Photoinitiators and their applications

Compounds of formula Ia or Ib

• wherein
• n is 1 or 2;
• PI is a group of formula IIa, IIb or IIc
• PI′ is a group of formula IIIa or IIIb
• Ar is phenyl, biphenylyl or benzoylphenyl, each of which is unsubstituted or substituted 1 to 5 times by halogen, C1-C12alkyl, C3-C12alkenyl, C5-C6cycloalkyl, phenyl-C1-C3alkyl, —COOH, —COO(C1-C4alkyl), —OR7, —SR8, —SOR8, —SO2R8, —CN, —SO2NH2, —SO2NH(C1-C4alkyl), —SO2—N(C1-C4alkyl)2, —NR9R10, —NHCOR9, or by a group of formula IV,
• or Ar is a group of formula V or VI
• Ar2 is
• each of which is unsubstituted or substituted 1 to 5 times by halogen, C1-C12alkyl, C3-C12alkenyl, C5-C6cycloalkyl, phenyl-C1-C3alkyl, —COOH, —COO(C1-C4alkyl), —OR7, —SR8, —SOR8, —SO2R8, —CN, —SO2NH2, —SO2NH(C1-C4alkyl), —SO2—N(C1-C4alkyl)2, —NR9R10, —NHCOR9, or by a group of formula IV;
• or Ar2 is a group of formula Va or VIa
• G is unbranched or branched C1-C7alkylene,
• L and E independently of one another are a direct bond, —O—, —S— or —N(R6)—, provided that L and E are not both a direct bond simultaneously;
• R1 and R2 independently of one another are R7O—;
• C1-C8alkyl, which is unsubstituted or substituted by OH, C1-C4alkoxy, SR8, CN, (C1-C8alkyl)O(CO)—, (C1-C4alkyl)-(OC)O— or —N(R3)(R4);
• or R1 and R2 independently of one another are C3-C6alkenyl, phenyl, chlorophenyl, R7—O-phenyl, R8—S-phenyl or phenyl-C1-C3-alkyl, or R1 and R2 together are unbranched or branched C2-C9alkylene, C3-C9oxaalkylene or C3-C9azaalkylene, or R1 and R2 independently of one another are a radical of formula VII or VIII
• p is 0 or 1;
• Ar3 is phenyl, naphthyl, furyl, thienyl or pyridiyl, each of which is unsubstituted or substituted by halogen, SH, OH, C1-C12alkyl, OH-substituted C1-C4alkyl, halogen-substituted C1-C4alkyl, SH-substituted C1-C4alkyl, N(R17)2-substituted C1-C4alkyl, C1-C12alkoxy-substituted C1-C4alkyl, (C1-C18alkyl)O(OC)-substituted C1-C4alkyl, CH3O(CH2CH2O)mCO-substituted C1-C4alkyl, (C1-C4alkyl)(OC)O-substituted C1-C4alkyl, C1-C12alkoxy, (C1-C18alkyl)(OC)O-substituted C1-C4alkoxy, CH3O(CH2CH2O)mCO-substituted C1-C4alkoxy, —(OCH2CH2)mOH, —(OCH2CH2)mOCH3, C1-C8alkylthio, phenoxy, —COO(C1-C18alkyl), —CO(OCH2CH2)mOCH3, phenyl or benzoyl;
• m is 1 to 20;
• M1 is —NR3R4 or —OH, or, when R1 and R2 are R7O—, M1 is Ar;
• M1′ is a group
• or, when R1 and R2 are R7O—, M1′ is Ar2;
• R1′ and R3′ independently of one another are a direct bond, C1-C12alkylene, or phenylene;
• E1 is —CH2—, —O—, —N(R6)— or —S—;
• R3 is hydrogen, C1-C12alkyl;
• C2-C4alkyl, which is substituted by OH, SH, C1-C4alkoxy, CN or —COO(C1-C4alkyl);
• or R3 is C3-C5alkenyl, C5-C12-cycloalkyl or phenyl-C1-C3alkyl;
• R4 is C1-C12alkyl;
• C2-C4alkyl, which is substituted by OH, SH, C1-C4alkoxy, CN or —COO(C1-C4alkyl);
• or R4 is C3-C5alkenyl, C5-C12-cycloalkyl, phenyl-C1-C3alkyl;
• phenyl which is unsubstituted or substituted by halogen, C1-C12alkyl, C1-C4alkoxy or —COO(C1-C4alkyl);
• or R4 together with R2 is C1-C7alkylene, phenyl-C1-C4alkylene, o-xylylene, 2-butenylene, C2-C3oxaalkylene or C2-C3azaalkylene;
• or R3 and R4 together are C3-C7alkylene, optionally interrupted by —O—, —S—, —CO— or —N(R6)— and which C3-C7alkylene is unsubstituted or substituted by OH, SH, C1-C4alkoxy or —COO(C1-C4alkyl);
• R6 is hydrogen, C1-C12alkyl, OH-substituted C1-C12alkyl, SH-substituted C1-C12alkyl or HS—(CH2)n—COO-substituted C1-C12alkyl;
• C2-C12alkyl, which is interrupted by —O—,
• —NH— or —S—;
• or R6 is C3-C5alkenyl, phenyl-C1-C3-alkyl, —CH2CH2CN, C1-C4alkyl-CO—CH2CH2—, OH-substituted C1-C4alkyl-CO—CH2CH2—, SH-substituted C1-C4alkyl-CO—CH2CH2—, C2-C8alkanoyl, OH-substituted C2-C8alkanoyl, SH-substituted C2-C8alkanoyl or benzoyl;
• R7 is hydrogen, C1-C12alkyl, C3-C12-alkenyl, cyclohexyl, hydroxycyclohexyl;
• C1-C4alkyl, which is mono- or polysubstituted by Cl, Br, CN, SH, —N(C1-C4alkyl)2, piperidinyl, morpholinyl, OH, C1-C4alkoxy, —OCH2CH2CN, —OCH2CH2COO(C1-C4alkyl), —O(CO)R19, —COOH, —COO(C1-C8alkyl), —CONH(C1-C4alkyl), —CON(C1-C4alkyl)2,
• —CO(C1-C4alkyl) or by
• or R7 is 2,3-epoxypropyl, —(CH2CH2O)nH;
• phenyl which is unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy or —COO(C1-C4alkyl);
• or R7 is phenyl-C1-C3alkyl, tetrahydropyranyl, tetrahydrofuranyl, —COOR19, —COO(C1-C8alkyl), —CONH(C1-C4alkyl), —CON(C1-C8alkyl)2, —Si(R20)(R21)2, or —SO2R22;
• R8 is hydrogen, C1-C12alkyl, C3-C12alkenyl, cyclohexyl, hydroxycyclohexyl;
• C1-C4alkyl, which is mono- or polysubstituted by Cl, Br, CN, SH, —N(C1-C4alkyl)2, piperidinyl, morpholinyl, OH, C1-C4alkoxy, —OCH2CH2CN, —OCH2CH2COO(C1-C4alkyl), —O(CO)R19, —COOH, —COO(C1-C8alkyl), —CON(C1-C4alkyl)2,
• —CO(C1-C4alkyl) or
• or R8 is 2,3-epoxypropyl, phenyl-C1-C3alkyl, phenyl-C1-C3hydroxyalkyl;
• phenyl which is unsubstituted or mono- or poly-substituted by halogen, SH, C1-C4alkyl, C1-C4alkoxy or —COO(C1-C4alkyl);
• or
• R8 is 2-benzothiazyl, 2-benzimidazolyl, —CH2CH2—O—CH2CH2—SH or —CH2CH2—S—CH2CH2—SH;
• R9 and R10 independently of one another are hydrogen, C1-C12alkyl;
• C2-C4alkyl, which is substituted by OH, SH, C1-C4alkoxy, CN or —COO(C1-C4alkyl);
• or R9 and R10 independently of one another are C3-C5alkenyl, cyclohexyl, phenyl-C1-C3alkyl;
• phenyl which is unsubstituted or mono- or poly-substituted by C1-C12alkyl or halogen;
• or R9 and R10 together are C2-C7alkylene, optionally interrupted by —O—, —S—, —CO— or —N(R6)—;
• R11 and R12 independently of one another are a direct bond, —CH2—, —CH2CH2—, —O—, —S—, —CO— or —N(R6)—;
• provided that R11 and R12 are not a direct bond simultaneously;
• R13 is hydrogen, C1-C8alkyl or phenyl;
• R14, R15 and R16 independently of one another are hydrogen or C1-C4alkyl;
• R17 is hydrogen, C1-C8alkyl or phenyl;
• R19 is C1-C4alkyl, C2-C4alkenyl or phenyl;
• R20 and R21 independently of one another are C1-C4alkyl or phenyl;
• R22 is C1-C18alkyl;
• or phenyl which is unsubstituted or substituted by C1-C14alkyl;
• A1 and A2 independently of one another are a direct bond, —X[(CH2)lX′]q—[(C6H4)oX″]r—, —O—, —S— or —N(R6)—;
• X, X′ and X″ independently of each other are a direct bond, —O—, —S—, —N(R6)—, —O(CO)—, —COO— —NHCO—, —CONH— or —CO—;
• l is an integer from 0 to 10;
• q is an integer from 0 to 5:
• o and r independently of one another are an integer 0, 1 or 2;
• CT when n is 1, is a group of formula IXa, IXb, Xa or Xb,
• or, when n is 2, CT is a group of formula XI and XII,
• Y is —W(R8)s;
• Y′ is —W(R8)t—R25—;
• W is S, Si, Se, P, Br, Cl, Sn, —O—O—, S(═O), S(═O)2, or P(═O);
• Z is —COOR7, —CONR9R10, —CN, or —Ar;
• Z′ is —COOR25—, —CONR9R25—, or —Ar2—;
• s is an integer from 0 to 3;
• t is an integer 0, 1 or 2;
• u is 0 or 1;
• R23 and R24 independently of one another are hydrogen, or C1-C8alkyl;
• or R23 and R24 together are C5-C7cyloalkyl;
• and
• R25 is a direct bond, C1-C4alkylene or phenylene.