Granted Patent B2

US 12,528,889 · App. 17/764,714 · Granted Jan 20, 2026

Inventors: Angelo Casiraghi (Milano MI, IT); Gabriele Norcini (Comabbio, IT); Stephen Postle (Bradenton, FL)

Assignee: IGM RESINS ITALIA S.R.L.

C08F2/50C08K5/1545C08K5/5397C09D11/101

Abstract

Claims (109)

1 . A combination of photoinitiators comprising:

a′ 60 to 90% by weight, of at least one Norrish Type I photoinitiator selected from acylphosphine oxides;

b′ 1 to 20% by weight, of at least one, Norrish Type II photoinitiator selected from ketocoumarins; and

c′ 0 to 20% by weight, of at least one co-initiator.

2 . The combination of claim 1 comprising,

a″ 0 to 30% by weight, of a solid photoinitiator belonging to Norrish Type I photoinitiators and 50 to 80% by weight of a liquid photoinitiator belonging to Norrish Type I photoinitiators selected from acylphosphine oxides;

b″ 5 to 20% by weight, of at least one photoinitiator belonging to Norrish Type II photoinitiators selected from ketocoumarins; and

c″ 10 to 20% by weight, of at least one co-initiator.

3 . The combination of claim 2 , wherein said at least one liquid or solid acylphosphine oxide is selected from the following Formulas (I) to (IV):

wherein

R 1 , R 2 , R 3 , R 1a , R 2a and R 3a independently of each other are C1-C4alkyl, C1-C4alkoxy or halogen;

X is a direct single bond and R 4 is C1-C28alkyl, substituted C1-C28alkyl or C1-C28alkoxy; or

X is O, NR 5 , S or a direct single bond;

Y is O or S;

n is 1;

R 4 , is hydrogen, (CO)R 6 , (CO)OR 6 , (CO)NR 5 R 6 , (SO 2 )—R 6 , [Si(R 7 )(R 8 )] o —Si(R 7 )(R 8 )(R 9 ), [Si(R 7 )(R 8 )—O] o —Si(R 7 )(R 8 )(R 9 ), C1-C28alkyl, C2-C28alkyl which is interrupted by one or more O, NR 5 , S, (CO), (CO)O, or SO 2 ; wherein said C1-C28 alkyl or interrupted C2-C28 alkyl is unsubstituted or substituted by one or more substituents selected from the group consisting of

OH, C6-C14 aryl, [Si(R 7 )(R 8 )] o —Si(R 7 )(R 8 )(R 9 ), [Si(R 7 )(R 8 )—O] o —Si(R 7 )(R 8 )(R 9 ), N(R 5 ) 2 ,

propenoyloxy, 2-methylpropenoyloxy, C3-C12cycloalkyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4alkoxy or by OH, C3-C12cycloalkyl which is interrupted by one or more O, NR 5 or S and which interrupted C3-C12cycloalkyl is unsubstituted or substituted by C1-C4alkyl, C1-C4-alkoxy or by OH, and C6-C14 aryl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy or by OH; or R 4 , is C6-C10 aryl which is unsubstituted or substituted by one or more C1-C12 alkyl, C2-C20 alkyl which is interrupted by one or more O, C1-C12-alkoxy or by OH; or R 4 if X is NR 5 , together with R 5 and the N-atom forms a 5 or 6-membered saturated ring which is uninterrupted or interrupted by O or NR 5 and which uninterrupted or interrupted ring is unsubstituted or substituted by one or more C1-C4alkyl, C1-C4alkoxy or by OH;

A is PF 6 , SbF 6 , AsF 6 or B(C 6 F 5 ) 4 ;

R 5 is hydrogen, (CO)R 6 , phenyl, C1-C12alkyl, C2-C12alkyl which is interrupted by one or more O, wherein said C1-C12 alkyl or interrupted C2-C12alkyl is unsubstituted or substituted by one or more C3-C7cycloalkyl, OH or by NCO,

C3-C12 cycloalkyl which is unsubstituted or substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, OH or by NCO;

R 6 is C1-C12 alkyl, C2-C12 alkyl which is interrupted by one or more O, wherein said C1-C12 alkyl or interrupted C2-C12 alkyl is unsubstituted or substituted by one or more C3-C7-cycloalkyl, OH, NCO or by phenyl which is substituted by NCO;

or R 6 is C3-C12 cycloalkyl, C2-C10 alkenyl which is unsubstituted or substituted by one or more C1-C4alkyl, OH or C1-C4 alkoxy;

or R 6 is C6-C14 aryl which is unsubstituted or substituted by C1-C12 alkyl, C1-C12 alkoxy, NCO or by NCO-substituted C1-C12 alkyl;

or R 5 and R 6 together with the N-atom form a 5 or 6-membered saturated ring which is uninterrupted or interrupted by O or NR 5 and which uninterrupted or interrupted ring is unsubstituted or substituted by one or more C1-C4alkyl, C1-C4alkoxy or by OH;

R 7 , R 8 and R 9 independently of each other are C1-C4alkyl, C6-C14aryl or C1-C4 alkoxy;

o is 0-10;

Y 1 is a bond, O, S, NRs, O(CO)—* or O(CO)—CH 2 —O—*, wherein the asterix denotes the bond to the phenyl ring of the group (A), (B), (D), or (E);

Y 2 is a bond, O, S or NRs;

R 11 and R 12 independently of each other are C1-C10 alkyl, C2-C10 alkenyl or phenyl-C1-C4-alkyl which is unsubstituted or substituted by C1-C4 alkyl, or R11 and R12 together with the C-atom to which they are attached are cyclohexyl or cyclopentyl;

Z is OH or NR 13 R 14 ;

Z 1 is C1-C12 alkoxy or C2-C12 alkoxy which is interrupted by one or more O, wherein said C1-C12 alkoxy or interrupted C2-C12 alkoxy is unsubstituted or substituted by OH;

R 13 and R 14 independently of each other are C1-C12 alkyl, C1-C12 alkyl which is substituted by one or more OH or halogen; or R 13 and R 14 together with the N-atom to which they are attached form a 5- or 6-membered unsaturated or saturated ring, which ring is uninterrupted or interrupted by O or NR 15 ;

R 15 is C1-C4 alkyl;

R 16 is hydrogen or C1-C4 alkyl;

provided that

(i) if R 1 , R 2 and R 3 as C1-C4 alkyl are CH 3 and X is O, then R 4 as C1-C28 alkyl is not methyl, ethyl, n-propyl, 2-propyl, n-butyl, 1-methyl-prop-1-yl, tert-butyl, n-hexyl;

(ii) if R 1 and R 3 as halogen are Cl, R 2 is hydrogen and X is O, then R 4 as substituted C3-C10 aryl is not 4-butyl-phenyl;

(iii) if R 1 and R 3 as C1-C4alkoxy are methoxy, R 2 is hydrogen and X is NRs, and R 4 together with R 5 and the N-atom forms a 5 or 6-membered saturated ring, then said ring is not piperid-1-yl;

wherein

Ar 1 and Ar 2 independently of each other are

 or naphthyl which is unsubstituted or substituted one or more times by R 1 , R 2 , R 3 or R′;

R 1 and R 3 independently of each other are C1-C4 alkyl, C1-C4 alkoxy or halogen; R 2 is hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy or C2-C20 alkoxy which is interrupted by one or more O;

Q is C1-C4 alkylene;

R 4 is methyl or ethyl;

R′ and R″ independently of each other are hydrogen or PG-Y—R′″—X—;

PG is a polymerizable group or methyl or ethyl;

Y is a direct single bond, O or S;

X is a direct single bond, O or S; R′″ is a direct single bond, C1-C20alkylene or C2-C20 alkylene which is interrupted by one or more O;

R 5 is C3-C30alkyl which is unsubstituted or substituted by one or more of the groups selected from OH and

 or R 5 is C2-C28 alkyl which is interrupted by one or more O or C3-C8 cycloalkylene and which interrupted C3-C28 alkyl is unsubstituted or substituted by one or more of the groups selected from OH and

 and

optionally a compound of formula R 5 —OH, wherein R 5 is as defined above;

Formula (III)

wherein

R 1 is C1-C4alkyl, C1-C4 alkoxy or halogen;

R 2 is hydrogen, C1-C4alkyl, C1-C4 alkoxy or halogen and

R 3 is C1-C20 alkyl, cyclopentyl, cyclohexyl, phenyl-C1-C4 alkyl or a group of the following formula

or R 3 is naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, the naphthyl, biphenylyl and O-, S- or N-containing 5- or 6-membered heterocyclic ring radicals being unsubstituted or substituted by C1-C4 alkyl, C1-C4 alkoxy, halogen, C1-C4 alkylthio;

R 4 , R 5 , R 6 , R 7 and R 8 are each independently of the others hydrogen, halogen, C1-C20 alkyl, cyclopentyl, cyclohexyl, C2-C12 alkenyl, C2-C20 alkyl interrupted by one or more non-consecutive O atoms, phenyl-C1-C4 alkyl, C1-C20 alkoxy, or phenyl that is unsubstituted or substituted by one or two C1-C4 alkyl or/and C1-C4 alkoxy substituents; and

wherein

each A represents independently of one another O, S, NR 3 ;

G is a residue of the multifunctional compound (core) G-(A-H) m+n , wherein each A-H represents an alcoholic or amino or thiol group;

m and n are both integer numbers and m+n is comprised between 3 and 10;

n is comprised between 3 and 8;

R 1 , R 2 are independently of one another, a radical selected from C1-C18alkyl, C6-C12aryl and C5-C12cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered heterocyclic radical containing oxygen and/or nitrogen and/or sulfur atoms; where each of said radicals may be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals;

R 2 may also be R 1 —(C=O)—;

Y is O or S;

R 3 is hydrogen or C1-C4alkyl;

with the proviso that the photoinitiators of formula (IV) do not contain photocurable ethylenically unsaturated groups.

4 . The combination of claim 1 , wherein said at least one ketocoumarin is selected from Formulas (V) to (VII):

wherein

R 1 and R 2 are, each independently, a C1-C4 alkyl group

R 3 is selected from:

a branched C6-C20 alkyl group or a mixture of linear and branched C6-C20 alkyl groups;

a C6-C20 alkyl-aryl, an aryl C6-C20 alkyl, a C6-C20 alkyl-heteroaryl, a heteroaryl-C6-C20 alkylene oxide, a —COO-C6-C20 alkyl and a COOaryl;

G is a residue of an optionally alkoxylated polyhydroxy compound;

m, n and p are numbers and m+n+p has a value ranging from 2 to 10;

p has a value ranging from 0 to 8;

x is an interger number with a value ranging from 0 to 10, and when x is 0, the phenyl group is directly linked to the carbonyl group;

Y represents, each independently a direct single bond or a substituted or unsubstituted divalent linking group comprising 1 to 14 carbon atoms;

Z represents a radically polymerizable functional group;

R 3 represents, each independently hydrogen, alkyl C1-C12, substituted or unsubstituted phenyl, aryl or heteroaryl, cycloalkyl C5-C6, alkyl C1-C12 which is substituted with —SH, —N(alkyl C1-C6) 2 , piperidino, morpholino, piperazino, —OH, —O(alkyl C1-C12), —COOH; or C1-C12 alkoxy;

R 1 , R 2 are, each independently, hydrogen, alkyl C1-C12, substituted or unsubstituted phenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, cycloalkyl C5-C6, alkyl C1-C12 which is substituted with —SH, —N(alkyl C1-C6) 2 , piperidino, morpholino, piperazino, —OH, —O(alkyl C1-C12), COOH; or C1-C12alkoxy; and

wherein R 1 is hydrogen or a substituted or unsubstituted C1-C12 alkyl group;

Cou is a coumarin group of Formula (a):

wherein

R 2 , R 3 , R 4 and R 5 are, independently of one another, hydrogen; or —S—R7, where R7 is hydrogen, C1-C12alkyl, C2-C12alkenyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C5-C6cycloalkyl, C1-C12alkyl which is substituted with SH, —N(C1-C6 alkyl) 2 , piperidino, morpholino, piperazino, —OH, —O(C1-C12alkyl), —COOH; or C1-C12alkoxy; and at least one of R 2 , R 3 , R 4 and R 5 is different from H;

R 6 is hydrogen, a hydroxyl group or an alkyl group having from 1 to 4 carbon atoms;

or Cou is a substituted or unsubstituted naphtha-coumarin group of formula:

provided that at least one of R 2 , R 3 , R 4 and R 5 is different from H and that, when Cou is (a) and at least one of R 2 , R 3 , R 4 and R 5 is C1-C12 alkoxy or when Cou is (b), (c) or (d), R 1 is a substituted or unsubstituted C1-C12 alkyl group.

5 . A photocurable composition comprising at least one combination according to claim 1 , at least one ethylenically unsaturated compound and, optionally, one or more additives.

6 . The photocurable composition according to claim 5 characterized in that the at least one ethylenically unsaturated compound is selected from alkyl or hydroxyalkyl (metha)acrylates, oligomeric polyinsatured compounds, acrylated epoxy resins, acrylated, vinyl-ether, acrylate polyurethanes and acrylated polyethers.

7 . The photocurable composition according to claim 5 , comprising:

(i) from 80 to 99% by weight of at least one ethylenically unsaturated compound;

(ii) from 1 to 20% by weight of a combination comprising:

a′ 60 to 90% by weight, of at least one Norrish Type I photoinitiator selected from acylphosphine oxides:

b′ 1 to 20% by weight, of at least one Norrish Type II photoinitiator selected from ketocoumarins;

c′ 0 to 20% by weight, of at least one co-initiator.

8 . A method for photocuring photopolymerizable compositions, coatings, adhesives and inks, which method comprises:

coating or printing a photopolymerizable composition according to claim 5 onto a substrate, and

photopolymerizing said coated or printed composition with a light source on said substrate or photopolimerizing at least one photocurable composition according to claim 5 .

9 . The combination of photoinitiators according to claim 1 , comprising

70 to 85% by weight of said at least one Norrish Type I photoinitiator;

5 to 20% by weight of said at least one Norrish Type II photoinitiator; and

5 to 20% by weight of said at least one co-initiator.

10 . The combination of claim 2 comprising,

a″ 10 to 30% by weight of said solid photoinitiator belonging to Norrish Type I photoinitiators and 50 to 80% by weight of a liquid photoinitiator belonging to Norrish Type I photoinitiators selected from acylphosphine oxides; and

b″ 10 to 15%-by weight, of said at least one photoinitiator belonging to Norrish Type II photoinitiators selected from ketocoumarins.

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (27)