DK171353B1 - Acylphosphine oxide compounds for use as photoinitiators - Google Patents

Description

in DK 171353 B1

The present invention relates to novel acyl phosphine oxide compounds. The compounds can be used as photoinitiators in photopolymerizable masses, e.g. coating agents, lacquers and inks, and reproduction materials.

A number of photoinitiators of the most diverse structures are already known, for example. aromatic peptones such as acetophenone and benzophenone derivatives; benzyl dimethyl ketal (German Publication No. 20 03 132), benzoin ether (German Publication No. 16 94 149), thioxanthone (German Publication No. 20 03 132 and countless others. However, photopolymerizable masses cured with such initiator systems present an undesirable yellow staining which makes the application of these systems impossible on clear (or white) surfaces or as coatings for color reproduction.

A further disadvantage is the often insufficient storage stability of the finished sensitized resin mixture, which, despite storing in the dark, is often only durable for a few days.

The present invention relates to acylphosphine oxide compounds of the general formula I as defined in claim 1. 1 2 3 4 5 6

Specifically, according to the invention, such acyl 2-phosphine oxide compounds of the general formula 3 of claim 1 are provided, wherein a at least 2 times substituted 4 phenyl group which at least at both of the carbon atoms adjacent to the attachment site of the carbonyl group 6 carries substituents A and B, which are the same or different, and which denotes up to 6 carbon atom-containing alkyl, 5-7 carbon atom-containing cycloalkyl groups, phenyl groups or halogen groups, preferably chlorine or bromine atoms, or represents at least one at The 2,8-position with A or B is substituted α-naphthyl group or at least in the 1,3-position represents a β-naphthyl group substituted with A and B.

With respect to the general formula I, for the acylphosphine oxide compounds of the present invention, the following should be stated: R * represents a straight or branched alkyl group having from 10 to 6 C atoms, such as methyl, ethyl, i-propyl, n-propyl, n -butyl, amyl or n-hexyl, cyclopentyl, cyclohexyl, aryl, phenyl, halogen-substituted aryl, as mono- or dichlorophenyl, alkyl-substituted phenyl, as methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl or dimethylphenyl, alkoxy-substituted aryl, such as methoxyphenyl, ethoxyphenyl or dimethoxyphenyl.

In addition to the meaning of R *, R 1 represents an alkoxy group of 1-6 carbon atoms, such as methoxy, ethoxy, i-propoxy or butoxy, an aryloxy group, such as phenoxy, an aryl-substituted alkoxy group, such as benzoyloxy; Optionally, R * is connected to R 2 to a benzo-1,3,2-dioxophospholane ring.

R ^ represents in particular an ethyl, i-propyl, n-butyl, i-butyl, tert-butyl, i-amyl, n-hexyl, heptyl, n-octyl, 2-25 ethylhexyl, i-nonyl, dimethylheptyl, lauryl, stearyl, cyclopropyl, cyclobutyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, norbornadienyl, adamantyl, dimethyloctyl dimethylnonyl, dimethyldeyl, methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl, isopropylphenyl, methoxyphenyl, di methoxyphenyl, i-propoxyphenyl, thiomethoxyphenyl, a-DK 171353 B1 and β -naphthyl, thiophenyl, pyridyl, β-acetoxyethyl or β-carboxyethyl group, preferably a 2,6-dimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 2,6-dibromophenyl -, 2-Chloro-6-methoxyphenyl-, 2-chloro-6-methylthiophenyl-, 2,4,6-trimethylphenyl-, 2,4,6-trimethoxyphenyl-, 2,3,4 , 6-Tetramethylphenyl, 2,6-dimethyl-4-tert.-butylphenyl, 1,3-dimethoxy-naphthalene-2-, 1,3-dichloro-naphthalene-2, 2,8-dimethoxynapthaline-1 group .

r! and optionally contains additional C-C double bonds which allow the photoinitiator to be polymerized in the binder.

Examples of the acylphosphine oxide compounds of this invention include: isobutyryl-methylphosphinic acid methyl ester isobutyryl-phenylphosphinic acid methyl ester

Phenylphosphinsyremethylester pivaloyl-2-ethylhexanoyl-phenylphosphinsyremethylester phenylphosphinsyreisopropylester pivaloyl-p-toluyl-phenylphosphinsyremethylester 20 o-toluyl-2,4-dimethylbenzoyl phenylphosphinsyremethylester phenylphosphinsyremethylester-p-tert-butyl-phenylphosphinsyreisopropylester pivaloyl (4-methylphenyl) -phospinsyremethylester pivaloyl-phenylphosphinsyrevinylester 25 acryloyl-diphenyl phosphine oxide phenylphosphinsyremethylester isobutyry1-pivaloyl-diphenylphosphine oxide 1- methyl-L-cyclohexanoyl-diphenyl phosphine oxide 2-ethylhexanoyl-diphenyl phosphine oxide 30 p-toluyl-diphenyl phosphine oxide o-toluyl-diphenyl phosphine oxide p-tert-butyldiphenylphosphinoxid DK 171 353 B1 4 3-pyridylcarbonyl-diphenyl phosphine oxide acryloyldiphenylphosphinoxid benzoyl diphenylene phosphine oxide 2.2-dimethyl-heptanoyl-diphenylphosphine oxide terephthaloyl bis-diphenylphosphine oxide adipoyl-bis-diphenylphosphine oxide in addition especially 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester 2.6-dimethoxybenzoyl 2,6-dimethylbenzoyl-diphenylphosphine oxide 2,6-dimethoxybenzoyl-diphenylphosphine oxide 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 2,3,6-trimethylbenzoyl-diphenylphosphine oxide trimethoxybenzoyl diphenylphosphine oxide 2,6-dichlorobenzoyl-phenylphosphinic acid ethyl ester 2,6-dichlorobenzoyl-diphenylphosphine oxide 2-chloro-6-methylthio-benzoyl-diphenylphosphinoxide 2,6-dimethylthio-benzoyl-diphenylphosphinoxide 2,3,4,6-6 2,6-dichlorobenzoyl-naphthylphosphinic acid ethyl ester 1,3-dimethylnaphthalene-2-carbonyl-diphenylphosphine oxide 2,8-dimethylnaphthalene-1-carbonyl dichlorornaphthalin-2-carbonyl diph enylphosphinoxid. Particularly preferred are aroylphenylphosphinic acid ester or aroyldiphenylphosphine oxide, whose aroyl group is each substituted with alkyl, alkoxy, halogen, alkylthio groups or mixtures thereof, each time in the o-position. 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine acid ester, 2,6-dichlorobenzoyl or 2,6-dimethoxybenzoyl diphenylphosphine oxide.

The preparation of such compounds is by reaction of acid halides of the formula 0 R 3 -HX X = Cl, Br, 10 with phosphines of the formula R * R 2 = straight or branched-β-OR-C ^-Cg-alkyl, or cycloalkyl with 5 or 6 C atoms. 1 2 3 4 5 6 7 8 9 10 11

The reaction may be carried out in a solvent, e.g.

2 is a hydrocarbon or hydrocarbon mixture such as petroleum ether, toluene, cyclohexane, an ether, other usual 4 inert organic solvents or also without solvent at temperatures between -30 ° C and + 130 ° C, preferably at 10 ° C. -100 ° C. The product can be crystallized from the solvent for 7 days or left after evaporation or distilled in vacuo.

8

ISLAND

9 311 10

The preparation of the acid halide RJCX and of the substituted phosphine R 1 R 2 POR 3 takes place according to methods well known to those skilled in the art (e.g., Weygand-Hilgetag, Organisch-Chemische Experimentierkunst, pp. 246-256, Publisher JA Barth, Leipzig 1970 and K. Kasse DK 171353 B1 6 in Houben-Weyl, Volume 12/1, pp. 208-209, Publisher G. Thieme, Stuttgart).

The compounds of the invention may e.g. are prepared according to the following reaction scheme: 5 0, - 0CH - Λ - 10

CH-O

+ CH3C1 © J 8 or $ ^ P- ° CH3 + -> @ Γ CH3 (pi ° ssS *

JpP + CK3C1 © is DK 171353 B1 7 or

Cl C1 @ h? (° CH3) 2 + <oV </ - + CH3 Cl

“1 CH3 ° L

5 or βχ r-fft fol! s vi · βτ v toj> ζ

Suitable phosphines are e.g. methyl-dimethoxyphosphin, butyl dimethoxyphosphin, phenyldimethoxyphosphin, tolyldi 15-methoxyphosphine, phenyldiethoxyphosphin, tolyldiethoxy-phosphine phenyldiisopropoxyphosphin, tolyldiisopropoxyl-phosphine phenyldibutoxyphosphin, toluyldibutoxyphosphin or dimethylmethoxyphosphin, dibutylmethoxyphosphin, di-phenylmethoxyphosphin, diphenylethoxyphosphin, diphenyl-20 propoxyphosphin, diphenylisopropoxyphosphin, diphenylbutoxyphosphine or similar starting materials leading to the subject compounds.

As acid halides, chlorides and bromides are suitable, especially preferred are the acid chlorides.

DK 171353 B1 8

Examples of the compounds in question are in particular the following (without this being regarded as a restriction): DK 171353 B1 9

Table 1: Examples of the compounds of the invention (Ph = phenyl)

Compound Mp. kp. Yield. , _ J Analysis (C °) (C °) ch3 o λ ca.-c—- ioK / o.3 = £ 5: ber.6o, o 7.02: 2 | o 5 Cil3 c «^ 3 fun .59, £ 8; : 2, t 0 -: 6 ^:, 2 = é5 s · 6 «, o6 7, e3 1: .03 / 2 ° 3 '63.3 S.: 11 (0 c-3 9 151 70: 65, £ = 5.17: 1.51 csj "6 '* 7:, £ ::> c 0 Th 10 fop-X: = 5 75;" * 5.00 5.31?, £? C - · ·' 75.3 5.2 5.3 CK3 CSj 0 PJj 107 'ES' "75.00 5.51?. £? ^ 0Λ · 7«. 7 5, co, 5 0 Ta £ 2, fOpiC 136 £ J Σ "70.2- 6.35 £.; £ 0 76 "76.0 6.5 3.7

^ S

“3 C23 15 o c Λ2 * · £ · ^) Ρ? Ϊ12 '205':" 71.51 t, -o llj £ l 0 0 "71.8 p.6 11, c o ^ Cv. P-2 61 · .71.33 6.6-10, i ii CK3 Cdi 0 71.0 6.5 11.0 0 / CS, ®v A-CH 3 ^ - 120 / 0.5 = 60: .. £ 2, £ S 7.2 * .j «7” * 3 “3 0 '' · 63.0 é, o nji 20 DK 171353 B1 10

Table 1: Examples of the compounds of the invention (Ph = phenyl)

Compound Mp. Kp. Yield (C °) (C °) rl73e 'a 5 0 Fb csj ca, - 907 ber.73 »68 7 *' 9 9.06" Η ^ ° fun.73 · 6 8 · 1 3 · 6 «J CSj O r -3? X? I CH.-CO-Cr ^ -CC -? ^ - 90 ^ "66.28 6.11 9.01 * CS. O? B · 65.9 δ.i 8.5 CH-0 G-Ci (CH2), -; 10 / 0.3 c = cO: 1-52, U3 5.22 15, C5 of o "'es, m 52, i 9, i: i> 9 i S * 10 / - \ ©? (O / —1—? lii - <5:« 77,52 *, 7S 3.71 "-> '77.7 * .3 8, s 0 -CCjHj' -: C2 ° / 0.05 SS 60 in li 58, il 6, SS 13.71 ch3 - ^ όΝ0Η3 11- 53.9 6.7 13, 5

CH 2 O

--- 80 26 i li 73.62 7.06 9.51 O? B tf 73.3 7.1 9.5

ISLAND

ic CH, Si, C - 90 i '1 73.68 7.89 9.06 lj / £ N / / \ ✓ e3 ^ 2 / CN K "73.8« -1 * · * ch3 o »« 3

The present compounds exhibit a structure which has very good reactivity as photoinitiators for photopolymerizable monomers having at least one C-C polyvalent bond and mixtures thereof and with each other and with known DK 171353 B1 11 additives. The present acylphosphine oxide compounds are particularly well suited as photoinitiators in photo-polymerizable masses for coatings and varnishes as well as for reproduction materials. With respect to yellowing the varnishes or coatings thus produced, they are far superior to the known photoinitiators (e.g. benzyldimethyl ketal).

For this purpose, acylphenylphosphinic esters or acyldiphenylphosphine oxides are preferred if acyl groups are derived from a secondary or tertiary substituted aliphatic carboxylic acid such as pivalic acid, 1-methylcyclohexane carboxylic acid, norbornene carboxylic acid, α, α-α-α 13 carbon atoms), 2-ethylhexane carboxylic acid, or of a substituted aromatic carboxylic acid such as p-methylbenzoic acid, o-methylbenzoic acid, 2,4-dimethylbenzoic acid, p-tert-butylbenzoic acid, 2,4,5-trimethylbenzoic acid, p-methoxybenzoic acid or p thiome-thylbenzoesyre.

In particular, the preferred o-substituted aroyldiphenylphosphine oxides or aroylphenylphosphinic esters possess excellent storage stability with extremely high reactivity in photopolymerizable monomers. This is especially true for the most widely used resins based on styrene-containing unsaturated polyesters and for the styrene-free acrylic acid esters. With the aforementioned initiators, even those with white pigmented varnish cure without yellowing, but also colored pigmented resins can be processed. In terms of these properties, they outperform the known photoinitiators, such as e.g. benzyl dimethyl ketal or <x -30 hydroxyisobutyrophenone.

Furthermore, it has surprisingly been found that these advantages are maintained or can be enhanced when combining the preferred aroyl diphenylphosphine oxides with known photoinitiators.

Particularly effective synergistic mixtures are obtained by combinations with known photoinitiators based on aromatic 5 ketones, especially benzyl dimethyl ketal, α-hydroxyisobutyro-phenone, diethoxyacetophenone, benzophenone and 2-methylthio-xanthol, 2-isopropyldioxanthone, and 2-chlorothioxanthone.

To this end, by the addition of tertiary amines such as methyldiethanolamine, their well known promoting effect is further utilized. By combining the present initiators with e.g. benzyl dimethyl ketal has succeeded in producing surprisingly effective, highly storage-stable, amine-free, photopolymerizable masses which may also be pigmented.

As photopolymerizable monomers, the usual compounds and substances with polymerizable C-C double bonds which are activated by e.g. aryl, carbonyl, amino, amide, amido, ester, carboxy, or cyanide groups, with halogen atoms or C-C double or C-C triple bonds. Mention may be mentioned, for example, vinyl ether and vinyl ester, styrene, vinyl toluene, acrylic acid and methacrylic acid as well as their esters with mono- and polyhydric alcohols, their nitriles or amides, maleic and fumar esters, and N-vinylpyrrolidone, N-vinylcaprolactamer, N-vinylcarbazole and 25 allylic esters such as diallyl phthalate.

As polymerizable high molecular weight compounds, e.g. The following are suitable: unsaturated polyesters prepared from α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid optionally in admixture with unsaturated or aromatic dicarboxylic acids such as adipic acid, phthalic acid, tetrahydrophthalic acid or terephthalic acid, by reaction with alkanediol, butanediol, DK 171353 B1 13 neopentylglycol or oxalkylated bisphenol A; epoxide acrylates, made from acrylic or methacrylic acid and aromatic or aliphatic diglycidyl ethers and urethane acrylates (eg made from hydroxyalkyl acrylates 5 and polyisocyanates), and polyester acrylates (eg made from hydroxyl group-containing unsaturated polyester and acrylic - and methacrylic acid).

Optionally, the photopolymerizable coatings, lacquers and inks may also be available as aqueous dispersions or used directly.

The photopolymerizable compounds, the composition of which can be predetermined by one of ordinary skill in the art, may be known in the art to include saturated and / or unsaturated polymers, as well as additional additives such as inhibitors of the thermal polymerization, paraffins, pigments, dyes, peroxides, reaction aids, fillers, matting agents and glass fibers, as well as stabilizers for thermal or photochemical degradation.

Such mixtures are known to those skilled in the art and the amount of addition depends on the individual application.

The compounds of this invention are usually used for this purpose at a concentration of from 0.001 to 20%, especially from 0.10 to 15%, preferably from 0.1 to 5%, based on the photopolymerizable mass used. They may optionally be combined with accelerators which counteract the inhibitory influence on the photopolymerization of the air oxygen.

Such accelerators or synergists are e.g. secondary and / or tertiary amines such as methyldiethanolamine, dimethylethanolamine, triethylamine, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, benzyldimethylamine, dimethylaminoethyl acrylate, N-phenylglycine, N-methyl-N-phenylglycine DK 171353 B1 14, and anal. known compounds for those skilled in the art.

To accelerate the cure, additional aliphatic and aromatic halides can be used such as e.g. 2-chloromethyl naphthalene, 1-chloro-2-chloromethylnaphthalene, and radiolabels such as peroxides and azo compounds.

As radiation sources for the polymerization of such mixtures, such light is used, the light of which is preferably in the absorption range of the compounds of the present invention, ie. between 230 and 450 nm. Particularly suitable are mercury-low pressure jets, medium pressures and high-pressure jets, as well as (super-actinic) fluorescent lamps or pulse jets. The lamps mentioned may be doped.

The present photoinitiators are also particularly suitable for photopolymerization of reproduction materials, especially for the production of printing plates and embossing molds, and consist predominantly of a photoinitiator-containing mixture of a) at least one monomer with at least one photopolymerizable olefinically unsaturated double bond, and b) at least one organic polymer. binder.

To this end, it is possible with the present photoinitiators to achieve a significantly faster cure of photopolymeric reproduction systems than with the prior art photoinitiators, and at the same time to improve the relief structure of the photopolymer relief forms. 1

Among the aforementioned acylphosphine oxide compounds, for such photopolymerizable reproduction materials, particularly those of formula (I) DK 171353 B1 15 bsL.3 (I) II ''

ISLAND

5 in which R 1 and represents the groups described above and R 2 represents a tertiary alkyl group of 4-18 C atoms or a tertiary cycloalkyl group of 5 or 6 ring carbon atoms, or represents a cycloalkyl group or aryl group which at least in both ortho positions to the carbonyl group contains the substituents A and B bonded, wherein A and B represent alkyl, alkoxy, alkoxyalkyl, alkylthio, cycloalkyl or aryl groups or halogen atoms, and A and B being the same or different.

The term "in both ortho positions of the carbonyl group 15 contains the substituents A and B bonded" is understood to mean that the substituents A and B are bonded to both of the ring atoms which may be substituents adjacent to the site of attachment to the carbonyl group. This means that the α-naphthyl group at least in the 2,8 position and the β-20 naphthyl group at least in the 1,3 position contain the substituents A and B bonded. At the cyclohexyl group, the substituent and A and B are at the 2,6 position, at the cyclopentyl group at the 2,5 position. Such R 1 -bonded containing acylphosphine oxide compounds may e.g. is illustrated by Structures formulas II-VII

DK 171353 B1 16 K ^ -PQ-CO- ^ iT ^ (II); RV-PO-CO 2) (III)

B B

A. A

R ^ 2-po-co - / \ jn (iv) κ1κ2-ρο-σο- / ~ Λ (ν)

B ”X

\ x

A

R'R2-? 0-C0-ri ## ^ Sv ^^ i! ^ XXJ (VI)

B

Wherein X optionally represents additional substituents in the cycloalkyl, phenyl, naphthyl or heterocyclic groups having the meaning of A or B.

However, in the highly suitable acylphosphine oxide linkages for photopolymerizable masses, R- may optionally also represent a tertiary alkyl or cycloalkyl group (each time having a tertiary atom adjacent to the carbonyl group) such as e.g. tert-butyl, 1,1-dimethylheptyl, 1- methylcyclohexyl or 1-methylcyclopentyl. 1 2 3 4 5 6 Particularly suitable for photopolymerizable reproduction masses are phosphine oxide compounds of formula I wherein R * is 3 equals aryl having 6-12 C atoms, such as e.g. naphthyl, tolu-4 yl and especially phenyl, and R 1 is C 1 -C 4 alkoxy as methoxy or ethoxy and especially aryl having 6-12 C atoms, preferably 6 phenyl. Surprisingly high efficiencies with simultaneous high stability are photopolymerizable reproductive materials DK 171353 B1 17 with acylphosphine oxide compound of Formula I, whose acyl group -CO-R 2 is derived from a tertiary aliphatic or cycloaliphatic carboxylic acid or at least in the 2.6 position ( with A and B) substituted benzoic acid. Particularly suitable acyl groups of this kind are the 2,2-dimethyl-C 4 -C 6 alkanoyl, 2-methyl-2-ethyl-C 4 -C 6 alkanoyl group and the benzoyl group, as in the 2,6-, 2,3,6- The 2,4,6 or 2,3,5,6 position carries the substituents A and B, especially the C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups or halogen atoms.

The reproduction materials may contain the phosphine oxide compounds of formula I as the sole photoinitiators, usually in an amount of 0.005-10 and especially in an amount of 0.005-5% by weight based on the entire amount of the photopolymerizable reproductive material, however, the phosphine oxide compounds may also , as indicated above, is used in combination with well-known photoinitiators and / or with tert-amines in photopolymerizable reproduction materials.

The total concentration of initiator system (photoinitiators plus amine) for this purpose is between 0.05 and 15% by weight based on the entire amount of the photopolymerizable reproduction material, the amine proportion being preferably at least half of the total initiator content.

For the mixture of (a) and (b) which form the basis of the subject matter of reproduction, low molecular weight compounds having at least one photopolymerizable olefinically unsaturated double bond are well known to such masses as monomers used, and they form tolerable mixtures with the thus selected polymeric binder and has a boiling point above 100 ° C at atmospheric pressure. Generally, they have molecular weights below 2000 and especially below 1000. Preferred are monomers having 2 or more olefinically unsaturated photopolymerizable double bonds alone or in mixtures with monomers having only a 5 olefinically unsaturated photopolymerizable double bond, the proportion of monomers having only one double bond generally only ca. 5-50 and preferably 5-30% by weight of the total monomer amount. The nature of the monomers used extends greatly to the nature of the polymeric binder used simultaneously. Thus, especially for mixtures with unsaturated polyester resins, especially allyl compounds containing 2 or more double bonds are suitable, e.g. maleic acid dialkyl ester, allyl acrylate, diallyl phthalate, trimellitic acid di and trialkyl ester or ethylene glycol bisallyl carbonate as well as di- and polyacrylates and methacrylates suitable for preparation by esterification of diols or polyols with acrylic acid or methacrylic acid. di- and tri- (meth) acrylates of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight up to approx.

500, 1,2-propanediol, 1,3-propanediol, neopentyl glycol (2,3-dimethylpropanediol), 1,4-butanediol, 1,1,1-trimethylolpropane, glycerol or pentaerythritis; further the monoacrylates and monomethacrylates of such diols and polyols such as e.g. ethylene glycol or di, tri or tetraethylene glycol monoacrylate, monomers having 2 or more olefinically unsaturated linkages containing urethane and / or amide groups such as e.g. the aliphatic diolenes of the aforementioned kind, organic diisocyanates and hydroxyalkyl (meth) acrylates prepared low molecular weight compounds. Mention should also be made of acrylic acid, methacrylic acid and derivatives thereof such as e.g. (meth) acrylamide, N-hydroxymethyl (meth) acrylamide or (meth) acrylates of monoalcohols having 1-6 C atoms. The mixture of allyl monomers with di- or DK-171353 B1 19 polyacrylates is particularly suitable. If the mixture is selected with polyamide as a polymeric binder, the monomeric species besides the di- and polyacrylates are particularly suitable, which in addition to the double bonds also contain 5 amide and / or urethane groups such as e.g. derivatives of acrylamides e.g. reaction products of 2 moles of N-hydroxy-methyl (meth) acrylamide with 1 mole of an aliphatic diol such as e.g. ethylene glycol, xylylene bisacrylamide or alkylene bisacrylamide having 1-8 C atoms in the acrylic group. For the preparation of reproductive materials which can be developed with aqueous alkaline solution, e.g. for the production of printing plates with polyvinyl alcohol, polyvinyl alcohol alkoxylation products or polyvinylpyrrolidone as polymeric binder are particularly suitable for water-soluble monomers such as e.g. hydroxyethyl (meth) acrylate or mono and di (meth) acrylates of polyethylene glycols having a molecular weight of about 200-500. For combination with elastomeric diene polymers as binder e.g. with polystyrene-polyisoprene-polystyrene three-block copolymers, polystyrene-polybutadiene two-block polymers or polystyrene-polyisoprene two-block copolymers are particularly suitable polyacrylates or methacrylates of polyols and especially glycols having at least 4 C atoms.

As organic polymeric binders b) for the mixture of the photopolymerizable reproduction materials and especially for the production of printing plates and embossing molds, the polymers known for this purpose come into question, in addition they must be generally tolerable with the low molecular weight compounds a) and - for the skilled artisan. of course - be soluble in a suitable developer solvent or dispersible herein to allow for the leaching of the unlit and non-crosslinked portions of the layer of the photopolymerizable reproduction materials upon imaging of these. Suitable DK 171353 B1 20 saturated or unsaturated binders may be mentioned linear polyamides and especially alcohol-soluble copolyamides as described in French Patent Specification No. 1,520,856, cellulose derivatives, especially aqueous-alkaline washable cellulose derivatives, vinyl alcohol polymers and polymers. vinyl esters of aliphatic monocarboxylic acids having 1-4 C atoms such as vinyl acetate, of varying degree of saponification, polyurethanes, polyether urethanes and polyester urethanes, and unsaturated polyester resins, such as those of e.g. is disclosed in German Publication No. 20 40 390. Among the polyesters of linear or branched nature produced by the reaction of unsaturated and possibly saturated and possibly polyunsaturated carboxylic acids with di- and optionally polyalcohols, especially those with a higher acid number are preferred. especially an acid number between 75 and 160, as they lead to excellent dispersibility and solubility in the masses in alkaline, aqueous developer solvents. With regard to the composition and preparation of unsaturated polyester resins, reference should be made to the available literature e.g. the book of Η. V. Boenig, Unsaturated Polyesters, Structure and Properties, Amsterdam 1964.

The reproduction material at issue consists predominantly ie. greater than 50 and preferably from 70 to 100% by weight of the photoinitiator-containing mixture consisting of a) and b). The content of this mixture of polymeric binder usually ranges from 45 to 90 and especially from 45 to 65% by weight based on the sum of the amount of polymer b) and the photopolymerizable low molecular weight compounds a). 1

It is often advantageous also to add the usual amount of known inhibitors to the thermal polymerization, such as e.g. hydroquinone, p-methoxyphenol, m-dinitrobenzene, p-quinone, methylene blue, β-naphthol, N-nitrosamines such as N-nitrosodiphenylamine, phenothiazine, phosphoric acetic ester such as triphenylphosphite or the salts and especially the salts - and the aluminum salts of N-nitroso-cyclohexyl-hydroxylamine.

The materials may also contain additional additives such as plasticizers, saturated low molecular weight compounds with amide groups, waxes, etc.

The further processing of the photopolymerizable reproduction materials e.g. for photopolymer printing plates exhibiting the reproductive material in a 10-layer form as a relief-shaped layer can be made in known manner and depends on the nature of the mixture a) plus b) and whether the mass is liquid or solid. The reproduction of reproductive materials (for example, for relief molds) is done in known manner by imaging illumination with actinic light. Following the imaging illumination, for the manufacture of relief molds or photoresists, the non-illuminated portions of the layer of the reproductive material are removed mechanically or per se in a known manner, or washed out with a suitable developer solvent, and the resulting molds, e.g. relief printing molds are in many cases suitably dried and post-illuminated completely.

A particular advantage is that with the reproduction materials it is often possible, even to relinquish a pre-illumination, before the image illumination of the layers of the photopolymerizable reproduction materials, and yet satisfactory illumination times can be worked. Another unexpected advantage is that, as mentioned in Example 30 39, the layers of the aforementioned reproduction materials, when processed into relief printing molds, provide an improved relief structure, e.g. printing results in a clearly improved reproduction of negative print.

DK 171353 B1 22

The parts and percentages mentioned in the following examples are, unless otherwise indicated, in parts by weight and percentages. Volume parts relate to parts like liters per kilogram.

To a mixture of 1350 volumes of petroleum ether (boiling range 40-70 ° C), 180 volumes of N, N-diethylaniline and 67 volumes of methanol was added with stirring at 0 ° C 225 parts of diphenyl chlorophosphine dissolved in 220 volumes of 10 volumes of petroleum ether. The mixture was then further stirred for 2 hours at room temperature. After cooling to approx. +5 ° C was extracted with the separated amine hydrochloride, then the filtrate was distilled at 10-20 torr, to remove the light boiling part. Then, the diphenylmethoxyphosphine was distilled off at 0.1-1 torr. Boiling point q 5 120-124 ° C. Yield: 175 parts (80% calculated on diphenyl chlorophosphine).

To 36.2 parts of pivaloyl chloride, 64.8 parts of diphenylmethoxophosphine were added dropwise with stirring at 30-60 ° C. After the addition was complete, the reaction was allowed to react for a further 30 minutes, then cooled to 0-10 ° C and recrystallized from the precipitated product with cyclohexane.

Yield: 69.5 parts of pivaloyl diphenylphosphone oxide (81% of theory).

25 Kp. 110-112 ° C, HMR (CDCl 3, δ), 1.33 (S), 7.4-8.0 (M)

Analysis C ^H ^O₂P (286)

C Η P

Calculated 71.33 6.64 10.84

Found: 71.0 6.5 11.0 DK 171353 B1 EXAMPLE 2 23

To 77 parts of toluic acid chloride are added 108 parts of methoxydiphenylphosphine (prepared as in Example 1) dissolved in 200 parts by volume of toluene. The mixture is then heated at 50 DEG C. for 60 minutes, after which the precipitate of toluyl diphenylphosphine oxide is cooled and extracted. Cyclohexane yield is recrystallized from 117 parts (73% of theory), mp 105 ° C.

HMR (CDCl3, δ): 2.35 (S), 7.2-8 (m) Analysis C20H17 ° 2P (320)

C Η P

Calculated 75.00 5.31 9.69

Found: 75.3 5.8 9.3 EXAMPLE 3 In analogy to Example 2, 77 parts of 2-15 methylbenzoic acid chloride and 108 parts of methoxyphenylphosphine make up 134 parts of 2-methylbenzoyl diphenylphosphine oxide. Yield 84% of theory, mp, 107 ° C.

NMR (CDCl 3, δ): 2.5 (S), 7.2-8 (m), 8.8 (m)

Analysis C20Hi702P

20

C Η P

Calculated 75.0 5.31 9.69

Found: 74.7 5.4 9.5 DK 171353 B1 EXAMPLE 4 24 In analogy to Example 1, 41.3 parts of p-tert.-butyl benzoic acid chloride are reacted with 45.4 parts of methoxyphenylphosphine dissolved in 20 parts of toluene. at 50 ° C for 90 minutes. After 5 evaporation of the solvent and rotary evaporator is recrystallized with cyclohexane. Yield: 63 parts (83% of theory) m.p. 136 ° C.

NMR (CDCl 3, δ): 1.3 (S), 7.3-8.1 (m), 8.5 (d)

Analysis C23H23O2P (362) 10

C Η P

Calculated 76.24 6.35 8.56

Found: 76.0 6.5 8.7 EXAMPLE 5 In analogy to Example 2, 52 parts of terephthalic acid chloride dissolved in 200 parts of toluene and 108 parts of methoxydiphenylphosphine are prepared 46 parts of terphthaloyl bis-diphenylphosphine oxide (yield 35% of the theoretical). Mp. 205 ° C.

NMR (CDCl 3, δ): 6.8-8.2 (m)

Analysis C32H24O4P2 (534)

C Η P

Calcd 71.91 4.49 11.61

Found: 71.8 4.8 11.0 EXAMPLE 6 DK 171353 B1 25

Proceeding as in Example 2, 80 parts of 1-methyl-1-cyclohexane carboxylic acid chloride and 108 parts of methoxy-5-xydiphenylphosphine without solvent are obtained 100 parts of 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide as an oily crude product which is purified by chromatography silica gel (eluent toluene). Yield: 42 parts (26% of theory). Mp. 80 ° C.

NMR (CDCl 3, δ): 1.4 (s), 1.1-1.6 (m), 2.1-2.4 (m), 7.3-8.0 (m)

Analysis C2qh23 ° 2p (326) 15

C Η P

Calculated 73.62 7.06 9.51

Found: 73.3 7.1 9.6 Example 7 In analogy to Example 1, 88 parts of 2-methyl-2-20-ethylhexanoic acid chloride and 108 parts of methoxydiphenylphosphine are obtained 165 parts of 2-methyl-2-ethylhexanoyl diphenylphosphine oxide as an oily crude product. Column chromatography on silica gel (eluent toluene / ether 3: 1) gives the product as a light yellowish oil. Yield 154 parts (90% of theory).

NMR (CDCl 3, δ): 1.2 (s), 0.5-2.2 (m), 7.3-8.1 (m) DK 171353 B1 26

Analysis C21H27O2P (342)

C Η P

Calculated 73.68 7.89 9.06

Found: 73.9 8.1 9.4 EXAMPLE 8 5

Analogously to Example 1, 43.2 parts of methoxydiphenylphosphine are added dropwise to 35.3 parts of 2,2-dimethylheptane carboxylic acid (Versatic acid chloride) at 50 ° C. The mixture is stirred for 3 hours at 50 ° C, cooled to 15 ° C and the mixture is stirred in a slurry of 60 g of silica gel in 350 ml of toluene, then further stirred for 1 hour under ice-cooling. The solvent is then suctioned off and the solvent is distilled off under reduced pressure. Versatoyl diphenylphosphine oxide remains as a viscous oil. Yield 62 parts (90% of theoretic) NMR (CDCl 3, δ) s 0.4-2.3 (m), 7.2-8.1 (m)

Analysis C2H2702P (342) 20

C Η P

Calculated 73.68 7.89 9.06

Found: 73.6 8.1 8.6 Example 9

To a mixture of 600 parts by volume of petroleum-25 ether, 263 parts of Ν, h-diethylaniline and 120 parts of isopropanol, 143 parts of phenyl dichlorophosphine are dropped over 1 hour at 0 ° C. Thereafter, the mixture is stirred for an additional hour at room temperature, after which, after working up as in example, in Example 17, distillate 1. The diisopropoxyphenylphosphine distills at 68-72 ° C / 0.3 nun. Yield 126 parts (69% of theory).

5 158 parts of diisopropoxyphenylphosphine are slowly added to 84 parts of pivalic acid chloride with vigorous stirring at 50-60 ° C. The mixture is further stirred for 2 hours and fractionated in vacuo. The pivaloylphenylphosphinic acid isopropyl ester distills at 119-121 ° C / 0.5 mm. Yield 112 parts (60% of theory).

NMR (CDCl 3 / δ) 1.25 (S), 1.33 (t), 4.5 (m), 7.3-8 (m)

Analysis C ^^ j jOPP (268) 15

C Η P

Calculated 62.68 7.84 11.57

Found: 63.0 8.0 11.4 Example 10

To a mixture of 1000 volumes of toluene, 421 volumes of 20 parts of Ν, Ν-diethylaniline and 100 volumes of methanol is added at 0 ° C 214 parts of phenyl dichlorophosphine. The mixture is then stirred for an additional hour at room temperature, the precipitate consisting of amine hydrochloride is extracted and fractionated. The di-methoxyphenylphosphine distills at 46-50 ° C / 0.2-0.3 25 mm. Yield 190 parts (93% of theory).

To 78.7 parts of pivaloyl chloride, 110.5 parts of dimethoxyphenylphosphine are dropped at 15 ° C. The reaction mixture is then heated for an additional 30 minutes at 50 ° C and then the reaction mixture is distilled off. The pivaloylphenylphosphinic acid methyl ester crosses at 104-107 ° C / 0.3 nun. Yield 101.3 parts (65% of theory).

NMR (CDCl3, δ): 1.3 (S), 3.75 (d), 7.4-8 (m)

Analysis → 2 ^ 17 ^ 3 ^ (240)

C Η P

Calculated 60.0 7.08 12.9

Found: 59.8 6.9 12.4 EXAMPLE 11 10

To 163 parts of 2-ethylhexanoic acid chloride, 170 parts of dimethoxyphenylphosphine are dropped at 30 ° C (Example 4). Then stir for 50 minutes at 50 ° C and fractionate in oil vacuum.

2-Ethylhexanoylphenylphosphinic acid methyl ester passes at 160-168 ° C / 1.2 mm. Yield 230 parts (81% of theory).

NMR (CDCl 3, δ): 0.6-2 (m), 3.2 (q), 3.8 (d), 7.3-8 Analysis c15 H22 ° 3p i2®1)

C Η P

Calculated 64.06 7.83 11.03

Found: 63.8 8.1 11.0 Example 12

To 155 parts of 4-methylbenzoyl chloride dissolved in 250 parts by volume of toluene are added 170 parts of dimethoxyphenyl phosphine at 30 ° C. The reaction mixture is then allowed to react for 50 minutes, then cooled to 0 ° C and the precipitate is extracted. After recrystallization with cyclohexane, 4-methylbenzoylphenylphosphinic acid methyl ester melts at 99-101 ° C.

5 Yield 180 parts (65% of theory).

NMR: 2.25 (S), 3.7 (d), 7-8.1 (m)

Analysis C ^H ^C ^P (274) 10

C Η P

Calculated 65.69 5.47 11.31

Found: 65.7 5.6 11.0 ERSEMRØL, 13

To a mixture of 1350 volumes of petroleum ether (boiling range 40-70 ° C) 180 volumes of N, N-diethyl-aniline and 67 volumes of methanol are added with stirring at 0 ° C 225 parts of diphenyl chlorophosphine dissolved in 220 volumes of petroleum ether. The mixture is then stirred for 2 hours at room temperature. After cooling to approx. +5 ° C is extracted with the separated amine hydrochloride and the filtrate is then distilled at 10-20 torr to remove all light boiling. Subsequently, the diphenylmethoxyphosphine is fractionated at 0.1-1 torr. Mp 120-124 ° C. Yield: 175 parts (80% based on diphenyl chlorophosphine).

25

To a reflux stirrer and drip funnel, 648 parts of methoxydiphenylphosphine are slowly added to 547.5 parts of 2,4,6-trimethylbenzoyl chloride at 50-55 ° C. The mixture is further stirred for 4-5 hours at 50 ° C, after which the flask contents are dissolved at 30 ° C in ether and petroleum ether is added to incipient cloudiness. Upon evaporation, the crystalline crystalline solution produces 110 parts (47% of theory) of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, m.p. 89-92 ° C, pale yellow crystals.

EXAMPLE 14 In an apparatus as in Example 13, 20 parts of 2,6-dimethoxybenzoyl chloride are slurried in 20 parts by volume of toluene, and to this mixture, 21.6 parts of 10 methoxydiphenylphosphine is added dropwise with stirring. Then, stir for 3 hours at 50 ° C and then recrystallize directly with toluene. You get 32 parts of yellow crystals with m.p. 124-126 ° C.

EXAMPLE 16 15

To a mixture consisting of 1000 parts by volume toluene, 421 parts by volume Ν, Ν-diethylaniline and 100 parts by volume of methanol, 214 parts of phenyl dichlorophosphine are added at 0 ° C. Thereafter, stir for an additional 1 hour at room temperature, the precipitate of amine hydrochloride is suctioned and fractionated. The dimethoxyphenylphosphine distills at 46-50 ° C / 0.2-0.3 mm. Yield: 190 parts (93% of theoretical yield).

To 182.5 parts of 2,4,6-trimethylbenzoyl chloride, 170 parts of dimethoxyphenylphosphine are dropped at 25 ° C. The mixture is kept for another 5 hours at 50 ° C, then the slightly yellowish oil is dissolved at 70-80 ° C in cyclohexane and the product is crystallized after cooling to 5 ° C. You get slightly yellow crystals, m.p. 51-52 ° C; yield-30 tea: 81% of theory.

Additional compounds prepared analogously to Examples 13-16 are shown in Table 2.

DK 171353 B1 31 __ TABLE 2 _

Analysis

Yield Kgp. Mp. ° C Η P

_ te (mm) ___ 2.4.6- Trimethyl- 87? - 80.81 Calculated 75.86 6.03 8.91 Benzoyl diphenylphosphate Found 75.9 6.1 8.9 Bin oxide 2.4.6- Trimethyl- 81? - 51-52 Calculated 67.55 6.29 10.26 Benzoylphenylphosphi Found 67.5 6.5 10.1 Nfluoromethyl ester 2.6- Dichlorobenzoyl-82? - 154-159 Calculated 60.8 3.47 8.27 diphenylphosphine oxide Found 60.9 3.7 8.1 2.4- Dichlorobenzoyl-76? - 116-117 Calculated 60.8 3.47 8.27 diphenylphosphine oxide Found 60.9 3.6 8.3 3.4- Dimethylbenzoyl 90? - 72-74 Calculated 75.45 5.69 9.28 diphenylphosphine oxide Found 75.2 5.7 8.9 EXEMEFIC .17

A covering pigmented varnish is prepared from a mixture of 5 parts of 100 parts of the reaction product of bisphenol-A-diglycidyl ether and 2 moles of acrylic acid, 122 parts of butanediol-1,4-diacrylate, 6 parts of n-butanol, 122 parts of TiO2 pigment. Varnishes of this type are well known to those skilled in the art. To this mixture 6.5 parts of 2-methylbenzoyl diphenylphosphine oxide are added as a photoinitiator. The finished formulated varnish is ironed out to a thickness of 75 μ on glass plates and irradiated with a Hg high-pressure lamp (output 80 W / cm arc length). The distance of the lacquer film was 10 cm. The sample was drawn under the lamp in an inert gas atmosphere on a conveyor belt which could be continuously adjusted for the flow rate.

At belt speeds of up to 6 m / min. you got rubbing, cured and completely white lacquer films.

Example 17 32

To a binder consisting of 65 parts of a reaction product of bisphenol A-diglycidyl ether with 2 equivalents of 5 acrylic acid and 35 parts of butanediol-1,4-diacrylate was added 3 parts of photoinitiator each time. This mixture was applied in a layer thickness of 80 μm with a protractor on glass plates and irradiated (Hg high pressure lamps, 80 W / cm arc length, distance 10 cm). The maximum possible conveyor belt velocity was measured by which the samples could be passed under the lamp to obtain the necessary irradiation to obtain layer-resistant, rub-resistant surfaces. The following values were measured: _TABLE 3_ _ Curing activity of photoinitiators_

Maximum conveyor belt speed

Under Under air, to-Under inert statement of 3% N-

Initiator__ air gas phenylglycine_

Pivaloylphosphonic acid diethyl-ester

Pivaloylphenylphosphinic acid methyl ester

Toluyl-phenylphosphinic acid methyl ester 2-ethylhexanoyl-phenylphosphate 40-phinic acid methyl ester

Toluyl-diphenylphosphine oxide-70 2-methylbenzoyl-diphenyl-70 phosphine oxide

Pivaloyl diphenylphosphine 11 150 25 Oxide_ EXAMPLE 19 33

To a varnish prepared in Example 18 was added 3% N-phenylglycine. Then, as in Example 14 5, the lacquer was transferred to glass plates and illuminated. The results are shown in Table 3.

EXAMPLE 20 10 By esterification of 431 parts of maleic anhydride and 325 parts of phthalic anhydride with 525 parts of propylene glycol-1,2, an unsaturated polyester is prepared. After addition of 0.01% hydroquinone, a 66% solution in styrene is prepared from the polyester. 97 parts of this UP resin are added 1.5 parts 15 pivaloyl diphenylphosphine oxide.

For light curing experiments, 100 parts of this mixture are added 10 parts of 1% solution of paraffin (softening range 50-52 ° C) in styrene, and the resin is applied to glass plates with a film application equipment a layer thickness of 400 µ. After approx.

For 1 minute, the film is illuminated with fluorescent lamps (Philips "TLA" 05/50 W) spaced 4 cm away. 1

After a light time of 4 minutes, the film has a shaft hardness of 76 s (after Konig) and is abrasive and polished.

EXAMPLE 21 A binder prepared as in Example 18 is mixed each time with 3 parts of a photoinitiator as in Table 3, and then applied in a layer thickness of 76 µ on white photo paper, after which it is drawn in inert gas at a rate of 72 m / min. under a Hg high-pressure lamp (output 80 W / cm arc length- 1717353 B1 34 de). The thus hardened specimen was impact resistant and shiny.

As Table 4 shows, the compounds of this invention far exceed those known in the art, characterized by the initiators benzildimethylketal and the mixture benzidimethylketa / benzophenone / methylethanolamine.

TABLE 4 _ Yellowing of Photopolymerized Varnishes_

Application Yellowing according to

Initiator__ concentration Yellowness Index +)

Benzildimethylketal_ 3% 9.20_

Benzildimethylketal / - 6% 8.15 benzophenone / methyldiethanolamine (2: 1: 3)

Pivaloyl diphenylphos 3% -3.33 phinoxide p-toluyl diphenylphos 3% -3.72 phinoxide

Pivaloyl-phenylphos- 3% -2.34 Phinic acid methyl ester Yellowness Index according to ASTM D 1925-G7 with equipment from

Zeiss EXAMPLE 22 10 To measure the curing activity of the subject photopolymer in saturable unsaturated polyester resins, the temperature course was recorded during illumination. For this purpose, the following resins are prepared:

Resin A: Melt condensation of maleic acid, ophthalic acid, ethylene glycol and propylene glycol-1,2 in molar ratio of 1: 2: 2.4: 0.85 gives an unsaturated polyester with an acid number of 50.

DK 171353 B1 35

Resin Bs Of maleic acid, tetrahydrophthalic acid and diethylene glycol in a molar ratio of 1: 0.5: 1.5, an UP resin with acid number 46 is obtained. When used, both resins were dissolved in styrene and stabilized with 100 ppm hydroquinone.

10 g of such resin was sensitized with 0.35% of the photon initiator in question and then irradiated in a white tin tray (cross section 3.8 cm) which was coated with a polyurethane resin foam to heat insulate 5. As a source of radiation, a UV field (87 x 49 cm) consisting of 10 side-by-side lamps served (TUV 40 W / 0.5, Philips, the distance to the sample was 10 cm). The temperature course of the resin was recorded during curing by means of a thermocouple with printer. The measured values obtained are listed in Table 5.

TABLE 5_

Temperature course during photopolymerization_

Concentration Cure time Maximum tration obtained (time between sample temperature

Photoinitiator Resin 25 ° C and TmAV) Tmay (° C) _

Pivaloyl-phenyl 0.35% A 18 min 106 phosphine and 15 s acid methyl ester 0.35% B__13 min_ 112

Toluyl diphenyl 0.35% A 15 min 122 Phosphine Oxide 15 s 0.35% B__10 min__133 4-tert.-Butyl 0.35% A 14 min 120 Benzoyl Diphenyl 55 Ph Phosphine Oxide

Terephthaloyl bis 0.35% A 21 min 109 diphenylphosphine oxide EXAMPLE 23 DK 171353 B1 36 In a binder consisting of 65 parts of a reaction product of bisphenol A diglycidyl ether and acrylic acid, 35 parts 5 butane-1 , 4-diol diacrylate and 3 parts methylethanolamine dissolve 3 parts photoinitiator. The finished mixture is applied to glass sheets in a layer of 60 μm thickness and passed over a distance of 10 cm under a high-pressure mercury lamp (output 80 W / cm arc length). The reactivity is stated as the maximum possible 10 conveyor belt velocity at which a continuous scratch-hardening of the lacquer film is obtained.

_TABLE 6_ _Reactivity of the Photo Initiators_

reactivity

Photoinitiator (transport rate _m / min) _ 2.4-dichlorobenzoyl diphenyl- <10 phosphine oxide__ 3.4-dimethylbenzoyl diphenyl- <10 phosphine oxide _ 2.4.6-trimethylbenzoyl diphenylphosphine oxide__ 2.6-dimethoxybenzoyl diphenyl-ethylene phosphate oxide more reactivity than derivatives which carry substituents at other positions of the benzoyl group.

EXAMPLE 24 DK 171353 B1 37

A paint system analogous to Example 23 is added to the following photoinitiator combinations and tested as described in Example 23.

Reacti- Pendulum hardness after white Konig (sec) at 12

Photoinitiator system __ (m / min) m / min_ 3 parts benzophenone__12__97_ 2 parts benzophenone 1 part 2,4,6-trimethylbenz 75 213 zoyl diphenylphosphine oxide 3 parts 2,4,6-trimethylbenzo-70 188 yldiphenylphosphine oxide dimethoxybenzoyl 75 210 diphenylphosphine oxide 3 parts 2,6-dimethoxybenzoyl 70 183 diphenylphosphine oxide EXAMPLE 25 In a mixture consisting of 55 parts of a bisphenol A diglycide ether and acrylic acid, 45 parts butane diol diacrylate, 45 parts butane diol diacrylate, Three parts of methyldiethanolamine dissolve the following photoinitiators. The finished mixture is applied with a screw line (80 µm) to glass plates 15 and passed through two Hg high-pressure lamps (80 W / cm) located one behind the other. The transport hand speed, at which it is still possible to obtain a scratch-hardening cure, characterizes the reactivity of the initiator system.

In another experiment, the above composition is ironed out at a layer thickness of 200 µ. After UV curing, the layer is removed, washed with acetone and then the cured thickness of the layer is determined. Thus, a cure target is obtained.

Reactivity - Softness through- Berger the layer thickness Photoinitiator __ (m / min) (% rem.) __ feeling_ 2 parts 2-methylthioxane-12 66 130 µ thon____ 1.5 parts 2-methylthioxane 0.5 parts 2 , 4,6-Trim-76 140 µmethylbenzoyl diphenylphosphine oxide 1.0 parts 2-methylthio-xanthone 1.0 parts 2,4,6-trimethomethane 78 140 µmethylbenzoyl diphenylphosphine oxide _ 2 parts 2,4,6-trimethyl-6 EXAMPLE 26 10 In a mixture consisting of 55 parts of a reaction product of bisphenol A diglycide ether and acrylic acid, 45 parts of butane diol diacrylate and 55 parts of rutile pigment, dissolve the photoinitiators to be compared. The finished varnish is applied to glass plates at a thickness of 80 μπι and thus cures 15 as described in Example 25. It is found that benzild methyl ketal or α-hydroxyisobutyrophenone alone does not effect cure of the pigmented varnish. However, without significant adverse effect on the cure, they may be added to part of the present initiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

Pendulum hardness in sec.

Concentrated on a transport initiator traction band rate of 2.4.6 trimethylbenzoyl 3% 81 56 diphenylphosphine oxide 2.4.6 trimethylbenzoyl-2% phenylphosphine oxide 78 43 g-hydroxyisobutyrophenone 1% 2.4.6 trimethylbenzoyl-2% phenylphosphine oxide 71 61

Benzildimethylketal 1% α-hydroxyisobutyrophenone 3% each time only benzildimethylketal_ 3% superficially dry_ EXAMPLE 27

By esterification of 431 parts of maleic anhydride and 325 parts of phthalic anhydride with 525 parts of propylene glycol-1,2, an unsaturated polyester is prepared. After the addition of 0.01% hydroquinone, the polyester produces a 66% solution in styrene and dissolves the photoinitiator.

For light curing tests, 100 parts of this mixture are added 10 parts of 1% solution of paraffin (softening range 50-52 ° C) in styrene, and the resin is applied to glass sheets with a film coating equipment at a layer thickness of 400 µ. After approx. For 1 minute, the films are illuminated with fluorescent lamps (Philips TLA05 / 40 W) spaced 4 cm away. This test was repeated after storage in the dark for 5 days at 60 ° C in the photopolymerizable mixture. After a lighting time of 2 minutes for each sample, the following results were obtained:

Photo Initiator Concentrate Pendulum hardness after traction Konig_ immediately after 5 days ___ at 60 ° C_ 2.4.6- trimethylbenzoyl- 1% 73 73 phenylphosphine oxide 2.6 2.6-dimethoxybenzoyl- 2% 62 60 phenylphosphine oxide _

Pivaloyl diphenylphosphine 2% 60 oxide (comparison) ____

Benzyl dimethyl ketal 2% 45 40 (comparative) ____ α-hydroxyisobutyrophenone 2% 20 19 (comparative) ____ EXAMPLE 28

By esterification of 143 parts of tetrahydrophthalic anhydride and 175 parts of maleic anhydride with 260 diethylene glycol, an unsaturated polyester resin is prepared which dissolves to 64% styrene and stabilized with 0.01% hydroquinone.

For light curing experiments, 100 parts of this solution, 20 parts of TiCl 2, 10 parts of 1% paraffin solution in control 15 are added as well as each time the initiator in the specified amount. The resin is applied with a layer thickness of 60 μm on glass plates and is irradiated immediately for 20 seconds under a Hg high-pressure lamp (100 W / cm arc length) at a distance of 10 cm.

The following results are obtained: DK 171353 B1 41

Concentration Pendulum hardness by initiators ter Konig (sec) 2.4.6-trimethylbenzoyl-1% 126 diphenylphosphine oxide-2.6-dimethoxybenzoyl-1% 81 diphenylphosphine oxide-3,4-dimethylbenzoyl-2% phenylphosphine oxide

Benzil, methyl diethyl 2% + 4% 32 nolamine

While the resins sensitized to the initiators of the present invention showed no appreciable decrease in reactivity after 5 days at 60 ° C, the material added to benzil / amine was already gelled.

EXAMPLE 29 10 To 100 parts of a resin prepared as described in Example 28, 15 parts of a 0.7% solution of paraffin (mp 50-52 ° C) are added in styrene in which the photoinitiator has been dissolved. Then, the resin is added an additional 3% brightly colored pigment, rubbed 100 µm thick film 15 on glass and illuminated for 20 seconds as in Example 10. The results show that the said initiators are also suitable for curing heavily pigmented lacquers or inks, even if they are combined with suitable or little suitable initiators for that purpose ie. the 20 exhibit a synergistic effect.

DK 171353 B1 42

Initiator Pendulum hardness after Konig in sec.

by pigmentation with_

Heliogen-Heliogen-Lithol scar green 8721 blue 8070 layer 4300 2 parts 2,4,6-trimethyl-123 129 161 benzoyldiphenylphosphine oxide 1 part 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1 part benzild dimethyl 129 125 170 ketal____ 2 Examples 30 5 A 65% methanolic solution of a mixture of 60% of a copolyamide of adipic acid, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane and ε-caprolacam is prepared. % of the diether of 1 mole of ethylene glycol and 2 moles of N-hydroxymethylacrylamide, 13.2% of benzenesulfonamide and 1.8% of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and 0.2% of the aluminum salt of N-nitrosocyclohexylhydroxylamine and 0.01% of a black dye (Color-Index No. 12 195). The solution is poured into layers on a steel plate provided with an adhesive lacquer so that after drying at approx. At 70 ° C, a layer of the photopolymerizable reproduction materials with a layer thickness of 680 μιη is obtained. The resulting photopolymer printing plate is thus illuminated, as indicated in the text, in a text-wise manner through a paper, after which the unlit layers are washed with an alcohol-water mixture. The plate requires a sound-free reproduction of a 3% raster tone value DK 171353 B1 43 with a raster line width of 60 lines per second. a minimum illumination time of 4 minutes, with illumination with fluorescent lamps at a distance of 5 cm.

EXAMPLE 31

Proceed as in Example 30 but use only 11.4% benzenesulfonamide and a further 1.8% methyldiethanolamine. The minimum illumination time is only 3 minutes.

EXAMPLE 32

Proceed as in Example 30, however, as a phosphine oxide compound, 1.8% 2,6-dimethoxybenzoylphenylphosphine oxide is used as a photoinitiator. The minimum illumination time is 4.5 minutes.

EXAMPLE 33

Proceed as in Example 31, however, 1.8% 2.6-20 dimethoxybenzoyl diphenylphosphine oxide is used as the initiator. The minimum illumination time is only 2.5 minutes.

EXAMPLE 34

Proceeding as in Example 31, however, 1.8% of Versatoylldiphenylphosphine oxide (2,2-dimethyloctanecarbonylphenylphosphine oxide) is used as the initiator. The minimum illumination time is 3.5 minutes.

Comparative Experiment A 30

Proceed as in Example 30, however, as a photoinitiator 1.8% benzyl dimethyl ketal is used. Under otherwise similar conditions, the minimum illumination time here is 5 minutes. Thus, the reproduction materials of DK 171353 B1 44 have a 25-100% increased reactivity in comparison.

EXAMPLE 35 5

Proceed as in Example 30. Addition of dye is however omitted and instead of the aluminum salt, the potassium salt of N-nitrosocyclohexylhydroxylamine is added. The prepared layer of the photopolymerizable reproduction material has a dry layer thickness of 500 μπι. The plates require sound-free generation of a 3% grid tone value with a grid line width of 34 lines per second. cm, such as e.g. is often used for printing newspapers, a minimum illumination time of 50 seconds if illumination is made with a commercially available iron doped mercury high pressure lamp at a distance of 60 cm with an electrical power consumption of the UV burner of 3000 Watts / hour. The further work up of the plate is thus done as described in Example 30.

EXAMPLE 36

Work is done as in Example 35, however, only 11.4% benzenesulfonamide is used. Further, the mass contains 1.8% methyl diethanolamine. The minimum illumination time is only 35 seconds.

EXAMPLE 37 30 Proceed as in Example 35, however 11.4% benzene sulfonamide and an additional 0.9% methyl diethanolamine and 0.9% benzild dimethyl ketal are used. Further, instead of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1.8% of 2,6-dimethoxybenzoyl diphenylphosphine oxide is used. The minimum illumination time here is also 35 seconds.

Comparative Experiment B 5

Proceed as in Example 35, however, as a photoinitiator 1.8% benzyl dimethyl ketal is used. The minimum illumination time is 55 seconds under the specified conditions.

EXAMPLE 38

For 650 parts of an unsaturated polyester consisting of fumaric acid, trimellithic anhydride and triethylene glycol with an acid number of 140, 400 parts of a mixture of equal parts 15 tetraethylene glycol in methacrylate and diallyl phthalate, 2 parts hydroquinone and 7 parts 2,4,6-trimethylbenzoyl diphenyl are mixed. phosphine oxide. The liquid reproduction material thus obtained is added to 110 ppm N-nitrosodiphenylamine. 1 2 3 4 5 6 7 8 9 10 11 In a manner known per se, relief printing molds 2 are made from the reproduction material. To this end, the 3 liquid reproduction materials are poured into layers on steel sheets, 4 provided with adhesive varnish and distributed using a doctor blade 5 to layer thicknesses of 800 μπι, and the layers are then covered to exclude air with 6 µm strong transparent poly. 7 ester foil. The liquid layers of the reproduction material 8 are illuminated through the negative placed on the polyester foil 9 with a commercially available mercury pressure lamp. The negative and the polyester film are removed and then the 11 unlit layers of the reproduction material are washed out with a 0.5% aqueous soda solution. The prepared relief molds are dried and re-illuminated every 2 minutes. As the correct illumination time, at which all the required picture elements, ie: raster with 40 lines / cm and a tone value of 3%, detached DK 171353 B1 46 points with a diameter of the printed surface of 0.3 mm, fine lines with a cross section of 0.3 mm, fine lines with a cross section of 0.07 mm, are properly anchored to the carrier metal, under the given conditions 9 light units were measured with a 5 commercially available lighting machine. The relief is correct and corresponds to the claims made.

Comparative Experiments C

Exactly as in Example 38, however, 8 parts of benzyl dimethyl ketal were used instead of the 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

With this liquid reproduction material, a required illumination time of 23 illumination units was determined after the above procedure. one with the factor of 2.5 longer illumination time.

EXAMPLE 39 20 294 parts of a partially saponified polyvinyl acetate (saponification 82 mol%, average molecular weight equal to 500) are dissolved in 294 parts water at 90 ° C for several hours with stirring. After cooling to 70 ° C, 200 parts of a monomeric mixture consisting of 180 parts of 2-hydroxyethyl methacrylate, 20 parts of 1,1-trimethylolpropane triacrylate, 10 parts of 2,4,6-trimethylbenzoyl diphenylphosphine oxide and 2 parts of di-tert-butyl-p-cresol. The homogeneous viscous solution is filtered and evaporated under reduced pressure. A 30 µm strong non-adhesive layer of the reproduction material is obtained by applying to an adhesive coated steel plate and 24 hours drying at room temperature. After 2 seconds of pre-illumination and subsequent illumination of 40 seconds through a negative in a fluorescent fluorescent lamp DK 171353 B1 47 and subsequent leaching with water in a spray washer and drying at 100 ° C, a cliche with good relief structure and excellent mechanical properties is obtained. Several thousands of prints can be printed with this form. The relief printing forms give 5, in printing attempts, excellent readable negative print, which fully meets the requirements for the production of newspapers.

EXAMPLE 40 A printing plate is prepared as described in Example 39 with the reproduction material, however, instead of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, it contains the same amount of 2,6-dimethoxybenzoyl diphenylphosphine oxide. The pre-lighting time is approx. 2 seconds, the required time for 15 pictorial illumination 45 seconds.

Comparative experiments D and E

As described in Example 39, a printing plate was prepared with the reproduction material, which, however, as a photoinitiator, contained the same amounts of the known initiators benzyl dimethyl ketal (Comparative experiment D) or of benzoin isopropyl ether (Comparative experiment E). Comparison of the required illumination time of reproduction materials with the same amount content of the photoinitiator in question showed the following results: DK 171353 Bl 48

Reproduction Material Contains- Pre-illumination Imaging _ illumination 2.4.6- dimethylbenzoyl diphenyl-2 sec. 40 sec.

phosphine oxide (Ex. 39) ___ 2.6-dimethoxybenzoyl diphenyl-2 sec. 45 sec.

phosphine oxide (Ex. 40) ___

Benzildimethylketal 4 sec. 90 sec.

(comparative experiment D) _ _

Benzoin isopropyl ether 6 sec. 120 sec.

(comparative experiment E) _ _

Comparison of relief printing molds made from the illuminated printing plates from Comparative Experiment D and relief printing molds prepared from Example 39 showed that Comparative Experiment D yielded poorly formed and blurred negative prints.

EXAMPLE 41 oa Comparative Experiment F

10

As in Example 39 and Comparative Experiment D, special printing plates were prepared in the same manner which differed only in that in one case they contained 2,4,6-triethylbenzoyl diphenylphosphine oxide (Example 41) and in the other case contained benzyl dimethyl ketal (Comparative Experiment F). ) in the photopolymerizable layer of the reproduction material. Adjacent to each other, the various plates without illumination were imaged directly with a commercially available iron doped mercury high pressure lamp with a reflector at a distance of 74 cm and with an electric power consumption of the 5 kW / h UV burner through a negative.

The required minimum illumination time was determined. This was for 60 seconds for the pressure plates prepared as in Example 41 (they refer to), for pressure plates made as comparative experiment F 110 seconds.

Claims (7)

1. Acylphosphine oxide compounds for use as photoinitiators, characterized in that they have the general formula O R ^ J-C-R 3 (I) || Wherein R 1 represents a straight or branched alkyl group of 1-6 carbon atoms, a cyclohexyl or cyclopentyl group, an aryl group, a halogenated, alkyl or alkoxy substituted aryl group or a thienyl or pyridyl group; represents the same as R 1, where R * and R 2 are the same or different, or represents an alkoxy group of 1-6 carbon atoms, an aryloxy or an aryalkoxy group, or R 1 and 20 together with the P atom form a benzo group. 1,3,2-dioxaphospholane ring; represents a straight or branched alkyl group having 2-18 carbon atoms, a 3-12 carbon atom-containing cycloaliphatic group, an alkyl, alkoxy or alkylthiosubstituted phenyl or naphthyl group, thienyl or pyridyl group, a β-acetoxyethyl or β-carboxyethyl group or R 1 represents the group in R 1 30 'x, II and wherein R * and have the above meanings and X represents a phenylene group or a 2-6 carbon atom-containing aliphatic or a 3 to 6 carbon atom-containing cycloaliphatic divalent group; 5 and optionally at least one of the groups R 10 CH3 (or Cl) CH30 (or C2H50) and 15 are excluded. Acylphosphine oxide compounds according to claim 1, characterized in that it represents a tertiary aliphatic group. Acylphosphine oxide compounds according to claim 1, characterized in that R 1 represents a mono-, di- or trialkyl-substituted phenyl group, wherein the alkyl group or alkyl groups contain 1-8 carbon atoms. Acylphosphine oxide compounds according to claim 1, characterized in that R 1 represents a at least 2 times substituted phenyl group which carries at least two of the same or different substituents A and B adjacent to the carbonyl group adjacent to the carbonyl group adjacent to the carbonyl group. -6 carbon atom-containing alkyl, alkoxy or alkylthio groups, 5-7 carbon atom-containing cycloalkyl groups, phenyl groups or halogen atoms, or 52 DK 171353 B1 R · * represents a α-naphthyl group substituted at least at the 2,8-position with A and B or at least in the 1,3-position with A and B substituted β-naphthyl group. Acylphosphine oxide compounds according to claim 4, characterized in that they denote a 2,4,6-trimethylphenyl, 2,3,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-bis (methylthio) -phenyl or a 2,3,5,6-tetramethyl-phenyl group. 10 Acylphosphine oxide compounds according to claim 4, characterized in that R 1 represents 1,3-dimethyl-naphthalene-2, a 2,8-dimethyl-naphthalene-1-, 1,3-dimethoxynaphthalene-2 or a 2, 8-dimethoxynaphthalene-1 group. Acylphosphine oxide compounds according to claim 4 or 5, characterized in that R 1 and R 2 represent phenyl or C 1 -C 6 alkyl-substituted phenyl.