DIELECTRIC COPOLYMER MATERIALS

Abstract

The present invention relates to a polymerizable mixture which can be used to form a dielectric material for the preparation of passivation layers in electronic devices. The polymerizable mixture 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. There is further provided a method for forming said copolymers and an electronic device containing said copolymers as dielectric material. Beyond that, the present invention relates to a manufacturing method for preparing a packaged microelectronic structure and to a microelectronic device comprising said packaged microelectronic structure formed by said manufacturing method.

Claims

1. Polymerizable mixture comprising a first monomer and a second monomer, wherein the first monomer is one or more compound represented by Formula (1), and wherein the second monomer is one or more bi- or multifunctional compound capable of reacting with the first monomer to give a copolymer:
P.sup.1-Sp.sup.1-(MG-Sp.sup.1).sub.m-P.sup.1   Formula (1) wherein: m is an integer from 1 to 60; P.sup.1 denotes ##STR00053## Sp.sup.1 denotes at each occurrence a spacer group (Sp) or a single bond; MG is a rod-shaped mesogenic group, which is preferably selected from Formula (2):
-(A.sup.21-Z.sup.21).sub.k-A.sup.22-(Z.sup.22-A.sup.23).sub.l-   Formula (2) wherein: A.sup.21 to A.sup.23 are independently and at each occurrence independently of one another an aryl group, heteroaryl group, heterocyclic group, alicyclic group or cyclic imide group optionally being substituted by one or more identical or different groups L; Z.sup.21 and Z.sup.22 are independently and at each occurrence independently from each other, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR.sup.01—, —NR.sup.01—C)—, —NR.sup.01—CO—NR.sup.02, —NR.sup.01—CO—O—, —O—CO—NR.sup.01——OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S.sup.—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S.sup.—, —SCF.sub.2.sup.—, —CH.sub.2CH.sub.2—, —(CH.sub.2).sub.4—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═N—, —N═CH—, —N═N—, —CH═CR.sup.01—, —CY.sup.01═CY.sup.02—, —C≡C—, —CH′CH—COO—, —OCO—CH═CH—, or a single bond; R.sup.01 and R.sup.02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms; L is F, Cl, Br, I, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR.sup.xxR.sup.yy, —C(═O)OR.sup.xx, —C(═O)R.sup.xx, —NR.sup.xxR.sup.yy, —OH, —SF.sub.5, or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, —CN or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 6 C atoms; R.sup.xx and R.sup.yy independently of each other denote H or alkyl with 1 to 12 C-atoms; Y.sup.01 and Y.sup.02 each, independently of one another, denote H, alkyl having 1 to 12 C atoms, aryl, F, Cl, or CN; and k and l are each and independently 0, 1, 2, 3 or 4.

2. Polymerizable mixture according to claim 1, wherein the spacer groups Sp are selected from the formula Sp′-X′, so that the radical “P.sup.1-Sp.sup.1-” corresponds to the formula “P.sup.1-Sp′-X′-”, wherein: Sp′ denotes (a) straight chain or branched chain alkylene having 1 to 40, preferably 1 to 30 C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by —O—, —S—, —NH—, —NR.sup.01—, —CO—, —COO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —NR.sup.01—CO—O—, ——O—CO—NR.sup.01—, —NR.sup.01—CO—NR.sup.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.sup.x-G-Sp.sup.y-, wherein Sp.sup.x and Sp.sup.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.sup.01—, —NR.sup.01—CO—, —NR.sup.01—CO—NR.sup.01—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═N—, —N═C—, —N═N—, —CH═CR.sup.01—, —CY.sup.01=CY.sup.02—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond; R.sup.01 and R.sup.02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms; and Y.sup.01 and Y.sup.02 each, independently of one another, denote H, F, Cl or CN.

3. Polymerizable mixture according to claim 1, wherein the spacer groups Sp are selected from the list consisting of —(CH.sub.2).sub.p1—, —(CH.sub.2CH.sub.2O).sub.q1—CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2—S—CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2—NH—CH.sub.2CH.sub.2—, —(SiR.sup.01R.sup.02—O).sub.p1—, —(CH.sub.2).sub.p1—(cyclo-C.sub.6H.sub.8R.sup.01R.sup.02)—(CH.sub.2).sub.p1—, and ##STR00054## wherein: p1 is an integer from 1 to 60; q1 is an integer from 1 to 12; and R.sup.01 and R.sup.02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms.

4. Polymerizable mixture according to claim 1, wherein A.sup.21 to A.sup.23 denote independently and, in case of multiple occurrence, independently of one another, a moiety selected from the following groups a) to e): a) trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 4,4′-bicyclohexylene, in which one or more non-adjacent CH.sub.2 groups may be replaced by —O— and/or —S— and wherein one or more H atoms may be replaced by a group L; b) 1,4-phenylene, 1,3-phenylene, 4,4′-biphenylene, 2,5-thiphene and 2,6-dithieno[3,2-b:2′,3′-d]thiophene in which one or two CH groups may be replaced by N and where one or more H atoms may be replaced by a group L; c) tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobut-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophen-2,5-diyl, which may be substituted one or more groups L; d) saturated, partially unsaturated or completely unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, of which one or more can also be replaced by heteroatoms, preferably selected from the group consisting of bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, ##STR00055## ##STR00056## where one or more H atoms may be replaced by a group L, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N, and where M denotes —O—, —S—, —CH.sub.2—, —CHY.sup.03— or —CY.sup.03Y.sup.04—; Y.sup.03, Y.sup.04 denote independently of each other one of the meanings given above for R.sup.01, F, Cl, CN, OCF.sub.3 or CF.sub.3, and preferably H, F, Cl, CN, OCF.sub.3 or CF.sub.3; W.sup.5, W.sup.6 denote independently of each other —CH.sub.2CH.sub.2—, —CH═CH—, —CH.sub.2—O—, —O—CH.sub.2—, —C(R.sup.cR.sup.d)— or —O—; R.sup.c, R.sup.d denote independently of each other H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl; and R.sup.03, R.sup.04 denote independently of each other H, F, straight chain or branched chain alkyl having 1 to 12 C atoms where one or more H atoms may be replaced by F; e) cyclic imides selected from the group consisting of: ##STR00057## where one or more H atoms may be replaced by a group L, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N.

5. 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.

6. Polymerizable mixture according to claim 1, wherein the second monomer is one or more bi- or multifunctional compound comprising two or more polymerizable groups (P) which are selected from groups containing a C═C double bond, which preferably react with P.sup.1 in a radical or ionic chain polymerization or in a 2+2 cycloaddition, groups containing two conjugated C═C double bonds, which preferably react with P.sup.1 in a 4+2 cycloaddition, nucleophilic groups ,which preferably react with P.sup.1 in a nucleophilic addition, and 1,3-dipolar groups, which preferably react with P.sup.1 in a 1,3-dipolar cycloaddition.

7. Polymerizable mixture according to claim 6, wherein the second monomer is one or more of: (a) an organic compound represented by Formula (4):
QP.sup.2).sub.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.sub.2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR.sup.xxR.sup.yy, —C(═O)OR.sup.xx, —C(═O)R.sup.xx, —NR.sup.xxR.sup.yy, —OH, —SF.sub.5, or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or aloxycarbonyloxy with 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, —CN or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonloxy with 1 to 6 C atoms, and which may optionally contain one or more hetero atom groups selected from N, O and S; P.sup.2 denotes a polymerizable group (P) as defined in claim 6; and x is an integer from 2 to 10; (b) a polyhedralsilsesquioxane compound represented by the following structure:
(R).sub.y-x(SiO.sub.1.5).sub.yL-P.sup.2).sub.x   Structure (1), wherein: R is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.6-C.sub.10-aryl, or C.sub.1-C.sub.6-alkoxy; L is C.sub.1-C.sub.12-alkylene or C.sub.1-C.sub.12-oxyalkylene, wherein one or more non-adjacent C atoms may be replaced, independently of one another, by —SiR.sup.05R.sup.06—, wherein R.sup.05 and R.sup.06 each, independently of one another, denote H or alkyl having 1 to 6 C atoms; P.sup.2 denotes a polymerizable group (P) as defined in claim 6; y is an integer from 6 to 12; and x is an integer from 2 to 12, wherein y-x≥0; or (c) a functionalized inorganic nanoparticle which comprises polymerizable groups P.sup.2 on its surface, wherein: P.sup.2 denotes a polymerizable group (P) as defined in claim 6.

8. Method for forming a copolymer comprising the following steps: (i) providing a polymerizable mixture according to claim 7; and (ii) polymerizing said polymerizable mixture to obtain a copolymer.

9. Method for forming a copolymer according to claim 8, wherein the polymerizable mixture further comprises one or more radical initiators.

10. Copolymer, obtainable by the method for forming a copolymer according to claim 8.

11. Copolymer comprising at least one repeating unit which is derived from the first monomer and at least one repeating unit which is derived from the second monomer as defined in claim 1.

12. Copolymer according to claim 11, wherein the repeating unit derived from the first monomer comprises a structural unit represented by Formula (5):
[-Sp.sup.1-(MG-Sp.sup.1).sub.m-]  Formula (5) wherein Sp.sup.1, MG and m are defined as in claim 1.

13. Electronic device comprising a copolymer according to claim 10.

14. Electronic device according to claim 13, wherein the copolymer forms a dielectric layer.

15. Manufacturing method for preparing a packaged microelectronic structure, in which a substrate is provided with a dielectric layer, wherein the method comprises the following steps: (1) applying a polymerizable mixture according to claim 1 to a surface of a substrate; and (2) curing said polymerizable mixture to form a dielectric layer.

16. Manufacturing method for preparing a packaged microelectronic structure according to claim 15, wherein the polymerizable mixture further comprises one or more radical initiators.

17. Microelectronic device comprising a packaged microelectronic structure obtainable by the manufacturing method according to claim 15.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0066] FIG. 1: Cross-sectional view of fan-in and fan-out WLP with die (1) and fan-out area (2).

DETAILED DESCRIPTION

[0067] Definitions

[0068] The term “liquid crystal”, “mesomorphic compound”, or “mesogenic compound” (also shortly referred to as “mesogen”) means a compound that under suitable conditions of temperature, pressure and concentration can exist as a mesophase or in particular as a LC phase. Non-amphiphilic mesogenic compounds comprise for example one or more calamitic, banana-shaped or discotic mesogenic groups.

[0069] The term “calamitic” means a rod- or board/lath-shaped compound or group. The term “banana-shaped” means a bent group in which two, usually calamitic, mesogenic groups are linked through a semi-rigid group in such a way as not to be co-linear. The term “discotic” means a disc- or sheet-shaped compound or group.

[0070] The term “mesogenic group” or its abbreviation “MG” means a group with the ability to induce liquid crystal (LC) phase behavior. Mesogenic groups, especially those of the non-amphiphilic type, are usually either calamitic or discotic. The compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behavior only in mixtures with other compounds, or when the mesogenic compounds or the mixtures thereof are polymerized. For the sake of simplicity, the term “liquid crystal” is used hereinafter for both mesogenic and LC materials.

[0071] A calamitic mesogenic compound is usually comprising a calamitic, i.e. rod- or lath-shaped, mesogenic group consisting of one or more aromatic or alicyclic groups connected to each other directly or via linkage groups, optionally comprising terminal groups attached to the short ends of the rod, and optionally comprising one or more lateral groups attached to the long sides of the rod, wherein these terminal and lateral groups are usually selected e.g. from carbyl or hydrocarbyl groups, polar groups like halogen, nitro, hydroxy, etc., or polymerizable groups.

[0072] A discotic mesogenic compound is usually comprising a discotic, i.e. relatively flat disc- or sheet-shaped mesogenic group consisting for example of one or more condensed aromatic or alicyclic groups, like for example triphenylene, and optionally comprising one or more terminal groups that are attached to the mesogenic group and are selected from the terminal and lateral groups mentioned above.

[0073] The term “reactive mesogen” or its abbreviation “RM” means a polymerizable mesogenic or liquid crystalline compound, which is preferably a monomeric or oligomeric compound.

[0074] The term “spacer” or “spacer group”, also referred to as “Sp” below, is known to the person skilled in the art and is described in the literature. Unless stated otherwise, the term “spacer” or “spacer group” above and below denotes a flexible organic group, which in a polymerizable mesogenic compound (“RM”) connects the mesogenic group and the polymerizable group(s).

[0075] The term “polymer” includes, but is not limited to, homopolymers, copolymers, for example, block, random, and alternating copolymers, terpolymers, quaterpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible configurational isomers of the material. These configurations include, but are not limited to isotactic, syndiotactic, and atactic symmetries. A polymer is a molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units (i.e. repeating units) derived, actually or conceptually, from molecules of low relative mass (i.e. monomers). In the context of the present invention polymers are composed of more than 60 monomers.

[0076] The term “oligomer” is a molecular complex that consists of a few monomer units, in contrast to a polymer, where the number of monomers is, in principle, unlimited. Dimers, trimers and tetramers are, for instance, oligomers composed of two, three and four monomers, respectively. In the context of the present invention oligomers may be composed of up to 60 monomers.

[0077] The term “monomer” as used herein refers to a polymerizable compound which can undergo polymerization thereby contributing constitutional units (repeating units) to the essential structure of a polymer or an oligomer. Polymerizable compounds are functionalized compounds having one or more polymerizable groups. Large numbers of monomers combine in polymerization reactions to form polymers. Monomers with one polymerizable group are also referred to as “monofunctional” or “monoreactive” compounds, compounds with two polymerizable groups as “bifunctional” or “direactive” compounds, and compounds with more than two polymerizable groups as “multifunctional” or “multireactive” compounds. Compounds without a polymerizable group are also referred to as “non-functional” or “non-reactive” compounds.

[0078] The term “homopolymer” as used herein stands for a polymer derived from one species of (real, implicit or hypothetical) monomer.

[0079] The term “copolymer” as used herein generally means any polymer derived from more than one species of monomer, wherein the polymer contains more than one species of corresponding repeating unit. In one embodiment the copolymer is the reaction product of two or more species of monomer and thus comprises two or more species of corresponding repeating unit. It is preferred that the copolymer comprises two, three, four, five or six species of repeating unit. Copolymers that are obtained by copolymerization of three monomer species can also be referred to as terpolymers. Copolymers that are obtained by copolymerization of four monomer species can also be referred to as quaterpolymers. Copolymers may be present as block, random, and/or alternating copolymers.

[0080] The term “block copolymer” as used herein stands for a copolymer, wherein adjacent blocks are constitutionally different, i.e. adjacent blocks comprise repeating units derived from different species of monomer or from the same species of monomer but with a different composition or sequence distribution of repeating units.

[0081] Further, the term “random copolymer” as used herein refers to a polymer formed of macromolecules in which the probability of finding a given repeating unit at any given site in the chain is independent of the nature of the adjacent repeating units. Usually, in a random copolymer, the sequence distribution of repeating units follows Bernoullian statistics.

[0082] The term “alternating copolymer” as used herein stands for a copolymer consisting of macromolecules comprising two species of repeating units in alternating sequence.

[0083] “Electronic packaging” is a major discipline within the field of electronic engineering, and includes a wide variety of technologies. It refers to inserting discrete components, integrated circuits, and MSI (medium-scale integration) and LSI (large-scale integration) chips (usually attached to a lead frame by beam leads) into plates through hole on multilayer circuit boards (also called cards), where they are soldered in place. Packaging of an electronic system must consider protection from mechanical damage, cooling, radio frequency noise emission, protection from electrostatic discharge maintenance, operator convenience, and cost.

[0084] The term “microelectronic device” as used herein refers to electronic devices of very small electronic designs and components. Usually, but not always, this means micrometer-scale or smaller. These devices typically contain one or more microelectronic components which are made from semiconductor materials and interconnected in a packaged structure to form the microelectronic device. Many electronic components of normal electronic design are available in a microelectronic equivalent. These include transistors, capacitors, inductors, resistors, diodes and naturally insulators and conductors can all be found in microelectronic devices. Unique wiring techniques such as wire bonding are also often used in microelectronics because of the unusually small size of the components, leads and pads.

[0085] “Nanoparticles” as used herein are particles with a mean diameter in the range from 1 to 100 nm. More preferably, nanoparticles have a mean diameter in the range from 20 to 80 nm, more preferably from 40 to 60 nm.

Preferred Embodiments

[0086] Polymerizable Compound

[0087] The present invention relates to a polymerizable mixture comprising a first monomer and a second monomer, wherein the first monomer is one or more compound represented by Formula (1), and wherein the second monomer is one or more bi- or multifunctional compound capable of reacting with the first monomer to give a copolymer:

P.sup.1-Sp.sup.1-(MG-Sp.sup.1)m-P.sup.1   Formula (1)

[0088] wherein:

[0089] m is an integer from 1 to 60;

[0090] P.sup.1 denotes

##STR00005##

[0091] Sp.sup.1 denotes at each occurrence a spacer group (Sp) or a single bond;

[0092] MG is a rod-shaped mesogenic group, which is preferably selected from Formula (2):

-(A.sup.21-Z.sup.21).sub.k-A.sup.22-(Z.sup.22-A.sup.23).sub.l-   Formula (2)

[0093] wherein:

[0094] A.sup.21 to A.sup.23 are independently and at each occurrence independently of one another an aryl group, heteroaryl group, heterocyclic group, alicyclic group or cyclic imide group optionally being substituted by one or more identical or different groups L;

[0095] Z.sup.21 and Z.sup.22 are independently and at each occurrence independently from each other, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR.sup.01—, —NR.sup.01—CO—, NR.sup.01—CO—NR.sup.02, —NR.sup.01—CO—O—, —O—C—NR.sup.01—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —CH.sub.2CH.sub.2—, —(CH.sub.2).sub.4—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═N—, —N═CH—, —N═N—, —CH═CR.sup.01—, —CY.sup.01═CY.sup.02—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond;

[0096] R.sup.01 and R.sup.02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms;

[0097] L is F, Cl, Br, I, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR.sup.xxR.sup.yy, —C(═O)OR.sup.xx, —C(═O)R.sup.xx, —NR.sup.xxR.sup.yy, —OH, —SF.sub.5, or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, —CN or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 6 C atoms;

[0098] R.sup.xx and R.sup.yy independently of each other denote H or alkyl with 1 to 12 C-atoms;

[0099] Y.sup.01 and Y.sup.92 each, independently of one another, denote H, alkyl having 1 to 12 C atoms, aryl, F, Cl, or CN; and

[0100] k and l are each and independently 0, 1, 2, 3 or 4.

[0101] Points of attachment (binding sites) of structural elements presented in this patent application may be indicated by

##STR00006##

wherein * represents the structural element and

##STR00007##

a binding site.

[0102] The polymerizable group P.sup.1 is a maleimide group which is capable to undergo a polymerization reaction such as, for example, a radical or ionic chain polymerization reaction, or a polyaddition reaction (e.g. cycloadditions, such as 2+2 cycloadditions, 4+2 cycloadditions (Diels-Alder reactions) or 1,3-dipolar cycloadditions, or nucleophilic additions, such as Michael reactions), or which is capable to undergo a polymerization analogous reaction such as, for example, an addition to a polymer backbone by one of the aforementioned reaction types.

[0103] It is preferred that the index m is an integer from 1 to 50, more preferably from 2 to 30, and most preferably from 3 to 20.

[0104] It is preferred that Z.sup.21 and Z.sup.22 are independently and at each occurrence independently from each other —COO—, —OCO—, —CO—O—, —O—CO—, —OCH.sub.2—, —CH.sub.2O—, —CH.sub.2CH.sub.2—, —(CH.sub.2).sub.4—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond.

[0105] Preferably, k and l are each and independently 0, 1 or 2, more preferably k and l are 1.

[0106] Preferred spacer groups Sp are selected from the formula Sp′-X′, so that the radical “P.sup.1-Sp.sup.1-” corresponds to the formula “P.sup.1-Sp′-X′-”, wherein:

[0107] Sp′ denotes [0108] (a) straight chain or branched chain alkylene having 1 to 40, preferably 1 to 30, C atoms, which is optionally mono- or poly-substituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by —O—, —S—, —NH—, —NR.sup.01—, —SiR.sup.01R.sup.02—, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —NR.sup.01—CO—O—, —O—CO—NR.sup.01—, —NR.sup.01—CO—NR.sup.01—, —CH═CH—or —C≡C— in such a way that O and/or S atoms are not linked directly to one another, or [0109] (b) -Sp.sup.x-G-Sp.sup.y-, wherein Sp.sup.x and Sp.sup.y denote independently of each other alkylene having 1 to 20 C atoms, preferably 1 to 12 C atoms, or a single bond; G denotes cycloalkylene having 3 to 20 C atoms, preferably 5 to 12 C atoms, which is optionally mono- or polysubstituted by alkyl having 1 to 20 C atoms, preferably 1 to 12 C atoms; [0110] X′ denotes —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR.sup.01—, —NR.sup.01—CO—, —NR.sup.01—CO—NR.sup.01—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═N—, —N═C—, —N═N—, —CH═CF.sup.01—, —CY.sup.01═CY.sup.02—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, preferably —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR.sup.0—, —NR.sup.01—CO—, —NR.sup.01—CO—NR.sup.01— or a single bond; [0111] R.sup.01 and R.sup.02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms; and [0112] Y.sup.01 and Y.sup.02 each, independently of one another, denote H, F, Cl or CN.

[0113] Preferred groups Sp′ are in each case selected from straight chain methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, and octadecylene, cyclo-hexylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

[0114] More preferred spacer groups Sp are selected from the list consisting of —(CH.sub.2).sub.p1—, —(CH.sub.2CH.sub.2O).sub.q1—CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2—S—CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2—NH—CH.sub.2CH.sub.2—, —(SiR.sup.01R.sup.02—O).sub.p1—, —(CH.sub.2).sub.p1—(cyclo-C.sub.6H.sub.8R.sup.01R.sup.02)—(CH.sub.2).sub.p1—, and

##STR00008##

wherein: [0115] p1 is an integer from 1 to 60, preferably from 1 to 36, more preferably from 1 to 12; [0116] q1 is an integer from 1 to 12, preferably from 1 to 3; and [0117] R.sup.01 and R.sup.02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms.

[0118] Most preferred groups Sp are —(CH.sub.2).sub.p1—, —O—(CH.sub.2).sub.p1—, —O—(CH.sub.2).sub.p1—O—, —OCO—(CH.sub.2).sub.p1—, and —OCOO—(CH.sub.2).sub.p1—, in which p1 is an integer from 1 to 36, preferably from 1 to 12.

[0119] In a preferred embodiment of the present invention, the groups A.sup.21 to A.sup.23 denote independently and, in case of multiple occurrence, independently of one another, a moiety selected from the following groups a) to e): [0120] a) trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 4,4′-bicyclohexylene, in which one or more non-adjacent CH.sub.2 groups may be replaced by —O— and/or —S— and wherein one or more H atoms may be replaced by a group L; [0121] b) 1,4-phenylene, 1,3-phenylene, 4,4′-biphenylene, 2,5-thiphene and 2,6-dithieno[3,2-b:2′,3′-d]thiophene in which one or two CH groups may be replaced by N and where one or more H atoms may be replaced by a group L; [0122] c) tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobut-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophen-2,5-diyl, which may be substituted one or more groups L; [0123] d) saturated, partially unsaturated or completely unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, of which one or more can also be replaced by heteroatoms, preferably selected from the group consisting of bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl,

##STR00009## ##STR00010## [0124] where one or more H atoms may be replaced by a group L, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N, and where [0125] M denotes —O—, —S—, —CH.sub.2—, —CHY.sup.03— or —CY.sup.03Y.sup.04; [0126] Y.sup.03, Y.sup.04 denote independently of each other one of the meanings given above for R.sup.01, F, Cl, CN, OCF.sub.3 or CF.sub.3, and preferably H, F, Cl, CN, OCF3 or CF.sub.3; [0127] W.sup.5, W.sup.6 denote independently of each other —CH.sub.2CH.sub.2—, —CH═CH—, —CH.sub.2—O—, —O—CH.sub.2—, —C(R.sup.cR.sup.d)— or —O—; [0128] R.sup.c, R.sup.d denote independently of each other H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl; and [0129] R.sup.03, R.sup.04 denote independently of each other H, F, straight chain or branched chain alkyl having 1 to 12 C atoms where one or more H atoms may be replaced by F; [0130] e) cyclic imides selected from the group consisting of:

##STR00011## [0131] where one or more H atoms may be replaced by a group L, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N.

[0132] It is preferred that the first monomer comprised in the polymerizable mixture according to the present invention is one, two, three or four compound(s) represented by Formula (1).

[0133] Preferred compounds according to Formula (1) are:

##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018##

where the radicals and indices have the following meanings: [0134] L is F, Cl, Br, I, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR.sup.xxR.sup.yy, —C(═O)OR.sup.xx, —O(═O)R.sup.xx, —NR.sup.xxR.sup.yy, —OH, —SF.sub.5, or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 20 C atoms, preferably 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, preferably F, —CN or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 6 C atoms; [0135] R.sup.xx and R.sup.yy independently of each other denote H or alkyl with 1 to 12 C atoms; [0136] r is 0, 1, 2, 3 or 4; [0137] s is 0, 1, 2 or 3; [0138] t is 0, 1 or 2; [0139] Z.sup.21 and Z.sup.22 are independently and at each occurrence independently from each other, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR.sup.01—, —NR.sup.01—CO—, —NR.sup.01—CO—NR.sup.02, —NR.sup.01—CO—O—, —O—CO—NR.sup.01—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —CH.sub.2CH.sub.2—, —(CH.sub.2).sub.4—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═N—, —N═CH—, —N═N—, —CH═CR.sup.01—, —CY.sup.01═CY.sup.02—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond, preferably —COO—, —OCO—, —CO—O—, —O—CO—, —OCH.sub.2—, —CH.sub.2O—, —CH.sub.2CH.sub.2—, —(CH.sub.2).sub.4—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond; [0140] R.sup.01 and R.sup.02 each, independently of one another, denote H or alkyl having 1 to 12 C atoms; [0141] Sp.sup.1 denotes at each occurrence a space group (Sp) as defined above or a single bond;

[0142] P.sup.1 denotes

##STR00019##

and [0143] m is an integer from 1 to 60, preferably from 1 to 50, more preferably from 2 to 30, and most preferably from 3 to 20.

[0144] More preferred compounds according to Formula (1) are:

##STR00020##

where the radicals and indices have one of the meanings as defined above.

[0145] Particularly preferred compounds according to Formula (1) are:

##STR00021## ##STR00022##

where the radicals and indices have one of the meanings as defined above.

[0146] Most preferred compounds according to Formula (1) are:

##STR00023## ##STR00024## ##STR00025##

wherein [0147] n is an integer from 1 to 60, preferably from 1 to 36, and more preferably from 6 to 12; and [0148] m is an integer from 1 to 60, preferably from 1 to 50, more preferably from 2 to 30, and most preferably from 3 to 20.

[0149] In the compounds of formulae M1 to M33 and the corresponding sub-formulae, the ring group

##STR00026##

is preferably

##STR00027##

wherein [0150] L is at each occurrence independently from each other F, Cl, Br, I, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR.sup.xxR.sup.yy, —C(═O)OR.sup.xx, —C(═O)R.sup.xx, —NR.sup.xxR.sup.yy, —OH, —SF.sub.5, or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 20 C atoms, preferably 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, preferably F, —CN or straight chain or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 6 C atoms; and [0151] R.sup.xx and R.sup.yy are defined according to the definitions given above.

[0152] The compounds represented by Formula (1) can be prepared by any standard synthesis. Usually, the compound is retrosynthetically cut into smaller units and formed stepwise from suitable precursor compounds. For this purpose, known standard reactions can be used. It has proven to be particularly advantageous to attach the maleimide groups P.sup.1 at a late stage of the synthesis, typically at the very last step of the synthesis. By doing so, undesirable side-reactions or premature polymerization of the compound can be avoided.

[0153] Preferably, a precursor represented by Formula (3):

X-Sp.sup.1-(MG-Sp.sup.1).sub.m-X   Formula (3)

is reacted with

##STR00028##

to form a polymerizable compound represented by Formula (1):

P.sup.1-Sp.sup.1-(MG-Sp.sup.1).sub.m-P.sup.1   Formula (1)

[0154] wherein X is NH.sub.2;

[0155] P.sup.1 is

##STR00029##

and

[0156] Sp.sup.1, MG, and m have one of the definitions as given above.

[0157] The second monomer comprised in the polymerizable mixture according to the present invention is one or more, preferably one, two, three or four, bi- or multifunctional compound(s) capable of reacting with the first monomer to give a copolymer.

[0158] It is preferred that the second monomer is one or more, preferably one, two, three or four, bi- or multifunctional compound(s) selected from organic compounds, polyhedralsilsesquioxane compounds and functionalized inorganic nanoparticles.

[0159] It is further preferred that the second monomer is one or more, preferably one, two, three or four, bi- or multifunctional compound(s) comprising two or more polymerizable groups (P) (reactive groups) which are selected from groups containing a C═C double bond, which preferably react with P.sup.1 in a radical or ionic chain polymerization or in a 2+2 cycloaddition, groups containing two conjugated C═C double bonds, which preferably react with P.sup.1 in a 4+2 cycloaddition (Diels-Alder reaction), nucleophilic groups, which preferably react with P.sup.1 in a nucleophilic addition (Michael reaction), and 1,3-dipolar groups, which preferably react with P.sup.1 in a 1,3-dipolar cycloaddition.

[0160] Preferred groups containing a C═C double bond are selected from:

[0161] CH.sub.2═CW.sup.1—COO—, CH.sub.2═CW.sup.1—CO—,

##STR00030##

CH.sub.2═CW.sup.2—(O).sub.k3—, CW.sup.1.sub.2═CH—CO—(O).sub.k3—, CW.sup.1.sub.2═CH—CO—NH—, CH.sub.2═CW.sup.1—CO—NH—, CH.sub.3—CH═CH—O—, CH.sub.2═CH—CH.sub.2—O—, (CH.sub.2═CH).sub.2CH—O—CO—, (CH.sub.2═CH—CH.sub.2).sub.2CH—O—CO—, (CH.sub.2═CH).sub.2CH—O—, (CH.sub.2═CH—CH.sub.2).sub.2N—, (CH.sub.2═CH—CH.sub.2).sub.2N—CO—, CH.sub.2═CW.sup.1—CO—NH—, CH.sub.2═CH—(CO—O).sub.k1-Phe-(O).sub.k2—, CH.sub.2═CH—(CO).sub.k1-Phe-(O).sub.k2—, or Phe-CH═CH—; [0162] wherein [0163] W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, preferably H or CH.sub.3; [0164] W.sup.2 denotes H or alkyl having 1 to 5 C atoms, preferably H or CH.sub.3; [0165] W.sup.3 and W.sup.4 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, preferably H or CH.sub.3; [0166] Phe denotes 1,4-phenylene, which is optionally substituted by one or more radicals L as being defined above; and [0167] k.sub.1, k.sub.2 and k.sub.3 each, independently of one another, denote 0 or 1; and [0168] k.sub.4 is an integer from 1 to 10.

[0169] Preferred groups containing two conjugated C═C double bonds are selected from: CW.sup.1.sub.2═CW.sup.1—CW.sup.1═CW.sup.1—; wherein [0170] W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, preferably H or CH.sub.3.

[0171] Preferred nucleophilic groups are selected from: HS—(CH.sub.2).sub.k5—CO—(O).sub.k3—, HS—(CH.sub.2).sub.k5—CO—, HS—(CH.sub.2).sub.k5—(O).sub.k3—, HS—(CH.sub.2).sub.k5—O—CO—, HS—(CH.sub.2).sub.k5—CO—NH—, HS—(CH.sub.2).sub.k5—NH—CO—, HS-Phe-(O).sub.k2—, H.sub.2N—(CH.sub.2).sub.k5—CO—(O).sub.k3—, H.sub.2N—(CH.sub.2).sub.k5—CO—, H.sub.2N—(CH.sub.2).sub.k5—(O).sub.k3—, H.sub.2N—(CH.sub.2).sub.k5—O—CO—, H.sub.2N—(CH.sub.2).sub.k5—CO—NH—, H.sub.2N—(CH.sub.2).sub.k5—NH—CO—, or H.sub.2N-Phe-(O).sub.k2—; wherein [0172] k.sub.2 and k.sub.3 each, independently of one another, denote 0 or 1; and [0173] k.sub.5 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0, 1 or 2.

[0174] Preferred 1,3-dipolar groups are selected from:

##STR00031##

wherein: [0175] W.sup.5 denotes at each occurrence independently from each other H, phenyl or alkyl having 1 to 5 C atoms, preferably phenyl or CH.sub.3.

[0176] Particularly preferred polymerizable groups (P) are selected from: [0177] CH.sub.2═CW.sup.1—COO—, CH.sub.2═CW.sup.1—CO—,

##STR00032##

CH.sub.2═CW.sup.2—(O).sub.k3—, CW.sup.12═CH—CO—(O).sub.k3—, CH.sub.3—CH═CH—O—, CH.sub.2═CH—CH.sub.2—O—, HS—(CH.sub.2).sub.k5—CO—(O).sub.k3—, HS—(CH.sub.2).sub.k5—CO—, HS—(CH.sub.2).sub.k5—(O).sub.k3—, HS—(CH.sub.2).sub.k5—O—CO—, H.sub.2N—(CH.sub.2).sub.k5—CO—(O).sub.k3—, H.sub.2N—(CH.sub.2).sub.k5—CO—, H.sub.2N—(CH.sub.2).sub.k5—(O).sub.k3—, or H.sub.2N—(CH.sub.2).sub.k5—O—CO—; wherein [0178] W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, preferably H or CH.sub.3; [0179] W.sup.2 denotes H or alkyl having 1 to 5 C atoms, preferably H or CH.sub.3; [0180] W.sup.3 and W.sup.4 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, preferably H or CH.sub.3; [0181] k.sub.3 denotes 0 or 1; and [0182] k.sub.5 is an integer from 0 to 10, preferably from 0 to 5, more preferably 0, 1 or 2.

[0183] Preferred organic compounds to be used as second monomer are represented by Formula (4):

QP.sup.2).sub.x   Formula (4),

wherein: [0184] Q denotes a hydrocarbon group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, which may be optionally substituted with one or more substituents L, wherein Lis as defined above, and which may optionally contain one or more hetero atoms selected from N, O and S; [0185] P.sup.2 denotes a polymerizable group (P) as defined above; and x is an integer from 2 to 10, preferably from 2 to 4, more preferably x=2.

[0186] As it is apparent from Formula (4), the group Q has x binding sites, each of which binds one of the x polymerizable groups P.sup.2.

[0187] In a preferred embodiment Q is represented by O(Sp.sup.2).sub.2, N(Sp.sup.2).sub.3 , NH(Sp.sup.2).sub.2, C(Sp.sup.2).sub.4, CH(Sp.sup.2).sub.3, or CH.sub.2(Sp.sup.2).sub.2, wherein is Sp.sup.2 is a linear alkylene chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a branched alkylene chain having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, or an aromatic or heteroaromatic moiety having 3 to 14 carbon atoms, preferably an aromatic moiety having 6 to 14 carbon atoms, wherein each Sp.sup.2.is bound to a polymerizable group P.sup.2.

[0188] In a further preferred embodiment Q is represented by “Ar-Sp.sup.3-Ar”, wherein Ar is an aromatic or heteroaromatic moiety having 3 to 14 carbon atoms, preferably an aromatic moiety having 6 to 14 carbon atoms, and Spa is a linear alkylene chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a branched alkylene chain having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, or an aromatic or heteroaromatic moiety having 3 to 14 carbon atoms, preferably an aromatic moiety having 6 to 14 carbon atoms, wherein each Ar is bound to a polymerizable group P.sup.2.

[0189] In a further preferred embodiment Q is represented by “Sp.sup.4-Y-Sp.sup.4”, wherein Y is a mono- or polycyclic alkane moiety having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and Sp.sup.4 is absent or a linear alkylene chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a branched alkylene chain having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, or an aromatic or heteroaromatic moiety having 3 to 14 carbon atoms, preferably an aromatic moiety having 6 to 14 carbon atoms, wherein each Sp.sup.4 is bound to a polymerizable group P.sup.2.

[0190] In a particularly preferred embodiment Q is selected from

##STR00033##

[0191] Particularly preferred organic compounds are selected from the group consisting of:

##STR00034## ##STR00035##

[0192] Preferred polyhedralsilsesquioxane compounds to be used as second monomer are represented by the following structure:

(R).sub.y-x(SiO.sub.1.5).sub.yL-P.sup.2).sub.x   (Structure 1),

wherein: [0193] R is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.6-C.sub.10-aryl, or C.sub.1-C.sub.6-alkoxy; [0194] L is C.sub.1-C.sub.12-alkylene or C.sub.1-C.sub.12-oxyalkylene, more preferably C.sub.1-C.sub.6-alkylene or C.sub.1-C.sub.6-oxyalkylene, wherein one or more non-adjacent C atoms may be replaced, independently of one another, by —SiR.sup.05R.sup.06—, wherein R.sup.05 and R.sup.06 each, independently of one another, denote H or alkyl having 1 to 6 C atoms, more preferably H, CH.sub.3 or CH.sub.2CH.sub.3; [0195] P.sup.2 denotes a polymerizable group (P) as defined above; [0196] y is an integer from 6 to 12; and x is an integer from 2 to 12, wherein [0197] y-x≥0.

[0198] Preferred C.sub.1-C.sub.6-alkyl substituents are: methyl, ethyl, propyl, butyl, pentyl and hexyl.

[0199] Preferred C.sub.2-C.sub.6-alkenyl substituents are: ethenyl, propenyl, butenyl, pentenyl and hexenyl.

[0200] Preferred C.sub.6-C.sub.10-aryl substituents are: phenyl, tolyl, xylyl and naphthyl.

[0201] Preferred C.sub.1-C.sub.6-alkoxy substituents are: methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy.

[0202] Preferred C.sub.1-C.sub.2-alkylene substituents are: methylene, ethylene, propylene, butylene, pentylene and hexylene.

[0203] Preferred C.sub.1-C.sub.2-oxyalkylene substituents are: methyleneoxy, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy and hexyleneoxy.

[0204] Preferred C.sub.1-C.sub.4-alkyl substituents are: methyl, ethyl, propyl and butyl.

[0205] In a particularly preferred embodiment, the group L in Structure (1) is selected from the group consisting of —(CH.sub.2).sub.n—, —O—(CH.sub.2).sub.n—, —SiH.sub.2—(CH.sub.2).sub.n—, —OSiH.sub.2—(CH.sub.2).sub.n—, —Si(CH.sub.3).sub.2—(CH.sub.2).sub.n—, —OSi(CH.sub.3).sub.2—(CH.sub.2).sub.n—, —Si(CH.sub.2CH.sub.3).sub.2—(CH.sub.2).sub.n—, and —OSi(CH.sub.2CH.sub.3).sub.2—(CH.sub.2).sub.n—, wherein n is an integer from 1 to 6, preferably from 2 to 4, more preferably 3.

[0206] Particularly preferred polyhedralsilsesquioxane compounds are based on the following Structures 2 to 5, wherein x R substituents are replaced by x (-L-P.sup.2):

##STR00036##

wherein R, L and P.sup.2 have the same meanings as defined above; and wherein x is an integer from 2 to 6 in Structure 2; x is an integer from 2 to 8 in Structure 3; x is an integer from 2 to 10 in Structure 4; and x is an integer from 2 to 12 in Structure 5.

[0207] The polyhedralsilsesquioxane compounds shown above can be readily prepared from available precursors, and are easily incorporated into the polymerizable mixture by appropriate mixing conditions. For example, maleimide substituted polyhedralsilsesquioxanes and their preparation are described in US 2006/0009578 A1 the disclosure of which is herewith incorporated by reference.

[0208] Preferred functionalized inorganic nanoparticles to be used as second monomer are inorganic nanoparticles which comprise polymerizable groups P.sup.2 on their surface, wherein P.sup.2 denotes a polymerizable group (P) as defined above. Preferred polymerizable groups (P) for the functionalized inorganic nanoparticles are selected from maleimide, dimethylmaleimide, acrylate, methacrylate, allyl ether and vinyl ether groups, which are either bound directly or via a group L to the surface of the inorganic nanoparticle.

[0209] Preferred functionalized inorganic nanoparticles are represented by the following structures:

##STR00037##

[0210] wherein represents an inorganic nanoparticle; [0211] P.sup.2 denotes a polymerizable group (P); [0212] L is C.sub.1-C.sub.12-alkylene or C.sub.1-C.sub.12-oxyalkylene, more preferably C.sub.1-C.sub.6-alkylene or C.sub.1-C.sub.6-oxyalkylene; and [0213] x is an integer 2.

[0214] Preferred materials for the inorganic nanoparticles are selected from SiO.sub.2, TiO.sub.2, ZrO.sub.2, Fe.sub.2O.sub.3, MgTiO.sub.3, CaTiO.sub.3, SrTiO.sub.3 and BaTiO.sub.3. The inorganic nanoparticles may be solid or hollow.

[0215] Particularly preferred functionalized inorganic nanoparticles to be used as second monomer in the present invention are:

##STR00038##

wherein L and x are defined as above.

[0216] The above representations of the functionalized inorganic nanoparticles serve for illustrative purposes only and should not be construed as limiting.

[0217] It is preferred that the functionalized inorganic nanoparticles to be used as second monomer in the present invention have a degree of functionalization of 0.001 to 5 mmol/g, more preferably 0.01 to 1 mmol/g and most preferably 0.05 to 0.5 mmol/g. The degree of functionalization indicates the molar amount of polymerizable groups P.sup.2 per unit mass of the functionalized inorganic nanoparticles.

[0218] The degree of functionalization may vary, depending on the conditions for functionalizing the inorganic nanoparticles. The person skilled in the art is able to select suitable conditions for the functionalization of inorganic nanoparticles from literature known procedures, so that individually adapted functionalized nanoparticles with different polymerizable groups and different degrees of functionalization can be prepared. Suitable functionalized inorganic nanoparticles and precursors thereof are also available from commercial sources, such as, for example, from Sigma Aldrich (e.g. 3-aminopropyl functionalized silica, 660442 Aldrich) or nanoComposix. Inc., San Diego, USA.

[0219] The present invention further provides a method for forming a copolymer comprising repeating units which are derived from the first monomer and repeating units which are derived from the second monomer. The copolymer is a dielectric copolymer which may be linear or crosslinked.

[0220] The method for forming a copolymer comprises the following steps: [0221] (i) providing a polymerizable mixture according to the present invention; and [0222] (ii) polymerizing said polymerizable mixture to obtain a copolymer.

[0223] The polymerizable mixture comprises a first monomer and a second monomer as defined above. It is preferred that the total content of the first monomer in the polymerizable mixture is from 50 to 99.9 wt.-%, more preferably from 80 to 99 wt.-% and most preferably from 90 to 95 wt.-%, based on the total weight of polymerizable monomers. It is preferred that the total content of the second monomer in the polymerizable mixture is from 0.1 to 50 wt.-%, more preferably from 1 to 20 wt.-% and most preferably from 5 to 10 wt.-%, based on the total weight of polymerizable monomers.

[0224] It is preferred that the polymerizable mixture provided in step (i) is substantially free of solvent. Substantially free of solvent means that the content of total residual solvent in the polymerizable starting material is not more than 10 wt.-%, preferably not more than 5 wt.-%, and more preferably not more than 1 wt.-%, based on the total weight of polymerizable monomers. Alternatively, it is preferred that the polymerizable mixture provided in step (i) comprises one or more solvents, preferably in an amount of more than 10 wt.-%, more preferably in an amount of more than 25 wt.-%, and most preferably in an amount of more than 50 wt.-%, based on the total weight of polymerizable monomers.

[0225] It is preferred that the polymerizable mixture is polymerized in step (ii) by a radical or ionic chain polymerization reaction or a polyaddition reaction. Preferred polyaddition reactions are cycloadditions, such as 2+2 cycloadditions, 4+2 cycloadditions (Diels-Alder reactions) or 1,3-dipolar cycloadditions, or nucleophilic additions, such as Michael reactions.

[0226] The above-mentioned reaction types and associated reaction conditions (such as e.g. catalysts, solvents, temperature, time, concentration, etc.) are known to the person skilled in the art.

[0227] For example, radical or ionic polymerizations may be carried out in the presence of radical or ionic polymerization initiators, which can be activated thermally and/or photochemically. The skilled person is familiar with suitable radical and ionic polymerization initiators. For example, cycloadditions may occur photochemically or in the presence of Lewis acids. The skilled person is familiar with suitable photochemical conditions and suitable Lewis acids.

[0228] It is preferred that the polymerizable mixture provided in step (i) further comprises one or more radical initiators. Preferred radical initiators are thermally activated radical initiators and/or photochemically activated radical initiators.

[0229] Preferred thermally activated radical initiators are: tert-amyl peroxy-benzoate, 4,4-azobis(4-cyanovaleric acid), 1,1′-azobis(cyclohexanecarbo-nitrile), 2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxy isopropyl carbonate, cumene hydroperoxide (CHP), cyclohexanone peroxide, dicumyl peroxide (DCP), lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, and potassium persulfate.

[0230] Preferred photochemically activated radical initiators are: acetophenone, p-anisil, benzil, benzoin, benzophenone, 2-benzoylbenzoic acid, 4,4′-bis(diethylamino)benzophenone, 4,4′-bis(dimethylamino)benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, 4-benzoylbenzoic acid, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, methyl 2-benzoylbenzoate, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone, (±)-camphorquinone, 2-chlorothioxanthone, 4,4′-dichlorobenzophenone, 2,2-diethoxyacetophenone, 2,2-Dimethoxy-2-phenylacetophenone, 2,4-diethylthioxanthen-9-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1,4-dibenzoylbenzene, 2-ethylanthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, 2-isopropylthioxanthone, lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate, 2-methyl-4′-(methylthio)-2-morpholino-propiophenone, 2-isonitrosopropiophenone, 2-phenyl-2-(p-toluenesulfonyl-oxy)acetophenone, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. Typically, such initiators are radical polymerization initiators which may be photochemically activated.

[0231] Further preferred photochemically activated radical initiators are:

##STR00039## ##STR00040##

[0232] Preferably, the initiators for radical polymerization are activated thermally by exposure to heat or photochemically by exposure to radiation such as UV and/or visible light.

[0233] Exposure to heat involves exposure to an elevated temperature, preferably in the range from 40 to 200° C., more preferably 50 to 180° C.

[0234] Exposure to radiation involves exposure to visible light and/or UV light. It is preferred that the visible light is electromagnetic radiation with a wavelength from >380 to 780 nm, more preferably from >380 to 500 nm. It is preferred that the UV light is electromagnetic radiation with a wavelength of 380 nm, more preferably a wavelength from 100 to 380 nm. More preferably, the UV light is selected from UV-A light having a wavelength from 315 to 380 nm, UV-B light having a wavelength from 280 to 315 nm, and UV-C light having a wavelength from 100 to 280 nm.

[0235] As UV light sources Hg-vapor lamps or UV-lasers are possible, as IR light sources ceramic-emitters or IR-laser diodes are possible and for light in the visible area laser diodes are possible.

[0236] Preferred UV light sources are light sources having a) a single wavelength radiation with a maximum of <255 nm such as e.g. 254 nm and 185 nm Hg low-pressure discharge lamps, 193 nm ArF excimer laser and 172 nm Xe2 layer, or b) broad wavelength distribution radiation with a wavelength component of <255 m such as e.g. non-doped Hg low-pressure discharge lamps.

[0237] In a preferred embodiment of the present invention the light source is a xenon flash light. Preferably, the xenon flash light has a broad emission spectrum with a short wavelength component going down to about 200 nm.

[0238] It is preferred that the polymerization in step (ii) takes place in a time range of up to 5 h, more preferably up to 1 h, most preferably up to 0.5 h.

[0239] It is further preferred that the polymerization of the polymerizable mixture in step (ii) takes place at elevated temperature, preferably at a temperature in the range from 25 to 200° C., more preferably at a temperature in the range from 25 to 150° C.

[0240] There is further provided a copolymer which is obtainable or obtained by the above-mentioned method for forming a copolymer according to the present invention. The copolymer is preferably a linear or crosslinked copolymer, more preferably a linear copolymer.

[0241] There is also provided a copolymer which comprises at least one repeating unit derived from the first monomer and at least one repeating unit derived from the second monomer as defined above.

[0242] More preferably, the repeating unit derived from the first monomer in said copolymer comprises a structural unit represented by the following Formula (5):

[-Sp.sup.1-(MG-Sp.sup.1).sub.m-]  Formula (5)

wherein Sp.sup.1, MG and m have one of the above-mentioned definitions.

[0243] Preferably, the copolymers according to the present invention have a molecular weight M.sub.w, as determined by GPC, of at least 2,000 g/mol, more preferably of at least 4,000 g/mol, even more preferably of at least 5,000 g/mol. Preferably, the molecular weight M.sub.w of the copolymers is less than 50,000 g/mol. More preferably, the molecular weight M.sub.w of the copolymers is in the range from 5,000 to 20,000 g/mol.

[0244] Moreover, there is provided an electronic device comprising a copolymer according to the present invention. For the electronic device it is preferred that the copolymer forms a dielectric layer, more preferably a dielectric layer forming part of a redistribution layer. The dielectric layer serves to electrically separate one or more electronic components being part of the electronic device from each other.

[0245] Finally, there is provided a manufacturing method for preparing a packaged microelectronic structure, in which a substrate is provided with a dielectric layer, wherein the method comprises the following steps: [0246] (1) applying a polymerizable mixture according to the present invention to a surface of a substrate; and [0247] (2) curing said polymerizable mixture to form a dielectric layer.

[0248] It is preferred that the polymerizable mixture further comprises one or more inorganic filler materials. Preferred inorganic filler materials are selected from nitrides, titanates, diamond, oxides, sulfides, sulfites, sulfates, silicates and carbides which may be optionally surface-modified with a capping agent. More preferably, the filler material is selected from the list consisting of AlN, Al.sub.2O.sub.3, BN, BaTiO.sub.3, B.sub.2O.sub.3, Fe.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, ZrO.sub.2, PbS, SiC, diamond and glass particles.

[0249] Preferably, the total content of the inorganic filler material in the polymerizable mixture is in the range from 0.001 to 90 wt.-%, more preferably 0.01 to 70 wt.-% and most preferably 0.01 to 50 wt.-%, based on the total weight of the polymerizable mixture.

[0250] It is preferred that the polymerizable mixture applied in step (1) is substantially free of solvent. Substantially free of solvent means that the content of total residual solvent in the polymerizable mixture is not more than 10 wt.-%, preferably not more than 5 wt.-%, and more preferably not more than 1 wt.-%, based on the total weight of polymerizable monomers.

[0251] However, depending on which kind of application method is used for applying the polymerizable mixture in step (1), it is preferred that the polymerizable mixture comprises one or more solvents, preferably in an amount of more than 10 wt.-%, more preferably in an amount of more than 25 wt.-%, and most preferably in an amount of more than 50 wt.-%, based on the total weight of polymerizable monomers.

[0252] The method by which the polymerizable mixture is applied in step (1) is not particularly limited. Preferred application methods for step (1) are dispensing, dipping, screen printing, stencil printing, roller coating, spray coating, slot coating, spin coating, stereolithography, gravure printing, flexo printing or inkjet printing.

[0253] The polymerizable mixtures of the present invention may be provided in the form of a formulation suitable for gravure printing, flexo printing and/or ink-jet printing. For the preparation of such formulations, ink base formulations as known from the state of the art can be used.

[0254] Alternatively, the polymerizable mixture of the present invention may be provided in the form of a formulation suitable for photolithography. The photolithography process allows the creation of a photopattern by using light to transfer a geometric pattern from a photomask to a light-curable composition. Typically, such light-curable composition contains a photo-chemically activatable radical polymerization initiator. For the preparation of such formulations, photoresist base formulations as known from the state of the art can be used.

[0255] The layer of the polymerizable mixture, which is applied in step (1), has preferably an average thickness of 1 to 50 μm, more preferably 2 to 30 μm, and most preferably 3 to 15 μm.

[0256] It is preferred that the curing in step (2) is carried out by a radical or ionic chain polymerization reaction or a polyaddition reaction. Preferred polyaddition reactions are cycloadditions, such as 2+2 cycloadditions, 4+2 cycloadditions (Diels-Alder reactions) or 1,3-dipolar cycloadditions, or nucleophilic additions, such as Michael reactions. Preferred curing conditions correspond to the preferred polymerization conditions as given above for the method for forming a copolymer.

[0257] It is preferred that the polymerizable mixture applied in step (1) further comprises one or more radical initiators. Preferred radical initiators are described above.

[0258] There is also provided a microelectronic device which comprises the packaged microelectronic structure prepared according to the above-mentioned manufacturing method.

[0259] The present invention is further illustrated by the examples following herein-after which shall in no way be construed as limiting. The skilled person will acknowledge that various modifications, additions and alternations may be made to the invention without departing from the spirit and scope of the invention as defined in the appended claims.

EXAMPLES

[0260] A) Synthesis of Oligomer 4

##STR00041##

[0261] Step 1: Triethylamine (49.7 g, 0.49 mol) was dissolved in 0.7 L of anhydrous toluene, followed by the addition of anhydrous methane sulfonic acid (48.6 g, 0.5 mol). The mixture was stirred at room temperature for 10 minutes before carefully adding diamine 2 (Priamine™, Croda, 77.4 g, 0.14 mol) and dianhydride 1 (50 g, 0.07 mol). Next, the reaction mixture was heated to reflux using a Dean-Stark apparatus for 12 h.

[0262] Step 2: The reaction mixture was cooled to room temperature and maleic anhydride (8.7 g, 0.09 mol) was added slowly, followed by the addition of an additional 10 g of anhydrous methane sulfonic acid. The mixture was reheated to reflux for about 12 h using a Dean-Stark trap. After cooling to room temperature, an additional 200 ml of toluene were added and stirring was stopped. The upper (toluene solution) fraction was carefully separated and the salt fraction was washed twice with toluene (2×500 ml). The toluene solutions were combined and filtered through a glass funnel which was tightly packed with silica gel. The silica gel was washed with an additional 100 ml of toluene and the toluene was removed under reduced pressure to produce 70 g (85%) of a yellow waxy resin (4).

[0263] B) Synthesis of Additives (Maleimides)

1. Synthesis of Tris-(2-maleimidoethyl)-amine (5)

[0264] ##STR00042##

[0265] Step 1: Furan-maleic anhydride adduct (Alfa Aesar, 28.5 g, 0.17 mol) was dissolved in 750 ml methanol. Tris(2-aminoethyl)amine (Alfa Aesar, 5 g, 0.03 mol) dissolved in 250 ml methanol was added dropwise at 0° C. Next, the reaction mixture was heated at reflux for 4 h. Methanol was removed and the concentrated solution (approx. 350 ml) was left to crystallize at 4° C. overnight. The obtained yellow crystals were filtered and washed with ethyl acetate (19.6 g, 38%).

[0266] Step 2: 7.4 g (0.013 mol) of the product obtained in step 1 was dissolved in 300 ml toluene. The solution was heated to reflux. After 20 h the solvent was removed under reduced pressure and the residual solid was dissolved in ethyl acetate and purified by flash chromatography to give maleimide (5) (DCM/ethyl acetate 60/40). Yield: 4 g (84%).

[0267] .sup.1H-NMR (500 MHz, CDCl.sub.3): δ=6.68 (s, 6H), 3.52 (t, J=6.6 Hz, 6H), 2.71 (t, J=6.6 Hz, 6H) ppm.

2. Synthesis of 1,1′-((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis-(1H-pyrrole-2,5-dione) (8)

[0268] ##STR00043##

[0269] Step 1: 2,2′-Bis(4-aminophenyl)hexafluoropropane (6) (abcr, 22.8 g, 66.8 mmol) was suspended in 95 ml THF. Maleic anhydride (Sigma, 13.2 g, 134 mmol) was added and the reaction mixture was stirred at room temperature for 1 h. The obtained solid was filtered, washed with ethyl acetate and dried under vacuum to give compound (7) (35.2 g, 99% yellow crystals).

[0270] .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ=12.94 (s, 2H), 10.56 (s, 2H), 7.72 (d, J=9.0 Hz, 4H), 7.31 (d, J=8.5 Hz, 4H), 6.49 (d, J=12.0 Hz, 2 H), 6.32 (d, J=12.0 Hz, 2H) ppm.

[0271] Step 2: 35.2 g (66.4 mmol) of the product obtained in step 1 was treated with 125 mL acetic anhydride, 6.5 g (80 mmol) sodium acetate and butylated hydroxytoluene (80 mg). The reaction mixture was heated at 90° C. for 2 h. The solution was quenched with 400 ml water and the precipitate was filtered, washed with methanol and dried under vacuum to give maleimide (8). Yield: 21.8 g of maleimide (8) (66%).

[0272] .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ=7.58-7.47 (m, 8H), 7.24 (s, 4H) ppm.

3. Synthesis of 1,1′-(cyclohexane-1,1-diylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione) (11)

[0273] ##STR00044##

[0274] Step 1: 1,1′-Bis(4-aminophenylene)cyclohexane (9) (abcr, 10 g, 37.5 mmol) was suspended in 40 ml THF. Maleic anhydride (Sigma, 7.4 g, 75 mmol) was added and the reaction mixture was stirred at room temperature for 1 h. The obtained solid was filtered, washed with ethyl acetate and dried under vacuum to give compound (10) (16.5 g, 95% yellow crystals).

[0275] .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ=12.82 (s, 2H), 10.36 (s, 2H), 7.62-7.44 (m, 4H), 7.36-7.21 (m, 4H), 6.46 (d, J=12.1 Hz, 2H), 6.29 (d, J=12.1 Hz, 2 H), 2.22 (d, J=5.7 Hz, 4H) 1.48-1.43 (m, 6H) ppm.

[0276] Step 2: 16.5 g (35.7 mmol) of the product obtained in step 1 was treated with 146 mL acetic anhydride, 3.5 g (42.8 mmol) sodium acetate and butylated hydroxytoluene (80 mg). The reaction mixture was heated at 90° C. for 2 h. The solution was quenched with 400 ml water and the precipitate was filtered, washed with methanol and dried under vacuum. Yield: 10.1 g of maleimide (11) (66%).

[0277] .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ=7.51-7.35 (m, 4H), 7.34-7.20 (m, 4H), 7.16 (s, 4H), 2.39-2.23 (m, 4H) 1.60-1.39 (m, 6H) ppm.

[0278] C) Preparation of Blends & Freestanding Films

[0279] General procedure for blend preparation: A solution of oligomer 4 in toluene (25 wt.-%) was mixed with different amounts of additive (if necessary, dissolved in DMAc or cyclopentanone) and appropriate amounts of a radical starter.

[0280] Preparation of freestanding films: Freestanding polymer films were prepared by doctor blading onto glass substrate either cured thermally or photo-induced (more specified conditions see different examples). The films could be removed from the glass substrate by rinsing the polymer with water.

[0281] Mechanical & Thermal Properties:

[0282] Tensile strength and elongation at break (E2B) were measured on a mechanical testing machine (500 N Zwicki). Young's modulus (modulus) was calculated by dividing the tensile stress by the extensional strain in the elastic (initial, linear) portion of the physical stress-strain curve. Film dimension were typically 25 mm long, 15 mm wide and thicknesses between 25-100 μm). The measurements were performed according to the following parameter set: premeasurement: 0.1 N at an extension rate of 10 mm/min; main extension rate of 50 mm/min. All experiments were conducted at room temperature (23±2° C.).

[0283] Thermomechanical analysis (TMA) was performed on 402F3 TMA (Netzsch) in tension mode. The coefficient of thermal expansion (CTE) was measured in the range from 20-300° C. under N.sub.2 atmosphere.

Example 1

Oligomer 4 with 1,1′-(Methylenedi-4,1-phenylene)-bismaleimide (Aldrich, BMI1)

[0284] ##STR00045## [0285] (a) Curing conditions: Oligomer 4+1 wt.-% AIBN, 1 h at 175° C. (hotplate).

TABLE-US-00001 0 wt.-% 5 wt.-% 10 wt.-% 20 wt.-% 40 wt.-% of BMI1 of BMI1 of BMI1 of BMI1 of BMI1 Modulus     0.231  0.123.sup.   0.127.sup.  — — [GPa] E2B [%]  97 99  .sup.  120   .sup.  — — CTE 4086* 36.sup.#   30.sup.#   140.sup.# 240.sup.# [ppm/K] *CTE between 25-35° C. .sup.#CTE between 140-170° C. [0286] (b) Curing conditions: Oligomer 4+10 wt.-% BMI1+1 or 5 wt-% DCP, 1 h at 175° C. (hotplate).

TABLE-US-00002 0 wt.-% BMI 1 10 wt.-% BMI1 10 wt.-% BMI1 +5 wt.-% DCP +1 wt.-% DCP +5 wt.-% DCP Modulus [GPa]    0.12     0.177 0.21 E2B [%] 216 126 122 CTE [ppm/K] 2016* 1097* 633* | −32.sup.# *CTE between 25-35° C. .sup.#CTE between 140-170° C.

Example 2

Oligomer 4 with Maleimide 5

[0287] ##STR00046## [0288] (a) Curing conditions: Oligomer 4+5 wt.-% maleimide (5)+5 wt.-% N1919T (Adeka), 10 min room temperature, 10 min 100° C. (hotplate), 10 J/cm.sup.2 (broadband), 30 min 175° C. (hotplate).

TABLE-US-00003 0 wt.-% 5 wt.-% Maleimide (5) Maleimide (5) Modulus [GPa]     0.077 0.416 E2B [%] 277 141 CTE [ppm/K] 1232* 633* | −32.sup.# *CTE between 25-35° C. .sup.#CTE between 140-170° C.

[0289] (b) Curing conditions: Oligomer 4+5 wt.-% maleimide (5)+5 wt.-%

[0290] Irgacure OXE-02 (BASF), 10 min room temperature, 10 min 100° C. (hotplate), 10 J/cm.sup.2 (broadband), 30 min 175° C. (hotplate).

TABLE-US-00004 0 wt.-% 5 wt.-% Maleimide (5) Maleimide (5) Modulus [GPa]     0.120 0.668 E2B [%] 210 98 CTE [ppm/K] 2465* 633* | −32.sup.# *CTE between 25-35° C. .sup.#CTE between 140-170° C.

Example 3

Oligomer 4 with pentaerythritol tetraacrylate (Sigma-Aldrich, Acrylate 1)

[0291] ##STR00047##

[0292] Curing conditions: Oligomer 4+various amounts of Acrylate 1+5 wt.-% DCP, 1 h 175° C. (hotplate).

TABLE-US-00005 0 wt.-% 5 wt.-% 10 wt.-% Acrylate 1 Acrylate 1 Acrylate 1 Modulus [GPa]     0.120 0.281 0.490 E2B [%] 216 136 70 CTE [ppm/K] 2364* 16*2|160.sup.# 184*|211.sup.# *CTE between 25-35° C. .sup.#CTE between 140-170° C.

Example 4

Oligomer 4 with (Octahydro-1H-4,7-methanoindene-2,5-diyl)bis(methylene) diacrylate (Sigma-Aldrich, Acrylate 2)

[0293] ##STR00048##

[0294] Curing conditions: Oligomer 4+various amounts of Acrylate 2+5 wt.-% DCP, 1 h 175° C. (hotplate).

TABLE-US-00006 0 wt.-% 5 wt.-% 10 wt.-% 20 wt.-% Acrylate 2 Acrylate 2 Acrylate 2 Acrylate 2 Modulus [GPa]     0.120 0.317 0.385 0.510 E2B [%] 216 147 126 43 CTE [ppm/K] 2364* 204*|30.sup.# 212*|−16.sup.# — *CTE between 25-35° C. .sup.#CTE between 140-170° C.

Example 5

Oligomer 4 with Dimethylmaleimide-SiO.SUB.2 .(50 nm, nanoComposix) (DMMI-SiO.SUB.2.)

[0295] ##STR00049## [0296] (a) Curing conditions: Oligomer 4+DMMI-SiO.sub.2 (nanoComposix, Inc., 50 nm)+5 wt.-% OXE-02, 10 min room temperature, 10 min 100° C. (hotplate), 10 J/cm.sup.2 (broadband).

TABLE-US-00007 0 wt.-% DMMI-SiO.sub.2 0.5 wt.-% DMMI-SiO.sub.2 Modulus [GPa] 0.120 0.437 E2B [%] 210 178 [0297] (b) Curing conditions: Oligomer 4+DMMI-SiO.sub.2 (nanoComposix, Inc., 50 nm)+1 wt.-% AIBN, 1 h 175° C. (hotplate).

TABLE-US-00008 1 wt.-% DMMI-SiO.sub.2 5 wt.-% DMMI-SiO.sub.2 Modulus [GPa] 0.162 0.151 E2B [%] 122 163

Example 6

Oligomer 4 with Acrylate-POSS (Hybridplastics)

[0298] ##STR00050##

[0299] Curing conditions: Oligomer 4+various amounts of Acrylate-POSS (HybridPlastics®, MA0736—Acrylo POSS Cage Mixture)+5 wt.-% DCP, 1 h 175° C. (hotplate).

TABLE-US-00009 0 wt.-% 5 wt.-% 10 wt.-% Acrylate- POSS Acrylate-POSS Acrylate- POSS Modulus [GPa]     0.120 0.105 0.109 E2B [%] 216 170 134 CTE [ppm/K] 2364* 177*|143.sup.# 189*|201.sup.# *CTE between 25-35° C. .sup.#CTE between 140-170° C.

Example 7

Oligomer 4 with Maleimide (8)

[0300] ##STR00051##

[0301] Curing conditions: Oligomer 4+various amounts of maleimide (8)+5 wt % Irgacure OXE-02 (BASF), 10 min room temperature, 10 min 100° C. (hotplate), 10 J/cm.sup.2 (broadband), 30 min 175° C. (hotplate).

TABLE-US-00010 0 wt.-% 5 wt.-% 10 wt.-% Maleimide (8) Maleimide (8) Maleimide (8) Modulus [GPa] 0.213 0.580 0.753 E2B [%] 153 140 77

Example 8

Oligomer 4 with Maleimide (11)

[0302] ##STR00052##

[0303] Curing conditions: Oligomer 4+various amounts of maleimide (11)+5 wt % Irgacure OXE-02 (BASF), 10 min room temperature, 10 min 100° C. (hotplate), 10 J/cm.sup.2 (broadband), 30 min 175° C. (hotplate).

TABLE-US-00011 0 wt.-% 5 wt.-% 10 wt.-% Maleimide (11) Maleimide (11) Maleimide (11) Modulus [GPa] 0.213 0.580 0.500 E2B [%] 153 90 3