Functionalized photoinitiators

Mixtures of compounds of formula (VI):

• wherein,
• the arrows denote substitution at the aromatic ring without specifically indicating a relative position to the depicted keto-group if not mentioned otherwise,
• B is either missing so that the two aromatic rings are substituted with a hydrogen, or where n or m are not zero, with either R1 or R2 at the position where B is depicted to be bound at the aromatic ring, or is
• sulfur or oxygen,
• n is 0, 1 or 2,
• R1 is selected from the group consisting of hydrogen, C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2, fluoro, chloro and COOR5 with R5 being hydrogen or C1-C18-alkyl,
• m is 0, 1 or 2,
• R2 is selected from the group consisting of hydrogen, C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio, C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2, fluoro, chloro and COOR5, with R5 being hydrogen or C1-C18-alkyl, and
• wherein
• v is 0 or 1,
• the substituents L-Het-[[CHR3CHR4O]y1-E], where present, and L-Het-[[CHR3CHR4O]y2-E]independently of each other occupy the ortho-, meta or the para-position at their respective aromatic ring and with respect to the keto-function depicted in formula (I), and
• wherein
• L is independently missing or is a methylene group so that Het is either directly bound to the aromatic ring or via a methylene group,
• Het is independently sulphur, oxygen, N(C1-C18-Alkyl), NH or N,
• t is 1 for Het=sulphur, oxygen, N(C1-C18-Alkyl), NH, and
• is 2 for for Het=N,
• R3 and R4 are either identically hydrogen or one of R3 and R4 is hydrogen and the other is methyl, and
• if t is 1,
• y1 and y2 independently of each other is an integer of 0 or more,
• whereby,
• the sum of y1 and y2 is at least 1 for v=1, or
• y2 is at least lwhere v=0,
• if t is 2,
• all y1 and y2 independently of each other is an integer of 0 or more, whereby
• the sum of all y1 and all y2 is at least 1 for v=1, or
• the sum of all y2 is at least 1 where v=0,
• and
• E independently identically is H2C═CH—CO—, (CH3)HC═CH—CO— or H2C═C(CH3)—CO—,
• wherein with respect to the number of repeating units y1 and y2 are at least 50 wt.-% of the total weight of the compounds of formula (VI) within the mixture, wherein
• y2, where v is 0 and t is 1, or
• at least one of y1 and y2, where both t are 1, or
• at least one of all y2, where v=0 and t is 2, or
• at least one of all y1 and all y2, where v=1 and where at least one t is 2,
• is 3 or more,
• wherein no single compound of formula (VI) is present in an amount of more than 50 wt.-% with respect to the total weight of the compounds of formula (VI), and
• wherein the total amount of compounds of formula (Vi) present in the mixture comprising the compounds of formula (VI) having at least one of p and q being 5 or larger is 20 wt.-% or less.

A photo-curable composition, comprising

• (a) at least one ethylenically unsaturated component;
• and
• (b) at least a mixture comprising:
• compounds of formula (IV):
• wherein
• the arrows denote substitution at the aromatic ring without specifically indicating the relative position to the depicted keto-group if not otherwise mentioned,
• B is either missing so that the two aromatic rings are substituted with a hydrogen, or where n or m are not zero, with either R1 or R2 at the position where B is depicted to be bound at the aromatic ring, or is
• sulfur or oxygen,
• whereby B is preferably missing or sulfur and more preferably B is missing
• n is 0, 1 or 2,
• R1 is selected from the group consisting of C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2, fluoro, chloro and COOR5 with R5 being hydrogen or C1-C18-alkyl,
• m is 0, 1 or 2,
• R2 is selected from the group consisting of C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio, C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2, fluoro, chloro and COOR5, with R5 being hydrogen or C1-C18-alkyl, and
• v is 0 or 1,
• the substituents L-Het[[CHR3CHR4O]p—H]t, if present, and L-Het-[CHR3CHR4O]q—H]t independently of each other occupy the ortho-, meta or the para-position at their respective aromatic ring and with respect to the keto-function depicted in formula (IV), and
• wherein,
• L is independently missing or is a methylene group so that Het is either directly bound to the aromatic ring or via a methylene group,
• Het is independently sulphur, oxygen, N(C1-C18-Alkyl), or N,
• t is 1 for Het=sulphur, oxygen, N(C1-C18-Alkyl), and
• is 2 for for Het=N,
• R3 and R4 are either identically hydrogen or one of R3 and R4 is hydrogen and the other is methyl,
• and
• p and q independently of each other is an integer of 0 or more,
• wherein with respect to the number of repeating units p and q,
• at least 50 wt.-% of the total weight of the compounds of formula (IV) within the mixture are those of formula (IV), wherein
• q, where v is 0 and t is 1, or
• at least one of p and q, where both t are 1, or
• at least one of all q, where v=0 and t is 2, or
• at least one of all p and all q, where v=l1 and where at least one t is 2,
• is 3 or more,
• wherein no single compound of formula (IV) is present in an amount of more than 50 wt.-% with respect to the total weight of the compounds of formula (IV) in the mixture, and
• wherein the total amount of compounds of formula (IV) present in the mixture comprising the compounds of formula (IV) having at least one of p and q being 5 or larger is 20 wt.-% or less,
• or
• compounds of formula (VI):
• wherein,
• the arrows denote substitution at the aromatic ring without specifically indicating a relative position to the depicted keto-group if not mentioned otherwise,
• B is either missing so that the two aromatic rings are substituted with a hydrogen, or where n or m are not zero, with either R1 or R2 at the position where B is depicted to be bound at the aromatic ring, or is
• sulfur or oxygen,
• n is 0, 1 or 2,
• R1 is selected from the group consisting of hydrogen, C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2, fluoro, chloro and COOR5 with R5 being hydrogen or C1-C18-alkyl,
• m is 0, 1 or 2,
• R2 is selected from the group consisting of hydrogen, C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio, C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2, fluoro, chloro and COOR5, with R5 being hydrogen or C1-C18-alkyl, and
• wherein
• v is 0 or 1,
• the substituents L-Het-[[CHR3CHR4O]y1-E], where present, and L-Het-[[CHR3CHR4O]y2-E]independently of each other occupy the ortho-, meta or the para-position at their respective aromatic ring and with respect to the keto-function depicted in formula (I), and
• wherein
• L is independently missing or is a methylene group so that Het is either directly bound to the aromatic ring or via a methylene group,
• Het is independently sulphur, oxygen, N(C1-C18-Alkyl), NH or N,
• t is 1 for Het=sulphur, oxygen, N(C1-C18-Alkyl), NH, and
• is 2 for for Het=N,
• R3 and R4 are either identically hydrogen or one of R3 and R4 is hydrogen and the other is methyl, and
• if t is 1,
• y1 and y2 independently of each other is an integer of 0 or more,
• whereby,
• the sum of y1 and y2 is at least 1 for v=1, or
• y2 is at least 1 where v=0,
• if t is 2,
• all y1 and y2 independently of each other is an integer of 0 or more, whereby
• the sum of all y1 and all y2 is at least 1 for v=1, or
• the sum of all y2 is at least 1 where v=0,
• and
• E independently identically is H2C═CH—CO—, (CH3)HC═CH—CO— or H2C═C(CH3)—CO—,
• wherein with respect to the number of repeating units y1 and y2 are at least 50 wt.-% of the total weight of the compounds of formula (VI) within the mixture, wherein
• y2, where v is 0 and t is 1, or
• at least one of y1 and y2, where both t are 1, or
• at least one of all y2, where v=O0 and t is 2, or
• at least one of all y1 and all y2, where v=l1 and where at least one t is, 2
• is 3 or more, and wherein no single compound of formula (VI) is present in an amount of more than 50 wt.-% with respect to the total weight of compounds of formula (VI), and
• wherein the total amount of compounds of formula (IV) present in the mixture comprising the compounds of formula (IV) having at least one of p and q being 5 or larger is 20 wt.-% or less,
• or
• compounds of formula (VIIa):
• wherein
• the arrows denote substitution at the aromatic ring without specifically indicating a relative position to the depicted keto-group if not mentioned otherwise hereinafter,
• B is either missing so that the two aromatic rings are substituted with a hydrogen, or where n or m are not zero, with either R1 or R2 at the position where B is depicted to be bound at the aromatic ring, or is
• sulfur or oxygen,
• n is 0, 1 or 2,
• R1 is selected from the group consisting of hydrogen, C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2, fluoro, chloro and COOR5 with R5 being hydrogen or C1-C18-alkyl,
• m is 0, 1 or 2,
• R2 is selected from the group consisting of hydrogen, C1-C18-alkyl, C2-C18-alkenyl, C1-C18-alkoxy, C1-C18-alkylthio, C6-C14-aryl, C6-C14-aryloxy, C6-C14-arylthio, —N(R5)2O fluoro, chloro and COOR5, with R5 being hydrogen or C1-C18-alkyl, and
• wherein
• the substituent L-O[CHR3CHR4O]y3— occupies the ortho-, meta or the para-position at the aromatic ring and with respect to the keto-function depicted in formula (VIIa), and
• wherein
• L is independently missing or a methylene group so that Het is either directly bound to the aromatic ring or via a methylene group,
• R3 and R4 are either identically hydrogen or one of R3 and R4 is hydrogen and the other is methyl, and
• y3 is an integer of 1 or more,
• w is an integer of 2 or more, and
• Rz is R(CO)x with R being an x-valent organic residue with 1 or more carbon atoms.