US 6,569,602 B1Granted

Ionization radiation imageable photopolymer compositions

AssigneeE. I. Du Pont de Nemours and Company

InventorYing Wang

Life of this patent

Estimating the term…

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.

Claims19

Dependent claims

A light stable 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:
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);
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;
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);
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,
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
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.

34 more elements

A light stable 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:
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);
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 CnH2−1 (n=1 to 20);
and acetamide;
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);
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,
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,
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
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.

35 more elements

A light stable 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:
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);
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;
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);
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,
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,
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2−1 (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.

38 more elements

A light stable 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:
where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen;
aliphatic groups CnH2n+1 and CH2n−1 (n=1 to 20);
unsaturated aliphatic groups CnH2n−1 (n=1 to 20);
aliphatic groups with aide or acrylamide substituent, and aliphatic groups with R′O— substituent where R′ represents aliphatic group, CnH2n+1 and CnH2n−1 (n=1 to 20);
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 CnH2−1 (n=1 to 20);
and acetamide;
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);
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,
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,
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
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.

34 more elements

A light stable 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:
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);
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 CnH2−1 (n=1 to 20);
and acetamide;
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);
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 CnH2−1 (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 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,
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,
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
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.

36 more elements

Dependencies are inferred from the claim text.

Facts

Application: 09/314,435Filed 18 May 1999 · us provisional application
Priority: 5 Oct 1998
Granted: 27 May 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
US 6,569,602 B1This patent

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

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Abstract

A light stable 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:
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);
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;
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);
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,
where R1, R2, and R3 are selected from the group consisting of hydrogen and aliphatic groups, CnH2n+1 and CnH2−1 (n=1 to 20);
(b) carboxylic acid, —COOH;
(c) epoxides,
where R1, R2, and R3 are selected from:
hydrogen or aliphatic groups, CnH2n+1 and CnH2n−1 (n=1 to 20);
and
(d) vinyls,
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.

34 more elements

Facts

Application

09/314,435Filed 18 May 1999 · us provisional application

Priority

5 Oct 1998

Granted

27 May 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