FI68241C - PHOTOPOLYMER SERIES - Google Patents

Description

«ISite» a ADVERTISING PUBLICATION, _ Λ. ^ 8 11 UTLÄGGNINGSSKRIFT 6 8241 • 2 \ S C (45) Patent granted on 12 August 1985

Patent applications (51) Kv.lk//lnt.CI.* C 07 F 3/28, C 09 0 3Λ8, 7/12 FINLAND —FINLAND (21) Patent application - Patentansölcning 792196 (22) HaicemispilvS - Ansöknlngsdag 12.07.79 ( 23) Starting date —Giltighetsdag 12.07.79 (41) Has become public - Blivit offentlig 15.01 .80

National Board of Patents and Registration NShtäväks Date of publication and hearing. - 30 Qh <85

Patent and registration authorities '' Ansttkan udagd och utl.skriften publicerad (32) (33) (31) Pyydetty etuoikeus — Begird priority 1 ^ +. 07.78 1 ^ .03.79 »1 ^ .03.79 Federal Republic of Germany - Förbundsrepubliken Tyskland (DE) P 2830927.5, p 290999 ^ .3, p 2909992.1 (71) BASF Aktiengesel1schaft, D-6700 Ludwigshafen, Federal Republic of Germany- Förbundsrepublik ) Peter Lechtken, Frankenthal, Ingolf Buethe, Mannheim,

Bernd Bronstert, Frankenthal, Anton Hesse, Luetzelsachsen,

Gerhard Hoffmann, Otterstadt, Manfred Jacobi, Frankenthal,

John Lynch, Ludwigshafen, Werner Trimborn, Limburgerhof,

This invention relates to a photopolymerizable pulp which can be used in coatings, varnishes and inks. This invention relates to photopolymerizable pulp which can be used in coatings, varnishes and inks.

Various photoinitiators have been used in known photopolymerizable pulps, e.g. aromatic ketones such as acetophenone and benzophenone derivatives and benzyl ketals, e.g. benzyl dimethyl ketal (DE application 2 261 383), however, light-inducible polymerizable masses cured with such initiator systems exhibit undesired yellowing, making these systems unsuitable for light (or white) surfaces or color-accurate image surfaces.

A further disadvantage is the often insufficient storage capacity of pre-sensitized resin mixtures, as the mixtures often only last for a few days, even in the dark.

2 68241

The light-polymerizable mass according to the invention is characterized in that it contains, as a photoinitiator, an acylphosphine oxide compound of the general formula R \ 0 3 P-Ö-R (I) R 2 in which R · * "is a straight-chain or branched alkyl group having 1 -6 carbon atoms, a cyclohexyl, cyclopentyl, phenyl or naphthyl, halogen, alkyl or alkoxy-substituted phenyl or naphthyl, pyridyl or thienyl group; 2 1 12 R is a meaning according to R , wherein R and R 2 may be the same or different, or R is an alkoxy group having 1 to 6 carbon atoms, a phenoxy or benzyloxy group, 1 2 or R and R together form an o-phenylenedioxy group, R is straight-chain or branched an alkyl group having 2 to 18 carbon atoms, a cycloaliphatic group having 3 to 12 carbon atoms, an alkyl, alkoxy or alkylthio-substituted phenyl or naphthyl group, a pyridyl, furyl or thienyl group, or R is a group oy

Il S

-x-C-P.

sv 1 2 wherein R and R 11a have the meaning given above and X is phenylene or an aliphatic divalent group having 2 to 6 carbon atoms or a cycloaliphatic divalent group having 3 to 6 carbon atoms; 13 and optionally one or more of R 1 -R 2 is olefinically unsaturated.

In particular, acylphosphine oxide compounds of the formula I in which 3 R is a tertiary aliphatic group or mono-, di- or trialkyl-substituted phenyl are used in the pulps according to the invention, the alkyl group or groups having 1 to 8 carbon atoms. Preferably R is also phenyl, pyridyl, furyl or

II

68241 a nyl group in which at least both carbon atoms adjacent to the carbonyl group attachment point have substituents A and B, which may be identical or different, and which are alkyl, alkoxy or alkylthio groups having 1 to 6 carbon atoms, cycloalkyl groups having 5 to 7 carbon atoms, phenyl groups or halogen atoms, in particular chlorine or bromine atoms, or R is a naphthyl group having at least 2,8-substituents A and B or a N-naphthyl group having at least 1,3-positions as substituents A and B.

In the general formula (I) of the acylphosphine oxide compounds, the symbols may have the following meanings: R 1 may be e.g. methyl, ethyl, isopropyl, n-propyl, n-butyl, amyl, n-hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, mono- or dichlorophenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, thiophenyl, pyridyl or furyl.

2 1 R may, in addition to the above meanings of R, be alkoxy, such as methoxy, ethoxy, isopropoxy, butoxy, ethyloxyethoxy, or phenoxy or benzyloxy, or 1 2 R and R together form an o-phenylenedioxy group, 3 R may be ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, isoamyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl, isononyl, dimethylheptyl, lauryl, stearyl, cyclopropyl, cyclobutyl, cyclopentyl, 1- methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, norbornadienyl, adamantyl, dimethyloctyl, dimethylnonyl, dimethyldecyl, methylphenyl, dimethylphenyl, trimethylphenylphenylphenoxyphenyl, dimethoxyphenyl, isopropylphenyl, methoxyphenyl, methoxy , thienyl, pyridyl, β-acetoxyethyl or β-carboxyethyl.

J 3 R is preferably 2,6-dimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 2,6-dibromophenyl, 2-chloro-6-methoxyphenyl, 2-chloro-6-methylthiophenyl, 2 , 4,6-trimethyl-4,648,111 phenyl, 2,4,6-trimethoxyphenyl-2 / 3,4,6-tetramethylphenyl, 2,6-dimethyl-4-tert-butylphenyl, 1,3-dimethylnaphthalene-2,2 , 8-dimethylnaphthalene-1,3,3-dimethoxynaphthalene-2,1,3-dichloronaphthalene-2,2,8-dimethoxynaphthalene-1,2,4,6-trimethylpyridine-3,2,4-dimethoxy -furan-3 or 2,4,5-trimethylthiophene-3 «12 R and R may further have CC double bonds which allow the photoinitiator to be polymerized into a binder.

Particularly preferred acylphosphine oxide compounds are aroylphenylphosphinic acid esters or aroyldiphenylphosphine oxides having alkyl, alkoxy, halogen, alkylthio groups as substituents at the o-position of the aroyl group; examples are 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenyl-phosphinic acid methyl ester, 2,6-dichlorobenzoyl- or 2,6-dimethoxybenzoyldiphenylphenylphenylphenylphosphine oxide.

These compounds are prepared by introducing an acid halide of formula

O

R 3 ~ fe-X X = Cl, Br, to react with a phosphine of formula R 14 4 P-OR R = straight or side chain R C 1 -C 6 alkyl or cycloalkyl having 5-6 C atoms.

The reaction may be carried out in a solvent such as a hydrocarbon or a hydrocarbon mixture such as petroleum ether, toluene, cyclohexane, ether and other common inert organic solvents, or also without a solvent at a temperature between -30 ° C and + 130 ° C, preferably 10-100 ° C. The product can be crystallized directly from the solvent, obtained as a residue after evaporation of the solvent, or distilled in vacuo. Acid halides 0 3II 12 4 R CX and substituted phosphine RR POR are recovered by methods known from the literature (e.g. Weygand-Hilgetag, Organisch-Chemische Experimentierkunst, 4, Auf1., Pp. 246-256, AND Barth-Verlag, Leipzig). 1970 and K. Sasse, Houben-Weyl, Band 12/1, pp. 208-209, G. Thieme-Verlag, Stuttgart).

The process for the preparation of the compounds of the invention can be described, for example, as follows: 6 68241 <5> <- ♦ JoAcl - '-' ^ OCH3 CYLf ^ CH, CH3 ° \ ° (of + CH3Cl

Cor δ or ©> * », -. joA- -

(®T

ΓοΊ o ^ S0 ^ cJOJ * CHjCl C§j s or CX C1 © -p (och3) 2 + + CH3Cl MC1 ChA / 3 ci or ^ - 1½¾.

(of M, »/ · LOJ p 7 68241

Suitable phosphines as starting materials are for example methyl-dimetoksifosfiini, butyylidimetoksifosfiini, phenyldimethoxyphosphine, tolyylidimetoksifosfiini, fenyylidietok-sifosfiini, tolyylidietoksifosfiini, phenyldiisopropylsilyl isopropoksifos-olefin, tolyl isopropoksyylifosfiini, fenyylidibutoksifosfiini, toluyylidibutoksifosfiini or dimetyylimetoksifosfiini, di-butyylimetoksifosfiini, dimetyylibutoksifosfiini, difenyylimetok-sifosfiini, difenyylietoksifosfiini, diphenylpropoxyphosphine, diphenylisopropoxyphosphine and diphenylbutoxyphosphine.

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

Examples of compounds of formula I are in particular the following:

Table 1:

Examples of compounds of the invention (Ph = phenyl)

Analysis

Compound SP- (° o Kp. (0c) Yield chp CHj 0 Ph CH.-C - C— - 10Hn / 0.3 mn 65 ί calc. 60.0 7.03 12.9 2 cHj o ^ ocHj obtained 59 , 8 £,? 12, t

Q

CH 2 \ ίί ^ ch ^ P ^ - l6 »/ l, 2 nn 65 · shot. 60.06 7.53 11.03 3 2 c «JOchj obtained 63.8 3.1 li.o /“ 2 CHj 0 Ph. , 101 - 70: xasK. 55.69 5, »7 11.31 XXX) δ 0CH3 obtained 6 = .7 5.5 11.0 CHj 0 Ph 105 - 73 ί calc. 75.00 5.31 9.69 O 2 Ph obtained 75.3 5.8 9.3 CH 2 CH 2. 0 Ph 107 - en; calc. 75.00 5.31 9. £ 9 (Oj ä \ h obtained 73.7 5. * 9.5 0 Ph 136 - 83 5 calculated 76.21 6.35 8.55 CH5n (Tph obtained 76.0 5.5 8.7 ' c ^ \ CH3 CHj phJ-C ^ oVc-PPha 205 - 35 ί laSk · 71.51 l. * 9 11.61 2 3 2 obtained 71.8 4.B u, co CH, Jk \ PPh, 11 »- 81 ί calculated 71.33 6.6 »10.3» cK ^ ^ cHj o obtained 71 * ° 6.5 11.0 0 xCHj CH3'c p ° ”CH' ^ ch - 120 / 0.5 cm 60 ί calculated 62.68 7.8 »11.57 CHj 'CHj Orh' 3 6J · 0 δ · ° 11 * il 9 f. ρ, ο 4 1

Continued from Table 1:

The compound Sp. Kp. Yield Analysis

(° C) (° C) C H P

0 Ph CHJ. CH1 ^ CH1 - 90 i calc. 75.68 7.89 9.06 'ch ^' cHj '”' 'co Ph obtained 75.6 3, ia, 6 CHj' 'cHj O CHj 0 Ph cHj-co-cHj-c -— c-pv - 3 oi count. 66.28 6.11 9.01 CH 2 O obtained 65.3 6, J 8.6 CH, O 0-CH (CH 2), '• s, / * * ^? - 51 ° / 0.3 m. 52, “J 9.22 15.05 CH 2 O CH 2 obtained 82.1 9.1 11.9 <?> 0 (c) -: -? 156 - 65 5 shots. 77.52 1.73 3.71 0X? H obtained 77.7 1.3 3.9 0 ^ 002Η5 fQY ^ ·? - 102 ° / 0.05 m 60! calcd 53.11 6.69 15.71 O CHj yield 53.9 6.7 13.5 CHj 0 Ph eo 'ass calc. 73.62 7.06 3.51 0 Ph obtained 73.3 7.1 9.5 o ^ CH 2 ^ C Ph - 90 5 calc. 75.63 7.89 9.05 C-Hj CH2 ^ P ^ obtained 73.9 a, l 9.1 CHj CKj 0 Ph CH3 10 68241

The reactivity of the acylphosphine oxides used as photoinitiators under the action of light with polymerizable monomers having at least one C-C multiple bond is very good. The acylphosphine oxide compounds are particularly well suited as photoinitiators for the light polymerizable compositions of the invention for use in coatings and varnishes. They are by far superior to known photoinitiators (e.g., benzyldimethylketal) because the coatings and varnishes containing them do not turn yellow.

Preferred in this case are acyl-phenyl-phosphinic acid esters or acyldiphenylphosphine oxides having an acyl residue of a secondary or tertiary substituted aliphatic carboxylic acid such as pivalic acid, ocylic acid, 1-methylcyclohexanecarboxylic acid, norbornene is 9 to 13 carbon atoms), 2-ethylhexanecarboxylic acid, or a substituted aromatic carboxylic acid such as p-methylbenzoic acid, o-methylbenzoic acid, 2,4-dimethylbenzoic acid, p-tert-butylbenzoic acid, 2,4,5, -trimethylbenzate , a derivative of p-methoxybenzoic acid or p-thiomethylbenzoic acid.

Particularly preferred o-disubstituted aroyl-diphenylphosphine oxides or aroyl-phenylphosphinic acid esters have excellent storage stability in light-polymerizable monomers with very good reactivity. This applies in particular to the most commonly used styrene-containing unsaturated polyester-based resins as well as styrenic acrylic acid esters. The initiators of the formula I can be used to cure lacquered pigments which are white to white, but also resins pigmented in color. In terms of these properties, they are by far superior to known photoinitiators such as, for example, benzyldimethylketal or oC-hydroxyisobutyrophenone.

It was further surprisingly found that these advantages are maintained or even enhanced if the primary aroyl diphenylphosphine oxides are used in conjunction with known photoinitiators.

Particularly effective synergistic mixtures are obtained in combination with known photoinitiators based on 11,682,241 aromatic ketones, in particular with benzyldimethylketal, Q6-hydroxyisobutyrophenone, diethoxyacetophenone, benzophenone and 2-methylthioxanthone-thiophylthioxanthone, 2-isopropylthioxanthionine. The addition of tertiary amines, such as methyldiethanolamine, then takes advantage of their known accelerating effect. By combining the initiators of the formula I with, for example, benzyldimethyl ketal, it is possible to produce surprisingly effective, very storage-resistant, amine-free, light-polymerizable pulps, which can possibly also be pigmented.

Suitable light-polymerizable monomers are the customary compounds and substances having polymerizable C-C double bonds activated, for example, by an aryl, carbonyl, amino, amide, amido, ester, carboxy or cyanide group. halogen atoms or C-C double or C-C triple bonds. Examples are vinyl ethers, vinyl esters, styrene, vinyl toluene, acrylic acid and methacrylic acid and their esters with monohydric or polyhydric alcohols, their nitriles or amides, maleic and fumaric acid esters and N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinyl .

Suitable polymerizable high molecular weight compounds are, for example: unsaturated polyesters prepared from ut (unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid, such as a mixture of ethanedioic acid with ethanidic acid, optionally saturated or aromatic dicarboxylic acids; , propylene glycol, butanediol, neopentyl glycol or oxyalkylated Bisphenol A; e.g., hydroxyl-containing saturated, polyesters and acrylic or methacrylic acid).

In certain cases, light-polymerized coatings, varnishes and inks may also be in the form of aqueous dispersions or convertible into these for use.

12 68241

Depending on the intended use, saturated and / or unsaturated polymers and other additives such as inhibitors can be added to the polymerizable compounds under the influence of light to prevent thermal polymerization, paraffin, pigments, dyes, peroxides, flow promoters, fillers and opacifiers, opacifiers and opacifiers. cleavage.

Such mixtures are familiar to the person skilled in the art. The method of addition 3a and the amounts of addition depend on the intended use.

The compounds of the formula I are then generally used in an amount of 0.001 to 20%, in particular 0.01 to 15%, in particular 0.1 to 5%, based on the amount of light-polymerizable mass. They can be used in combination with accelerators which remove the anti-polymerization effect of air oxygen.

Suitable accelerators or synergists include, for example, secondary and / or tertiary amines such as methyldiethanolamine, dimethylethanolamine, triethylamine, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, benzyldimethylamine, dimethylaminoacylacetyl, dimethylaminoethyl ethyl. corresponding compounds known to the skilled artisan. Aliphatic and aromatic halides such as 2-chloromethylnaphthalene, 1-chloro-2-chloromethylnaphthalene, as well as radical generating compounds such as peroxides and azo compounds can be further used to accelerate curing.

Radiation sources are used to initiate the polymerization of the mixtures according to the invention, the radiation wavelength corresponding to the absorption range of the compounds of the formula I, i.

2 3 0 to 4 50 nm light. Particularly suitable are mercury-Mata blade radiators, medium-high pressure and high pressure radiators, as well as (superactin) luminescent tubes or pulsed radiators. Said lamps may be optionally subsidized.

! 13 68241

The parts and percentages mentioned in the following examples refer to units of weight, unless otherwise indicated. Volume parts relate to parts like a liter to a kilo.

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 are added at 0 ° C with stirring 225 parts of diphenylchlorophosphine dissolved in 220 volumes of petroleum ether. The mixture is then stirred for a further 2 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 torr to remove all easily boiling parts. It is then distilled by fractionation of diphenylmethoxyphosphine under a vacuum of 0.1 to 1 torr. Kp. q j. 120-124 ° C. Yield: 175 parts (80% based on diphenylchlorophosphine).

Q

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 pivaloyl diphenylphosphine oxide (81% of theory).

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

Analysis for C 17 H 19 O 3 P (286): C 71.33 H 6.64 P 10.84 Found: C 71.0 H 6.5 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 min. At 50 ° C, then cooled, the toluyldiphenylphosphine oxide precipitate is filtered off and recrystallized from cyclohexane. Yield 117 parts (73% of theory), m.p. 105 ° C.

14 68241 HMR (CDCl 3, δ): 2.35 (S); 7.2-8 (m).

Analysis calculated for C 75 H 12 N 2 O (320): C 75.00 H 5.31 P 9.69 Found: C 75.3 H 5.8 P9.3.

Example 3 From 77 parts of 2-methylbenzoic acid chloride and 108 parts of methoxydiphenylphosphine, 134 parts of 2-methylbenzoyl-diphenylphosphine oxide are prepared according to Example 2. Yield 84% (theoretical, m.p. 107 ° C.

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

Analysis for C 20 H 17 O 2 • (320) Calc .: 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 of 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 C 23 H 23 O 2 P * 362) Calcd: C 76.24 H 6.35 P 8.56 Found: C 76.0 H 6.5 P 8.7.

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

NMR (CDCl 3, δ): 6.8-8.2 (m)

Analysis for C 32 H 24 O 4 P 2 (534) Calc'd C 71-91 H 4'49 p Hf61 Found: C 71.8 H 4.8 P 11.0.

Example 6

By the procedure of Example 2, 80 parts of 1-methyl-1-cyclohexanecarboxylic acid chloride and 108 parts of methoxydiphenylphosphine are obtained without solvent in 100 parts of 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide as an oily crude product, which

II

68241 is purified by chromatography on silica gel (eluent toluene).

Yield: 42 parts (26% of theory), m.p. 80 ° C.

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

Analysis for C 20 H 23 O 2 P (326) Calc .: 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 on silica gel (eluent: toluene / ether 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 (342) Calc .: C 73.68 H 7.89 P 9.06 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 ° 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 is 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)

Analysis for C 21 H 27 O 2 P (342) calcd *: c 73.68 H 7.89 P 9.06 found: C 73.6 H8.1 P 8.6

Example 9

To a mixture of 600 volumes of petroleum ether, 263 parts of Ν, Ν-diethylaniline and 120 parts of isopropanol are added dropwise over 1 hour 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).

16 68241 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-phenylphosphinic acid isopropyl ester is distilled off at 119-121 ° C / 0.5 mm.

Yield 112 parts (60% of theory).

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

Analysis: ^ 14 ^ 21 ^ 3 ^ (268): calcd .: C 62.68 H 7.84 P 11.57 found: C 63.0 H8.0 P 11.4

Example 10

To a mixture of 1000 parts by volume of toluene, 421 parts by volume of Ν, Ν-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. Then heat for another 30 min. At 50 ° C and then the reaction mixture is distilled. Pivaloylphenylphosphinic acid methyl ester distills at 104-107 ° C / 0.3 mm.

Yield: 101.3 parts (65% of theory) NMR (CDCl 3, cf): 1/3 (S), 3.75 (d); 7.4-8 (m).

Analysis: C-H 2 O 2 P (240) Calc .: C 60.0 H 7.08 P 12.9 Found: C 59.8 H 6.9 P 12.4.

Example 11 163 parts of 2-ethylhexanoic acid chloride are added dropwise at 30 ° C to 170 parts of dimethoxyphenylphosphine (Example 4). It is then stirred for 50 min. At 50 ° C, followed by fractionation in an oil vacuum.

2-Ethyl-hexanoyl-phenyl-phosphinic acid methyl ester distills at 160-168 ° C / 1.2 mm.

Il 68241

Yield: 230 parts (81% of theory) NMR (CDCl 3 / iT): 0.6-2 (m); 3.2 (q); 3.8 (d), 7.3-8 (m).

Analysis: C 15 H 22 O 3 P (281) Calcd: C 64.06 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 30 ° 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-methyl-benzoyl-phenyl-phosphinic 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. ^ H ^ O ^ P (274) calc. : C 65.69 H 5.47 P 11.31

13 _L O

found: C 65.7 H 5.6 P 11.0.

Example 13

To a mixture of 1350 parts by volume of petroleum ether (boiling range 40-70 ° C), 180 parts by volume of Ν, Ν-diethylaniline and 67 parts by volume of methanol are added, at 0 ° C with stirring, 225 parts of diphenylchlorophosphine dissolved in 220 parts by volume of petroleum ether.

The mixture is then stirred for a further 2 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 torr to remove any readily boiling material. The diphenylmethoxyphosphine is then distilled by fractionation under a vacuum of 0.1-1 torr. KpQ g 120-124 ° C. Yield: 175 parts (80% based on diphenylchlorophosphine).

In a stirred apparatus equipped with a reflux condenser and a dropping funnel, 648 parts of methoxide and 1-phosphine 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. M.p .: 89-92 ° C, slightly yellowish crystals.

18 68241

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 3 hours at 50 ° C and then recrystallize directly from toluene. 32 parts of yellowish crystals are obtained, m.p. 124-126 ° C.

Example 15

91 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 8 hours. The contents of the flask are distilled under a vacuum of 0.4 mm and a fraction of 120-122 ° C / 0.4 mm is collected. 51 parts of 2,4,6-trimethylbenzoylphosphonic acid diethyl ester (36% of theory) are obtained as a slightly yellowish liquid.

Example 16

To a mixture of 1000 parts by volume of toluene, 421 parts by volume of Ν, Ν-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 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 5 hours at 50 [deg.] C., the slightly yellowish oil is dissolved at 70-80 [deg.] C. in cyclohexane and then the product is crystallized by cooling to 5 [deg.] C. Slightly yellowish crystals are obtained, m.p. 51-52 ° C? yield: 81% of theory.

Other compounds prepared according to Examples 13-16 are listed in Table 2.

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20 68241

Example 17 ^ n '

The coating pigmented lacquer is prepared from a mixture of 100 parts of the reaction product of Bisphenol-A-diglycidyl ether and two moles of acrylic acid, 122 parts of butanediol 1,4-diacrylate, 6 parts of n-butanol, 122 parts of TiCl 2 pigment. Varnishes of this quality are known to a person skilled in the art. To this mixture is added 6.5 parts of 2-methylbenzoyl-diphenylphosphine oxide as a photoinitiator. The pre-mixed lacquer is granulated on glass plates to a thickness of 75 μ and irradiated with a high-pressure Hg ampoule (power 80 W / cm of sheet length). The distance between the lamp and the lacquer film was 10 cm. The samples were drawn under a lamp protected by a neutral gas atmosphere with a conveyor belt whose flow rate was adjustable continuously.

At belt speeds up to 6 m / min, scratch-resistant, through-cured and completely white lacquer films are obtained.

Example 18

To the binder containing 65 parts of the reaction product of Bisphenol-A-diglycidyl ether and two acrylic acid equivalents and 35 parts of butanediol 1,4-diacrylate are added in each case three parts of photoinitiator. These mixtures are drawn to a thickness of 80 μ η on a glass plate and irradiated (Hg high-pressure lamp, 80 W / cm sheet length, distance 10 cm). The irradiation time required to obtain a hard, scratch-resistant surface of the nail is indicated by the maximum possible speed of the conveyor belt at which the samples can be drawn under the lamp. In this case, the following values were measured, for example: u 68241 * Ί J_

Table 3: Curing activity of photoinitiators

Initiator Maximum conveyor speed ra / min in air in neutral air, added gas 3% N-phenyl-protected glycine

Pivaloylphosphonic acid diethyl ester - 10

Pivaloylphenylphosphinic acid methyl ester 10 150 10

Toluylphenylphosphinic acid methyl ester 10 70 25 2-Ethylhexanoyl-phenylphosphinic acid methyl ester - 40

Toluyl-diphenylphosphine oxide - 70 25 2-methylbenzoyl-diphenylphosphine oxide - 70

Pivaloyl diphenylphosphine oxide 11,150 25

Example 19

To the varnish prepared according to Example 18 is added 3% N-phenylglycine. It is then drawn onto glass plates as in Example 14 and exposed. The results are shown in Table 3.

Example 20

Esterification of 431 parts of maleic anhydride and 325 parts of phthalic anhydride with 525 parts of propylene glycol-1,2 produces an unsaturated polyester. After adding 0.01% of hydroquinone, a 66% solution of styrene is prepared from the polyester. To 97 parts of this UP resin, 1.5 parts of pivaloyl diphenylphosphine oxide are added.

For photocuring experiments, 10 parts of a 1% styrene solution of paraffin (softening range 50-52 ° C) is added to 100 parts of this mixture, and the resin is applied to glass plates with a film-drawing device at a clearance depth of 400 μl. After about a minute of ventilation, the films are exposed to fluorescent lamps (Philips TLA 05/40 W) placed at a distance of 4 cm.

22 6 8 2 41 After an exposure time of 4 minutes, the films have a Pendel hardness of 76 s (according to König) and are resistant to abrasion and drag.

Example 21

The binder prepared according to Example 18 is in each case mixed with three parts of the photoinitiator according to Table 3 and then drawn into a 76 μm layer on white photographic paper and drawn under a neutral gas-protected speed 72 m / min under an Hg high-pressure lamp (power 80 W / cm sheet length). The samples thus cured were nail hard and glossy. As shown in Table 4, the compounds of the invention are significantly superior to the prior art using typical initiators benzyl dimethyl ketal and a mixture of benzyl dimethyl ketal / benzophenone / methyl diethanolamine.

Table 4; Yellowing of light-polymerizable varnishes

Initiator Used Yellowing as measured by concentration- Yellowness-Index'n +) tio

Benzyldimethyl ketal 3% 9.20

Benzyldimethylketal / benzophenone / methyldiethanol 6% 8.15 nolamine (2: 1: 3)

Pivaloyl diphenylphosphine oxide 3% to 3.33 p-toluyl diphenylphosphine oxide 3% to 3.72

Pivaloyl-phenyl-phosphinic acid methyl ester 3% to 2.34 2) Yellowness-Index according to ASTM D 1925-G7 on DMC 25 / Zeiss.

Example 22

To measure the curing activity of the compounds of the invention in light-polymerizable unsaturated polyester resins, the change in temperature was recorded during exposure. For this purpose, the following resins were prepared: 23 68241

Resin A: Condensation of maleic acid, o-phthalic acid, ethylene glycol and propylene glycol-1.2 in a molar ratio of 1: 2: 2.4: 0.85 in the molten state gives an unsaturated polyester having an acid number of 50.

Resin B: Maleic acid, tetrahydrophthalic acid and diethylene glycol are obtained in a molar ratio of 1: 0.5: 1.5 with an UP resin having an acid number of 46.

For use, both resins are dissolved in 65% styrene and stabilized using 100 ppm hydroquinone.

10 g of such a resin are sensitized with 0.35% of the photoinitiator in question and then irradiated in a white sheet metal chamber (diameter 3.8 cm) immersed in polyurethane hard foam for thermal insulation. The irradiation source is a UV field (87 x 49 cm) with ten lamps placed side by side (TUV 40 / 0.5, Phillips, sample distance 10 cm); the change in temperature during curing is recorded via a thermocouple by a plotter. The measured values obtained are summarized in Table 5.

Table%: Temperature change during light polymerization

Photoinitiator Concentration Resin Curing- Time achieved maximum test (time between 25 ° C and temperature T, T,, o ^, max max (C)) -

Pivaloyl-phenylphosphine 0.35% A 18 min 106 15 s F-acid methyl ester (, 0.35% B 13 min 112

Tolyl-diphenylphosphine- 0.35% A 15 min 122 oxide 15 s, 0.35% B 10 min 133 5 s 4-tert-butyl-benzoyl-0.35% A 14 min 120 55 «5 diphenylphosphine oxide

Terephthaloyl-bis-diphenyl-0.35% A 21 min 109 15 s

-phosphinoxide

Example 23

To a binder prepared from 65 parts of the reaction product of Bishenol-A-di-glycidyl ether and acrylic acid, 35 parts of butane 24 68241 1,4-diol diacrylate and 3 parts of methyldiethanolamine are dissolved in 3 parts of a photoinitiator. The finished mixture is applied to glass plates in a layer with a thickness of 60 μ η and transported at a distance of 10 cm from a mercury-medium lamp (power 80 W / cm of sheet length). Reactivity is reported as the maximum possible speed of the conveyor belt, whereby the hardening of the lacquer film to scratch resistance is still achieved.

Table 6; Reactivity of photoinitiators

Photoinitiator Reactivity (transport rate m / min) 2,4-Dichlorobenzoyldiphenylphosphine oxide K. 10 2,6-Dichlorobenzoylphenylphosphine oxide 30 3,4-Dimethylbenzoyldiphenylphosphine oxide <10 2,4,6-Trimethylbenzoyldiphenylphosphinylphosphinylphosphinylphosphinylphosphine phosphine

Thus, the reactivity of benzyldimethyl ketal 60 2,6-substituted derivatives is substantially higher than that of derivatives in which the substituents are at other positions on the benzoyl residue.

Example 24

The lacquer system of Example 23 is provided with the following photoinitiator combinations and tested as in Example 23.

Photoinitiator system Reactivity Pendel hardness (m / min) according to König (sec) at a rate of 12 min / min 3 parts benzophenone 12 97 2 parts benzophenone 1 part 2,4,6-triraethylbenzoyl diphenylphosphine oxide 75 213 3 parts 2, 4,6-Trimethylbenzoyl-diphenylphosphine oxide 70 188 2 parts of benzophenone 1 part of 2,6-dimethoxybenzoyl-diphenylphosphine oxide 75 210 3 parts of 2,6-dimethoxybenzoyl-diphenylphosphine oxide 70 183 25 68241

Example 25

The following photoinitiators are dissolved in a mixture of 55 parts of the reaction product of Bisphenol-A-diglycidether and acrylic acid, 45 parts of butanediol diacrylate, 55 parts of rutile pigment and 3 parts of methyldiethanolamine. The finished mixture is applied in a spiral (80 μm) to glass plates and passed past two HG high-pressure lamps (80 W / m each) placed in series. The speed of the conveyor belt at which curing to scratch resistance is still possible indicates the reactivity of the initiator system.

In a second batch, the above composition is granulated into a 200 μ thick layer. After UV curing, the layer is removed, washed with acetone and then the thickness of the cured layer is determined. This gives a measured value for through-curing.

Photoinitiator Reactivity Whiteness- Through- (m / min) According to Berger's feeling, the thickness of the layer (% Rem.) 2 parts 2-methylthioxanthone 12 66 130 μl 1.5 parts 2-methylthioxanthone Λ 0.5 parts 2,4,6 -trimethylbenzo-V 20 76 140 n

ylphenylphosphine oxide J

1.0 part of 2-methylthioxanthone Λ 1.0 part of 2,4,6-trimethylbenzo-1 20 78 140 u

ylphenylphosphine oxide -J

2 parts of 2,4,6-trimethylbenzo- ") 6 7nylphosphine oxide X f *

Example 26

Comparable photoinitiators are dissolved in a mixture of 55 parts of the reaction product of Bisphencl-A-digly · ether and acrylic acid, 45 parts of butanediol diacrylate and 55 parts of rutile pigment. The finished varnish is drawn on glass sheets to a thickness of 80 pa and cured as described in Example 25. It is noted that benzyldimethylketal11a or oC-hydroxyisobutyrophenone alone has no pigmented lacquer hardening effect. However, without substantially affecting curing, they can replace part of the 2,4,6-trimethylbenzoyldiphenylphosphine oxide initiator of the invention.

26 68241

Initiator Concentration Pendel hardness per second at a belt speed of 6 m / min 12 m / min 2.4.6-Trimethylbenzoyl-diphenylphosphine oxide 3% 81 56 2.4.6-Trimethylbenzoyl-diphenylphosphine oxide 2% L 78 43

6β-hydroxyisobutyrophenone 1% J

2,4,6-trimethylbenzoyl-6, diphenylphosphine oxide /

Benzyl dimethyl ketal 1 i J

-hydroxyisobutyrophenone 3% ”) in each case dry, benzyldimethyl ketal 3% of surface area

Example 27

Esterification of 431 parts of maleic anhydride and 325 parts of phthalic anhydride with 525 parts of propylene glycol-1,2 produces an unsaturated polyester. After adding 0.01% hydroquinone, a 66% styrene solution is prepared from the polyester and the photoinitiator in question is dissolved therein.

For photocuring experiments, 10 parts of a 1% styrene solution of paraffin (softening range 50-52 ° C) is added to 100 parts of this mixture, and the resin is applied to glass plates with a film-drawing device having a groove depth of 400 γ. After about a minute of ventilation, the films are illuminated with fluorescent lamps (Philips TLA 05/40 W) placed at a distance of 4 cm. This experiment was repeated after the light-polymerizable mixture was stored in the dark for 5 days at 60 ° C.

After exposure times of 2 minutes, the following results are obtained: 27 68241

Photoinitiator Concentration Pendel hardness according to König (sec.) Immediately after 5 days at 60 ° C 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1% 73 73 2,6-dimethoxybenzoyldiphenylphosphine oxide 2% 62 60

Pivaloyl diphenylphosphine oxide (comparison) 2% 60 10

Benzyldimethyl ketal (comparison) 2% 45 40 o6-hydroxy-isobutyrophenone (comparison) 2% 20 19

Example 28

Esterification of 143 parts of tetrahydrophthalic anhydride and 175 parts of maleic anhydride with 260 parts of diethylene glycol produces an unsaturated polyester resin which is dissolved in styrene to a 64% solution and stabilized with 0.01% hydroquinone.

For photocuring experiments, to 100 parts of this solution are added 20 parts of TiCl 2, 10 parts of a 1% styrene solution of paraffin, and each initiator in the amounts indicated. The resin is drawn with a squeegee onto glass sheets to a thickness of 60 and immediately exposed for 20 seconds under a high-pressure Hg lamp (100 W / cm base length) at a distance of 10 cm. The following results are obtained:

Initiator Pendel hardness concentration according to König (sec.) 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide 1% 126 2,6-Dimethoxybenzoyl-diphenylphosphine oxide 1% 81 3,4-Dimethyl-benzoyl-diphenylphosphine oxide 2% 20

Benzyl, methyldiethanolamine 2% + 4% 32 28 68241

When the resin-sensitized resins of the invention did not show any significant decrease in reactivity after storage at 60 ° C for 5 days, the benzyl / amine-containing batch was already gelled.

Example 29 To 100 parts of the resin prepared according to Example 28 is added 15 parts of a 0.7% solution of paraffin (m.p. 50-52 ° C) in styrene in which a photoinitiator has been dissolved. An additional 3% of colored pigment is added to the resin, drawn on a glass with a squeegee into 100-thick films and exposed for 20 seconds. as in Example 10. It can be seen from these results that the initiators according to the invention are also suitable for curing colored pigments or inks, even when combined with previously known initiators which are unsuitable or only poorly suited for this purpose, i. they show a synergistic effect.

Initiator Pendel hardness according to König 1 in seconds after preparations for pigmentation

Heliogen Heliogen LitholgrUn 8721 blau 7080 scharlach 4300 2 parts 2,4,6-trimethyl-benzoyldiphenylphosphine oxide 123 129 161 1 part 2,4,6-trimethyl-benzoyldiphenylphosphine oxide 129 125 170 1 part benzyldimethyl-> ketal 2 parts benzyldimethyl ketal 49 only surface 169 cured

Claims (11)

29 68241 A light-polymerizable compound for use in photopolymerizable coatings, varnishes and inks, characterized in that it contains, as a photoinitiator, an acylphosphine oxide compound of the general formula R10-PC-R3 (I) R2-R or a branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl, cyclopentyl, phenyl or naphthyl, halogen, alkyl or alkoxy-substituted phenyl or naphthyl, pyridyl or thienyl group; 2 1 12 R: 11a has the meaning of R, where R and R may be 2 identical or different, or R is an alkoxy group in which 1 2 is 1 to 6 carbon atoms, a phenoxy or benzyloxy group, or R and R together form No-fenyleenidioksiryhmän; 3 R is a straight or branched alkyl group having 2 to 18 carbon atoms, a cycloaliphatic group having 3 to 12 carbon atoms, an alkyl, alkoxy or alkylthio-substituted phenyl or naphthyl group, 3 pyridyl, furyl or thienyl groups, or R is a group 0 V -X-C-P 2 R 2 ', NSn \ 20 XR 12 wherein R and R 11 have the meaning given above and X is phenylene or an aliphatic divalent group having 2 to 6 carbon atoms or a cycloaliphatic divalent group having 3 to 6 carbon atoms; and wherein optionally one or more of R to R is olefinically unsaturated. The light-polymerizable mass according to claim 1, characterized in that the acylphosphine oxide compound R used as a photoinitiator has a tertiary aliphatic group. 30 68241 The light-polymerizable mass according to claim 1, characterized in that in the acylphosphine oxide compound R used as a photoinitiator, R is a mono-, di- or tri-alkyl-substituted phenyl group, wherein the alkyl group or groups have 1 to 8 carbon atoms. The light-polymerizable mass according to claim 1, characterized in that the acylphosphine oxide compound R used as a photoinitiator has a phenyl, pyridyl, furyl or thienyl group having at least two substituents having at least two carbon atoms adjacent to the carbonyl group attachment point. are substituents A and B, which may be the same or different, and are alkyl, alkoxy or alkylthio groups having 1 to 6 carbon atoms, 3 cycloalkyl groups having 5 to 7 carbon atoms, phenyl groups or halogen atoms, or R is a cC-naphthyl group having at least The 2,8-position has substituents A and B, or a naphthyl group having at least 1,3-position a substituent A and B. Light-polymerizable mass according to Claim 4, characterized in that in the acylphosphine oxide compound R used as photoinitiator, R is 2,4,6-trimethylphenyl, 2,3,6-trimethylphenyl, 2,6- a dimethoxyphenyl, 2,6-dichlorophenyl, 2,6-bis (methylthio) phenyl or 2,3,5,6-tetramethylphenyl group. Light-polymerizable pulp according to Claim 4 or 5, characterized in that, in the acylphosphine oxide compound used as photoinitiator 1 2, R and R are phenyl or -C8-alkyl-substituted phenyl groups. Light-polymerizable mass according to one of the preceding claims, characterized in that it contains an acylphosphine oxide compound together with a secondary and / or tertiary amine. Light-polymerizable pulp according to one of the preceding claims, characterized in that it contains 0.001 to 20%, preferably 0.01 to 4%, of the acylphosphine oxide compound used as photoinitiator. Light-polymerizable pulp according to one of the preceding claims, characterized in that the acylphosphine oxide compound used as photoinitiator is present in coatings, varnishes and inks in a mixture ratio of acylphosphine oxide compound: aromatic ketone 10: 1 to 1:30, preferably 1: 1 - 1:10. Light-polymerizable mass according to Claim 9, characterized in that it contains 0.5 to 15% of tert-amine as accelerator. Light-polymerizable pulp according to one of the preceding claims, characterized in that it contains an acylphosphine oxide compound together with a tert-amine and benzophenone or thioxanthone, which may have methyl, isopropyl, chlorine or chloromethyl substituents, or Bent -silyldimethyl ketal, benzoin isopropyl ether, oi. -hydroxyisobutyrophenone, diethoxyacetophenone or p-tert-butyl-trichloroacetophenone, the total amount of photoinitiators being 1-20% of the total amount of photopolymerizable mixture. 32 Patentkrav 68241