Ternary photoinitiator system for curing of epoxy/polyol resin compositions

Claim 2

A photopolymerizable composition comprising: (a) an epoxy resin; (b) a hydroxyl-containing material; and (c) a photoinitiator system comprising: (i) an iodonium salt; (ii) a visible light sensitizer; and (iii) an electron donor compound, wherein the photoinitiator system has a photoinduced potential greater than or equal to that of 3-dimethylamino benzoic acid in a standard solution of 2.9×10 -5 moles/g diphenyl iodonium hexafluoroantimonate and 1.5×10 -5 moles/g camphorquinone in 2-butanone.

Claim 3

The composition of claim 1 wherein the donor compound is described by the following structural formula: ##STR6## wherein R 1 are independently H; C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, COOH, COOC 1-18 alkyl, (C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, or SO 3 R 2 ; or aryl that is optionally substituted by one or more electron withdrawing groups, where R 2 is H; C 1-18 alkyl that is optionaly substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, COOH, COOC 1-18 alkyl, (C 1-18 alkyl( 0-1 -CO--C 1-18 alkyl, or SO 3 H,; or R 1 is aryl that is optionally substituted by one or more electron withdrawing groups; or the R 1 groups together may form a ring; and Ar is aryl that is substituted by one or more electron withdrawing groups.

Claim 4

The composition of claim 2 wherein the aryl group is substituted by one or more carboxylic acid, carboxylic acid ester, ketone, aldehyde, sulfonic acid, sulfonate, or nitrile groups.

Claim 5

The composition of claim 2 wherein the aryl group is substituted by one or more moieties selected from the group consisting of --COOH, --COOC 1-18 alky, --SO 3 R 2 , --CN, --CO--C 1-18 alkyl and --C(O)H groups, where R 2 is H, C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, COOH, COOC 1-18 alkyl, (C 1-18 alkyl) 0-1 --CO--C 1-18 alkyl, SO 3 H, CN or halogen groups, or aryl that is optionally substituted by one or more electron withdrawing groups.

Claim 6

The composition of claim 1 wherein the donor compound is selected from the group consisting of 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid, 4-dimethylaminobenzoin, 4-dimethylaminobenzaldehyde, 4-dimethylaminobenzonitrile and 1,2,4-trimethoxybenzene.

Claim 7

The composition of claim 1 wherein the donor compound is an alkyl, aryl polyether.

Claim 8

The composition of claim 1 wherein the donor compound is an alkyl, aryl polyether having the structural formula: ##STR7## wherein n=1-3 each R 3 is independently H or C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, substituted aryl, --COOH, --COOC 1-18 alkyl, --(C 1-18 alkyl) 0-1 -COH, --(C 1-18 alkyl) 0-1 CO--C 1-18 alkyl, --CO--C 1-18 alkyl, --C(O)H or --C 2-18 alkenyl groups, or the R 3 groups together may form a ring and each R 4 can be C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, substituted aryl, --COOH, --COOC 1-18 alkyl, --(C 1-18 alkyl) 0-1 -COH, --(C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, --CO--C 1-18 alky, C(O)H or --C 2-18 alkenyl groups.

Claim 9

The composition of claim 1 wherein the iodonium salt is an aryl iodonium salt.

Claim 10

The composition of claim 1 wherein the iodonium salt comprises diphenyliodonium chloride, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, or a mixture thereof.

Claim 11

The composition of claim 1 wherein the sensitizing compound comprises a ketone.

Claim 12

The composition of claim 1 wherein the sensitizing compound comprises an alphadiketone.

Claim 13

The composition of claim 1 wherein the sensitizing compound comprises a ketocoumarin, aminoarylketone, or a para-substituted aminostyrylketone compound.

Claim 14

The composition of claim 1 wherein the sensitizing compound comprises camphorquinone.

Claim 15

The composition of claim 1 wherein the composition cures to a tack-free gel within 60 seconds after exposure to visible light.

Claim 16

The composition of claim 1 wherein the epoxy resin comprises a cycloaliphatic epoxide or diepoxide.

Claim 17

The composition of claim 1 wherein the epoxy resin comprises a bisphenol-A diepoxide.

Claim 18

The composition of claim 1 wherein the epoxy resin contains ethylenic unsaturation.

Claim 19

The composition of claim 1 further comprising an ethylenically unsaturated compound.

Claim 20

The composition of claim 16 wherein the ethylenically unsaturated compound is an ester of acrylic acid or methacrylic acid.

Claim 21

The composition of claim 16 wherein the ethylenically unsaturated compound comprises methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethyleneglycol diacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexacrylate or a mixture thereof.

Claim 22

A photopolymerizable composition comprising: (a) an epoxy resin; (b) a hydroxyl-containing material; and (c) a photoinitiator system comprising: (i) a diaryliodonium hexafluoroantimonate or diaryliodonium hexafluorophosphate; (ii) camphorquinone and (iii) an electron donor described by the following structural formula: ##STR8## wherein R 1 are independently H; C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, COOH, COOC 1-18 alkyl, (C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, or SO 3 R 2 ; or aryl that is optionally substituted by one or more electron withdrawing groups; where R 2 is H; C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, COOH, COOC 1-18 alkyl, (C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, or SO 3 H,; or R 1 is aryl that is optionally substituted by one or more electron withdrawing groups; or the R 1 groups together may form a ring; and Ar is aryl that is substituted by one or more electron withdrawing groups.

Claim 23

A photopolymerizable composition comprising: (a) an epoxy resin; (b) a hydroxyl-containing material; and (c) a photoinitiator system comprising: (i) a diaryliodonium hexafluoroantimonate or diaryliodonium hexafluorophosphate; (ii) camphorquinone and (iii) an electron donor described by the following structural formula: ##STR8## wherein R 1 are independently H; C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, COOH, COOC 1-18 alkyl, (C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, or SO 3 R 2 ; or aryl that is optionally substituted by one or more electron withdrawing groups; where R 2 is H; C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, COOH, COOC 1-18 alkyl, (C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, or SO 3 H,; or R 1 is aryl that is optionally substituted by one or more electron withdrawing groups; or the R 1 groups together may form a ring; and Ar is aryl that is substituted by one or more electron withdrawing groups.

Claim 24

A photopolymerizable composition comprising: (a) an epoxy resin; (b) a hydroxyl-containing material; and (c) a photoinitiator system comprising: (i) a diaryliodonium hexafluoroantimonate or diaryliodonium hexafluorophosphate; (ii) camphorquinone and (iii) an electron donor described by the following structural formula: ##STR9## wherein n=1-3 each R 3 is independently H or C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, substituted aryl, --COOH, --COOC 1-18 alkyl, --(C 1-18 alkyl) 0-1 -COH, --(C 1-18 alkyl 0-1 -CO--C 1-18 alkyl, --CO--C 1-18 alkyl, --C(O)H or --C 2-18 alkenyl groups, or the R 3 groups together may form a ring and each R 4 can be C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, substituted aryl, --COOH, --COOC 1-18 alkyl, --(C 1-18 alkyl) 0-1 -COH, --(C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, --CO--C 1-18 alkyl, --C(O)H or --C 2-18 alkenyl groups.

Claim 25

A photopolymerizable composition comprising: (a) an epoxy resin; (b) a hydroxyl-containing material; and (c) a photoinitiator system comprising: (i) a diaryliodonium hexafluoroantimonate or diaryliodonium hexafluorophosphate; (ii) camphorquinone and (iii) an electron donor described by the following structural formula: ##STR9## wherein n=1-3 each R 3 is independently H or C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, substituted aryl, --COOH, --COOC 1-18 alkyl, --(C 1-18 alkyl) 0-1 -COH, --(C 1-18 alkyl 0-1 -CO--C 1-18 alkyl, --CO--C 1-18 alkyl, --C(O)H or --C 2-18 alkenyl groups, or the R 3 groups together may form a ring and each R 4 can be C 1-18 alkyl that is optionally substituted by one or more halogen, --CN, --OH, --SH, C 1-18 alkoxy, C 1-18 alkylthio, C 3-18 cycloalkyl, aryl, substituted aryl, --COOH, --COOC 1-18 alkyl, --(C 1-18 alkyl) 0-1 -COH, --(C 1-18 alkyl) 0-1 -CO--C 1-18 alkyl, --CO--C 1-18 alkyl, --C(O)H or --C 2-18 alkenyl groups.

Claim 28

The method of claim 23 wherein the composition additionally comprises an ethylenically unsaturated compound.

Claim 29

A photopolymerizable dental composition comprising: (a) an epoxy resin; (b) a hydroxyl-containing material; and (c) a photoinitiator system comprising: (i) an iodonium salt; (ii) a visible light sensitizer; and (iii) an electron donor compound, wherein the photoinitiator system has a photoinduced potential of at least about 100 mV relative to a standard solution of 2.9×10 -5 moles/g diphenyl iodonium hexafluoroantimonate and 1.5×10 -5 moles/g camphorquinone in 2-butanone.

Claim 30

A photopolymerizable dental composition comprising: (a) an epoxy resin; (b) a hydroxyl-containing material; and (c) a photoinitiator system comprising: (i) an iodonium salt; (ii) a visible light sensitizer; and (iii) an electron donor compound, wherein the photoinitiator system has a photoinduced potential of at least about 100 mV relative to a standard solution of 2.9×10 -5 moles/g diphenyl iodonium hexafluoroantimonate and 1.5×10 -5 moles/g camphorquinone in 2-butanone.

Claim 31

A composition of claim 25, wherein said composition is a dental adhesive composition.

Claim 32

A composition of claim 25, wherein said composition is a dental composite material composition.

Claim 33

A composition of claim 25, wherein said composition is a dental sealant composition.

Claim 34

A composition of claim 25, wherein said composition is an orthodontic adhesive composition.

Claim 35

A composition of claim 1, wherein said composition is a graphic arts imaging composition.

Claim 36

A composition of claim 1, wherein said composition is selected from the group consisting of photoresist compositions, solder mask compositions electronic conformal coating compositions, coated abrasive compositions and magnetic media compositions.