FI69085C - FOTOPOLYMERISERBAR REGISTRERINGSMASSA ISYNNERHET FOER FRAMSTAELLNING AV TRYCKPLATTOR OCH RELIEFFORMAR - Google Patents

Description

69085

The present invention relates to a photopolymerizable recording medium, in particular for the production of printing plates and embossing molds, which contains an acylphosphine oxide compound as a photoinitium-10 initiator.

Several photoinitiators of different structures are now known, e.g. aromatic ketones such as acetophenone and benzophenone derivatives and benzyl ketals, e.g. benzyl dimethyl ketal (DE 22 61 383), benzoin ether (DE 16 94 149), thioxanthone (DE 20 03 132) ym However, the effect of light on polymerizable masses cured with such initiator systems exhibits undesired yellowing, rendering these systems unsuitable for light (or white) surfaces or as color-accurate image surfaces.

On the downside, pre-sensitized resin blends often have insufficient storage stability, with blends often remaining in the dark for often only a few days despite storage. Acylphosphines, the use of which as photoinitiators is also known from U.S. Pat. No. 3,668,093, also have insufficient storage stability.

The present invention relates to a photopolymerizable recording mass, in particular for the production of printing plates and embossing molds, comprising a mixture of 30 photoinitiators comprising a) at least one low molecular weight compound having at least one photopolymerizable olefinic unsaturated double bond and b) at least one organic polymer -sideainetta.

The recording composition according to the invention is characterized in that it contains, as a photoinitiator, an acylphosphine oxide compound of the formula ___ - · ΤΓ ^ 2 69085

R1 O

PCR (I) • yS h R 1 o 5 wherein R 1 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 ring carbon atoms, or an optionally halogen-, alkyl- or alkoxy-substituted aryl - 2 1 1 is a group, R 11a is a meaning according to R, wherein R and 2 R may be the same or different from each other or 2 10 R is an alkoxy, aryloxy or arylalkoxy group or 12 3 R and R are joined together as a ring; R is a tertiary alkyl group having 4 to 18 carbon atoms or a tertiary cycloalkyl group having 5 or 6 ring carbon atoms or a cycloalkyl group, an aryl group or a pyridyl, furyl or thienyl group bonded to both ortho to the carbonyl group. positions A and B, wherein A and B are alkyl, alkoxy, alkoxyalkyl, alkylthio, cycloalkyl or aryl groups or halogen atoms, and A and B may be the same or different.

Suitable acylphosphine oxide compounds of the formula I for use in the pulp according to the invention are those in which 2 R is a phenyl, pyridyl, furyl or thienyl group having at least two carbon atoms adjacent to the carbonyl group attachment point 25 which may be identical or different from 1 to 4. Alkyl, alkoxy or alkylthio groups having 6 carbon atoms, cycloalkyl groups having 5 to 7 carbon atoms, phenyl groups or halogen, preferably chlorine or 3 bromoatro, or R is a <x-naphthyl group having substituents at at least 2.8 positions A and B, or a β-naphthyl group having at least 1,3-positions as substituents A and B.

The present invention further relates to a method of making embossing molds using a light polymerizable recording mass according to the invention.

3 69085

Among the meanings of the substituents of formula (I), the following may be mentioned in detail: R 1 may be straight or branched alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, isopropyl, n-prop-5-yl, n-butyl, amyl or n- hexyl, cyclopentyl, cyclohexyl, aryl such as phenyl or naphthyl, halogen-substituted aryl such as mono- or dichlorophenyl, alkyl-substituted phenyl such as methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl or di-10-methylphenyl, di-10-methylphenyl - phenyl, ethoxyphenyl or dimethoxyphenyl, in addition to the meaning corresponding to 12 R, R may be an alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, isopropoxy, butoxy or ethyloxyethoxy, an aryloxy group, such as phenoxy, methylphenoxy, an aryl-substituted alkoxy group such as benzyloxy, 12 R and R may form a ring, such as in acylphosphonic acid-o-phenyl esters, R · * may be tert-butyl, dimethylheptyl, 1-20 methylcyclic lopentyl, 1-methylcyclohexyl, dimethyloctyl, dimethylnonyl, dimethyldecyl, dimethylphenyl, trimethylphenyl, dimethoxyphenyl, of- and? -n & f-style, pyridyl, β-acetoxyethyl or β-carboxyethyl, preferably 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-dimethylnaphthalene-2,2,8-dimethylnaphthalene-1,30 1,3-dimethoxynaphthalene-2, 1,3-dichloronaphthalene-2,2,8-dimethoxynaphthalene-1,2,4,6-trimethylpyridine-3,2,3-dimethoxyfuran-3 or 2,4,5-trimethylthiophene-3.

1 2 R and R may additionally have C-C double bonds which allow the photoinitiator to be polymerized to the binder.

4 69085

Particularly preferred compounds of the formula I are aroyl-phenylphosphinic acid esters or aroyldiphenylphosphine oxides in which the o-position of the aroyl group is substituted by alkyl, alkoxy, 5-halogen, alkylphenoxyphenylphenylphenylphenylphenylphosphinoylbenzoylbenzoyl , 2,4,6-trimethylbenzoyl-phenyl-phosphinic acid methyl ester, 2,6-dichlorobenzoyl or 2,6-dimethoxy-benzoyldiphenylphosphine oxide.

These compounds can be prepared by reacting an acid halide of formula

O

15 R3-C-X X = Cl, Br, R1 \ 4

react with a phosphine of formula P-OR

R2 / 20 4 16 R = straight-chain or side-chain C1-C4-alkyl or cycloalkyl radical having 5 to 6 carbon atoms.

The reaction may be carried out without a solvent or in a solvent, e.g. a hydrocarbon or hydrocarbon mixture such as petroleum ether, toluene, cyclohexane, ether or other common inert organic solvent at a temperature in the range of -30 to + 130 ° C, preferably 10 to 100 ° C. . The product can be crystallized directly from the solvent, recovered after evaporation of the solvent as an evaporation residue or O 3 "distilled in vacuo. Recovery of acid halides R CX and substituted 5 69085 12 4 phosphine RR POR takes place in a manner known in the art (e.g. Weygand-Hilgetag, Organisier-Chemis , Aufl., Pp. 246-256, JA Barth-Verlag, Leipzig 1970 and K. Sasse, Houben-Weyl, Band 12/1, 5 pp. 208-209, G. Thieme-Verlag, Stuttgart).

The process for the preparation of acylphosphine oxides can be represented by the following reactions: - N - 'OCHj 15 CH3 ch3 ° \ S roT "* * CH3Cl

Coj 5 20 or ΊοΊ 0 25 X> -0CH, - ♦ foj C1 -> (of ’^

„(¾ o r /" 'J

· «I · 1 t ° rs or F1 C1 <§Η · (0ίΗ3) 2 * <pVc {- ~ * CH3C1 Λι 3 ci or ____ ΤΓ ~ ______ 6 69085 (οχ, Λ (qX« (gί'Φ 3 0CH3 10 Suitable phosphine starting materials are, for example, methyl lidimetoksifosfiini, butyylidimetoksifosfiini, phenyldiisopropylsilyl methoxyphosphine, tolyylidimetoksifosfiini, fenyylidietoksi-phosphine, tolyylidietoksifosfiini, phenyl di-iso-phosphine, tolyl isopropoksyylifosfiini, fenyylidibutok- 15 sifosfiini, toluyylidibutoksifosfiini or dimetyylimetoksi-phosphine, dibutyylimetoksifosfiini, dimetyylibutoksifosfiini, diphenylmethoxyphosphine, diphenylethoxyphosphine, diphenylpropoxyphosphine, diphenylisopropoxyphosphine and diphenylbutoxyphosphine.

Suitable chlorides and bromides for acid halides, in particular acid chlorides.

Examples of photoinitiators used in the recording media according to the invention are the following: 7 69085

table 1

Examples of compounds of formula I (Ph phenyl)

Analysis

Yfr ^ iQte SP (0c> Kp. <Oc) Yield c h p ch3 2 Ph CH 2 -C-C-P 2 - 100 / 0.3 mn 65 i calc. 60.0 7.08 12 ,? CH} δ ocHj obtained 59.8 6 ,? 12. * · o / CH -'Sy CH- "s, / PVl y <10 CH · 2 CH- 2 CH P - 16 * 1 / 1.2 nn 65 S löSK. Gö, 06 7.53 11.03 chj ö och3 obtained 63.8 3.1 no CH ^ 101 - 70: calc · 65.69 5.V7 1:, 31

Az 6 O 5 Cli obtained 65.7 5.5 :: .0 CH.

15 J

0 Ph frY ^ r 'i ° 5 - 73 i calc. 75.00 5.31? .6? o? h obtained 75.> 5.8?, j CH j CH, 0 Ph ΟΛ 107 - a *; calc. 75.00 5.31?, Ί? ö Ph obtained 75.7 5, i?, 5 0 Ph 136 - 33 ϊ calc. 76.2 * 5.35 s, * 6 CK3 ^ Ö ^ Ph obtained 76, c 5.5 8.7 c ^ CH, CH, 25 O o

Ph2P-cVc) -C-PPh2 205 - 35 «calc. 71.51 1.19 11.61 ow o obtained 71> β «, β u.c o CK3 ^ 30 c pphj 11 * - 81 'calc. 71.33 6.6t 10, su ch, ^ vcHj ö obtained n> ° 6 · 5 n> ° O / CH, CH, / «s. .-CH 7 1 3'C ^ Pv '' CH, - 120 / 0.5 «= 60 i -LaSK. £ 2.68 7.86 11.57 ch, "^ oh, o Ph obtained 63.0 e.o n, <* 8 69085

Continued in Table 1

The compound Sp. Kp. Yield Analysis

(° C) (° C) C H P

O

«/ 5 CH CH_ CH C-P - 90% calc. 73.68 7.89 9.06 CH CH 2 O Ä obtained 73.6 8.1 8.6 2 2 \ ^ 3 ^ 3 0 CH O Ph "1 J li ^ _ _ ηη CHo-C-O-CH "-C - CP 90% calc. 66.28 6.11 9.01 1ϋ 3 2 | CH3 o obtained 65.9 6.1 8.6 CH3 / 5 ^ (> <31 (013) 2 'c P ^ f - 51 ° / 0.3 im »80% calculated 52.43 9.22 15.05 / \ Il \ 15 CH3 CH3 O CH3 obtained 52.1 9.1 14.9 / CT \ 166 - 65% calculated 77.52 4.78 8.71 (yy o Ph) - \ I / obtained 77.7 4.8 8.4 (O) -LP.

N— / n \ O Ph 20 3 ^ - 102 / 0.05 nm 60% calc. 58.41 6.64 13.71 O CH- 3 obtained 58.9 6.7 13.5 CH O Ph 25 (kV »\ O Ph 80 - 26% calculated 73.62 7.06 9.51 obtained 73.3 7.1 9.6

O

M DU

30 CH CH C s S '2 \ / 2 \ / v / / CH C XP - - 90% calc. 73.68 7.89 9.06 CH3 ^ 3 fH2? it is to be understood here that the substituents A and B are attached to the two ring carbon atoms adjacent to the point of attachment of the carbonyl group in which the substituents may be present. This means that the substituents A and B of subsII 69085 are bound to at least the 2.8-position in the cL-naphthyl residue and to at least the 1.3-position in the β-naphthyl residue. In the cyclohexyl residue the substituents A and B are in the 2,6-positions, in the cyclopentyl residue in the 2.5-position. Such acylphosphine oxide compounds containing R3 residues can be represented, for example, by structural formulas II-VII, R1-PO-CCM ^ iT ^ (ii)? r1r2-po-co - (III) A A - _R1R2-PO-CO - (IV); «V-PO-CO-Q (y) 15 x b r1r2-po-co ^ J <n ^ <. a (J, R (r) -po-co- (N, S, O (VII) 20 BB ZU χ wherein X corresponds to any other substituents on cycloalkyl, phenyl, naphthyl or heterocyclic radicals having A meaning according to A and B.

However, acylphosphine oxide compounds which are well suited to the polymerizable pulps under the influence of light may also have a tertiary alkyl or cycloalkyl residue (each having one tertiary C atom in the position adjacent to the carbonyl group), such as tert-butyl, 1,1-dimethylheptyl, 1-methyl or 1-methylcyc-30 lopentyl.

The phosphine oxide compounds of the formula I in which RA is aryl having from 6 to 12 carbon atoms, 2, such as naphthyl, toluyl and in particular phenyl, and R is 35 C 1 -C 4 alkoxy, such as methoxy, are very suitable for light-polymerizable storage media. or ethoxy and corresponds in particular to 10,69085 aryl having 6 to 12 carbon atoms, mainly phenyl. Surprisingly high-performance, with excellent stability at the same time, are light-polymerizable storage compositions containing acyl-phosphine oxide compounds of the formula I in which the acyl residue -CO-R is a derivative of a tertiary aliphatic or cycloaliphatic carboxylic acid, a benzoic acid or a benzoic acid The 2,6-positions have substituents (A and B). Very suitable acyl residues of this type are 2,2-dimethyl-C4-C8-10 alkanoyl, 2-methyl-2-ethyl-C1-C10-alkanoyl residues and benzoyl residues having 2,6-, 2,3,6 The -, 2,4,6 or 2,3,5,6-position has substituents A and B, in particular C 1 -C 4 alkyl radicals or halogen atoms.

The recovery masses according to the invention may contain, as the sole photoinitiators, phosphine oxide compounds of the formula I generally in an amount of 0.005 to 10, in particular 0.005 to 5% by weight, based on the total amount of light-polymerizable storage mass, although phosphine oxide compounds can also be used in light-polymerized polymers. in storage masses, as mentioned above, in connection with known photoinitiators and / or with tert-amines.

The total concentration of the initiator mixture (photoinitiators + amines) is then 0.05 to 15% by weight of the total amount of talc polymerizable by the action of light 25, the amines accounting for substantially at least half of the total initiator content.

The mixture of a) and b) which forms the basis of the talc masses according to the invention are suitable as low molecular weight compounds having at least one light-polymerizable, olefinically unsaturated double bond, the monomers used in such masses in a manner known per se, in so far as they together with selected polymeric binders form compatible blends and have a boiling point above atmospheric pressure above 100 ° C.

They generally have a molecular weight of less than 2,000 and in particular 11,69085 less than 1,000. Preference is given to monomers having two or more olefinically unsaturated, light-polymerizable double bonds, either alone or in admixture with monomers having only one olefinically unsaturated, light-polymerizable double bond, wherein the proportion of monomers having only one double bond is generally only about 5-50 and mainly 5-30% by weight of the total amount of monomers. The quality of the monomers used depends largely on the quality of the polymeric binder used with it. Thus, allyl compounds containing two or more double bonds, such as maleic acid dialkyl esters, allyl acrylate, diallyl phthalate, trimellitic acid diacrylic and triallyl esters, or ethylene glycolate diaconate, samoincarboxylic bisallyl, are particularly suitable for mixtures with unsaturated polyester resins. which can be prepared by esterification of diols or polyols with acrylic acid or methacrylic acid, such as ethylene glycol, diethylene glycol, tri-ethylene glycol, polyethylene glycol having a molecular weight of up to about 500, 1,2-propanediol, 1,3-propanediol , di- and tri (meth) acrylates of neopentyl glycol (2,2-dimethylpropanediol), 1,4-butanediol, 1,1,1-trimethylolpropane, Gly-serine or pentaerythritol; monoacrylates and monomethacrylates of diols and polyolefins, such as, for example, ethylene glycol or di-, tri- or tetraethylene glycol monoacrylate, monomers having two or more olefinically unsaturated bonds and ureas containing , such as small molecule compounds prepared from aliphatic diols, organic diisocyanates and hydroxyalkyl (meth) acrylates as mentioned above. Mention should also be made of acrylic acid, methacrylic acid as well as their derivatives, such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide or (meth) acrylates of monoalcohols having 1 to 6 carbon atoms. Mixtures of allyl monomers with di- or polyacrylates are very suitable. If mixtures are selected in which the polymer binder is polyamides, in addition to di- and polyacrylates, in addition to the double bonds, amide and / or urethane groups, such as derivatives of acrylamides, e.g. reaction products formed from 2 mol of N, are particularly suitable. -hydroxymethyl (meth) acrylamide with a mole of an aliphatic diol such as ethylene glycol, xylylene bisacrylamide or alkylene bisacrylamides having 1 to 8 carbon atoms in the alkylene residue. Water-soluble monomers such as hydroxyethyl (meth) acrylate are particularly suitable for the preparation of water-alkali-developed recording compositions, e.g. for printing plates with polyvinyl alcohol, polyvinyl alcohol alkoxylation products or polyvinylpyrrolidone as polymer binders. molecular weight is about 200-500, mono- and di (meth) acrylates. For a combination in which the binder is diene polymers in the nature of elastomers, e.g. atoms, polyacrylates or -met-25 acrylates.

Suitable organic polymeric binders are b) light-known polymers used for this purpose in the production of polymerizable talents, and in particular in the production of printing plates and embossing molds, which must be compatible with the small-molecule compounds a) used and, as is obvious, -pergulate with a suitable developer solvent to allow rinsing of the unexposed and non-crosslinked portions of the film of the polymerizable recording compositions after their pictorial exposure.

i3 69085

Suitable saturated and unsaturated binders are the linear polyamides and in particular the alcohol-soluble mixed polyamides described in FR Patent 1,520,356, cellulose derivatives, in particular water-5 alkali-washable cellulose derivatives vinyl ester polymers and copolymers, such as vinyl acetate, which may have varying degrees of saponification, polyurethanes, polyether urethanes 10 and polyester urethanes, and unsaturated polyester resins, which are described in e.g. - or possibly polybasic carboxylic acids to react with di- and possibly polyalcohols, those having a high acid number, and in particular between 75 and 160, are preferred because they are using to obtain soils with a good dispersibility or solubility in temporal aqueous developing solvents.

For the composition and preparation of unsaturated polyester resins, reference should be made to the available literature, e.g., H.V. In Boening’s Unsatured Polyesters, Structure and Properties, Amsterdam 1964.

The talc masses according to the invention mainly contain, i.e., a mixture of a) and b) containing more than 50 and mainly 70-100% by weight of photoinitiator. This mixture contains the polymer-binder b) generally from about 45 to 90% by weight and in particular from 45 to 65% by weight, based on the sum of the amounts of the polymers b) and the low-molecular-weight compounds a) polymerizable by light.

It is often convenient to add conventional inhibitors to the polymerizable pulps to prevent thermal polymerization, such as hydroquinone, p-methoxyphenol, m-dinitrobenzene, p-quinone, methylene blue, 14,69085 n-naphthol, N-nitrosol, N-nitrosodiphenylamine, phenothiazine, phosphoric acid esters such as triphenylphosphite or N-nitrosocyclohexylhydroxylamine salts and especially alkali and aluminum-5 salts.

The pulps may also contain other common additives such as plasticizers, saturated small molecule compounds with amide groups, waxes, etc.

The further processing of the light-polymerizable recording masses 10, e.g. into light-polymerized printing plates with recording masses as an embossing layer, can take place in a known manner and depends on the quality of the mixture a) + b) and whether the mass is liquid or solid. The further processing of the recording masses (e.g. into raised-15 image molds) takes place in a known manner by exposure to actinic light as shown. After the exposure shown in the figure, in order to produce embossing molds or photoresists, mechanically unexposed parts are removed from the recording mass layer in a known manner or washed with suitable developing solvents and the resulting molds, e.g. embossing molds, dried, in many cases further post-exposed.

A very advantageous fact is that when using talc masses, it is often even possible to perform pre-exposure before the exposure of these light-polymerizable recording masses as shown, and yet the work can be performed with good exposure times. A major unexpected advantage is also that when using the recording mass layers according to the invention, as shown in Example 29, their further processing gives embossing molds which give better embossing structures, which results in a clearly better reproduction of inverted fonts, e.g.

The parts and percentages mentioned in the following examples 35 are by weight unless otherwise indicated. Volume parts relate to parts, such as a liter per kilogram.

15 p. VLP. , 69085

Example 1

To a mixture of 1,350 parts by volume of petroleum ether (boiling range 40-70 ° C), 180 parts by volume of N, N-diethylaniline and 67 parts by volume of methanol are added at 0 ° C 5 with stirring 225 parts of diphenylchlorophosphine dissolved in 220 parts by volume of petroleum ether. . The mixture is then stirred for a further two hours at room temperature. After cooling to about 5 ° C, the separated amine hydrochloride is filtered off and the filtrate is first distilled under a vacuum of 10-20 Tor-10 r to remove all boiling parts. The mixture is then distilled by fractionation of diphenylmethoxyphosphine under a vacuum of 0.1 to 1 torr. Kp. Mp 120-124 ° C. Yield: 175 parts (80% based on diphenylchlorophosphine).

36.2 parts of pivaloyl chloride are added dropwise at 30-60 ° C with stirring to 64.8 parts of diphenylmethoxyphosphine. After the addition is complete, the mixture is allowed to react for a further 30 minutes, cooled to 0-10 ° C and the precipitated product is recrystallized from cyclohexane. Yield: 69.5 parts of pivaloyldiphenylphosphine oxide (81% of theory), m.p. 110-112 ° C.

HMR (CDCl 3, <5), 1.33 (S), 7.4 - 8.0 (M).

Analysis for C ^ H ^ O ^ P (286):

Calculated: C 71.33 H 6.64 P 10.84 25 Found: C 71.0 H6.5 P 11.0

Example 2 To 77 parts of toluic acid chloride are added 108 parts of methoxydiphenylphosphine (prepared according to Example 1) dissolved in 200 parts by volume of toluene. It is then heated for 60 minutes at 50 [deg.] C., then cooled, the tolyldiphenylphosphine oxide precipitate is filtered off and recrystallized from cyclohexane. Yield 117 parts (73% of theory), m.p. 105 ° C.

HMR (CDCl 3, ε): 2.35 (S), 7.2-8 (m).

35 Analysis C2QH1702P (320)

Calculated: C 75.00 H 5.31 P 9.69

Found: C 75.3 H5.8 P9.3 16

Example 3 690 8 5 77 parts of 2-methylbenzoic acid chloride and 108 parts of methoxydiphenylphosphine are prepared according to Example 2 in 134 parts of 2-methylbenzoyl-diphenylphosphine oxide. Yield 84% of theory, m.p. 107 ° C.

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

Analysis for C20H17 ° 2P (320)

Calculated: C 75.0 H 5.31 P 9.69 Found: C 74.7 H 5.4 P 9.5 Example 4 41.3 parts of p-tert-butylbenzoic acid chloride are reacted according to Example 1 with 45.4 parts methoxydiphenylphosphine, dissolved in 20 parts of toluene, at 50 ° C for 90 minutes. After evaporation of the solvent on a rotary evaporator, it is recrystallized from 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 for C23H2302P (362)

Calculated: C 76.24 H 6.35 P 8.56 20 Found: C 76.0 H6.5 P8.7

Example 5 From 52 parts of terephthalic acid chloride dissolved in 200 parts of toluene and 108 parts of methoxydiphenylphosphine, 46 parts of terephthaloyl-25 bis-diphenylphosphine oxide are prepared according to Example 2 (yield 35% of theory), m.p. 205 ° C.

NMR (CDCl 3, δ): 6.8 - 8.2 (m).

Analysis for C 32 H 24 ° 4 ^ 2 ^ 34)

Calculated: C 71.91 H 4.49 P 11.61 30 Found: C 71.8 H 4.8 P 11.0

Example 6

In the procedure of Example 2, 80 parts of 1-methyl-1-cyclohexanecarboxylic acid chloride and 108 parts of methoxydiphenylphosphine are obtained in a solvent-free manner with 100 parts of 1-methyl-cyclohexylcarbonylcarbonyldiphenylphosphine oxide Yield: 42 parts (26% of theory), m.p. 80 ° C.

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

Analysis for C20H23 ° 2P (326)

Calculated: 73.62 H 7.06 P 9.51 Found: 73.3 H 7.1 P 9.6

Example 7 88 parts of 2-methyl-e-ethylhexanoic acid chloride and 108 parts of methoxydiphenylphosphine are obtained according to Example 1 in 165 parts of 2-methyl-2-ethyl-hexanoyl-diphenylphosphine oxide as an oily crude product. Chromatography on the column with silica gel (eluent: toluene / ether-15 ter 3: 1) gives the product as a slightly 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 for C21H2702P (342)

Calculated: C 76.68 H 7.89 P 9.06 20 Found: C 73.9 H 8.1 P 9.4

Example 8

In analogy to Example 1, 43.2 parts of methoxydiphenylphosphine are added dropwise at 50 [deg.] C. to 35.3 parts of 2,2-dimethyl-heptanecarboxylic acid chloride (versatin acid chloride). After stirring for 3 hours at 50 [deg.] C., cooling to 15 [deg.] C., the mixture is added with stirring to a suspension of 60 g of silica gel in 350 ml of toluene, the mixture is further stirred for 1 hour under ice-cooling. The solid is filtered off and the solvent distis-30 is discharged under reduced pressure. Versatoyl diphenyl phosphine oxide remains as a viscous oil.

Yield 62 parts (90% of theory).

NMR (CDCl 3): 0.4-2.3 (m); 7.2-8.1 (m)

Analysis c2ih27 ° 2P (342) Calc .: C 73.68 H 7.89 P 9.06 35 Found: C 73.6 H 8.1 P8.6 18 69085

Example 9

To a mixture of 600 parts of petroleum ether, 263 parts of Ν, Ν-diethylaniline and 120 parts of isopropanol are added dropwise over 5 hours at 0 ° C 143 parts of phenyldichlorophosphine. The mixture is then stirred for a further hour at room temperature, and then the solvent is distilled off after the treatment according to Example 1. Diisopropoxy-phenylphosphine is distilled off at 68-72 ° C / 0.3 mm, yield 126 parts (69% of theory).

158 parts of diisopropoxyphenylphosphine are added slowly with stirring at 50-60 ° C to 84 parts of pivalic acid chloride. The mixture is further stirred for two hours, and fractionated in vacuo. Pivaloyl-phenylphosphine-15-nitric acid isopropyl ester is distilled off 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 14 H 21 ClO 3 P (268: Calc .: C 62.68 H 7.84 P 11.54 Found: C 63.0 H 8.0 P 11.4

Example 10

To a mixture of 1000 parts by volume of toluene, 421 parts by volume of Ν, ian-diethylaniline and 100 parts by volume of methanol are added at 0 ° C 214 parts of phenyldichlorophosphine. It is then stirred for a further hour at room temperature, the amine hydrochloride precipitate is filtered off and fractionated. Dimethoxyphenylphosphine distills at 46-50 ° C / 0.2-0.3 mm. Yield: 190 parts (93% of theory).

78.7 parts of pivaloyl chloride are added dropwise at 15 ° C to 110.5 parts of dimethoxyphenylphosphine. It is then heated for a further 30 minutes at 50 [deg.] C. and then the reaction mixture is distilled. Pivaloylphenylphosphinic acid ethyl ester distills at 104-107 ° C / 0.3 mm. Yield 101.3 parts (65% of theory).

35 NMR (CDCl 3, δ): 1.3 (S), 3.75 (d), 7.4-8 (m).

li 19 69085

Analysis for C ^ H ^ O ^ P (240)

Calculated: C 60.0 H 7.08 P 12.9 Found: C 59.8 H6.9 P 12.4

Example 11 5,163 parts of 2-ethylhexanoic acid chloride are added dropwise at 30 [deg.] C. to 170 parts of dimethoxyphenylphosphine (Example 4). It is then stirred for 50 minutes at 50 [deg.] C. and then fractionated in an oil vacuum.

1-Ethyl-hexanoyl-phenylphosphinic acid methyl ester is distilled 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 (m).

Analysis for C 10 H 22 ° 3 P (281) 15 Calculated: C 64.04 H 7.83 P 11.03

Found: C 63.8 H 8.1 P 11.0

Example 12 155 parts of 4-methylbenzoyl chloride dissolved in 250 parts by volume of toluene are added at 170 ° C to 170 parts of dimethoxyphenylphosphine.

The mixture is then allowed to react for 60 minutes, then cooled to 0 ° C and the precipitate is filtered off. After recrystallization from cyclohexane, 4-methylbenzoyl-phenylphosphinic acid methyl ester melts at 99-25 101 ° C. Yield: 180 parts (65% of theory).

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

Analysis for C15H15 ° 3P (274)

Calculated: C 65.69 H 5.47 P 11.31 Found: C 65.7 H5.6 P 11.0 30 Example 13

To a mixture of 1,350 parts by volume of petroleum ether (boiling range 40-70 ° C), 180 parts by volume of N, N-diethylaniline and 67 parts by volume of methanol are added at 0 ° C with stirring 225 parts of diphenylchlorophosphine dissolved in 35,220 parts by volume. petroleum ether. The mixture is then stirred for a further two hours at room temperature. After cooling to about 20 69085 5 ° C, the separated amine hydrochloride is filtered off and the filtrate is first distilled under a vacuum of 10-20 torr to remove any readily boiling material. The diphenylmethoxyphosphine is then distilled by fraction-5 under a vacuum of 0.1 to 1 torr. kP_ c 120-124 ° C. Rule:

U r D

175 parts (80% based on diphenylchlorophosphine).

In a stirred apparatus equipped with a reflux condenser and a dropping funnel, 10,648 parts of methoxydiphenylphosphine are slowly added to 547.5 parts of 2,4,6-trimethylbenzoyl chloride at 50-55 ° C. It is then stirred for a further 4-5 hours at 50 [deg.] C., the contents of the flask are dissolved in ether at 30 [deg.] C. and petroleum ether is added until turbidity begins. On cooling, 910 parts (87% of theory) of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide crystallize out. Sp. 89-92 ° C, slightly yellowish crystals.

Example 14 20 parts of 2,6-dimethoxybenzoyl chloride are suspended in 20 parts by volume of toluene in the apparatus of Example 13 and 21.6 parts of methoxydiphenylphosphine are added dropwise to this mixture at 50-55 ° C with stirring. Stir for an additional three hours at 50 ° C and then recrystallize directly from toluene. 32 parts of yellowish crystals are obtained, m.p. 124-126 ° C.

Example 15 25 parts of 2,4,6-trimethylbenzoyl chloride are first introduced into the apparatus of Example 13. To this is added 83 parts of triethyl phosphite at 60 ° C over 15 minutes and then stirred at 80 ° C for a further eight hours. The contents of the flask are distilled under a vacuum of 0.4 mm and the fraction of talc 30 is taken at 120-122 ° C / 0.4 mm. 51 parts of 2,4,6-trimethylbenzoylphosphonic acid diethyl ester (36% of theory) are obtained in the form of a slightly yellowish liquid.

Example 16

To a mixture of 1,000 volumes of toluene, 35,421 volumes of Ν, Ν-diethylaniline and 100 volumes of methanol is added at 0 ° C 214 parts of phenyldichlorophosphite.

II

21 69085 nia. It is then stirred for a further hour at room temperature, the amine hydrochloride precipitate is filtered off and fractionated. Dimethoxyphenylphosphine distills between 46-50 ° C / 0.2-0.3 mm. Yield: 190 parts (93% of theory).

To 182.5 parts of 2,4,6-trimethylbenzoyl chloride is added dropwise at 50 ° C 170 parts of dimethoxyphenylphosphine. The mixture is kept for a further five hours at 50 [deg.] C., the slightly yellowish oil is dissolved at 70-80 [deg.] C. with cyclohexa-10 and then the product is crystallized by cooling to 5 [deg.] C. 2,4,6-Trimethylbenzoylphenylphosphinic acid methyl ester is obtained as pale yellow crystals, m.p. 51-52 ° C, yield: 81% of theory.

Other compounds prepared according to Examples 15-16 are listed in Table 2.

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Example 17

A 65% methanol solution is prepared from a mixture of 60% adipic acid, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane and β-caprolactam mixed poly-5-amide, 25% 1 mole of ethylene glycol and 2 moles of N-hydroxymethylacrylic, , 2% benzenesulfonamide and 1.8% 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 0.2% aluminum salt of N-nitrosocyclohexylhydroxylamine and 0.1% black dye (Color Index No. 12 195). The solution is cast in a layer on a steel plate with an adhesive varnish so that, after drying at about 70 ° C, the light-polymerizable recording masses form a layer with a thickness of 680 μm. The resulting photopo-15 polymer printing plate is exposed, as indicated in the text, through the original as shown, and the unexposed portions of the layer are then washed away with an alcohol-water mixture. The plate requires a 3% raster tone value to produce a perfect image, with a raster line comprising 60 vii-20 va / cm, a minimum exposure time of four minutes when exposure occurs with high-actin luminescent tubes at a distance of 5 cm.

Example 18

However, as in Example 17, only 11.4% of benzenesulfonamide and an additional 1.8% of methyldiethanolamine are used. The minimum exposure time is only three minutes.

Example 19

The procedure is as in Example 17, using 1.8% 2,6-dimethoxybenzoyldiphenylphosphine oxide as the phosphine oxide compound as the photoinitiator. The minimum exposure time is 4.5 minutes.

Example 20

The procedure is as in Example 18, using 1.8% 2,6-dimethoxybenzodiphenylphosphine oxide as initiator. The minimum exposure time is only 2.5 minutes.

24

Example 21 69085

The procedure is as in Example 18, but using 1.8% versatoyl diphenylphosphine oxide (2,2-dimethyloctanecarbonyl-diphenylphosphine-5 oxide) as initiator. The minimum exposure time is 3.5 minutes.

Comparative test

The procedure is as in Example 17, but using 1.8% benzyldimethyl ketal as the photoinitiator. Otherwise, under comparable conditions, the minimum exposure time is 10 to five minutes. The reactivity of the recording compositions according to the invention is thus 25-100% higher compared to these.

Example 22

The procedure is as in Example 17. However, the addition of dye 15 is omitted and the potassium salt of N-nitrosocyclohexylhydroxylamine is used instead of the aluminum salt. The dry film thickness of the light-polymerizable prepared talc mass layer is 500 μm. The plate requires a 3% raster tone value to form a perfect image, with a raster line comprising 34 lines / cm, often selected, for example, when printing leaves, a minimum exposure time of 50 seconds when exposed to a commercially available high-pressure iron-doped mercury lamp with a reflector of 50 cm: n and a UV burner with an electrical input of 25,000 watts / hour. Other further processing of the plate takes place as described in Example 17.

Example 23

However, as in Example 22, only 11.4% benzenesulfonamide is used. The pulp also contains 1.8% methyldiethanolamine. The minimum shutter speed is only 35 seconds.

Example 24

However, as in Example 22, only 11.4% benzenesulfonamide and in addition 0.9% methyldiethanolamine and 0.9% benzyldimethylketal are used.

69085 25 In addition, 1.8% of 2,6-dimethoxybenzoyl-diphenylphosphine oxide is used instead of 2,4,6-trimethylbenzoyldiphenylphosphine oxide. The minimum exposure time is still 35 seconds.

5 Comparative experiment B

The procedure is as in Example 22, except that 1.8% benzyldimethyl ketal is used as the photoinitiator. The minimum exposure time is 55 seconds under the specified conditions.

Example 10 650 parts of a mixture of unsaturated polyester made from fumaric acid, trimelitic anhydride and diethylene glycol with an acid number of 140 are mixed with 400 parts of a mixture of equal amounts of tetraethylene glycol-15 collide methacrylate and diallyl phthalate, 2 parts of hydroquinate, 2 parts of hydro 4,6-trimetyylibentsoyylidifenyylifos-finioksidia. 110 ppm of N-nitrosodiphenylamine are added to the formed liquid storage mass.

20 embossing molds are made from the recording mass in a known manner. For this purpose, liquid talc masses are cast on carrier steel plates with adhesive lacquer with a grit, adjusting to a layer thickness of 800 μm, and then the layers are covered with a transparent polyester film 6 · ωη: η thick to avoid air traps. The liquid layers of the recording masses are exposed through a negative calculated on a polyester film with a commercially available mercury-medium pressure lamp as shown. Negatives and polyester films are removed and then the unexposed layers of the recording compositions are washed with 0.5% aqueous soda solution. The resulting embossing molds are dried and each is post-exposed simultaneously for two minutes. For a perfect exposure time with all the necessary pixels - it is: a raster with 40 lines / cm and a tone value of 3%, va-35 press dots with a weight of 0.3 mm on the heavy surface, fine lines with a cross section of 26 69085 0.07 mm - are correctly anchored to the carrier plate, reported, measured by a commercially available exposure machine under the above conditions, 9 exposure units. The embossing is flawless and meets the requirements.

5 Comparative experiment C

The procedure is exactly the same as in Example 38, but using 8 parts of benzyldimethyl ketal instead of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

10 When using this liquid talent, the exposure time required by the method described above is determined to be 23 exposure units, i. the shutter speed is 2.5 times longer.

Example 26 294 parts of partially saponified polyvinyl acetate (degree of saponification 82 mol%, average degree of polymerization = 500) are dissolved in 294 parts of water with stirring for several hours at 90 ° C. After cooling to 70 [deg.] C., 200 parts of a monomer mixture containing 180 parts of 2-hydroxyethyl methacrylate, 20 parts of 1,1,1-trimethylpropane triacrylate, 10 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2 parts of 2, 6-di-tert-butyl-p-cresol. The homogeneous, viscous solution is filtered and degassed in vacuo. Applying this to a steel plate with an adhesive varnish and drying for 24 hours at room temperature gives a non-stick recording mass layer of 550 .mu.m. After two seconds of pre-exposure followed by exposure to a 40-second negative in a flat-panel exposure apparatus equipped with a luminescent tube and then washing with water in a jet washing tower and then imaging at 100 ° C, an image plate with good embossing structure and mechanical properties is obtained. excellent and from which several thousand prints can be printed. Embossing-35 printing forms provide well-formed il 27 69085 readable reverse letters in the printing test, which fully satisfy the requirements of newspapers.

Example 27

Using a recording mass, a printing plate is prepared, as in Example 39, but with the same amount of 2,6-dimethoxybenzoyl-diphenylphosphine oxide instead of 2,4,6-trimethylbenzoyldiphenylphosphine oxide. The pre-exposure time is about two seconds, and the time required for image exposure is 45 seconds.

10 Comparative test D and E

As described in Example 26, a printing plate is prepared using a recording mass which, however, contains benzyl dimethyl ketal (Comparative Experiment D) or benzo-15-isopropyl ether (Comparative Experiment E) as initiators to the same extent as the photoinitiator. A comparison of the exposure times required for recording masses prepared using each photoinitiator to the same extent gave the following results:

Recording mass containing pre-exposure 20 exposure 2.4.6-trimethylbenzoyldiphenylphosphine oxide (eg 26) 2 s 40 s 2.6-dimethoxybenzoyldiphenylphosphine oxide (eg 27) 2 s 45 s 25 Benzyldimethyl ketal (comparative test D) 4 s 90 s

Benzoin isopropyl ether (Comparative Test E) 6 s 120 s The embossing molds prepared from the thus exposed printing plates according to Comparative Experiment D 30 give less formed and inaccurate inverted fonts in the printing test compared to the embossing molds prepared according to Example 19.

Example 28 and Comparative Experiment F

35 As in Example 26 and Comparative Experiment D, printing plates are prepared separately in the same way, except that they only contain 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Example 28) in one case and benzyldimethyl crystalline in another case (Comparative Experiment D). F) the effect of light on the recording mass in the 5 polymerizable layers. Different plates are illuminated in parallel without pre-exposure directly using a negative with a commercially available high-pressure iron-doped mercury lamp with a reflector distance of 75 cm and an electric power of 5 kW / hour with a UV burner, and the required minimum exposure times are determined. They are 60 seconds when using the printing plates according to Example 28 (according to the invention) and 110 seconds when using the printing plates according to Comparative Experiment F.

Claims (7)

1. Photopolymerizable registration mass, in particular for the production of printing plates and relief forms, consisting of a photoinitiator-containing mixture containing a) at least one low molecular weight compound with at least one photopolymerizable olefinically unsaturated double bond, and at least one organic compound, wherein at least one wherein R3 is an alkyl radical of 1-6 carbon atoms, a cycloalkyl radical of 5 or 6 ring carbon atoms, or an optionally halogenated, alkylated or alkoxy-substituted aryl residue; R 112 has the meaning of R, wherein R and R may be the same or different, or R is for an alkoxy, aryloxy or aryl alkoxy residue, or R and R may be linked to one another in a ring; R is a tertiary alkyl radical having 4-18 C atoms or a tertiary cycloalkyl radical having 5 or 6 ring carbon atoms, or a cycloalkyl radical, aryl radical or a pyridyl, furyl or thienyl radical which contains at least in both ortho positions of the carbonyl group substituents A and B, wherein A and B are alkyl, alkoxy, alkoxyalkyl, alkylthio, cycloalkyl or aryl residues or halogen atoms and A and B may be the same or different. Photopolymerizable registration mass according to claim 1, characterized in that it