CA1142949A - Sensitizers for photopolymerisation - Google Patents
Sensitizers for photopolymerisationInfo
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- CA1142949A CA1142949A CA000396116A CA396116A CA1142949A CA 1142949 A CA1142949 A CA 1142949A CA 000396116 A CA000396116 A CA 000396116A CA 396116 A CA396116 A CA 396116A CA 1142949 A CA1142949 A CA 1142949A
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Abstract
ABSTRACT
Novel aromatic-aliphatic ketones of the formula:
Novel aromatic-aliphatic ketones of the formula:
Description
Sens_tizers for photop_ly~erisation The invention relates to the use of aromatic aliphatic ketones w~lich are substituted in the ~-position as sensitizers for the photopolymerisation of unsaturated compvunds or for the photochemical crosslinking of polyolefins, as well as to the photopolymerisable and crosslinkable systems which contain such sensitizers.
Photochemical polymerisation processes have attained substantial importance in the art, especially in those cases where thin layers have to be hardened in a short time, for example in the hardening of varnish coatings or in the drying of printing inks. Compared with conventional hardening methods, W
irradiation in the presenoe of photosensitizers has a number of advantages, the most important of which is the great speed of the photohardening. The speed is heavily de~endent on the photosensitizer employed and there has been no lack of attempts to replaoe the conventional sensitizers by ever better and m~re effec-tive compounds. AmDng the most effective photosensitizers are derivatives of benzoin, in particuLar ~le benzoin ethers described for example in German patent speci~ication ~ ~L
.,~""~, '~
<3~
Photochemical polymerisation processes have attained substantial importance in the art, especially in those cases where thin layers have to be hardened in a short time, for example in the hardening of varnish coatings or in the drying of printing inks. Compared with conventional hardening methods, W
irradiation in the presenoe of photosensitizers has a number of advantages, the most important of which is the great speed of the photohardening. The speed is heavily de~endent on the photosensitizer employed and there has been no lack of attempts to replaoe the conventional sensitizers by ever better and m~re effec-tive compounds. AmDng the most effective photosensitizers are derivatives of benzoin, in particuLar ~le benzoin ethers described for example in German patent speci~ication ~ ~L
.,~""~, '~
<3~
2 --1,694,149, derivatives of a-hydroxymethylbenzoin described in German Offenlegungsschrift 1,923,266, and the dialkoxy-acetophenones and benzil monoketals aescxibed for example in German Offenlegungsschrift 2,261,383 or 2,232,365.
~-Aminoacetophenones and a-diaminoace-tophenones have re-cently been proposed as photosensitizers in US patent spe-cification 4,084,034 and a-hydroxy-a-alkylolacetophenones and their ethers in German Offenlegungsschrift 2,357,866.
The shortcomings of these known photosensitizers are in some cases an insufficient storage life in the dark of the photopolymerisable systems mixed with such sensitizers. A
number of benzoin derivatives tend to cause yellowing of the hardened compositions. Other sensitizers are insuffi-ciently reactive - a feature which is observed in the rela-tively lengthy hardening times - or their solubility in the photopolymerisable systems is too low or they are rapidly rendered inacti~e by atmospheric oxygen. There is therefore a need in the art for photosensitizers which are readily soluble in the substrate and, while having a good storage life in the dark, initiat0 the photopolymerisation more rapidly and give a higher polymer yield per unit of time than the known photosensitizers. By using such improved photosensittzers it would be possible to exploit better the expensive industrial UV irradiation plants.
It has been found that compounds of the following formulae I, II, III and IV possess the re~lired properties as photosensitizers. In particular, they effect a rapid photopolymerisation and do not have the shortcomings referred to or possess them to a much lesser degree than the known photosensitizers. Furthermore, they are suitable for the photochemical crosslinking of polyolefins. The invention relates to the use of the compounds of the for-mulae I, II, III or IV
~.~429~
O Rl Ar ~ C - C - X]
12 n O X X O
Il 1 3 1 11 Ar - C - C - R C - C - Ar II
O R Rl O
Ar C - C - X' - C - C - Ar III
12 ¦ -.
o ~o ¦¦ I ` x IV
wherein n is 1 cr 2, Ar in formula I, if n is 1, and in formulae II and III, represents C6-C]4 aryl which is unsubstituted or substituted by one or more members selected from the group consisting of Cl, Br, CN, OH, Cl-C12alkyl, -Oalk, -Ophenyl, -Salk, -SCH2CH20EI, Sphenyl, -SO2alk, -SO2phenyl, -COOalk, -SO2NH2, 2 )2~ NHalk, N(alk)2, -NHCOalk or represents thienyl, pyridyl, furyl, indanyl or -tetrahydronaph-thyl, and alk represents a lower alkyl radical of 1 to 4 carbon atoms, and Ar in formula I, if n is 2, represents C6-C12arylene, a -phenylene-T-phenylene group or a divalent 9,10-dihydroanthracene radical, X represen-ts one of the groups -NR4R5, -oR6, -oSiR (R )2 or toge-ther with Rl represents a -o-CH(R9)-, -O-CH(R9)-0-(CH2)1 2-or -O-Cl-C4alkylene group, X' represents one of -the groups -NR10-, N(C6 C14arYl) ' -N ~ -~ -N(RlO)-Rll-N(Rlo)-~ -Q-, _o_R12_o_, -O-SiR7R8-O-or -O-SiR R -O-SiR R -O-, Y represents a direct bond or -CH2-, Z represents -O~, -S-, -SO2-, -CH2-, or -C(CH3~2-, nt5 -O- -S-, -SO2-~ -CH2-' CH2C 2 6 2 2 -CH=CH-, R in formula I, if n is 1 and X is -OR , repre-sents Cl-C~alkyl which is unsubstituted or substituted by C~-C8acyloxyj -NR R , -COOalk or CN, or represents C3-C5 alkenyl, C5-C6cycloalkyl or C7-Cgphenylalkyl, and in all other cases represents Cl-C8alkyl which is unsubstituted or substituted by -OH, Oalk, C2~C8acyloxy, -NR R , -COOalk or -CN, or is C3-C4alkenyl, C5-C6cycloalkyl or C7-Cgphenyl-alkyl, R has one of the meanings assigned to R or re-presents a -CH2CH2R 3 group, or together with R represents C2-C~alkylene or C3-Cgoxa- or azaalkylene, R represents a direkt bond, Cl-C6alkylene, C2-C6oxaalkylene, C2-C6thia-, s~oxathia- or S-dioxothiaalkylene, phenylene, diphenylene or a -phenylene-T-phenylene group, or together with both substituents R and both carbon atoms to which these sub-stituents are attached, forms a cyclopentane, cyclohexene, endomethylenecyclohexane or cyclohexane ring, R4 represents Cl-C12alkyl, C2-C~alkyl substituted by -OH, Oalk or -CN
or represents C3-C5alkenyl, cyclohexyl, C7-Cgphenylalkyl, phenyl or phenyl which is substituted by Cl, alk, OH, Oalk or -COOalk, R represents Cl-C12alkyl, C2-C4alkyl which ls substituted by OH, Oalk or CN or represents C3-C5alkenyl, cyclohexyl or C7-Cgphenylalkyl, or together with ~ re-presents C4-C5alkylene which can be interrupted b~ -O- or -NR , or, in the case of compounds of the formula I, to-gether with R represents Cl-C~alkylene or phenylalkylene or C2-C3oxa- or azaalkylene, R represents hydrogen, Cl-C12alkyl, Cl-C8alkyl which is substituted by Cl, Br, OX, Oalk, Salk, C2-C8acyloxy, -COOalk, -CONHalk, -CON(alk)2 or CN, or represents C3-C5alkenyl, cyclohexyl, benzyl, phenyl which is unsubstituted of substituted by Cl or alk, or :, 9~YI
2-tetrahydropyranyl, R7 and R are the same or différent and represent C1-C4alkyl or phenyl, R represents hydrogen, Cl-C8alkyl or C6-C~aryl, R represents Cl-C8alkyl, cyc]o-hexyl or benzyl, R represents C2-C8alkylene, xylylene, phenylene or a -phenylene-T-phenylene group, R represents C2-C8alkylene, C~-C6oxaalkylene or xylylene, R represents -CONH2, -CONHalk, -CON(alk)2, -P(O)(Oalk)2, Z-pyridyl or 2-oxo-1-pyrrolidinyl, R represents cl-C4alkyl~ -CH2CH2CN
or -CH2CH2COOalk, as sensitizers for the photopolymerisa-tion of unsaturated compounds and for the photochemical crosslinking of polyolefins.
These compounds are accordin~ly aromatic-alipha-tic ketones, the a-carbon atom of which is tertiary and which are substituted by a hydroxyl or amino yroup or the etherification or silylation products thereof. The alipha-tic residue can also be cycloaliphatic or araliphatic or linked to the aromatic residue with ring closure, which corresponds to the benzocyclic ketones of the ~ormula IV.
Of the substituents listed above, R1, R2, R9 and R10 can be alkyl of 1 to 8 carbon atoms, for example methyl, ethyl, propyl, bu~yl, hexyl or octyl. R , R and R6 as alkyl can be unbranched or branched alkyl of 1 to 12 carbon atoms, for example methyl, ethyl, isopropyl, tert-butyl, isoamyl, n-hexyl, 2-ethylhexyl, n-decyl or n-dodecyl. Alk represents a lower alkyl radical of 1 to ~
carbon atoms, for example methyl, ethyl, isopropyl, n-butyl or tert-butyl.
Rl, R2 and R6 as hydroxyalkyl, alko~yalkyl or acyloxyalkyl can be for example hydroxymethyl, 1-hydroxy-ethyl, 2-hydroxyethyl, 2-isopropoxyethyl, l-hydroxyiso-butyl, l-acetyloxybutyl, l-acryloyloxyhexyl, l-hydroxy-~7~
octyl, 3-benzoyloxypropyl, methoxymethyl or isobutyloxy-methyl. The acyl radical can be the radical o~ an alipha~ic or aromatic carboxylic acid. Preferably they are l-hydroxy-alkyl radicals and their ethers or esters. R and R as hydroxyalkyl or alkoxyalkyl can be for example 2-hydroxy-ethyl, 2-butoxyethyl, 2-methoxypropyl, 3-hydroxypropyl or 2-ethoxybutyl. Preferably they are 2-hydroxyalkyl radicals and the ethers thereof.
Rl and R as alkyl which is substituted by -NR4R5 can be for example dibutylaminomethyl, 2-piperidino-ethyl or 2-dimethylaminopropyl.
Rl, R , R , R or R as CN-substituted alkyl can be for example 2-cyanoethyl, 2-cyanopropyl or 4-cyanobutyl-whilst Rl, R2 and R4 can also be for example cyanomethyl, 2-cyanohexyl or 4-cyanooctyl. The 2-cyanoethyl radical is preferred.
Rl, R2 and R6 as alkyl substituted by -COOalk can be for example -CH2COOC2H5, -CH2CH2COOCH3, -(CH2)3-COOCH3 or -CH2CH(C2H5)-COOC~Hg. R6 as alkyl substitute~
by -CONHalk or -CONH(alk)2 can be for example -CH2CONHCH3, ~CH2CH2CON(CH3)2 or -CH2CH(CH3~-CONHC4Hg.
Rl, R , R , R and R as alkenyl can be for example allyl, methallyl or 2-butenyl.
Rl and R2 as cycloalkyl can be cyclopentyl or cyclohexyl. Rl, R , R and R as phenylalkyl can be for example benzyl, phenylethyl or dimethylbenzyl.
Ar as aryl or substituted phenyl can be Eor example phenyl, naphthyl, phenanthryl, anthracyl, diphenyl-yl, chlorophenyl, bromophenyl, dichlorophenyl, mesityl, /
~f~2~9 isopropylphenyl, phenoxyphenyl, cyanophenyl, p-nonylphenyl, hydroxyphenyl, tolyl, tert-butylphenyl, xylyl, isoprop~l-chlorophenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, chlorotolyl, bromoxylyl, methylthiophenyl, phenylthio- -phenyl, butylsulfophenyl, phenylsulfophenyl, ethoxycarbo-nylphenyl, tert -butoxycarbonylphenyl, methylaminosulfo-phenyl, dipropylaminosulfophenyl, dimethylaminophenyl, benzoylaminophenyl or acetylaminophenyl.
R as aryl can be for example phenyl, tolyl, naphthyl, diphenylyl or phenanthryl.
Rl and R together can represent alkylene or oxa-alkylene or azaalkylene. In this case, Rl and R together with the carbon atom to which they are attached form a cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, tetrahydrofurane, tetrahydropyrane, pyrroli-dine or piperidine ring.
~ and R together can represen~ alkylene or phenylalkylene o~ 1 to 9 carbon atoms or oxaalkylene ox azaalkylene. In this case, R2 and R5 together wlth the carbon atom to which R2 is attached and the nitrogen atom to which R is attached form a 3- to 6-membered ring, for example an aziridine, azetidine, pyrrolidine, imidazolid-ine, piperidine, piperazine or morpholine ring.
R4 and R together can represent alkylene of 4 to 5 carbon atoms which can be interrupted by ~0- or -NRl -. In this case, R and ~ together with the nitrogen atom to which they are attached form a pyrrolidine, piperi-dine, morpholine, 4-alkylpiperazine, 4~cyanoethyl-piperazine or 4-alkoxycarbonylethylpiperazine ring.
X and R together can represenk a -O-CH~R )-, -O-C~15R )~O-(CH2)1 2- or -O Cl-C4alkylene group. In this case, Rl and X together with the carbon atom to which they are attached form an oxirane, oxetane, oxalane, tetra-hydropyrane, 1,3-dioxolane or 1,3-dioxane ring which can be substituted by alkyl or aryl.
~ 3 can be alkylene of 1 to 16 carbon atoms and R and Rl can be alkylene of 2 to 8 carbon atomsO
Examples of such alkylene groups, within the stated number of carbon atoms, are: methylene, 1,2-ethylene, 1,3-propyl-ene, 1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexyl-ene, 2-methyl-3-ethyl-1,4-butylene or 1,8-octylene. R3 can also be oxaalkylene, thiaalkylene and mono- or dioxothia-alkylene of 2 to 6 carbon atoms, for example 2-oxa-1,3-propylene, 3-oxa-2,4-pentylene, 3-oxa-2,4-pentylene, 3-oxa-l,S-pentylene, -C~2SCH2-, -CH2CH2SOCH2CH2- or --(CH2)3-S02-(cH2)3 Ar can be arylene of 6 to 12 carbon atoms, for example phenylene, naphthylene or diphenylene.
If Y is a direct bond, the compounds of the formula IV constitute derivatives of indanone, cumarone or thiocumaranone. If ~ is C~2, they are derlvatives of tetralone, chromanone or thiochromanone.
A particular object of the invention is the use of compounds of the formula I or II, wherein X is a -NR R
group. These compounds are arylalkyl ketones which are branched at the ~-carbon atom and substituted by amino groups.
A further particular object of the invention is .~ ., ~z~
the use of compounds of the formula I or II, wherein X re-presents a _oR6 group. These compounds are arylalkyl ketones which are branched in the ~-position and substi-tuted by hydroxyl or ether groups.
Yet a further object of the invention is the use of compounds of the formula I or II, wherein X represents a -OSiR (R8)2 group. These compounds are aralkyl ketones which are branched in the ~-position and substituted by siloxy groups. The -OSiR (R )2 group is for example tri-meth~lsiloxy, dimethylphenylsiloxy, methyldiphenylsiloxy or triphenylsiloxy.
Preferably, the in~ention is concerned with the use of compounds of the formulae I, II, III or IV, wherein n is 1 or 2, Ar, if n is 1, represents C6-C14aryl which is unsubstituted or substituted by one or more members se lected from the group consisting of Cl, Br, Cl-C12alkyl, -Oalk, -Ophenyl, -COOalk, -N(alk)2 or -NHCOalk, or repre-sents indanyl, or tetrahydronaphthyl, and alk represents a lower alkyl radical of 1 to 4 carbon atoms, and, if n is 2, represents C6-C12arylene or a -phenylene-T-phenylene group, X represents one of the groups NR R or ~OR , X' represents one of the groups -N~N-, -N(R10)-Rl -N(R10)-or -O-R 2_o, Y represents a direct bond or CH2-, Z
represents -O-, -CH2 or -C(CH3)2-, T represents -O-, -CH2-or -CH2C~2-, Rl in formula I, if n is 1 and X is -oR6, represents Cl-C8alkyl which is unsubstituted or substi-tuted by -COOalk or CN, or represents C7-Cgphenylalkyl, and in all other cases represents Cl-C8alkyl which is un-substituted or substituted by -OH, Oalk, -COOalk or -CN, or is C7-C~phenylalkyl, R has one of the meanings assigned to R or is C~-C4alkenyl or a -C~2CH2R group, or to-gether with R represents C2-~6alkylene or C3-C'4oxa- or azaalkylene, R represents a direct bond or Cl-C6alkylene or together with both substituents R and both carbon atoms to which these substituents are attached fcrms a cyclo-pentane or cyclohexane ring, R represents Cl-C12alkyl, C2-C4alkyl which is substituted by OH, Oalk or CN or re-presents C3-C5alkenyl, P~ represents Cl-Cl2alkyl, C2-C4-alkyl which is substituted by OH, OalK or CN or represents C3-C5alkenyl, or together with R represents C4-C5alkylene which can be interrupted by -O- or -NR14, R represents hydrogen, Cl-C12alkyl, Cl-C6alkyl which is substituted by Cl; Br, OH, Oalk, -COOalk or CN, or is C3-C5alkenyl, benz-yl, phenyl, or together with R represents C~-C4alkylene or -CH2-O-CH2-, R represents Cl-C8alkyl, R represents C2-C~alkylene, R represents C2~C8alkylene, C4-C6oxa-alkylene or xylylene, R represents -CONH2, -CONHalk',:
-CON(alk)2, -P(O)(Oalk)2 or 2-pyridyl, and R14 represents Cl-c4alkyl~ -CH2CH2CN or -CH2CH2-COOalk-Among these compounds, preferred compounds arethose of the formula I, especially those compounds of the formula I in which n is 1 and X is OH and Rl and R to-gether represent C2-C5alkylene.
Most preferably, the invention :Ls concerned wlth the use of compounds o~ the formulae I, II or III, whereln n is 1 or 2, Ar, if n is l, represents C6-C14aryl which is unsubstituted or substituted by halogen, Cl-Cl2alkyl or Oalk, or represents indanyl or tetrahydronaphthyl, and alk represents a lower alkyl radical of 1 to 4 carbon atoms, and, if n is 2, represents C6-Cl2arylene or a -phenylene-T-phenylene group, X represents one of the groups -NR R or -OR , X' represents one of the groups - ~ - or -o-Rl2_o , T represents -O-, -CH2- or -CH2CH2-, R represents Cl-C8-alkyl, R represents Cl-C8alkyl or C3-C4alkenyl, R re-presents a direct bond or Cl-C6alkylene, R represents g4~
Cl-C12alkyl, R represents Cl-C12alkyl or together with R4 represents C~C5alk~1ene which can be interrupted by -O-or -NR14-, R represents hydrogen, C1-C12alkyl, Cl-C6alkyl-which is substituted by OH, Oalk, COOalk or CN, or re-presents C3-C5alkenyl, benzyl, phenyl, or together with R2 represents -CH2-O-CH2-, R represents C2-C8alkylene and R represents c1-c4alkYl-Among these compounds, those compounds o~ theformula I or II are preferred in which X represents allyl-oxy, Cl-C6hydroxyalko~y or alkoxyalkoxy, -OCH2CH2CN, -OC~2CH2COOalk, benzyloxy or phenyloxy, or together with R represents -O-~H2 O-, and also the compounds of the ~ormulae I, II or III in which Ar represents p-phenoxy-phenyl or a tetrahydronaphthalene radical.
Examples of eligible compounds of the formula I, wherein n is 1, are: 2-hydroxy-2-methyl-propiophenone, 2~hydroxy-2-ethyl-propiophenone, 2-hydroxy-2-butyl-propio-phenone, 2-methoxy-2-methyl-propiophenone, 2-hydro~y-2-methyl-(p-chloropropiophenone), 2-hydroxy-2-methyl-(3,4-dichloropropiophenone), 2-hydroxy-2-methyl-(p-methoxypro-piophenone), 2-hydroxy-2-methyl-(2,4-dimethoxypropio-phenone), 2-hydroxy-2~methyl~-(p-phenoxypropiophenone), 2-hydroxy-2-methyl-(p-acetylaminopropiophenone), 2-hydroxy-2-methyl~(p-methylpropiophenone), 2-methoxy-2-methyl-(o-methylpropiophenone), 2-hydroxy-2-methyl-(m-methylpropio-phenone), 2-hydroxy-2-methyl-(2,4-dimethylpropiophenone), 2-hydroxy-2-methyl-(3,4-dimethylpropiophenone), 2-hydroxy-2-methyl-(p-butylpropiophenone), 2-hydroxy-2-methyl-(p-tert.-butylpropiophenone), 2-hydroxy-2-methyl-(p-isopropyl-propiophenone), 2-hydroxy-2-methyl-(p-octylpropiophenone), 2-hydroxy-2-methyl-(p-laurylpropiophenone), 2-methoxy-2-methyl-(o-chloropropiophenone), 2-methoxy-2-methyl-(o-methylpropiophenone), 2-hydroxy-2-methyl-(p-methylthio-propiophenone), 2-hydroxy-2-methyl-(p-dimethylaminopropio-phenone), 2-hydroxy-2-methyl-(p-carboethoxy-propiophenone), 2-phenoxy-2-methylpropiophenone, 2-allyloxy-2 methyl-propiophenone, 2-benzyloxy-2-methylpropiophenone, 2-(2-methoxycarbonylethoxy)-2-methyl-propiophenone, 2-(2-cyano-ethoxy)-2-methyl-propiophenone, 2-ethoxy-2-methylpropio-phenone, 2-methoxyethoxy-2-methyl-propiophenone, 2-hydroxy-methoxy-2-methylpropiophenone, 2-hydroxyethoxy-2-methyl-propiophenone, 2-acetoxymethoxy-2-methylpropiophenone, 2-benzoyloxymethoxy-2-methylpropiophenone, 2-(o-hydroxy-phenoxy)-2-methylpropiophenone, 3-benzoyl-3-hydroxyheptane, 2-benzoyl-2-hydroxypentane, 3-benzoyl-3-hydroxypentane, 2-(2-carboethoxyphenoxy)-2-methylpropiophenone, 2-methyl-2-piperidino-2-phenyl-3-hydroxypropiophenone, 2-methyl-2-morpholino-3-phenyl 3-hydroxypropiophenoner 2-methyl-2-di-methylamino-3-phenyl-3-hydroxy-propiophenone, ~-hydroxy-a-a-bis-(cyanoethyl)-acetophenone, Y-hydroxy-Y-benzoyl-pimelate diethylether, 2-hydroxy-2-methyl-3-phenyl-3-di-methylaminopropiophenone, 2-di-~2-hydroxyethyl)-amino-2-methyl-3-phenylpropiophenone, 2-methyl-2,3-dipiperidino-3~
phenylpropiophenone, 2,3-bis-(dimethylamino)-3-phenyl-propiophenone, 2-hydroxy-2,3-dimethyl-3-phenyl-3-dimethyl--amino-propiophenone, 2-dimethylamino-2-methylpropiophenorle, 2-diethylamino-2-methylpropiophenone, 2-dibutylamino-2-methylpropiophenone, 2-di-hydroxyethylamino-2-methylpropio-phenone, 2-piperidino-2-methylpropiophenone, 2-(2-methyl-piperidino)-2-methylpropiophenone, 2-morpholino-2-methyl-propiophenone, 2-piperazino~2-methylpropiophenone, 2-(~-methylpiperazino)-2 methylpropiophenone, 2-~4-carboethoxy-ethylpiperazino)-2-methyl-propiophenone, 2-pyrrolidino-2-methylpropiophenone, 2~methylphenylamino-2-methylpropio-phenone, l-benzoyl-cyclohexanol, l-benzoyl-cyclopentanol, l-benzoyl-cyclopropanol, 3-p-methoxybenzoyl-3-dimethyl-aminoheptane, 6-(2-hydroxyisobutyryl)-tetraline, 5-(2-hydroxyisobutyryl~-indane, 6-(2-dimethylamino-isobutyryl)-Z9~9 tetraline, 6-(2-morpholino-isobutyryl)-tetraline, 6-(2-piperidino-isobutyryl)-tetraline, 6-~2-piperazino-iso-butyryl)-tetraline, 2-(2-methoxybenzoyl)-2-diallylamino-propane, 2~(2-thenoyl)-2-piperidinopropane, 2-(2-naphthoyl)-2-acetoxybutane, 2-p-phenylbenzoyl-2-di-(2-hydroxyethyl)-~ aminopropane, l-methyl-2-o-chloroben~oyl-piperidin, 1-benzyl-2-benzoyl-3-phenylaziridine, 1-cyclohexyl~2-benzoyl-
~-Aminoacetophenones and a-diaminoace-tophenones have re-cently been proposed as photosensitizers in US patent spe-cification 4,084,034 and a-hydroxy-a-alkylolacetophenones and their ethers in German Offenlegungsschrift 2,357,866.
The shortcomings of these known photosensitizers are in some cases an insufficient storage life in the dark of the photopolymerisable systems mixed with such sensitizers. A
number of benzoin derivatives tend to cause yellowing of the hardened compositions. Other sensitizers are insuffi-ciently reactive - a feature which is observed in the rela-tively lengthy hardening times - or their solubility in the photopolymerisable systems is too low or they are rapidly rendered inacti~e by atmospheric oxygen. There is therefore a need in the art for photosensitizers which are readily soluble in the substrate and, while having a good storage life in the dark, initiat0 the photopolymerisation more rapidly and give a higher polymer yield per unit of time than the known photosensitizers. By using such improved photosensittzers it would be possible to exploit better the expensive industrial UV irradiation plants.
It has been found that compounds of the following formulae I, II, III and IV possess the re~lired properties as photosensitizers. In particular, they effect a rapid photopolymerisation and do not have the shortcomings referred to or possess them to a much lesser degree than the known photosensitizers. Furthermore, they are suitable for the photochemical crosslinking of polyolefins. The invention relates to the use of the compounds of the for-mulae I, II, III or IV
~.~429~
O Rl Ar ~ C - C - X]
12 n O X X O
Il 1 3 1 11 Ar - C - C - R C - C - Ar II
O R Rl O
Ar C - C - X' - C - C - Ar III
12 ¦ -.
o ~o ¦¦ I ` x IV
wherein n is 1 cr 2, Ar in formula I, if n is 1, and in formulae II and III, represents C6-C]4 aryl which is unsubstituted or substituted by one or more members selected from the group consisting of Cl, Br, CN, OH, Cl-C12alkyl, -Oalk, -Ophenyl, -Salk, -SCH2CH20EI, Sphenyl, -SO2alk, -SO2phenyl, -COOalk, -SO2NH2, 2 )2~ NHalk, N(alk)2, -NHCOalk or represents thienyl, pyridyl, furyl, indanyl or -tetrahydronaph-thyl, and alk represents a lower alkyl radical of 1 to 4 carbon atoms, and Ar in formula I, if n is 2, represents C6-C12arylene, a -phenylene-T-phenylene group or a divalent 9,10-dihydroanthracene radical, X represen-ts one of the groups -NR4R5, -oR6, -oSiR (R )2 or toge-ther with Rl represents a -o-CH(R9)-, -O-CH(R9)-0-(CH2)1 2-or -O-Cl-C4alkylene group, X' represents one of -the groups -NR10-, N(C6 C14arYl) ' -N ~ -~ -N(RlO)-Rll-N(Rlo)-~ -Q-, _o_R12_o_, -O-SiR7R8-O-or -O-SiR R -O-SiR R -O-, Y represents a direct bond or -CH2-, Z represents -O~, -S-, -SO2-, -CH2-, or -C(CH3~2-, nt5 -O- -S-, -SO2-~ -CH2-' CH2C 2 6 2 2 -CH=CH-, R in formula I, if n is 1 and X is -OR , repre-sents Cl-C~alkyl which is unsubstituted or substituted by C~-C8acyloxyj -NR R , -COOalk or CN, or represents C3-C5 alkenyl, C5-C6cycloalkyl or C7-Cgphenylalkyl, and in all other cases represents Cl-C8alkyl which is unsubstituted or substituted by -OH, Oalk, C2~C8acyloxy, -NR R , -COOalk or -CN, or is C3-C4alkenyl, C5-C6cycloalkyl or C7-Cgphenyl-alkyl, R has one of the meanings assigned to R or re-presents a -CH2CH2R 3 group, or together with R represents C2-C~alkylene or C3-Cgoxa- or azaalkylene, R represents a direkt bond, Cl-C6alkylene, C2-C6oxaalkylene, C2-C6thia-, s~oxathia- or S-dioxothiaalkylene, phenylene, diphenylene or a -phenylene-T-phenylene group, or together with both substituents R and both carbon atoms to which these sub-stituents are attached, forms a cyclopentane, cyclohexene, endomethylenecyclohexane or cyclohexane ring, R4 represents Cl-C12alkyl, C2-C~alkyl substituted by -OH, Oalk or -CN
or represents C3-C5alkenyl, cyclohexyl, C7-Cgphenylalkyl, phenyl or phenyl which is substituted by Cl, alk, OH, Oalk or -COOalk, R represents Cl-C12alkyl, C2-C4alkyl which ls substituted by OH, Oalk or CN or represents C3-C5alkenyl, cyclohexyl or C7-Cgphenylalkyl, or together with ~ re-presents C4-C5alkylene which can be interrupted b~ -O- or -NR , or, in the case of compounds of the formula I, to-gether with R represents Cl-C~alkylene or phenylalkylene or C2-C3oxa- or azaalkylene, R represents hydrogen, Cl-C12alkyl, Cl-C8alkyl which is substituted by Cl, Br, OX, Oalk, Salk, C2-C8acyloxy, -COOalk, -CONHalk, -CON(alk)2 or CN, or represents C3-C5alkenyl, cyclohexyl, benzyl, phenyl which is unsubstituted of substituted by Cl or alk, or :, 9~YI
2-tetrahydropyranyl, R7 and R are the same or différent and represent C1-C4alkyl or phenyl, R represents hydrogen, Cl-C8alkyl or C6-C~aryl, R represents Cl-C8alkyl, cyc]o-hexyl or benzyl, R represents C2-C8alkylene, xylylene, phenylene or a -phenylene-T-phenylene group, R represents C2-C8alkylene, C~-C6oxaalkylene or xylylene, R represents -CONH2, -CONHalk, -CON(alk)2, -P(O)(Oalk)2, Z-pyridyl or 2-oxo-1-pyrrolidinyl, R represents cl-C4alkyl~ -CH2CH2CN
or -CH2CH2COOalk, as sensitizers for the photopolymerisa-tion of unsaturated compounds and for the photochemical crosslinking of polyolefins.
These compounds are accordin~ly aromatic-alipha-tic ketones, the a-carbon atom of which is tertiary and which are substituted by a hydroxyl or amino yroup or the etherification or silylation products thereof. The alipha-tic residue can also be cycloaliphatic or araliphatic or linked to the aromatic residue with ring closure, which corresponds to the benzocyclic ketones of the ~ormula IV.
Of the substituents listed above, R1, R2, R9 and R10 can be alkyl of 1 to 8 carbon atoms, for example methyl, ethyl, propyl, bu~yl, hexyl or octyl. R , R and R6 as alkyl can be unbranched or branched alkyl of 1 to 12 carbon atoms, for example methyl, ethyl, isopropyl, tert-butyl, isoamyl, n-hexyl, 2-ethylhexyl, n-decyl or n-dodecyl. Alk represents a lower alkyl radical of 1 to ~
carbon atoms, for example methyl, ethyl, isopropyl, n-butyl or tert-butyl.
Rl, R2 and R6 as hydroxyalkyl, alko~yalkyl or acyloxyalkyl can be for example hydroxymethyl, 1-hydroxy-ethyl, 2-hydroxyethyl, 2-isopropoxyethyl, l-hydroxyiso-butyl, l-acetyloxybutyl, l-acryloyloxyhexyl, l-hydroxy-~7~
octyl, 3-benzoyloxypropyl, methoxymethyl or isobutyloxy-methyl. The acyl radical can be the radical o~ an alipha~ic or aromatic carboxylic acid. Preferably they are l-hydroxy-alkyl radicals and their ethers or esters. R and R as hydroxyalkyl or alkoxyalkyl can be for example 2-hydroxy-ethyl, 2-butoxyethyl, 2-methoxypropyl, 3-hydroxypropyl or 2-ethoxybutyl. Preferably they are 2-hydroxyalkyl radicals and the ethers thereof.
Rl and R as alkyl which is substituted by -NR4R5 can be for example dibutylaminomethyl, 2-piperidino-ethyl or 2-dimethylaminopropyl.
Rl, R , R , R or R as CN-substituted alkyl can be for example 2-cyanoethyl, 2-cyanopropyl or 4-cyanobutyl-whilst Rl, R2 and R4 can also be for example cyanomethyl, 2-cyanohexyl or 4-cyanooctyl. The 2-cyanoethyl radical is preferred.
Rl, R2 and R6 as alkyl substituted by -COOalk can be for example -CH2COOC2H5, -CH2CH2COOCH3, -(CH2)3-COOCH3 or -CH2CH(C2H5)-COOC~Hg. R6 as alkyl substitute~
by -CONHalk or -CONH(alk)2 can be for example -CH2CONHCH3, ~CH2CH2CON(CH3)2 or -CH2CH(CH3~-CONHC4Hg.
Rl, R , R , R and R as alkenyl can be for example allyl, methallyl or 2-butenyl.
Rl and R2 as cycloalkyl can be cyclopentyl or cyclohexyl. Rl, R , R and R as phenylalkyl can be for example benzyl, phenylethyl or dimethylbenzyl.
Ar as aryl or substituted phenyl can be Eor example phenyl, naphthyl, phenanthryl, anthracyl, diphenyl-yl, chlorophenyl, bromophenyl, dichlorophenyl, mesityl, /
~f~2~9 isopropylphenyl, phenoxyphenyl, cyanophenyl, p-nonylphenyl, hydroxyphenyl, tolyl, tert-butylphenyl, xylyl, isoprop~l-chlorophenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, chlorotolyl, bromoxylyl, methylthiophenyl, phenylthio- -phenyl, butylsulfophenyl, phenylsulfophenyl, ethoxycarbo-nylphenyl, tert -butoxycarbonylphenyl, methylaminosulfo-phenyl, dipropylaminosulfophenyl, dimethylaminophenyl, benzoylaminophenyl or acetylaminophenyl.
R as aryl can be for example phenyl, tolyl, naphthyl, diphenylyl or phenanthryl.
Rl and R together can represent alkylene or oxa-alkylene or azaalkylene. In this case, Rl and R together with the carbon atom to which they are attached form a cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, tetrahydrofurane, tetrahydropyrane, pyrroli-dine or piperidine ring.
~ and R together can represen~ alkylene or phenylalkylene o~ 1 to 9 carbon atoms or oxaalkylene ox azaalkylene. In this case, R2 and R5 together wlth the carbon atom to which R2 is attached and the nitrogen atom to which R is attached form a 3- to 6-membered ring, for example an aziridine, azetidine, pyrrolidine, imidazolid-ine, piperidine, piperazine or morpholine ring.
R4 and R together can represent alkylene of 4 to 5 carbon atoms which can be interrupted by ~0- or -NRl -. In this case, R and ~ together with the nitrogen atom to which they are attached form a pyrrolidine, piperi-dine, morpholine, 4-alkylpiperazine, 4~cyanoethyl-piperazine or 4-alkoxycarbonylethylpiperazine ring.
X and R together can represenk a -O-CH~R )-, -O-C~15R )~O-(CH2)1 2- or -O Cl-C4alkylene group. In this case, Rl and X together with the carbon atom to which they are attached form an oxirane, oxetane, oxalane, tetra-hydropyrane, 1,3-dioxolane or 1,3-dioxane ring which can be substituted by alkyl or aryl.
~ 3 can be alkylene of 1 to 16 carbon atoms and R and Rl can be alkylene of 2 to 8 carbon atomsO
Examples of such alkylene groups, within the stated number of carbon atoms, are: methylene, 1,2-ethylene, 1,3-propyl-ene, 1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexyl-ene, 2-methyl-3-ethyl-1,4-butylene or 1,8-octylene. R3 can also be oxaalkylene, thiaalkylene and mono- or dioxothia-alkylene of 2 to 6 carbon atoms, for example 2-oxa-1,3-propylene, 3-oxa-2,4-pentylene, 3-oxa-2,4-pentylene, 3-oxa-l,S-pentylene, -C~2SCH2-, -CH2CH2SOCH2CH2- or --(CH2)3-S02-(cH2)3 Ar can be arylene of 6 to 12 carbon atoms, for example phenylene, naphthylene or diphenylene.
If Y is a direct bond, the compounds of the formula IV constitute derivatives of indanone, cumarone or thiocumaranone. If ~ is C~2, they are derlvatives of tetralone, chromanone or thiochromanone.
A particular object of the invention is the use of compounds of the formula I or II, wherein X is a -NR R
group. These compounds are arylalkyl ketones which are branched at the ~-carbon atom and substituted by amino groups.
A further particular object of the invention is .~ ., ~z~
the use of compounds of the formula I or II, wherein X re-presents a _oR6 group. These compounds are arylalkyl ketones which are branched in the ~-position and substi-tuted by hydroxyl or ether groups.
Yet a further object of the invention is the use of compounds of the formula I or II, wherein X represents a -OSiR (R8)2 group. These compounds are aralkyl ketones which are branched in the ~-position and substituted by siloxy groups. The -OSiR (R )2 group is for example tri-meth~lsiloxy, dimethylphenylsiloxy, methyldiphenylsiloxy or triphenylsiloxy.
Preferably, the in~ention is concerned with the use of compounds of the formulae I, II, III or IV, wherein n is 1 or 2, Ar, if n is 1, represents C6-C14aryl which is unsubstituted or substituted by one or more members se lected from the group consisting of Cl, Br, Cl-C12alkyl, -Oalk, -Ophenyl, -COOalk, -N(alk)2 or -NHCOalk, or repre-sents indanyl, or tetrahydronaphthyl, and alk represents a lower alkyl radical of 1 to 4 carbon atoms, and, if n is 2, represents C6-C12arylene or a -phenylene-T-phenylene group, X represents one of the groups NR R or ~OR , X' represents one of the groups -N~N-, -N(R10)-Rl -N(R10)-or -O-R 2_o, Y represents a direct bond or CH2-, Z
represents -O-, -CH2 or -C(CH3)2-, T represents -O-, -CH2-or -CH2C~2-, Rl in formula I, if n is 1 and X is -oR6, represents Cl-C8alkyl which is unsubstituted or substi-tuted by -COOalk or CN, or represents C7-Cgphenylalkyl, and in all other cases represents Cl-C8alkyl which is un-substituted or substituted by -OH, Oalk, -COOalk or -CN, or is C7-C~phenylalkyl, R has one of the meanings assigned to R or is C~-C4alkenyl or a -C~2CH2R group, or to-gether with R represents C2-~6alkylene or C3-C'4oxa- or azaalkylene, R represents a direct bond or Cl-C6alkylene or together with both substituents R and both carbon atoms to which these substituents are attached fcrms a cyclo-pentane or cyclohexane ring, R represents Cl-C12alkyl, C2-C4alkyl which is substituted by OH, Oalk or CN or re-presents C3-C5alkenyl, P~ represents Cl-Cl2alkyl, C2-C4-alkyl which is substituted by OH, OalK or CN or represents C3-C5alkenyl, or together with R represents C4-C5alkylene which can be interrupted by -O- or -NR14, R represents hydrogen, Cl-C12alkyl, Cl-C6alkyl which is substituted by Cl; Br, OH, Oalk, -COOalk or CN, or is C3-C5alkenyl, benz-yl, phenyl, or together with R represents C~-C4alkylene or -CH2-O-CH2-, R represents Cl-C8alkyl, R represents C2-C~alkylene, R represents C2~C8alkylene, C4-C6oxa-alkylene or xylylene, R represents -CONH2, -CONHalk',:
-CON(alk)2, -P(O)(Oalk)2 or 2-pyridyl, and R14 represents Cl-c4alkyl~ -CH2CH2CN or -CH2CH2-COOalk-Among these compounds, preferred compounds arethose of the formula I, especially those compounds of the formula I in which n is 1 and X is OH and Rl and R to-gether represent C2-C5alkylene.
Most preferably, the invention :Ls concerned wlth the use of compounds o~ the formulae I, II or III, whereln n is 1 or 2, Ar, if n is l, represents C6-C14aryl which is unsubstituted or substituted by halogen, Cl-Cl2alkyl or Oalk, or represents indanyl or tetrahydronaphthyl, and alk represents a lower alkyl radical of 1 to 4 carbon atoms, and, if n is 2, represents C6-Cl2arylene or a -phenylene-T-phenylene group, X represents one of the groups -NR R or -OR , X' represents one of the groups - ~ - or -o-Rl2_o , T represents -O-, -CH2- or -CH2CH2-, R represents Cl-C8-alkyl, R represents Cl-C8alkyl or C3-C4alkenyl, R re-presents a direct bond or Cl-C6alkylene, R represents g4~
Cl-C12alkyl, R represents Cl-C12alkyl or together with R4 represents C~C5alk~1ene which can be interrupted by -O-or -NR14-, R represents hydrogen, C1-C12alkyl, Cl-C6alkyl-which is substituted by OH, Oalk, COOalk or CN, or re-presents C3-C5alkenyl, benzyl, phenyl, or together with R2 represents -CH2-O-CH2-, R represents C2-C8alkylene and R represents c1-c4alkYl-Among these compounds, those compounds o~ theformula I or II are preferred in which X represents allyl-oxy, Cl-C6hydroxyalko~y or alkoxyalkoxy, -OCH2CH2CN, -OC~2CH2COOalk, benzyloxy or phenyloxy, or together with R represents -O-~H2 O-, and also the compounds of the ~ormulae I, II or III in which Ar represents p-phenoxy-phenyl or a tetrahydronaphthalene radical.
Examples of eligible compounds of the formula I, wherein n is 1, are: 2-hydroxy-2-methyl-propiophenone, 2~hydroxy-2-ethyl-propiophenone, 2-hydroxy-2-butyl-propio-phenone, 2-methoxy-2-methyl-propiophenone, 2-hydro~y-2-methyl-(p-chloropropiophenone), 2-hydroxy-2-methyl-(3,4-dichloropropiophenone), 2-hydroxy-2-methyl-(p-methoxypro-piophenone), 2-hydroxy-2-methyl-(2,4-dimethoxypropio-phenone), 2-hydroxy-2~methyl~-(p-phenoxypropiophenone), 2-hydroxy-2-methyl-(p-acetylaminopropiophenone), 2-hydroxy-2-methyl~(p-methylpropiophenone), 2-methoxy-2-methyl-(o-methylpropiophenone), 2-hydroxy-2-methyl-(m-methylpropio-phenone), 2-hydroxy-2-methyl-(2,4-dimethylpropiophenone), 2-hydroxy-2-methyl-(3,4-dimethylpropiophenone), 2-hydroxy-2-methyl-(p-butylpropiophenone), 2-hydroxy-2-methyl-(p-tert.-butylpropiophenone), 2-hydroxy-2-methyl-(p-isopropyl-propiophenone), 2-hydroxy-2-methyl-(p-octylpropiophenone), 2-hydroxy-2-methyl-(p-laurylpropiophenone), 2-methoxy-2-methyl-(o-chloropropiophenone), 2-methoxy-2-methyl-(o-methylpropiophenone), 2-hydroxy-2-methyl-(p-methylthio-propiophenone), 2-hydroxy-2-methyl-(p-dimethylaminopropio-phenone), 2-hydroxy-2-methyl-(p-carboethoxy-propiophenone), 2-phenoxy-2-methylpropiophenone, 2-allyloxy-2 methyl-propiophenone, 2-benzyloxy-2-methylpropiophenone, 2-(2-methoxycarbonylethoxy)-2-methyl-propiophenone, 2-(2-cyano-ethoxy)-2-methyl-propiophenone, 2-ethoxy-2-methylpropio-phenone, 2-methoxyethoxy-2-methyl-propiophenone, 2-hydroxy-methoxy-2-methylpropiophenone, 2-hydroxyethoxy-2-methyl-propiophenone, 2-acetoxymethoxy-2-methylpropiophenone, 2-benzoyloxymethoxy-2-methylpropiophenone, 2-(o-hydroxy-phenoxy)-2-methylpropiophenone, 3-benzoyl-3-hydroxyheptane, 2-benzoyl-2-hydroxypentane, 3-benzoyl-3-hydroxypentane, 2-(2-carboethoxyphenoxy)-2-methylpropiophenone, 2-methyl-2-piperidino-2-phenyl-3-hydroxypropiophenone, 2-methyl-2-morpholino-3-phenyl 3-hydroxypropiophenoner 2-methyl-2-di-methylamino-3-phenyl-3-hydroxy-propiophenone, ~-hydroxy-a-a-bis-(cyanoethyl)-acetophenone, Y-hydroxy-Y-benzoyl-pimelate diethylether, 2-hydroxy-2-methyl-3-phenyl-3-di-methylaminopropiophenone, 2-di-~2-hydroxyethyl)-amino-2-methyl-3-phenylpropiophenone, 2-methyl-2,3-dipiperidino-3~
phenylpropiophenone, 2,3-bis-(dimethylamino)-3-phenyl-propiophenone, 2-hydroxy-2,3-dimethyl-3-phenyl-3-dimethyl--amino-propiophenone, 2-dimethylamino-2-methylpropiophenorle, 2-diethylamino-2-methylpropiophenone, 2-dibutylamino-2-methylpropiophenone, 2-di-hydroxyethylamino-2-methylpropio-phenone, 2-piperidino-2-methylpropiophenone, 2-(2-methyl-piperidino)-2-methylpropiophenone, 2-morpholino-2-methyl-propiophenone, 2-piperazino~2-methylpropiophenone, 2-(~-methylpiperazino)-2 methylpropiophenone, 2-~4-carboethoxy-ethylpiperazino)-2-methyl-propiophenone, 2-pyrrolidino-2-methylpropiophenone, 2~methylphenylamino-2-methylpropio-phenone, l-benzoyl-cyclohexanol, l-benzoyl-cyclopentanol, l-benzoyl-cyclopropanol, 3-p-methoxybenzoyl-3-dimethyl-aminoheptane, 6-(2-hydroxyisobutyryl)-tetraline, 5-(2-hydroxyisobutyryl~-indane, 6-(2-dimethylamino-isobutyryl)-Z9~9 tetraline, 6-(2-morpholino-isobutyryl)-tetraline, 6-(2-piperidino-isobutyryl)-tetraline, 6-~2-piperazino-iso-butyryl)-tetraline, 2-(2-methoxybenzoyl)-2-diallylamino-propane, 2~(2-thenoyl)-2-piperidinopropane, 2-(2-naphthoyl)-2-acetoxybutane, 2-p-phenylbenzoyl-2-di-(2-hydroxyethyl)-~ aminopropane, l-methyl-2-o-chloroben~oyl-piperidin, 1-benzyl-2-benzoyl-3-phenylaziridine, 1-cyclohexyl~2-benzoyl-
3-phenyla~iridine, 2-o-toluyl-2-(trimethylsiloxy)-propane, : 2-hydroxy-2-methyl-(p-isopropylpropiophenone), 2-hydroxy-methoxy-2-methyl-propiophenone, 2-hydroxymethoxy-2-methyl-~2,5-dimethylpropiophenone), 2-hydroxymethoxy-2-methyl-(p-isopropylpropiophenone~, 5-methyl-5-b~nzoyl-1,3-dioxolane, 2,5-dimethyl-5~benzoyl-1,3-dioxolane, 2-phenyl-5-methyl-5-benzoyl-1,3-di- xolane, 5-methyl-5-(p-isopropylbenzoyl)-1,3-dioxolane, 2,3-epoxy-2-methyl-3-phenylpropiophenone, 2-acetoxymethoxy-2-methylpropiophenone, 2-benzoyloxy-methoxy-2-methylpropiophenone, 2-hydroxy-2-methyl-3-dime-thylaminopropiophenone, 2-methoxy-2-methyl-3-dimethylamino-propiophenone, 2-hydroxy-2-methyl~3-morpholinopropio-' phenone, 2-hydroxy-2-methyl-4-N,N-diethylcarbamoylbutyro~
phenone, 2-morpholino-2-methyl-4-N,N-diethylcarbamoyl-butyrophenone, 2-hydroxy-2-methyl-4-(2-pyridyl)-butyro-phenone, 2-hydroxy-2-methyl-4-diethyl-phosphonobutyro-phenone, 2-hydroxy-2-benzylpropiophenone, 2-hydroxy-2-(p-methylbenzyl)-propiophenone, 2-hydroxy-2-cyclohexylpropio-phenone, 2-hydroxy-2-cyclopentylpropiophenone, 2-~2-' .
hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-allyl-propiophenone, 2-hydroxy-2-methyl-4-~2-oxo-1-pyrrolidinyl)-butyrophenone, 2-methyIthio-2-methyl-propiophenone.
Examples of compounds of the formula I, wherein n is 2, are: 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl oxide, 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl, 4,4'-bis (a-hydroxy-isobutyryl)-diphenyl sulfide, 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl methane, 4,4'-bis-(a-piperid-!~i ino-isobutyryl~-diphenyl oxide, 4,4'-bis-[a-(isopropyl-amino)-isobutyryl]-diphenyl, 4,4'-bis-~a-benzoyloxy-iso-butyryl)-diphenyl oxide, 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl ethane.
~ Examples of compounds of the formula II are: 1,4-diphenyl-2,3-dimethyl-2,3-dihydroxy-butanedione-1,4, 2,4-dibenzoyl-2,4-dihydroxypentane, 2,9-dibenzoyl-2,9-dimethyl-3,8-dioxadecane, 2,7-dibenzoyl-2,7-dimethyl-3,6-dioxa-octane, 1,6-diphenyl-2,5-dimethyl-2,5-dihydroxy-hexane-dione-1,6, 1,4-diphenyl-2,3-dimethyl-2,3-bis-(dimethyl-amino)-butanedione-1,4, 1,4-diphenyl-2,3-dimethyl-2,3-di-piperidyl-butanedione-1,4, 1,2-bis-hydroxy-1,2-bis-benzoyl-cyclohexane, 1,2-bis-dimethylamino-1,2-bis-benzoyl-cyclo-hexane, 1,2-bis-morpholino-1,2-bis-benzoyl-cyclohexane, bis-(3-hydroxy-3-benzoylbutyl)-sulfone.
Examples of compounds of the formula III are:
1,4-b~s-(l-benzoyl-isopropyl)-piperazine, 2,7-dibenzoyl-2,7 dimethyl-3,6-dioxaoctane, 2,9-dibenzoyl-2,9-dimethyl-3,8-dioxadecane, 2,6-dibenzoyl-2,6-dimethyl-3,5-dioxahep-tane, N,N-bis-(a-benzoyl-isopropyl)-butylamine, N,N'-dl.~
methyl-N,N'-bis-(a-benzoyl-isopropyl)-ethylenediarnine.
Examples of compounds of the formula IV are:
1-o~o-2-dimethylamino-2-methyl-1,2,3,4-tetrahydronaphthal-ene, l-oxo-2-hydroxy-2-m~thyl-1,2,3,4-tetrahydronaphthal-ene, l-oxo-2-hydroxy-2-methylindane.
Some of the compounds of the formulae I, II, III
and IV are known compoundsl and others are novel.
Known compounds are those of the formula I, wherein n is l, Ar represents phenyl, phenyl which is sub-stituted by methyl or methoxy, or is furyl, Rl and R are methyl or Rl and R2 together represent alkylene and X is hydroxyl, methoxy or nitrophenoxy.
Xnown compounds are those of the formula I, wherein n is 1, Ar represents phenyl, chlorophenyl or di~
phenylyl, Rl and R2 are methyl or morpholinomethyl, or and R together are alkylene and X is a -NR R group, in which each of R5 and R6 is alkyl or benzyl or R5 and R to-gether represents alkylene or oxaalkylene.
A known compound is also a compound of the for-mula II, wherein Ar represents phenyl, R represents me-~ ' thyl, X represents hydroxy and R3 is a direct bond.
The known compounds have up to now not been proposed as photosensitizers.
The compounds of the formulae I, II, III or IV, in so far as they are novel, also constitute an object of the invention. Accordinyly, the invention also relates to:
a) Compounds of the formula I, wherein n is 1, Ar repre-sentsC10-Cl4aryl~ C6 C14aryl which is substituted by one ore more members selected from the-group consisting oE CN, OH, -Ophenyl, -Salk, -SO2alk, -SO2phenyl, -COOalk, ~SO2N~2, -SO2NHalk~ -SO2N(alk)2, -NHalk or -NHCOalk or represents thienyl, pyridyl, indanyl or tetrahydronaphthyl, X is OH
or -Oalk, and Rl and R are as previously defined.
b) Compounds of the formula I, wherein n is 1, X is a _oR6 group and R6 represents Cl-C6alkyl which is substituted by OH or Oalk or represents allyl, cyclohexyl, benzyl, phenyl which is unsubstituted or substituted by Cl or alk, or to-gether with R represents C3-C4alkylene or -CH2-O-CH2-, and Ar, R and R are as previously defined.
~Z9~9 c) Compounds of the formula I, wherein n is 1, X is -OSiR (R )2 or together with R represents one of the groups -O-CH(R )-, -O-CH(R )-O-(CH2)1-2- or -OCl-C4alkylene, R is C2-C4alkyl or phenyl, and Ar, R , R and R are as previously defined.
d) Compounds of the formula I, wherein n is 1, Ar is phenyl, halogenphenyl or diphenylyl, X is a -NR R group, R is C2~C8alkyl, Cl-C8alkyl which is substituted by OH, Oalk, C2-C8acyloxy, COOalk or CN, or is C5-C6cycloalkyl or C -Cgphenylalkyl, R has one of the meanings assigned to R~ or is llyl or a -CH2CH2Rl group together with R
is C4-C6alkylene or C3-C4oxa- or azaalkylene, and R , R
and Rl are as previously defined.
e) Compounds of the formula I, wherein n is 1, Ar is phenyl which is substituted by CN, OH, alk, Oalk, -Ophenyl, -Salk, -SO2alk, -SO2phenyl, -COOalk, -SO2NH2, -SO2NHalk, -SO2N(alk)2, NHalk, -N(alk)2 or -NHCOalk or is naphthyl, thienyl, pyridyl, furyl, indanyl or tetrahydronaphthyl, X is a -~R R group and R , R , R and R are as previously defined.
f) Compounds of the formula I, wherein n is 2 and Ar, X, Rl and R are as pre~iously defined.
g) Compounds o~ the formula II, wherein R is a direct bond, X is one of the groups -NR R , -OR , OSiR (R )2' R6 is Cl-C12alkyl, C2-C4alkyl which is substituted by OH
or Oalk or is allyl, cyclohexyl, benzyl, phenyl which is unsubstituted or substituted by C1 or alk, and Ar, R , R4, R5, R7 and R are as previously defined.
h) Compounds of the formula II, wherein R represents Cl-C6 ~lkylene, C2-C6oxaalkylene, C2-C6thia-, ~-oxothia- or S-di-oxothiaalkylene, phenylene, diphenylene or a -phenylene-T-phenylene group, and Ar, R , X and T are as previously defined.
i) Compounds of the formula III, wherein Ar, R , R and X' are as previously defined.
k) Compounds of the formula IV, wherein R , X, Y and Z are as previously defined.
These novel compounds can be prepar~d by methods analogous to those for obtaining the known compounds, whereby different methods are possible.
Accordingly, the compounds of the formula I can be prepared from aromatic-aliphatic ketones by the follow-ing reaction steps:
Ar ~ CO-CHRlR2] ~ A ~ CO CBrR1R2] CH30Na _~
n ~ n As HX it is possible to use amines [C.L. Stevens, Ch. Huny Chany, J. Org. Chem. 27 (1962), 4392] or water or carboxylic acids [C.L. Stevens, E. Farkas, J. Am. Chem.
Soc. 74 (1952), 618 and C.L. Stevens, S.J. Dykstra, J. Am.
Chem. Soc. 75 (1953), 5976].
In many cases the direct reaction of the a-bromo~
ketones to give compounds of the formula I
O R
~r E co CBrR R ~ R
g ~ ~
is also possible, for example with amines, alkal!ihydroxides or alkali phenoxides. Instead o~ bromine compounds it is also possible to use the corresponding chlorine compounds.
-The resulting hydroxyketones of the formula I(X=OH) can be etherified or O-silylated by the conventional methods.
Compounds of the formula III are obtained by using a difunctional compound of the formula H-X'-H instead of the monofunctional compound HX in the above reactions.
The compounds of the formula II can be prepared analogously to those of the formula I by using diketones of the generaI formula Rl 2 R2 Ar- CO - CH~ R - CH -CO - Ar i The compounds of the formula IV are obtained in analogous manner starting rom cyclic ketones of the formu-la Rl ~7,~,Z,~b Compounds of the formula I, wherein R is a sub-stituted alkyl group, can be obtained from the compounds of the formula Ar~CO-CH(R2)-X]n by reaction with aldehydes (Rl = hydroxyalkyl) or with a vinyl compound which is cap-able of addition, for example with acrylated or acrylonit-rile, In the same way, a -CH~CH2-R13 group can be intro-duced as R , starting from a compound Ar~CO-CH(R ~~X]n. If both R and R are substituted alkyl, then both substi-~s~'j g tuents can be introduced jointly by reaction of a compoundAr~C0-CH2-X]n with at least 2 moles of an aldehyde or a vinyl compound. The corresponding alkoxyalkyl and acyloxy-alkyl groups can be obtained from the hydroxyalk~l groups Rl and/or R by etherification or esterification. Compounds of the formulae II, III and IV containing substituted alkyl groups as R or R can be obtained in analogous manner.
Compounds in which X together with R is a -0-CH
(R9) group are a-oxydoketones and can be obtained by epoxi--- dation of the corresponding a-vinyl ketones. Reaction of the oxydoketones with secondary amines affords compounds in which either X is 0~ and Rl is an aminoalkyl group, or in which X is N~4R and Rl is a hydroxyalkyl group.
Addition of bromine to the a-vinyl ketones yields a,~-dibromoketones of the formula Ar~C0-CBr(R ) CBralk~n.
Reaction of the dibromoketones with one mole of a primary amine yields the corresponding ~-aziridinoketones [J. Chem. Soc. 65 (1943), 312~, and reaction with 2 moles o~ a secondary amine yields compounds of the formula I, wherein ~ is -NR R and R is an aminoalkyl radical ~J. Am.
Chem. Soa. 74 (1952), 1886].
Aminoalkyl groups Rl and/or R can also be intro-duced by the Mannich reaction, wherein ketones of the for-m~la Ar~C0-CHR ~X]n or Ar~C0-CH2-X]n are reacted with 1 or 2 moles of formaldehyde and a secondary amine.
Whereas all these methods of synthesis start from an aromatic-aliphatic ketone into which a substituent X is introduced in a different manner, it is also possible in specific cases to introduce the substituent X during the ketone synthesis by the Friedel-Crafts reaction in accor-' ~ 20 -dance with the reaction scheme:
Rl R
I AlC13 X-C-COC1 + ArH ~ Ar-CO-C-X
rrhis presupposes that the substituent X is not attacked under the conditions o the Friedel-Crafts reac-tion. In this way it is possible for example by using heterocyclic carboxylic acid chlorides to prepare compounds of the formula I, in which X and Rl together with the car-bon atom to which they are attached form a heteroring.
.
According to the invention, the compounds o~ the ~ormulae I, II, III and IV can be used as sensitizers for the photopolymerisation of unsaturated compounds or systems which contain such compounds.
Such compounds are for example unsaturated mono-mers, such as esters of acrylic or methacrylic acid, for example methacrylate, ethylacrylate, n- or tert-butyl~
acrylate, isooctylacrylate or hydro~yethylacrylate, methyl-or ethylmethacrylate, ethylene diacrylate, neopentyl di-acrylate, trimethylolpropane trisacrylate, pentaerythritol tetraacrylate or pentaerythritol trisacrylate; acrylo-nitrile, methacrylonitrile, acrylamide, methacrylamide, N-substituted acrylamides and methacrylamides; vinyl esters, such as vinyl acetate, vinyl propionate, vinyl acrylate or vinyl succinate; other vinyl compounds, such as vinyl ethers, styrene/ alkyl styrenes, halostyrenes, divinyl benzene, vinyl naphthalene, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride; allyl compounds, such as diallyl phthalate, diallyl maleate, triallyl iso-cyanurate, triallyl phosphate or ethylene glycol diallyl ether and the mixtures of such unsaturated monomers.
~L~4Z~9 , Photopolymerisable compounds are in addition un~
saturated oligomers or polymers and the mixtures thereof with unsaturated monomers. These include thermoplastic resins which contain unsaturated groups, such as fumaric acid ester groups, allyl groups or acrylate or methacrylate groups. These unsaturated groups are usually bound through functional groups to the main chain of these linear poly-mers~ Mixtures of oligomers with simply and poly-unsatu-rated monomers are ~ery important. Examples of such oligomers are unsaturated polyesters, unsaturated acrylic resins and isocyanate or epoxide modified acrylate oligo-mers as well as polyether acrylate oligomers. Examples of poly-unsaturated compounds are in particular the acrylates of diols and polyols, for example hexamethylene diacrylate or pentaerythritol tetracrylate. Acrylates are also preferred as simply unsaturated monomers, for example butyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethyl-hexyl acrylate or 2-hydroxypropyl acrylateO By choosing rom the diferent representatives of the three component$, the opportunity is afforded to vary the consistency of the unpolymerised mixture as well as the plasticity of the polymerised resin.
In addition to these three-component mixtures, two-component mixtures especially are of great importance among the polyester resins. These usually consist of an un-saturated po]yester and a vinyl compoundO The unsaturated polyesters are oligomer esterification products of at least one unsaturated dicarboxylic acid, for example maleic, fumaric or citraconic acid, and usually of at least one saturated dicarboxylic acid, for example phthalic acid, succinic acid, sebacic acid or isophthalic acid, with glycols, for example ethylene glycol, propanediol~l,2, di-or triethylene glycol or tetramethylene glycol, whilst monocarboxylic acids and monoalcohols are generally also 2~
used concurrently for the modification. These unsaturated polyesters are normally dissolved in a vinyl or allyl com-pound, styrene being preferably used for this purpose.
Photopolymerisable systems which are used for the different purposes usually contain, in addition to the photopolymerisable compounds and the photosensitizeri a number of other ingredients. It is therefore often customary to add heat inhibitors in order to prevent a premature polymerisation, especially during the preparation of the systems by mixing the components. Hydroquinone, hydroquinone derivatives, p-methoxyphenyl, ~-naphthylamine or ~-naphthols are used for example for this purpose.
Furthermore, small amounts o UV absorbers can be added~
for example those o~ the benztriazole or benzophenone type.
To increase the storage life in the dark, it is possible to add copper compounds, suc~ as copper naph-thenate, copper stearate or copper octoate, phosphorus com-pounds, such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phos-phate, quaternary ammonium compounds, such as tetramekhyl-ammonium chloride or, trimethylbenzylammonium chloride, or hydroxylamine derivatives, for example N-diethylhydrox-ylamine. In addition, the photopolymerisable systems can contain chain transfer agents, for example N-methyl-di-ethanolamine, triethanolamine or cyclohexene.
In order to exclude the inhibiting action of atmospheric oxygen, paraffin or similar wax-like substan-ces are ~requPntly added to the photohardening systems.
On account of their poor solubility in the polymer, these substances float at the beginning of the polymerisation and form a transparent surface layer which prevents the entry of air.
Z~9L9 The atmospheric oxygen can also be deactivated h~ introduc-ing autoxidisable groups, for example allyl groups, into the resin to be hardened.
-Depending on the end-use, photopolymerisable systems also contain fillers, such as silicic acid, talc or gypsum, pigments, dyes, fibres, thixotropic agents or levelling agents.
Combinations with known photosensitizers, such as benzoin ethers, dia~koxy acetophenones or benzyl ketals, can also be used. Combinations of the photosensitizers of the invention with amines and/or aromatic ketones can be used especially for the photopolymerisation of thin layers and printing inks. Examples of amines are triethylamine, N-methyldiethanolamine, N-dimethylethanolamine or p-di-methylaminobenzoate. Examples of ketones are benzophenone, substituted benzophenone derivatives, Michler's ketone, anthraquinone and antraquinone derivatives, as well as thioxanthone and the derivatives thereof.
Photohardening is of great importance for print-ing inks, since the dryin~ time of the binder is a decisive factor in the production speed of printing pro-ducts and should be in the order of fractions of seconds.
The sensitizers of the invention are also very suitable for photohardening systems for the manufacture of printing plates. l~lixtures of soluble linear polyamides with photo-polymerisable monomers, for example acrylamides, and a photosensitizer, are usually employed for this purpose.
Films or plates prepared from these systems are exposed via the negative (or positive) of the original and the un-hardened portions are subsequently eluted with a solvent.
%~q~9 - 2~ -A further field of use of UV hardening is metal coating, for example in the varnish coating of metal sheeting for tubes, cans or bottle caps, as well as the UV
hardening of pIastic coatings, for example of floor or wall coverings based on PVC.
Exemplary of the UV hardening of paper coatings is the colourless varnish coating of labels, gramophone record sleeves or book jackets.
According to the invention, the compounds of the formulae I, II, III and IV can also be used as sensitizers for the photochemical crosslinking of polyolefins, for example polypropylene, polybutene, polyisobutylene and also copolymers, for example ethylene/propylene copolymers, but preferably polyethylene of low, medium or high density.
The photosensitizers are advantageously used for the above fields of use in amounts of 0.1 to 20 % by weight, preferably about 0.5 to 5 % by weight~ based on the photopol~merisable or crosslinkahle system. The term "system" is to be understood as meaning the mlxture of the photopolymerisab~e or crosslinkable compound, the photosensitizer and the other fillers and additives, as it is used in the respective application.
The addition of the photosensitizers to the photopolymerisable systems is accomplished in general by simple stirring, since most of these systems are 1uid or readily soluble. Usually the sensitizers of the inv~ntion dissolve in the system, thereby ensuring their uniform distribution and the transparency of the polymers.
The polymerisation is carried out by the known methods of polymerisation by irradiation with light which ~!
is rich in shortwave radiation. Suitable light sources are for e~ample mercury medium pressure, high pressure and low pressure lamps, as well as superactinic fluorescent tubes, the emission peaks of which are in the range between 250 and 400 nm.
The following Examples describe the manufacture and use of compounds of the formula I in more detail. Parts and percentages are by weight.
~anufacture and properties of the compounds used in Exam le~ 1 to 6 P ~ ._ The compounds listed in Table 1 where obtained by one or more of the methods A to L.
Method A Chlorination of aromatic-aliphatic ketones Ar~CO-CR R H] n + n C12 ~ Ar~Co-CR R Cl]n ~ n HC1 The ketone is dissolved in an inert solvent, preferably in tetrachloromethane, and the calculated amount of chlorine is introduced into the solution at 40-80C. Nitrogen is then introduced to remove dissolved HCl. Finally, the sol-vent is distilled off. Purification of the chloroketone is usually not necessary and the product can subsequently be reacted by method ~, F or H.
Method B Bromination of aromatic--aliphatic ke-tones Ae~C0-CR R H]n ~ n Br2 ~ Ar~C0-CR R Br]n + n HBr The calculated amount of bromine is added dropwise at room temperature to a solution of the ketone, for example in CCl~. Working up and further processing are effected as in Method A.
Method C Chlorination with sulfury.l chloride Ar~C0-CR R H] n S02 C12 Ar~C0-CR R -Cl~n + n S02 + n HCl The sulfuryl chloride is added dropwise at 40C to a solu-tion of the ketone in CC14. Working up and further process-ing as in Method A.
;, Method D Preparation of the epoxide intermediate Ar~CO-CR R Hal] ~ n NaOCH3 ---D Ar~CI - CR R ]n ~ n NaHal Hal = Cl or Br The haloketone is dissolved in methanol and a solution of the stoi~hiometric amount of sodium methoxide in methanol is added dropwise at reflux temperature. The methanol is then distilled off and the residue is poured into ice-water and extracted with ether. The ethereal solution is washed with water, dried over Na2S04, dried and concentrated. The residue is purified by recrystallisation or vacuum distil~
lation. The epoxide can subsequently be reacted by Method E or G.
Method E Hydrolysis of the epoxide ~ 1 2] H+ 1 2 The epoxide is covered with 2 to 5 times its weight of water and the mixture is refluxed for 1 to 2 hours with the addition of a catalytic amount of mineral acid. After cooling, the reaction mixture is extracted with ether. The ethereal solution is washed with water, dried over Na2SO~, and concentrated. The residue (crude hydroxyketone) is purified by distillation or crystallisation or column chromatography. The properties of the pure a-hydroxyketones are indicated in Table 1.
Method F a~Hydroxyketones from ~-haloketones Ar~CO-CR R Hal]n t n NaOH ~ Ar~CO-CR R OH]n ~ n NaHal The c~-haloketone is refluxed in dilute or concentrated sodium hydroxide solution 120 % excess of NaOH). When the hydrolysis is complete Icheck by chromatography), the crude hydroxyketone is isolated and purified as described in Method E. The pure hydroxyketones are listed in Table 1.
Method G a-Aminoketones from the epoxides Ar~ ~ CR R ] +n R R NH Ar~CO-CR R -NR R ] + n CH30H
The epoxide is treated with the stoichiometric amount of the amine, either without a solvent or with the addition of a small amount of toluene or xylene, and reacted for about lO to 20 hours at 100-200C. When using low boiling amines, for example dimethylamine or diethylamine, the ~
reaction is carried out in an autoclave. The reaction mix-ture is diluted with benzene and extracted with dilute hydrochloric acid. The aqueous acid solution is made alkaline with NaOH and extracted with ether. The ethereal solution is washed with water, dried oVer Na2SO~ and con-centrated. The crude product is purifi.ed by distillation or crystallisation. The a-amineketones are listed in Table 1.
M hod H a-~ninoketones from the a-haloketones Ar~CO-CR R Hal~n ~ 2n R R NH ~ Ar~CO-CRlR -NR4R ]
+ n R R NH2Hal The a-haloketone, undiluted or diluted with toluene, is mixed with 2 molar equivalents of the amine and the mix-ture is heated for 10 to 20 hours to 100-200C. When using low boilingamines, forexample dimethylamine or diethylamine, the reaction is carried out in an autoclave. Isolation and 2~4~
purification are effected as in Me-thod G.
Method I Introduction of a carbalkoxyethyl group C~2C~2COOAlX
ArtCO-CHRl-X]n + n CH2 = CH-COOAlk -~Ar~CO-CP~l-X . ] n The ketone is dissolved in dimethyl sulfoxide. To the solu-tion are then added 1.1 molar ecuivalents of NaOH in the form of 4N sodium hydroxide solution and, with cooling, 1.1 molar equivalents of acrylate are added dropwise at room temperature. The reaction mixture is diluted with ice-water and extracted with toluene. The toluene solution is washed neutral with water, dried over Na2SO~ and concentra-ted. The crude product is purified by column chromatography or crystallisation.
Method K Etherification of hydroxyketones Ar~CO-CR ~ -OH] ~ n R Hal ~ n NaOH Ar~CO-CR R -OR ]
+ n NaHal The a-hydroxyketone i5 dissolved in about 4 times its weight of dimethyl sulfoxide and, while cooling to 10-20C and with stirring, 1 molar equivalent o~ the alkyl halide R6Hal and 1 molar equivalent of concentrated sodium hydroxide solution are added dropwise simultaneously from t~o drip funnels. The reaction mixture is then stirred for 3 hours at room temperature. Precipitated sodium halide is then removed by filtration, the filtrate is washed with water, dried over Na2S04 and concentrated. The crude product -is purified by column chromatography~ crystallisation or vacuum distillation. Examples of eligible halogen compounds are melhyl iodide, isopropyl bromide, all~ll bromide, cyclo-hexyl bromide, benzyl chloride or ethyl chloroacetate.
Instead of using an alkyl halide, it is also possible to use a dialkyl sulfate or alkylaryl sulfonate as etherifying reagent.
Method L Cyclisation of X and R
~r-C0-C'~Hal~R ~ CH20 --~ Ar-C0-CR Hal-CH20~ MaOC~3 Ar-C0- ~ H~ + Na;~al -~ C~30~1 Paraformaldehyde is dissolved in 20 times its weight of methanol. To the solution is then added l molar equivalent of sodium methoxide tdissolved in a small amount of methanol).
~hile cooling to 0-5C, a concentrated solution of the a-haloketone is added dropwise. The reaction mixture is sub-sequently stirred for l hour at 5-10C and for l hour at room temperature. The reaction mixture is diluted with ether to 2 to 3 times its volume and poured into ice-water. The aqueous mixture is extracted 3 times with ether and the ethereal extracts are washed with water, dried over Na2S04 and concentrated. The crude product is puriEied by distil-lation or colurnn chromatography.
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phenone, 2-morpholino-2-methyl-4-N,N-diethylcarbamoyl-butyrophenone, 2-hydroxy-2-methyl-4-(2-pyridyl)-butyro-phenone, 2-hydroxy-2-methyl-4-diethyl-phosphonobutyro-phenone, 2-hydroxy-2-benzylpropiophenone, 2-hydroxy-2-(p-methylbenzyl)-propiophenone, 2-hydroxy-2-cyclohexylpropio-phenone, 2-hydroxy-2-cyclopentylpropiophenone, 2-~2-' .
hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-allyl-propiophenone, 2-hydroxy-2-methyl-4-~2-oxo-1-pyrrolidinyl)-butyrophenone, 2-methyIthio-2-methyl-propiophenone.
Examples of compounds of the formula I, wherein n is 2, are: 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl oxide, 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl, 4,4'-bis (a-hydroxy-isobutyryl)-diphenyl sulfide, 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl methane, 4,4'-bis-(a-piperid-!~i ino-isobutyryl~-diphenyl oxide, 4,4'-bis-[a-(isopropyl-amino)-isobutyryl]-diphenyl, 4,4'-bis-~a-benzoyloxy-iso-butyryl)-diphenyl oxide, 4,4'-bis-(a-hydroxy-isobutyryl)-diphenyl ethane.
~ Examples of compounds of the formula II are: 1,4-diphenyl-2,3-dimethyl-2,3-dihydroxy-butanedione-1,4, 2,4-dibenzoyl-2,4-dihydroxypentane, 2,9-dibenzoyl-2,9-dimethyl-3,8-dioxadecane, 2,7-dibenzoyl-2,7-dimethyl-3,6-dioxa-octane, 1,6-diphenyl-2,5-dimethyl-2,5-dihydroxy-hexane-dione-1,6, 1,4-diphenyl-2,3-dimethyl-2,3-bis-(dimethyl-amino)-butanedione-1,4, 1,4-diphenyl-2,3-dimethyl-2,3-di-piperidyl-butanedione-1,4, 1,2-bis-hydroxy-1,2-bis-benzoyl-cyclohexane, 1,2-bis-dimethylamino-1,2-bis-benzoyl-cyclo-hexane, 1,2-bis-morpholino-1,2-bis-benzoyl-cyclohexane, bis-(3-hydroxy-3-benzoylbutyl)-sulfone.
Examples of compounds of the formula III are:
1,4-b~s-(l-benzoyl-isopropyl)-piperazine, 2,7-dibenzoyl-2,7 dimethyl-3,6-dioxaoctane, 2,9-dibenzoyl-2,9-dimethyl-3,8-dioxadecane, 2,6-dibenzoyl-2,6-dimethyl-3,5-dioxahep-tane, N,N-bis-(a-benzoyl-isopropyl)-butylamine, N,N'-dl.~
methyl-N,N'-bis-(a-benzoyl-isopropyl)-ethylenediarnine.
Examples of compounds of the formula IV are:
1-o~o-2-dimethylamino-2-methyl-1,2,3,4-tetrahydronaphthal-ene, l-oxo-2-hydroxy-2-m~thyl-1,2,3,4-tetrahydronaphthal-ene, l-oxo-2-hydroxy-2-methylindane.
Some of the compounds of the formulae I, II, III
and IV are known compoundsl and others are novel.
Known compounds are those of the formula I, wherein n is l, Ar represents phenyl, phenyl which is sub-stituted by methyl or methoxy, or is furyl, Rl and R are methyl or Rl and R2 together represent alkylene and X is hydroxyl, methoxy or nitrophenoxy.
Xnown compounds are those of the formula I, wherein n is 1, Ar represents phenyl, chlorophenyl or di~
phenylyl, Rl and R2 are methyl or morpholinomethyl, or and R together are alkylene and X is a -NR R group, in which each of R5 and R6 is alkyl or benzyl or R5 and R to-gether represents alkylene or oxaalkylene.
A known compound is also a compound of the for-mula II, wherein Ar represents phenyl, R represents me-~ ' thyl, X represents hydroxy and R3 is a direct bond.
The known compounds have up to now not been proposed as photosensitizers.
The compounds of the formulae I, II, III or IV, in so far as they are novel, also constitute an object of the invention. Accordinyly, the invention also relates to:
a) Compounds of the formula I, wherein n is 1, Ar repre-sentsC10-Cl4aryl~ C6 C14aryl which is substituted by one ore more members selected from the-group consisting oE CN, OH, -Ophenyl, -Salk, -SO2alk, -SO2phenyl, -COOalk, ~SO2N~2, -SO2NHalk~ -SO2N(alk)2, -NHalk or -NHCOalk or represents thienyl, pyridyl, indanyl or tetrahydronaphthyl, X is OH
or -Oalk, and Rl and R are as previously defined.
b) Compounds of the formula I, wherein n is 1, X is a _oR6 group and R6 represents Cl-C6alkyl which is substituted by OH or Oalk or represents allyl, cyclohexyl, benzyl, phenyl which is unsubstituted or substituted by Cl or alk, or to-gether with R represents C3-C4alkylene or -CH2-O-CH2-, and Ar, R and R are as previously defined.
~Z9~9 c) Compounds of the formula I, wherein n is 1, X is -OSiR (R )2 or together with R represents one of the groups -O-CH(R )-, -O-CH(R )-O-(CH2)1-2- or -OCl-C4alkylene, R is C2-C4alkyl or phenyl, and Ar, R , R and R are as previously defined.
d) Compounds of the formula I, wherein n is 1, Ar is phenyl, halogenphenyl or diphenylyl, X is a -NR R group, R is C2~C8alkyl, Cl-C8alkyl which is substituted by OH, Oalk, C2-C8acyloxy, COOalk or CN, or is C5-C6cycloalkyl or C -Cgphenylalkyl, R has one of the meanings assigned to R~ or is llyl or a -CH2CH2Rl group together with R
is C4-C6alkylene or C3-C4oxa- or azaalkylene, and R , R
and Rl are as previously defined.
e) Compounds of the formula I, wherein n is 1, Ar is phenyl which is substituted by CN, OH, alk, Oalk, -Ophenyl, -Salk, -SO2alk, -SO2phenyl, -COOalk, -SO2NH2, -SO2NHalk, -SO2N(alk)2, NHalk, -N(alk)2 or -NHCOalk or is naphthyl, thienyl, pyridyl, furyl, indanyl or tetrahydronaphthyl, X is a -~R R group and R , R , R and R are as previously defined.
f) Compounds of the formula I, wherein n is 2 and Ar, X, Rl and R are as pre~iously defined.
g) Compounds o~ the formula II, wherein R is a direct bond, X is one of the groups -NR R , -OR , OSiR (R )2' R6 is Cl-C12alkyl, C2-C4alkyl which is substituted by OH
or Oalk or is allyl, cyclohexyl, benzyl, phenyl which is unsubstituted or substituted by C1 or alk, and Ar, R , R4, R5, R7 and R are as previously defined.
h) Compounds of the formula II, wherein R represents Cl-C6 ~lkylene, C2-C6oxaalkylene, C2-C6thia-, ~-oxothia- or S-di-oxothiaalkylene, phenylene, diphenylene or a -phenylene-T-phenylene group, and Ar, R , X and T are as previously defined.
i) Compounds of the formula III, wherein Ar, R , R and X' are as previously defined.
k) Compounds of the formula IV, wherein R , X, Y and Z are as previously defined.
These novel compounds can be prepar~d by methods analogous to those for obtaining the known compounds, whereby different methods are possible.
Accordingly, the compounds of the formula I can be prepared from aromatic-aliphatic ketones by the follow-ing reaction steps:
Ar ~ CO-CHRlR2] ~ A ~ CO CBrR1R2] CH30Na _~
n ~ n As HX it is possible to use amines [C.L. Stevens, Ch. Huny Chany, J. Org. Chem. 27 (1962), 4392] or water or carboxylic acids [C.L. Stevens, E. Farkas, J. Am. Chem.
Soc. 74 (1952), 618 and C.L. Stevens, S.J. Dykstra, J. Am.
Chem. Soc. 75 (1953), 5976].
In many cases the direct reaction of the a-bromo~
ketones to give compounds of the formula I
O R
~r E co CBrR R ~ R
g ~ ~
is also possible, for example with amines, alkal!ihydroxides or alkali phenoxides. Instead o~ bromine compounds it is also possible to use the corresponding chlorine compounds.
-The resulting hydroxyketones of the formula I(X=OH) can be etherified or O-silylated by the conventional methods.
Compounds of the formula III are obtained by using a difunctional compound of the formula H-X'-H instead of the monofunctional compound HX in the above reactions.
The compounds of the formula II can be prepared analogously to those of the formula I by using diketones of the generaI formula Rl 2 R2 Ar- CO - CH~ R - CH -CO - Ar i The compounds of the formula IV are obtained in analogous manner starting rom cyclic ketones of the formu-la Rl ~7,~,Z,~b Compounds of the formula I, wherein R is a sub-stituted alkyl group, can be obtained from the compounds of the formula Ar~CO-CH(R2)-X]n by reaction with aldehydes (Rl = hydroxyalkyl) or with a vinyl compound which is cap-able of addition, for example with acrylated or acrylonit-rile, In the same way, a -CH~CH2-R13 group can be intro-duced as R , starting from a compound Ar~CO-CH(R ~~X]n. If both R and R are substituted alkyl, then both substi-~s~'j g tuents can be introduced jointly by reaction of a compoundAr~C0-CH2-X]n with at least 2 moles of an aldehyde or a vinyl compound. The corresponding alkoxyalkyl and acyloxy-alkyl groups can be obtained from the hydroxyalk~l groups Rl and/or R by etherification or esterification. Compounds of the formulae II, III and IV containing substituted alkyl groups as R or R can be obtained in analogous manner.
Compounds in which X together with R is a -0-CH
(R9) group are a-oxydoketones and can be obtained by epoxi--- dation of the corresponding a-vinyl ketones. Reaction of the oxydoketones with secondary amines affords compounds in which either X is 0~ and Rl is an aminoalkyl group, or in which X is N~4R and Rl is a hydroxyalkyl group.
Addition of bromine to the a-vinyl ketones yields a,~-dibromoketones of the formula Ar~C0-CBr(R ) CBralk~n.
Reaction of the dibromoketones with one mole of a primary amine yields the corresponding ~-aziridinoketones [J. Chem. Soc. 65 (1943), 312~, and reaction with 2 moles o~ a secondary amine yields compounds of the formula I, wherein ~ is -NR R and R is an aminoalkyl radical ~J. Am.
Chem. Soa. 74 (1952), 1886].
Aminoalkyl groups Rl and/or R can also be intro-duced by the Mannich reaction, wherein ketones of the for-m~la Ar~C0-CHR ~X]n or Ar~C0-CH2-X]n are reacted with 1 or 2 moles of formaldehyde and a secondary amine.
Whereas all these methods of synthesis start from an aromatic-aliphatic ketone into which a substituent X is introduced in a different manner, it is also possible in specific cases to introduce the substituent X during the ketone synthesis by the Friedel-Crafts reaction in accor-' ~ 20 -dance with the reaction scheme:
Rl R
I AlC13 X-C-COC1 + ArH ~ Ar-CO-C-X
rrhis presupposes that the substituent X is not attacked under the conditions o the Friedel-Crafts reac-tion. In this way it is possible for example by using heterocyclic carboxylic acid chlorides to prepare compounds of the formula I, in which X and Rl together with the car-bon atom to which they are attached form a heteroring.
.
According to the invention, the compounds o~ the ~ormulae I, II, III and IV can be used as sensitizers for the photopolymerisation of unsaturated compounds or systems which contain such compounds.
Such compounds are for example unsaturated mono-mers, such as esters of acrylic or methacrylic acid, for example methacrylate, ethylacrylate, n- or tert-butyl~
acrylate, isooctylacrylate or hydro~yethylacrylate, methyl-or ethylmethacrylate, ethylene diacrylate, neopentyl di-acrylate, trimethylolpropane trisacrylate, pentaerythritol tetraacrylate or pentaerythritol trisacrylate; acrylo-nitrile, methacrylonitrile, acrylamide, methacrylamide, N-substituted acrylamides and methacrylamides; vinyl esters, such as vinyl acetate, vinyl propionate, vinyl acrylate or vinyl succinate; other vinyl compounds, such as vinyl ethers, styrene/ alkyl styrenes, halostyrenes, divinyl benzene, vinyl naphthalene, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride; allyl compounds, such as diallyl phthalate, diallyl maleate, triallyl iso-cyanurate, triallyl phosphate or ethylene glycol diallyl ether and the mixtures of such unsaturated monomers.
~L~4Z~9 , Photopolymerisable compounds are in addition un~
saturated oligomers or polymers and the mixtures thereof with unsaturated monomers. These include thermoplastic resins which contain unsaturated groups, such as fumaric acid ester groups, allyl groups or acrylate or methacrylate groups. These unsaturated groups are usually bound through functional groups to the main chain of these linear poly-mers~ Mixtures of oligomers with simply and poly-unsatu-rated monomers are ~ery important. Examples of such oligomers are unsaturated polyesters, unsaturated acrylic resins and isocyanate or epoxide modified acrylate oligo-mers as well as polyether acrylate oligomers. Examples of poly-unsaturated compounds are in particular the acrylates of diols and polyols, for example hexamethylene diacrylate or pentaerythritol tetracrylate. Acrylates are also preferred as simply unsaturated monomers, for example butyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethyl-hexyl acrylate or 2-hydroxypropyl acrylateO By choosing rom the diferent representatives of the three component$, the opportunity is afforded to vary the consistency of the unpolymerised mixture as well as the plasticity of the polymerised resin.
In addition to these three-component mixtures, two-component mixtures especially are of great importance among the polyester resins. These usually consist of an un-saturated po]yester and a vinyl compoundO The unsaturated polyesters are oligomer esterification products of at least one unsaturated dicarboxylic acid, for example maleic, fumaric or citraconic acid, and usually of at least one saturated dicarboxylic acid, for example phthalic acid, succinic acid, sebacic acid or isophthalic acid, with glycols, for example ethylene glycol, propanediol~l,2, di-or triethylene glycol or tetramethylene glycol, whilst monocarboxylic acids and monoalcohols are generally also 2~
used concurrently for the modification. These unsaturated polyesters are normally dissolved in a vinyl or allyl com-pound, styrene being preferably used for this purpose.
Photopolymerisable systems which are used for the different purposes usually contain, in addition to the photopolymerisable compounds and the photosensitizeri a number of other ingredients. It is therefore often customary to add heat inhibitors in order to prevent a premature polymerisation, especially during the preparation of the systems by mixing the components. Hydroquinone, hydroquinone derivatives, p-methoxyphenyl, ~-naphthylamine or ~-naphthols are used for example for this purpose.
Furthermore, small amounts o UV absorbers can be added~
for example those o~ the benztriazole or benzophenone type.
To increase the storage life in the dark, it is possible to add copper compounds, suc~ as copper naph-thenate, copper stearate or copper octoate, phosphorus com-pounds, such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phos-phate, quaternary ammonium compounds, such as tetramekhyl-ammonium chloride or, trimethylbenzylammonium chloride, or hydroxylamine derivatives, for example N-diethylhydrox-ylamine. In addition, the photopolymerisable systems can contain chain transfer agents, for example N-methyl-di-ethanolamine, triethanolamine or cyclohexene.
In order to exclude the inhibiting action of atmospheric oxygen, paraffin or similar wax-like substan-ces are ~requPntly added to the photohardening systems.
On account of their poor solubility in the polymer, these substances float at the beginning of the polymerisation and form a transparent surface layer which prevents the entry of air.
Z~9L9 The atmospheric oxygen can also be deactivated h~ introduc-ing autoxidisable groups, for example allyl groups, into the resin to be hardened.
-Depending on the end-use, photopolymerisable systems also contain fillers, such as silicic acid, talc or gypsum, pigments, dyes, fibres, thixotropic agents or levelling agents.
Combinations with known photosensitizers, such as benzoin ethers, dia~koxy acetophenones or benzyl ketals, can also be used. Combinations of the photosensitizers of the invention with amines and/or aromatic ketones can be used especially for the photopolymerisation of thin layers and printing inks. Examples of amines are triethylamine, N-methyldiethanolamine, N-dimethylethanolamine or p-di-methylaminobenzoate. Examples of ketones are benzophenone, substituted benzophenone derivatives, Michler's ketone, anthraquinone and antraquinone derivatives, as well as thioxanthone and the derivatives thereof.
Photohardening is of great importance for print-ing inks, since the dryin~ time of the binder is a decisive factor in the production speed of printing pro-ducts and should be in the order of fractions of seconds.
The sensitizers of the invention are also very suitable for photohardening systems for the manufacture of printing plates. l~lixtures of soluble linear polyamides with photo-polymerisable monomers, for example acrylamides, and a photosensitizer, are usually employed for this purpose.
Films or plates prepared from these systems are exposed via the negative (or positive) of the original and the un-hardened portions are subsequently eluted with a solvent.
%~q~9 - 2~ -A further field of use of UV hardening is metal coating, for example in the varnish coating of metal sheeting for tubes, cans or bottle caps, as well as the UV
hardening of pIastic coatings, for example of floor or wall coverings based on PVC.
Exemplary of the UV hardening of paper coatings is the colourless varnish coating of labels, gramophone record sleeves or book jackets.
According to the invention, the compounds of the formulae I, II, III and IV can also be used as sensitizers for the photochemical crosslinking of polyolefins, for example polypropylene, polybutene, polyisobutylene and also copolymers, for example ethylene/propylene copolymers, but preferably polyethylene of low, medium or high density.
The photosensitizers are advantageously used for the above fields of use in amounts of 0.1 to 20 % by weight, preferably about 0.5 to 5 % by weight~ based on the photopol~merisable or crosslinkahle system. The term "system" is to be understood as meaning the mlxture of the photopolymerisab~e or crosslinkable compound, the photosensitizer and the other fillers and additives, as it is used in the respective application.
The addition of the photosensitizers to the photopolymerisable systems is accomplished in general by simple stirring, since most of these systems are 1uid or readily soluble. Usually the sensitizers of the inv~ntion dissolve in the system, thereby ensuring their uniform distribution and the transparency of the polymers.
The polymerisation is carried out by the known methods of polymerisation by irradiation with light which ~!
is rich in shortwave radiation. Suitable light sources are for e~ample mercury medium pressure, high pressure and low pressure lamps, as well as superactinic fluorescent tubes, the emission peaks of which are in the range between 250 and 400 nm.
The following Examples describe the manufacture and use of compounds of the formula I in more detail. Parts and percentages are by weight.
~anufacture and properties of the compounds used in Exam le~ 1 to 6 P ~ ._ The compounds listed in Table 1 where obtained by one or more of the methods A to L.
Method A Chlorination of aromatic-aliphatic ketones Ar~CO-CR R H] n + n C12 ~ Ar~Co-CR R Cl]n ~ n HC1 The ketone is dissolved in an inert solvent, preferably in tetrachloromethane, and the calculated amount of chlorine is introduced into the solution at 40-80C. Nitrogen is then introduced to remove dissolved HCl. Finally, the sol-vent is distilled off. Purification of the chloroketone is usually not necessary and the product can subsequently be reacted by method ~, F or H.
Method B Bromination of aromatic--aliphatic ke-tones Ae~C0-CR R H]n ~ n Br2 ~ Ar~C0-CR R Br]n + n HBr The calculated amount of bromine is added dropwise at room temperature to a solution of the ketone, for example in CCl~. Working up and further processing are effected as in Method A.
Method C Chlorination with sulfury.l chloride Ar~C0-CR R H] n S02 C12 Ar~C0-CR R -Cl~n + n S02 + n HCl The sulfuryl chloride is added dropwise at 40C to a solu-tion of the ketone in CC14. Working up and further process-ing as in Method A.
;, Method D Preparation of the epoxide intermediate Ar~CO-CR R Hal] ~ n NaOCH3 ---D Ar~CI - CR R ]n ~ n NaHal Hal = Cl or Br The haloketone is dissolved in methanol and a solution of the stoi~hiometric amount of sodium methoxide in methanol is added dropwise at reflux temperature. The methanol is then distilled off and the residue is poured into ice-water and extracted with ether. The ethereal solution is washed with water, dried over Na2S04, dried and concentrated. The residue is purified by recrystallisation or vacuum distil~
lation. The epoxide can subsequently be reacted by Method E or G.
Method E Hydrolysis of the epoxide ~ 1 2] H+ 1 2 The epoxide is covered with 2 to 5 times its weight of water and the mixture is refluxed for 1 to 2 hours with the addition of a catalytic amount of mineral acid. After cooling, the reaction mixture is extracted with ether. The ethereal solution is washed with water, dried over Na2SO~, and concentrated. The residue (crude hydroxyketone) is purified by distillation or crystallisation or column chromatography. The properties of the pure a-hydroxyketones are indicated in Table 1.
Method F a~Hydroxyketones from ~-haloketones Ar~CO-CR R Hal]n t n NaOH ~ Ar~CO-CR R OH]n ~ n NaHal The c~-haloketone is refluxed in dilute or concentrated sodium hydroxide solution 120 % excess of NaOH). When the hydrolysis is complete Icheck by chromatography), the crude hydroxyketone is isolated and purified as described in Method E. The pure hydroxyketones are listed in Table 1.
Method G a-Aminoketones from the epoxides Ar~ ~ CR R ] +n R R NH Ar~CO-CR R -NR R ] + n CH30H
The epoxide is treated with the stoichiometric amount of the amine, either without a solvent or with the addition of a small amount of toluene or xylene, and reacted for about lO to 20 hours at 100-200C. When using low boiling amines, for example dimethylamine or diethylamine, the ~
reaction is carried out in an autoclave. The reaction mix-ture is diluted with benzene and extracted with dilute hydrochloric acid. The aqueous acid solution is made alkaline with NaOH and extracted with ether. The ethereal solution is washed with water, dried oVer Na2SO~ and con-centrated. The crude product is purifi.ed by distillation or crystallisation. The a-amineketones are listed in Table 1.
M hod H a-~ninoketones from the a-haloketones Ar~CO-CR R Hal~n ~ 2n R R NH ~ Ar~CO-CRlR -NR4R ]
+ n R R NH2Hal The a-haloketone, undiluted or diluted with toluene, is mixed with 2 molar equivalents of the amine and the mix-ture is heated for 10 to 20 hours to 100-200C. When using low boilingamines, forexample dimethylamine or diethylamine, the reaction is carried out in an autoclave. Isolation and 2~4~
purification are effected as in Me-thod G.
Method I Introduction of a carbalkoxyethyl group C~2C~2COOAlX
ArtCO-CHRl-X]n + n CH2 = CH-COOAlk -~Ar~CO-CP~l-X . ] n The ketone is dissolved in dimethyl sulfoxide. To the solu-tion are then added 1.1 molar ecuivalents of NaOH in the form of 4N sodium hydroxide solution and, with cooling, 1.1 molar equivalents of acrylate are added dropwise at room temperature. The reaction mixture is diluted with ice-water and extracted with toluene. The toluene solution is washed neutral with water, dried over Na2SO~ and concentra-ted. The crude product is purified by column chromatography or crystallisation.
Method K Etherification of hydroxyketones Ar~CO-CR ~ -OH] ~ n R Hal ~ n NaOH Ar~CO-CR R -OR ]
+ n NaHal The a-hydroxyketone i5 dissolved in about 4 times its weight of dimethyl sulfoxide and, while cooling to 10-20C and with stirring, 1 molar equivalent o~ the alkyl halide R6Hal and 1 molar equivalent of concentrated sodium hydroxide solution are added dropwise simultaneously from t~o drip funnels. The reaction mixture is then stirred for 3 hours at room temperature. Precipitated sodium halide is then removed by filtration, the filtrate is washed with water, dried over Na2S04 and concentrated. The crude product -is purified by column chromatography~ crystallisation or vacuum distillation. Examples of eligible halogen compounds are melhyl iodide, isopropyl bromide, all~ll bromide, cyclo-hexyl bromide, benzyl chloride or ethyl chloroacetate.
Instead of using an alkyl halide, it is also possible to use a dialkyl sulfate or alkylaryl sulfonate as etherifying reagent.
Method L Cyclisation of X and R
~r-C0-C'~Hal~R ~ CH20 --~ Ar-C0-CR Hal-CH20~ MaOC~3 Ar-C0- ~ H~ + Na;~al -~ C~30~1 Paraformaldehyde is dissolved in 20 times its weight of methanol. To the solution is then added l molar equivalent of sodium methoxide tdissolved in a small amount of methanol).
~hile cooling to 0-5C, a concentrated solution of the a-haloketone is added dropwise. The reaction mixture is sub-sequently stirred for l hour at 5-10C and for l hour at room temperature. The reaction mixture is diluted with ether to 2 to 3 times its volume and poured into ice-water. The aqueous mixture is extracted 3 times with ether and the ethereal extracts are washed with water, dried over Na2S04 and concentrated. The crude product is puriEied by distil-lation or colurnn chromatography.
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Example 1 A resin mixture consisting of 80 parts of Plex* 6616 (acrylate resin, available from Rohm, Darmstadt), 20 parts of trimPthylolpropane-trisacrylate and 2 parts of photosensitiæer is applied with a film drawing device to glass plates in a thickness of 40 ~. These films are exposed to air for about 20 seconds and then irradiated with a mercury medium pressure lamp (Hanovia device, ~del 45080). Irl the course of the irradiation, the samples are passed underneath the lamp on a conveyer belt at a speed such that -the effective exposure time is 0.16 second per run.
Table 2 indicates the number of runs (R) which were ne oe ssary in order to obtain non-tacky films. In additian, the hardness of the filn was determined with a pendulum devioe by the method of Konig. The final column indicates the storage stability of the resin-photosensitizer mL~ture in the dark at 60C~
*Trademark - 41 -.~
2~9 Table 2 _ _ . _ Pendulum hardness accord~ Storage Photosensitizer Runs ing ~o Konig after stability number of runs (R) in days _ ~ _ .
1 4 78(4R) 94(6R) 98(8R) >30 2 4 101(4R) 114(4R) 116(8R) >30 3 4 116(4R) 119(8R) 131(8R) ~30 12 3 95(3R) 101(4R) 103(5R) 24 3 73(5R) 26 3 95(3R) 102~4R) 107(5R) <30 37 4 47(3R) 72(4R) 88(5R) <30 __ _ a-hydroxypro- 3 68(3R) 75(4R) 87~5R) piophenone (comparison) a-methylbenzoin. 5 49(3R) 69(4R) 91(5R) (comparison) benzoin-tert- 5 93(5R) 106(7R) 113(9R) <30 butylether (cc~parison) 2-phenyl-di- 6 112(6R) 121(8R) 130(lOR) ~30 mp~thoxyacetor phenone (comparison) p-met~yl-~,a-di- 8 92(8R)lOO(lOR) 109(12R) <5 morpholinoace-tophenone (oomparison) a,a-dimorpholino- 17 84(17R)98(19R) ~1 aoetophenone (cJ~mparison) . _ ''.1 ~4;2~
Example 2 Resin mixtures consisting of 60 parts of Uvimer* DV-530 (urethane acrylate, available frQm PolychrGme)~ 37 parts of hexanedioldiacrylate and 3 parts of photosensitizer were applied in a film thickness of 30 ~m to glass plates and irradiated as described in Example 1. The follcwing results were ob-tained.
Table 3 _ _ _ . _ _ . _ No. of runs Pendulum hardness Photo ænsitizer necessary until wipe- according to Konig as proof a function of R
_ . . .
1 3 129(3R) 157(7R) 2 3 . 144(3R) 163(7R) diethoxyaoe to- 10 156(lOR) phenone (comparison) benzoin tert- 12 136(12R) butyl ether (ccmparison) 2-phenyldi- 8 155(8R) methoxyaceto-phenone (ocmparison) _ __ _ *Trademark 43 Example 3 2% of photosensitizer was dissolved in an unsaturated polyester resin (Crystic* PKE 306, available from Maeder, Killwangen, Switzerland). These resin mixtures were applied in a film thickness of 60 ~m to glass plates. The films were irradiated as d~scribed in Example 1. The number of runs through the expo-sure device until the films were ~ipe-proof as well as the pendulum hardness as a function of R are reported in Table 4.
Table 4 . _ _ No. of runs PendNlum hardness Photosensitizerneoessary until wipe-according to Konig as proof a function of R
_ _ 1 13 21(13R) 34(15R? 62(17R) 2 8 20(8R) 31(lOR) 89(12R) 28(lOR) 71(12R) 109(12R) *Trademark - 44 -Example 4 A resin mixture consistiny of 90 parts of Laromer* LR 8496 (acryla~e resin available from BASF, West Germany), 10 parts of hexanediol diacrylate, 0.5 part of ~yK 300 (levelling assistant available fr~ ByK-Mallinckrodt, West German~v) and 3 parts of photosensitizer for hardening in the air or 0.5 part of photos~nsitizer for hardening under nitrogen, is applied electrcmotively to cardboard boxes with a 15 ~ helix. After brief exposure to air, hardening is effected with a UV devi oe (model PPG-QC-pro oe sser~ with a W lamp of 80 watts/om.
m~ nE~uumlm transportation speed at which non-tacky films were obtained in air or under nitrogen is reported in Table 5 in m~min.
Table S
___ .
Photosensitizer Transportation speed (m~min) air nitrogen __ ., __ 12 3,3 80 _ 20 _ 90 *Trademark - 45 -Example 5 A resin mIxture consisting of 70 part5 of Ebercyl* 593 (polyester acrylate available from UGB, Belgium), 30 parts of trimethylolpropane trisacry-late, 0.5 part of ByK 300 (levell mg assistant available from ByK-Mallinckrodt, West Germany) and 3 parts of photosensitizer, is applied to glass plates in a layer of 30-40 ~. After brief exposure to air, hardening is effected with a UV
laboratory device (model PPG/QC-processer) with a W lamp of 80 watts/cm. After the UV har~ening, the plates are stored for 1/2 hour under normal climatic con-ditions and then the hardness of the layers is determined using the pendulum de-vioe of gonig. The hardness values as a function of the transportation speedunder the lamp are reported in Table 6.
Table 6 Photosensitizer Pendulum hardness in sec.
10 m~min. 25 m~min.
.
17 160 1~4 21 155 1~3 27 16~ 154 39 162 14~
_ _. .
*Trademark - 46 -
. O O O S
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~ ~ 1~ 1~ ~
_ __ . _ .~ .
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~ ,_ ~ O ~ . ~ o ~ ~ o r~
:~ ~ :}: ~ :~ ~ ~
t~----t~ t~-----C_) C~--~ C~----C~
~ 0=~ ) 0=0 ' O'=t ~ -0=~
1~ o// \~
hl 11 l ll l ll l ll _ G D ~ ~ ~
~~ / \~ / '~ / \\ /
O v i ~ 1 cn O
C~
'_ _ __ _ _ _ _ .
_ . ~
O h ~ ~ .
~T V
~ ' a r~ ~
~ V : -9~
Example 1 A resin mixture consisting of 80 parts of Plex* 6616 (acrylate resin, available from Rohm, Darmstadt), 20 parts of trimPthylolpropane-trisacrylate and 2 parts of photosensitiæer is applied with a film drawing device to glass plates in a thickness of 40 ~. These films are exposed to air for about 20 seconds and then irradiated with a mercury medium pressure lamp (Hanovia device, ~del 45080). Irl the course of the irradiation, the samples are passed underneath the lamp on a conveyer belt at a speed such that -the effective exposure time is 0.16 second per run.
Table 2 indicates the number of runs (R) which were ne oe ssary in order to obtain non-tacky films. In additian, the hardness of the filn was determined with a pendulum devioe by the method of Konig. The final column indicates the storage stability of the resin-photosensitizer mL~ture in the dark at 60C~
*Trademark - 41 -.~
2~9 Table 2 _ _ . _ Pendulum hardness accord~ Storage Photosensitizer Runs ing ~o Konig after stability number of runs (R) in days _ ~ _ .
1 4 78(4R) 94(6R) 98(8R) >30 2 4 101(4R) 114(4R) 116(8R) >30 3 4 116(4R) 119(8R) 131(8R) ~30 12 3 95(3R) 101(4R) 103(5R) 24 3 73(5R) 26 3 95(3R) 102~4R) 107(5R) <30 37 4 47(3R) 72(4R) 88(5R) <30 __ _ a-hydroxypro- 3 68(3R) 75(4R) 87~5R) piophenone (comparison) a-methylbenzoin. 5 49(3R) 69(4R) 91(5R) (comparison) benzoin-tert- 5 93(5R) 106(7R) 113(9R) <30 butylether (cc~parison) 2-phenyl-di- 6 112(6R) 121(8R) 130(lOR) ~30 mp~thoxyacetor phenone (comparison) p-met~yl-~,a-di- 8 92(8R)lOO(lOR) 109(12R) <5 morpholinoace-tophenone (oomparison) a,a-dimorpholino- 17 84(17R)98(19R) ~1 aoetophenone (cJ~mparison) . _ ''.1 ~4;2~
Example 2 Resin mixtures consisting of 60 parts of Uvimer* DV-530 (urethane acrylate, available frQm PolychrGme)~ 37 parts of hexanedioldiacrylate and 3 parts of photosensitizer were applied in a film thickness of 30 ~m to glass plates and irradiated as described in Example 1. The follcwing results were ob-tained.
Table 3 _ _ _ . _ _ . _ No. of runs Pendulum hardness Photo ænsitizer necessary until wipe- according to Konig as proof a function of R
_ . . .
1 3 129(3R) 157(7R) 2 3 . 144(3R) 163(7R) diethoxyaoe to- 10 156(lOR) phenone (comparison) benzoin tert- 12 136(12R) butyl ether (ccmparison) 2-phenyldi- 8 155(8R) methoxyaceto-phenone (ocmparison) _ __ _ *Trademark 43 Example 3 2% of photosensitizer was dissolved in an unsaturated polyester resin (Crystic* PKE 306, available from Maeder, Killwangen, Switzerland). These resin mixtures were applied in a film thickness of 60 ~m to glass plates. The films were irradiated as d~scribed in Example 1. The number of runs through the expo-sure device until the films were ~ipe-proof as well as the pendulum hardness as a function of R are reported in Table 4.
Table 4 . _ _ No. of runs PendNlum hardness Photosensitizerneoessary until wipe-according to Konig as proof a function of R
_ _ 1 13 21(13R) 34(15R? 62(17R) 2 8 20(8R) 31(lOR) 89(12R) 28(lOR) 71(12R) 109(12R) *Trademark - 44 -Example 4 A resin mixture consistiny of 90 parts of Laromer* LR 8496 (acryla~e resin available from BASF, West Germany), 10 parts of hexanediol diacrylate, 0.5 part of ~yK 300 (levelling assistant available fr~ ByK-Mallinckrodt, West German~v) and 3 parts of photosensitizer for hardening in the air or 0.5 part of photos~nsitizer for hardening under nitrogen, is applied electrcmotively to cardboard boxes with a 15 ~ helix. After brief exposure to air, hardening is effected with a UV devi oe (model PPG-QC-pro oe sser~ with a W lamp of 80 watts/om.
m~ nE~uumlm transportation speed at which non-tacky films were obtained in air or under nitrogen is reported in Table 5 in m~min.
Table S
___ .
Photosensitizer Transportation speed (m~min) air nitrogen __ ., __ 12 3,3 80 _ 20 _ 90 *Trademark - 45 -Example 5 A resin mIxture consisting of 70 part5 of Ebercyl* 593 (polyester acrylate available from UGB, Belgium), 30 parts of trimethylolpropane trisacry-late, 0.5 part of ByK 300 (levell mg assistant available from ByK-Mallinckrodt, West Germany) and 3 parts of photosensitizer, is applied to glass plates in a layer of 30-40 ~. After brief exposure to air, hardening is effected with a UV
laboratory device (model PPG/QC-processer) with a W lamp of 80 watts/cm. After the UV har~ening, the plates are stored for 1/2 hour under normal climatic con-ditions and then the hardness of the layers is determined using the pendulum de-vioe of gonig. The hardness values as a function of the transportation speedunder the lamp are reported in Table 6.
Table 6 Photosensitizer Pendulum hardness in sec.
10 m~min. 25 m~min.
.
17 160 1~4 21 155 1~3 27 16~ 154 39 162 14~
_ _. .
*Trademark - 46 -
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula:
(I) wherein Ar represents aryl of 6 to 14 carbon atoms, phenyl substituted by Cl, Br, CN, OH, alk, -Oalk, -Salk, -SO2alk, -SO2phenyl, -COOalk, -SO2NH2, -SO2NHalk, -SO2N(alk)2, -Nalk, -N(alk)2, phenoxy or -NHCOalk, wherein alk represents a C1 to C4 lower alkyl radical, or Ar represents thienyl, pyridyl or furyl;
R1 represents C1-C8-alkyl optionally substituted by C2-C8 acyloxy, -COO-(C1-C4)alkyl or -CN, or repre-sents C5-C6 cycloalkyl or C7-C9 phenylalkyl;
R2 has one of the meanings assigned to R1 or represents allyl, methallyl, 2-carbamoylethyl, 2-(N-C1-C4-alkyl-carbamoyl)ethyl, 2-(N,N-di-C1-C4-alkylcarbamoyl)-ethyl, 2-(2-pyridyl)ethyl, 2-(2-oxo-1-pyrrolidinyl)-ethyl or 2-(di-O-C1-C4-alkylphosphono)ethyl; or R1 and R2 together represent alkylene of 4 to 6 carbon atoms or oxaalkylene or azaalkylene of 3 to 4 carbon atoms; or R1 and R2 are both hydroxymethyl; and R3 represents C1-C6alkyl which is substituted by OH
or Oalk, or represents allyl, cyclohexyl, benzyl phenyl which is optionally substituted by Cl or alk, or R3 together with R2 represents C3-C4alkylene or -CH2-O-CH2.
(I) wherein Ar represents aryl of 6 to 14 carbon atoms, phenyl substituted by Cl, Br, CN, OH, alk, -Oalk, -Salk, -SO2alk, -SO2phenyl, -COOalk, -SO2NH2, -SO2NHalk, -SO2N(alk)2, -Nalk, -N(alk)2, phenoxy or -NHCOalk, wherein alk represents a C1 to C4 lower alkyl radical, or Ar represents thienyl, pyridyl or furyl;
R1 represents C1-C8-alkyl optionally substituted by C2-C8 acyloxy, -COO-(C1-C4)alkyl or -CN, or repre-sents C5-C6 cycloalkyl or C7-C9 phenylalkyl;
R2 has one of the meanings assigned to R1 or represents allyl, methallyl, 2-carbamoylethyl, 2-(N-C1-C4-alkyl-carbamoyl)ethyl, 2-(N,N-di-C1-C4-alkylcarbamoyl)-ethyl, 2-(2-pyridyl)ethyl, 2-(2-oxo-1-pyrrolidinyl)-ethyl or 2-(di-O-C1-C4-alkylphosphono)ethyl; or R1 and R2 together represent alkylene of 4 to 6 carbon atoms or oxaalkylene or azaalkylene of 3 to 4 carbon atoms; or R1 and R2 are both hydroxymethyl; and R3 represents C1-C6alkyl which is substituted by OH
or Oalk, or represents allyl, cyclohexyl, benzyl phenyl which is optionally substituted by Cl or alk, or R3 together with R2 represents C3-C4alkylene or -CH2-O-CH2.
2. 2-Allyloxy-2-methyl-propiophenone.
3. 2-Benzyloxy-2-methyl-propiophenone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000396116A CA1142949A (en) | 1977-12-22 | 1982-02-11 | Sensitizers for photopolymerisation |
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH15884/77 | 1977-12-22 | ||
| CH1588477 | 1977-12-22 | ||
| CH2518/78 | 1978-03-08 | ||
| CH251878 | 1978-03-08 | ||
| CH972378 | 1978-09-18 | ||
| CH9723/78-1 | 1978-09-18 | ||
| CA000318328A CA1234242A (en) | 1977-12-22 | 1978-12-20 | Sensitizers for photopolymerisation |
| CA000396116A CA1142949A (en) | 1977-12-22 | 1982-02-11 | Sensitizers for photopolymerisation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142949A true CA1142949A (en) | 1983-03-15 |
Family
ID=27508131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000396116A Expired CA1142949A (en) | 1977-12-22 | 1982-02-11 | Sensitizers for photopolymerisation |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1142949A (en) |
-
1982
- 1982-02-11 CA CA000396116A patent/CA1142949A/en not_active Expired
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