METAL-CLATTED LAMINATES CONTAINING POLYORGANOSILOXANES

Description

[0001] The present invention relates to metal-clad laminates containing crosslinkable organopolysiloxane compounds. State of the art:

[0002] According to DIN 40802 Sheet 2, copper-clad electrical laminates consist of a laminate coated on one or both sides with electrolytic copper foil with a purity of at least 99.5%. The laminate serves as the carrier and insulation material, while the copper layer is used to create the conductor tracks. Three products have gained importance in electrical laminates. The laminate consists of laminated paper, epoxy laminated paper, or epoxy resin glass fabric.

[0003] Despite its higher price compared to laminated paper, epoxy resin glass fabric is increasingly being used, especially in telecommunications technology, where higher frequencies are used. The advantages of this electrical laminate include high mechanical strength, better electrical properties when exposed to moisture, and low dielectric losses at high frequencies.

[0004] The production of electrical laminates proceeds as follows. The paper or fabric sheets for the laminate, such as fiberglass sheets, are impregnated with a resin that acts as a binder. Epoxy polyester, phenol, or melamine are commonly used for this purpose. The impregnated sheets are then dried, pre-condensing the resin to the desired degree.

[0005] With the progressive expansion of high-frequency technology into the GHz range for wireless communications, the need for materials suitable for its implementation is increasing. This affects all areas of materials such as copper foils, binders, glass fibers, etc. Regarding binders, the epoxy resins traditionally used for the production of copper-clad laminates or for circuit board manufacturing are no longer suitable for GHz applications due to their high dielectric loss factors. Polytetrafluoroethylene, which has a very low dielectric loss factor and is well-suited for high-frequency applications in this respect, has other disadvantages, particularly poor processability and poor adhesion properties, which make an alternative desirable.Polyphenylene ethers, hydrocarbon resins, and bismaleimides, as well as variants such as bismaleimide triazine resins and combinations of the aforementioned organic polymers, are currently being intensively researched as binders for this application area because they combine low dielectric loss factors with good mechanical and thermal properties and water repellency. Polyorganosiloxanes possess excellent heat resistance, weathering stability, and hydrophobicity, are flame-resistant, and have low dielectric loss factors.

[0006] These property profiles qualify the polyphenylene ethers, bismaleimides, bismaleimide triazine and hydrocarbon resins as well as the polyorganosiloxanes for use as binders for the production of high-frequency capable copper-clad laminates and components, such as circuit boards and antennas.

[0007] It therefore makes sense to use silicone resins both as binders for these high-frequency applications and to combine the positive properties of silicones with those of the aforementioned organic polymers to symbiotically enhance their performance. Corresponding experiments have already been documented in the state of the art.

[0008] In polyorganosiloxanes, neighboring silicon atoms are predominantly bonded to each other via oxygen atoms. However, other ways in which neighboring silicon atoms can be bonded to each other are also known, such as units bridged by organic residues.

[0009] Organic residues that bridge neighboring silicon atoms, for example, always arise as a result of a hydrosilylation reaction in which an Si-H group adds to an unsaturated silicon-bonded organic residue. Such reactions are primarily known for curing a preparation containing these two types of functional groups after application of the preparation to permanently fix an achieved application result, see, for example, US 2018 / 0370189. They can also be used to produce polyorganosiloxanes containing organic residues bridging neighboring silicon atoms, thereby forming a further processable species. In these cases, the preformed silicone structures and compositions are retained, and block copolymer structures are always formed, retaining the starting structures as their constituent block segments.A statistical distribution of the organic substituents bridging two silicon atoms is not possible in this way. Furthermore, the number of bridging units is limited by the number of terminal functional groups. Particularly if this approach is chosen to fix a final state once it has been reached, it should be noted that the curing reaction causes volume shrinkage, which leads to stresses in the cured matrix and limits or reduces mechanical performance. This approach is therefore unsuitable for incorporating any number of such bridging units into an organopolysiloxane structure, for example, if they have a particular function for a chosen application, and is limiting, for example, for the invention as set forth in US 2018 / 0370189.

[0010] US 10316148 teaches organopolysiloxanes of the formula (R 1< SiO 3 / 2 ) a (XR 2< 2 SiO 1 / 2 ) b (O 1 / 2 SiR 2< 2 YR 2< 2 SiO 1 / 2) ) c , where R 1< and R 2< are each independently C 1 -C 20 alkyl groups, C 6 -C 20 aryl groups or C 7 -C 20 aralkyl groups. If X is a C 2 -C 12 alkanediyl group or a linear Si-H functional siloxane radical comprising 2 - 7 Si units and having a bridging C 2 -C 12 alkanediyl group, then Y is a linear bridging siloxane group having 2 to 7 siloxane units, wherein Y is in each case incorporated into the organopolysiloxane according to the invention via a bridging C 2 -C 12 alkanediyl group.

[0011] If X represents a C 2 -C 12 alkanediyl group or a Si-H terminated siloxane radical consisting of two siloxane units, in which the two siloxane units are connected by a bridging silphenylene radical, Y represents a siloxane radical comprising two siloxane units, in which the two siloxane units are connected to one another by a bridging silphenylene radical and the radical Y is in each case incorporated into the organopolysiloxane according to the invention via a bridging C 2 -C 12 alkanediyl group.

[0012] X and Y are chosen such that they lead to the formation of exclusively linear structures, so that in principle block copolymers of polyorganosiloxanes are present in which the (R 1< SiO 3 / 2 ) units form the three-dimensional silicone resin block and the (XR 2< 2 SiO 1 / 2 ) b (O 1 / 2 SiR 2< 2 YR 2< 2 SiO 1 / 2) ) c units form the linear block. Unsaturated organic radicals that could be reacted by a radical reaction are not present. These are completely consumed in the formation reaction of the polyorganosiloxanes according to the invention by hydrosilylation, in which the Si-H groups are used in excess, so that Si-H-terminated polyorganosiloxanes are formed. a is a number from 0.65 to 0.9, b is a number from 0.1 to 0.35 and c is a number from 0 to 0.1, where a+b+c=1.

[0013] The organopolysiloxanes of this invention are prepared by a hydrosilylation reaction of a polyorganosiloxane (R 1< SiO 3 / 2 ) d (R 5< R 2< 2 SiO 1 / 2 ) e where R 5< is an olefinically unsaturated C2 - C12 alkenyl group, d is a number from 0.65 to 0.9 and e is a number from 0.1 - 0.35 with a linear Si-H terminal polyorganosiloxane of the formula HR 3< 2 SiO(R 3< 2 SiO) n SiR 3< 2 H or a disilylbenzene of the formula HR 3< 2 Si-C 6 H 4 -SiR 3< 2 H, where both a double and a single hydrosilylation of the doubly Si-H terminated siloxane components is possible.

[0014] Both the alkanediyl-bridged and the phenylene-bridged building blocks are exclusively embedded in linear segments of the polysiloxane structure, in which the silicon atoms bridged by the alkanediyl group or the phenylene group are always bonded to only one other silicon atom and are not the starting point for branching through bonds to several silicon atoms.

[0015] The polyorganosiloxanes according to US 10316148 exhibit a high refractive index, high transparency, and good processability for use in optical semiconductor elements. Due to the formation reaction by hydrosilylation, they contain platinum as an impurity.

[0016] US 2015 / 0144987 teaches hydrosilylatable preparations of alkenyl-functional three-dimensional polyorganosiloxanes, linear alkenyl-functional polyorganosiloxanes, linear Si-H terminal polyorganosiloxanes containing silphenylene groups, optionally a further linear Si-H terminated component that does not contain a silphenylene unit, and a hydrosilylation catalyst. After curing by hydrosilylation, the preparations of this invention, like the polyorganosiloxanes of US 10316148, also possess both adjacent alkanediyl-bridged and phenylene-bridged silicon atoms. The phenylene-bridged silphenylene units are always linear polyorganosiloxane segments in which the silicon atoms bridged by the phenylene group are always bound to only one other silicon atom by a Si-O-Si bond and are not the starting point for branching by bonds to several silicon atoms.Due to the hydrosilylation reaction, these polyorganosiloxanes also contain platinum as an impurity.

[0017] The preparations have high Abbe numbers, good color stability in optical semiconductor elements and are used for encapsulation thereof.

[0018] US 6072016 teaches linear polyorganosiloxanes containing silphenylene groups that are crosslinkable via terminal condensable groups. They do not contain Si-H functions or aliphatically unsaturated groups.

[0019] US 6252100 discloses processes for the preparation of linear organopolysiloxanes containing structural units in which two R 2 Si units are linked to one another via a bifunctional α, ω-alkanediyl radical having 2 to 18 C atoms.

[0020] US 6034225 describes linear organopolysiloxanes with aliphatically unsaturated radicals, which contain, among other things, at least one unit of the formula O 1 / 2 R 2 SiO x YRSiO 2 / 2 , which may contain a branch, and optionally also O 1 / 2 R 2 SiO x YR 2 SiO 1 / 2 units, which in turn would be purely linear. When x = 0, either a dialkyl unit is linked to an alkylsiloxy unit, which is linked to two adjacent silicon atoms via oxygen atoms, or / and two dialkylsiloxy units are linked to one another via the spacer Y. Y is a bifunctional radical of the formula - (CR 3< 2 ) n CHR 3< -, where R 3< is an aliphatically saturated hydrocarbon radical or H and n is zero or an integer from 1 to 7. Organopolysiloxane compounds with active hydrogen in the form of H-Si compounds and hydrocarbon bridges between two Si atoms are described in EP 786 463 A1 as well as JP 06,107,949 and US 4849491.

[0021] US 20100137544 teaches polyorganosiloxanes which contain at least one structural unit of the general formula (I) per molecule: O 3-a / 2 R a Si-Y(SiR a O 3-a / 2 ) b, where R can be the same or different and denotes a monovalent Si-C bonded organic radical having 1 to 30 C atoms, which may contain one or more N and / or O atoms; Y denotes a di- to twelve-valent organic radical having 1 to 30 C atoms, which may contain one or more O atoms and which may be unsaturated; a is 0 or 1 and b is an integer from 1 to 11.

[0022] Document WO 2014 / 100656 A1 discloses the preparation of an organopolysiloxane of the present formula (I). This polymer is used for the production of metal-plated laminates. Task:

[0023] The present invention is dedicated to the task of providing polyorganosiloxanes that are three-dimensionally crosslinkable under radical polymerization conditions and that possess dielectric properties suitable for use as binders for high-frequency applications. This includes, as a pure binder, a dielectric loss factor of no more than 0.0040 at 10 GHz, good wetting of any fillers present that reduce the dielectric loss factor, and the production of tack-free prepregs.

[0024] The present invention relates to metal-clad laminates which contain crosslinkable, ie curable organopolysiloxane compounds of the formula (I) [O 3-a / 2 R a S1-Y(SiR a O 3-a / 2 ) b ] c (R 1< SiO 3 / 2 ) d (R 2< 2 SiO 2 / 2 ) e (R 3< 3 SiO 1 / 2 ) f (SiO 4 / 2 ) g (I) where R can be the same or different and is either a hydrogen radical or a monovalent Si-C-bonded, optionally heteroatom-substituted organic hydrocarbon radical having 1 to 18 C atoms, which may also be an unsaturated hydrocarbon radical, Y is a divalent to dodecavalent organic radical having 1 to 24 C atoms, optionally substituted by heteroatoms, where the Y radical is always bonded to the silicon atoms by a Si-C bond, which are connected to one another by the Y radical, R 1< independently of one another is a hydrogen radical or a preferably Si-C-bonded unsaturated C1 - C18 hydrocarbon radical, which may optionally be substituted by heteroatoms, which may optionally also be bonded to the silicon atom via an oxygen atom, where the R 1< radicals can each assume their meaning independently of one another,so that several radicals R 1< in the organopolysiloxane according to formula (I) can denote different radicals from the defined group, the radicals R 2< and R 3< independently of one another denote a hydrogen radical or an optionally unsaturated Si-C-bonded C1 - C18 hydrocarbon radical, which can optionally be substituted by heteroatoms, or a C1 - C12 hydrocarbon radical bonded via an oxygen atom and optionally containing heteroatoms, where the radicals R 2< and the radicals R 3< can each assume their meaning independently of one another, so that several radicals R 2< or several radicals R 3< which are bonded to the same silicon atom can denote different radicals from the defined group, where, based on all Si-C-bonded radicals Y, R, R 1<, R 2< and R 3< as 100 mol%, at least 0.1 mol%, preferably at least 3 mol%, particularly preferably at least 5 mol%, in particular at least 7 mol% aliphatic,ie must be olefinically or acetylenically unsaturated radicals, a is 0, 1 or 2, where the indices a on both sides of the group Y can assume their meaning independently of one another, so that different a's can independently of one another have different values ​​within the stated value range, b is a number with a value of 1 to 11, preferably 1, c is a value of 0.1 to 0.99, preferably from 0.2 to 0.98, particularly preferably from 0.25 to 0.8, in particular from 0.3 to 0.8, d is a value of 0 to 0.8, preferably from 0.1 to 0.7, particularly preferably from 0.1 to 0.6, in particular from 0.1 to 0.5, e is a value of 0 to 0.5, preferably from 0 to 0.2, f is a value of 0.01 to 0.6 and g is a value of 0 to 0.2, where c+d+e+f+g = 1. ,

[0025] The organopolysiloxane compounds of formula (I) serve as binders and / or adhesion promoters for the metal-clad laminates. The organopolysiloxane compounds of formula (I) are crosslinked prior to application of the laminates. The laminates are preferably metal-clad laminates. The laminates are preferably used in electronic components, preferably in high-frequency applications, especially those operating at frequencies of 1 GHz and above.

[0026] Surprisingly, it has been found that suitable polyorganosiloxanes or preparations thereof carrying unsaturated organic functional groups are particularly well suited for this purpose, which, in addition to regular siloxane units linked to one another by oxygen atoms, also contain structural groups in which adjacent silicon atoms are not linked to one another by oxygen atoms, but which are bridged by bridging alkylene, aralkylene or arylene units bonded on both sides by Si-C bonds, provided that at the same time polar heteroatom-substituted groups on the polyorganosiloxane are avoided, ie are reduced as far as possible by suitable measures according to the state of the art, including in particular alkoxy groups and silanol groups.

[0027] Polar groups such as alkoxy groups, especially with short alkyl groups and silanol groups, have higher dielectric loss factors themselves and also contribute to increasing the dielectric loss factor by forming points of attack for moisture.

[0028] Since the electronegativity difference between silicon and oxygen, according to the Allred and Rochow electronegativity scale, is 1.76 µm, which is greater than the electronegativity difference between silicon and carbon according to the same table, the Si-C bond has a lower polarity than the Si-O bond. It is therefore expected that replacing Si-O bonds with Si-C bonds will contribute to reducing the overall polarity of organopolysiloxanes and thus to reducing the dielectric loss factor of the corresponding components. This effect is all the more pronounced the more Si-O bonds can be replaced by Si-C bonds. Reducing the polarity in the organopolysiloxane framework, for example, by introducing Si-C bonds instead of Si-O bonds, thus makes a significant contribution to the broad applicability of such organopolysiloxanes.

[0029] Since polydiorganosiloxanes, as oils, lack binder properties, they are unsuitable as binders for metal-clad composites. Consequently, US 2018 / 0370189 also uses silicone resins as binders, which are simply adjusted in viscosity with silicone oils and cured to form block copolymers. However, the actual binder is the silicone resin, not the silicone oil. However, there are no references to the targeted adaptation and optimization of the silicone resins used for the application described in US 2018 / 0370189, as the existing possibilities for this were apparently not recognized.

[0030] The present invention improves and further develops the prior art according to US 2018 / 0370189. In order to specifically utilize the effect of the reduced polarity of the siloxane backbone, it is not sufficient to create Si-C-bonded organic residues bridging neighboring silicon atoms solely by curing any Si-H groups and Si-olefin groups present through hydrosilylation at the end of an application process. The associated volume shrinkage due to the addition reaction according to US 2018 / 0370189 places excessive limitations on the property-related application of this option.

[0031] The organopolysiloxane compounds of formula (I) have a dielectric loss factor of no more than 0.0040 at 10 GHz.

[0032] The organopolysiloxane compounds of formula (I) in the context of the present invention include both polymeric and oligomeric organosiloxanes.

[0033] In particular, structures of the formula (Ia) are also included, [O 3-a / 2 R a Si-Y(SiR a O 3-a / 2 ) b ] c (R 3< 3 SiO 1 / 2 ) f (Ia) for which d, e and g are each 0. This limiting structure is included in the scope of the invention and is meant by. Therein, the proportion of Si-C bonded bridging organic radicals is particularly high and the structure is practically only terminated by the terminating units (R 3< 3 SiO 1 / 2 ) f. In a preferred embodiment of (Ia), the value for a = 2. All details for R, R 3< , a, b and c as stated above also remain valid for (Ia).

[0034] Examples of R, R 1< , R 2< and R 3< are saturated or unsaturated hydrocarbon radicals which may contain aromatic or aliphatic double bonds, e.g. alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl and tert.- Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl and the 2-ethylhexyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, tetradecyl radicals such as the n-tetradecyl radical, hexadecyl radicals such as the n-hexadecyl radical and octadecyl radicals such as the n-octadecyl radical, cycloalkyl radicals such as the cyclopentyl, cyclohexyl and 4-ethylcyclohexyl radical, cycloheptyl radicals, norbornyl radicals and methylcyclohexyl radicals, aryl radicals such as the Phenyl, biphenyl, naphthyl, anthryl, and phenanthryl radicals; alkaryl radicals such as o-, m-, and p-tolyl radicals, xylyl radicals, and ethylphenyl radicals; aralkyl radicals such as the benzyl radical; alkenyl radicals such as the 7-octenyl, 5-hexenyl, 3-butenyl, allyl, and vinyl radicals, as well as the alpha- and β-phenylethyl radicals.

[0035] Preferred heteroatoms that can be present in the radicals R, R 1< , R 2< , and R 3< are oxygen atoms. Nitrogen atoms, phosphorus atoms, sulfur atoms, and halogen atoms such as chlorine atoms and fluorine atoms are also possible.

[0036] Examples of preferred organic radicals R, R 1< , R 2< , and R 3< containing heteroatoms are radicals containing acryloyloxy or methacryloyloxy radicals of acrylic acid or methacrylic acid, as well as the acrylic acid esters or methacrylic acid esters of unbranched or branched alcohols having 1 to 15 carbon atoms. Preferred such radicals are those derived from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.These radicals are preferably not bonded directly to the silicon atom, but are bonded via a hydrocarbon spacer which may comprise 1 to 12 carbon atoms, preferably comprising 1 or 3 carbon atoms and not comprising any further heteroatoms apart from the heteroatoms contained in the acryloyloxy or methacryloyloxy radical.

[0037] Further preferred radicals R, R 1< , R 2< and R 3< comprising heteroatoms are those of the formula (II).

[0038] Preferably, the hydrocarbon radicals R, R 1< , R 2< and R 3< are selected from methyl, phenyl, vinyl, acryloyloxy and methacryloyloxy radicals and the acrylic acid esters or methacrylic acid esters of unbranched or branched alcohols having 1 to 15 C atoms.

[0039] In formula (II), R 4< , R 5< , R 6< , R 7< , R 8< and R 9< independently of one another represent a hydrogen radical, a hydrocarbon group or a hydrocarbon group substituted by foreign atoms, where at least one of the radicals R 4< , R 5< , R 6< , R 7< or R 8< is always a hydrocarbon group which is bonded to the silicon atom via an Si-C or an Si-OC bond, wherein it is preferred that this hydrocarbon group, via which the radical of formula (II) is bonded to a silicon atom, is a C3 hydrocarbon group which contains no heteroatoms. Alternatively, the radical R 4< , R 5< , R 6< , R 7< or R 8< can also be a chemical bond, so that the radical of formula (II) is bonded directly to the silicon atom via this radical, which represents a chemical bond, via an Si-C bond.

[0040] Examples of radicals R 4< , R 5< , R 6< , R 7< , R 8< or R 9< are the hydrogen radical, saturated hydrocarbon radicals such as methyl, ethyl, n-propyl, iso-propyl, the primary, secondary and tertiary butyl radical, the hydroxyethyl radical, aromatic radicals such as the phenylethyl radical, the phenyl radical, the benzyl radical, the methylphenyl radical, the dimethylphenyl radical, the ethylphenyl radical, heteroatom-containing radicals such as the hydroxymethyl radical, the carboxyethyl radical, the methoxycarbonylethyl radical and the cyanoethyl radical and acrylate and methacrylate radicals such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, t-butyl acrylate, t-Butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate, olefinically or acetylenically unsaturated hydrocarbon residues.

[0041] Optionally, the adjacent radicals R 4< and R 6< as well as the adjacent radicals R 5< and R 7< can also be linked to one another to form the same cyclic saturated or unsaturated radical, so that fused polycyclic structures are formed.

[0042] Examples of phenol radicals of the formula (II) are the phenol radical, the ortho-, meta- or para-cresol radical, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol radical, 2-methyl-6-phenylphenol radical, 2,6-diphenylphenol radical, 2,6-diethylphenol radical, 2-methyl-6-ethylphenol radical, 2,3, 5-, 2,3,6- or 2,4,6-trimethylphenol radical, 3-methyl-6-tertiary-butylphenol radical, thymol radical and 2-methyl-6-allylphenol radical, which may optionally be substituted on the oxygen atom.

[0043] Preferred examples of fluorine-containing radicals are the trifluoropropyl, nonafluorohexyl and heptadecafluorooctyl radicals.

[0044] Y is preferably a linking organic unit having 1 to 24 carbon atoms between preferably two to twelve siloxanyl units. Y is preferably divalent, trivalent, or tetravalent, especially divalent.

[0045] Preferred bridging aromatic radicals Y are those of the formula (IIIa), (IIIb) and (IIIc) where the radicals R 10< , R 11< , R 12< and R 13< may be a hydrogen radical or an optionally substituted hydrocarbon radical or a group of the formula OR 14< where R 14< is a hydrocarbon radical. Adjacent radicals such as, for example, R 10< and R 12< or R 11< and R 13< in formula (IIIa) may be coupled to one another to form cyclic radicals, thus forming fused ring systems.

[0046] Typical examples of such bridging aromatic radicals are the p-, m- or o-phenylene radical, the 2-methyl-1,4-phenylene radical, the 2-methoxy-1,4-phenylene radical, with the p-phenylene radical being particularly preferred.

[0047] Optionally, several such radicals can also be coupled together, so that, for example, two or more units of formula (IIIa) are coupled together, and this oligomeric bridging structural element is present by bonding the corresponding carbon atoms of the terminal aromatic rings to silicon atoms. The aromatic units can be directly bonded to one another or they can be coupled together by a bridging group such as an alkanediyl unit, for example, a methylene group, a 1,2-ethanediyl group, a 1,1-ethanediyl group, a 2,2-dimethylpropyl group, or a sulfone group.

[0048] Further examples of aromatic bridging units are those in which two optionally substituted phenol rings are bridged via an alkanediyl or other unit. Typical representatives are 2,2-bis(4-hydroxyphenyl)propane residues substituted on the phenol oxygen (substituted bisphenol A residues), 2,2-bis(4-hydroxyphenyl)methane residues (substituted bisphenol F residues), and bis(4-hydroxyphenyl)sulfone residues (bisphenol S residues), where the phenol oxygen atoms are typically substituted with residues of the type -(C 3 H 6 )-, where the -(C 3 H 6 )- residues are bonded to silicon atoms Si-C, thereby creating the bridge.

[0049] Preferred Y radicals not bridged by an aromatic unit are alkanediyl, alkenediyl and alkynediyl radicals, which may optionally contain heteroatoms and which may contain aromatic groups as substituents, but which do not take over or contribute to the bridging function in these radicals.

[0050] Typical examples are the methylene radical, the methine radical, the tetravalent carbon, the 1,1-ethanediyl and the 1,2-ethanediyl group, the 1,4-butanediyl and the 1,3-butanediyl group, the 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonadiyl, 1,10-decanediyl, 1,11-undecanediyl and the 1,12-dodecanediyl group, the 1,2-diphenylethanediyl group, the 1,2-phenylethanediyl group, the 1,2-cyclohexylethanediyl group. If a linear bridging unit has more than one carbon atom and the substitution pattern allows it, each of these groups can act as a bridge not only through alpha-omega connectivity, i.e. bridging through the first and last atom of a linear unit, but also through any other connectivity, i.e. the use of other chain carbon atoms.In addition, typical examples are not only the linear representatives of the bridging hydrocarbons mentioned, but also their isomers, which in turn can have a bridging effect by binding different C atoms of the hydrocarbon structure to silicon atoms.

[0051] Examples of particularly preferred radicals from the group of non-aromatic heteroatom-free hydrocarbon radicals are -CH 2 CH 2 -, -CH(CH 3 )-, -CH=CH-, -C(=CH 2 )- and -C≡C-.

[0052] Examples of typical fluorine-substituted bridging radicals Y are the -C(CF 3 ) 2 -, the -C(H)FC(H)F- and the -C(F 2 )-C(F 2 )- radical.

[0053] Examples of typical heteroatom-containing bridging radicals include the ethyleneoxypropylene radical and the ethyleneoxybutylene radical. Also typical are glycol radicals or phenylene ether radicals that are terminated on both sides with -(CH 2 ) n - or -CH 2 -CH(R 15< )-C(=O)O, where n is typically 3 to 8 and R 15< is a hydrogen atom or a methyl group, and bonded to the silicon atoms via this terminal group.

[0054] All lists are only examples and should not be understood as limiting.

[0055] The organopolysiloxane compounds of formula (I) can vary in viscosity over a wide range depending on the average number of structural units per molecule forming them or can also be solids.

[0056] Liquid organopolysiloxane compounds of formula (I) have, in the uncrosslinked state at 25°C, viscosities of preferably 20 to 8,000,000 mPas, particularly preferably 20 to 5,000,000 mPas, in particular 20 to 3,000,000 mPas.

[0057] Solid organopolysiloxane compounds of formula (I) in the uncrosslinked state have glass transition temperatures in the range of preferably 25°C to 250°C, particularly preferably 30°C to 230°C, in particular 30°C to 200°C. Organopolysiloxanes that contain bridging phenylene units and that have a total aromatic content of at least 20 mol%, based on all Si-C-bonded substituents, have proven particularly suitable. Phenylene units are understood to include both monomeric and oligomeric, as well as substituted and unsubstituted phenylene units, as illustrated in the examples for the nature of the bridging substituents of this type.

[0058] The organopolysiloxane compounds of formula (I) can be prepared by any method. A preferred method for preparing these compounds is the hydrolysis and cocondensation of compounds of the general formula (IV) X 3 -aRaSi-Y(SiR a X 3-a ) b (IV) with compounds of the formula (V) R 16< h SiX 4-h (V), where X is a hydrolyzable group, h is an integer from 0 to 3, where R 16< for h = 1 is a radical R 1<, for h = 2 is a radical R 2< and for h = 3 is a radical R 3< and R, Y, a and b have the meaning already given.

[0059] The compounds (IV) are obtained by state-of-the-art processes, with the reaction types used depending heavily on the composition of the respective compound (IV). Typically, compounds (IV) are obtained, for example, from olefinically unsaturated organic precursors, such as acetylene, diallyl or divinyl compounds, and Si-H-functional silicone building blocks by hydrosilylation.

[0060] Grignard reactions from halogenated organic precursors and subsequent reaction with halogenated or alkoxylated organosilanes are also conceivable processes. Metal halide exchange reactions of halogenated organic precursors with alkyl alkali metal compounds, such as butyllithium, and known subsequent reactions for linking with silicone building blocks can also be used. Such processes are known to the person skilled in the art and are easily accessible and understandable from the available literature. Since these processes are not the subject of the invention, only a reference to the documented and searchable prior art is provided here.

[0061] The relative proportions in which the compounds of formula (IV) are cocondensed with the compounds of formula (V) are determined by the values ​​of the indices c, d, e, f and g in formula (I).

[0062] Preferably, X is a halogen, acid or alkoxy group, particularly preferably a chlorine, acetate, formate, methoxy or ethoxy group.

[0063] The organosiloxanes thus obtained can optionally be further modified and altered by further reactions, such as equilibration, so that almost any branched siloxane oligomers and polymers and silicone resins can be prepared by applying known processes according to the prior art, all of which are understood to be organopolysiloxanes in the context of the present invention.

[0064] Cohydrolysis is preferably carried out by dosing a mixture of compounds (IV) and (V) into water or dilute acids while cooling. For gaseous acids such as HCl, dosing into a concentrated aqueous HCl solution is also useful if the released acid is to be recovered as a gas. Depending on the nature of the group X, the hydrolysis is more or less exothermic, so cooling is necessary both to ensure safe reaction execution and, if necessary, to avoid side reactions in corresponding synthesis sequences. However, to complete the reactions, it may be advantageous and necessary to apply elevated temperatures.

[0065] Reaction times are generally very short in the case of chlorosilanes, so the time required to carry out the process in batch mode depends primarily on the cooling capacity. Alternatively, the cohydrolysis of (IV) and (V) can also be carried out continuously, for which loop, column, and tubular reactors are suitable.

[0066] To remove residual acids, good washing with water, clean phase separation and purification of the hydrolysis product in vacuum are advantageous.

[0067] The process can be performed at normal pressure. However, depending on the objective, higher or lower pressure is also practical.

[0068] By using the groups of the formula (R 3< 3 SiO 1 / 2 ) f , it is possible to control the molecular weight as well as to reduce the alkoxy and silanol groups during the synthesis.

[0069] The latter form during the synthesis, provided this is carried out in a hydrolytic process, which is the preferred embodiment. If a chlorosilane precursor is used to generate the groups of the formula (R 3< 3 SiO 1 / 2 ) f , symmetrical disiloxanes are also formed from these precursors during the synthesis. These disiloxanes can, however, be cleaved again under the conditions of acid hydrolysis and are therefore still available as terminating groups for reactions with silanol groups that are formed on the organopolysiloxane after hydrolysis of the chlorosilane starting materials. This achieves the reduction of the silanol groups. Since alkoxy groups, particularly those with small alkyl radicals, also form silanol groups under the conditions of acid hydrolysis with the elimination of short-chain alcohols, the alkoxy groups are also reduced by the use of the terminating groups. These can also be used in excess, since possiblyRemaining disiloxanes can usually be distilled off after the synthesis has been completed, especially if they are exclusively or predominantly substituted with short-chain alkyl radicals, especially methyl radicals.

[0070] The chlorosilanes or disiloxanes forming these terminal groups can also be added separately in a final step of the synthesis, and the silanol groups can be reduced using acidic hydrolytic conditions. It is advantageous to always use an excess of terminating chlorosilanes and to remove the resulting disiloxanes by distillation. Vinyldimethylchlorosilane, dimethylchlorosilane, or trimethylchlorosilane are particularly advantageous for this purpose, as the resulting disiloxanes are particularly easy to separate by distillation. Alternatively, it is also possible to use the disiloxanes directly and select hydrolytic conditions; in this case, the addition of a sufficient amount of catalytic acid, preferably hydrochloric acid, is required. Typically, between 50 and 1000 ppm of hydrochloric acid is used in this case, based on the amount of siloxane in the reaction mixture.

[0071] Residual silanol contents of less than 1 percent by weight are achieved. Since the exhaustive elimination of silanol contents to the technically possible minimum is not the subject of the invention, this step was not further optimized.

[0072] The metal-clad laminates preferably contain preparations containing organopolysiloxane compounds of formula (I) and other components.

[0073] The organopolysiloxane compounds of formula (I) are chemically curable, meaning they can be cured by a chemical reaction to form a crosslinked, insoluble network. Curing occurs via the olefinically unsaturated groups described above. Typically, either a radical polymerization reaction is used for curing or, if silicon-bonded hydrogen is present as a residue in addition to the olefinically or acetylenically unsaturated functional groups, a hydrosilylation cure.

[0074] The organopolysiloxane compounds of formula (I) all possess aliphatically unsaturated functional groups, via which they are chemically crosslinkable. Possible chemical crosslinking reactions include the known reactions according to the prior art, in particular radical crosslinking, which can be initiated using suitable radiation sources such as UV light, as well as by unstable chemical compounds that decompose into radicals, and addition crosslinking, for example, by hydrosilylation of the olefinically unsaturated group with an Si-H function in the presence of a suitable hydrosilylation catalyst, which is another component of the preparations.

[0075] To achieve sufficient curing, a sufficient amount of functional groups must be present. At least 1.0 functional groups on average must be present per molecule of organopolysiloxane compounds of the formula (I) to achieve sufficient curing; preferably, at least 1.1, in particular at least 1.2, functional groups on average are present per molecule of organopolysiloxane compounds of the formula (I). The functional groups can be different, so that, for example, some of the functional groups are an Si-H group and another part of the functional groups represents an olefinically unsaturated group that is radically curable or hydrosilylatable. Other combinations of complementary functional groups are also conceivable, where complementary means that the selected combinations of functional groups can react with one another.If only one type of functional group is present, for example, only olefinically or acetylenically unsaturated functional groups that are radically curable, the corresponding number of these functional groups must be present. For copolymerization to form a homogeneous matrix, it is important to ensure sufficient copolymerizability of the selected olefinic and acetylenic groups. The combination of olefinic groups that are not copolymerizable with each other is also possible, provided the resulting matrix of two or more individual polymers remains compatible with each other and does not form separate phases that separate into distinct domains.

[0076] A suitable initiator can therefore be present as a further component of the preparations to start the radical polymerization. Examples of suitable initiators include, in particular, examples from the field of organic peroxides, such as di-tert-butyl peroxide, dilauryl peroxide, dibenzoyl peroxide, dicumyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl cumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-ditert-butylperoxycyclohexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert.-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dibenzyl peroxydicarbonate, diisopropylbenzene dihydroperoxide, [1,3-phenylenebis(1-methylethylidene)]bis[tert-butyl]peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, dicetyl peroxydicarbonate, acetylacetone peroxide, acetylcyclohexanesulfonyl peroxide, tert-amyl hydroperoxide, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxyisopropyl carbonate, tert-amyl peroxyneodecanate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl monoperoxymaleate, this list being only illustrative and not restrictive. If necessary, mixtures of different initiators can also be used for radical reactions. The suitability of an initiator or initiator mixture for radical reactions depends on its decomposition kinetics and the required conditions to be met.By taking sufficient account of these general conditions, the expert will be able to select a suitable initiator.

[0077] Organopolysiloxane compounds of formula (I) that contain silicon-bonded hydrogen in addition to olefinically and acetylenically unsaturated groups can be cured by a hydrosilylation reaction. Suitable catalysts to promote the hydrosilylation reaction can be present as additional components of the preparations.

[0078] Examples of such catalysts are compounds or complexes of the noble metal group containing platinum, ruthenium, iridium, rhodium, and palladium, preferably metal catalysts from the platinum group or compounds and complexes from the platinum group. Examples of such catalysts are metallic and finely divided platinum, which can be on supports such as silicon dioxide, aluminum oxide, or activated carbon, compounds or complexes of platinum such as platinum halides, e.g.PtCl 4 , H 2 PtCl 6 x6H 2 O, Na 2 PtCl 4 x4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H 2 PtCl 4 x6H 2 O and cyclohexanone, platinum-vinyl-siloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, with or without detectable inorganically bound halogen, bis-(gamma-picoline)-platinum chloride, trimethylenedipyridineplatinum chloride, dicyclopentadieneplatinum dichloride, dimethylsulfoxyethenylplatinum(II) dichloride, cyclooctadieneplatinum dichloride, norbornadieneplatinum dichloride, gammapicolineplatinum dichloride, Cyclopentadiene platinum dichloride, as well as reaction products of platinum tetrachloride with olefin and primary or secondary amine or primary and secondary amine such as the reaction product of platinum tetrachloride dissolved in 1-octene with sec-butylamine or ammonium platinum complexes.In a further embodiment, complexes of iridium with cyclooctadienes, such as µ-dichloro-bis(cyclooctadiene)-diiridium(I), are used.

[0079] This list is illustrative and not limiting. The development of hydrosilylation catalysts is a dynamic field of research that continually produces new, effective species that can naturally also be used in this field.

[0080] The hydrosilylation catalyst preferably comprises compounds or complexes of platinum, preferably platinum chlorides and platinum complexes, in particular platinum-olefin complexes and particularly preferably platinum-divinyltetramethyldisiloxane complexes.

[0081] In the curing process, the hydrosilylation catalyst is used in amounts of 2 to 250 ppm by weight, preferably in amounts of 3 to 150 ppm, in particular in amounts of 3 to 50 ppm.

[0082] The organopolysiloxane compounds of formula (I) are particularly suitable for use as binders for the production of metal-clad electrical laminates, for example as used for the production of printed circuit boards in electronic devices, in particular for high-frequency applications.

[0083] These metal-clad electrical laminates may, but are not required to, contain reinforcing materials. This means they may, for example, contain reinforcing fabrics such as fiber fabrics or nonwovens, or they may be free of them. If reinforcing materials are included, they are preferably arranged in layers. A reinforcing layer can be composed of a variety of different fibers. Such reinforcing layers help control shrinkage and provide increased mechanical strength.

[0084] If a reinforcing layer is used, the fibers forming this layer can be selected from a wide variety of options. Non-limiting examples of such fibers include glass fibers, such as E-glass fibers, S-glass fibers, and D-glass fibers; silica fibers; polymer fibers, such as polyetherimide fibers, polysulfone fibers, polyetherketone fibers, polyester fibers, polycarbonate fibers, aromatic polyamide fibers, or liquid crystalline fibers. The fibers can have a diameter of 10 nm to 10 µm. The reinforcing layer has a thickness of at most 200 µm, preferably at most 150 µm.

[0085] A preferred application is the use of the organopolysiloxane compounds of formula (I) as binders or cobinders together with organic binders for the production of metal-clad laminates from glass fiber composites for the further production of printed circuit boards. The preferred metal is copper.

[0086] The organopolysiloxane compounds of formula (I) can be used as the sole binder. Organic binders can also be present as further components of the preparations. Organic binders can be used, for example, in organic monomers, oligomers, and polymers. Organic monomers, oligomers, and polymers typically used for this purpose include polyphenylene ethers, bismaleimides, bismaleimide triazine copolymers, hydrocarbon resins, both aliphatic such as polybutadiene, and aromatic such as polystyrene, as well as hybrid systems which have both aliphatic and aromatic character such as styrene-polyolefin copolymers, whereby the form of the copolymers is again fundamentally not restricted, epoxy resins, cyanate ester resins, and optionally others, whereby the selection is to be understood as illustrative and not restrictive.

[0087] Preferred organic monomers, oligomers, and polymers are oligomeric and polymeric polyphenylene ethers, monomeric, oligomeric, and polymeric bismaleimides, oligomeric and polymeric hydrocarbon resins, and bismaleimide triazine copolymers. The organic monomers, oligomers, and polymers can optionally be used in admixture with one another.

[0088] The proportion of organic monomers, oligomers and polymers in the preparations with the organopolysiloxane compounds of the formula (I), if the organic components are used, is between 10 and 90% based on the mixture of the organopolysiloxane compounds of the formula (I) and the organic monomers, oligomers and polymers as 100%, preferably 20 - 90%, in particular 30 - 80%.

[0089] In addition, both the organopolysiloxane compounds of formula (I) and the mixtures thereof with organic monomers, oligomers or polymers can be dissolved in further organic monomers, optionally with olefinically or acetylenically unsaturated groups, as reactive diluents, such as styrene, alpha-methylstyrene, para-methylstyrene and vinylstyrene, chloro- and bromostyrene.

[0090] Likewise, the preparations may contain as further constituents typical non-reactive solvents for dissolving the organopolysiloxane compounds of the formula (I) and optionally mixtures thereof with organic monomers, oligomers and polymers, such as, for example, aliphatic or aromatic solvents such as aliphatic mixtures with certain boiling ranges, toluene, xylene, ethylbenzene or mixtures of the same aromatics, ketones such as acetone, methyl ethyl ketone, cyclohexanone, carboxylic acid esters such as ethyl acetate, methyl acetate, ethyl formate, methyl formate, propionic acid methyl ester, propionic acid ethyl ester, wherein good solubility in particular of the mixtures of organopolysiloxane compounds of the formula (I) with organic monomers, oligomers and polymers is most easily achieved in aromatic solvents such as toluene, xylene, ethylbenzene and mixtures thereof.

[0091] In the case where the organopolysiloxane compounds of formula (I) are used in combination with an organic oligomer or polymer, or mixtures thereof, it is essential that organopolysiloxane compounds of formula (I) are used that are compatible with the organic components of choice and do not lead to phase separation. In these cases, organopolysiloxane compounds of formula (I) richer in phenyl groups should generally be used, since phenyl groups increase compatibility with the organic components. In particular, organopolysiloxane compounds of formula (I) richer in aromatics should be used with organic polymers richer in aromatics, such as polyphenylene ethers or aromatic hydrocarbon resins. Both the bridging aromatic groups and aromatic substituents terminally bonded to silyl units contribute to the compatibility adjustment.

[0092] The exact amount of aromatic groups necessary to adjust the compatibility of the organopolysiloxane compounds of formula (I) with a specific selection of organic binders must be determined depending on the selection of organic binders.

[0093] Just as it is possible to mix a plurality of organic polymers, which are optionally selected from different polymer classes, and to use them in the binder preparation. It is also possible to combine a plurality of organopolysiloxane compounds of the formula (I) with one another in a binder preparation. This means that according to the invention, only a single organopolysiloxane compound of the formula (I) can be used as a binder, and several organopolysiloxane compounds of the formula (I) can be combined with one another to form a binder preparation. Likewise, according to the invention, only one organopolysiloxane compound of the formula (I) can be combined with one or more organic polymers to form a binder preparation. It is also possible according to the invention to combine a plurality of organopolysiloxane compounds of the formula (I) with one or more different organic polymers to form a binder preparation.

[0094] The compatibility of one or more organopolysiloxane compounds of formula (I) with one or more organic oligomers or polymers can be easily determined by mixing a mixture of the organic binder(s) with the organopolysiloxane compound(s) of formula (I), advantageously in a solvent that dissolves all selected components. The solvent is then removed by state-of-the-art methods, for example, by distillation or spray drying, and the resulting residue is evaluated visually or with the aid of microscopic, optionally electron microscopic, methods. Compatible mixtures can be recognized by the fact that no silicone domains separate from the organic components and are recognizable as a separate phase.

[0095] The preparations may contain additional formulation components, such as additives, which may optionally also include silanes, such as antifoam and deaerating agents, wetting and dispersing agents, flow control agents, compatibilizers, adhesion promoters, curing initiators, catalysts, stabilizers, fillers including pigments, dyes, inhibitors, flame-retardant additives, and crosslinking aids. In addition to compatibility tests for suitable miscibility behavior, compatibility tests with regard to reactivity may also be required to prevent premature gelling and ensure that sufficiently rapid polymerization or copolymerization of all components is achieved during curing, as well as tests for adequate wetting and, where appropriate, other properties.This must be taken into account when drafting the text.

[0096] Examples of fillers that can be used are ceramic fillers such as silicas, for example precipitated silicas or pyrogenic silicas, which can be both hydrophilic and hydrophobic and are preferably hydrophobic and which can furthermore also be functionally and optionally reactively provided with organic groups on their surface, quartz, which can optionally be surface-treated or surface-functionalized so that it can optionally carry reactive functional groups on the surface, aluminum oxides, aluminum hydroxides, calcium carbonate, talc, mica, clay, kaolin, magnesium sulfate, carbon black, titanium dioxide, zinc oxides, antimony trioxide, barium titanate, strontium titanate, corundum, wollastonite, zirconium tungstate, ceramic hollow spheres, aluminum nitride, silicon carbide, beryllium oxide, magnesium oxide, magnesium hydroxide, solid glass spheres, hollow glass spheres and boron nitride.Core-shell particles made of various materials can be used as additional fillers, such as silicone resin spheres coated on the surface with silica, or polymer-coated elastomer particles, whereby the elastomer particles can optionally also be silicone elastomers, and a typical example of a surface coating of such an elastomer particle is a polymethyl methacrylate shell. The ceramic fillers preferably have particle sizes, expressed as a D 90 value, of 0.1 µm to 10 µm. Fillers are preferably present in amounts of 0.1 to 60 percent by weight, preferably 0.5 to 60 percent by weight, in particular 1 to 60 percent by weight, based on the total binder formulation consisting of binder(s), reactive monomers, additives, and fillers as 100%. This means that the amount of any non-reactive solvent used is not counted.

[0097] Among the fillers, those that are thermally conductive are particularly noteworthy. These include aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, zinc oxide, zirconium silicate, magnesium oxide, silicon oxide, and aluminum oxide.

[0098] In principle, the binder preparations can contain flame-retardant additives in an amount of typically 5 to 25 percent by weight. However, a special feature of the organopolysiloxane compounds of formula (I) is that they reduce the need for flame-retardant additives, since the organopolysiloxane compounds of formula (I) themselves already exhibit flame-retardant properties. Polysilsesquioxanes and siloxanes are known to exhibit flame-retardant properties, and it is well known in the art for them to be used as flame-retardant additives themselves. It is therefore a particular advantage of the present invention that it succeeds in combining the function of the binder with the function of flame retardancy. Depending on the amount of organopolysiloxane compounds of formula (I) used, the amount of flame-retardant additives can be reduced.At an amount of at least 20 percent by weight based on the total mixture of all binders and reactive organic monomers used, the amount of flame-retardant additives is preferably only 0 to 10 percent by weight, particularly preferably 0 to 8 percent by weight, in particular 0 to 5 percent by weight, ie it is possible to dispense with the use of a flame-retardant additive when using the organopolysiloxane compounds of the formula (I), depending on the selection of the organopolysiloxane and the amount used.

[0099] Typical examples of flame-retardant additives are hydrates of the metals Al, Mg, Ca, Fe, Zn, Ba, Cu, or Ni, and borates of Ba and Zn. The flame-retardant additives can be surface-treated and may optionally contain reactive groups on the surface. The flame-retardant additives can also be halogenated organic flame-retardant additives, such as hexachloroendomethylenetetrahydrophthalic acid, tetrabromophthalic acid, or dibromoneopentyl glycol. Examples of other flame-retardant additives include melamine cyanurate, phosphorus-containing components such as phosphinates, diphosphinates, phosphazenes, vinylphosphazenes, phosphonates, phosphaphenantrene oxides, and fine-grained melamine polyphosphates.

[0100] Other examples of brominated flame-retardant additives include bispentabromophenylethane, ethylenebistetrabromophthalimide, tetradecabromodiphenoxybenzene, decabromodiphenyl oxide, and brominated polysilsesquioxanes. Some flame-retardant additives enhance each other's effectiveness synergistically. This is the case, for example, with the combination of halogenated flame retardant additives with antimony trioxide.

[0101] The preparations may also contain, as additional ingredients, antioxidants, stabilizers against degradation by weathering, lubricants, plasticizers, coloring agents, phosphorescent or other agents for the purpose of marking and traceability, and antistatic agents.

[0102] Crosslinking aids used include, in particular, polyunsaturated, radically curable or hydrosilylatable monomers and oligomers, as illustrated in the following non-limiting examples. These include, for example, diolefinically unsaturated components such as symmetrically olefinically unsaturated disubstituted disiloxanes, such as 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetramethyl-1,3-dipropylmethacryloyldisiloxane, diolefinically unsaturated disubstituted organic monomers or oligomers, such as conjugated and non-conjugated dienes, such as 1,9-decadiene and 1,3-butadiene. This also includes triply olefinically unsaturated monomers or oligomers such as 1,2,4-trivinylcyclohexane, triallyl cyanurates or triallyl isocyanurates, tri(meth)acrylates, such as trimethylolpropane trimethacrylate.

[0103] This also includes four-fold unsaturated substituted monomers and oligomers such as 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetraphenyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,2-bis[[(2-methyl-1-oxoallyl)oxy]methyl]-1,3-propanediylbismethacrylate (pentaerythritol tetramethacrylate), tetraallyl orthosilicate, tetra-allyl-cia,cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylate, tetraallylsilanes, glyoxalbis(diallylacetal).

[0104] Since hydrosilylation curing is also conceivable in addition to radical curing, multiply Si-H functional components can also act as crosslinkers, such as 1,1,3,3-tetramethyl-1,3-disiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 1,4-bis(dimethylsilyl)benzene or multiply chain and / or terminal Si-H functional oligo- and polyorganosiloxanes.

[0105] Suitable catalysts or initiators for the radical curing of binder preparations made from organopolysiloxane compounds of formula (I) and organic monomers, oligomers, and polymers are the same as those already mentioned above, i.e., in particular, peroxides. In addition, other radical initiators are suitable for initiating the radical curing of both the organopolysiloxane compounds of formula (I) alone and the described binder preparations, such as azo components such as α,α'azobis(isobutyronitrile), redox initiators such as combinations of peroxides such as hydrogen peroxide and iron salts, or azides such as acetyl azide.

[0106] The organopolysiloxane compounds of formula (I) or the preparations containing them can be used for the application according to the invention both in solvent-free and solvent-based forms. They are generally used as solvent-based preparations to facilitate the homogeneous distribution of all components of the formulation and the wetting and saturation of any reinforcing layer used. A reinforcing layer is generally included. This is preferably a glass fiber fabric. The saturation of the reinforcing layer can be achieved by impregnating the preparation. Various technical solutions are available for this, including continuous processes where appropriate, and the selection of these for producing the metal-clad laminates according to the invention is in no way restricted.Non-limiting examples of application techniques include dipping, optionally applying webs of reinforcing material via roller systems in continuous processes, spraying, flooding, doctoring, etc. An advantage of the present invention is that all available technologies can be applied without restriction or modification, and no special new process is required for the use of the organopolysiloxane compounds of formula (I). In this respect, the present invention is entirely within the available state of the art in the production of metal-clad laminates. What is new is the use of the organopolysiloxane compounds of formula (I) for the production of the respective metal-clad laminates, which was previously unknown.

[0107] Impregnation is followed by a drying step, in which any solvent used is removed. State-of-the-art methods are also used for the drying process. These include, in particular, thermally induced evaporation with or without vacuum. By appropriately adjusting the reactivity and tackiness of the binder mixture used, storable composite materials are obtained after this step under suitable conditions, such as cooling, which can be further processed at a later date if necessary.

[0108] In a final step of the process, the binder preparation is polymerized using state-of-the-art methods. Any initiators used for radical polymerization are heated above their decomposition temperature, causing them to decompose to form radicals and initiate radical polymerization of the binder preparation. Radiation curing methods are also generally applicable.

[0109] If hydrosilylation curing is used instead of radical polymerization, a temperature must be applied in this step that is suitable for deactivating the inhibitor used with the hydrosilylation catalyst and releasing the catalytic activity of the hydrosilylation catalyst.

[0110] This step is generally carried out at elevated temperature, preferably from 100 to 390°C, more preferably from 100 to 250°C, especially from 130 to 200°C, with the temperature being effective for a time of preferably 5 to 180 minutes, more preferably 5 to 150 minutes, especially 10 to 120 minutes. Furthermore, it is customary to apply elevated pressure in this step. Typical pressures are in the range of 1 to 10 MPa, more preferably 1 to 5 MPa, especially 1 to 3 MPa.

[0111] The lamination of the composite material with a conductive metal layer occurs in this second step by applying a layer of at least one selected metal to one or both sides of the composite material consisting of the reinforcement layer and binder preparation before curing. This means that between the first step, consisting of impregnation and drying, and the second step, comprising the chemical curing of the binder preparation, the composite from the first step is laminated with at least one type of conductive metal.

[0112] In particular, at least one of the following can be considered as conductive metals: copper, stainless steel, gold, aluminum, silver, zinc, tin, lead, and transition metals. The thickness of the conductive layer, its shape, size, or surface texture are not fundamentally restricted. The conductive metal layer preferably has a thickness of 3 to 300 µm, particularly preferably 3 to 250 µm, in particular 3 to 200 µm. The thickness of the two layers of at least one type of conductive metal, if two layers are used, can vary and does not have to be identical. It is particularly preferred that the conductive metal is copper, and if two conductive layers of conductive metal are used, both layers are copper. The conductive metal is preferably used in the form of a foil made of the metal in question.The average roughness Ra of the metal foil used is preferably at most 2 µm, more preferably at most 1 µm, in particular at most 0.7 µm. The lower the surface roughness, the better the suitability of the respective foil for use in high-frequency applications, which are the preferred goal of the present invention. To improve the adhesion between the conductive metal layer and the composite of binder preparation and reinforcing layer, various prior art methods can be used, such as the use of an adhesion-promoting layer, the electroplating of the metal layer on the composite of binder preparation and reinforcing layer, or vapor deposition. The layer of conductive metal can sit directly on the composite of binder preparation and reinforcing layer or be bonded to it by an adhesion-promoting layer.

[0113] If no reinforcing layer is used, a layer of the binder preparation containing the organopolysiloxane compounds of formula (I) is preferably produced by depositing a layer of binder preparation on a carrier, such as a release film or release plate. In principle, any material from which the dried or cured binder preparation can be subsequently removed is suitable for the carrier, such as polytetrafluoroethylene, polyester, and the like. The removability and film-forming properties on the respective carrier material must be determined individually depending on the binder composition. The statements made regarding the process remain equally valid for this reinforcement-free variant.

[0114] Multilayer structures can be created from the reinforced or unreinforced composite materials from the first step and the laminated composite materials from the second step. For example, stacking several lengths of the composite materials from the first step alternately with the laminated laminates from the second step. The uncured composite materials from the first step are then cured in a process that essentially corresponds to the procedure for producing metal-clad laminates. To create thicker layers, multiple layers of the reinforced or unreinforced composites from the first step can also be stacked one on top of the other in direct succession.

[0115] The organopolysiloxane compounds of formula (I) can be used not only for the production of metal-clad laminates but also in corrosion-protective preparations, in particular for use for the purpose of corrosion protection at high temperatures.

[0116] In addition, the organopolysiloxane compounds of formula (I) and preparations containing them can also be used for corrosion protection of reinforcing steel in reinforced concrete. Corrosion-inhibiting effects in reinforced concrete are achieved both when the organopolysiloxane compounds of formula (I) and preparations containing them are incorporated into the concrete mix before it is molded and cured, and when the organopolysiloxane compounds of formula (I) or preparations containing them are applied to the surface of the concrete after the concrete has cured.

[0117] In addition to the purpose of corrosion protection on metals, the organopolysiloxane compounds of formula (I) can also be used to manipulate other properties of preparations containing the organopolysiloxane compounds of formula (I) or of solids or films obtained from preparations containing the organopolysiloxane compounds of formula (I), such as: Control of the electrical conductivity and the electrical resistance Control of the leveling properties of a preparation Control of the gloss of a moist or cured film or an object Increasing the weathering resistance Increasing the chemical resistance Increasing the color stability Reducing the tendency to chalking Reducing or increasing the static and sliding friction on solids or films obtained from preparations containing organopolysiloxane compounds of the formula (I) Stabilizing or destabilizing foam in the preparation containing the preparation according to the invention Improving the adhesion of the preparation containing the organopolysiloxane compounds of the formula (I) to substrates Control of the filler and pigment wetting and dispersing behavior, Control of the rheological properties of the preparation containing the organopolysiloxane compounds of the formula (I), Control of the mechanical properties, such as e.g.Flexibility, scratch resistance, elasticity, extensibility, bending ability, tear resistance, rebound behavior, hardness, density, tear resistance, compression set, behavior at different temperatures, coefficient of expansion, abrasion resistance as well as other properties such as thermal conductivity, flammability, gas permeability, resistance to water vapor, hot air, chemicals, weathering and radiation, sterilizability, of solids or films available which contain the organopolysiloxane compounds of the formula (I) or preparations containing them, control of the electrical properties, such as dielectric loss factor, dielectric strength, dielectric constant, tracking resistance, arc resistance, surface resistance, specific breakdown resistance, control of the mechanical properties, such asFlexibility, scratch resistance, elasticity, extensibility, bending ability, tear resistance, rebound behavior, hardness, density, tear resistance, compression set, behavior at different temperatures of solids or films obtainable from the preparation containing the organopolysiloxane compounds of formula (I).

[0118] Examples of applications in which the organopolysiloxane compounds of formula (I) can be used to manipulate the properties described above are the production of coating materials and impregnations and coatings and coverings obtained therefrom on substrates such as metal, glass, wood, mineral substrates, synthetic and natural fibers for the production of textiles, carpets, floor coverings or other goods that can be produced from fibers, leather, plastics such as films, and molded parts.The organopolysiloxane compounds of formula (I) can also be used in preparations, with appropriate selection of the preparation components, as additives for the purposes of defoaming, promoting flow, hydrophobizing, hydrophilizing, filler and pigment dispersing, filler and pigment wetting, substrate wetting, promoting surface smoothness, and reducing adhesion and slip resistance on the surface of the cured composition obtainable from the additive-containing preparation. The organopolysiloxane compounds of formula (I) can be incorporated into elastomer compositions in liquid or cured solid form. They can be used for the purpose of reinforcement or to improve other performance properties, such as controlling transparency, heat resistance, yellowing tendency, or weathering resistance.

[0119] All symbols in the above formulas have their meanings independent of each other. In all formulas, the silicon atom is tetravalent. Examples:

[0120] The following examples serve to further explain the invention. They are to be understood as illustrative, not limiting.

[0121] All percentages are based on weight. Unless otherwise stated, all handling is carried out at room temperature of 23°C and under atmospheric pressure (1.013 bar). Unless otherwise stated, all data describing product properties are based on room temperature of 23°C and atmospheric pressure (1.013 bar).

[0122] The devices are commercially available laboratory devices, such as those offered for sale by numerous device manufacturers. Ph stands for one phenyl radical = C 6 H 5 -. Me stands for one methyl radical = CH 3 -. Me 2 stands for two methyl radicals. PPE stands for polyphenylene ether. HCl stands for hydrogen chloride.

[0123] In this text, substances are characterized by data obtained by instrumental analysis. The underlying measurements are either performed according to publicly available standards or determined using specially developed procedures. To ensure the clarity of the presented teaching, the methods used are listed below.

[0124] In all examples, parts and percentages are by weight unless otherwise stated. Viscosity:

[0125] Unless otherwise stated, viscosities are determined by rotational viscometric measurement according to DIN EN ISO 3219. Unless otherwise stated, all viscosity data apply at 25°C and a standard pressure of 1013 mbar. Refractive index:

[0126] The refractive indices are determined in the wavelength range of visible light, unless otherwise stated, at 589 nm at 25°C and normal pressure of 1013 mbar according to the standard DIN 51423. Transmission:

[0127] The transmission is determined by UV-VIS spectroscopy. A suitable instrument is the Analytik Jena Specord 200.

[0128] The measurement parameters used are: Range: 190 - 1100 nm, Step size: 0.2 nm, Integration time: 0.04 s, Measurement mode: Step mode. First, the reference measurement (background) is performed. A quartz plate, attached to a sample holder (dimensions of the quartz plate: H x W approx. 6 x 7 cm, thickness approx. 2.3 mm), is placed in the sample beam path and measured against air.

[0129] Next, the sample is measured. A quartz plate with a sample applied to it (approximately 1 mm thick) is attached to the sample holder. It is placed in the sample beam path and measured against air. Internal comparison with the background spectrum yields the sample's transmission spectrum. Molecular compositions:

[0130] The molecular compositions are determined by nuclear magnetic resonance spectroscopy (for terminology see ASTM E 386: High-resolution nuclear magnetic resonance spectroscopy (NMR): Terms and Symbols), measuring the 1< H nucleus and the 29< Si nucleus. Description 1< H-NMR measurement

[0131] Solvent: CDCl3, 99.8% Sample concentration: approx. 50 mg / 1 ml CDCl3 in 5 mm NMR tubes

[0132] Measurement without addition of TMS, spectra referencing of residual CHCl3 in CDCl3 to 7.24 ppm Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Probe head: 5 mm BBO probe head or SMART probe head (Bruker) Measurement parameters:

[0133] Pulprog = zg30 TD = 64k NS = 64 or 128 (depending on the sensitivity of the probe head) SW = 20.6 ppm AQ = 3.17 s D1 = 5 s SFO1 = 500.13 MHz O1 = 6.175 ppm Processing parameters:

[0134] SI = 32k WDW = EM LB = 0.3 Hz

[0135] Depending on the type of spectrometer used, individual adjustments of the measurement parameters may be necessary. Description 29< Si-NMR measurement

[0136] Solvent: C6D6 99.8%d / CCl4 1:1 v / v with 1 wt% Cr(acac) 3 as relaxation reagent Sample concentration: approx. 2 g / 1.5 ml solvent in 10 mm NMR tubes Spectrometer: Bruker Avance 300 Probe head: 10 mm 1H / 13C / 15N / 29Si glass-free QNP probe head (Bruker) Measurement parameters:

[0137] Pulprog = zgig60 TD = 64k NS = 1024 (depending on the sensitivity of the probe head) SW = 200 ppm AQ = 2.75 s D1 = 4 s SFO1 = 300.13 MHz O1 = -50 ppm Processing parameters:

[0138] SI = 64k WDW = EM LB = 0.3 Hz

[0139] Depending on the type of spectrometer used, individual adjustments of the measurement parameters may be necessary. Molecular weight distributions:

[0140] Molecular weight distributions are determined as weight-average Mw and number-average Mn using gel permeation chromatography (GPC or size exclusion chromatography (SEC)) with a polystyrene standard and a refractive index detector (RI detector). Unless otherwise stated, THF is used as the eluent and DIN 55672-1 is applied. Polydispersity is the ratio Mw / Mn. Determination of dielectric properties: Df, Dk

[0141] The dielectric properties are determined according to IPC TM 650 2.5.5.13 using a Keysight / Agilent E8361A network analyzer using the split-cylinder resonator method at 10 GHz.

[0142] Synthesis example 1:Preparation of an organopolysiloxane compound of formula (I): Synthesis reproduced according to DE 102005040323, Example 1, leads to the result described therein: A mixture of 109 g of redistilled 1,2-bis(methyldichlorosilyl)ethane and 820 g of vinyldimethylchlorosilane is cooled to 10°C. While stirring and simultaneous cooling, a total of 1.7 l of 5% HCl solution is metered in over approximately 80 minutes at a rate sufficient to maintain the temperature of the reaction mixture at 10-20°C. The mixture is then stirred vigorously for 30 minutes, after which the phases are separated. The siloxane phase is washed four times with 1 l of water each time, neutralized with 0.5 l of 5% NaHCO3 solution, and washed again with 1 l of water. Volatile hydrolysis products are separated in vacuum up to 80°C (mainly divinyltetramethyldisiloxane).149.8 g of a clear liquid are obtained as residue, which has a viscosity of 7.2 mm 2< / s (25°C) and an iodine number of 169.6, which means exactly one C=C double bond per 149.8 g.

[0143] The ratio of end groups to branching unit is 2.57. The product contains approximately 90% of the 1,2-bis(methyldichlorosilyl)ethane used in hydrolyzed form. Synthesis example 2: Preparation of a silphenylene-bridged organopolysiloxane compound of formula (I). Synthesis of the silphenylene precursor:

[0144] 1,4-Bis(dimethoxyphenylsilyl)benzene according to the literature procedure by Xunjun Chen, Minghao Yi, Shufang Wu, Lewen Tan, Yixin Xu, Zhixing Guan, Jianfang Ge and Guoqiang Yin: Synthesis of Silphenylene-Containing Siloxane Resins Exhibiting Strong Hydrophobicity and High Water Vapor Barriers, Coatings 2019, 9, 481; doi:10.3390 / coatings9080481 www.mdpi.com / journal / coatings 1,4-Bis(dimethoxyphenylsilyl)benzene is obtained by reacting trimethoxyphenylsilane with a Grignard reagent obtained from 1,4-dibromobenzene according to the given literature procedure in "2.2. Synthesis of the 1,4-Bis(Dimethoxyphenylsilyl)Benzene (BDMPD)". The structure was confirmed by 1< H NMR spectroscopy and comparison with the cited literature.

[0145] A mixture of 845.2 g (= 4 mol) of phenyltrichlorosilane, 546.7 g (1.3 mol) of 1,4-bis(dimethoxyphenylsilyl)benzene, 198.7 g (0.8 mol) of 3-(trimethoxysilyl)propyl methacrylate, and 820 g of xylene is metered into a receiver containing 2400 g of deionized water over a period of 4 hours. The receiver is at room temperature of 23°C at the beginning of the metering. The temperature rises due to the exothermic heat evolution of the reaction. The metering is controlled so that the internal temperature in the reaction vessel never exceeds 50°C. If necessary, the metering rate is reduced.

[0146] After the addition is complete, the mixture is stirred for 15 minutes. The stirrer is then turned off. The organic and aqueous phases separate. The lower, clear, and colorless aqueous phase, consisting essentially of a concentrated aqueous hydrochloric acid solution, is drained off.

[0147] 1 liter of deionized water is added to the organic phase remaining in the reaction vessel and mixed while stirring. After 30 minutes, the stirrer is turned off and the phases are allowed to separate again. The aqueous phase settles at the bottom and is drained off. If the aqueous phase settles to the top, wash with a 10% sodium chloride aqueous solution instead of deionized water, or add 100 g of sodium chloride for another 30 minutes, and then carry out the phase separation again. This process is repeated until the residual HCl content in the organic phase is below 20 ppm. The residual HCl content is determined by acid-base titration according to the state of the art. Two washes with deionized water or 10% aqueous NaCl solution are usually sufficient. Water is then removed from the system using xylene as a water entrainer at 110°C until no more water is obtained.

[0148] At this stage of synthesis, the resulting product contains approximately 3 percent by weight of silanol groups, which, due to their polarity, interfere with the intended application. To reduce the silanol content, the following procedure is used: 200 g of water is added to the previously distilled xylene reaction mixture. Then, 265.1 g (2.2 mol) of vinyldimethylchlorosilane are slowly added, adjusting the metering rate to keep the reaction temperature (internal temperature in the reaction vessel) below 50°C. After the metering is complete, the mixture is stirred for 60 minutes without heating or cooling to allow the reaction of the silanol groups with the vinyldimethylchlorosilane or the resulting tetramethyldivinyldisiloxane to complete.

[0149] The aqueous phase is separated as described above and then washed three times with one liter of water each time, as described above. If necessary, phase separation can be improved by heating the heating jacket to 60°C with the stirrer turned off. After the washing steps, the HCl content in the xylene solution is less than 20 ppm.

[0150] The amount of xylene is reduced by distillation in vacuum (20 mbar) at 110°C until a solution of 80% resin in 20% xylene is obtained.

[0151] In the resulting product, no methoxy groups are detectable by 1< H NMR. This means that the methacrylate-functional trimethoxysilane has completely condensed in, and the resulting methanol was removed during workup. The proportion of silanol groups was reduced to approximately 0.9 weight percent (determined by 1< H NMR) by post-treatment.

[0152] The following molecular weights were determined by SEC (eluent toluene): Mw = 7347 g / mol, Mn = 2903 g / mol, polydispersity PD = 2.53.

[0153] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 11.54% H 2C =C(CH 3 )C(=O)-O-(CH 2 ) 3 -SiO 3 / 2: 11.98% O 2 / 2 (Ph)Si-C 6 H 4 -Si(Ph)O 2 / 2: 19.23% PhSiO 3 / 2: 57.25%

[0154] The silanol groups are bound to the PhSiO 3 / 2 units. Synthesis example 3: Preparation of an organopolysiloxane compound of formula (I) with a phenylene bridge.

[0155] The synthesis according to Synthesis Example 2 is repeated, whereby, in contrast to Synthesis Example 2, the following quantities are used: Phenyltrichlorosilane: 281.7 g (= 1.3 mol) 1,4-Bis(dimethoxyphenylsilyl)benzene: 1202.7 g (2.9 mol)

[0156] The remaining procedure is the same as in Synthesis Example 3. The following result is obtained: Methoxy groups are not detectable by NMR. The residual silanol content is 0.8 percent by weight.

[0157] SEC: Mw = 8347 g / mol, Mn = 3953 g / mol, polydispersity PD = 2.11.

[0158] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 10.93% H 2 C=C(CH 3 )C(=O)-O-(CH 2 ) 3 -SiO 3 / 2: 10.89% O 2 / 2 (Ph)Si-C 6 H 4 -Si(Ph)O 2 / 2: 49, 96% PhSiO 3 / 2: 28.22% Synthesis example 4: Preparation of an organopolysiloxane compound of formula (I) with an alkylene bridge.

[0159] The synthesis according to Synthesis Example 2 is repeated, whereby, in contrast to Synthesis Example 2, the following quantities are used: Phenyltrichlorosilane: 422.6 g (= 2 mol) 1,2-Bis(dichloromethylsilyl)ethane: 341.35 g (1.35 mol) Vinyldimethylchlorosilane: 403.7 g (3.35 mol)

[0160] No 1,4-bis(dimethoxyphenylsilyl)benzene is used.

[0161] In this synthesis, 271.2 g (2.25 mol) of vinyldimethylchlorosilane are added directly to the chlorosilane mixture, which is metered into the water reservoir in the first step. The remaining 132.6 g (1.1 mol) are used to reduce the silanol groups as in Synthesis Example 3.

[0162] The remaining procedure is the same as in Synthesis Example 3. The following result is obtained: Methoxy groups are not detectable by NMR. The residual silanol content is 0.9 weight percent.

[0163] SEC: Mw = 6974 g / mol, Mn = 2812 g / mol, polydispersity PD = 2.48.

[0164] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 50, 39% O 2 / 2 (Me)Si-C 2 H 4 -Si(Me)O 2 / 2: 19, 56% PhSiO 3 / 2: 30.05% Synthesis example 5:Preparation of an organopolysiloxane compound of formula (I) with alkylene and phenylene bridges.

[0165] The synthesis according to Synthesis Example 2 is repeated, whereby, in contrast to Synthesis Example 2, the following quantities are used: Phenyltrichlorosilane: 422.6 g (= 2 mol) 1,2-Bis(dichloromethylsilyl)ethane: 512.0 g (2 mol) 1,4-Bis(dimethoxyphenylsilyl)benzene: 986.2 g (2.4 mol) Vinyldimethylchlorosilane: 403.7 g (3.35 mol)

[0166] In this synthesis, 271.2 g (2.25 mol) of vinyldimethylchlorosilane are added directly to the chlorosilane mixture, which is metered into the water reservoir in the first step. The remaining 132.6 g (1.1 mol) are used to reduce the silanol groups as in Synthesis Example 3.

[0167] The remaining procedure is the same as in Synthesis Example 3. The following result is obtained: Methoxy groups are not detectable by NMR. The residual silanol content is 0.9 weight percent.

[0168] SEC: Mw = 4974 g / mol, Mn = 1966 g / mol, polydispersity PD = 2.53.

[0169] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 34.49% O 2 / 2 (Me)Si-C 2 H 4 -Si(Me)O 2 / 2: 20, 31% O 2 / 2 (Ph)Si-C 6 H 4 -Si(Ph)O 2 / 2: 24, 64% PhSiO 3 / 2: 20.56% Synthesis example 6: Preparation of an organopolysiloxane compound of formula (I) with alkylene and phenylene bridges.

[0170] The synthesis according to Synthesis Example 6 is repeated, using the following amounts in contrast to Synthesis Example 6: 1,2-bis(trimethoxysilyl)ethane: 540.0 g (2 mol)

[0171] No 1,2-bis(dichloromethylsilyl)ethane is used in this example.

[0172] The remaining procedure is the same as in Synthesis Example 6. The following result is obtained: Methoxy groups are not detectable by NMR. The residual silanol content is 0.8 percent by weight.

[0173] SEC: Mw = 5768 g / mol, Mn = 2074 g / mol, polydispersity PD = 2.78.

[0174] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 32.78% O 3 / 2 Si-C 2 H 4 -SiO 3 / 2: 21.01% O 2 / 2 (Ph)Si-C 6 H 4 -Si(Ph)O 2 / 2: 23.48% PhSiO 3 / 2: 22.73% Synthesis example 7: Preparation of an organopolysiloxane compound of formula (I) with an alkylene bridge.

[0175] The synthesis according to Synthesis Example 6 is repeated, using the following amounts in contrast to Synthesis Example 6: 1,2-bis(chlorodimethylsilyl)ethane: 580.6 g (2.7 mol)

[0176] No 1,2-bis(dichloromethylsilyl)ethane is used.

[0177] No 3-(trimethoxysilyl)propyl methacrylate is used. The remaining procedure is the same as in Synthesis Example 3. The following result is obtained: Methoxy groups are not detectable by NMR. The residual silanol content is 0.8 percent by weight.

[0178] SEC: Mw = 5637 g / mol, Mn = 1964 g / mol, polydispersity PD = 2.87.

[0179] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 11.96% O 1 / 2 (Me 2 )Si-C 2 H 4 -Si(Me 2 )O 1 / 2: 19.56% PhSiO 3 / 2: 68.48% Comparison example 1: non-inventive organopolysiloxane synthesis without bridging Si-C-bonded units

[0180] The syntheses according to Synthesis Examples 2, 3, and 4 are repeated, except that, in contrast to Synthesis Examples 2-4, no raw materials with bridging units are used. This means that no 1,4-bis(dimethoxyphenylsilyl)benzene and no 1,2-bis(dichloromethylsilyl)ethane are used.

[0181] The amounts given for these raw materials are replaced as follows: In Synthesis Example 2, no 1,4-bis(dimethoxyphenylsilyl)benzene is used and the synthesis is otherwise carried out unchanged as given. Result: Product name V1.2

[0182] The residual methoxy content is undetectable by 1H NMR. The silanol content is 1.1 percent by weight.

[0183] The following molecular weights were determined by SEC (eluent toluene): Mw = 3657 g / mol, Mn = 1759 g / mol, polydispersity PD = 2.07.

[0184] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 14.96% H 2 C=C(CH 3 )C(=O)-O-(CH 2 ) 3 -SiO 3 / 2: 15.81% PhSiO 3 / 2: 69.23%

[0185] In Synthesis Example 3, the specified amount of 1,4-bis(dimethoxyphenylsilyl)benzene is replaced with phenyltrichlorosilane in molar equivalent. All other details remain unchanged. Result: Product name V1.3

[0186] Methoxy groups are not detectable by NMR. The residual silanol content is 1.0 percent by weight.

[0187] SEC: Mw = 3477 g / mol, Mn = 1385 g / mol, polydispersity PD = 2.51.

[0188] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 11.03% H 2 C=C(CH 3 )C(=O)-O-(CH 2 ) 3 -SiO 3 / 2: 11.36% PhSiO 3 / 2: 77.61%

[0189] In Synthesis Example 4, the specified amount of 1,4-bis(dimethoxyphenylsilyl)benzene is replaced with phenyltrichlorosilane in molar equivalent. All other details remain unchanged. Result: Product name V1.4

[0190] Methoxy groups are not detectable by NMR. The residual silanol content is 0.9 percent by weight.

[0191] SEC: Mw = 1576 g / mol, Mn = 885 g / mol, polydispersity PD = 1.78.

[0192] According to 29< Si-NMR, the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1 / 2: 51.35% PhSiO 3 / 2: 48.65%

[0193] Application example 1: Use of the organopolysiloxanes according to synthesis examples 1 - 7 for the production of metal-clad laminates and comparison with comparative examples V1.2, V1.3 and V1.4.

[0194] The organopolysiloxanes prepared according to Synthesis Examples 1 to 7 and the Comparative Example were used as binders to produce copper-clad laminates with a glass fiber-reinforced composite layer. The following raw materials were used: Copper foil: 35 µm thick copper foil (285 ± 10 g / m ) from Jiangtong-yates Copper Foil Co. Ltd., with a surface roughness of Rz ≤ 8 µm and a mean roughness of Ra ≤ 0.4 µm, purity ≥ 99.8%.

[0195] Glass fiber: E-glass fiber type 1080 E manufactured by Changzhou Xingao Insulation Materials Co. Ltd. Thickness 0.055 ± 0.012 mm, 47.5 ± 2.5 g / m 2< .

[0196] In this example, the organopolysiloxane from Synthesis Example 1 was used solvent-free; all others were used as a solution in xylene. The solutions for the organopolysiloxanes from Synthesis Examples 4, 5, 6, and 7 and Comparative Example C1.4 each contained 90% organopolysiloxane and 10% xylene. For the organopolysiloxanes from Synthesis Examples 2 and 3, as well as Comparative Examples C1.2 and C1.3, preparations of 80% organopolysiloxane and 20% xylene were used.

[0197] To initiate curing, the organopolysiloxanes were each mixed with 1 weight percent of dicumyl peroxide, which was evenly distributed in the resin matrix by stirring.

[0198] Laminates were produced by impregnating 30 x 30 cm glass fiber layers layer by layer with the respective organopolysiloxane, optionally as a xylene solution, using a deaerator roller to ensure that no bubbles were formed. The glass fiber layers were placed on a dimensionally stable, flat stainless steel base, onto which a layer of copper foil was applied before the first layer of glass fiber was placed. A total of three layers of glass fiber fabric were impregnated one after the other. To remove any solvent, the impregnated fabrics were dried to constant weight at 60°C in a vacuum drying oven at 10 mbar. A second layer of copper foil was then applied on top of the impregnated glass fiber layer, and another dimensionally stable stainless steel plate was placed on top. The laminate was baked in a heatable press at 2 MPa pressure, for 120 minutes at 200°C and 30 mbar vacuum.Copper-clad laminates with a total thickness of 260 ± 20 µm are obtained.

[0199] The dielectric properties were determined according to IPC TM 650 2.5.5.13 using a Keysight / Agilent E8361A network analyzer using the split-cylinder resonator method at 10 GHz. The values ​​obtained are shown in Table 1: Organopolysiloxane from D k D f Synthesis example 1 2,76 0,0022 Synthesis example 2 2, 98 0,0027 Synthesis example 3 2, 67 0,0029 Synthesis example 4 2,76 0,0023 Synthesis example 5 2, 89 0,0028 Synthesis example 6 2,84 0,0025 Synthesis Example 7 2,56 0,0026 Comparison example V1.2* 3,36 0,0045 Comparison example V1.3* 3,25 0,0049 Comparison example V1.4* 3,29 0,0048 *not according to the invention

[0200] The D k and D f values ​​achieved for the copper-clad laminates made from the organopolysiloxane compounds of formula (I) are significantly lower than the D f and D k values ​​achieved with the organopolysiloxanes from the comparative examples. Since the lowest possible dielectric loss factors and dielectric constants are desired for high-frequency applications, the effect of the invention is clearly evident.

[0201] Application Example 2 Use of the organopolysiloxanes according to Synthesis Examples 1 - 7 and the organopolysiloxanes according to Comparative Example 1 for the production of metal-clad laminates using filler.

[0202] In contrast to Application Example 1, 49.5% precipitated silica of type Q 033 (manufacturer: Suzhou Ginet New Materials Technology Co Ltd, spherical silicon dioxide particles, D 99 ≤ 3 µm, SiO 2 ≥ 99%) was homogeneously incorporated into the resins and resin solutions using a commercially available dissolver. For the resin preparations in which xylene was used in Application Example 1, 30% and 40% xylene were used instead of 10% and 20% xylene, respectively.

[0203] Instead of directly constructing the laminate without a prepreg intermediate, this time prepregs were produced by impregnating the glass fiber layers with the resin formulation as individual layers on a polytetrafluoroethylene film and then drying them to constant weight in a vacuum drying cabinet. Three layers of impregnated glass fiber fabric produced in this way were then stacked on top of each other on a copper foil, and the stack was sealed with a layer of copper foil. This multilayer structure was pressed and cured between two dimensionally stable stainless steel plates in a vacuum press under the conditions specified in Example 1, analogously to Application Example 1.

[0204] The obtained laminates had thicknesses of 290 ± 20 µm.

[0205] The dielectric properties shown in Table 2 were measured on the obtained laminates: Organopolysiloxane from D k D f Synthesis example 1 2,96 0,0031 Synthesis example 2 2,92 0,0033 Synthesis example 3 2,79 0,0034 Synthesis example 4 2,99 0,0030 Synthesis example 5 3,00 0,0034 Synthesis example 6 2,89 0,0032 Synthesis Example 7 3,05 0,0035 Comparison example V1.2* 3,56 0,0060 Comparison example V1.3* 3,54 0,0063 Comparison example V1.4* 3,50 0,0066 *not according to the invention

[0206] The increase in the Dk and Df values ​​is attributed to additional polarization effects at the interfaces between the precipitated silica and the organopolysiloxanes. However, the inventive production of metal-clad laminates with an organopolysiloxane compound of formula (I) is also successful in this case, and the advantage over non-inventive organopolysiloxanes is clearly evident in this case as well. Application example 3: selected synthesis examples with higher viscosity and solid materials over prepreg

[0207] In contrast to Application Example 2, no filler was used this time. Under these conditions, prepregs can only be produced with organopolysiloxanes that dry sufficiently tack-free. Therefore, for this example, only the organopolysiloxanes from Synthesis Examples 2 to 7 and the organopolysiloxanes C1.2 and C1.3 from Comparative Example 1 were used. They were diluted with 10 and 20% xylene, respectively, as indicated in Application Example 1. The organopolysiloxane from Synthesis Example 1 is nevertheless in accordance with the invention, because the possibility of producing a tack-free prepreg is also fulfilled if this is achieved by suitable measures, such as filling with suitable fillers or blending with other organopolysiloxanes or suitable organic polymers.Since these are measures for preparing formulations according to the state of the art for producing binder formulations for metal-clad laminates, the tackiness of a prepreg produced from a pure organopolysiloxane compound of formula (I) without further formulation measures does not contradict the subject matter of the invention.

[0208] Otherwise, the procedure corresponds to that described in application example 2.

[0209] The obtained laminates had thicknesses of 270 ± 20 µm.

[0210] The dielectric properties shown in Table 3 were measured on the obtained laminates: Organopolysiloxane from D k D f Synthesis example 2 2,96 0,0025 Synthesis example 3 2,70 0,0026 Synthesis example 4 2,70 0,0025 Synthesis example 5 2,85 0,0026 Synthesis example 6 2,82 0,0023 Synthesis Example 7 2,55 0,0027 Comparison example V1.2* 3,38 0,0049 Comparison example V1.3* 3,30 0,0050 *not according to the invention

[0211] The D k and D f values ​​achieved for the copper-clad laminates made from the organopolysiloxanes according to the invention are significantly lower than the D f and D k values ​​achieved with the organopolysiloxanes from the comparative examples. Since the lowest possible dielectric loss factors and dielectric constants are desired for high-frequency applications, the effect of the invention is clearly evident.

[0212] Application Example 4 Use of the organopolysiloxanes according to Synthesis Examples 1 - 7 and Comparative Example 1 in a mixture with organic polymers for the production of metal-clad laminates.

[0213] The procedure is essentially the same as that described in Application Example 2. Unlike Application Example 2, no filler was used.

[0214] Instead, organic polymers were mixed with the organopolysiloxanes. The final solvent-free mixtures always contained 30 weight percent organopolysiloxane and 70 weight percent organic polymers. The organic polymers used were triallyl isocyanurate, NORYL SA 9000, an alpha-omega methacrylate-terminated polyphenylene ether supplied by SABIC, Mn = 2500 g / mol, Tg = 160°C, and B 3000 from Nippon Soda, a liquid polybutadiene with an Mn = 3200 and a viscosity at 45°C of 210 poise and more than 85% 1,2-vinyl structure in the polymer chain.

[0215] The polymers were always used in the same ratio. They were dissolved or dispersed in xylene, with 30 parts by weight of SA 9000, 25 parts by weight of B 3000, and 15 parts by weight of triallyl isocyanurate being dispersed with 100 parts by weight of xylene.

[0216] The resulting preparation was mixed with the organopolysiloxane solutions prepared according to Application Example 2 such that the resulting solution contained the specified mixing ratio of 30% organopolysiloxane to 70% organic components. These solutions were then used to produce prepregs as described in Application Example 2.

[0217] The obtained laminates had thicknesses of 290 ± 20 µm.

[0218] The dielectric properties shown in Table 4 were measured on the obtained laminates: with the organopolysiloxane from D k D f Synthesis example 1* 2,99 0,0029 Synthesis example 2 2,63 0,0022 Synthesis example 3 2,57 0,0024 Synthesis example 4 2,68 0,0021 Synthesis example 5 2,66 0,0023 Synthesis example 6 2,59 0,0022 Synthesis Example 7 2,60 0,0023 Comparison example V1.2* 3,16 0,0040 Comparison example V1.3* 3,01 0,0041 Comparison example V1.4* 3,21 0,0042 *not according to the invention* The preparation of organopolysiloxane according to Synthesis Example 1 and the organic components is inhomogeneous, which is evident in an electron micrograph due to domain formation. Compatibilization could be achieved by increasing the silicon-bonded phenyl content or by reducing the aromatic content in the organic part of the preparation.

[0219] The D k and D f values ​​achieved for the copper-clad laminates using the organopolysiloxanes of the invention are significantly lower than the D f and D k values ​​achieved with the organopolysiloxanes from the comparative examples. Since the lowest possible dielectric loss factors and dielectric constants are desired for high-frequency applications, the effect of the invention is clearly evident.

Claims

1. Metal-clad laminates comprising crosslinkable, organopolysiloxane compounds of the formula (I)         [O3-a / 2RaSi-Y(SiRaO3-a / 2)b]c(R1SiO3 / 2)d(R22SiO2 / 2)e(R33SiO1 / 2)f(SiO4 / 2)g     (I) where R may be identical or different and is either a hydrogen radical or a monovalent SiC-bonded organic hydrocarbon radical having 1 to 18 carbon atoms and optionally substituted with heteroatoms, Y is a divalent to dodecavalent organic radical having 1 to 24 carbon atoms and optionally substituted with heteroatoms, where the radical Y is always attached by an Si-C bond to the silicon atoms connected to each other by the radical Y, R1 is independently of one another a hydrogen radical or an SiC-bonded unsaturated C1-C18 hydrocarbon radical that may optionally be substituted with heteroatoms and that optionally may also be attached to the silicon atom via an oxygen atom, where the radicals R1 may each assume their meaning independently of one another, such that a plurality of radicals R1 in the organopolysiloxane according to formula (I) may be different radicals from the defined group, the radicals R2 and R3 are independently of one another a hydrogen radical or an optionally unsaturated SiC-bonded C1-C18 hydrocarbon radical that may optionally be substituted with heteroatoms, or a C1-C12 hydrocarbon radical that optionally contains heteroatoms and is attached via an oxygen atom, where the radicals R2 and the radicals R3 may each assume their meaning independently of one another, such that a plurality of radicals R2 or a plurality of radicals R3 attached to the same silicon atom may be different radicals from the defined group, where, based on all SiC-bonded radicals Y, R, R1, R2 and R3 as 100 mol%, at least 0.1 mol% must be aliphatically unsaturated radicals, a is 0, 1 or 2, where the indices a on either side of the group Y may assume their meaning independently of one another, such that different a may independently of one another be different values within the range of values specified, b is a number having a value from 1 to 11, c is a value from 0.1 to 0.99, d is a value from 0 to 0.8, e is a value from 0 to 0.5, f is a value from 0.01 to 0.6 and g is a value from 0 to 0.2, where c+d+e+f+g is 1.

2. Metal-clad laminates according to Claim 1, in which the hydrocarbon radicals R, R1, R2 and R3 are selected from methyl, phenyl, vinyl, acryloyloxy and methacryloyloxy radicals and the acrylic esters or methacrylic esters of unbranched or branched alcohols having 1 to 15 carbon atoms.

3. Metal-clad laminates according to either of the preceding claims, in which Y is divalent, trivalent or tetravalent.

4. Metal-clad laminates according to any of the preceding claims, comprising formulations that contain organopolysiloxane compounds of the formula (I) and further constituents.

5. Metal-clad laminates according to Claim 4, in which the further constituents are selected from hydrosilylation catalyst, initiator for the free-radical polymerization, organic binders, solvents, formulation components, adhesion promoters, curing initiators, catalysts, stabilizers, fillers, inhibitors, flame-retardant additives, crosslinking aids, antioxidants, stabilizers against degradation due to weathering, lubricants, plasticizers, colourants, phosphorescent agents or other agents for the purposes of marking and traceability, and antistats.

6. Metal-clad laminates according to any of the preceding claims, in which the metal is copper.