DE3827735A1 - Novel 6-acyl-(6H)-dibenz[c,e][1,2]oxaphosphorin-6-oxides, their preparation and use as photoinitiators - Google Patents

Abstract

The invention relates to 6-acyl-(6H)-dibenz[c,e][1,2]oxaphosphorin-6-oxides of the formula I <IMAGE> in which each of the radicals R<1>, R<2> and R<3> can be contained one or more times and R<1>, R<2> and R<3> denote halogen having an atomic number of 9 to 35 or alkyl or alkoxy in each case having 1 to 6 carbon atoms and Ar denotes an aromatic hydrocarbon radical having 6 to 10 carbon atoms. It further relates to a process for the preparation of such compounds and to their use as photoinitiators in polymerisable materials. It further relates to 6-alkoxy-(6)-dibenz[c,e][1,2]-oxaphosphorins of the formula II <IMAGE> in which R<1> and R<2> have the meaning indicated and R<4> denotes alkyl having 1 to 6 C atoms, at least one R<1>, however, being halogen.

Description

The invention relates to new 6-acyl- (6H) -dibenzo [c, e] [1,2] oxaphosphorine-6-oxyde, theirs Preparation and their use as photoinitiators in photopolymerizable compositions.

There are already a number of photoinitiators on the Basis of Acylphosphinsäureestern and also Acylphosphanoxyden known (EP-PS 7 508). Acylphenylphosphinsäurephenylester, containing the acyl- (6H) -dibenz [c, e] [1,2] oxaphosphorine Structurally closest to 6-oxides are in this Patent specification includes structurally. About her synthesis and physical data, however, are not given made. The related acyl-phenylphosphinic acid alkyl esters and especially acyl-diphenylphosphine oxides can only on technically complex intermediate stages (Dichloro-phenyl-phosphane or chloro-diphenyl-phosphine) be won.

The invention has now set itself the goal of new To provide acyl phosphorus compounds, which in technical are particularly easy to produce and still meet the high requirements of the practice.

Subject of the invention are 6-Acyl- (6H) -dibenzo [c, e] [1,2] oxaphosphorin-6-oxide of general formula I (see formula sheet), wherein each the radicals R¹, R² and R³ may be present one or more times can and and R¹, R² and R³ halogen with an atomic number from 9 to 35, alkyl or alkoxy each having 1 to 6, preferably 1 to 4 carbon atoms and Ar a aromatic hydrocarbon radical with 6 to 10 Mean carbon atoms. As alkyl groups are methyl  and ethyl and as alkoxy methoxy especially prefers. In many cases, the compounds contain at least one chlorine atom, but appropriate at most 2 chlorine atoms, of which in turn appropriate represents at least one R³. Everyone is useful Substituent R¹ and R² only present at most once, especially as R¹, and preferably not present at all.

Except for the compounds mentioned in the examples Substances according to the invention are for example the 6- (3-Chloro-benzoyl) - and the 6- (2,6-dichloro-benzoyl) - (6H) - dibenz [c, e] [1,2] called oxaphosphorine-6-oxide, furthermore the 6-benzoyl- (6H) -2- or -4-chloro-, 6- (2- or 3-methyl- benzoyl) - (6H) -2- or -4-chloro-, 6- (2,4- or 2,6- or 3,4- or 3,5-dimethylbenzoyl) - (6H) -2- and -4-chloro, respectively 6- (2,4,6-trimethylbenzoyl) -4-chloro, 6- or 2- 3-chlorobenzoyl) - (6H) -2- and -4-chloro- and the 6- (2,6-dimethoxybenzoyl) - (6H) -2- or -4-chloro-dibenz [c, e] [1,2] oxaphosphorin-6-oxide.

The invention also provides a method for Preparation of the cited 6-acyl- (6H) -dibenz [c, e] [1,2] oxaphosphorine-6-oxide, which is characterized in that 6-alkoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine of general formula II (see formula sheet) with acyl chlorides the general formula

Cl-CO-Ar-R3 (III)

implements, in which R¹, R², R³ and Ar have the abovementioned meaning and R⁴ is alkyl, suitably having 1 to 6 carbon atoms. there become the 6-acyl- (6H) -dibenz [c, e] [1,2] oxaphosphorin-6 oxyde of formula I obtained in good yields.

In the compounds of formula II R⁴ is preferably Methyl or ethyl, but may also be propyl, isopropyl or the various butyl, pentyl and hexyl radicals represent. The radicals R¹ and R² can except methyl and ethyl or methoxy and ethoxy as alkyl the propyl, Isopropyl or one of the different butyl radicals contain.  

The reaction can be in the presence or absence of a Catalyst, such as a tertiary amine, z. B. triethylamine or dimethylaniline, and in a solvent such as Hydrocarbon or hydrocarbon mixture such as Petroleum ether, toluene, cyclohexane, an ether, such as Dibutyl ether or tetrahydrofuran, or other common, towards the reactants inert organic Solvents are carried out. However, it is preferred the reaction without solvent.

The reaction is carried out appropriately so that to a Component the second is gradually added, where Alkyl chloride is split off. It is preferable that To submit benzoyl chloride. The implementation takes place in the Usually at temperatures of 50 to 150 ° C, preferably from 70 to 130 ° C and in particular from 80 to 120 ° C. The Production is generally carried out at atmospheric pressure. However, since alkyl chloride is split off, it may be appropriate be to work at reduced pressure. That's it preferably, at the reaction temperature used apply such pressure that the alkyl chloride in vapor form can be removed and condensed for itself. Thereby the workup of the reaction product is facilitated. The resulting compounds of formula I are for example by crystallization or distillation under reduced pressure, especially in a high vacuum cleaned.

The compounds used as starting materials of general formula II are z. T. known. New are above all the compounds in which R¹ is halogen, especially chlorine. The known can be smooth from the corresponding 6-Chloro- (6H) -dibenz [c, e] [1,2] oxaphosphorines. A synthesis route of these compounds of the general formula II, which is also applicable to the new compounds, is specified in the formula sheet. Leave levels 1 and 2 practice in a drop-in procedure  and sum up like that. The procedure is basically in DE-PS 20 34 887 described. In level 3 will be while tertiary amines, such as triethylamine, used, and it can be worked at room temperature. It's clear it can be seen that this method is very much in practice easy to perform. The required formation of a P-C bond to form an aryl-phosphorus compound runs in a way that compared to the otherwise known Compounds is incomparably easy.

The compounds of the invention show a very good Reactivity as photoinitiators for photopolymerization unsaturated compounds having at least one C-C- Multiple bond and mixtures thereof with each other and with Additives. Such photopolymerizable mixtures, such as they z. B. for the production of moldings such as printing plates and Relief forms used to be included as essential Ingredients at least one binder, at least one low molecular weight polymerizable monomer and at least a photoinitiator.

The photoinitiators of the invention must with the Monomers compatible and in a suitable Developer solvent to be soluble or dispersible washing out the unexposed and crosslinked parts a layer of the photopolymerizable recording compositions to allow for their imagewise exposure.

Suitable photopolymerizable monomers are the customary Compounds and substances with polymerisable C-C- Double bonds, the z. Aryl, carbonyl, amino, Amide, amido, ester, carboxy or cyanide groups, Halogen atoms or C-C double or C-C triple bonds are activated. Examples include vinyl ethers and Vinyl ester, styrene, the various vinyl toluenes, Acrylic and methacrylic acid and their esters with a and / or polyhydric alcohols, their nitriles or amides,  Mono- or diacrylates or methacrylates of oligomers Glycols or acrylic and methacrylic esters of Reaction products of polyhydric alcohols with glycols, such as trimethylolpropane triethoxytriacrylate, maleic and Fumarester and N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole and allyl ester the diallyl phthalate.

The binders may be saturated or unsaturated. Examples which may be mentioned are linear polyamides and especially alcohol-soluble copolyamides, as described in FR-PS 15 20 856 cellulose derivatives, in particular aqueous alkaline washable cellulose derivatives, vinyl alcohol Polymers and polymers and copolymers of vinyl esters saturated aliphatic monocarboxylic acids having 2 to 4 C atoms, such as vinyl acetate or vinyl propionate, with different degrees of saponification, polyurethanes, Polyether urethanes and polyester urethanes, and unsaturated ones Polyester resins, as described below. Also suitable are oligomeric or polymeric epoxy acrylates or methacrylates, manufactured from acrylic or Methacrylic acid and aromatic or aliphatic Diglycidyl ethers, urethane acrylates and methacrylates (e.g. prepared from hydroxyalkyl acrylates or methacrylates and polyisocyanates), as well as polyester acrylates or -methacrylates (eg prepared from hydroxyl-containing saturated polyesters and acrylic or methacrylic acid), Polyether acrylates or methacrylates prepared from diols aliphatic or aromatic nature and acrylic or Methacrylic acid, amine acrylates or methacrylates and Melamine acrylates or methacrylates (eg prepared from Methylolderivaten of amines or melamine and acrylic or methacrylic acid).

Also suitable are elastomeric block copolymers containing at least two thermoplastic non-elastomeric polymer blocks having a glass transition temperature above 25 ° C and between the non-elastomeric polymer blocks an elastomeric polymer block having a glass transition temperature below 10 ° C. Examples which may be mentioned are polystyrene-polyisoprene-polystyrene block copolymers, as described in US Pat. No. 3,265,725. Instead of the styrene components, polymers of homologues and analogues of styrene, such as α- methylstyrene and the various vinyltoluenes can also be used.

Optionally, the photopolymerizable compositions also present as aqueous dispersions or for use to be brought.

The photopolymerizable compositions, their composition for the respective purpose of use familiar to the expert is, in a conventional manner saturated and / or unsaturated polymers and other additives such as Inhibitors against thermal polymerization, paraffin, Pigments, dyes, peroxides, leveling agents, Fillers, matting agents and glass fibers as well Stabilizers against thermal or photochemical degradation be added. Type and amount of additives depend on respective purpose.

The compounds of the invention are generally in a concentration of 0.001 to 20, suitably 0.01 to 15 or 10%, preferably from 0.1 to 5%, based on the weight of the photopolymerizable composition used. You can optionally combine with accelerators become the inhibitory influence of atmospheric oxygen eliminate the photopolymerization. Such accelerator or synergists are mainly tertiary amines such as Methyl diethanolamine, dimethylethanolamine, triethylamine, Triethanolamine, ethyl p-dimethylaminobenzoate, Benzyl dimethylamine, dimethylaminoethyl acrylate, N-methyl N-phenylglycine and analogous, known in the art  Links. To speed up the curing can furthermore aliphatic and / or aromatic Halogen compounds serve as 2-chloromethylnaphthalene, 1-chloro-2-chloromethylnaphthalene, as well as radical generators such as Peroxides and azo compounds.

According to a further advantageous embodiment can the compounds of the invention in combination with other photoinitiators in all weight ratios, Suitably from 0.5: 1 to 30: 1, preferably from 0.8: 1 to 10: 1 and in particular from 1: 1 to 3: 1 are used. Such suitable initiators are, for. B. aromatic ketones and their functional derivatives, such as ketals, z. B. Benzil dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Diethoxyacetophenone, benzophenone and derivatives of Thioxanthone or mixtures of these. The total salary these combinations are generally between 1 and 20%, based on the weight of the total polymerizable mass.

A particular advantage of these photoinitiator combinations is that this is a significant increase in the Curing speed and better hardness of the cured films is achieved. Another advantage of Photoinitiator combinations is that for the production radiation-curable mass resulting costs by the caused by organophosphorus compounds, be significantly reduced.

Another totally unexpected advantage of the aforementioned Combinations of the known and inventive Photoinitiators is that even pigmented systems in Layer thicknesses of well over 100 microns are cured can.

The curing rate can be increased by the addition secondary and / or tertiary amino compounds in addition  increase. Suitable z. B. triethylamine, Benzylmethylamine, benzyldimethylamine or those with aliphatic hydroxyl groups such as diethanolamine, N-methyl diethanolamine, phenyl diethanolamine and the other tertiary amino compounds mentioned above or mixtures thereof.

The photoinitiators of the invention can be used with the be combined in such a way that the corresponding emission range of the UV lamps fully the Absorption range of the initiator combination corresponds (eg 300-420 nm or 200-420 nm).

The recording compositions of the invention exist predominantly, d. H. to more than 50 and preferably to 70 to 100 wt .-% of the photoinitiator-containing mixture of Monomers and binders. The content of this mixture polymeric binder is generally about 45 to 90 and in particular 45 to 65 wt .-%, based on the sum the amounts of monomers and binder.

The processing of the photopolymerizable recording materials to Photopolymerdruckplatten can in the usual way and depends on whether the mass is liquid or is fixed. It is done by imagewise exposure, z. B. with actinic light. Thereafter, for the production of Relief printing plates or photoresists the unexposed Shares of the layer of the recording materials in the usual way mechanically removed or with a suitable Washed out developing solvent and the resulting Molds dried, in some cases still full nachbelichtet.

It is of particular advantage that it is compatible with the recording masses is often possible, even on a pre-exposure the imagewise exposure of layers of these  to dispense with photopolymerizable recording materials, while still working with good exposure times can. An unexpectedly great advantage is further that Layers of the recording compositions according to the invention improved their processing into relief printing forms Relief structures show what z. B. when printing to a significantly improved reproduction of negatives.

As radiation sources for the polymerization of such It is advantageous to use mixtures of triggering light those that light mainly in the absorption area of the send out compounds of the invention, d. H. between 200 or 300 and 450 nm. Particularly suitable are mercury Low-pressure lamps, medium-pressure and high-pressure lamps, and (superactinic) fluorescent tubes or Pulse emitter. The lamps mentioned may optionally be doped.

Preparation Examples 1. 6-Benzoyl- (6H) -dibenzo [c, e] [1,2] oxaphosphorine-6-oxide

56 g (0.399 mol) of benzoyl chloride were added under nitrogen atmosphere heated to 80 to 85 ° C. While stirring were 92 g (0.4 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dripped within 90 minutes. Then the Temperature gradually increased up to 130 ° C. It was held at this temperature until no development of Methyl chloride was more visible. The residue became digested at room temperature with 70 ml of toluene. One received 116 g (90% of theory) of the above compound, after a rapid recrystallization from ethanol had a mp of 134 to 135 ° C.

C₁₉H₁₃O₃P (320)
Calc .: 71.25% C, 4.06% H, 9.69% P;
found: 71.2% C, 4.1% H, 9.5% P.

2. 6- (2-Methyl-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine 6-oxide

61.8 g (0.4 mol) of 2-methylbenzoyl chloride were added Nitrogen atmosphere heated to 80 ° C. While stirring were 92 g (0.4 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine while two dripped at three hours. Then the Temperature gradually increased to 115 ° C. After finished Reaction was added at room temperature 50 ml of acetone. After crystallization, 103 g (77% of Theory) of the abovementioned compound of melting point 102 ° to 104 ° C.

C₂₀H₁₅O₃P (334)
Calc .: 71.86% C, 4.49% H, 9.28% P;
found: 71.8% C, 4.42% H, 9.1% P.

3. 6- (3-Methyl-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine 6-oxide

46.6 g (0.3 mol of 3-methylbenzoyl chloride were added Nitrogen atmosphere heated to 85 ° C. While stirring were 69 g (0.3 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dropwise. Then the temperature gradually increased to 115 ° C increased. After the reaction was at room temperature 50 ml of toluene added. After crystallization, received 85 g (84% of theory) of the above-mentioned compound from Mp 108 to 111 ° C.

C₂₀H₁₅O₃P (334)
Calc .: 71.86% C, 4.49% H, 9.28% P;
Found: 71.9% C, 4.4% H, 9.2% P.

4. 6- (4-Methylbenzoyl) - (6H) -dibenzo [c, e] [1,2] - oxaphosphorin-6-oxide

30.8 g (0.2 mol) of 4-methylbenzoyl chloride were added Nitrogen atmosphere heated to 80 ° C. While stirring were 46 g (0.2 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dropped in one hour. Then the temperature became slowly increased to 110 ° C. After completion of the implementation The residue crystallized slowly at room temperature out. This gave 60 g (90% of theory) of the above  A compound which after recrystallization from toluene Fp. Of 124 to 125 ° C had.

C₂₀H₁₅O₃P (334)
Calc .: 71.86% C, 4.49% H, 9.28% P;
found: 71.0% C, 4.6% H, 9.0% P.

5. 6- (4-tert-butyl-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

39.2 g (0.2 mol) of 4-tert-butyl-benzoyl were under Nitrogen atmosphere heated to 80 ° C. While stirring were 46 g (0.2 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dropwise. The temperature then gradually increased to 120 ° C elevated. After the reaction was 45 ml of toluene added. At room temperature, the product crystallized. This gave 52 g (70% of theory) of the above Connection with a mp 151-155 ° C.

C₂₃H₂₁O₃P (376)
Calc .: 73.40% C, 5.59% H, 8.25% P;
found: 73.4% C, 5.6% H, 8.1% P.

6. 6- (2,4-Dimethylbenzoyl) - (6H) -dibenzo [c, e] [1,2] - oxaphosphorin-6-oxide

33.7 g (0.2 mol) of 2,4-dimethylbenzoyl chloride were added Nitrogen atmosphere heated to 80 ° C. While stirring were 46 g (0.2 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dropwise. The approach started already too crystallize. As a result, the temperature slowly rose 135 ° C with the proviso that at 90 ° C toluene as Diluent was added. From the crystals received after trituration with toluene 5 g (83% of theory) the above-mentioned compound of mp. 166 ° C.

C₂₁H₁₇O₃P (348)
Calc .: 72.41% C, 4.89% H, 8.91% P;
Found: 72.3% C, 4.7% H, 8.8% P.

7. 6- (2,6-dimethylbenzoyl) - (6H) -dibenzo [c, e] [1,2] - oxaphosphorin-6-oxide

16.85 g (0.1 mol) of 2,6-dimethylbenzoyl chloride were under Nitrogen atmosphere heated to 80 ° C. While stirring were  23 g (0.1 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorin dropwise. The temperature slowed to 122 ° C elevated. It was kept at this temperature until no Escape of methyl chloride was more evident. To on cooling, 30 ml of toluene were added. After this Crystallization gave 22.5 g (65% of theory) the above-mentioned compound having a melting point of 128 to Had 130 ° C.

C₂₁H₁₇O₃P (348)
Calc .: 72.41% C, 4.89% H, 8.91% P;
Found: 72.3% C, 4.7% H, 8.8% P.

8. 6- (3,4-Dimethyl-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

50.6 g (0.3 mol) of 3,4-dimethylbenzoyl chloride were under Nitrogen atmosphere heated to 80 ° C. While stirring were 69 g (0.3 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dropwise. In the course of dripping, the Crystallization, the temperature was therefore at 100 ° C. elevated; at the same time an additional 100 ml of toluene dropwise. After completion of the dropwise addition, it returned to reflux heated. After completion of the implementation and after the Crystallization gave 87 g (83% of theory) of above-mentioned compound having a melting point of 160 to 162 ° C would have.

C₂₁H₁₇O₃P (348)
Calc .: 72.41% C, 4.89% H, 8.91% P;
found: 72.46% C, 4.8% H, 8.8% P.

9. 6- (3,5-Dimethyl-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

67.4 g (0.4 mol) of 3,5-dimethylbenzoyl chloride were under Nitrogen atmosphere heated to 80 ° C. While stirring were 92 g (0.4 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dripped for two hours. The temperature was here gradually increased to 115 ° C. After completion of the reaction  50 ml of acetone were added at room temperature. To the crystallization gave 113 g (81% of theory) the above-mentioned compound of mp. 120 to 124 ° C.

C₂₁H₁₇O₃P (348)
Calc .: 72.41% C, 4.89% H, 8.91% P;
found: 72.3% C, 4.8% H, 8.9% P.

10. 6- (2,4,6-trimethylbenzoyl) - (6H) -dibenzo [c, e] [1,2] - oxaphosphorin-6-oxide

18.25 g (0.1 mol) of 2,4,6-trimethylbenzoyl chloride heated to 85 ° C under a nitrogen atmosphere. While stirring were 23 g (0.1 mol) of 6-methoxy- (6H) -dibenz [c, e] [1,2] - dripped oxaphosphorin. The temperature became slow increased to 105 ° C. It was at this temperature held until no more escape of methyl chloride was recognized. After completion of the reaction was toluene added. After crystallization, 27 g (75% of theory) of the above compound of mp. 109 ° C.

C₂₂H₁₅O₃P (362)
Calc .: 72.93% C, 5.25% H, 8.56% P;
found: 72.7% C, 5.3% H, 8.3% P.

11. 6- (3-Methoxy-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

42.6 g (0.25 mol) of 3-Methoxybenzoylchlorid were under Nitrogen atmosphere heated to 70 ° C. While stirring were 57.5 g (0.25 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dropwise. Then the temperature slowly rose Increased 120 ° C. It was kept at this temperature until no more leakage of methyl chloride was seen. After cooling to 90 ° C, 90 ml of toluene were added. After crystallization gave 65 g (75% of Theory) of the above-mentioned compound, mp. 116-118 ° C.

C₂₀H₁₅O₄P (350)
Calc .: 68.57% C, 4.29% H, 8.86% P;
Found: 68.5% C, 4.3% H, 8.7% P.

12. 6- (2,4-Dimethoxy-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

35.1 g (0.175 mol) of 2,4-dimethoxybenzoyl chloride were added Nitrogen atmosphere heated to 70 ° C. While stirring were 40.3 g (0.175 mol) of 6-methoxy- (6H) -dibenz [c, e] [1,2] - Oxaphosphorin added dropwise during 2 hours. Then it became the temperature slowly increased to 110 ° C. It was at this Temperature maintained until no escape of methyl chloride could be seen more. After cooling to 60 ° C were Added 70 ml of toluene. After crystallization, received 50 g (75% of theory) of the abovementioned compound from mp. 112 to 115 ° C.

C₂₁H₁₇O₅P (380)
Calc .: 66.32% C, 4.47% H, 8.16% P;
Found: 66.3% C, 4.2% H, 8.0% P.

13. 6- (3,5-Dimethoxy-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

35.1 g (0.175 mol) of 3,5-dimethoxy-benzoyl were under Nitrogen atmosphere heated to 80 ° C. While stirring were 40.3 g (0.175 mol) of 6-methoxy- (6H) -dibenz [c, e] [1,2] - Oxaphosphorin added dropwise for one hour. simultaneously the temperature was gradually increased to 115 ° C. To After the reaction was added at 80 ° C 60 ml of toluene. After crystallization, 49 g (74% of theory) were obtained. the above compound of mp. 140 to 142 ° C.

C₂₁H₁₇O₅P (380)
Calc .: 66.32% C, 4.47% H, 8.16% P;
Found: 66.2% C, 4.5% H, 8.1% P.

14. 6- (2,6-Dimethoxy-benzoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

60.1 g (0.3 mol) of 2,6-dimethylbenzoyl chloride were added Nitrogen atmosphere heated to 85 ° C. Then 69 g (0.3 mol) 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorin added dropwise with stirring. Then the temperature became slow increased to 125 ° C. After completion of the reaction and cooling 150 ml of toluene were added. After crystallization  was obtained 99 g (87% of theory) of the above Connection of mp. 96 to 98 ° C.

C₂₁H₁₇O₅P (380)
Calc .: 66.32% C, 4.47% H, 8.16% P;
Found: 66.1% C, 4.4% H, 8.2% P.

15. 6- (3,4,5-trimethoxybenzoyl) - (6H) -dibenzo [c, e] [1,2] - oxaphosphorin-6-oxide

35.6 g (0.154 mol) of 3,4,5-trimethoxybenzoyl chloride heated to 100 ° C under nitrogen atmosphere. Then were 35.5 g (0.154 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] - Oxaphosphorin added dropwise with stirring and the temperature then increased to 115 ° C. After completion of the reaction were 70 ml of toluene was added at 90 ° C and then cooled further. After crystallization, 44 g (70% of theory) were obtained. the above-mentioned compound of mp. 147-149 ° C.

C₂₂H₁₉O₆P (410)
Calc .: 64.39% C, 4.63% H, 7.56% P;
found: 64.2% C, 4.4% H, 7.4% P.

16. 6- (2-Chlorobenzoyl) - (6H) -dibenzo [c, e] [1,2] oxaphosphorine 6-oxide

52.5 g (0.3 mol) of 2-chlorobenzoyl chloride were under Nitrogen atmosphere heated to 80 ° C. Well were under Stir 69 g (0.3 mol) of 6-methoxy- (6H) -dibenz [c, e] [1,2] - Oxaphosphorin added dropwise. During the dripping was on Cooled to 60 ° C, then the temperature at 60-70 ° C left. After completion of the reaction, 40 ml of toluene at 45 ° C. added. This gave 92 g (89% of theory) of above-mentioned compound of mp. 108 to 110 ° C.

C₁₉H₁₂ClO₃P (354.5)
Calc .: 64.32% C, 3.39% H, 10.1% Cl, 8.75% P;
Found: 64.2% C, 3.4% H, 9.9% Cl, 8.6% P.

17. 6- (4-chlorobenzoyl) - (6H) -dibenzo [c, e] [1,2] oxaphosphorine 6-oxide

35 g (0.2 mol) of 4-chlorobenzoyl chloride were added Nitrogen atmosphere heated to 90 to 100 ° C. Well were 46 g of 6-methoxy- (6H) -dibenz [c, e] [1,2] - with stirring dripped oxaphosphorin. The internal temperature then became  gradually increased to 130 ° C. After completion of the implementation was digested with 50 ml of toluene. This gave 60 g (85% of Theory) of the abovementioned substance, mp. 125-131 ° C.

C₁₉H₁₂ClO₃P (354.5)
Calc .: 64.32% C, 3.39% H, 10.1% Cl, 8.75% P;
Found: 64.1% C, 3.3% H, 9.7% Cl, 8.4% P.

18. 6- (2-Naphthoyl) - (6H) -dibenzo [c, e] [1,2] oxaphosphorine 6-oxide

50 g (0.262 mol) of 2-naphthoyl chloride were under Nitrogen atmosphere heated to 80 ° C. While stirring were 60.3 g (0.262 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] - Oxaphosphorin dripped in two hours. Subsequently The internal temperature was gradually raised to 125 ° C. After completion of the reaction, 110 ml of toluene was added. After crystallization, 87 g (90% of theory) were obtained. the above-mentioned compound of mp. 151 to 153 ° C.

C₂₃H₁₅O₃P (370)
Calc .: 74.59% C, 4.05% H, 8.38% P;
Found: 74.5% C, 4.0% H, 8.2% P.

19. 6- (1-Naphthoyl) - (6H) -dibenzo [c, e] [1,2] oxaphosphorine 6-oxide

50 g (0.262 mol) of 1-naphthoyl chloride were under Nitrogen atmosphere heated to 80 to 85 ° C. While stirring were 60.3 g (0.262 mol) of 6-methoxy- (6H) -dibenz [c, e] [1,2] - dripped oxaphosphorin. The reaction was exothermic. The temperature was then gradually increased to 125 ° C. After completion of the reaction at 40 ° C 90 ml of toluene added. After crystallization, 77 g (80% of theory) of the above compound from mp. 149 to 151 ° C.

C₂₃H₁₅O₃P (370)
Calc .: 74.59% C, 4.05% H, 8.38% P;
found: 74.4% C, 4.0% H, 8.1% P.

20. 6- (1- (2-Methylnaphthoyl)) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine-6-oxide

96.7 g (0.473 mol) of 1- (2-methylnaphthoyl) chloride were added Nitrogen atmosphere heated to 85 ° C. While stirring were  109 g (0.473 mol) of 6-methoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorine dripped in 2 to 3 hours. Subsequently The internal temperature was gradually raised to 120 ° C. To After completion of the reaction, after cooling to 50 ° C, 100 ml Added toluene. After crystallization, 142 g (78% of theory) of the above compound, according to Recrystallization from toluene had a mp of 155-156 ° C.

C₂₄H₁₇O₃P (384)
Calc .: 75.00% C, 4.43% H, 8.07% P;
Found: 74.9% C, 4.4% H, 8.0% P.

21. 6- (4-Methyl-benzoyl) - (6H) -2-chloro-dibenz [c, e] [1,2] - oxaphosphorin-6-oxide a) Preparation of 6-methoxy- (6H) -2-chlorodibenz [c, e] [1,2] - oxaphosphorins over three stages 1st stage: dichloro (2-phenyl-4-chloro-phenoxy) -phosphine

79.5 g (0.389 mol) of 2-phenyl-4-chloro-phenol were with 65.7 g (0.478 mol) of phosphorus trichloride slowly up to Heated to 150 ° C. At the same time hydrogen chloride escaped. After the reaction was distilled at 0.027 kPa. At a temperature of 145 to 146 ° C, 80 g (67%) Theory, based on 2-phenyl-4-chloro phenol) of the abovementioned substance (see formula sheet, Formula V with R¹ = 2-chloro and R² = H)

C₁₂H₈Cl₃OP (305.5)
Calc .: 47.14% C, 2.62% H, 34.86% Cl, 10.15% P;
found: 47.0% C, 2.6% H, 34.3% Cl, 9.6% P.

2nd Step: 6-Chloro- (6H) -2-chloro-dibenz [c, e] [1,2] -oxaphosphorine

165 g (0.54 mol) of dichloro (2-phenyl-4-chloro-phenoxy) -phosphine and 1.1 g of anhydrous zinc chloride were heated to 150 ° C; Thereafter, the temperature gradually increased to 250 ° C elevated. It was kept at this temperature until no Hydrogen chloride gas escaped more. After completion of the implementation was distilled at 0.027 kPa. At 160 ° C went 105 g (72.5% of theory) of the above substance of  Formula VI (see formula sheet with R¹ = 2-chloro and R² = Hydrogen) from the solidification point 40.5 ° C over.

C₁₂H₇Cl₂OP (269)
Calc .: 53.53% C, 2.60% H, 26.39% Cl, 11.52% P;
Found: 53.3% C, 2.9% H, 25.5% Cl, 11.5% P.

3rd stage: 6-methoxy- (6H) -2-chloro-dibenz [c, e] [1,2] - oxaphosphorin

94 g (0.349 mol) of 6-chloro (6H) -2-chloro-dibenz [c, e] [1,2] - Oxaphosphorin were dissolved at 70 ° C in 40 ml of toluene. This solution was added from a heated dropping funnel a mixture of 11.2 g (0.349 mol) of abs. Methanol, 35.4 g (0.349 mol) of triethylamine and 150 ml of abs. Toluene at 20 ° C under cooling within 90 minutes under lively Added dropwise. It was still at this temperature Stirred for 4 hours; then was from the triethylamine hydrochloride filtered off with suction and washed with toluene. The filtrate was freed from toluene in a vacuum of the water jet pump and then distilled at 0.027 kPa. At 170 ° C went 72 g (78% of theory) of the above-mentioned compound of Formula II (see formula sheet with R¹ = 2-chloro, R² = hydrogen and R⁴ = methyl) of mp. 46 to 49 ° C over.

C₁₃H₁₀ClO₂P (264.5)
Calcd .: 58.98% C, 3.78% H, 13.42% Cl, 11.72% P;
Found: 58.9% C, 3.8% H, 13.3% Cl, 11.4% P.

b) Inventive implementation

17.8 g (0.115 mol) of 4-methylbenzoyl chloride were added Nitrogen atmosphere heated to 100 ° C. While stirring were 30.4 g (0.115 mol) of 6-methoxy- (6H) -2-chloro dibenz [c, e] [1,2] oxaphosphorin from a heated Dropping funnel added dropwise. The temperature became gradual increased to 115 ° C. It was kept at this temperature, until no more methyl chloride escaped. The residue became after completion of the reaction with 15-20 ml of toluene digested. you received 36 g (85% of theory) of the above compound from mp 144 to 148 ° C.

C₂₀H₁₄ClO₃P (368.5)
Calc .: 65.13% C, 3.80% H, 9.63% Cl, 8.41% P;
found: 65.3% C, 3.9% H, 9.1% Cl, 7.6% P.

22. 6- (2,4,6-trimethylbenzoyl) - (6H) -2-chloro-dibenzene [C, e] [1,2] oxaphosphorin-6-oxide

22.8 g (0.125 mol) of 2,4,6-trimethylbenzoyl chloride heated to 100 ° C under a nitrogen atmosphere. While stirring 33.1 g (0.125 mol) of 6-methoxy- (6H) -2-chloro dibenz [c, e] [1,2] oxaphosphorin dripped in. The temperature was slowly increased to 120 ° C. It was at this Temperature maintained until no more methyl chloride escaped. The residue was digested after cooling with acetone. This gave 30 g (60% of theory) of the above Connection of mp. 145 to 146 ° C.

C₂₂H₁₈ClO₃P (396.5)
Calc .: 66.58% C, 4.54% H, 8.95% Cl, 7.82% P;
found: 66.6% C, 4.4% H, 8.8% Cl, 7.6% P.

23. 6- (4-Chloro-benzoyl) - (6H) -2-chloro-dibenz [c, e] [1,2] - oxaphosphorin-6-oxide

16.1 g (0.092 mol) of 4-chlorobenzoyl chloride were added Nitrogen atmosphere heated to 90 ° C. While stirring were 24.4 g (0.092 mol) of 6-methoxy- (6H) -2-chloro-dibenz [c, e] [1,2] - Oxaphosphorin added dropwise from a heated dropping funnel. The temperature was gradually raised to 140 ° C. It was held at this temperature until no more methyl chloride escaped. The residue, after cooling with 20 ml Toluene digested. This gave 27 g (75% of theory) of above-mentioned compound of mp. 183-185 ° C.

C₁₉H₁₁Cl₂O₃P (389)
Calcd .: 58.61% C, 2.83% H, 7.97% P;
Found: 58.6% C, 2.8% H, 7.6% P.

applications

24. A solution of 91.2 g of a styrene-isoprene-styrene Triblock copolymers with 15% styrene content, 8 g 1,6-hexanediol diacrylate, 0.5 g of 6- (2,4,6-trimethyl-benzoyl- (6H) -dibenz [c, e] [1,2] oxaphosphorine 6-oxide and 0.3 g of 2,6-di-tert. Butyl-4-methylphenol in 100 g toluene was added to a 125 μm thick, biaxially stretched and heat-set polyester film  (Polyethylene terephthalate) using a Metal frame poured into a 6 mm thick layer. To Evaporation of the toluene was on the free surface of the 3 mm thick photopolymer layer one with an adhesive layer provided 125 microns thick, biaxially stretched and heat-set Polyester film (polyethylene terephthalate) launched and the Multilayer element in a platen press at 110 ° C below Use of 2.8 mm thick spacers pressed for 5 minutes. After stripping the uncoated polyester film was the photopolymer layer with a commercial UV Flat exposure unit (emitted wavelength range 320-400 nm; Intensity of the UV scattered light 14 mW / cm²) 220 seconds through the remaining polyester film and then 15 minutes imagewise exposed from the free side of the film. To washing out the unexposed image areas with Tetrachloroethane became a high-pressure elastic mold good relief formation (relief depth 1.0 mm) and a hardness obtained from 63 ° Shore-A.

25. 145.5 of a copolymeric, internally plasticized Polyvinyl alcohol (®Mowiol 04 / Ml Hoechst AG) were dissolved by stirring in 147 g of water at 90 ° C. After cooling 90 g of 2-hydroxyethyl methacrylate, with stirring, were heated to 70 ° C., 10 g of trimethylolpropane triacrylate, 5 g of 6- (2,4,6-trimethyl- benzoyl) - (6H) -dibenzo [c, e] [1,2] oxaphosphorine-6-oxide and 1 g of 2,6-di-tert-butyl-4-methylphenol added. The homogeneous viscous solution was applied to a 125 μm thick polyester film (Polyethylene terephthalate) layered so applied that after drying for 48 hours at room temperature, approx. 1.2 mm thick, non-adhesive photosensitive layer resulted. On the free layer surface was a with a polyurethane adhesive according to DE-OS 15 97 515 versehenes 0.3 mm thick aluminum sheet and the multilayer element in a plate press at 120 ° C using of 0.6 mm thick spacers pressed for 5 minutes. To the stripping of the uncoated polyester film was the  Photosensitive layer imagewise for 5 minutes with a commercially available UV flat imagesetter (emitted wave range 320 to 400 nm; Intensity of the UV scattered light 10 mW / cm²) exposed. After washing out the unexposed Image areas with warm water became a high-pressure mold with good relief formation and a hardness of 90 ° Shore-A receive.

26. Photopolymer flexographic printing plates

A solution of 91 g of a styrene-isoprene-styrene Triblock copolymers with 15% styrene content, 8 g Hexanediol-1,6-diacrylate, 0.3 g of 2,6-di-tert.-butyl-4 methylphenol and 1 g of 6- (2,4,6-trimethylbenzoyl) - (6H) -dibenzene [c, e] [1,2] oxaphosphorine 6-oxide (experiment A) or 1 g 2,4,6- Trimethylbenzoyl-diphenylphosphanoxid (Comparative Experiment V 26.1) in 100 g of toluene, was added to a 125 μm thick biaxially stretched and heat-set polyester film (Polyethylene terephthalate) using a metal frame poured into a 6 mm thick layer. After evaporation of the Toluene was the 3 mm thick photopolymer layer between two 125 μm thick, biaxially stretched and heat-set Polyester films (polyethylene terephthalate) using of 2.8 mm thick spacers in a platen press Pressed at 110 ° C for 5 minutes. After stripping the Polyester films became the photopolymer layer with a commercially available UV flat imagesetter (emitted Wavelength range 320-400 nm; Intensity of UV scattered light 14 mW / cm 2) from each side for 30 minutes exposed. The hardness was 65 ° Shore A for test A each and V 26.1, the modulus of elasticity (150 mm long and 15 mm wide sample strips, clamping length 100 mm) 6.5 N / mm² at Experiment A and 5.2 N / mm² at V 26.1 (mean value of 5 measurements, standard deviation ± 0.3 N / mm²). The determination of abrasion according to DIN 53 516 gave for experiment A 170.0 ± 5.4 mg and for V 26.1 213 ± 6.3 mg (each mean and Standard deviation of 5 measurements).  

With the compound of the invention are thus at same Shore A hardness, a larger modulus of elasticity and a clearly greater abrasion resistance compared to the Obtained according to V 26.1. The abrasion resistance is a measure of the expected shelf life corresponding printing plates during the printing process.

27th and 28th photopolymer planographic printing plates

27. A solution of 3.92 g of a copolymer Methyl methacrylate and methacrylic acid with the middle Molecular weight 35,000 and acid number 86, 3.92 g Trimethylolpropane triacrylate, 0.107 g of 6- (1-naphthoyl) - (6H) - dibenz [c, e] [1,2] oxaphosphorine 6-oxide, 0,084 g of the Azo dye from 2,4-dinitro-6-chloro-benzenediazonium salt and 2-methoxy-5-acetylamino-N-cyanoethyl-N-hydroxyethylaniline and 0.07 g of 4-dimethylamino-4'-methyldibenzalacetone in 51.4 ml of 2-butane was stirred, filtered and on a Plate spinner on electrolytically roughened and Anodized aluminum spun on. The plates were Dried at 90 ° C for 2 minutes; the coating weight was 3.5 g / m². After application of a cover layer, the Photopolymer layer under a combined negative original, consisting of a halftone step wedge, line elements and 60s and 120s dot matrix elements with an 8kW Xenon copier exposed. The exposed plate was 1 minute with a developer of 3 parts by weight Sodium metasilicate × 9 H₂O, 0.03 parts by weight Coconut fatty amine-ethylene oxide reaction product and 96.97 Parts by weight of demineralized water developed. Then was fixed with 1% phosphoric acid and finally dyed with black grease. there has been a Planographic printing plate with good resolution of image areas receive.  

28. Example 27 was modified in such a way that instead 0.107 g of 6- (1-naphthoyl) - (6H) -dibenzo [c, e] [1,2] -oxaphosphorine 6-oxide now yields 0.21 g of 6- (1- (2-methylnaphthoyl)) - (6H) -dibenz [c, e] [1,2] -oxaphosphorine 6-oxide used and added to the of 4-dimethylamino-4'-methyldibenzalacetone was omitted. It also gave a planographic printing plate with good resolution the picture places.

29. Dry photoresist plate

A solution of 27.5 g of a terpolymer n-hexyl methacrylate, methacrylic acid and styrene (60: 30: 10) with an average molecular weight of 35,000 and the Acid number 195, 18.3 g trimethylolpropane triacrylate, 0.92 g 6- (1- (2-Methylnaphthoyl)) - (6H) -dibenz [c, e] [1,2] -oxaphosphorin- 6-oxide and 0.05 g of the azo dye from 2,4-dinitro-6-chloro benzenediazonium salt and 2-methoxy-5-acetylamino-N-cyanoethyl N-hydroxyethylaniline in 92.8 ml of butanone and 2 ml of ethanol was stretched on a biaxially and heat-set Polyethylene terephthalate film thickness 25 microns so spun, that after drying at 110 ° C, a layer thickness of 35 microns was obtained. A dry resist film was obtained with a commercial laminator at 120 ° C on a laminated with 35 μm thick copper foil Laminate laminated and 90 seconds with an 8 kW Xenon copier was exposed imagewise. As template served a line template with line widths and distances down to 80 microns. After exposure, the polyester film became peeled off and the layer by spraying with a 1% sodium carbonate solution developed within 2 minutes. The plate was then poured into a 15% ammonium peroxydisulfate solution dipped from 50 ° C. The unexposed parts of the Layer corresponding copper surfaces were etched away, and the remaining exposed layer was trichloroethane removed, after which a perfect negative copper image of original image template was obtained.  

30.-47. Pigmented UV thick-film casting compounds

There were various pigmented Dickschichtvergußmassen based on a combination of epoxy acrylates following Composition examined:

a) Epoxy acrylate prepolymer 77.5 parts by weight b) Tripropylene glycol diacrylate 2.5 parts by weight c) dipropylene glycol diacrylate 20.0 parts by weight d) pigment 0.1-5 parts by weight e) photoinitiator mixture 5.0 parts by weight

The epoxy-acrylate prepolymer component consisted of a Combination of 4 different types, namely ®Roskydal LS 2812 (acid number at most 5, OH number at most 300, Viscosity 300 Pa · s) from Bayer AG, Leverkusen, Germany, ®Setacure AP 569 (acid number at most 5, viscosity 100-150 Pa · s) from the company Synthese-Chemie, Bergen op Zoom, Netherlands, ®Ebecryl 600 (aromatic bisphenol A Acrylate, acid number at most 8, molecular weight 500, Viscosity 4000-8000 mPa · s) and Ebecryl 170 PA, both from the company UCB in Drogenbos, Belgium, in weight ratio from 40: 20: 10: 7.5. The first three types are neutral Epoxy acrylate prepolymers. The Ebecryl 170 PA is a carboxyl-containing prepolymer. As pigments were various products such as ®heliogen blue (BASF AG, Ludwigshafen, Germany), carbon black, titanium dioxide, iron oxide, ®Hostaperm Yellow, Hostaperm Scarlet GO used. The Photoinitiator mixture consisted of equal parts of 2-hydroxy 2-methylpropiophenone and an acylphosphine oxide, and that the individual, in Examples 2 to 4, 6, 8 to 17, 19 and 21 to 23 listed substances.

The pigmented Dickschichtvergußmassen were on a Aluminum substrate in layer thicknesses of 100-5000 μm applied. The curing took place under a Hg High pressure lamp (80 W / cm) depending on layer thickness and pigment in 5-10 minutes. It created potting compounds with brilliant Surface, good adhesion and high chemical resistance.  

48. Highly pigmented UV topcoats

In the formulation mentioned in Examples 30-47, the Pigment content can be increased to 30-60%. The hereby resulting coatings were with layer thicknesses of 5-100 microns applied and on a UV pass line with Hg high-pressure lamps (2 × 20 cm-100 W / cm) at one Throughput speed between 1 and 10 m / min, the adjusted depending on the layer thickness and the type of pigment was cured. The application was carried out by doctoring or rollers. By adding solvents (setting on about 70% solids content), the paint material could also be processed by injection molding, z. For manufacturing of coatings on glass, polyester films, various Metal substrates, etc.

49.-66. Highly pigmented UV coatings for pad printing or screen printing process

There were pigmented paints for pad printing or Siedruckanwendung consisting of

a) Epoxy acrylate prepolymer (Roskydal LS 2812) 35.0 parts by weight b) hexanediol acrylate 16.0 parts by weight c) titanium dioxide 50.0 parts by weight d) photoinitiator combination (as in Examples 30 to 47) 5.0 parts by weight

examined. The paint films were in a UV pass line at 1-15 m / min throughput, which varies according to the Layer thickness and the type of pigment has been adjusted, cured by 2 Hg high-pressure lamps (2 × 20 cm-100 W / cm).

The application was carried out z. B. for printing polyester films Polycarbonate, various metal substrates, etc.

67th-84th Highly pigmented and clear UV matt coatings

There were varnishes based on a slightly different combination of epoxy acrylates when compared to Examples 30 to 47 was based. The paint system consisted of  

a) Epoxy acrylate prepolymer 72.5 parts by weight b) Tripropylene glycol diacrylate 7.5 parts by weight c) dipropylene glycol diacrylate 20.0 parts by weight d) Mattier 5.0 parts by weight e) pigment (as in Examples 30-47) 10.0 parts by weight f) photoinitiator combination (as in Examples 30 to 47) 5.0 parts by weight

The epoxy-acrylate prepolymer component consisted of a Combination of Roskydal LS 2812, Setacure AP 569, Ebecryl 170 PA and Ebecryl 600 in the weight ratio of 40: 20: 10: 2.5. The matte was ®Pergopak M, a Urea-formaldehyde condensation product, the Fa. Martinswerk GmbH, Bergheim / Erft, Germany.

With this paint system were glass surfaces and Polyester films coated and on a UV pass line at a flow rate of 5-10 m / min, again depending on the type of pigment and the layer thickness Hardened (2 Hg high-pressure lamps 20 cm in length, 100 W / cm).

85th-102nd UV fillers

There were highly filled, UV-curable, styrene-free Fillers, the z. B. suitable for car repair are examined on the basis of the following recipe:

a) Epoxy acrylate prepolymer 36.25 parts by weight b) Tripropylene glycol diacrylate 3.75 parts by weight c) dipropylene glycol diacrylate 10.0 parts by weight d) Active Silica (®Aerosil 300) 1.0 parts by weight e) iron oxide (®Bayferrox 316) 0.07 parts by weight f) titanium dioxide 2.1 parts by weight g) Talc (Finntalc M 40) 38.5 parts by weight h) photoinitiator combination (as in Examples 30 to 47) 4.5 parts by weight

The epoxy-acrylate prepolymer component consisted of Roskydal LS 2812, Setacure AP 570 (acid number at most 4, Viscosity 80-120 Pa · s), Ebecryl 170 PA and Ebecryl 600 im Weight ratio of 20: 10: 5: 1.25.  

The masses were applied to metal and mixed with Hg High pressure lamps (400 W) hardened for 10-15 min. After the UV Curing, the coatings can be both wet and be ground dry.

103. UV clearcoats

In the formulation mentioned in Examples 85 to 102 were the pigments (components d) to g)) are omitted and so on Clearcoats produced. One observed a clear increase the curing speed and the hardness of the coatings.

104.-107th Pigmented lacquers for wood materials and furniture

A mixture of the photon initiators 6- (2,4-6- Trimethyl-benzoyl) - (6H) -dibenz [c, e] [1,2] oxaphosphorin-6- oxide (Example 10) and 2-hydroxy-2-methyl-1-phenylpropan-1-one tested in various synthetic resins. This was the product Example 10 at the hot water bath (80-90 ° C) in the 2-hydroxy-2-methyl-1-phenylpropan-1-one to a 50% Solution solved. This solution remained during the Processing time of a few days at 20-25 ° C clear.

Then, trial paints of the following components manufactured:

resin 76.5 parts by weight ®Bayertitan RKB 3 (pigment) 9.0 parts by weight tripropylene 10.0 parts by weight initiator mixture 4.5 parts by weight

The synthetic resins used were those of Vianova Kunstharz AG, Werndorf near Graz, Austria, in
Example 104 an epoxy acrylate (Vectar VTE 5940),
Example 105 an epoxy acrylate (Vectra VTE 5286),
Example 106 a melamine acrylate (Vectar VTE 5956),
Example 107 an unsaturated polyester (Viapal UP 586 E).

Viaktin VTE 5940 is a UV-curable, presensitized acrylic-modified epoxy resin, 80% in 1,6-hexanediol diacrylate, the dynamic viscosity / 25 ° C of 7000- 11 000 mPa · s, the color number according to DIN 6162 under 7 and the Acid number according to DIN 53 402 under 17. Viactin VTE 5286 is a electron beam curable, acrylic modified epoxy resin, 80% in hexanediol-1,6-diacrylate, the same ratios has as Viaktin VTE 5940. Viaktin VTE 5956 is a non-UV presensitized, 100% melamine acrylate dynamic viscosity / 25 ° C of 400-2000 mPa · s and the Color number according to DIN 6162 of at most 1. Viapal UP 586 U is a photopolymerizable unsaturated Glossy polyester resin, 67% in styrene with the dynamic Viscosity / 20 ° C of 750-1000 mPa · s, the color number after DIN 6162 under 2 and the acid number according to DIN 53 402 under 30.

The paints were treated with a hand-scraper

• a) on glass to layer thicknesses of 30 microns and 60 microns and
• (b) for the examination of the Erichsentiefung on original Erichsen sheets to layer thicknesses of 30 microns and 60 microns

reared. Curing was carried out by irradiation with a UV high pressure lamp (lamp power 80 watts / cm) at one Feed rate of 0.5 m / min.

The films were then on the pendulum damping after Persoz according to the French standard NFT 30016, the Erichsentiefung tested to DIN 53 156 and chemical resistance. To In the latter test they were each 5 minutes a) one Mixture of equal parts by weight of ethanol and water, b) acetone, c) methyl ethyl ketone (MEK) and d) Parts by weight of isopropanol and water and for 30 minutes Exposed to water. The results are in the following table compiled. It can be seen that a good cure took place.  

Results (measured data)

formula sheet

Claims (11)

1. 6-acyl- (6H) -dibenzo [c, e] [1,2] oxaphosphorin-6-oxide of the formula I wherein each of R¹, R² and R³ may be mono- or polysubstituted, and R¹, R² and R³ are halogen of atomic number of 9 to 35, alkyl or alkoxy each of 1 to 6 carbon atoms and Ar is an aromatic hydrocarbon group of 6 to 10 carbon atoms mean. 2. Compounds according to claim 1, characterized by at least one of the features that

• a) at least one of R¹, R² and R³ is chlorine, preferably R¹, R² and R³ together contain at most two chlorine atoms, at least one of which represents R³,
• b) alkyl or alkoxy groups each contain 1 to 4 carbon atoms, preferably alkyl being methyl or ethyl and alkoxy being methoxy,
• c) they contain only at most one radical R¹ and R² and preferably no radicals R¹ and R², and
• d) they contain at least one radical R³, preferably in the form of one or two ortho radicals and optionally also a radical in the para position.

3. Compounds according to claim 1 or 2, characterized characterized in that Ar represents the benzene ring.   4. A process for the preparation of compounds according to one or more of claims 1 to 3, characterized in that a compound of formula II with an acyl chloride of formula Cl-CO-Ar-R³ (III), wherein R¹, R², R³ and Ar have the meaning given in claims 1 to 3 and R⁴ alkyl, suitably having 1 to 6 C-atoms and preferably methyl or Ethyl, means. 5. The method according to claim 4, characterized in that at temperatures of 50 to 150 ° C, preferably from 70 to 130 ° C and in particular from 80 to 120 ° C works. 6. Use of compounds according to one or more of claims 1 to 3 or those according to the method obtained according to claim 4 or 5, as Photoinitiators in polymerizable compositions. 7. Embodiment according to claim 6, characterized that the compounds are present in an amount of 0.001 to 20, suitably from 0.01 to 15 and preferably from 0.1 to 5%, based on the weight of the photopolymerizable composition, are present. 8. Embodiment according to claim 7 or 8, characterized characterized in that the polymerizable compositions in the form of radiation-curable coatings, in particular Clearcoats or pigmented paints or printing inks,  or potting, filling or sealing compounds are present, the compounds of claim 1 in a concentration from 0.001 to 20, preferably from 0.01 to 10 wt .-% contain. 9. Embodiment according to claim 7, 8 or 9, characterized characterized in that the compounds according to claim 1 in combination with other photoinitiators, in particular aromatic ketones and / or thioxanthone derivatives be used, appropriate in the weight ratio of 0.5: 1 to 30: 1, preferably in the 0.8: 1 to 10: 1 and in particular from 1: 1 to 3: 1, the total content of Photoinitiators suitably between 1 and 20%, based on the weight of the total polymerizable mass is. 10. Embodiment according to claim 9, characterized characterized in that at least one accelerator secondary and / or tertiary amino compound co-used becomes. 11. 6-Alkoxy- (6H) -dibenzo [c, e] [1,2] oxaphosphorines of the formula II wherein R¹ and R² have the meaning given in claims 1 to 3 and R⁴ is alkyl having 1 to 6 C atoms, but wherein at least one R¹ is halogen.