 has the meaning of R1, where R1 and R2 can be identical or different to one another, or represent an alkoxy radical having 1 to 6 carbon atoms, an aryloxy or an arylalkoxy radical, or R1 and R2 are connected to one another to form a ring; denotes a cycloalkyl radical, aryl radical, napthyl radical, an S-, N- or O-containing five- or six-membered heterocyclic radical which contains the substituents A and B bonded at least in the two positions ortho to the carbonyl group, A and B being identical or different and represent alkyl, cycloalkyl, aryl, alkoxy, thioalkyl, carbalkoxy, cyano groups or halogen atoms.

The feature "in the two ortho positions to the carbonyl group die Substituents A and B are bound in the context of the invention to be understood as that the substituents A and B on the two to the point of attachment with the carbonyl group adjacent carbon atoms, which may be substituted, are bonded. this means that the oC-naphthyl radical at least in the 2,8-positions and the ß-naphthyl radical contains the substituents A and B bonded at least in the 1,3-positions.

The curing rates of the molding, impregnation and coating compounds exceed very clearly those of all previously known light-curable Compositions based on unsaturated polyester resins. The sensitized resins are in In contrast to those according to German patent application P 28 30 928.6, sufficient storage-stable and can therefore be used as stable, light-curable one-component systems handle well.

The molding, impregnating and coating compositions, like resins, show according to German patent application P 28 30 928.6 when exposed to UV radiation is practical no yellowing of the molding material and therefore stand out advantageously from conventional UV initiators, for example benzil ketals and benzoin ethers.

Another advantage is the fast curing of glass fiber reinforced Molding compositions which contain the new W initiators should be mentioned in thick layers. This has a particularly beneficial effect on the UV curing of laminates that are used in hand, Winding, centrifugal or fiber spraying processes can be manufactured. Correspondingly cheap Results also result from the UV curing of glass fiber-free, kneadable molding compounds. With the same exposure time, the molding compositions according to the invention can produce a cure a thicker layer than with a known one based on benzil dimethyl ketal.

For the production of the light-curable form, impregnation and coating compositions Usable starting components a) to e) are as follows: a) As unsaturated For the purposes of the invention, polyesters are not just the customary unsaturated polycondensation products to be understood from preferably dicarboxylic acids and glycols, but also those containing urethane groups unsaturated polyesters and unsaturated vinyl ester resins.

The usual unsaturated polyesters are preferably suitable Polycondensation products from polybasic, in particular dibasic, carboxylic acids and their esterifiable derivatives, in particular their anhydrides, which with polyvalent, in particular dihydric alcohols are linked in an ester-like manner, and optionally additional residues of monohydric carboxylic acids and / or residues of monohydric alcohols and / or Containing residues of hydroxycarboxylic acids, with at least some of the residues above Ethylenically unsaturated copolymerizable groups must have L J as Polyhydric, especially dihydric, optionally unsaturated alcohols are suitable the usual, in particular acyclic groups, cyclic groups as well as both Kinds of group-containing alkanediols and oxaalkanediols such as ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,14-butanediol, 1,6-hexanediol, 2,2-dimethylpropanediol - 1,3, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-cyclohexanediol, 2,2-bis (p-hydroxycyclohexyl) propane, trimethylolpropane monoallyl ether or 1,4-butenediol. Furthermore, monohydric, trihydric or higher alcohols, such as e.g. Ethylhexanol, fatty alcohols, benzyl alcohols, 1,2-di- (allyloxy) -propanol- (3), glycerine, Pentaerythritol or trimethylolpropane can also be used in minor amounts. The polyhydric, especially dihydric alcohols are generally stoichiometric or approximately stoichiometric amounts with polybasic, especially dibasic Carboxylic acids or their condensable derivatives implemented.

Suitable carboxylic acids or their derivatives are dibasic olefinic unsaturated, preferably .X, J3-olefinically unsaturated carboxylic acids, e.g. Maleic acid, fumaric acid, chloromaleic acid, itaconic acid, citraconic acid, methylene glutaric acid and mesaconic acid or its esters or, preferably, their anhydrides.

Other modifying agents can also be added to the polyester active dibasic, unsaturated and / or saturated, as well as aromatic carboxylic acids, such as succinic acid, glutaric acid, c§-methylglutaric acid, adipic acid, sebacic acid, Pimelic acid, phthalic anhydride, o-phthalic acid, isophthalic acid, terephthalic acid, Dihydrophthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6-endomethylene-1,2,3,6- -tetrahydrophthalic acid, Endomethylene tetrachlorophthalic acid or hexachloroendomethylene tetrahydrophthalic acid be condensed, furthermore mono-, tri- and higher basic carboxylic acids, such as e.g. ethylhexanoic acid, fatty acids, methacrylic acid, propionic acid, benzoic acid, 1,2,4-benzenetricarboxylic acid or 1,2,4,5-benzene tetracarboxylic acid. Maleic acid or their anhydride and fumaric acid.

As the maximum crosslinking capacity present in such polyesters plays a large role in the performance of the low-profile system is intended for this Area of application the largest part, i.e. 50 to 100 t., Of that built into the polyester Dicarboxylic acids can be unsaturated.

Mixtures of unsaturated polyesters, including those in the Vinyl monomers (b) have only limited solubility and can crystallize easily can also be used advantageously. Such easily crystallizing unsaturated Polyesters can e.g. from fumaric acid, adipic acid, terephthalic acid, ethylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.

Unsaturated polyesters with preferably terminal ones are also suitable Double bonds.

The unsaturated polyesters have acid numbers from 10 to 200, preferably from 20 to 85 and average molecular weights from about 800 to 6,000, preferably from about 1.00b to 4,000.

The amorphous and optionally crystallizable unsaturated polyesters are generally azeotropic by melt condensation or condensation under Bedin-J from their starting components according to continuous or discontinuous processes.

With regard to the composition of unsaturated polyesters, for example also on the book by H.V. Boenig, Unsaturated Polyesters: Structure and Properties, Amsterdam, 1964.

Instead of unsaturated polyesters - as already mentioned - Unsaturated polyesters containing urethane groups are used. For this purpose, the above-mentioned unsaturated polyester with organic polyisocyanates, preferably implemented aliphatic, cycloaliphatic and especially aromatic diisocyanates thereby extending the unsaturated polyester chain and increasing the molecular weight enlarged. Suitable for chain extension are, for example, aliphatic diisocyanates, such as 1,4-butane diisocyanate and 1,6-hexane diisocyanate, cycloaliphatic diisocyanates, such as 1,3- and 1,14-cyclohexane diisocyanate, 1-methyl-2,4- and 2,6-cyclohexane diisocyanate as well as the corresponding isomer mixtures, isophorone diisocyanate and 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures and preferably aromatic diisocyanates such as 2,4- and 2,6-toluylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,14'- and 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures and 1,5-naphthylene diisocyanate.

For the production of the unsaturated polyesters containing urethane groups the starting components are expediently at temperatures from 0 to 120 0C, preferably 15 to 600C in such amounts that the ratio of Zerewitinoff-active hydrogen atoms, preferably bound to OH and COOH groups, the unsaturated polyester to NCO groups of the polyisocyanates 1: 0.1 to 0.9, preferably 1: 0.2 to 0.7. The obtained urethane group-containing unsaturated polyesters have acid numbers from 2 to 30, preferably from 5 to 20, and average molecular weights from about 1,000 to 10,000, preferably from about 1,500 to 6,000.

Have suitable unsaturated vinyl ester resins for the purposes of the invention the characteristic grouping -CO-OCH2CHOH-CH20- and contain terminal polymerizable unsaturated groups. The vinyl ester resins are made by reacting approximately equivalent amounts of a polyepoxy resin and an unsaturated monocarboxylic acid, for example of 2 equivalents of methacrylic acid with two equivalents of a polyepoxide resin.

Vinyl ester resins of the type mentioned are described, for example, in US Pat U.S. Patent 3,367,992 which discloses dicarboxylic acid half esters of hydroxy acrylates or methacrylates be reacted with polyepoxy resins. According to U.S. Patents 3,066,112 and 3,179,623 Vinyl ester resins obtained from monocarboxylic acids such as acrylic and methacrylic acids; an alternative production method is also mentioned here, according to which a glycidyl methacrylate is used or acrylate with the sodium salt of a dihydric phenol, e.g. bisphenol A, is made to react. Vinyl ester resins based on epoxy - novolac resins are described in U.S. Patent No. 3,301,743. Vinyl ester resins are disclosed in U.S. Patent No. 3,256,226 disclosed in which the molecular weight of the polyepoxide by reaction of a dicarboxylic acid is increased with the polyepoxy resin and with acrylic acid.

Modified vinyl ester resins, L J, are also suitable for example those according to DE-OS 25 34 039 (equivalent to US Pat. No. 3,947,422) are the half-ester groups and by reaction of the second hydroxyl group of the group -CO-OCH2.CHOH-CH20- with a dicarboxylic acid anhydride, e.g. the anhydride of maleic acid, citraconic acid, Phthalic acid, tetrabromophthalic acid, etc.

can be obtained.

The light-curable molding, impregnating and coating compositions according to the invention Generally contain 10 to 80% by weight, preferably 15 to 70% by weight, based on the total weight of components (a) and (b) of an unsaturated polyester, one urethane group-containing unsaturated polyester or an unsaturated vinyl ester resin or mixtures of the components (a) mentioned.

b) As copolymerizable, ethylenically unsaturated monomeric compounds come the usual for the production of unsaturated polyester mold, impregnation and Coating compositions used allyl and preferably vinyl compounds in question, such as Styrene, substituted styrenes such as p-chlorostyrene or vinyl toluene, esters of acrylic acid and methacrylic acid with 1 to 18 carbon atoms containing alcohols, such as methacrylic acid methyl ester, Butyl acrylate, ethylhexyl acrylate, hydroxypropyl acrylate, dihydrodicyclopentadienyl acrylate, Butanediol diacrylate and (meth) acrylic acid amides, allyl esters, such as diallyl phthalate, and vinyl esters such as vinyl ethylhexanoate, vinyl pivalate and others.

Mixtures of the olefinically unsaturated compounds mentioned are also suitable Monomers. Preferably suitable as component (b) are styrene, methylstyrene, chlorostyrene, Vinyl toluene, divinyl benzene and diallyl phthalate.

Component (b) is in the polyester mold, impregnation and Coating compositions generally in an amount from 20 to 90, preferably from 30 Up to 85% by weight, based on the total weight of components (a) and (b).

c) The light-curable molding, impregnating and coating compositions according to the invention are stabilized with the usual inhibitors (c). May be mentioned by way of example phenolic inhibitors such as hydroquinone, substituted hydroquinones, catechol, tert-butylpyrocatechol, ring-substituted pyrocatechin derivatives; Quinones, like Benzoquinone, naphthoquinone, chloranil, nitrobenzenes, such as m-dinitrobenzene, thiodiphenylamine, N-nitroso compounds such as N-nitrosodiphenylamine and salts of N-nitroso-N-cyclohexylhydroxylamine as well as their mixtures. Salts are also suitable as additional stabilizers divalent copper, for example copper naphthenate or octoate and quaternary Ammonium salts of the structure LNR5R65R7, R8j X-, in which R55 R6> R7 and R8 are an alkyl radical with 1 to 20 carbon atoms, an aryl radical with 6 to 14 carbon atoms or an aralkyl radical having 7 to 30 carbon atoms and X a halogen atom, preferably Mean chloride.

The addition of selected UV absorbers to light stabilize the curing products in some cases causes a slight reduction in the UV curing speed, but which can still be accepted. Those from the ranks are suitable of oxibenzophenone, salicylic acid esters and oxiphenylbenzotriazole.

The inhibitors are generally contained in the molding, impregnating and coating compositions in an amount of 0.005 to 0.5, preferably 0.01 to 0.2% by weight, based on components a) and b). J 'd) According to the invention, acylphosphine oxide compounds of the formula are used as UV sensitizers (d) into consideration. Examples of acylphosphine oxide compounds that may be mentioned are: acylphosphine oxides and acylphosphinic acid esters. With regard to formula (I), the following should be stated in detail: R1 can be a straight-chain or branched alkyl radical with 1 to 6 carbon atoms, such as methyl, ethyl, i-propyl, n-propyl, n-butyl, amyl -, n-hexyl, cyclopentyl, cyclohexyl, aryl, such as phenyl, naphthyl, halogen-substituted aryl, such as mono- or dichlorophenyl, alkyl-substituted phenyl, such as methylphenyl, ethylphenyl, isopropylphenyl, tert- Butylphenyl, dimethylphenyl, alkoxy-substituted aryl, such as methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, S or N-containing five- or six-membered rings, such as thiophenyl, pyridyl, R2 can have the meaning of R1 and furthermore be an alkoxyl radical with 1 to 6 carbon atoms, such as methoxyl, ethoxyl, i-propoxyl, butoxyl, ethoxyethoxyl, aryloxy radical, such as phenoxy, methylphenoxy, benzyloxy, R1 can be connected to R2 to form a ring , such as

in acyl-phosphonic acid-o-phenylene esters.

R3 can be a cycloalkyl, aryl, naphthyl radical, an S, N or O-containing five- or six-membered heterocyclic radical, e.g. a furyl, pyrrolyl, Thienyl, pyranyl or pyridyl radical, at least in the two ortho positions contains the substituents A and B bonded to the carbonyl group, A and B being the same or are different and represent an optionally branched alkyl radical with 1 to 6, preferably 1 to 4 carbon atoms, e.g. a methyl, ethyl, Propyl, iso-propyl, butyl, iso-butyl and tert-butyl radicals; one if necessary substituted cycloalkyl radical, e.g. cyclohexyl radical, an optionally substituted Aryl radical, e.g. the phenyl or toluyl radical, an alkoxy or thioalkyl radical 1 to 6, preferably 1 to 4 carbon atoms in the alkyl radical, e.g. the methoxy, thoxy, propoxy, iso-propoxy, n-butoxy, methylthio, ethylthio, propylthio, -iso-propylthio-, n-butyl-thio-, sec-butylthio and tert-butylthio radical; a carbalkoxy group with 1 to 6, preferably 1 to 4 carbon atoms in the alcohol radical, e.g. the carbomethoxy, Carboethoxy, carbopropoxy, carboisopropoxy, carbobutoxy and carbo-sec-butoxy groups; a cyano group or a halogen atom, for example a chlorine, bromine or iodine atom.

R1 and R2 can also contain C-C double bonds, which allow polymerize the UV sensitizer into the binder.

Acylphosphine oxide compounds containing bonded R3 can be illustrated, for example, by the structural formulas II to VII, where X is optionally further substituents in the cycloalkyl, aryl, naphthyl or heterocyclic radicals which have the meanings of A or B.

As examples of the UV sensitizers which can be used according to the invention may be mentioned: 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester 2,6-dimethoxybenzoyl-phenylphosphinic acid methyl ester 2,6-dimethylbenzoyl-diphenylphosphine oxide 2,6-dimethoxybenzoyl-4iphenylphosphine oxide 2o4o6-trimethylbenzoyl-phenylphosphinic acid methyl ester 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 2,3,6 -Trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-tolylphosphinic acid methyl ester 2,4,6-trimethoxybenzoyl diphenylphosphine oxide 2,6-Dichlorobenzoyl-phenylphosphinic acid ethyl ester 2,6-dichlorobenzoyl-diphenylphosphine oxide 2-chloro-6-methylthio-benzoyl-diphenylphosphine oxide 2,6-dimethylthio-benzoyl-diphenylphosphine oxide 2,3,4,6-tetramethylbenzoyl-diphenylphosphine oxide 2-phenyl-6-methylbenzoyl-diphenylphosphine oxide 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-naphthylphosphinic acid ethyl ester 2,6-dichlorobenzoyl-naphthylphosphinic acid ethyl ester 1, 3-dimethylnaphthalene-2-carbonyl-diphenylphosphine oxide 2,8-Dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide 1,3-Dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide 1,3-dichloronaphthalene-2-carbonyl-diphenylphosphine oxide 2,4,6-trimethylpyridine-3-carbonyl-diphenylphosphine oxide 2,4-dimethylquinoline-3-carbonyldiphenylphosphine oxide 2,14-dimethylfuran-3-carbonyl-diphenylphosphine oxide 2,4-Dimethoxyfuran-3-carbonyl-diphenylphosphine oxide, 2,4,5-trimethyl-thiophene-3-carbonyl-phenylphosphinic acid methyl ester 2,4,5-Trimethyl-thiophene-3-carbonyl-diphenylphosphine oxide Preferably use find: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 2,6-dimethoxybenzoyl-diphenylphosphine oxide 2,6-dichlorobenzoyl-diphenylphosphine oxide 2,3,5,6-tetramethyl-benzoyl-diphenylphosphine oxide 2,4,6-Trimethylbenzoyl-phenylphosphinic acid methyl ester.

Such compounds can be prepared by reacting acid halides of the formula X = Cl, Br, with phosphines of the formula R4 = straight-chain or branched C1- to C6-alkyl, or cycloalkyl with 5 or 6 carbon atoms. or also without a solvent at temperatures between -30 ° C and + 110 ° C, preferably at 10 to 70 ° C. The product can be crystallized out directly from the solvent, remains after evaporation or is distilled in vacuo.

Obtaining the acid halides and the substituted phosphine RlRdPORq is carried out by methods which are known to the person skilled in the art from the literature (for example K. Sasse in Houben-Weyl, Vol. 12/1, pp. 208-209, G. Thieme-Verlag, Stuttgart).

The process for the preparation of the compounds according to the invention can be described by way of example as follows: Suitable phosphines are, for example methyl-dimethoxyphosphin, butyl dimethoxyphosphin, rbxyphosphin phenyldimethoxyphosphine, Toluyldimethoxyphosphin, Phenyldiäthoxyphosphin, Toluyldiäthoxyphosphin, Phenyldiisopropoxyphosphin, Tolyldiisopropoxyphosphin, Phenyldibutoxyphosphin, Tolyldibutoxyphosphin or Dimethylmethoxyphosphin, Dibutylmethoxyphosphin, Dimethylbutoxyphosphin, Diphenylmethoxyphosphin, Diphenyläthoxyphosphin, Diphenylpropoxyphosphin, Diphenylisoprop-, Diphenylbutoxyphosphin or similar output 'Materials that lead to the compounds according to the invention.

Suitable acid halides are chlorides and bromides, particularly preferred however, are acid chlorides.

Particularly preferred as UV sensitizers for unsaturated polyester resin urethane group-containing unsaturated polyester resins and unsaturated vinyl ester resins are acyl-phenyl-phosphinic acid esters and acyldiphenylphosphine oxides, their acyl radicals differs from a di-ortho-substituted aromatic carboxylic acid, such as 2,4,6-trimethylbenzoic acid, 2,6-dimethoxy-benzoic acid, 2,6-dichloro-benzoic acid or 2,3,5,6-tetramethylbenzoic acid derive.

The acylphosphine oxide compounds which can be used according to the invention are In amounts of from 0.005 to 5% by weight, preferably from 0.01 to 3% by weight, based on the weight of the unsaturated polyester (a) and ethylenically unsaturated monomers Compounds (b) used.

e) As under point (e) falling polyester resp.

Vinyl ester resin additive components come into consideration, for example: Paraffins, thickeners, initiators, fillers, reinforcing agents, lubricants, inert solvents, shrinkage-reducing additives and / or more in the case of unsaturated ones Auxiliary materials that can be used in polyester compositions.

Paraffins that are present in the light-curable form, impregnation and coating compounds are used, have melting points of 25 to 90 ° C, preferably 45 to 600C. Particularly proven and therefore used in particular a paraffin with a melting point of 46 to IL80C.

instead of paraffins, other waxy substances can also be used, for example the paraffin oxidation products known as so-called montan wax or their Esters, carnauba wax, long-chain fatty acids such as stearic acid, stearyl stearate, Ceresin and the like. Be used.

To reduce the evaporation of monomers and to form a The unsaturated molding compositions contain a tack-free surface from 0.01 to 5% by weight, preferably 0.05 to 1% by weight, in particular 0.1 to 0.5% by weight, paraffin, based on the total weight of components a) and b).

Suitable thickeners are, for example, those based on Alkaline earth oxides such as calcium oxide, calcium hydroxide, magnesium hydroxide and preferably Magnesium oxide and mixtures of these oxides or hydroxides. These can also be partial be replaced by zinc oxide.

The content of the polyester or vinyl ester molding compositions according to the invention of thickeners is generally 0.5 to 5, preferably 1 to 3% by weight, based on the mixture of components a) and b).

In addition to the acylphosphine oxide compounds according to the invention, additional initiators are used for example: peroxides, e.g. peresters, such as tert-butyl peroctoate, tert-butyl perpivalate, Percarbonates such as bis (14-tert-butylcyclohexyl) peroxydicarbonate, diacyl peroxides, such as benzoyl peroxide, dialkyl peroxides, such as di-tert.-butyl peroxide and dicumyl peroxide, Hydroperoxides, such as cyclohexanone peroxide, methyl ethyketone peroxide, cumene hydroperoxide and tert-butyl hydroperoxide, optionally in combination with metal accelerators, e.g. cobalt II salts of ethylhexanoic acid or naphthenic acid; as well as azo compounds, like azo-diisobutyronitrile and C-C-labile compounds like tetraphenyl- Eernsteinsäuredinitril, Tetraphenyl-ethanediol and / or α, α, α ', α'-tetrasubstituted Dibenzyl compounds as described, for example, in Kunststoffe 66, 693 (1976) are. Leave thick laminate structures with glass fibers and quartz sand> e.g. for pipes then cure themselves advantageously by UV radiation when in addition to the invention Acylphosphine oxide compounds additionally thermally decomposing initiators in low levels Quantities, for example 0.05 to 1% by weight, preferably 0.1 to 0.3% by weight, based to the total weight of components a) and b) are also used. These initiators break down into radicals due to the heat generated during photopolymerization, see above that the curing can also take place in deeper layers, which the UV light is insufficient recorded.

The use of photoinitiator combinations is also particularly advantageous from the acylphosphine oxide compounds according to the invention and known photoinitiators for example aromatic ketones, e.g. benzil ketals such as benzil dimethyl ketal, Benzoin ethers and esters, such as benzoin isopropyl ethers, α-hydroxyisobutyrophenone, Diethoxyacetophenone or p-tert-butyltrichloroacetophenone (i.a.

DE-AS 22 59 161), aromatic disulfides (DE-AS 12 33 594) and / or Naphthalenesulfonyl chlorides (DE-AS 22 59 161). With the photoinitiator combinations mentioned it is possible in numerous cases, with comparable exposure times lower ones To achieve residual styrene content of UP resin molded materials than with the inventive Acylphosphine oxide compounds alone, although the curing activity (measured on Temperature rise of the resin sample during exposure) drops. The photoinitiator combinations Expediently contain 15 to 85% by weight, preferably 25 to 75% by weight, of acylphosphine oxide compounds and 15 to 85% by weight, preferably 25 to 75% by weight of an aromatic ketone, aromatic Disulfides and / or flaphthalenesulfonyl chloride, the percentages by weight are based on the total weight of the mixture, and are used in amounts of 0.005 to 7% by weight, preferably from 0.01 to 4% by weight, based on the weight of the components (a) and (b) are used.

The curable, unsaturated molding, impregnating and coating compositions according to the invention In addition, the usual fillers, reinforcing materials and lubricants are usually inert Solvents, shrinkage-reducing additives and, if necessary, other auxiliaries added.

Suitable fillers are, for example, the usual fine-powdered or granular ones inorganic or organic fillers that are permeable to long-wave UV light are like aluminum oxide hydrate, quartz sand, finely dispersed silica, As best, talc, Barium sulfate, light spar (calcium sulfate) and mica.

Inorganic or organic reinforcing materials can be used as reinforcing materials Fibers or flat structures, optionally woven from them, such as mats, e.g. such made of glass, asbestos, cellulose and synthetic organic high polymers such as polyamide, Polyacrylonitrile and polyesters, for example terephthalates.

The fillers and reinforcing agents can be used in amounts from 5 to 200 % By weight, preferably 10 to 70% by weight, based on the total weight of the components a) and b) can be used. In many cases it is a combination of powdery and fibrous fillers (e.g.

for container production). After the lamination process, the laminate Covered with a film permeable to UV radiation and with low-energy UV radiation from fluorescent tubes (e.g. TAK 40 W / 05, Philips) over a longer period of time or cured with high-pressure mercury vapor lamps (HOK 6, 80 W / cm, Philips) in a very short time will.

Zinc, magnesium and calcium stearate, for example, are used as lubricants and also polyalkylene ether waxes.

As inert solvents which may also be used as well come ketones, esters, hydrocarbons in amounts up to 100 wt.%, based on the components a), in question. As a shrinkage-reducing agent that may also be used as well Additives are, for example, thermoplastic polymers such as polystyrene, styrene copolymers, Polyvinyl acetate or poly (meth) acrylates in amounts of 1 to about 30 wt., Based on the components a) + b), into consideration.

As radiation sources for hardening the molding, impregnating and coating compounds are for example fluorescent tubes, high-pressure mercury tubes and direct To call sunlight.

The molding, impregnating and coating compositions according to the invention can contain used in many technical fields.

They are suitable, for example, as 1st fine-layer resins, which are only approx. 0.5 mm thick layers are used to protect the laminate behind its hydrolysis-sensitive fiberglass. These resins have to meet high requirements meet the hardening activity and the molding materials must only have a slight yellowing exhibit. The transparent fine layers are made by spraying or painting brought to a shape, then gelled or hardened by UV radiation tet and then applied the glass fiber-containing molding compound.

2. Fiber-reinforced molded materials a) Draw light panels for the construction sector are characterized by high transparency and low yellowing. For the production of flat, longitudinally or transversely corrugated light panels are continuously working Machines in action. The light-stabilized UP resins are used to make glass silk mats soaked between cover films, - vented and finally hardened by cold curing. By using the acylphosphine oxide initiators according to the invention, the Curing also more efficient - by UV radiation from Hg high-pressure steam emitters or also manage so-called blue light lamps (Lit.

about light plate production: P.H. Selden, "Glass fiber reinforced plastics", Page 610, Springer-Verlag Berlin-Heidelberg-New York, 1967).

b) Discontinuous process for the production of fiber-reinforced, in particular glass fiber reinforced molding materials that are suitable for UV curing, are: hand lay-up process, fiber spraying, centrifugal and winding processes (description s. P.H. Selden, "Glass fiber reinforced plastics").

Articles of everyday use that are manufactured using these processes can include, for example, boats, container panels (both sides with glass fiber reinforced Plastic-coated chipboard or blockboard), pipes, containers.

c) UP resin fine layers for molded materials containing glass fibers (GRP) and Paper laminates The surface quality of GRP and paper laminates can be increased by applying a fine layer can be significantly improved. The following advantages can be achieved: 1. GRP laminates such as corrugated sheets: a) Longer-lasting gloss retention when exposed to the elements and thus less pollution.

b) Slight decrease in transparency during outdoor exposure due to Protection of the glass-resin interface.

2. Paper laminates based on unsaturated polyester, urea or melamine resins: a) increase the surface gloss.

b) Surfaces that are less sensitive to the touch than those made of melamine resins.

c) The high transparency of the UP fine layer creates the optical one Impression like a surface coated with clear lacquer.

The fine layer itself must be placed on a carrier before the laminate is produced (e.g. foil). This is done by pulling a 20 to 200 / um on a release film thick UP resin layer, which is then W-hardened. Complete curing then takes place during the hardening of the laminate.

The production of fine layers by known methods has the following Disadvantages on: a) When curing with organic peroxides in the heat are high Styrene losses are recorded, so that there is a risk of undercuring.

b) Leave in the heat when curing with peroxide and accelerator the styrene losses are reduced, but the lower ones prove to be disadvantageous Processing time (30 to 60 minutes) and that of the accelerator (Co salts) caused intrinsic color of the molding material.

c) UV curing with known photoinitiators leads to yellowish Fine layers; the yellowing is intensified when exposed to the elements.

The above-mentioned deficiencies occur with the molding compositions according to the invention the other procedures do not occur. Rather, through rapid curing with UV light almost colorless fine layers are preserved that neither in daylight nor under artificial light yellow.

L J 7. Embeddings For use with casting resins that can be used for embedding electronic parts, for example the new sensitizers are ideally suited. When embedding opaque Objects must be provided for a uniform, all-round exposure.

The parts and percentages given in the examples relate to unless otherwise stated, by weight. Volume parts relate to parts how liters to kilograms.

The examples and comparative examples were made with the following unsaturated Polyester resins and vinyl ester resins: Resin A is one with 0.01% hydroquinone stabilized 65% styrenic solution of an unsaturated polyester from maleic acid, o-Phthalic acid, ethylene glycol and 1,2-propylene glycol in a molar ratio of 1: 2: 2.3 : 0.70. The unsaturated polyester has an acid number of 50.

Resin B is a 66% styrenic stabilized with 0.01% hydroquinone Solution of an unsaturated polyester from maleic acid, o-phthalic acid and 1,2-propylene glycol in a molar ratio of 1: 0.5: 1.5.

The unsaturated polyester has an acid number of 50.

Resin C is a 65% styrenic stabilized with 0.012% hydroquinone Solution of an unsaturated polyester from maleic acid, o-phthalic acid, 1,2-propylene glycol and diethylene glycol in a molar ratio of 1: 0.25: 1: 0.25. The unsaturated polyester has an acid number of 143.

Resin D is a styrenic goat stabilized with 0.01% hydroquinone Solution of an unsaturated polyester from maleic acid, tetrahydrophthalic acid and Diethylene glycol in a molar ratio of 1: 0.5: 1.5. The unsaturated polyester has a Acid number of 43.

Resin E is a styrenic goat stabilized with 0.01% hydroquinone Solution of an unsaturated polyester from maleic acid, o-phthalic acid and 1,2-propylene glycol in a molar ratio of 1: 1: 2.

The unsaturated polyester has an acid number of 52.

Resin F is a 65% styrenic stabilized with 0.01% hydroquinone Solution of an unsaturated polyester from maleic acid, o-phthalic acid and 1,2-propylene glycol in a molar ratio of 1: 2: 3.

The unsaturated polyester has an acid number of 30.

Resin G Commercially available vinyl ester resin (RDekrane 411-45 from Dow Chemical Co.> Midland, Mich. UNITED STATES).

As UV initiators for comparative examples, the following were included in the status the technology -related connections used: I benzil dimethyl ketal II benzoin isopropyl ether III methylol benzoin methyl ether IV pivaloyl diphenylphosphine oxide V Versatoyl-diphenylphosphine oxide VI 1-methylcyclohexanoyl-diphenylphosphine oxide VII Pivaloyl-phenylphosphinic acid methyl ester VIII p-toluyl-diphenylphosphine oxide IX 2-methylbenzoyl-diphenylphosphine oxide The examples according to the invention were carried out with the following acylphosphine oxides: X 2,4,6-trimethylbenzoyl-diphenylphosphine oxide XI 2,6-dimethoxybenzoyl-diphenylphosphine oxide XII 2,6-dichlorobenzoyl-diphenylphosphine oxide XIII 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide XIV 2,4,6-Trimethylbenzoyl-phenylphosphinic acid methyl ester Those which can be used according to the invention Acylphosphine oxide compounds are prepared in the following way: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (X) In a stirred apparatus with reflux condenser and dropping funnel at 50 to 55 ° C. 648 parts of methoxydiphenylphosphine to 547.5 parts of 2,4,6-trimethylbenzoyl chloride slowly admitted. The mixture is stirred for a further 4 to 5 hours at 50 ° C. and the contents of the flask are dissolved at 30 ° C. in ether and mixed with petroleum ether until the onset of turbidity. At the Cooling, 910 parts (87% of theory) of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide crystallize. Mp: 80 to 810 ° C., pale yellow crystals.

'2,6-Dimethoxybenzoyl-diphenylphosphine oxide (XI) in an apparatus as described for the preparation of initiator X, 20 parts of 2,6-dimethoxybenzoyl chloride are used suspended in 20 parts by volume of toluene and added to this mixture at 50 to 55 0C Stirring 21.6 parts of methoxydiphenylphosphine were added dropwise. The mixture is stirred for a further 3 hours 500C and then recrystallizes directly from toluene. 32 parts of yellowish are obtained Crystals, m.p .: 124-126 ° C.

Further initiators which can be used according to the invention and which, according to analogous Synthesized method can be found in Table 1.

Table 1 - Examples of acylphosphine oxide derivatives which can be used according to the invention Analysis Yield bp m.p. C H P (mm) [° C] (X) 2,4,6-trimethylenzoyl- 87% - 80-81 calc. 75.86 6.03 8.91 -diphenylphosphine oxide found. 75.9 6.1 8.9 (XI) 2,6-dimethoxybenzoyl- 88% - 124-126 calc. 68.85 5.19 8.47 -diphenylphosphine oxide found. 68.7 5.4 8.2 (XII) 2,6-dichlorobenzoyl 82% - 154-159 calc. 60.38 3.47 8.27 -diphenylphosphine oxide found. 60.9 3.7 8.1 (XIII) 2,3,5,6-tetramethyl- 63% - 123-125 calc. 76.24 6.36 8.56 benzoyl-diphenyl- found 76.2 6.5 8.4 phosphine oxide (XIV) 2,4,6-trimethylbenzoyl- 81% - 51-52 calc. 67.55 6.29 10.26 phenylphosphinic acid found. 67.5 6.5 10.1 methyl ester % V hardening act In order to measure the curing activity, the temperature profile in the unsaturated Polyester resin (UP resin) or vinyl ester resin recorded during UV exposure; a thermal sensor covered with a layer of wax, the one with a Temperature recorder (Tastotherm Script 3 N, standard probe T 300 from Deutsche Gulton GmbH) was connected to a tinplate lid filled with 10 g of UP resin with a Diameter of 5 cm (layer thickness of the UP resin 4.8 mm). To avoid heat loss During the UV exposure, the cover was embedded in rigid polyurethane foam. A W field consisting of 5 fluorescent tubes (TLAK 40 W / 05, Philips) served as the radiation source side by side. The distance between the radiator and the UP resin surface was 8.5 cm.

The registered temperature-time curves were considered to be characteristic Parameters for the curing activity are the curing time HZ250C T and the maximum achieved Hardening temperature Tmax max taken. The curing time is the period in which increases the sample temperature from 250C to Tmax.

Example 1 Preparations from UP resins A, B, C, D and the vinyl ester resin G with 0.2% of various sensitizers were made in the manner described above cured with UV light.

A comparison of the curing activity (Table 2) shows that with the initiators X to XIV according to the invention, the fastest curing times are possible. However, pivaloyl diphenyiphosphine oxide (IV) has the activity of 2,6-dichlorobenzoyl diphenylphosphine oxide (XII); in contrast to the initiators according to the invention, however, this is not the case Activity on storage in UP resins sharply decreases over time, as in Examples 2 and 3 prove.

Table 2 - UV curing of sensitized UP resins and a vinyl ester resin by exposure to fluorescent tubes UP resin UV initiator HZ25 ° C-Tmax @max [° C] respectively.

Vinyl ester (0.2%) [min / s] resin A I 8/00 114 B I 9/45 119 C I 10/15 123 D I 8/30 122 G I 15/53 63 A II 13/22 104 B II 13/07 109 C II 13/15 114 D II 11/15 108 A III 13/22 100 B III 11/30 117 C III 11/15 123 D III 9/08 122 A IV 7/30 107 B IV 6/45 116 C IV 6/38 123 D IV 5/30 123 A V 13/15 92 B V 13/15 81 C V 14/11 89 D V 11/00 96 A VI 11/15 94 B VI 9/57 95 C VI 10/30 104 D VI 8/38 107.

Continuation of table 2 UP resin UV initiator HZ25 ° C-Tmax Tmax [° C] respectively.

Vinyl ester (0.2%) [min / s] resin A X 4/30 125 B X 4/00 129 C X 3/38 127 D X 3/15 127 G X 5/35 92 A XI 5/23 120 B XI 5/00 123 C XI 4/25 132 D XI 4/15 125 G XI 6/30 91 A XII 7/08 105 B XII 6/35 111 D XII 5/51 115 G XII 10/45 72 A XIII 5/15 102 B XIII 4/45 119 D XIII 4/36 122 G XIII 6/30 87 A XIV 6/15 94 B XIV 4/38 110 G XIV 7/38 91 A VII 20/42 88 B VII 20/30 90 Example 2 preparations from UP resins A and D and various W initiators were sealed in Vessels stored at 600 C and then the curing activity at room temperature - as described in Example 1 - measured.

Table 3 compares the measurement results before and after storage. They show very clearly that only the initiators according to the invention X to XIV their Activity under the experimental conditions have kept constant while the others Acylphosphine oxides I-V and VI show a strong change in activity - prolongation of the hardening time Call HZ25 ° C-T by a factor of 3 or 2 after a short time. In the same Storage tests over a longer period of time at room temperature also point in this direction (Tab. 4). Table 3 - UV-sensitized curing activity test UP resins after storage at 60 ° C UV initiator UP resin UV curing before storage time curing after storage storage (0.2%) HZ25 ° C-Tmax Tmax [h] HZ25 ° C-Tmax Tmax [min / s] [° C] [min / s] [° C] IV A 7/30 107 40 24/30 40 VI A 11/15 94 40 22/48 57 X A 4/30 125 106 5/00 119 X A 4/30 125 66 4/53 122 X D 3/15 127 66 3/45 127 XI A 5/20 119 66 5/23 120 XI D 4/15 125 66 3/38 129 XII A 7/08 105 70 7/30 93 XII D 5/51 115 70 6/00 102 XIII A 5/15 102 70 4/25 100 XIV A 6/15 94 70 6/41 89 XIV B 4/38 110 70 6/00 102 example 3 preparations from UP resins A and D and various W initiators were used stored in closed vessels at room temperature in the dark and the curing activity measured from time to time according to the method described in Example 1. The results in Table 4 show that with the initiator X which can be used according to the invention, in contrast for initiators IV, VII, VIII and IX, storable UV-curable UP resins are obtained will.

Table 4 - Testing of the curing activity of UV-sensitized UP resins after storage at room temperature UV initiator UP resin storage - HZ25 ° C - Tmax Tmax storage HZ25 ° C-Tmax Tmax Storage HZ25 ° C-Tmax Tmax time time time [min / s] [° C] [min / s] [° C] [min / s] [° C] [d] [d] [d] VII (0.35) A 0 18/15 106 3 18/00 109 10 25/30 105 VII (0.35) D 0 13/00 112 10 14/45 124 17 17/50 110 IV (0.35) A 1 7/10 105 7 9/10 91 19 22/00 71 IV (0.35) D 0 4/40 126 3 4/45 125 14 13/25 58 IV (0.20) D 0 5/50 127 3 7/15 104 14 28/10 48 VIII (0.35) D 0 10/05 133 - - - 14 24/25 57 IX (0.35) A 0 8/15 117 3 8/30 110 18 14/45 80 34> 36 54 X (0.20) A 0 4/30 118 14 4/15 114 63 4/00 113 X (0.35) A 0 5/38 118 14 5/45 109 63 6/00 106 Example 4 For assessment the light yellowing of UP resin molded materials was 4.8 mm thick washers (diameter 5 cm) from UP resins A, E and F, which are sensitized with various W initiators were hardened by exposure to fluorescent tubes (TL AK 40 W / 05, Philips) and then for 60 or 120 minutes at room temperature of the radiation from the same light sources exposed (5 fluorescent tubes side by side).

The distance between the radiation source and the circular surface was 8.5 cm.

The yellowing was determined using the yellowness index according to ASTM D 1925-67 judged. The measurement was carried out with the DMC 25 device from Zeiss in transparency.

The results in Table 5 clearly show that the molding materials from the preparations according to the invention are less yellowed in all cases, as such from known preparations containing benzil dimethyl ketal (I).

Table 5 - Yellowing of UV-cured UP resin molding materials UP resin W initiator Exposure yellowness index time of the molding material% g Ilminl E I (0.2) 60 13.18 E I (0.2) 120 14.56 F 1 (0.2) 60 13.88 F I (0.2) 120 16.38 E X (0.2) 60 3.78 E X (0.2) 120 4.19 F X (0.2) 60 3.82 F X (0.2) 120 4.19 A XI (0.2) 60 3.08 A X (0.15) 60 2.87 J L ii3example 5 UV curing of UP resin molding compositions a) 60 parts of the Preparations made from UP resin C with 0.1% W initiator X or with 0.1% benzil dimethyl ketal (I) were filled with 40 parts eMartinal BM 2 (Al203 .3H20, Martinswerke, Bergheim / Erft) and with 1.5% magnesium oxide "light" (manufacturer: Merck, Darmstadt) (based on UP resin) mixed.

Several layers of glass fiber mats (Vetrotex Textile glass mat M 123-40-450) measuring 10 x 12 cm soaked between polyester foils Thickened for three days at room temperature and finally by exposure to fluorescent tubes (TL AK 40 W / 05) hardened, with the help of a thermocouple the temperature profile was followed in the molding compound. The distance between the spotlights (5 fluorescent tubes next to each other) to the surface of the molding compound was 8 cm; the exposure time corresponded to the period of time in which the molding compound had reached the maximum curing temperature.

After the molding materials had cooled down, the Barcol hardness (Impressor 935) determined at the bottom and top.

The results of Table 6 clearly show the advantages of the invention Recognize preparation with UV initiator X. With three layers of fiberglass mats - accordingly a layer thickness of 3.8 to 4.5 mm - an exposure time of 5 min 15 is sufficient s, with a layer thickness of 6.6 to 7.2 mm (7 layers of glass fiber mats) one of these of approx. 13 min to achieve sufficient curing of the molding compound.

In the case of the molding compound based on benzil dimethyl valley (I) In spite of doubling the exposure time, the laminate does not fully cure achieved with 7 layers of fiberglass mats.

Table 6 - UV curing of a resin mat based on UP resin C, Al2O3.3H2O and glass fiber mats initiator layer thickness 1) bearing glass UV hardening hardened Barcol hardness fiber mats HZ25 ° C-Tmax Tmax layer thickness above / below (0.1%) [mm] [min / s] [° C] [mm] X 3.8 - 4.5 3 5/15 78 3.8-4.5 92-94 / 92-94 X 6.6 - 7.3 7 13/15 80 6.6-7.3 91-96 / 85-91 I 6.6 - 7.2 7 25/20 62 4.5 24-96 / 0-10 1) Resin mat structure: 48.1% UP resin C, 32.1 % Al2O3.3H2O (Martinol BM2), 19.8% glass fiber mats (Vetrotex textile glass mat M 123-40-450) rt) Kneadable, glass fiber-free UP resin molding compounds by thickening preparations made of UP resins, filler Al203.3H20 for 3 days (Martinal BM 2, Martinswerkes Bergheim / Erft), 1.5% magnesium oxide "light" (rel. on UP resin) and W initiator X resp.

Benzildimethylketal (I) (in each case 0.1% based on UP resin). The UP resin to filler weight ratio was 60:40.

A 2 cm thick layer 35 was then placed in each sheet metal lid min exposed to radiation from fluorescent tubes (TL AK 40 W / 05, Philips), whereby the temperature profile with the help of a thermocouple, which is 1 cm deep into the molding compound immersed, was pursued. The distance between the radiator and the surface of the molding compound was 6 cm. After cooling, the uncured lower layer of molding compound became mechanical removed and the Barcol hardness (Impressor 935) of the newly created surface measured after cleaning.

In the case of the molding compound according to the invention, there was a 12.6 mm thick layer, in the case of the known molding composition containing benzil dimethyl ketal (I), one of these hardened from a thickness of only 7 mm (see Table 7).

fital Table 7 - UV curing of thickened resin-filler mixtures Initiator layer thickness UV curing hardened layer thickness Barcol hardness (0.1%) [mm] Tmax [° C] [mm] top / bottom X 20 63 12.6 93 / 65-70 I 20 42 7 93/67 example 6 preparations from UP resin A and UV sensitizers X and I and their Mixtures were made in a layer thickness of 10 mm with fluorescent tubes (TL-AK 40 W / 05, Philips) irradiated. The UP resin samples were in tinplate lids with a diameter of 5 cm, which is used to avoid major heat losses on a Cork board (5 mm thick) stood. The distance between the fluorescent tube and the resin surface was 8 cm. After exposure and cooling, the molding materials each became a Sawed out the rod, recording the entire layer thickness and its residual styrene content titrimetrically determined according to DIN 16 9) 45. The results obtained are in the table 8 summarized. They show that the residual styrene content of the molded material samples with the sensitizer combination X and I are lower than with the sensitizers X and I alone.

Table 8 - Residual styrene content of W-cured UP resin molding materials made from resin A At- W sensitizer exposure residual styrene play type amount wt.%, Time content based on 6 the weight gMini - [% by weight] of components (a) and (b) a X 0.1 10 1.35 20 1.3 b X + I 0.05 + 0.05 10 1.07 20 0.65 c X + I 0.075 + 0.025 10 1.06 20 0.8 d I 0.1 10 partially still liquid 20 1.15

Claims (1)

S tent claims 7 1. Light-curable molding, impregnating and coating compositions, containing a mixture of a) at least one ethylenically unsaturated copolymerizable polyester, b) at least one ethylenically unsaturated copolymerizable monomeric compound, c) an inhibitor, d) UV sensitizer and optionally e ) Paraffins, thermally decomposing initiators, metal or amine accelerators, fillers, reinforcing agents, lubricants, UV absorbers, inert solvents, shrinkage-reducing additives and / or other auxiliaries that can be used with unsaturated polyester materials, characterized in that the UV sensitizer consists of at least one acylphosphine oxide Compound of formula where R1 is a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, a cyclohexyl, cyclopentyl, aryl, halogen, alkyl or alkoxyl-substituted aryl, an S- or N-containing five- or six-membered heterocyclic radical ; R2 has the meaning of R1, where R1 and R2 can be identical or different to one another, or represent an alkoxy radical having 1 to 6 carbon atoms, an aryloxy or an arylalkoxy radical, or R1 and R2 are connected to one another to form a ring; R3 denotes a cycloalkyl radical, aryl radical, naphthyl radical, an S-, N- or O-containing five- or six-membered heterocyclic radical which contains the substituents A and B bonded at least in the two positions ortho to the carbonyl group, where A and B are the same or are different and represent alkyl, cycloalkyl, aryl, alkoxy, thioalkyl, carbalkoxy, cyano groups or halogen atoms. 2. Light-curable FQrm, impregnating and coating compositions according to claim i, characterized in that the UV sensitizer consists of an acylphosphine oxide compound of the formula I, where R1 and R2 have the abovementioned meaning and R3 in addition to the Residues A and B in the two ortho positions are further residues with the meaning of Contains A or B bound. 5. Light-curable molding, impregnating and coating compositions according to claim 1, characterized in that the UV sensitizer consists of an acylphosphine oxide compound of the formula I, where R1 and R2 are as defined above and R3 is a 2,4,6-trimethylphenyl radical is. 4. Light-curable molding, impregnating and coating compositions according to claim 1, characterized in that the acylphosphine oxide compounds in amounts of 0.005 until 5% by weight, based on ~ the total weight of components a) and b) can be used. 5. Light-curable molding, impregnating and coating compositions according to claim l, characterized in that they are acylphosphine oxide compounds as UV sensitizers of the formula I in combination with aromatic ketones, aromatic disulfides and / or Naphthalenesulfonyl chlorides in a weight ratio of 85: 15 to 15: contain. 6. Light-curable molding, impregnating and coating compositions according to claim 5, characterized in that benzil ketals, benzoin ethers and / or as aromatic ketones Benzoin esters can be used. 7. Moldings and / or coatings made from light-curable moldings, Impregnating and coating compositions according to Claim 1.