Claims
- 1. In a method for the photopolymerisation of unsaturated compounds or for the photochemical crosslinking of polyolefins employing a sensitizer, the improvement according to which the sensitizer is a compound of the formula ##STR58## wherein Ar is a member selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracyl, diphenylyl, chlorophenyl, bromophenyl, dichlorophenyl, mesityl, isopropylphenyl, phenoxyphenyl, cyanophenyl, p-nonylphenyl, hydroxyphenyl, tolyl, tert-butylphenyl, xylyl, isopropylchlorophenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, chlorotolyl, bromoxylyl, methylthiophenyl, phenylthiophenyl, butylsulfophenyl, phenylsulfophenyl, ethoxycarbonylphenyl, tert-butoxycarbonylphenyl, methylaminosulfophenyl, dipropylaminosulfophenyl, dimethylaminophenyl, benzoylaminophenyl and acetylaminophenyl,
- X represents --OR.sup.6,
- X' represents ##STR59## R.sup.1 represents (a) C.sub.1 -C.sub.8 alkyl, (b) C.sub.1 -C.sub.8 alkyl substituted by --OH, Oalk, C.sub.2 -C.sub.8 acyloxy, --NR.sup.4 R.sup.5, --COOalk or --CN, (c) C.sub.3 -C.sub.4 alkenyl, (d) C.sub.5 -C.sub.6 cycloalkyl or (e) C.sub.7 -C.sub.9 phenylalkyl,
- R.sup.2 has one of the meanings assigned to R.sup.1 or represents a --CH.sub.2 CH.sub.2 R.sup.13 group, or together with R.sup.1 represents C.sub.2 -C.sub.8 alkylene or C.sub.3 -C.sub.9 oxaalkylene or C.sub.3 -C.sub.9 azaalkylene,
- R.sup.3 represents a direct bond, C.sub.1 -C.sub.6 alkylene, C.sub.2 -C.sub.6 oxaalkylene, C.sub.2 -C.sub.6 thiaalkylene, S-oxathiaalkylene or S-dioxathiaalkylene, phenylene, diphenylene or a -phenylene-T-phenylene group, or together with both substituents R.sup.2 and both carbon atoms to which these substituents are attached, forms a cyclopentane, cyclohexene, endomethylenecyclohexane or cyclohexane ring,
- T represents --O--, --S--, --SO.sub.2 --, --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --, --CH.sub.2 OCH.sub.2 -- or --CH.dbd.CH--,
- R.sup.4 represents (a) C.sub.1 -C.sub.12 alkyl, (b) C.sub.2 -C.sub.4 alkyl substituted by --OH, Oalk or --CN, (c) C.sub.3 -C.sub.5 alkenyl, (d) cyclohexyl, (e) C.sub.7 -C.sub.9 phenylalkyl, (f) phenyl or (g) phenyl which is substituted by Cl, alk, OH, Oalk or --COOalk,
- R.sup.5 represents (a) C.sub.1 -C.sub.12 alkyl, (b) C.sub.2 -C.sub.4 alkyl which is substituted by --OH, Oalk or --CN, (c) C.sub.3 -C.sub.5 alkenyl, (d) cyclohexyl or (e) C.sub.7 -C.sub.9 phenylalkyl, or R.sup.4 and R.sup.5 together represent C.sub.4 -C.sub.5 alkylene which can be interrupted by --O-- or ##STR60## R.sup.6 represents (a) hydrogen, (b) C.sub.1 -C.sub.12 alkyl, (c) C.sub.1 -C.sub.8 alkyl which is substituted by Cl, Br, OH, Oalk, Salk, C.sub.2 -C.sub.8 acyloxy, --COOalk, CONHalk, --CON(alk).sub.2 or CN, (d) C.sub.3 -C.sub.5 alkenyl, (e) cyclohexyl, (f) benzyl, (g) phenyl, (h) phenyl substituted by Cl or alk, or (i) 2-tetrahydropyranyl,
- R.sup.13 represents --CONH.sub.2, --CONHalk, --CON(alk).sub.2, --P(O)(Oalk).sub.2, 2-pyridyl or 2-oxo-1-pyrrolidinyl, and
- R.sup.14 represents C.sub.1 -C.sub.4 alkyl, --CH.sub.2 CH.sub.2 CN or --CH.sub.2 CH.sub.2 COOalk.
- 2. A method according to claim 1 wherein the sensitizer is a compound according to claim 1 wherein
- R.sup.1 represents (a) alkyl of 1 to 8 carbon atoms, (b) alkyl of 1 to 8 carbon atoms substituted by OH, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.8 acyloxy, --COO--(C.sub.1 -C.sub.4)alkyl or --CN, (c) cycloalkyl of 5 or 6 carbon atoms, or (d) phenylalkyl of 7 to 9 carbon atoms,
- R.sup.2 has one of the meanings assigned to R.sup.1 or R.sup.1 and R.sup.2 together represent alkylene of 4 to 6 carbon atoms, oxaalkylene of 3 to 4 carbon atoms or azaalkylene of 3 to 4 carbon atoms,
- R.sup.3 represents a direct bond, alkylene of 1 to 6 carbon atoms, oxaalkylene of 2 to 6 carbon atoms, phenylene, diphenylene, a phenylene-T-phenylene group, or both substituents R.sup.2 together with R.sup.3 and both carbon atoms to which these substituents are attached form a cyclopentane or cyclohexane ring,
- T represents --O--, --S--, --SO.sub.2 --, --CH.sub.2 -- or --CH.dbd.CH--,
- R.sup.4 represents (a) alkyl of 1 to 12 carbon atoms, (b) alkyl of 2 to 4 carbon atoms which is substituted by --OH or --Oalk, (c) allyl, (d) cyclohexyl, (e) phenylalkyl of 7 to 9 carbon atoms, (f) phenyl or (g) phenyl which is substituted by Cl, alk, OH, --Oalk or --COOalk,
- R.sup.5 represents (a) alkyl of 1 to 12 carbon atoms, (b) alkyl of 2 to 4 carbon atoms which is substituted by --OH or --Oalk, (c) allyl, (d) cyclohexyl or (e) phenylalkyl of 7 to 9 carbon atoms, or R.sup.4 and R.sup.5 together represent alkylene of 4 to 5 carbon atoms which can be interrupted by --O--, --NH-- or --Nalk--, and
- R.sup.6 represents (a) hydrogen, (b) alkyl of 1 to 12 carbon atoms, (c) alkyl of 2 to 4 carbon atoms which is substituted by --OH or --Oalk, (d) allyl, (e) cyclohexyl, (f) benzyl, (g) phenyl, or (h) phenyl which is substituted by Cl or alk.
- 3. A method according to claim 1 wherein the sensitizer is a compound according to claim 1 wherein
- R.sup.1 represents (a) alkyl of 1 to 8 carbon atoms, (b) alkyl of 1 to 8 carbon atoms substituted by OH, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.8 acyloxy, --COO--(C.sub.1 -C.sub.4)alkyl or --CN, (c) cycloalkyl of 5 to 6 carbon atoms, or (d) phenylalkyl of 7 to 9 carbon atoms,
- R.sup.2 has one of the meanings assigned to R.sup.1 or represents allyl, methallyl, 2-carbamoylethyl, 2-(N--C.sub.1 -C.sub.4 alkylcarbamoyl)ethyl, 2-(N,N-di-C.sub.1 -C.sub.4 alkylcarbamoyl)ethyl, 2-(2-pyridyl)ethyl, 2-(2-oxo-1-pyrrolidinyl)ethyl or 2-(di-O-C.sub.1 -C.sub.4 alkylphosphono)ethyl, or R.sup.1 and R.sup.2 together represent alkylene of 4 to 6 carbon atoms, oxaalkylene of 3 to 4 carbon atoms, or azaalkylene of 3 to 4 carbon atoms,
- R.sup.3 is a direct bond, alkylene of 1 to 6 carbon atoms, oxaalkylene of 2 to 6 carbon atoms, thialkylene of 2 to 6 carbon atoms, S-oxothiaalkylene of 2 to 6 carbon atoms, S,S-dioxathia-alkylene of 2 to 6 carbon atoms, phenylene, diphenylene or a -phenylene-T-phenylene group or cyclohexylene, or both substituents R.sup.2 together with R.sup.3 and both carbon atoms to which these substituents are attached form a cyclopentane or cyclohexane ring,
- T represents --O--, --S--, --SO.sub.2 --, --CH.sub.2 -- or --CH.dbd.CH--,
- R.sup.4 represents (a) alkyl of 1 to 12 carbon atoms, (b) alkyl of 2 to 4 carbon atoms which is substituted by --OH or --Oalk, (c) allyl, (d) cyclohexyl, (e) phenylalkyl of 7 to 9 carbon atoms, (f) phenyl or (g) phenyl which is substituted by Cl, alk, OH, --Oalk or --COOalk,
- R.sup.5 represents (a) alkyl of 1 to 12 carbon atoms, (b) alkyl of 2 to 4 carbon atoms which is substituted by --OH or --Oalk, (c) allyl, (d) cyclohexyl or (e) phenylalkyl of 7 to 9 carbon atoms, or R.sup.4 and R.sup.5 together represent alkylene of 4 to 5 carbon atoms which can be interrupted by --O--, --NH-- or --Nalk--, and
- R.sup.6 represents (a) hydrogen, (b) alkyl of 1 to 12 carbon atoms, (c) alkyl of 2 to 4 carbon atoms which is substituted by --OH or --Oalk, (d) allyl, (e) cyclohexyl, (f) phenylalkyl of 7 to 9 carbon atoms, (g) phenyl or (h) phenyl which is substituted by Cl or alk.
- 4. A method according to claim 1 wherein the sensitizer is a compound according to claim 1 wherein
- R.sup.1 represents (a) C.sub.1 -C.sub.8 alkyl, (b) C.sub.1 -C.sub.8 alkyl substituted by --OH, --Oalk, --COOalk or --CN, or (c) C.sub.7 -C.sub.9 phenylalkyl,
- R.sup.2 has one of the meanings assigned to R.sup.1 or is alkyl or a --CH.sub.2 CH.sub.2 R.sup.13 group, or together with R.sup.1 represents C.sub.4 -C.sub.6 alkylene or C.sub.3 -C.sub.4 oxaalkylene or C.sub.3 -C.sub.4 azaalkylene,
- R.sup.3 represents a direct bond or C.sub.1 -C.sub.6 alkylene or together with both substituents R.sup.2 and both carbon atoms to which these substituents are attached forms a cyclopentane or cyclohexane ring,
- R.sup.4 represents (a) C.sub.1 -C.sub.12 alkyl, (b) C.sub.2 -C.sub.4 alkyl which is substituted by OH or Oalk or (c) allyl,
- R.sup.5 represents (a) C.sub.1 -C.sub.12 alkyl, (b) C.sub.2 -C.sub.4 alkyl which is substituted by OH or Oalk or (c) allyl or R.sup.4 and R.sup.5 together represent C.sub.4 -C.sub.5 alkylene which can be interrupted by --O-- or --Nalk--,
- R.sup.6 represents (a) hydrogen, (b) C.sub.1 -C.sub.12 alkyl, (c) C.sub.2 -C.sub.6 alkyl which is substituted by OH or Oalk, (d) allyl, (e) benzyl or (f) phenyl, and
- R.sup.13 represents --CONH.sub.2, --CONHalk, --CON(alk).sub.2, --P(O)(Oalk).sub.2 or 2-pyridyl.
- 5. A method according to claim 1 wherein the sensitizer is a compound according to claim 1 wherein
- R.sup.1 represents C.sub.1 -C.sub.8 alkyl,
- R.sup.2 represents C.sub.1 -C.sub.8 alkyl or allyl,
- R.sup.3 represents a direct bond or C.sub.1 -C.sub.6 alkylene,
- R.sup.4 represents C.sub.1 -C.sub.12 alkyl,
- R.sup.5 represents C.sub.1 -C.sub.12 alkyl or together with R.sup.4 represents C.sub.4 -C.sub.5 alkylene which can be interrupted by --O-- or --Nalk--, and
- R.sup.6 represents (a) hydrogen, (b) C.sub.1 -C.sub.12 alkyl, (c) C.sub.2 -C.sub.4 alkyl which is substituted by OH or Oalk, (d) allyl, (e) benzyl, or (f) phenyl.
- 6. A method according to claim 1 wherein the sensitizer is a compound according to claim 1 wherein X represents alkoxy, C.sub.1 -C.sub.6 hydroxyalkoxy, alkoxyalkoxy, benzyloxy or phenyloxy.
- 7. A method according to claim 1 wherein the sensitizer is a compound according to claim 1 wherein Ar represents p-phenoxy-phenyl.
- 8. A photopolymerisable system comprising at least one unsaturated photopolymerisable compound and 0.1 to 20% by weight of a compound according to claim 1 as photosensitizer.
- 9. A photopolymerisable system according to claim 8 wherein the amount of the compound is 0.5 to 5% by weight.
- 10. A photopolymerisable system according to claim 8 which contains one or more esters of acrylic or methacrylic acid as unsaturated compound.
- 11. A photopolymerisable system according to claim 8 which is a printing ink.
- 12. A photochemically crosslinkable system comprising a polyolefin and 0.1 to 20% by weight of a compound according to claim 1 as photosensitizer.
- 13. A system according to claim 12 wherein the amount of the compound is 0.5 to 5% by weight.
- 14. A photochemically crosslinkable system according to claim 12 wherein the polyolefin is a polyethylene.
Priority Claims (3)
Number |
Date |
Country |
Kind |
15884/77 |
Dec 1977 |
CHX |
|
2518/78 |
Mar 1978 |
CHX |
|
9723/78 |
Sep 1978 |
CHX |
|
Parent Case Info
This application is a continuation-in-part of application Ser. No. 970,016, filed Dec. 18, 1978.
US Referenced Citations (6)
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
970016 |
Dec 1978 |
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