Dielectric copolymer materials

Patent metadata

Field	Value
Publication number	US-11999893-B2
Application number	US-201917286052-A
Country	US
Kind code	B2
Filing date	Oct 15, 2019
Priority date	Oct 18, 2018
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

Abstract

A polymerizable mixture which can be used to form a dielectric material for the preparation of passivation layers in electronic devices comprises a first monomer and a second monomer which may react to form a copolymer providing excellent film forming capability, excellent thermal properties, and excellent mechanical properties. The polymerizable mixture can be used in a method for forming copolymers and the copolymers can be used in an electronic device as dielectric material. The copolymers can also be used in a manufacturing method for preparing a packaged microelectronic structure and microelectronic devices comprising the packaged microelectronic structure.

First claim

The invention claimed is:

1. A polymerizable mixture comprising:
a first monomer and a second monomer,
wherein the first monomer is one or more selected from formulae M1 to M31:

wherein:
m is an integer from 1 to 60;
P 1 denotes

Sp 1 denotes at each occurrence a spacer group Sp;
Z 21 and Z 22 are independently and at each occurrence independently from each other, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR 01 —, —NR 01 CO—, —NR 01 —CO—NR 02 , —NR 01 —CO—O, —O—CO—NR 01 , —O—CO—NR 01 , —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CH 2 CH 2 —, —(CH 2 ) 4 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 01 —, —CY 01 ═CY 02 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond;
R 01 and R 02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms;
L is Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR xx R yy , —C(═O)OR xx , —C(═O)R xx , —NR xx R yy , —OH, −SF 5 , straight chain alkyl or alkoxy having 1 to 20 C atoms, branched chain alkyl or alkoxy having 3 to 20 C atoms, straight chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy with 2 to 20 C atoms, or branched chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy having 4 to 20 C atoms wherein, in said alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy groups, one or more H atoms are each optionally replaced by F, Cl, —CN, straight chain alkyl or alkoxy having 1 to 6 C atoms, branched chain alkyl or alkoxy having 3 to 6 C atoms, straight chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy with 2 to 6 C atoms, or branched chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy with 4 to 6 C atoms;
R xx and R yy independently of each other denote H or alkyl with 1 to 12 C-atoms;
Y 01 and Y 02 each, independently of one another, denote H, alkyl having 1 to 12 C atoms, aryl, Cl, or CN;
r is 0, 1, 2, 3 or 4;
s is 0, 1, 2 or 3; and
t is 0, 1 or 2;

wherein the second monomer is one or more bi- or multifunctional compounds capable of reacting with the first monomer to give a copolymer, wherein the second monomer is one or more bi- or multifunctional compounds comprising two or more polymerizable groups, P, which are selected from groups containing a C═C double bond, groups containing two conjugated C═C double bonds, nucleophilic groups, and 1,3-dipolar groups.

2. The polymerizable mixture according to claim 1 , wherein the spacer groups Sp are selected from the formula Sp′-X′, so that the radical “P 1 -Sp 1 -” corresponds to the formula “P 1 -Sp′-X′-”,
wherein:
Sp′ denotes
(a) straight chain alkylene having 1 to 40 C atoms or branched chain alkylene having 3 to 40 C atoms, which, in each case, is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH 2 groups may each be replaced, independently of one another, by —O—, —S—, —NH—, —NR 01 , —SiR 01 R 02 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —NR 01 —CO—O—, —O—CO—NR 01 —, —NR 01 —CO—NR 01 —, —CH═CH—, or —C≡C— in such a way that O and/or S atoms are not linked directly to one another, or
(b) -Sp x -G-Sp y -, wherein Sp x and Sp y denote independently of each other alkylene having 1 to 20 C atoms or a single bond; G denotes cycloalkylene having 3 to 20 C atoms which is optionally mono- or polysubstituted by alkyl having 1 to 20 C atoms;
X′ denotes —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 01 —, —NR 01 —CO—, —NR 01 —CO—NR 01 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═C—, —N═N—, —CH═CR 01 —, —CY 01 ═CY 02 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond;
R 01 and R 02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms; and
Y 01 and Y 02 each, independently of one another, denote H, F, Cl or CN.

3. The polymerizable mixture according to claim 1 , wherein the spacer groups Sp are selected from —(CH 2 ) p1 —, —(CH 2 CH 2 O) q1 —CH 2 CH 2 —, —CH 2 CH 2 —S—CH 2 CH 2 —, —CH 2 CH 2 —NH—CH 2 CH 2 —, —(SiR 01 R 02 —O) p1 —, —(CH 2 ) p1 -(cyclo-C 6 H 8 R 01 R 02 )—(CH 2 ) p1 —, and

wherein:
p1 is an integer from 1 to 60;
q1 is an integer from 1 to 12; and
R 01 and R 02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms.

4. The polymerizable mixture according to claim 1 , wherein the second monomer is one or more bi- or multifunctional compound selected from organic compounds, polyhedralsilsesquioxane compounds, and functionalized inorganic nanoparticles.

5. The polymerizable mixture according to claim 1 , wherein the second monomer is one or more of:
(a) an organic compound represented by Formula (4):
Q P 2 ) x   Formula (4),

wherein:
Q denotes a hydrocarbon group having 1 to 50 carbon atoms which may be optionally substituted with one or more substituents L,
wherein L is F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR xx R yy , —C(═O)OR xx , —C(═O)R xx , —NR xx R yy , —OH, —SF 5 , straight chain alkyl or alkoxy having 1 to 20 C atoms, branched chain alkyl or alkoxy having 3 to 20 C atoms, straight chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 2 to 20 C atoms, branched chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 4 to 20 C atoms wherein in the alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy groups one or more H atoms are each optionally replaced by F, Cl, —CN, straight chain alkyl or alkoxy having 1 to 6 C atoms, branched chain alkyl or alkoxy having 3 to 6 C atoms, straight chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 2 to 6 C atom, or branched chain alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 4 to 6 C atoms, and which may optionally contain one or more hetero atom groups selected from N, O and S;
P 2 denotes a polymerizable group P as defined in claim 1 ; and
x is an integer from 2 to 10;
(b) a polyhedralsilsesquioxane compound represented by the following structure:
(R) y-x (SiO 1.5 ) y L-P 2 ) x   Structure (1),

wherein:
R is H, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 6 -C 10 -aryl, or C 1 -C 6 -alkoxy;
L is C 1 -C 12 -alkylene or C 1 -C 12 -oxyalkylene, wherein one or more non-adjacent C atoms may each be replaced, independently of one another, by —SiR 05 R 06 —, wherein R 05 and R 06 each, independently of one another, denote H or alkyl having 1 to 6 C atoms;
P 2 denotes a poly

Assignees

• Merck Patent Gmbh

Inventors

• Larbig Gregor
• Miskiewicz Pawel

Classifications

• C09K19/3895 Primary

  containing two or more mesogenic groups per monomer unit, e.g. polyitaconates, polymaleates · CPC title

• C09K19/408

  Polysiloxanes · CPC title

• C09K2019/0448

  the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate · CPC title

• C09K19/04 Primary

  characterised by the chemical structure of the liquid crystal components {, e.g. by a specific unit} · CPC title

• C09K19/20

  linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters {or ethers} · CPC title