Crystalline photo-polymerizable composition

Claim 2

A SUBSTANTIALLY DRY, PREDOMINANTLY CRYSTALLINE PHOTOIMAGEABLE COMPOSITION IN THE FORM OF A THIN LAYER RANGING FROM ABOUT 1 MICRON TO ABOUT 1 MILLIMETER IN THICKNESS, HAVING SUBSTANTIALLY HOMOGENEOUSLY DISTRIBUTED THERETHROUGH CLOSELY ARRAYED CRYSTALS CONSISTING ESSENTIALLY OF AT LEAST ONE SOLID ETHYLENICALLY UNSATURATED MONOMER MELTING IN THE RANGE 25* TO 100*C. AND CAPABLE OF FORMING A POLYMER HAVING A DEGREE OF POLYMERIZATION OF AT LEAST 10 BY FREERADICAL INITIATED, CHAIN PROPAGATING, ADDITION POLYMERIZATION, AND FOR EACH PART BY WEIGHT OF MONOMER, 0.001 TO 1 PART BY WEIGHT OF AN ORGANIC, LIGHT-SENSITIVE, FREE-RADICAL GENERATING SYSTEM FREE OF ALIPHATIC HALOGEN WHICH INITIATES AND SUBSEQUENTLY DOES NOT TERMINATE THE POLYMERIZATION, AT LEAST ONE COMPONENT OF WHICH HAS AN ACTIVE LIGHT ABSORPTION BAND WITH A MOLAR EXTINCTION COEFFICIENT OF 100 OR MORE MEASURED IN HEXANE IN THE RANGE OF 3300 TO 8000 A, SAID COMPOSITION HAVING A CRYSTALLINITY INDEX OF AT LEAST 0.2, BEING PHOTOPOLYMERIZABLE IN ATMOSPHERIC OXYGEN AND CAPABLE OF YIELDING A PHOTOIMAGE ON RECEIVING LIGHT TOTALLING 2000 $J./SQ.CM. OR LESS, SAID LIGHT BEING ACTIVE TO CAUSE SAID FREE-RADICAL GENERATING SYSTEM TO GENERATE FREE RADICALS.

Claim 3

Michler''s ketone, and

Claim 4

Michler''s ketone, and

Claim 5

A composition according to claim 1 in which the monomer is selected from the group consisting of N-phenyl-N-methyl acrylamide, pentaerythritol tetraacrylate, diacetone acrylamide, N-vinylsuccinimide, 4-acryloxybenzophenone, 1,4-bis(2-acryloxyethyl)benzene, and N-(2-acryloxyethyl)-succinimide.

Claim 6

A composition according to claim 1 in which the monomer is N-phenyl-N-methyl acrylamide.

Claim 7

2-mercaptobenzoxazole.

Claim 8

2-mercaptobenzoxazole.

Claim 9

A composition according to claim 1 in which the monomer is diacetone acrylamide.

Claim 10

A composition according to claim 1 in which the monomer is N-vinylsuccinimide.

Claim 11

A composition according to claim 1 in which the monomer is 1, 4-bis(2-acryloxyethyl)benzene.

Claim 12

A composition according to claim 1 wherein the monomer is acidic or basic and there is included a dye which is complementarily basic or acidic.

Claim 13

A composition according to claim 1 in which the free-radical generating system is selected from the group consisting of benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, alpha methyl benzoin, alpha methyl benzoin methyl ether, benzophenone, 4,4''-bis(dimethylamino)benzophenone, 4,4''-bis(diethylamino)benzophenone, 4-hydroxy-4''-dimethylamino benzophenone, 4-hydroxy-4''-diethylamino benzophenone, 4-acryloxy-4''-dimethylamino benzophenone, 4-acryloxy-4''-diethylamino benzophenone, 4-methoxy-4''-dimethylamino benzophenone, 2,4,5-triarylimidazole dimers and biacetyl.

Claim 14

A composition according to claim 1 wherein the free-radical generating system is a benzoin ether.

Claim 15

A composition according to claim 1 wherein the free-radical generating system is methyl benzoin ether.

Claim 16

A composition according to claim 1 wherein the free-radical generating system is ethyl benzoin ether.

Claim 17

A composition according to claim 1 wherein the free-radical generating system is phenyl benzoin ether.

Claim 18

A composition according to claim 1 wherein the free-radical generating system is alpha methyl benzoin.

Claim 19

A composition according to claim 1 wherein the free-radical generating system is 4,4''-bis(dimethylamino)benzophenone.

Claim 20

A composition according to claim 1 wherein the free-radical generating system is 4,4''-bis(diethylamino)benzophenone.

Claim 21

A composition according to claim 1 wherein the free-radical generating systEm is a 2,4,5-triarylimidazole dimer and 2-mercaptobenzoxazole.

Claim 22

A composition according to claim 1 wherein the free-radical generating system is a 2,4,5-triarylimidazole dimer and 4,4''-bis(dimethylamino)benzophenone.

Claim 23

A composition according to claim 1 wherein the free-radical generating system is 2-mercaptobenzoxazole and 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer.

Claim 24

A composition according to claim 1 comprising N-vinylsuccinimide, 2-mercaptobenzoxazole and 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer.

Claim 25

A substantially dry, predominently crystalline photoimageable composition in the form of a thin layer ranging from about 1 micron to about 1 millimeter in thickness, having substantially homogeneously distributed therethrough closely arrayed crystals consisting essentially of at least one solid ethylenically unsaturated monomer melting about 25*C. and capable of forming a polymer having a degree of polymerization of at least 10 by free-radical initiated, chain propagating, addition polymerization, and for each part by weight of monomer, 0.001 to 1 part by weight of an organic, light-sensitive, free-radical generating system free of aliphatic halogen which initiates and subsequently does not terminate the polymerization, at least one component of which has an active light absorption band with a molar extinction coefficient of 100 or more measured in hexane in the range of 3300 to 8000 A, and for each part by weight of monomer, 0.01 to 0.25 parts by weight of a nonpolymeric normally liquid organic compound which does not inhibit the polymerization of the monomer and does not absorb so much of the active incident light as to prevent the initiation of the polymerization by the free-radical generating system, said composition having a crystallinity index of at least 0.2, being photopolymerizable in atmospheric oxygen and capable of yielding a photoimage on receiving light totalling 2000 Mu j./sq.cm. or less, said light being active to cause said free-radical generating system to generate free radicals.

Claim 26

A substantially dry, predominently crystalline photoimageable composition in the form of a thin layer ranging from about 1 micron to about 1 millimeter in thickness, having substantially homogeneously distributed therethrough closely arrayed crystals consisting essentially of at least one solid ethylenically unsaturated monomer melting about 25*C. and capable of forming a polymer having a degree of polymerization of at least 10 by free-radical initiated, chain propagating, addition polymerization, and for each part by weight of monomer, 0.001 to 1 part by weight of an organic, light-sensitive, free-radical generating system free of aliphatic halogen which initiates and subsequently does not terminate the polymerization, at least one component of which has an active light absorption band with a molar extinction coefficient of 100 or more measured in hexane in the range of 3300 to 8000 A, and for each part by weight of monomer, 0.01 to 0.25 parts by weight of a nonpolymeric normally liquid organic compound which does not inhibit the polymerization of the monomer and does not absorb so much of the active incident light as to prevent the initiation of the polymerization by the free-radical generating system, said composition having a crystallinity index of at least 0.2, being photopolymerizable in atmospheric oxygen and capable of yielding a photoimage on receiving light totalling 2000 Mu j./sq.cm. or less, said light being active to cause said free-radical generating system to generate free radicals.

Claim 27

A composition according to claim 20 wherein at least one monomer is acidic or basic and there is included a dye which is complementarily basic or acidic.

Claim 28

A composition according to claim 20 comprising N-vinylsuccinimide, 2-mercaptobenzoxazole, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer and hexamethylene diacrylate.

Claim 29

A substantially dry, predominantly crystalline photoimageable composition in the form of a thin layer ranging from about 1 micron to about 1 millimeter in thickness, having substantially homogeneously distributed therethrough closely arrayed crystals consisting essentially of at least one nongaseous ethylenically unsaturated monomer capable of forming a polymer having a degree of polymerization of at least 10 by free-radical initiated, chain propagating, addition polymerization, and for each part by weight of monomer, 0.001 to 5 parts by weight of an organic, light-sensitive, free-radical generating system free of aliphatic halogen which initiates and subsequently does not terminate the polymerization, at least one component of which has an active light absorption band with a molar extinction coefficient of 100 or more measured in hexane in the range of 3300 to 8000 A, and for each part by weight of monomer, 0.01 to 250 parts by weight of a nonpolymerizable crystalline organic solid which melts in the range 25*-200*C., does not inhibit the polymerization of the monomer, and does not absorb so much of the active incident light as to prevent the initiation of the polymerization by the free-radical generating system, with the proviso that the free-radical generating system does not exceed 50% by weight of the combined weight of monomer, free-radical generating system and crystalline solid, said composition having a crystallinity index of at least 0.2 and capable of yielding a photoimage on receiving light totalling 2000 Mu j./sq.cm. or less, said light being active to cause said free-radical generating system to generate free radicals.

Claim 30

A substantially dry, predominantly crystalline photoimageable composition in the form of a thin layer ranging from about 1 micron to about 1 millimeter in thickness, having substantially homogeneously distributed therethrough closely arrayed crystals consisting essentially of at least one nongaseous ethylenically unsaturated monomer capable of forming a polymer having a degree of polymerization of at least 10 by free-radical initiated, chain propagating, addition polymerization, and for each part by weight of monomer, 0.001 to 5 parts by weight of an organic, light-sensitive, free-radical generating system free of aliphatic halogen which initiates and subsequently does not terminate the polymerization, at least one component of which has an active light absorption band with a molar extinction coefficient of 100 or more measured in hexane in the range of 3300 to 8000 A, and for each part by weight of monomer, 0.01 to 250 parts by weight of a nonpolymerizable crystalline organic solid which melts in the range 25*-200*C., does not inhibit the polymerization of the monomer, and does not absorb so much of the active incident light as to prevent the initiation of the polymerization by the free-radical generating system, with the proviso that the free-radical generating system does not exceed 50% by weight of the combined weight of monomer, free-radical generating system and crystalline solid, said composition having a crystallinity index of at least 0.2 and capable of yielding a photoimage on receiving light totalling 2000 Mu j./sq.cm. or less, said light being active to cause said free-radical generating system to generate free radicals.

Claim 31

A composition according to claim 23 wherein the composition is photopolymerizable in air and the monomer is a liquid.

Claim 32

A composition according to claim 23 wherein the composition is photopolymerizable in an inert atmosphere and the monomer is a liquid.

Claim 33

A composition according to claim 23 wherein the crystalline solid is selected from the group consisting of bibenzyl, biphenyl, pentamethylbenzene, p-diethoxybenzene, diphenoxyethane, cyclododecanol, 1,12-dodecanediol and octacosane.

Claim 34

A composition according to claim 23 wherein the crystalline solid is 1,2-diphenoxyethane.

Claim 35

A composition according to claim 23 wherein the crystalline solid is biphenyl.

Claim 36

A composition according to claim 23 wherein the crystalline solid is 1,2-diphenoxyethane and the monomer is selected from the group consisting of pentaerythritol triacrylate, N-(2-acryloxyethyl)succinimide, pentaerythritol tetraacrylate, 1,4-bis(2-acryloxyethyl)benzene and 4-acryloxybenzophenone.

Claim 37

A composition according to claim 23 wherein the crystalline solid is p-diethoxybenzene.

Claim 38

A composition according to claim 23 wherein the crystalline solid is cyclododecanol and the monomer is pentaerythritol triacrylate.

Claim 39

A composition according to claim 23 wherein the crystalline solid is octacosane and the monomer is pentaerythritol triacrylate.

Claim 40

A composition according to claim 23 comprising ethylene diacrylate, 4-acryloxy-4''-diethylaminobenzophenone, 2-mercaptobenzoxazole, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer, 4,4''-bis(diethylamino)benzophenone, and cyclododecanol.

Claim 41

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer, 2-mercaptobenzoxazole, 2,5-bis(p-diethylaminobenzylidene)cyclopentanone, 4-acryloxy-4''-diethylaminobenzophenone.

Claim 42

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer, 2-mercaptobenzoxazole, Michler''s ketone, and 3-acryloxybenzophenone.

Claim 43

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer, 2-mercaptobenzoxazole, 3-acryloxybenzophenone, and 4-dimethylamino-4''-(N-n-propyl-N-isoamylamino)benzophenone.

Claim 44

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazole dimer, 2-mercaptobenzoxazole, and 1,4-bis(2-acryloxyethyl)benzene.

Claim 45

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)-imidazole dimer, 2-mercaptobenzoxazole, 4-dimethylamino-4''-(N-n-propyl-N-isoamylamino)benzophenone, and 1,4-bis(2-acryloxyethyl)benzene.

Claim 46

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)-imidazole dimer, 2-mercaptobenzoxazole, Michler''s ketone, 2-o-chlorophenyl-4,5-diphenylimidazole dimer, and 3-acryloxybenzophenone.

Claim 47

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)-imidazole dimer, 2-mercaptobenzoxazole, Michler''s ketone, 2-o-chlorophenyl-4,5-diphenylimidazole dimer, and 4-acryloxybenzophenone.

Claim 48

A composition According to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)-imidazole dimer, 2-mercaptobenzoxazole, Michler''s ketone, and 2, 4-diacryloxybenzophenone.

Claim 49

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)-imidazole dimer, 2-mercaptobenzoxazole, Michler''s ketone, and N-(2-acryloxypropyl)succinimide.

Claim 50

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-di(m-methoxyphenyl)-imidazole dimer, 2-o-chlorophenyl-4,5-diphenylimidazole dimer, 2-mercaptobenzoxazole, and 4-acryloxydiphenylmethane.

Claim 51

A composition according to claim 23 comprising 1,2-diphenoxyethane, 2-o-chlorophenyl-4,5-(di-m-methoxyphenyl)-imidazole dimer, 2-o-chlorophenyl-4,5-diphenylimidazole dimer, 4, 4''-bis(dimethylamino)benzophenone, 2-mercaptobenzoxazole, N-(2-acryloxy-n-propyl)succinimide, and 2-phenyl-2-(p-acryloxyphenyl)propane.

Claim 52

A composition according to claim 23 wherein a. the unsaturated monomer has the formula

Claim 53

A composition according to claim 45 containing 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

Claim 54

A composition according to claim 46 containing 1,2-diphenoxyethane.

Claim 55

A composition according to claim 47 containing p( Alpha , Alpha -dimethylbenzyl)phenyl acrylate.

Claim 56

A composition according to claim 47 containing p-( Alpha , Alpha -dimethylbenzyl)phenyl methacrylate.

Claim 57

A composition according to claim 23 wherein the monomer is acidic or basic and there is included a dye which is complementarily basic or acidic.

Claim 58

A composition according to claim 50 comprising 6-acrylamidocaproic acid, benzoin methyl ether and crystal violet dye.

Claim 59

The process of photopolymerization comprising exposing a crystalline composition of claim 1 to light having a wavelength of 2000 to 8000 A.

Claim 60

The process of photopolymerization comprising exposing a crystalline composition of claim 20 to light having a wavelength of 2000 to 8000 A.

Claim 61

The process of photopolymerization comprising exposing a crystalline composition of claim 23 to light having a wavelength of 2000 to 8000 A.

Claim 62

The process of photopolymerization comprising exposing a crystalline composition of claim 1 to light having a wavelength of 2000 to 8000 A to form an image and then developing the image by volatilizing unreacted components.

Claim 63

The process of photopolymerization comprising exposing a crystalline composition of claim 20 to light having a wavelength of 2000 to 8000 A to form an image and then developing the image by volatilizing unreacted components.

Claim 64

The process of photopolymerization comprising exposing a crystalline composition of claim 23 to light having a wavelength of 2000 to 8000 A to form an image and then developing the image by volatilizing unreacted components.

Claim 65

The process of photopolymerization comprising exposing a crystalline composition of claim 7 to light having a wavelength of 2000 to 8000 A.

Claim 66

The process of photopolymerization comprising exposing a crystalline composition of claim 21 to light having a wavelength of 2000 to 8000 A.

Claim 67

The process of photopolymerization comprising exposing a crystalline composition of claim 50 to light having a wavelength of 2000 to 8000 A.

Claim 68

A composition according to claim 1 on a sUpport.

Claim 69

A composition according to claim 1 on a support comprising a conductive metal layer.

Claim 70

A composition according to claim 1 on a support comprising a conductive metal layer one surface of which is in contact with a coextensive surface of an insulating layer.

Claim 71

A composition according to claim 20 on a support.

Claim 72

A composition according to claim 20 on a support comprising a conductive metal layer.

Claim 73

A composition according to claim 20 on a support comprising a conductive metal layer one surface of which is in close contact with a coextensive surface of an insulating layer.

Claim 74

A composition according to claim 23 on a support.

Claim 75

A composition according to claim 23 on a support comprising a conductive metal layer.

Claim 76

A composition according to claim 23 on a support comprising a conductive metal layer one surface of which is in close contact with a coextensive surface of an insulating layer.

Claim 77

An assembly comprising a support sheet, a layer of a crystalline composition according to claim 1 one surface of which is adhered to the support sheet, and a transparent sheet adhered to the other surface of the crystalline layer, the said crystalline layer having better adhesion to the support sheet than to the transparent sheet.

Claim 78

An assembly comprising a support sheet, a layer of a crystalline composition according to claim 20 one surface of which is adhered to the support sheet, and a transparent sheet adhered to the other surface of the crystalline layer, the said crystalline layer having better adhesion to the support sheet than to the transparent sheet.

Claim 79

An assembly comprising a support sheet, a layer of a crystalline composition according to claim 23 one surface of which is adhered to the support sheet, and a transparent sheet adhered to the other surface of the crystalline layer, the said crystalline layer having better adhesion to the support sheet than to the transparent sheet.

Claim 80

A composition according to claim 70 wherein the crystalline layer contains pigment particles.

Claim 81

A composition according to claim 71 wherein the crystalline layer contains pigment particles.

Claim 82

A composition according to claim 72 wherein the crystalline layer contains pigment particles.

Claim 83

The process of adhesion comprising placing a crystalline composition of claim 1 in contacting relationship with two substrates and exposing the said crystalline composition to light having a wavelength of 2000 to 8000 A.

Claim 84

A composition according to claim 1 capable of yielding a photoimage on receiving light totalling 1000 Mu j./sq.cm. or less.

Claim 85

A composition according to claim 20 capable of yielding a photoimage on receiving light totalling 1000 Mu j./sq.cm. or less.

Claim 86

A composition according to claim 23 capable of yielding a photoimage on receiving light totalling 1000 Mu j./sq.cm. or less.