Oxime ester photoinitiators

Patent metadata

Field	Value
Publication number	US-2016377977-A1
Application number	US-201414903450-A
Country	US
Kind code	A1
Filing date	Jun 30, 2014
Priority date	Jul 8, 2013
Publication date	Dec 29, 2016
Grant date	—

Abstract

Compounds of the formula (I)

wherein
Q is a direct bond or an n-valent linking group; n is an integer 2, 3, or 4; Z is for example C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 5 -C 8 cycloalkylene or C 5 -C 8 cycloalkenylene; Y is for example C 6 -C 20 aryl or C 3 -C 20 heteroaryl; R 1 is for example hydrogen, C 2 -C 5 alkenyl, C 3 -C 8 cycloalkyl, C 1 -C 12 alkyl, phenyl, naphthyl, C 3 -C 20 heteroaryl, C 1 -C 8 alkoxy, benzyloxy or phenoxy; R 2 is for example C 1 -C 20 alkyl, C 2 -C 12 alkenyl, C 4 -C 8 cycloalkenyl, C 2 -C 12 alkinyl, C 3 -C 10 cycloalkyl, phenyl or naphthyl; R 15 , R 16 , R 17 , R 18 , R 19 and R 20 independently of each other for example are hydrogen, halogen, C 1 -C 20 alkyl, C 6 -C 20 aryl or C 4 -C 20 heteroaryl; provided that a compound wherein R 15 , R 16 , R 17 , R 15 , R 19 and R 20 are hydrogen, Y is thienyl, R 1 is methyl, R 2 is ethyl, n is 2, Q is a direct bond and Z is n-propylene and a compound wherein R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are hydrogen, Y is thienyl, R 1 is methyl, R 2 is ethyl, n is 2, Q as an n-valent linking group is methylene and Z is methylene are excluded; are reactive photoinitiators in particular in electronic applications.

First claim

1 .- 20 . (canceled)

21 . A compound of the formula (I)

wherein
Q is a direct bond or an n-valent linking group;
n is an integer 2, 3, or 4; wherein the multiple radicals R 1 , R 2 , Y and Z in the compound of formula I are identical or different;
Z is C 1 -C 20 -alkylene, C 1 -C 20 -alkylene which is interrupted by one or more of O, S, (CO)O, O(CO), phenylene, naphthylene or NR 8 , wherein the C 1 -C 20 -alkylene and interrupted C 1 -C 20 -alkylene is unsubstituted or substituted by at least one of halogen or OR 6 , or
Z is C 2 -C 20 -alkenylene, C 2 -C 20 -alkenylene which is interrupted by one or more of O, S, (CO)O, O(CO), phenylene, naphthylene or NR 8 , wherein the C 2 -C 20 -alkenylene and interrupted C 2 -C 20 -alkenylene is unsubstituted or substituted by at least one of halogen or OR 6 , or
Z is C 5 -C 8 -cycloalkylene, C 5 -C 8 -cycloalkenylene,

 wherein the groups C y H 2y and C z H 2z are uninterrupted or interrupted by one or more of O, S or NR 8 ;

x, y and z independently of each other are an integer 1, 2, 3 or 4;
Y is C 6 -C 20 -aryl or C 3 -C 20 -heteroaryl each of which is unsubstituted or substituted by one or more identical or different R 3 ;
R 1 is hydrogen, C 2 -C 5 -alkenyl, C 3 -C 8 -cycloalkyl or C 1 -C 12 -alkyl which is unsubstituted or substituted by one or more of halogen, phenyl or CN; or
R 1 is phenyl or naphthyl both of which are unsubstituted or substituted by one or more of C 1 -C 6 -alkyl, halogen, CN, OR 6 , SR 7 or NR 8 R 9 ; or
R 1 is C 3 -C 20 -heteroaryl, C 1 -C 8 -alkoxy, benzyloxy or phenoxy, wherein the C 3 -C 20 -heteroaryl, benzyloxy or phenoxy is unsubstituted or substituted by one or more of C 1 -C 6 -alkyl or halogen;

R 2 is C 1 -C 20 alkyl which is unsubstituted or substituted by one or more of halogen, COOR 6 , OR 6 , SR 7 , CONR 8 R 9 , NR 8 R 9 ,

 or
R 2 is C 2 -C 2-0 alkyl which is interrupted by one or more of O, S, SO, SO 2 , NR 8 or CO, or is C 2 -C 12 -alkenyl which is uninterrupted or is interrupted by one or more of O, CO or NR 8 , wherein the interrupted C 2 -C 20 -alkyl and the uninterrupted or interrupted C 2 -C 12 -alkenyl are unsubstituted or are substituted by one or more halogen; or
R 2 is C 4 -C 8 -cycloalkenyl, C 2 -C 12 -alkinyl, or C 3 -C 10 -cycloalkyl which is uninterrupted or is interrupted by one or more of O, S, CO or NR 8 ; or
R 2 is phenyl or naphthyl each of which is unsubstituted or substituted by one or more of OR 6 , SR 7 , NR 8 R 9 , COR 6 , CN, NO 2 , halogen, C 1 -C 20 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 20 -alkyl which is interrupted by one or more of O, S, CO or NR 8 , or each of which phenyl or naphthyl is substituted by C 3 -C 10 -cycloalkyl or by C 3 -C 10 -cycloalkyl which is interrupted by one or more of O, S, CO or NR 8 ;

R 3 is hydrogen, halogen, OR 6 , COOR 6 , CONR 8 R 9 , SR 7 , NR 8 R 9 , CN, or C 2 -C 20 -alkyl which is interrupted by one or more of O, S or NR 8 , wherein the interrupted C 2 -C 20 -alkyl is unsubstituted or substituted by one or more of halogen, OR 6 , COOR 6 , SR 7 , CONR 8 R 9 , C 6 -C 20 -aryl, C 3 -C 20 -heteroaryl, C 3 -C 20 -cycloalkyl or C 3 -C 20 -cycloalkyl which is interrupted by one or more O, S or NR 8 ; or
R 3 is C 1 -C 20 alkyl which is unsubstituted or substituted by one or more of halogen, OR 6 , SR 7 , COOR 6 , CONR 8 R 9 , NR 8 R 9 , phenyl, C 3 -C 8 -cycloalkyl or C 3 -C 20 -heteroaryl;

X is CO or a direct bond;
X 1 is O, S, SO or SO 2 ;
R 6 is hydrogen, phenyl-C 1 -C 3 -alkyl, C 1 -C 20 -alkyl, which is unsubstituted or substituted by one or more of halogen, OH, SH, CN, C 3 -C 6 -alkenoxy, O(C 1 -C 4 -alkyl), OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 -alkyl), O(CO)—(C 1 -C 4 -alkyl), O(CO)—(C 2 -C 4 )-alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C 1 -C 4 -alkyl), C 3 -C 20 cycloalkyl, SO 2 —(C 1 -C 4 -haloalkyl), O(C 1 -C 4 -haloalkyl) or C 3 -C 20 -cycloalkyl which is interrupted by one or more O; or
R 6 is C 2 -C 20 -alkyl which is interrupted by one or more of O, S or NR 8 , which interrupted C 2 -C 20 -alkyl is unsubstituted or is substituted by at least one of OH or CO—C 1 -C 4 -alkyl; or
R 6 is C 1 -C 8 -alkanoyl, C 2 -C 12 -alkenyl, C 3 -C 6 -alkenoyl, or C 3 -C 20 -cycloalkyl which is uninterrupted or interrupted by one or more of O, S, CO or NR 8 ; or
R 6 is C 1 -C 8 -alkyl-C 3 -C 10 -cycloalkyl which is uninterrupted or interrupted by one or more O; or
R 6 is benzoyl which is unsubstituted or substituted by one or more of C 1 -C 6 -alkyl, halogen, OH or C 1 -C 3 -alkoxy; or
R 6 is phenyl, naphthyl or C 3 -C 20 -heteroaryl, each of which is unsubstituted or substituted by one or more of halogen, OH, C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy, CN, NO 2 , phenyl-C 1 -C 3 -alkyloxy, phenoxy, C 1 -C 12 -alkylsulfanyl, phenylsulfanyl, N(C 1 -C 12 -alkyl) 2 or diphenylamino;

R 7 is hydrogen, C 2 -C 12 -alkenyl, C 3 -C 20 -cycloalkyl or phenyl-C 1 -C 3 -alkyl, wherein the C 2 -C 12 -alkenyl, C 3 -C 20 -cycloalkyl or phenyl-C 1 -C 3 -alkyl is uninterrupted or interrupted by one or more of O, S, CO or NR 8 ; or
R 7 is C 1 -C 20 -alkyl which is unsubstituted or substituted by one or more of OH, SH, CN, C 3 -C 6 -alkenoxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 -alkyl), O(CO)—(C 2 -C 4 )-alkenyl, O(CO)—(C 1 -C 4 -alkyl), O(CO)-phenyl or COOR 6 ; or
R 7 is C 2 -C 20 -alkyl which is interrupted by one or more of O, S, CO or NR 8 ; and which interrupted C 2 -C 20 -alkyl is unsubstituted or substituted by one or more of OH, CO—C 1 -C 8 -alkyl, C 2 -C 8 -alkanoyl or C 3 -C 6 -alkenoyl; or
R 7 is benzoyl which is unsubstituted or substituted by one or more of C 1 -C 6 -alkyl, halogen, OH, C 1 -C 4 -alkoxy or C 1 -C 4 -alkylsulfanyl; or
R 7 is phenyl, naphthyl or C 3 -C 20 -heteroaryl, each of which is unsubstituted or substituted by one or more of halogen, C 1 -C 12 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 -alkyloxy, phenoxy, C 1 -C 12 -alkylsulfanyl, phenylsulfanyl, N(C 1 -C 12 -alkyl) 2 , diphenylamino, (CO)O(C 1 -C 8 -alkyl), (CO)—C 1 -C 8 -alkyl or (CO)N(C 1 -C 8 -alkyl) 2 ;

R 8 and R 9 independently of each other are hydrogen, C 1 -C 20 -alkyl, C 2 -C 4 -hydroxyalkyl, C 2 -C 10 -alkoxyalkyl, C 2 -C 5 -alkenyl, C 3 -C 20 -cycloalkyl, phenyl-C 1 -C 3 -alkyl, C 1 -C 8 -alkanoyl, C 1 -C 8 -alkanoyloxy, C 3 -C 12 -alkenoyl, SO 2 —(C 1 -C 4 -haloalkyl) or benzoyl; or
R 8 and R 9 are phenyl, naphthyl or C 3 -C 20 -heteroaryl, each of which is unsubstituted or substituted by one or more of halogen, C 1 -C 4 -haloalkyl, C 1 -C 20 -alkoxy, C 1 -C 12 -alkyl, benzoyl or C 1 -C 12 -alkoxy; or
R 8 and R 9 together with the N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is uninterrupted or is interrupted by O, S, or NR 14 , and which 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more of C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, OR 6 , phenyl,

 or C 3 -C 20 -cyclalkyl;

R 10 is C 6 -C 20 -aryl or C 3 -C 20 -heteroaryl each of which is unsubstituted or substituted by one or more of phenyl, halogen, C 1 -C 4 -haloalkyl, CN, NO 2 , OR 6 , SR 7 , NR 8 R 9 or C 2 -C 20 -alkyl which is interrupted by one or more of O, S or NR 8 ,
or each of which is substituted by C 1 -C 20 -alkyl which is unsubstituted or substituted by one or more of halogen,

Assignees

• Basf Se

Inventors

• Tanaka Keita
• Kura Hisatoshi
• Kunimoto Kazuhiko
• Sameshima Kaori

Classifications

• G03F7/0007

  Filters, e.g. additive colour filters; Components for display devices · CPC title

• G03F7/027

  Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence) · CPC title

• G03F7/20

  Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00) · CPC title

• G03F7/0388

  with ethylenic or acetylenic bands in the side chains of the photopolymer · CPC title

• G03F7/033

  the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers · CPC title