DK172228B1 - Photopolymerizable mass for photopolymerizable coatings, lacquers and inks - Google Patents

Description

in DK 172228 B1

The present invention relates to a photopolymerizable mass for coatings, lacquers and inks.

A number of photoinitiators of the most diverse structures are already known, for example. aromatic peptones such as acetophenone and benzophenone derivatives and benzilkalate e.g. 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 yellowing which makes it impossible to use these systems on clear (or white) surfaces or as coatings for color reproductions.

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

This is solved according to the invention by a photopolymerizable mass for the above purpose, which is characterized by the characterizing part of claim 1.

In particular, the invention provides such masses containing acylphosphine oxide compounds of the general formula I as claimed, wherein R 3 represents a at least 2 times substituted phenyl group which, at least at both of the carbon atoms adjacent to the attachment site of the carbonyl group, bears the substituents. A and B which are the same or different and denote up to 6 carbon atom-containing alkyl, alkoxy or alkylthio groups, or R3 represents a substituted α-naphthyl group at least at the 2,8-position with A or B or at the 1,3-position with A and B substituted β-naphthyl group.

DK 172228 B1 2

With respect to the general formula I, for the acylphosphine oxide compounds of the present invention, R 1 represents a straight or branched alkyl group having 1-6 C atoms such as methyl, ethyl, i-propyl, n-propyl, n-butyl, amyl, n-hexyl; cyclopentyl, cyclohexyl, aryl as phenyl, naphthyl, halogen substituted aryl, as mono-, dichlorophenyl, alkyl-substituted phenyl, as methylphenyl, ethylphenyl, isopropylphenyl, tert-butyl, dimethyl -, alkoxy-substituted aryl-, such as methoxyphenyl, ethoxyphenyl, 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, but oxy; an aryloxy group such as phenoxy, ethylphenoxy or an aryl-substituted alkoxy group such as benzoyloxy.

R ^ represents an ethyl, i-propyl, n-butyl, i-butyl, tret.-butyl, i-amyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl -, 1-nonyl, dimethylheptyl, lauryl, stearyl, cyclopropyl, cyclobutyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, norbornadienyl, adamantyl, dimethyloctyl, dimethylnonyl, dimethyldeylcyl, methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl, isopropylphenyl, methoxyphenyl, dimethoxyphenyl, i-propoxyphenyl, thiomethoxyphenyl, a and β-naphthyl , 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-methyl-thiophenyl-, 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-dichloronaphthalene-2-, 2,8-dimethoxynaphthalene-1,2 , 4,6-trimethylpyridine-3 or 2,4,5-t rimethylthiophen-3 group.

DK 172228 B1 3 R1 and R2 may contain a C-C double bond which allows the photoinitiator to be polymerized in the binder.

As examples of the lots in the photopolymerizable acylphosphinoxidforbindelser used include: 5-isobutyryl-isobutyryl methylphosphinsyremethylester phenylphosphinsyremethylester phenylphosphinsyremethylester pivaloyl-2-ethylhexanoyl-pivaloyl-phenylphosphinsyremethylester phenylphosphinsyreisopropylester 10 2,4-dimethylbenzoyl-phenylphosphinsyremethylester p-tert-butyl-pivaloyl phenylphosphinsyreisopropylester ( 4-methyl-phenyl) -phospinsyremethylester pivaloyl-acryloyl-phenylphosphinsyrevinylester phenylphosphinsyremethylester 15 of sobutyryl-diphenylphosphine oxide pivaloyl-diphenylphosphine oxide 1-methyl-1-cyclohexanoyl-diphenyl phosphine oxide 2-ethylhexanoyl-diphenyl phosphine oxide 3-pyridylcarbonyl-diphenyl phosphine oxide 20 acryloyldiphenylphosphinoxid diphenylenphosphinoxid benzoyl-2, 2-dimethyl- heptanoyl-diphenylphosphine oxide terephthaloyl-bis-diphenylphosphine oxide adipoyl-bis-diphenylphosphine oxide, in particular 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester 2,6-dimethoxybenz zoyl-phenylphosphinic acid methyl ester 2,6-dimethylbenzoyl-diphenylphosphine oxide 2,6-dimethoxybenzoyl-diphenylphosphine oxide 2, 4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester 2,4,6,6-trimethylbenzoyl-diphenylphosphine oxide 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide 2,6-dimethylthio-benzoyl-diphenylphosphine oxide 2.3.4.6-tetramethylbenzoyl-diphenylphosphine oxide 2.4, 6-trimethylbenzoyl-naphthylphosphinic acid ethyl ester 1,3-dimethylnaphthalene-2-carbonyl-diphenyl-diphenylphosphine diphenylphosphine oxide 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide 1,3-dichloro naphthalene-2-carbonyl-diphenylphosphine oxide.

Particularly preferred are aroylphenylphosphinic acid ester or aroyldiphenylphosphine oxide whose aroyl group is each substituted at the o-position with alkyl, alkoxy, alkylthio groups or mixtures thereof, e.g. 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid ester, 2,6-dimethoxybenzoyl diphenylphosphine oxide.

The preparation of such compounds occurs by reaction of acid halides of the formula 0 R 3 -L X = Cl, Br, with phosphines of the formula r! R 2 = straight or branched 2 C, P-R 4 C 1 -C 6 alkyl, or R 5 cycloalkyl having 5 or 6 C atoms.

The reaction may be carried out in a solvent, e.g. a hydrocarbon or hydrocarbon mixture such as petroleum ether, toluene, cyclohexane, an ether, other conventional inert organic solvents or also without solvent at temperatures between -30 ° C and + 130 ° C, preferably at 10-100 ° C. . The product may be crystallized directly by the solvent or left after evaporation thereof, or distilled in vacuo.

0

II

The preparation of the acid halide R 1 CX and of the substituted phosphine R 1 R 2 POR 4 takes place according to methods well known to those skilled in the art (e.g.

10 Weygand-Hilgetag, Organic-Chemical Experimental Art, pp. 246-256, Forlag J.A. Barth, Leipzig 1970 and K. Kasse in Houben-Weyl, Volume 12/1, pp. 208-209, Publisher G. Thieme, Stuttgart).

Methods for the preparation of compounds of general formula I may e.g. is illustrated as follows: 20 25 DK 172228 B1 6

ISLAND

, _. OCH- ^ J] <° X '* - j s> CH,

5 CHrO O J

X> ~ J & * V

t ° T s or ®> “> · j§r ^ c '- (or CH3 IPX o rCY' ^ '3 lvv ^ N'v fol + CK, C1 (° Τ = 15 or

Cl (or? Loc? .-) 2 + (Oy ^ f - = - * 0: 1301

Cl U CE3 ° Cl 20 DK 172228 B1 7 or @> ra, · <§Cf - · «ν» (gr - «(gr y J> AND, 5 ^

Suitable phosphines are e.g. methyl-dimethoxy-phosphine, butyl -dimethoxyphosphin, phenyldimethoxyphosphin, tolyldime-thoxyphosphin, phenyldiethoxyphosphin, tolyldiethoxyphos-phin, phenyldiisopropoxyphosphin, tolyldiisopropoxylphos phin-10, phenyldibutoxyphosphin, toluyldibutoxyphosphin or dimethylmethoxyphosphin, dibutylmethoxyphosphin, diphenyl-methoxyphosphine, diphenylethoxyphosphin, diphenylpropoxy-phosphine diphenylisopropoxyphosphin, diphenylbutoxyphos -phine or similar starting materials leading to the desired compounds.

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

Examples of the compounds which can be prepared by these processes are shown in the following table: DK 172228 B1 8

Table 1: Examples of Acyl Phosphine Oxide Compounds (Ph = phenyl)

Compound Mp. kp. Yield (C °) (C °) c K p ch, o a CH -c-C—- 10a / 0.3 = £ 5 £ 0.0 7.32 li, 9 5 «- C ^ CCa, fun.59.3 £,? i2, - o '^ ch' ** 16 * 1 / 1,2 ~ £ 5 5 11 £ ^, 05 7.33 11.03 3 2 cs2 ό '63.3 S, i 11.0 γ-Γ

ISLAND

101 - 70 1 '/ 65.65 5.67 li, il

Xi) ·. 65.7 3, £ 11.0 CHj 0?!: 105 - 73 i 75.00 5.31 9.5? Γ? Λ "75.3 5.3 9.3 CH.

c: -:, o? s i07 _ sa: µ 75, co =, 3i 5. £ 9 [Oj c'Vb. · i1 *.? 5, t 9.5 0? B 136 - oj; ii 7ό, 21 · 5.35 £ »i £« 3 ^ Js2 ^ Γλ '·' · 76.0 5.5 S.7 'c

/ * V

CH 2 CH 2

0 C

? h,? - cVcYc - ?? b, '205 - 35 ί 11 71.91 M9 l-> 6l 0W 0 "71.8 M 11, c o CH 5L.

3'c '^ NvP? V na - 81; £ 71.33, 5t 10.5a CH 2 CH 2 O 11 71.0 5.5 11.0 O r./C=3 - 120 / 0.5 - £ 0 5 "£ 0. £ 7.2 «N.57 CH2 'cHj O * S" 63.0 c, o η, a DK 172228 B1 9

Table 1: Examples of Acyl Phosphine Oxide Compounds (Ph = phenyl)

Compound Mp. Kp. Yield, o λ «r.alyje (C °) (C. °) c k t 0 Π» CH, C -? ^ - 90; ought to. 73.53 7.29 9.00 <; <5 fun.73.5 '· 3 · «BJ Gj o ri, o? B CE.-C-j-C-C -? ^ - - 90:“ δδ> 23 5; 9.0: C3. 0? I 11 5 '., 9 0.1 8.5 2 CH, 0 C-CHCCH,), - 5l ° / o, J = a 30: "52.11) 9.22 15, C5 ckf" a - "52.1 9.1 is.9 ^ J>

<o) 2? s

/ Q V-J—? : £ 5 - 65 i «77.52 6.73 3.71 11 T * '~ ^ *»' 4 o CC-H = '' - I02 ° / 0, a5 = 3 £ 0: 1 '£ 3, u 6, £ 5 15.71 0XCHj ir '53, 5 5.7 · 13.5 c?:, o? i 20 - 25 or 75.52 7.05 9.51 o ^ Th il 73.3 7.1 9, 5

ISLAND

CH, d -: _ c? I SO i 11 75.53 7 Ti2 ^ o, c6 / y <fy / v - CH- CH, C "73.9 8.1 oa J t / \ * \ C-3 f20? : i CHj DK 172228 B1 10

Said compounds have very good reactivity as photoinitiators for photopolymerizable monomers having at least one C-C polyvalent bond and mixtures thereof with known additives. The acylphosphine oxide compounds are particularly suitable as photoinitiators in photopolymerizable masses for coatings and varnishes as well as for reproduction materials. They are far superior in yellowing the varnishes thus produced or coating the previously known photoinitiators (eg benzyldimethyl ketal).

For this purpose, acylphenylphosphinic acid 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-methylcyclohexanecarboxylic acid, norbornene carboxylic acid, a 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-thiomethylbenzoic acid.

Particularly, 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 initiators, even those with white pigmented varnish cure without yellowing, but even pigmented pigmented resins can be processed. In terms of these properties, they outperform the known photoinitiators such as e.g. benzyl dimethyl ketal or α-hydroxy-i sobutyrophenone.

DK 172228 B1 11

Furthermore, it has surprisingly been found that these advantages remain or can be enhanced when combining the preferred aroyl diphenylphosphine oxides with known photo-initiators.

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

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

Suitable as photopolymerizable monomers are 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, and their esters with mono- and polyhydric alcohols, their nitriles or amides, maleic and fumar esters, and N-vinylpyrrolidone, N-vinylcaprolactamer, N -vinylcarbazole and allyl esters such as diallyl phthalate.

As polymerizable high molecular weight compounds, e.g. The following are suitable: unsaturated polyesters prepared from 30 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, tea-trahydrophthalic acid or terephthalic acid ethylene glycol, propylene glycol, butanediol, 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 and polyisocyanates), and polyester acrylates (eg made from hydroxyl group-containing unsaturated polyesters and acrylics). and methacrylic acid).

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

The photopolymerizable compounds whose composition for each application can be calculated by those skilled in the art may, in the known manner, be added to saturated and / or unsaturated polymers as well as additional additives as inhibitors of the thermal polymerization, paraffins, pigments, dyes, peroxides, reaction aids, fillers, feeders and glass fibers, and stabilizers against 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 said compounds 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%, calculated 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 which are known compounds to those skilled in the art.

For accelerating curing, further aliphatic and aromatic halides can be used, 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 said lamps 15 may optionally be doped.

The photoinitiators are also particularly suitable for photopolymerization of reproduction materials, particularly 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 polymeric binder.

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

Of the aforementioned acylphosphine oxide compounds, for the said photopolymerizable reproduction materials 30, particularly those of formula (I) are particularly suitable for the formula (I).

R 1 P-1-R 3 (D

R2 ^ ||

ISLAND

in which R 1 and R 2 represent the groups described above, and R 3 represents a tertiary alkyl group of 4 to 18 C atoms or a tertiary cycloalkyl group of 5 or 6 ring carbon atoms.

The term "in both ortho positions of the carbonyl group contains substituents A and B" is understood to mean that substituents A and B are bonded to both of the ring atoms adjacent to the attachment site with the carbonyl group. This means that the α-naphthyl group at least in the 2,8-position and the β-naphthyl group at least in the 1,3-position contain the substituents A and B bonded. Forming R3-bound containing acylphosphine oxide compounds may e.g. is represented by the structural formulas III-Vi R1R2-F0-CO- - (III) R1R2-PO-CO- ^ (IV)

B B

A A

20 (V) hV-po-co 2 Q (vi) wherein X optionally represents additional substituents in the cycloalkyl, phenyl, naphthyl or heterocyclic groups, X having the meaning of A or B.

DK 172228 B1 15

ISLAND

However, in the highly suitable acylphosphine oxide compounds for photopolymerizable masses, R may also denote a tertiary alkyl or cycloalkyl group (each time having a tertiary atom adjacent to the carbonyl group) as e.g. tert-butyl, 1,1-dimethylheptyl, 1-methylcyclohexyl or 1-methylcyclopentyl.

Particularly suitable for photopolymerizable reproduction masses are phosphine oxide compounds of formula I wherein R 1 is equal to aryl having 6-12 C atoms, such as e.g. naphthyl and especially phenyl, and equal to C 1 -C 4 alkoxy as methoxy or ethoxy and especially aryl having 6 to 12 C atoms, preferably phenyl. Surprisingly high efficiencies with simultaneous high stability are photopolymerizable reproduction materials with acylphosphine oxide compounds of formula I whose acyl group -CO-R 2 is derived from a tertiary aliphatic or cycloaliphatic carboxylic acid or at least at 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 C1-C4 alkyl groups or C1-C4 alkoxy groups.

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

DK 172228 B1 16

For this purpose, the total concentration of initiator system (photoinitiators plus amine) 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 equal to half the total initiator content.

For the mixture of a) and b), which form the basis of the reproduction materials, low molecular weight compounds with at least one photopolymerizable olefinically unsaturated double bond are well known to those masses as used monomers if they form tolerable mixtures with the polymer thus selected. binder and has a boiling point above 100 ° C at atmospheric pressure. Generally, they have molecular weights below 2000 and especially below 1000.

Preferably, monomers having 2 or more olefinically unsaturated photopolymerizable double bonds alone or in mixtures with monomers with only one olefinically unsaturated photopolymerizable double bond, the proportion of monomers having only a double bond generally only about 20%. 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, in 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 bisisallyl carbonate, and di- and polyacrylates and methacrylates which can be prepared by esterification of diols or polyols with acrylic acid or methacrylic acid, such as 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, neopentylglycol (2,3-dimethylpropanediol), 1,4-butanediol, 1,1,1-trimethylolpropane, glycerol or pentaerythritis; further the monoacrylates and monomethacrylates of such diols and polyols as e.g. ethylene glycol or 5 di-, tri- or tetraethylene glycol monoacrylate, monomers having 2 or more olefinically unsaturated linkages containing urethane and / or amide groups such as the aliphatic diolenes of the aforementioned species, 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 polyacrylates is particularly suitable. If the mixture is selected with polyamide as a polymeric binder, the monomeric species, especially the di- and polyacrylates, are suitable, which in addition to the double bonds also contain amide and / or urethane groups such as e.g. derivatives of acrylamides e.g. reaction products of 2 moles of N-20 hydroxymethyl (meth) acrylamide with 1 mole of an aliphatic diesel 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 producing 25 printing plates with polyvinyl alcohol, polyvinyl alcohol alkoxylation products or polyvinylpyrrolidone as polymeric binder, particularly water-soluble monomers such as e.g. hydroxyethyl (meth) acrylate or mono- and di (meth) acrylates of polyethylene glycols having a molecular weight of from ca. 200-500. For combination with elastomeric diene polymers as binder e.g. polystyrene-polyisoprene-polystyrene three-block copolymers, polystyrene-polybutadiene two-block polymers or polystyrene-polyisoprene two-block copolymers are particularly suitable for 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 are considered, in addition to being 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 saturated or unsaturated binders include linear polyamides and especially alcohol-soluble copolyamides as disclosed in French Patent Specification no.

1,520,856, cellulose derivatives, especially aqueous-alkaline leachable cellulose derivatives, vinyl alcohol polymers and polymers and copolymers of vinyl esters of aliphatic monocarboxylic acids having 1-4 C atoms such as vinyl acetate, with various degree of saponification and polyurethanes, polyurethanes, polyurethanes, polyurethanes, polyurethanes, polyurethanes such as those who e.g. is disclosed in German Publication No. 20 40 390. Among the linear or branched polyesters of linear or branched kind produced by the reaction of unsaturated and optionally saturated and optionally polybasic carboxylic acids with di- and optionally polyalcohols, are particularly preferred. acid numbers between 75 and 160 as they lead to excellent dispersibility 30 and solubility of 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.

DK 172228 B1 19

Boenig, Unsaturated Polyesters, Structure and Properties, Amsterdam 1964.

The reproduction material at issue consists predominantly ie. more 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).

It is often also advantageous to add the usual copolymerizable materials to the photopolymerizable materials against the thermal polymerization, 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 alkali and 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 presenting, in layer form, the reproductive material as an embossed layer, can be made in known manner and is dependent on the nature of the mixture a) plus b) and whether the mass is liquid or solid. The work-up of reproduction materials (for example, for relief molds) is done in a known manner by imagery 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 reproduction material are mechanically or per se known to be 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 the layers of the subject reproduction materials, as mentioned in Example 39, in the processing into relief printing molds provide an improved relief structure, which e.g. printing results in a clearly improved reproduction of negative print.

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.

EXAMPLE 1 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 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 fractionally distilled at 0.1-1 torr. Co-dot q 5 120-124 ° C. Yield: 175 parts (80% calculated on diphenyl chlorophosphine).

DK 172228 B1 21

To 36.2 parts of pivaloyl chloride, 64.8 parts of diphenylmethoxyphosphine 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).

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

Analysis (286) 10

C Η P

Calculated 71.33 6.64 10.84

Found: 71.0 6.5 11.0 Example 2

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 ° 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 (CDCl 3, δ): 2.35 (S), 7.2-8 (m)

Analysis C₂QH ^ yO₂P (320)

C Η P

Calculated 75.00 5.31 9.69

Found: 75.3 5.8 9.3 DK 172228 B1 EXAMPLE 3 22 By analogy to Example 2, 77 parts of 2-methylbenzoic acid chloride and 108 parts of methoxyphenylphosphine are prepared 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 C20H17O2P

C Η P

Calculated 75.0 5.31 9.69

Found: 74.7 5.4 9.5 EXAMPLE 4 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 evaporation of the solvent on rotary evaporator, recrystallize 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)

C Η P

Calculated 76.24 6.35 8.56

Found: 76.0 6.5 8.7 20 EXAMPLE 5 23 In analogy to Example 2, 52 parts of terephthalic acid chloride dissolved in 200 parts of toluene and 108 parts of 5 methoxydiphenylphosphine are prepared 46 parts of terphthaloyl bis-diphenylphosphine oxide (yield 35% of theory). Mp. 205 ° C.

NMR (CDCl3, δ): 6.8-8.2 (m) Analysis C32H24 ° 4P2 (534)

C Η P

Calcd 71.91 4.49 11.61

Found: 71.8 4.8 11.0 EXAMPLE 6 Proceeding as in Example 2 is obtained from 80 parts of 1-methyl-1-cyclohexane carboxylic acid chloride and 108 parts of methoxydiphenylphosphine without solvent 100 parts of 1-methylcyclohexylcarbonyldiphenylphosphine oxide as an oily crude product which is purified by chromatography on 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)

C Η P

Calculated 73.62 7.06 9.51

Found: 73.3 7.1 9.6 Example 17 24 In analogy to Example 1, 88 parts of 2-methyl-2-ethylhexanoic acid chloride and 108 parts of methoxydiphenylphosphine are obtained from 5 165 parts of 2-methyl-2-ethylhexanoyl diphenylphosphine oxide as a 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)

Analysis C21H27O2P (342)

C Η P

Calculated 73.68 7.89 9.06

Found: 73.9 8.1 9.4 Example 8

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, after which it is further stirred for 1 hour under ice-cooling. The solvent is then suctioned off and distilled off under reduced pressure. Versatoyl diphenylphosphine oxide remains as a viscous oil.

Yield 62 parts (90% of theory) NMR (CDCl 3, δ): 0.4-2.3 (m), 7.2-8.1 (m) DK 172228 B1

Analysis ^ 21 ^ 27 ^ 2 ^ (342)

C Η P

Calculated 73.68 7.89 9.06

Found: 73.6 8.1 8.6 Example 9 5

To a mixture of 600 parts by volume of petroleum, 263 parts of N, N-diethylaniline and 120 parts of isopropanol, 143 parts of phenyl dichlorophosphine are dropped over 1 hour at 0 ° C. Then, stir for an additional 1 hour at 10 room temperature, and after working up as in Example 1, distill. The diisopropoxyphenylphosphine distills at 68-72 ° C / 0.3 mm. Yield 126 parts (69% of theory).

15 158 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 20 theoretical).

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

Analysis C14H21 ° 3P <268> 25

C Η P

Calculated 62.68 7.84 11.57

Found: 63.0 8.0 11.4 DK 172228 B1 EXAMPLE 10 26

To a mixture of 1000 parts by volume toluene, 421 parts by volume N, N-diethylaniline and 100 parts by volume of methanol, 5 at 0 ° C add 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 dimethoxyphenylphosphine distills at 46-50 ° C / 0.2-0.3 mm. Yield 190 parts (93% of theory).

10

To 78.7 parts of pivaloyl chloride, 110.5 parts of dimethoxyphenylphosphine are dropped at 15 ° C. The 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 passes at 104-107 ° C / 0.3 mm. Yield 101.3 parts (65% of theory).

NMR (CDCl 3, δ): 1.3 (S), 3.75 (d), 7.4-8 (m) Analysis C 21 H 17 ° 3 P (240)

C Η P

Calculated 60.0 7.08 12.9

Found: 59.8 6.9 12.4 EXAMPLE 11 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.

DK-172228 B1 27 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 C15H22 ° 3p (281)

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 dimethoxyphenylphosphine at 30 ° C. The reaction mixture is then allowed to react for 50 ml. 15 minutes, then cool at 0 ° C and the precipitate is extracted. After recrystallization with cyclohexane, 4-methylbenzoylphenylphosphinic acid methyl ester melts at 99-101 ° C.

Yield 180 parts (65% of theory).

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

Analysis C ^H₂OOP (274)

C Η P

Calculated 65.69 5.47 11.31

Found: 65.7 5.6 11.0 Example 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 is added with stirring at 0 ° C 225 parts of diphenyl chlorophosphine dissolved in 220 volumes. petroleum ether. The mixture is then stirred for 2 hours at room temperature. After cooling to approx. +5 ° C is filtered off 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. M.p. 5 120-124 ° C. Yield: 175 parts (80% based on diphenyl chlorophosphine).

10

To a reflux and drip funnel stirrer, 648 parts of methoxy-diphenylphosphine 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 content is dissolved at 30 ° C in ether and petroleum ether is added to incipient cloudiness. Upon cooling, 110 parts (47% of theory) crystallize 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 25 this mixture, 21.6 parts of methoxydiphenylphosphine are 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

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

5

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

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

TABLE 2_

Analysis_

Yield Kgp. Mp. ° C Η P

tea (mm) 2, 4,6-Trimethyl-87¾ - 80,81 Calculated 75, 86 6, 03 8, 91 benzoyl diphenylphosphate-Found 75.9 6.1 8.9 Phine oxide 2,4,6-Trimethyl-81% - 51-52 Calculated 67.55 6.29 10.26 Benzoylphenylphos- Found 67.5 6.5 10.1 Phinfluoromethyl 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 5 5, 2 5.7 3.9 EXAMPLE 17 DK 172228 B1 30

A covering pigmented varnish is prepared from a mixture 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-10 is ironed 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.

15

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

EXAMPLE,. 18 20

To a binder consisting of 65 parts of a reaction product of bisphenol-A-diglycidyl ether with 2 equivalents of acrylic acid and 35 parts of butanediol-1,4-diacrylate, 3 parts of photoinitiator were added each time. This mixture was applied at 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 at which the samples could be passed under the lamp was measured to obtain the necessary irradiation to obtain layer-proof, rub-resistant surfaces. The following values were measured: DK 172228 B1 31 TABLE 3 _ The curing activity of the photoinitiators_

Maximum conveyor belt speed

Under Under air, add-Under inert of 3% N-phe-

Initiator__ air gas_nylglycine_

Pivaloylphosphonic acid diethyl ester

Pivaloylphenylphosphine

Toluyl-phenylphosphine-acid methyl ester 2-ethylhexanoyl-phenyl-40-phosphinic acid methyl ester

Toluyl diphenylphosphate 70 phino oxide 2-methylbenzoyl diphen 70 phosphine oxide

Pivaloyl-diphenylphosphine Phosphine Oxide EXAMPLE 19

To a lacquer prepared in Example 18 was added 3% N-phenylglycine. Then, as in Example 14, 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 pivaloyl diphenylphosphine oxide.

5 For light curing tests, 100 parts of a 1% solution of paraffin (softening range 50-52 ° C) are added to 100 parts of this mixture and the resin is applied to glass sheets with a film application equipment at a layer thickness of 400 µ. After approx. For 1 minute, the film is illuminated with fluorescent lamps (Philips "TLA" 05/50 W) placed at a distance of 4 cm.

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 to 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). The thus hardened specimen was impact resistant and shiny.

As Table 4 shows, the compounds of this invention far exceed those known to date, characterized by the initiators benzyl dimethyl ketal and the mixture benzidimethylketa / benzophenone / methyl ethanolamine.

30 DK 172228 B1 33 _ 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 diphenylphosph 3% -3.33 phinoxide p-toluyl diphenylphose 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 SKSEHPEL-22

To measure the curing activity of the subject photo-polymerizable 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 the molar ratio of 1: 2: 2.4: 0.85 gives an unsaturated polyester with an acid number of 50.

Resin B: From maleic acid, tetrahydrophthalic acid and diethylene glycol at 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.

DK 172228 B1 34 10 g of such resin was sensitized with 0.35% of the photoinitiator in question and then irradiated in a white tin tray (cross section 3.8 cm) which, to be heat insulated, was coated with a polyurethane resin foam. As a source of radiation, a UV field (87 x 49 cm) consisting of 10 side-by-side lamps (TUV 40 / 0.5, Philips, served the sample distance was 10 cm). The temperature course of the resin was recorded during curing by means of a thermocouple with a 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) TmRV (° 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 15 In a binder consisting of 65 parts of a reaction product of bisphenol A diglycidyl ether and acrylic acid, 35 parts of butane-1,4-diol diacrylate and 3 3 parts of photo-initiator are seen. 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 conveyor belt velocity at which a continuous scratch-hardening of the lacquer film is obtained.

_TABLE 6_ _Reactivity of the Photo Initiators_

Reactivity (

Photoinitiator (m / min) - 2.4-dichlorobenzoyl diphenyl <10 phosphine oxide 3,4-dimethylbenzoyl diphenyl <10 phosphine oxide 2,4,6,6-trimethylbenzoyl diphenylphosphine oxide which carries substituents in other positions of the benzoyl group.

Example 24 A paint system analogous to Example 23 is added to the following photoinitiator combinations and tested as described in Example 23.

20 DK 172228 B1 36

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 2 parts benzophenone 1 part 2 6-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 reaction product 5 of bisphenol-A-diglycidyl ether and acrylic acid, 45 parts of bu-tandiol diacrylate, 45 parts ruti1 pigment and 3 parts methyl diethanolamine are dissolved below the photoinitiators listed.

The finished mixture is applied as a spiral (80 μπι) to glass plates and passed by two 10 Hg high-pressure lamps (80 W / cm) placed 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 target for the curing is obtained.

20 DK 172228 B1 37

Reactivity - Softness of Transparency terger Berger the layer thickness Photoinitiator __ (m / min) (% rem.) Boiling 2 parts 2-methylthioxane-12 66 130 µ thon______ 1.5 parts 2-methylthio-xanthone 0.5 parts 2 , 4,6-trimethylsulfonoxide, 4,6-trimethylsethoxyphenylphosphine oxide, 1.0 parts 2-methylthio-xanthone 1.0 parts 2,4,6-trimethylsulfonoxide, phosphate oxide 2 parts 2,4,6-trimethyl-6 81 70 µl benzoylphosphine oxide EXAMPLE 26 In a mixture consisting of 55 parts of a reaction product 5 of bisphenol-A-diglycidyl ether and acrylic acid, 45 parts of bu-tandiol diacrylate and 55 parts of rutile pigment, the photo-initiators to be compared are dissolved. The finished varnish is applied to a thickness of 80 μιη on glass plates and cured as described in Example 25. It is found that benzil-10-dimethylketal or α-hydroxyisobutyrophenone alone does not effect cure of the pigmented varnish. However, without a significant adverse effect on the cure, they can be added to a portion of the initiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

15 DK 172228 B1 38

Pendulum hardness in sec.

Concentrated on a transport initiator__tration band rate of_ 2.4.6-trimethylbenzoyl-3% 81 56 diphenylphosphine oxide___ 2.4.6-trimethylbenzoyl-2% phenylphosphine oxide 78 43 α-hydroxyisobutyrophenone__1% ___ 2.4.6-trimethylbenzoyl-2% phenylphosphine oxide 71 61

Benzildimethylketal_ 1% __ α-hydroxyisobutyrophenone 3% each time only benzildimethylketal_ 3% superficial dry_ EXAMPLE 21

By esterification of 431 parts of maleic anhydride and 325 parts of 5 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.

10 For light curing tests, 100 parts of this mixture are added 10 parts of a 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 light-fabric lamps (Philips TLA05 / 40 W) spaced 4 cm apart. This test was repeated after dark storage of the photopolymerizable mixture for 5 days at 60 ° C. After an illumination time of 2 minutes for each sample, the following results were obtained: 20 39 DK 172228 B1

Concentrate Pendulum Hardness after Konig Photoinitiator tration immediately after 5 days at ___60 ° C_ 2.4.6- trimethylbenzoyl- 1% 73 73 dlphenylphosphine oxide 2.6 2.6-dimethoxybenzoyl- 2% 62 60 phenylphosphine oxide____

Pivaloyl diphenylphosphate 2% 60 Phine Oxide (Comparison) ____

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

By esterification of 143 parts of tetrahydrophthalic anhydride and 5 175 parts of maleic anhydride with 260 diethylene glycol, an unsaturated polyester resin is dissolved, dissolved to 64% in styrene and stabilized with 0.01% hydroquinone.

For light curing experiments, 100 parts of this solution, 20 parts of TiO 2, 10 parts of 1% paraffin solution in styrene are added, and 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. You get the following results: 20 DK 172228 B1 40

Concentration Pendulum hardness of 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 with 5 benzil / amine was already gelled.

EXAMPLE 29

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 to the styrene in which the photoinitiator has been dissolved. Then, the resin is added another 3% brightly colored pigment, rubbed 100 µm thick films on glass and illuminated for 20 seconds as in Example 10. The results show that the initiators in question are also suitable for curing heavily pigmented paints or of inks, even if combined with suitable or little suitable usual initiators ie. they exhibit a synergistic effect.

DK 172228 B1 41

Initiator Pendulum hardness after Konig in sec.

by pigmentation with ____

Heliogen-Heliogen-Litholskar-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 μπι is obtained. The resulting photopolymer printing plate is thus illuminated, as indicated in the text, in a textual manner through a paper, after which the unlit layers are washed out with an alcohol-water bond. The plate requires a silent reproduction of a 3% grid tone value with a grid line width of 60 lines per second. cm a minimum exposure time of 4 minutes, where the illumination takes place with fluorescent lamps at a distance of 5 cm.

EXAMPLE 31 5

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 phos- phine 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-dimethoxybenzoyl diphenylphosphine oxide is used as the initiator. The minimum-20 candle lighting time is only 2.5 minutes.

EXAMPLE 34

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

Comparative Experiment A

30 As in Example 30, 1.8% benzyl dimethyl ketal is used as the photoinitiator. Under otherwise similar conditions, the minimum illumination time here is 5 minutes. Thus, the reproduction materials of DK 172228 B1 43 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 3,000 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-dimethoxy-benzoyl 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 b -38

For 650 parts of an unsaturated polyester consisting of fumaric acid, trimellithic anhydride and triethylene glycol with an acid number of 140, mixed with 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 phosphine oxide. The liquid reproduction material thus obtained is added to 110 ppm N-nitrosodiphenylamine.

In a manner known per se, relief printing forms are made from the reproduction material. To this end, the liquid reproduction materials are poured into layers on steel sheets provided with adhesive varnish and distributed using a 800 μπι layer thickness gauge, and the layers are then covered to exclude air with a 6 μια strong transparent polyester film. The liquid layers of the reproduction material are illuminated through the negative disposed on the polyester film with a commercially available mercury pressure lamp. The negative and polyester foil are removed and then the 30 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 45 dots 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, properly anchored to the carrier metal, were measured under the given conditions for 9 lighting units 5 with a commercially available lighting machine. The relief is correct and corresponds to the claims made.

Together, igingafors increase_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 μπι strong non-adhesive layer of the reproductive material is obtained by applying 30 adhesive sheets to a 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 tube surface lit and subsequently leaching with water in a spray washer as well as drying at 100 ° C, a cliche with good relief structure and excellent mechanical properties is obtained. properties. Several thousands of prints can be printed with this form. Relief printing forms, in printing experiments, provide excellent legible negative prints which are fully sufficient for the requirements of producing newspapers.

EXAMPLE 40 10

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.

15 The pre-lighting time is approx. 2 seconds, the required time for pictorial illumination 45 seconds.

Comparison test d Qg..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 benzildimethylketal (comparative experiment D) or of benzoin isopropyl ether (comparative experiment E), respectively.

25 Comparison of the required illumination time of reproduction materials with the same amount of content of the photoinitiator in question showed the following results:

Reproduction Material Contains - Pre-illumination Visual 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 made from Example 39 showed that Comparative Experiment D yielded poorly formed and blurred negative prints.

EXAMPLE 41 and Comparative Experiments 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-trimethylbenzoyl diphenylphosphine oxide (Example 41) and in the other case contained benzyl dimethyl ketal (Comparative Experiment F). ) in the photopolymerizable layer of the reproduction material. Next to each other, the various plates without illumination were imaged directly with a commercially available iron doped mercury high pressure lamp 20 with a reflector at a distance of 74 cm and with an electric power consumption of the 5 kW / hour UV burner through a negative. The required minimum illumination time was determined. This was for 60 seconds for the printing plates prepared as in Example 41 (they dealt with), for printing plates made as comparative experiment F 110 seconds.

Claims (12)

1. Photopolymerizable mass for photopolymerizable coating agents, lacquers and inks, characterized in that it contains as photoinitiators acyl phosphine oxide compounds of the general formula Rl ^ p. | .R3 10 r2 ^ - || <> 0 wherein R 1 represents a straight or branched alkyl group having 1-6 carbon atoms, a cyclohexyl or cyclopentyl group, an aryl, halogen, alkyl or alkoxy substituted aryl group, a thienyl or pyridyl group; R 2 is the same as R 1, wherein R 1 and R 2 are the same or different, or represent an alkoxy group of 1-6 carbon atoms, an aryloxy or an aryl alkoxy group, or R1 O 20 and R 1,2,3-dioxaphos-pholanring; OR represents a straight or branched alkyl group of 1-18 carbon atoms, a cycloaliphatic group of 3-12 carbon atoms, a phenyl group, a naphthyl group, an alkyl, alkoxy or thioalkoxy substituted phenyl or naphthyl group, a thienyl or pyridyl group. , β-acetoxyethyl or β-carboxyethyl group, or R 2 represents the group 30. ii / Rl II R o DK 172228 B1 50 wherein r! and has the above meanings, and X represents a phenylene group or an aliphatic or cycloaliphatic divalent group of 2-6 carbon atoms; 5 wherein optionally at least one of the groups R 1 - R 2 is olefinically unsaturated. Photopolymerizable mass according to claim 1, characterized in that R 1 in the 10 acylphosphine oxide compounds used as photoinitiators represents a tertiary aliphatic group. Photopolymerizable mass according to claim 1, characterized in that R 1 in the 15 acyl phosphine oxide compounds used as photoinitiators represents a mono-, di- or trialkyl-substituted phenyl group, wherein the alkyl group or alkyl groups contain 1-8 carbon atoms. Photopolymerizable mass according to claim 1, characterized in that R 1 in the acylphosphine oxide compounds used as photoinitiators represents a at least disubstituted phenyl group bearing at least both of the carbon atoms adjacent to the carbonyl group substituents A and B which are or 25, and which represents alkyl, alkoxy or alkylthio groups of 1-6 carbon atoms, or R 1 represents at least in the 2,8-positions with A and B substituted α-naphthyl group or at least one in the 1,3-positions with A and B substituted β-naphthyl group. 30 Photopolymerizable mass according to claim 4, characterized in that R 1 in the acylphosphine oxide compounds used as photoinitiators represents 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. Photopolymerizable mass according to claim 4, characterized in that in the acylphosphine oxide compounds used as photoinitiators, 1,3-dimethylnaphthalen-2, a 2,8-dimethylnaphthalene-1-, 1,3-dimethoxy-2 naphthalene-2 or a 2,8-dimethoxynaphthalene-1 group. 7. Photopolymerizable mass according to claim 4, characterized in that R · and R ^ in the acylphosphine oxide compounds used as photoinitiators have the meaning C ^-Cg alkyl substituted phenyl. Photopolymerizable mass according to any one of the preceding claims, characterized in that the mass contains secondary and / or tertiary amines. Photopolymerizable mass according to any one of the preceding claims, characterized in that the acylphosphine oxide compounds used as 20 photoinitiators are used at a concentration of 0.001% to 20%, preferably 0.01% to 4%. Photopolymerizable mass according to any one of the preceding claims, characterized in that the mass 25 contains aromatic ketones in a mixture ratio acyl-phosphine oxide compound: aromatic ketone from 10: 1 to 1:30, preferably 1: 1 to 1:10. Photopolymerizable mass according to claim 10, characterized in that, as a reaction promoter, a tert-amine is added at a concentration of 0.5 to 15%. DK 172228 B1 52 Photopolymerizable mass according to any one of the preceding claims, characterized in that the mass contains a tert-amine as well as a benzophenone and / or thi-oxanthone optionally substituted with methyl, isopropyl, chloro or chloromethyl groups or a benzil dimethyl ketal, benzoin isopropyl ether, α-hydroxyisobutyro-phenone, diethoxyacetophenone or p-tert-butyltrichloro-acetophenone such that the total content of photoinitiators is between 1% and 20% of the total amount of the photo-10 polymerizable mass.