US 2003/0180665 A1Published application

Ionization radiation imageable photopolymer compositions

AssigneeE. I. Du Pont de Nemours and Company

InventorYing Wang

Life of this patent

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Abstract

This invention discloses compositions that can be polymerized/crosslinked imagewise upon exposure to ionization radiation such as x-ray, electron beam, ion beam, and gamma-ray. This invention also discloses methods of use for these compositions for microfabrication of ceramics, for stereolithography, and for x-ray, e-beam, and ion-beam lithography which can be used for photoresists.

Claims31

Dependent claims

A composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of:
47
where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′O— substituent where R′ represents aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
48
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and acetamide;
49
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
and unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
50
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and amino-substituted aliphatic groups, CnH2,+1 and CnH2n−1 (n=1 to 20);
(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of:
(1) linear or branched aliphatic chains, —(CRH)n—, n=1-1000, where R represents an aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
(2) ethylene glycol chains, —(CH2CH2O)n— where n=1-1000;
(3) propylene glycol chains, —(CH(CH3)CH2O)n— where n=1-1000;
(4) cyclohexyl;
and
(5) isocyanurate, C3N3O3;
and
wherein the functional groups are selected from the group consisting of:
(a) acrylates,
51
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
52
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
53
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors.

41 more elements

A composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of:
54
where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′O— substituent where R′ represents aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
55
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and acetamide;
56
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
and unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
57
where R1 and R2 are selected from the group consisting of:
hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and amino-substituted aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of:
(1) linear or branched aliphatic chains, —(CRH)n—, n=1-1000, where R represents an aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
(2) ethylene glycol chains, —(CH2CH2O)n— where n=1-1000;
(3) propylene glycol chains, —(CH(CH3)CH2O)n— where n=1-1000;
(4) cyclohexyl;
and
(5) isocyanurate, C3N3O3;
and
wherein the functional groups are selected from the group consisting of:
(a) acrylates,
58
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
59
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
60
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors;
and
(D) 5 to 90 weight percent of a polymer binder.

43 more elements

A composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of:
61
where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′O— substituent where R′ represents aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
62
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and acetamide;
63
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
and unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
64
where R1 and R2 are selected from the group consisting of:
hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and amino-substituted aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of:
(1) linear or branched aliphatic chains, —(CRH)n—, n=1-1000, where R represents an aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
(2) ethylene glycol chains, —(CH2CH2O)n— where n=1-1000;
(3) propylene glycol chains, —(CH(CH3)CH2O)n— where n=1-1000;
(4) cyclohexyl;
and
(5) isocyanurate, C3N3O3;
and
wherein the functional groups are selected from the group consisting of:
(a) acrylates,
65
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
66
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
67
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors;
(D) 5 to 90 weight percent of a polymer binder;
and
(E) 5 to 90 weight percent of metallic particle or ceramic oxide fillers, said metallic filler is selected from group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb;
said oxide filler is selected from the group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W, and Si.

45 more elements

A composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of:
68
where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′O— substituent where R′ represents aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
69
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and acetamide;
70
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
and unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
71
where R1 and R2 are selected from the group consisting of:
hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and amino-substituted aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of:
(1) linear or branched aliphatic chains, —(CRH)n—, n=1-1000, where R represents an aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
(2) ethylene glycol chains, —(CH2CH2O)n— where n=1-1000;
(3) propylene glycol chains, —(CH(CH3)CH2O)n— where n=1-1000;
(4) cyclohexyl;
and
(5) isocyanurate, C3N3O3;
and
wherein the functional groups are selected from the group consisting of:
(a) acrylates,
72
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
73
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
74
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n−1 to 20);
and
(C) 5-90 weight percent of a polymer binder.

42 more elements

A composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of:
75
where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′— substituent where R′ represents aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
76
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and acetamide;
77
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
and unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
78
where R1 and R2 are selected from the group consisting of:
hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and amino-substituted aliphatic groups, CnH2n+1 n C2n−1 (n=1 to 20);
(B) from 10 to 90 weight percent of a multi functional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone selected from the group consisting of:
(1) linear or branched aliphatic chains, —(CRH)n—, n=1-1000, where R represents an aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
(2) ethylene glycol chains, —(CH2CH2O)n— where n=1-1000,
(3) propylene glycol chains, —(CH(CH3)CH2O)n— where n=1-1000;
(4) cyclohexyl;
and
(5) isocyanurate, C3N3O3;
and wherein the functional groups are selected from the group consisting of:
(a) acrylates,
79
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
80
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
81
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(C) 5 to 90 weight percent of a polymer binder;
and
(D) 5 to 90 weight percent of metallic or oxide fillers, said metallic filler is selected from group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb;
said oxide filler is selected from the group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W, and Si.

43 more elements

Dependencies are inferred from the claim text.

Facts

Application: 10/394,060Filed 21 Mar 2003
Priority: 5 Oct 1998
Published: 25 Sep 2003
Term ends: Not estimatedThe source records don’t support an estimate.

Classification17 codes

G03F 7/027
Photosensitive materials: non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
B33Y 70/10
Materials specially adapted for additive manufacturing: composites of different types of material, e.g. mixtures of ceramics and polymers or…
G03F 7/0037
Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g.…
G03F 7/038
Photosensitive materials: macromolecular compounds which are rendered insoluble or differentially wettable

Family

Application60/103,067Us provisional application · filed 5 Oct 1998
Application09/314,435Division · filed 18 May 1999
Application10/394,060Division · filed 21 Mar 2003
US 6,569,602 B1Related patent
US 6,916,598 B2Related patent
US 2003/0180665 A1This patent

From the US filing history. Foreign family members aren’t listed.

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Abstract

A composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of:
47
where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′O— substituent where R′ represents aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
48
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and acetamide;
49
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
and unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
50
where R1 and R2 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CnH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
and amino-substituted aliphatic groups, CnH2,+1 and CnH2n−1 (n=1 to 20);
(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of:
(1) linear or branched aliphatic chains, —(CRH)n—, n=1-1000, where R represents an aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
(2) ethylene glycol chains, —(CH2CH2O)n— where n=1-1000;
(3) propylene glycol chains, —(CH(CH3)CH2O)n— where n=1-1000;
(4) cyclohexyl;
and
(5) isocyanurate, C3N3O3;
and
wherein the functional groups are selected from the group consisting of:
(a) acrylates,
51
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
52
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
53
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors.

41 more elements

Facts

Application

10/394,060Filed 21 Mar 2003

Priority

5 Oct 1998

Published

25 Sep 2003

Term ends

Not estimatedThe source records don’t support an estimate.

Classification17 codes

G03F 7/027
Photosensitive materials: non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
B33Y 70/10
Materials specially adapted for additive manufacturing: composites of different types of material, e.g. mixtures of ceramics and polymers or…
G03F 7/0037
Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g.…
G03F 7/038
Photosensitive materials: macromolecular compounds which are rendered insoluble or differentially wettable

Family

Application60/103,067Us provisional application · filed 5 Oct 1998

Application09/314,435Division · filed 18 May 1999

Application10/394,060Division · filed 21 Mar 2003

US 6,569,602 B1Related patent

US 6,916,598 B2Related patent

US 2003/0180665 A1This patent

From the US filing history. Foreign family members aren’t listed.