Photocurable polymeric dielectrics and methods of preparation and use thereof

Patent metadata

Field	Value
Publication number	US-9923158-B2
Application number	US-201414467839-A
Country	US
Kind code	B2
Filing date	Aug 25, 2014
Priority date	Nov 24, 2008
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

Disclosed are polymer-based dielectric compositions (e.g., formulations) and materials (e.g. films) and associated devices. The polymers generally include photocrosslinkable pendant groups; for example, the polymers can include one or more coumarin-containing pendant groups.

First claim

What is claimed is:

1. A vinyl polymer, having a formula:

wherein:
Q is -(L″) p -L′″;
L″, at each occurrence, independently is selected from the group consisting of —Y″—, —(Y″) m —O—, —Y″—Si(R 4 ) 2 —, —O—Si(R 4 ) 2 —, and a covalent bond;
L′″ is linked to the coumarin moiety in the formula and is selected from the group consisting of —C(O)—, —C(O)—O—, —O—C(O)—, —C(O)—Y″′—O—, —O—Y″′—C(O)—, —C(O)—Y′″—NR 4 —, —NR 4 —Y′″—C(O)—, —O—S(O) k —, —O—Y′″—S(O) k —, and a covalent bond:
Y″, at each occurrence, is selected from the group consisting of a divalent C 1-6 alkyl group, a divalent C 2-6 alkenyl group, and a divalent C 6-14 aryl group, wherein each of the C 1-6 alkyl group, the C 2-6 alkenyl group, and the C 6-14 aryl group is optionally substituted with 1-5R 5 groups;
Y″′ is selected from the group consisting of a divalent C 1-6 alkyl group, a divalent C 2-6 alkenyl group, and a divalent C 6-14 aryl group, wherein each of the C 1-6 alkyl group, the C 2-6 alkenyl group, and the C 6-14 aryl group is optionally substituted with 1-5R 5 groups;
k is 0, 1, or 2;
m is 1, 2, 3, 4, 5, or 6;
p is an integer in a range from 1 to 10
W″ is selected from the group consisting of a) H, b) a halogen, c) a C 1-20 alkyl group, d) a C 2-20 alkenyl group, e) a C 1-20 haloalkyl group, f) a C 3-14 cycloalkyl group, g) a C 6-14 aryl group, h) a 3 -14 membered cycloalkyl group, and i) a 5-14 membered heteroaryl group, wherein each of the C 1-20 alkyl group, the C 2-20 alkenyl group, the C 1-20 haloalkyl group, the C 3-14 cycloalkyl group, the C 6-14 aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group is optionally substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, —CN, an oxo group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a —C(O)—C 1-6 alkyl group, a —C(O)—C 1-6 haloalkyl group, and a —C(O)—O—C 1-6 alkyl group;
x, x′, x″, and y independently are a real number, wherein 0<x<1.0 ≦x′<1.0≦x″<1.0<y<1 , and x+x′+x″+y=1
n is an integer in a range from 10 to 1,000;
R 1 and R 2 are independently selected from the group consisting of a) H, b) halogen, c) —CN, d) —NO 2 , e) —OR 4 , f) —N(R 4 ) 2 , g) —CHO, h) —C(O)R 4 , i) —C(O)OR 4 , j) —C(O)N(R 4 ) 2 , k) a C 1-20 alkyl group, l) a C 2-20 alkenyl group, m) a C 2-20 alkynyl group, n) a C 1-20 alkoxy group, o) a C 1-20 alkylthio group, p) a C 1-20 haloalkyl group, q) a —Y—C 3-14 cycloalkyl group, r) a —Y—C 6-14 aryl group, s) a —Y-3-14 membered cycloheteroalkyl group, and t) a —Y-5-14membered heteroaryl group, wherein each of the C 1-20 alkyl group, the C 2-20 alkenyl group, the C 2-20 alkynyl group, the Y—C 3-14 cycloalkyl group, the Y—C 6-14 aryl group, the Y-3 -14 membered cycloheteroalkyl group, and the Y-5-14 membered heteroaryl group is optionally substituted with 1-5 R 5 groups;
R 4 , at each occurrence, independently is selected from the group consisting of a) H, b) a C 1-20 alkyl group, c) a C 2-20 alkenyl group, d) a C 2-20 alkynyl group, e) a C 1-20 alkoxy group, f) a C 1-20 alkylthio group, g) a C 1-20 haloalkyl group, h) a —Y—C 3-14 cycloalkyl group, i) a —Y—C 6-14 aryl group, j) a —Y-3-14 membered cycloheteroalkyl group, and k) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-20 alkyl group, the C 2-20 alkenyl group, the C 2-20 alkynyl group, the Y—C 3-14 cycloalkyl group, the Y—C 6-14 aryl group, the Y-3-14membered cycloheteroalkyl group, and the Y-5-14 membered heteroaryl group is optionally substituted with 1-5 R 5 groups;
R 5 , at each occurrence, is independently selected from the group consisting of a) halogen, b) —CN, c) —NO 2 , d) —OH, e) —O—C 6-14 aryl, f) —NH 2 , g) —NH—C 1-10 alkyl, h) alkyl) 2 , —NH—C 6-14 aryl, j) —N(C 1-10 alkyl)-C 6-14 aryl, k) —N(C 6-14 aryl) 2 , l) —CHO, m) —C(O)—C 1-10 alkyl, n) —C(O)—C 6-14 aryl, o) —C(O)OH, p) —C(O)—OC 1-10 alkyl, q) —C(O)—OC 6-14 aryl, r) —C(O)NH 2 , s) —C(O)NH—C 1-10 alkyl, t) —C(O)N(C 1-10 alkyl) 2 , u) —C(O)NH—C 6-14 aryl, v) —C(O)N(C 1-10 alkyl)-C 6-14 aryl, w) —C(O)N(C 6-14 aryl) 2 , x) a C 1-10 alkyl group, y) a C 2-10 alkenyl group, z) a C 2-10 alkynyl group, aa) a C 1-10 alkoxy group, ab) a C 1-10 alkylthio group, ac) a C 1-10 haloalkyl group, ad) a —Y—C 3-14 cycloalkyl group, ae) a —Y—C 6-14 aryl group, af) a —Y-3-14 membered cycloheteroalkyl group, and ag) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-10 alkyl group, the C 2-10 alkenyl group, the C 2-10 alkynyl group, the Y—C 3-14 cycloalkyl group, the Y—C 6-14 aryl group, the Y-3-14 membered cycloheteroalkyl group, and the Y-5-14 membered heteroaryl group is optionally substituted with 1-5 substituents independently selected from the group consisting of a halogen, CN, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a —O—C 1-6 haloalkyl group, a —C(O)—C 1-6 alkyl group, a —C(O)—C 1-6 haloalkyl group, and a —C(O)—O—C 1-6 alkyl group, and
wherein Y, at each occurrence, is a divalent C 1-6 alkyl group, a divalent C 2-6 alkenyl group, a divalent C 2-6 alkenyl group, or a covalent bond.

2. A vinyl polymer, selected from the group consisting of:

wherein n is an integer in a range from 10 to 1,000.

3. The vinyl polymer of claim 1 , having one or more property, selected from the group consisting of:
a dielectric constant between 1.1 and 5.0;
a glass transition temperature (T g ) between about 100° C. and about 200° C.;
a solubility of greater than about 0.1 mg/mL in a solvent selected from the group consisting of anisole, xylene, cyclopentanone, cyclohexane, and cyclohexanone;
a maximum absorbance wavelength in a range of about 250 nm and about 450 nm; and
a weight average molecular weight (Mw) between about 10,000 Da and about 100,000 Da.

4. A method of preparing a dielectric material, the method comprising:
preparing a solution comprising the vinyl polymer of claim 1 ;
depositing the solution onto a substrate to provide a coating; and
exposing the coating to radiation to induce crosslinking and create a crosslinked dielectric material.

5. The vinyl polymer of claim 1 , having the formula:

6. The vinyl polymer of claim 1 , having the formula:

Assignees

• Basf Se
• Flexterra Inc

Inventors

• Quinn Jordan
• Yan He
• Zheng Yan
• Newman Christopher
• Koehler Silke Annika
• Facchetti Antonio
• Breiner Thomas

Classifications

• Y10T428/31938

  Polymer of monoethylenically unsaturated hydrocarbon · CPC title

• C09D125/18 Primary

  Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen · CPC title

• C08F212/32

  containing two or more rings · CPC title

• C08F212/22

  Oxygen · CPC title

• H01B3/447

  from acrylic compounds · CPC title