TW202110964A - Siloxane polymer composition and manufacturing method thereof - Google Patents

Abstract

A siloxane polymer composition and a manufacturing method thereof are provided. The method of making the siloxane polymer composition includes providing a first compound having the chemical formula SiR¹ _a R^2’ _4-a where a is from 1 to 3, R¹ is a reactive group, and R^2’ is an alkyl group or an aryl group, and providing a second compound having the chemical formula SiR³ _b R⁴ _c R^5’ _4-(b+c) where R³ is a cross-linking functional group, R⁴ is a reactive group, and R^5’ is an alkyl or aryl group, and where b = 1 to 2, and c = 1 to (4-b). The first and second compounds are polymerized together to form a siloxane polymer. The siloxane polymer can be then used in a final composition where the siloxane polymer comprises from 5 to 100% by weight, and filler (e.g. microparticles, nanoparticles, nanowires, etc.) comprises from zero to 95% by weight.

Description

Silicone polymer composition and its manufacturing method

The present invention relates to silicone polymer compositions. In particular, the present invention relates to a method of manufacturing a silicone polymer composition, the composition can be applied to a variety of fields, such as adhesives, for example, as a semiconductor (such as LED) packaging application die attach connection Agents, sealants, optical coatings, protective coatings and other applications.

The method of producing silicone polymers containing nanoparticles is disclosed in Jin et al., Organic Electronic, 2012, Vol. 13, pp. 53-57.

The prior art is also disclosed in US 201410030, CN 103059573, WO 2006112591, WO 2007001039, WO 2008046142, US 2010178478 and US 2005244658.

When the known composition is used as a one-component adhesive, it needs to be transported and stored at low temperatures to avoid premature cross-linking. A composition that can be transported and stored at room temperature without substantial polymerization or other undesired reactions is required.

The objective of the present invention is to solve at least part of the problems in the field.

The object of the present invention is to provide a novel production method for producing silicone polymer materials.

In one embodiment, there is provided ¹ _a ^'of a first compound _4-a, wherein a is 1 to 3, R ¹ is a reactive group, and R ^2' having the chemical formula SiR R ² is an alkyl group or an aryl group. Also provided having the formula _{^{SiR 3 b R 4 c R 5}} '4- (b + c) of a second compound, wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, and R ^5' is an alkyl group or Aryl, and wherein b=1 to 2, and c=1 to (4-b).

The first compound and the second compound are polymerized together to form a silicone polymer material. The silicone material can be mixed with metal particles, semi-metal particles or ceramic particles with an average particle size of less than 100 microns, and other coupling agents as appropriate.

The present invention provides a method for manufacturing a silicone polymer composition, which includes the following steps. Providing ¹ _{a ^'4-a} first compound of a first monomer, wherein a is 1 to 3, R ¹ is a reactive group, and R ^2' having the chemical formula SiR R ² is alkyl or aryl, or An oligomer with a molecular weight of less than 1000 g/mol. Providing a chemical formula _{^{SiR 3 b R 4 c R 5}} '4- (b + c) a second compound, wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, R ^5' is an alkyl or aryl group , And where b=1 to 2, and c=1 to (4-b), or an oligomer with a molecular weight of less than 1000 g/mol. The first compound and the second compound are polymerized together to form a silicone polymer. The silicone polymer is mixed with particles having an average particle size of less than 100 microns.

The present invention provides a silicone polymer composition which is mixed with particles with an average particle size of less than 100 microns.

The present invention provides a method for manufacturing a silicone polymer composition, which includes the following steps. Providing a following chemical formula as the first monomer of a first ^{_{compound: SiR 1 a R 2 '4}} -a or ^{_{R 2' 3-a R 1}} a SiR 11 SiR 1 a R 2 '3-a, wherein a is 1 To 3, R ¹ is a reactive group, R ^2'is an alkyl group or an aryl group, and R ^{11 is} independently an alkyl group or an aryl group, or an oligomer with a molecular weight of less than 2000 g/mol. Providing a second compound having the ^{_{formula: SiR 3 b R 4 c R}} 5 '4- (b + c) or _{^{R 5' 3- (b + c}} ) R 4 c R 3 b SiR 12 SiR 3 b R 4 c _{^{R 5 '3- (b + c}} ), wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, and R ^5' is an alkyl or aryl group, R ¹² is independently alkyl or aryl, And where b=1 to 2, and c=1 to (4-b), or an oligomer with a molecular weight of less than 2000 g/mol. The first compound and the second compound are polymerized together to form a silicone polymer. The silicone polymer is mixed with metal, semi-metal or ceramic particles with an average particle size of less than 100 microns.

Obtain a considerable advantage. Therefore, the silicone-particle composition can be used in many fields. It can be used for electronics or optoelectronics packaging, LED and OLED front-end and back-end processing, 3D, photovoltaic and display metallization, replacing for example, soldering of solder bumps in semiconductor packaging, printed electronic devices, OLED low work function cathode inks , ITO replacement ink, metal grid and other electrodes, high-resolution photovoltaic paste, LMO cathode paste, photovoltaic, power electronics and EMI, touch sensors and other displays, thermal or UV curable sealants or media Adhesives or sealants in electrical quality (just to name a few).

Reference will be made to the accompanying drawings illustrating some example embodiments below to more fully describe the various example embodiments. However, the inventive concept can be implemented in many different forms and should not be construed as being limited to the example embodiments set forth herein. In fact, these example embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the concept of the present invention to those skilled in the art. In the diagram, the size and relative size of layers and regions may be exaggerated for clarity.

It should be understood that when an element or layer is referred to as being “on,” “connected to,” or “coupled to” another element or layer, the element or layer can be directly on the other element or layer. On a layer, directly connected or coupled to another element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on another element or layer”, “directly connected to another element or layer”, or “directly coupled to another element or layer”, there are no intervening elements or layers. Similar numbers refer to similar elements throughout the text. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

It should also be understood that although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections Should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Therefore, without departing from the teaching of the concept of the present invention, the first element, component, region, layer or section discussed below may be referred to as a second element, component, region, layer or section.

In addition, relative terms such as "lower" or "bottom" and "upper" or "top" can be used herein to describe the relationship between one element and another element, as illustrated in the drawings. It will be understood that the relative terms are intended to cover different orientations of the device other than those depicted in the drawings. For example, if the device in one drawing is turned over, the elements described as being located on the "lower" side of other elements will then be oriented on the "upper" side of the other elements. Therefore, the exemplary term "lower" can therefore encompass the orientations of "lower" and "upper" depending on the specific orientation of the schema. Similarly, if the device in one of the drawings is turned over, the elements described as "below" or "below" the other elements will be oriented "above" the other elements. Therefore, the exemplary terms "below" or "below" can encompass both an orientation of above and below.

It should be noted that unless the context clearly dictates otherwise, as used herein, the singular forms "a" and "the" include plural indicators. In addition, it should be understood that when the term "including" is used in this specification, it specifies the existence of the stated features, steps, operations, elements and/or components, but does not exclude the addition of one or more other features, steps, operations, elements and components And/or its ethnic group. Unless otherwise defined, the meanings of all terms (including technical and scientific terms) used herein are the same as those commonly understood by those with ordinary knowledge in the technical field to which the present invention belongs. It should be further understood that terms (such as those defined in commonly used dictionaries) should be interpreted as having meanings consistent with their meanings in the context of related technologies and the present invention, and unless explicitly defined as such in this document, they will not be ideal Or over-formalize meaning to explain.

The lowercase letters used in the following formulas especially represent integers.

Seen in Figure 1, at step 16, providing a chemical formula SiR ¹ _a R ^{2 'of} the first compound _4-a wherein a is 1 to 3, R ¹ is a reactive group, and R ^2' is an alkyl group or Aryl.

At step 18 in FIG. 1, there is provided having the formula _{^{SiR 3 b R 4 c R 5}} '4- (b + c) of the second compound wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, and R ^5'is an alkyl group or an aryl group, and wherein b=1 to 2, and c=1 to (4-b).

At step 20, a third compound optionally present is provided together with the first compound and the second compound to be polymerized therewith. The third compound may have the chemical formula SiR ⁹ _f R ¹⁰ _g , wherein R ⁹ is a reactive group and f=1 to 4, and wherein R ¹⁰ is an alkyl group or an aryl group and g=4-f.

The first compound, the second compound, and the third compound can be provided in any order, and an oligomeric partially polymerized form of any of these compounds can be provided instead of the above-mentioned monomers.

As seen at step 22 in Figure 1, a catalyst is provided. The catalyst may be a base catalyst, or other catalysts as mentioned below. The provided catalyst should be able to polymerize the first compound and the second compound together. As mentioned above, the order of adding compounds and catalysts can be in any desired order. As can be seen at step 24, the various components provided together are polymerized to produce a silicone polymer material with the desired molecular weight and viscosity. At step 24, particles such as microparticles, nanoparticles or other desired particles are added, along with other optional components such as coupling agents, catalysts, stabilizers, then accelerators, and the like. The particles include a first particle group that is a nanometer particle with an average diameter of less than 50 nm and an aspect ratio greater than 10:1, and optionally, the particles include a second particle group that is a nanoparticle with an average particle size of less than 50 nm. The parts of steps 22 and 24 can be performed in any desired order. The first coupling agent is provided to the polymeric silicone material, and the first coupling agent is a monomer having the following chemical formula: SiR ⁶ _d R ⁷ _e R ⁸ _4-(d+e) where R ⁶ is a cross-linking functional group, R ⁷ is a reactive group, and R ⁸ is an alkyl group or an aryl group, and wherein d=1 to 2, and e=1 to (4-d), or an oligomer with a molecular weight of less than 1000 g/mol. The second coupling agent is provided to the polymeric silicone material, and the second coupling agent has the following chemical formula: SiR ⁶ _d R ⁷ _e R ⁸ _4-(d+e) where R ⁶ is a cross-linking functional group and R ⁷ is a reactive group The group, and R ⁸ is an alkyl group or an aryl group, and wherein d=1 to 2, and e=1 to (4-d), or an oligomer with a molecular weight of less than 1000 g/mol. The crosslinking functional group R ^{6 of the} first coupling agent is different from the crosslinking functional group R ^{3 of the} second compound.

Thus, in one example, by polymerizing the first compound and the second compound prepared silicon siloxane polymer, wherein the first compound has the following chemical ^{_{formula: SiR 1 a R 2 '4}} -a wherein a is 1 to 3, R ¹ is a reactive group, and R ^{2 'is} an alkyl or aryl group, or a molecular weight less than 1000 g / mole of the oligomers, and a second compound having the ^{_{formula: SiR 3 b R 4 c R}} 5' 4 _-(b+c) wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, and R ^5'is an alkyl group or an aryl group, and wherein b=1 to 2, and c=1 to (4- b), or its oligomers with a molecular weight of less than 1000 g/mol.

The first, second and third compounds and any of the compounds described below, if such compounds have more than one single type of "R" group, such as multiple aryl or alkyl groups, or multiple reactivity Groups, or a plurality of crosslinking functional groups, etc., a plurality of R groups are independently selected so as to be the same or different each time. For example, _^'2 is independently selected plurality of R ¹ groups in the same or different when the first compound is SiR ^{1 ₂} R _2. Similarly, a plurality of independently selected R ^{2 'group} is the same or different from each other so that. Unless expressly stated otherwise, the same applies to any other compounds mentioned herein.

The first compound may have 1 to 3 alkyl or aryl groups (R ^2' ) bonded to silicon in the compound. Combinations of different alkyl groups, different aryl groups, or combinations of both alkyl and aryl groups are possible. In the case of an alkyl group, the alkyl group preferably contains 1 to 18, more preferably 1 to 14 and especially more preferably 1 to 12 carbon atoms. A shorter alkyl group is envisioned, such as 1 to 6 carbons (e.g., 2 to 6 carbon atoms). The alkyl group may be branched with one or more, preferably two C1 to C6 alkyl groups at the α position or the β position. Specifically, the alkyl group is a low-carbon alkyl group containing 1 to 6 carbon atoms, which optionally carries 1 to 3 substituents selected from methyl and halogen. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl are particularly preferred. Cycloalkyl groups are also possible, such as cyclohexyl, adamantyl, norbornene or norbornyl.

If R ^2'is an aryl group, the aryl group may be a phenyl group, which optionally carries 1 to 5 substituents selected from halogen, alkyl, or alkenyl on the ring, or naphthyl, which is optionally in the ring structure There are 1 to 11 substituents selected from halogen, alkyl or alkenyl, and the substituents are optionally fluorinated (including perfluorinated or partially fluorinated). If the aryl group is a polycyclic aryl group, the polycyclic aryl group may be, for example, anthracene, naphthalene, phenanthrene, and tetracene, which may carry 1-8 substituents or may optionally contain 1 to 12 substituents. The alkyl, alkenyl, alkynyl or aryl group of carbon is "spaced" from the silicon atom. Monocyclic structures such as phenyl can also be spaced apart from silicon atoms in this way.

The silicone polymer is prepared by carrying out a polymerization reaction (preferably a base-catalyzed polymerization reaction) between the first compound and the second compound. Additional compounds optionally present as explained below may be included as part of the polymerization reaction.

The first compound may have any suitable reactive group R ¹ , such as hydroxyl, halogen, alkoxy, carboxyl, amine, or acyloxy. If, for example, the reactive group in the first compound is an -OH group, more specific examples of the first compound may include silane diol, especially such as diphenyl silane diol, dimethyl silane diol , Diisopropylsilane diol, di-n-propyl silane diol, di-n-butyl silane diol, di-tertiary butyl silane diol, diisobutyl silane diol, phenyl methyl silane diol And dicyclohexyl silane diol.

The second compound may have any suitable reactive group R ⁴ , such as a hydroxyl group, a halogen, an alkoxy group, a carboxyl group, an amine or an acyloxy group, which may be the same as or different from the reactive group in the first compound. In one example, the reactive group is not -H in the first compound or the second compound (or any compound that participates in the polymerization reaction to form a silicone polymer-such as the third compound, etc.), so that the resulting silicone The alkane polymer does not have any or substantially any H groups directly bound to the Si in the siloxane polymer.

A group R ^{5 'is} fully present in the second compound if, then independently an alkyl group or an aryl group, such as for the radicals R ² of the first ^compound'. Alkyl or aryl group R ^{5 'and} R ² may be the first group of compounds of ^the same or different.

The cross-linking reactive group R ^{3 of the} second compound can be any functional group that can be cross-linked by acid, base, free radical, or thermally catalyzed reaction. These functional groups can be, for example, any epoxide, amine, allyl, acid anhydride, oxetane, acrylate, alkenyl, alkynyl, or mercapto group.

In the case of an epoxy group, it can be a cyclic ether with three ring atoms that can be cross-linked using acid, base, and thermally catalyzed reactions. Examples of such epoxides containing crosslinking groups are glycidoxypropyl and (3,4-epoxycyclohexyl)ethyl (to name a few).

In the case of propylene oxide, it can be a cyclic ether with four ring atoms that can be cross-linked using acid, base, and thermally catalyzed reactions. Examples of such silanes containing propylene oxide include 3-(3-ethyl-3-oxetanylmethoxy) propyltriethoxysilane, 3-(3-methyl-3-oxetanylmethyl Oxy)propyltriethoxysilane, 3-(3-ethyl-3-oxetanylmethoxy)propyltrimethoxysilane or 3-(3-methyl-3-oxetanylmethoxy) Group) propyl trimethoxysilane (just to name a few).

In the case of alkenyl groups, such groups may have preferably 2 to 18, more preferably 2 to 14, and especially more preferably 2 to 12 carbon atoms. The olefinic (ie, two carbon atoms bonded to a double bond) group is preferably located at a position 2 or higher relative to the Si atom in the molecule. The branched alkenyl group is preferably branched at the α position or β position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl groups, optionally fluorinated or perfluorinated alkyl, alkenyl or alkynyl groups .

In the case of an alkynyl group, it may have preferably 2 to 18, more preferably 2 to 14, and especially more preferably 2 to 12 carbon atoms. The alkyne group (that is, the two carbon atoms bonded to the parametric bond) is preferably located at a position 2 or higher relative to the Si atom or the M atom in the molecule. The branched alkynyl group is preferably branched at the α position or the β position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl groups, optionally perfluorinated alkyl, alkenyl or alkynyl groups.

In the case of a mercapto group, it can be any organosulfur compound containing a carbon-bonded sulfhydryl group. Examples of mercapto group-containing silanes are 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

The reactive group in the second compound may be an alkoxy group. The alkyl residue of the alkoxy group can be straight or branched. Preferably, the alkoxy group is composed of a low-carbon number alkoxy group having 1 to 6 carbon atoms (such as methoxy, ethoxy, propoxy, and tertiary butoxy). Specific examples of the second compound are silanes, especially such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane , 3-(Trimethoxysilyl) propyl methacrylate, 3-(trimethoxysilyl) propyl acrylate, (3-glycidyloxypropyl) trimethoxysilane or 3-glycidoxy Propyl propyl triethoxy silane, 3-methacryloxy propyl trimethoxy silane, 3- propylene oxy propyl trimethoxy silane.

The third compound may be provided together with the first compound and the second compound to be polymerized therewith. The third compound may have the following chemical formula: SiR ⁹ _f R ¹⁰ _g where R ⁹ is a reactive group, and f=1 to 4, and where R ¹⁰ is an alkyl group or an aryl group, and g=4-f.

One such example is tetramethoxysilane. Other examples especially include phenylmethyldimethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, methyltrimethylsilane Oxysilane, methyl triethoxy silane, methyl tripropoxy silane, propyl ethyl trimethoxy silane, ethyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane Silane.

Although the polymerization of the first compound and the second compound can be carried out using an acid catalyst, a base catalyst is preferred. The base catalyst used for the base-catalyzed polymerization between the first compound and the second compound may be any suitable basic compound. Examples of such basic compounds are especially any amine, such as triethylamine, and any barium hydroxide, such as barium hydroxide, barium hydroxide monohydrate, barium hydroxide octahydrate. Other basic catalysts include magnesium oxide, calcium oxide, barium oxide, ammonia, ammonium perchlorate, sodium hydroxide, potassium hydroxide, imidazole or n-butylamine. In a specific example, the base catalyst is Ba(OH) ₂ . The base catalyst may be provided in a weight% of less than 0.5% relative to the first compound and the second compound together, or in a lower amount, such as a weight% of less than 0.1%.

The polymerization can be carried out in the molten phase or in a liquid medium. The temperature is in the range of about 20°C to 200°C, usually about 25°C to 160°C, especially about 40°C to 120°C. Generally, the polymerization is carried out under ambient pressure and the maximum temperature is set by the boiling point of any solvent used. The polymerization can be carried out under reflux conditions. Other pressures and temperatures are also possible. The molar ratio of the first compound to the second compound may be 95:5 to 5:95, especially 90:10 to 10:90, preferably 80:20 to 20:80. In a preferred embodiment, the molar ratio of the first compound to the second compound (or the second compound plus other compounds participating in the polymerization reaction-see below) is at least 40:60, or even 45:55 or higher.

In one example, the first compound has an -OH group as a reactive group and the second compound has an alkoxy group as a reactive group. Preferably, in terms of the amount of the first compound added, the total number of -OH groups is not greater than the total number of reactive groups (such as alkoxy) in the second compound, and is preferably less than in the second compound ( Or the second compound plus any other compound added together with the alkoxy group, such as the tetramethoxysilane added or the reactive group of the third compound involved in the polymerization reaction (as mentioned herein) total. In the case where the number of alkoxy groups exceeds the hydroxyl group, all or substantially all -OH groups will react and be removed from the siloxane, such as methanol (if the alkoxysilane is methoxysilane), ethanol (if the alkoxysilane is methoxysilane), ethanol (if the alkoxysilane is methoxysilane), all or substantially all -OH groups will react and be removed from the siloxane. The base silane is ethoxy silane) and so on. Although the number of -OH groups in the first compound and the number of reactive groups (preferably other than -OH groups) in the second compound may be substantially the same, it is preferred that the number of reactive groups in the second compound The total number of groups exceeds the -OH groups in the first compound by 10% or more, preferably 25% or more. In some embodiments, the number of reactive groups of the second compound exceeds the -OH groups of the first compound by 40% or more, or even 60% or more, 75% or more, or up to 100% or more . After polymerization, methanol, ethanol or other by-products of the polymerization reaction (depending on the selected compound) are removed, preferably evaporated in a drying chamber.

The obtained silicone polymer has any desired (weight average) molecular weight, such as 500 g/mol to 100,000 g/mol. The molecular weight can be at the lower end of this range (for example, 500 g/mol to 10,000 g/mol or better, 500 g/mol to 8,000 g/mol) or the molecular weight of the organosiloxane material can be at the upper end of this range ( Such as 10,000 g/mole to 100,000 g/mole or better, 15,000 g/mole to 50,000 g/mole). It may be necessary to mix a polymer organosiloxane material having a lower molecular weight with an organosiloxane material having a higher molecular weight.

The composition of the obtained polymer can be additionally adjusted to achieve good adhesion after final curing. This can then be on the filler to be mixed with the polymer or the substrate to be coated with the polymer. To achieve good bonding, silane with good bonding properties is used during polymer manufacturing. Compounds with polar groups (such as hydroxyl groups, epoxy groups, carboxyl groups, acid anhydrides, or amine groups) are examples of silanes that have good adhesion properties on various substrates.

Depending on the final desired use of the polymer, the silicone polymer obtained can then be combined with additional components. Preferably, the silicone polymer is combined with a filler to form a composition, such as a particulate filler having an average particle size of less than 100 microns, preferably less than 50 microns, and containing particles less than 20 microns. Additional components may be part of the composition, such as catalysts or curing agents, one or more coupling agents, dispersants, antioxidants, stabilizers, then accelerators and/or other required components, depending on the silicone material The final required use.

In one example, a reducing agent that can reduce the oxidized surface to its metallic form is included. The reducing agent can remove oxidation from the particles when the particles are metal particles with surface oxidation, and/or remove oxidation from metal bonding pads or other metals that have been oxidized or conductive areas, so as to improve the silicone particle material and its Electrical connection between deposited or adhered surfaces. The reducing agent or stabilizer may include ethylene glycol, β-D-glucose, polyethylene oxide, glycerin, 1,2-propylene glycol, N,N dimethylformamide, poly-sodium acrylate (PSA), Polyacrylic acid β-cyclodextrin, dihydroxybenzene, polyvinyl alcohol, 1,2-propanediol, hydrazine, hydrazine sulfate, sodium borohydride, ascorbic acid, hydroquinone family, gallic acid, pyrogallol, ethylene dichloride Aldehydes, acetaldehyde, glutaraldehyde, aliphatic dialdehyde family, trioxane, tin powder, zinc powder, formic acid. Additives such as stabilizers, for example antioxidants, such as Irganox (mentioned below) or diazine derivatives may also be added.

Cross-linked silicone or non-silicon resins and oligomers can be used to enhance cross-linking between silicone polymers. The functionality of the added cross-linked oligomer or resin is selected by the functionality of the silicone polymer. If, for example, epoxy-based alkoxysilanes are used during the polymerization of silicone polymers, epoxy-functional oligomers or resins can be used. The epoxy oligomer or resin can be any difunctional, trifunctional, tetrafunctional or higher functional epoxy oligomer or resin. Examples of these epoxy oligomers or resins can be 1,3-bis-2-(3,4-epoxycyclohexyl)ethyl 1,1,3,3-tetramethyldisiloxane, 1, 3-Diglycidoxypropyl 1,1,3,3-tetramethyldisiloxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy Cyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, 1,4-cyclohexane dimethanol diglycidyl ether, bisphenol A diglycidyl ether, 1,2-cyclohexane dicarboxylic acid diglycidyl Esters (just to name a few).

The curing agent added to the final formulation is any compound that can initiate and/or accelerate the curing process of the functional groups in the silicone polymer. These curing agents may be thermally and/or UV-activated (for example, thermal acid in the case of thermal activation of the polymerization reaction or photoinitiator in the case of UV activation). The crosslinking group in the silicone polymer as described above is preferably selected from epoxide, propylene oxide, acrylate, alkenyl, alkynyl, vinyl and Si-H groups. The curing agent is selected based on the cross-linking group in the silicone polymer.

In one embodiment, the curing agent for epoxy groups and propylene oxide groups may be selected from nitrogen-containing curing agents that exhibit blocked or reduced activity, such as primary amines and/or secondary amines. The definition "primary amine or secondary amine showing blocked or reduced reactivity" shall mean that it cannot react with the resin component or only has a very low ability to react with the resin component due to chemical or physical blocking, but it can After releasing the amine, it regenerates its reactivity, for example by melting it at an elevated temperature, by removing the sheath or coating, by the action of pressure or ultrasonic waves or other types of energy, to start the resin component The curing reaction of these amines.

Examples of heat-activatable curing agents include at least one organoborane or a complex of borane and at least one amine. The amine can be a complex organoborane and/or borane and can be decomplexed if necessary to release any type of organoborane or borane. The amine may include various structures, such as any primary amine or secondary amine or polyamine containing primary amine and/or secondary amine. The organoborane may be selected from alkyl borane. An example of such thermally activatable, particularly preferred borane curing agent is boron trifluoride. Suitable amine/(organic) borane complexes are purchased from commercial sources such as King Industries, Air Products, and ATO-Tech.

Other thermally activated curing agents used for epoxy groups are thermal acid generators, which can release strong acids at high temperatures to catalyze the crosslinking reaction of epoxy groups. These thermal acid generating agent may be, for example, ₄ having a ^{_{BF -, PF 6 -, SbF}} 6 -, CF 3 SO 3 - and _{(C 6 F 5) 4 B} - anion of any compound of onium salt type, such as sulfonium salts and Iodonium salt. Commercial examples of these thermal acid generators are K-PURE CXC-1612 and K-PURE CXC-1614 manufactured by King's Industries.

In addition, for polymer-containing epoxides and/or propylene oxide, curing agents, co-curing agents, catalysts, initiators or other additives designed to participate in or promote the curing of the adhesive formulation can be used, such as Acid anhydrides, amines, imidazoles, mercaptans, carboxylic acids, phenols, dicyandiamide, urea, hydrazine, hydrazine, amine-formaldehyde resins, melamine-formaldehyde resins, quaternary ammonium salts, quaternary phosphonium salts, triarylsulfur Onium salts, diaryliodonium salts, diazonium salts, and the like.

For acrylates, alkenyl and alkynyl crosslinking group curing agents can be heat or UV activated. Examples of thermal activation are peroxides and azo compounds. Peroxides are compounds containing unstable oxygen-oxygen single bonds, which are easily resolved into reactive free radicals via hemolytic cleavage. Azo compounds have R-N=N-R functional groups that can be decomposed into nitrogen and two organic free radicals. In both cases, free radicals can catalyze the polymerization of acrylate, alkenyl and alkynyl bonds. Examples of peroxides and azo compounds are di-tert-butyl peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl peracetate, 2,5-bis( Tertiary butylperoxy)-2,5-dimethyl-3-hexyne, dicumyl peroxide, benzyl peroxide, di-tertiary amyl peroxide, peroxybenzoic acid Tertiary butyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-carboxamidinopropane) dihydrochloride, diphenyldiazene, Diethyl azodicarboxylate and 1,1'-azobis(cyclohexanecarbonitrile) (just to name a few).

The photoinitiator is a compound that decomposes into free radicals when exposed to light and thus can promote the polymerization of acrylate, alkenyl, and alkynyl compounds. Commercial examples of these photoinitiators are Irgacure 149, Irgacure 184, Irgacure 369, Irgacure 500, Irgacure 651, Irgacure 784, Irgacure manufactured by BASF Jiagu 819, Yan Jiagu 907, Yan Jiagu 1700, Yan Jia Gu 1800, Yan Jia Gu 1850, Yan Jia Gu 2959, Yan Jia Gu 1173, Yan Jia Gu 4265.

One method of incorporating the curing agent into the system is to attach the curing agent or a functional group that can act as a curing agent to the silane monomer. Therefore, the curing agent will accelerate the curing of the silicone polymer. Examples of these types of curing agents attached to the silane monomer are γ-imidazolylpropyltriethoxysilane, γ-imidazolylpropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Mercaptopropyltriethoxysilane, 3-(triethoxysilyl)propyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3-aminopropyltrimethoxysilane And 3-aminopropyl triethoxysilane (just to name a few).

The then accelerator can be part of the composition and can be any suitable compound that can enhance the adhesion between the cured product and the surface of the coated product. The most commonly used adhesion promoter is functional silane, which contains alkoxy silane and 1 to 3 functional groups. Examples of adhesion promoters used in die attach products can be octyltriethoxysilane, mercaptopropyltriethoxysilane, cyanopropyltrimethoxysilane, 2-(3,4-cyclic Oxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxy silane, 3-(trimethoxysilyl) propyl methacrylate, 3-(trimethyl) (Oxysilyl) propyl acrylate, (3-glycidyloxypropyl)trimethoxysilane or 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane and 3-propenoxypropyltrimethoxysilane.

The formed polymeric siloxane will have a [Si-O-Si-O]n repeating main chain, and the organic functional groups on it will depend on the silicon-containing starting material. However, it is also possible to achieve [Si-O-Si-C]n or even [Si-O-Me-O]n (where Me is a metal) backbone.

In order to obtain the [Si-O-Si-C] main chain, ^{the chemical with the formula R 2} _3-a R ¹ _a SiR ¹¹ SiR ¹ _b R ² _3-b can be combined with the first compound and the second compound as described above And the third compound or any combination of these together, wherein a is 1 to 3, b is 1 to 3, R ¹ is a reactive group as explained above, R ² is an alkyl, alkenyl, alkynyl, Alcohol, carboxylic acid, dicarboxylic acid, aryl, polyaryl, polycyclic alkyl, heterocyclic aliphatic, heterocyclic aromatic and R ^{11 is} independently alkyl or aryl, or its molecular weight is less than 1000 Gram/mole of oligomer.

Examples of these compounds are 1,2-bis(dimethylhydroxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(dimethoxymethylsilane) Yl)ethane, 1,2-bis(methoxydimethylsilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3-bis(dimethylhydroxysilane) Yl)propane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(dimethoxymethylsilyl)propane, 1,3-bis(methoxydimethylsilyl) Propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(dimethylhydroxysilyl)butane, 1,4-bis(trimethoxysilyl)butane, 1, 4-bis(dimethoxymethylsilyl)butane, 1,4-bis(methoxydimethylsilyl)butane, 1,4-bis(triethoxysilyl)butane, 1,5-bis(dimethylhydroxysilyl)pentane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(dimethoxymethylsilyl)pentane, 1 ,5-bis(methoxydimethylsilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis(dimethylhydroxysilyl)hexane, 1 ,6-bis(trimethoxysilyl)hexane, 1,6-bis(dimethoxymethylsilyl)hexane, 1,6-bis(methoxydimethylsilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,4-bis(trimethoxysilyl)benzene, bis(trimethoxysilyl)naphthalene, bis(trimethoxysilyl)anthracene, Bis(trimethoxysilyl)phenanthrene, bis(trimethoxysilyl)norbornene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis(methoxydimethylsilane) Benzene and 1,4-bis(triethoxysilyl)benzene (just to name a few).

In one embodiment, in order to obtain the [Si-O-Si-C] backbone, the compound R ⁵ _3-(c+d) R ⁴ _d R ³ _c SiR ¹¹ SiR ³ _e R ⁴ _f R ⁵ _3-(e+f) where R ³ is a cross-linking functional group, R ⁴ is a reactive group, and R ⁵ is an alkyl group, alkenyl group, alkynyl group, alcohol, carboxylic acid, dicarboxylic acid, aryl group, poly Aryl group, polycyclic alkyl group, heterocyclic aliphatic group, heterocyclic aromatic group, R ^{12 is} independently an alkyl group or an aryl group, and wherein c=1 to 2, d=1 to (3-c), e =1 to 2, and f=1 to (3-e), or an oligomer with a molecular weight of less than 1000 g/mol, and the first compound, second compound, third compound or Any combination of these substances polymerizes together.

Examples of these compounds are 1,2-bis(vinyldimethoxysilyl)ethane, 1,2-bis(ethynyldimethoxysilyl)ethane, 1,2-bis(ethynyl) Dimethoxy)ethane, 1,2-bis(3-glycidoxypropyldimethoxysilyl)ethane, 1,2-bis[2-(3,4-epoxycyclohexyl) Ethyldimethoxysilyl)ethane, 1,2-bis(propylmethacrylate dimethoxysilyl)ethane, 1,4-bis(vinyldimethoxysilyl)benzene, 1,4-bis(ethynyldimethoxysilyl)benzene, 1,4-bis(ethynyldimethoxysilyl)benzene, 1,4-bis(3-glycidoxypropyldimethyl) Oxysilyl)benzene, 1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethoxysilyl]benzene, 1,4-bis(propyl methacrylate dimethoxy) (Silyl)benzene (just to name a few).

In one embodiment, the silicon having the formula siloxane monomer ^{_{R 1 a R 2 'b R}} 3 3- (a + b) Si-O-SiR 2' 2 -O-Si R 1 a R 2 'b R ³ _{3- (a + b)} wherein R ¹ is as explained above, the reactive group, R ^{2 'is} as explained above the alkyl or aryl group, R ³ is as hereinbefore explained by crosslinking functional group, and a =0 to 3, b=0 to 3, polymerized with the silane mentioned earlier or added as an additive to the final formulation.

Examples of these compounds are 1,1,5,5-tetramethoxy-1,5-dimethyl-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy Group-1,3,3,5-tetraphenyltrisiloxane, 1,1,5,5-tetraethoxy-3,3-diphenyltrisiloxane, 1,1,5,5 -Tetramethoxy-1,5-divinyl-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy-1,5-dimethyl-3,3 -Diisopropyltrisiloxane, 1,1,1,5,5,5-hexamethoxy-3,3-diphenyltrisiloxane, 1,5-dimethyl-1,5- Diethoxy-3,3-diphenyltrisiloxane, 1,5-bis(mercaptopropyl)-1,1,5,5-tetramethoxy-3,3-diphenyltrisiloxane Oxyane, 1,5-divinyl-1,1,5,5-tetramethoxy-3-phenyl-3-methyltrisiloxane, 1,5-divinyl-1,1, 5,5-Tetramethoxy-3-cyclohexyl-3-methyltrisiloxane, 1,1,7,7-tetramethoxy-1,7-divinyl-3,3,5, 5-tetramethyltetrasiloxane, 1,1,5,5-tetramethoxy-3,3-dimethyltrisiloxane, 1,1,7,7-tetraethoxy-3, 3,5,5-tetramethyltetrasiloxane, 1,1,5,5-tetraethoxy-3,3-dimethyltrisiloxane, 1,1,5,5-tetramethoxy Group-1,5-[2-(3,4-epoxycyclohexyl)ethyl]-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy-1, 5-(3-glycidoxypropyl)-3,3-diphenyltrisiloxane, 1,5-dimethyl-1,5-dimethoxy-1,5-2-(3 ,4-Epoxycyclohexyl)ethyl)-3,3-diphenyltrisiloxane, 1,5-dimethyl-1,5-dimethoxy-1,5-(3-glycidol (Oxypropyl)-3,3-diphenyltrisiloxane (just to name a few).

Added to the composition of additive (after the polymerization silicon siloxane material as noted above) of the can having the formula of Silane ^{_{compound: R 1 a R 2 'b}} SiR 3 4- (a + b) wherein R ¹ is a reaction groups, such as hydroxy, alkoxy, or acetyl group, R ^{2 'is} an alkyl or aryl group, R ³ is a cross-linking compound such as ethylene group, propylene oxide, alkenyl group, alkynyl group or an acrylate , A=0 to 1 and b=0 to 1.

Examples of such additives are tris-(3-glycidoxypropyl)phenylsilane, tris-[2-(3,4-epoxycyclohexyl)ethyl]phenylsilane, tris-(3-methyl Allyl oxy) phenyl silane, tris-(3- oxy) phenyl silane, tetra-(3-glycidoxy propyl) silane, tetra-(2-(3,4-epoxy) Cyclohexyl) ethyl) silane, tetra-(3-methacryloxy) silane, tetra-(3-propenoxy) silane, tri-(3-glycidoxypropyl) p-tolyl silane , Tris-[2-(3,4-epoxycyclohexyl)ethyl]p-tolylsilane, tris-(3-methacryloyloxy)p-tolylsilane, tris-(3-propenyloxy) )P-tolylsilane, tris-(3-glycidoxypropyl)hydroxysilane, tris-[2-(3,4-epoxycyclohexyl)ethyl]hydroxysilane, tris-(3-methylpropene) (Acryoxy) hydroxysilane, tris-(3-propenoxy) hydroxysilane.

The additive may also be any organic or silicone polymer, which may or may not react with the main polymer matrix, thus acting as a plasticizer, softener or matrix modifier, such as silicone. The additives can also be inorganic polycondensates, such as SiOx, TiOx, AlOx, TaOx, HfOx, ZrOx, SnOx, polysilazane.

The particulate filler can be conductive materials, such as carbon black, graphite, graphene, gold, silver, copper, platinum, palladium, nickel, aluminum, silver-plated copper, silver-plated aluminum, bismuth, tin, bismuth-tin alloy, plating Silver fiber, nickel-plated copper, silver and nickel-plated copper, gold-plated copper, gold-plated and nickel-plated copper, or it can be gold-plated, silver-gold, silver, nickel, tin, platinum, titanium polymer, such as polyacrylate , Polystyrene or silicone, but not limited to this. The filler can also be a semiconductor material, such as silicon, n-type or p-type doped silicon, GaN, InGaN, GaAs, InP, SiC, but is not limited thereto. In addition, the filler may be quantum dots or surface plasmon particles or phosphor particles. Other semiconductor particles or quantum dots, such as Ge, GaP, InAs, CdSe, ZnO, ZnSe, TiO ₂ , ZnS, CdS, CdTe, etc. are also possible.

The filler can be particles, which are any suitable metal particles or semi-metal particles, such as selected from gold, silver, copper, platinum, palladium, indium, iron, nickel, aluminum, carbon, cobalt, strontium, zinc, molybdenum, titanium , Tungsten, silver-plated copper, silver-plated aluminum, bismuth, tin, bismuth-tin alloy, silver-plated fiber or alloys or combinations of these substances. Metal particles that are expected to be transition metal particles (regardless of pre-transition metal or post-transition metal) are the same as semi-metals and metalloids. Semi-metal or metalloid particles such as arsenic, antimony, tellurium, germanium, silicon, and bismuth are envisioned.

Alternatively, it may be a non-conductive material, such as silicon dioxide, quartz, aluminum oxide, aluminum nitride, aluminum nitride coated with silicon dioxide, barium sulfate, aluminum oxide trihydrate, boron nitride, and the like. The filler may be in the form of particles or flakes, and may be micron-sized or nano-sized. The filler may include metal or semi-metal nitrides, oxynitrides, carbides, and oxycarbide ceramic compound particles. In particular, the filler may be particles, the particles being silicon, zinc, aluminum, yttrium, ytterbium, tungsten, titanium silicon, titanium, antimony, calcium, nickel, nickel, cobalt, molybdenum, magnesium, manganese, lanthanides, Ceramic particles of oxides of iron, indium tin, copper, cobalt aluminum, chromium, cesium or calcium.

It is also possible to include carbon particles and selected from carbon black, graphite, graphene, diamond, silicon carbonitride, titanium carbonitride, carbon nano-tree buds, and carbon nanotubes. The filler particles can be carbide particles, such as iron carbide, silicon carbide, cobalt carbide, tungsten carbide, boron carbide, zirconium carbide, chromium carbide, titanium carbide, or molybdenum carbide. The particles may alternatively be nitride particles, such as aluminum nitride, tantalum nitride, boron nitride, titanium nitride, copper nitride, molybdenum nitride, tungsten nitride, iron nitride, silicon nitride, indium nitride, Gallium nitride or carbon nitride.

Depending on the final application, any suitable size particles can be used. In many cases, small particles with an average particle size of less than 100 microns, and preferably less than 50 microns or even 20 microns are used. Submicron particles are also envisioned, such as less than 1 micron, or, for example, 1 nanometer to 500 nanometers, such as less than 200 nanometers, such as 1 nanometer to 100 nanometers, or even those less than 10 nanometers. In other examples, particles with an average particle size of 5 nanometers to 50 nanometers, or 15 nanometers to 75 nanometers, less than 100 nanometers, or 50 nanometers to 500 nanometers are provided. It is not slender, for example particles that are generally spherical or square, or flakes with a flat disc appearance (with smooth or rough edges), like slender whiskers, cylinders, wires, and other slender particles, such as those with 5: Particles with an aspect ratio of 1 or greater, or 10:1 or greater.

Very slender particles with extremely high aspect ratios, such as nanowires and nanotubes, are also possible. The high aspect ratio of the nanowire or nanotube can be 25:1 or greater, 50:1 or greater, or even 100:1 or greater. The average particle size of nanowires or nanotubes refers to the minimum size (width or diameter), because the length can be quite long, even up to a few centimeters long. As used herein, the term "average particle size" refers to the D50 value at the cumulative volume distribution curve where the diameter of 50% by volume of the particles is smaller than the stated value.

The particles may be a mixture of particles as mentioned elsewhere in this article, in which a first group of particles with an average particle size greater than 200 nanometers is provided together with a second group of particles with an average particle size less than 200 nanometers, for example, where the average particle size of the first group The particle size is greater than 500 nanometers and the average particle size of the second group is less than 100 nanometers (for example, the average particle size of the first group is greater than 1 micron, and the particle size of the second group is less than 50 nanometers, or even less than 25 nanometers). The melting point of the smaller particles is lower than the melting point of the larger particles, and the smaller particles melt or sinter at a temperature lower than the particles of the same material with an enlarged micrometer size. In one example, the average particle size of the smaller particles is less than 1 micron and melts or sinters at a temperature less than the overall temperature of the same material.

Depending on the selected particle material and average particle size, the melting and sintering temperatures will be different.

As an example, very small silver nanoparticles can be melted below 120°C and sintered at even lower temperatures. Therefore, if necessary, the melting or sintering temperature of the smaller particles can be equal to or lower than the solidification temperature of the polymer to form the melting or sintering particles that connect the larger particles together before the siloxane polymer material is completely cross-linked and solidified. Of the net. In one example, the smaller particles are melted or sintered together with the larger particles at a temperature below 130°C, such as below 120°C, or even sintered below 110°C, while the siloxane material is at a higher temperature. Undergo substantial crosslinking, such as substantial sintering or melting at lower than 110°C, but substantial polymerization at higher than 110°C (or, for example, substantial sintering or melting at lower than 120°C (or 130°C), but Substantial polymerization at higher than 120°C (or 130°C)). The sintering or melting of the smaller particles before the siloxane material substantially polymerizes allows the formed metal "grid" to have greater interconnectivity, which increases the final conductivity of the solidified layer. The substantial sintering or substantial polymerization of the smaller particles prior to melting reduces the amount of metal "grid" formed and reduces the conductivity of the final cured layer.

Of course, it is also possible to only provide particles with a smaller average particle size (such as sub-micron size), which can still achieve a lower sintering point and melting point compared to the same block (or the same particle with an average particle size greater than 1 micron). benefit.

In order to enhance the coupling with fillers and silicone polymers, coupling agents can be used. This coupling agent will increase the adhesion between the filler and the polymer and thus may increase the thermal conductivity and/or electrical conductivity of the final product. The coupling agent can be any silane monomer having the following formula: R ¹³ _h R ¹⁴ _i SiR ¹⁵ _j where R ¹³ is a reactive group, such as halogen, hydroxyl, alkoxy, acetoxy or acetoxy, R ¹⁴ is an alkyl group or an aryl group, and R ¹⁵ is a functional group including epoxy, anhydride, cyano, propylene oxide, amine, mercapto, allyl, alkenyl or alkynyl group, h=0 to 4, i=0 to 4, j=0 to 4, and h+i+j=4.

The coupling agent can be directly mixed with the filler, silicone polymer, curing agent and additives when preparing the final product, or the filler particles can be treated with the coupling agent before they are mixed with the particles.

If the particles are treated with a coupling agent before being used in the final formulation, different methods can be used, such as deposition from alcoholic solutions, deposition from aqueous solutions, bulk deposition on fillers, and deposition in anhydrous liquid phase. In the deposition from an alcohol solution, an alcohol/water solution is prepared and the pH of the solution is adjusted to slightly acidic (pH 4.5-5.5). Silane is added to this solution and mixed for a few minutes to allow partial hydrolysis. Then, filler particles are added and the solution is mixed for different periods of time from room temperature to reflux temperature. After mixing, the particles are filtered, rinsed with ethanol and dried in an oven to obtain surface-treated particles with the coupling agent. Deposition from an aqueous solution is similar to deposition from an alcohol solution, but uses pure water instead of alcohol as the solvent. If non-amine functionalization is used, the pH is adjusted again with acid. After mixing the particles with the water/silane mixture, the particles are filtered, rinsed and dried.

A large amount of deposition method is a method of mixing silane coupling agent and solvent without any water or pH adjustment. The filler particles are coated with a silanol solution using different methods such as spraying and then dried in an oven.

In anhydrous liquid phase deposition, silane is mixed with organic solvents such as toluene, tetrahydrofuran or hydrocarbons, the filler particles are refluxed in this solution and the additional solvent is removed by vacuum or filtration. The particles can also be dried in an oven later, but this is sometimes not needed due to the direct reaction between the particles and the filler under reflux conditions.

Examples of such silane coupling agents are bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, allyltrimethoxysilane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, (N-trimethoxysilylpropyl) polyethylene diimide, trimethoxysilyl propyl diethylene triethylene Amine, phenyltriethoxysilane, phenyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 1-trimethoxysilyl-2 (p, m-chloromethyl) phenylethane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, propyl isocyanate triethoxy silane, bis[3-(triethoxy) Silyl) propyl) tetrasulfide, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (Diphenylphosphino) ethyltriethoxysilane, 1,3-divinyltetramethyldisilazane, hexamethyldisilazane, 3-(N-styrylmethyl-2- (Aminoethylamino) propyltrimethoxysilane, N-(triethoxysilylpropyl)urea, 1,3-divinyltetramethyldisilazane, vinyltriethoxysilane, and Vinyltrimethoxysilane (just to name a few).

Depending on the type of particles added, the final product of silicone-particle curing can be a thermally conductive layer or film, such as having greater than 0.5 watts/meter·kelvin (W/() after final thermal curing or UV curing m·K)) thermal conductivity. Depending on the particle type selected, higher thermal conductivity materials are possible. The metal particles in the silicone composition can produce a thermal conductivity greater than 2.0 watts/meter·Kelvin, such as greater than 4.0 watts/meter·Kelvin or even greater than 10.0 watts/meter·Kelvin curing The final film. Depending on the final application, higher thermal conductivity may be required, such as greater than 50.0 watts/meter·Kelvin, or even greater than 100.0 watts/meter·Kelvin. However, in other applications, the particles can be selected to produce materials with low thermal conductivity if necessary.

In addition, if necessary, the final cured product may have a low resistivity, such as less than 1×10 ^-3 Ω·m, preferably less than 1×10 ^-4 Ω·m, and more preferably 1×10 ^-5 Ω·m. In addition, the sheet resistance of the deposited film is preferably less than 100,000, more preferably less than 10,000. However, many desired end uses of the material can have high resistivity.

In some cases, especially when the composition will be used in devices that require optical characteristics, although in some cases it may be necessary for the final cured silicone to have optical absorption characteristics, it is more likely that the material will desirably be highly transparent in the visible spectrum (Or in the spectrum of the final device of the operation), or will desirably highly reflect light in the visible spectrum (or in the spectrum of the operation device). As an example of a transparent material, a final cured layer with a thickness of 1 to 50 microns will transmit at least 85% of the visible light incident thereon, or preferably at least 90%, more preferably at least 92.5% and most preferably at least 95%. As an example of the reflective layer, the final cured layer can reflect at least 85% of the light incident on it, preferably at least 95% of the light incident on it at an angle of 90 degrees.

The material of the present invention may also contain stabilizers and/or antioxidants. These compounds are added to protect the material from degradation caused by the reaction with oxygen induced by substances such as heat, light or residual catalyst from the raw materials.

Suitable stabilizers or antioxidants herein are high molecular weight hindered phenols and polyfunctional phenols, such as phenols containing sulfur and phosphorus. Hindered phenols are well known to those skilled in the art and can be characterized as phenolic compounds that also contain sterically bulky radicals very close to their phenolic hydroxyl groups. Specifically, the tertiary butyl group is generally substituted on the benzene ring at at least one ortho position relative to the phenolic hydroxyl group. The presence of these three-dimensional large substituted radicals near the hydroxyl group is used to delay the stretching frequency and correspondingly delay its reactivity; this steric hindrance therefore provides phenolic compounds with its stable properties. Representative hindered phenols include: 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene; tetra-3( 3,5-Di-tert-butyl-4-hydroxyphenyl)-isopentaerythritol propionate; 3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid n-ten Octaalkyl ester; 4,4'-methylene bis(2,6-tertiary butyl-phenol); 4,4'-thio bis(6-tertiary butyl o-cresol); 2,6- Di-tert-butylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)-1,3,5 triazine; 3,5-di-tert-butyl And sorbitol hexa[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate]. Commercial examples of antioxidants are, for example, Yancanox 1035, Yancanox 1010, Yancanox 1076, Yancanox 1098, Yancanox 3114, Yancanox PS800, and Yancanox manufactured by BASF. Kesi PS802, Yanjia Norkesi 168.

Depending on the end use of the product, the weight ratio between silicone polymer and filler is between 100:0 and 5:95. The ratio between silicone polymer and cross-linked silicon or non-silicon resin or oligomer is between 100:0 and 75:25. The amount of curing agent calculated from the amount of silicone polymer is 0.1% to 20%. The amount of the follow-up accelerator based on the total amount of the formulation is 0 to 10%. The amount of antioxidant based on the total weight of the formulation is 0 to 5%.

As mentioned above, the silicone-particle composition can be used in many fields. It can be used for electronics or optoelectronics packaging, LED and OLED front-end and back-end processing, 3D, photovoltaic and display metallization, replacement of solder bumps such as solder bumps in semiconductor packaging, printed electronic devices, OLED low work function cathodes Ink, ITO replacement ink, metal grid and other electrodes, high-resolution photovoltaic paste, LMO cathode paste, photovoltaic, power electronics and EMI, touch sensors and other displays, thermal or UV curable sealants or Adhesives or sealants in dielectrics (just to name a few).

Depending on the curing mechanism and the type of catalyst activation, the final formulation is usually cured by heating the material to a higher temperature. For example, if a thermal acid generator is used, the material is placed in an oven for a specific period of time. It is also possible to cure by electromagnetic radiation, such as UV light.

The molecular weight of the silicone polymer formed by polymerizing the first compound and the second compound is about 300 g/mol to 10,000 g/mol, preferably about 400 g/mol to 5000 g/mol, and more preferably About 500 grams/mole to 2000 grams/mole. When the polymer is combined with particles of any desired size, the average particle size is preferably less than 100 microns, more preferably less than 50 microns, or even less than 20 microns. The silicone polymer is added at 10% to 90% by weight, and the particles are added at 1% to 90% by weight. If the end use of the silicone material requires optical transparency, the particles may be ceramic particles added at a lower weight %, such as 1 to 20 weight %. If conductivity is required, such as when silicone materials are used in semiconductor packaging, the particles may be metal particles added at 60% to 95% by weight.

The polymerization of the first and second compounds is carried out, and the particles are mixed with them to form a viscosity of 50 MPa-second to 100,000 MPa-second, preferably 1000 MPa-second to 75,000 MPa-second and more preferably 5000 MPa- Second to 50,000 MPa-second viscous fluid. Viscosity can be measured by a viscometer, such as a Brookfield viscometer or Cole-Parmer viscosity meter, which rotates a disc or cylinder in a fluid sample and measures it against The torque required to induce viscous resistance in motion. It can be rotated at any desired speed, such as 1 rpm to 30 rpm, preferably 5 rpm, and preferably when the material is measured at 25°C.

After polymerization, any additional required components may be added to the composition, such as particles, coupling agents, curing agents, and the like. The composition is shipped to the customer as a viscous material in a container that is shipped at ambient temperature without cooling or freezing. As the final product, the material can be used in the various applications mentioned above, and is usually cured by heat or UV to form a solid cured polymeric silicone layer.

The composition as disclosed herein preferably does not have any substantial solvent. Solvents can be added temporarily, such as for mixing curing agents or other additives with polymeric viscous materials. In this case, for example, the curing agent is mixed with the solvent to form a fluid material that can be subsequently mixed with the viscous silicone polymer.

However, due to the need to ship the substantially solvent-free composition to the customer and then apply it to the customer's device, the temporarily added solvent is removed in the drying chamber.

However, although the composition is substantially solvent-free, there may be traces of residual solvent that cannot be removed during the drying process. Removal of this solvent by reducing the shrinkage during the final curing process facilitates the deposition of the composition disclosed herein, minimizes shrinkage over time during the life of the device, and helps during the life of the device For the thermal stability of the material.

Knowing the final application of the composition, the required viscosity of the composition, and the particles to be included, it is possible to fine-tune the silicone polymer (starting compound, molecular weight, viscosity, etc.) so that it has particles and other components when incorporated In the composition, it can achieve the final characteristics required for subsequent delivery to customers. Due to the stability of the composition, it is possible to ship the composition at ambient temperature without any substantial changes in molecular weight or viscosity, even one week or even one month after manufacture to the end of the customer's use. Examples:

The following silicone polymer examples are provided to illustrate the invention and are not intended to be limiting.

Measure the viscosity of the silicone polymer with a Brookfield viscometer (spindle 14). The molecular weight of the polymer was measured by Agilent GPC.

Silicone polymer i: Diphenyl silane diol (60 g, 45 mol%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (55.67 g, 36.7 mol%) %) and tetramethoxysilane (17.20 g, 18.3 mol%) are filled with a 500 ml round bottom flask with a stir bar and a reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.08 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of the diphenylsilane diol and the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 1000 mPas and the Mw is 1100.

Silicone polymer ii: Diphenyl silane diol (30 g, 45 mol%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (28.1 g, 37 mol%) %) and dimethyldimethoxysilane (6.67 g, 18 mol%) are filled with a 250 ml round bottom flask with a stir bar and a reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.035 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of the diphenylsilane diol and the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 2750 mPas and the Mw is 896.

Silicone polymer iii: Diphenyl silane diol (24.5 g, 50 mol%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (18.64 g, 33.4 mol%) %) and tetramethoxysilane (5.75 g, 16.7 mol%) are filled with a 250 ml round bottom flask with stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.026 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of the diphenylsilane diol and the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 7313 mPas and the Mw is 1328.

Silicone polymer iv: Diphenyl silane diol (15 g, 50 mol%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (13.29 g, 38.9 mol%) %) and bis(trimethoxysilyl)ethane (4.17 g, 11.1 mol%) were filled with a 250 ml round bottom flask with a stir bar and a reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.0175 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of the diphenylsilane diol and the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 1788 mPas and the Mw is 1590.

Silicone polymer v: Diphenyl silane diol (15 g, 45 mol%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (13.29 g, 35 mol%) %) and vinyltrimethoxysilane (4.57g, 20mol%) are filled with a 250ml round bottom flask with stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.018 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of the diphenylsilane diol and the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 1087 mPas and the Mw is 1004.

Silicone polymer vi: Diisopropyl silane diol (20.05 g, 55.55 mol%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (20.0 g, 33.33 mol%) (Ear%) and bis(trimethoxysilyl)ethane (7.3 g, 11.11 mol%) were filled with a 250 ml round bottom flask with a stir bar and a reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.025 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of the diphenylsilane diol and the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 150 mPas and the Mw is 781.

Siloxane polymer vii: Diisobutylsilane diol (18.6 g, 60 mol%) and 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (17.32 g, 40 mol%) Ear%) Fill a 250 ml round bottom flask with a stir bar and a reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.019 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of the diphenylsilane diol and the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 75 mPas and the Mw is 710.

Considering the disclosed methods and materials, a stable composition is formed. A part of the composition may be a siloxane polymer having a repeating main chain of [-Si-O-Si-O]n, the main chain has an alkyl group or an aryl group, and the main chain has a functional cross-linking The other part is particles mixed with silicone materials, wherein the average particle size of the particles is less than 100 microns, and the particles are any suitable particles, such as metal, semi-metal, semiconductor or ceramic particles. The composition delivered to the customer can have a molecular weight of 300 g/mol to 10,000 g/mol, and a viscosity of 1000 MPa-second to 75000 MPa-second under a 5 rpm viscometer.

Viscous (or liquid) silicone polymers generally do not contain -OH groups, so they provide extended shelf life and allow storage or transportation at ambient temperature when necessary. Preferably, the silicone material does not have an -OH peak that can be detected by FTIR analysis. The stability of the formed silicone material is increased to allow storage before use, where the increase in viscosity (crosslinking) is minimal during storage, such as storage at room temperature for a period of 2 weeks less than 25%, preferably a period of 2 weeks Less than 15%, and more preferably less than 10%. In addition, storage, transportation, and subsequent application by the customer can all be performed in the absence of solvent (except for possible trace residues remaining after drying to remove the solvent), avoiding subsequent solvent capture in the layer of the final product (Solvent capture), shrinkage during polymerization, quality loss over time during device use, etc. Without applying heat or UV light, preferably higher than 100°C, no substantial cross-linking occurs during transportation and storage.

The composition with silicone polymer, particles and other possible additives (such as coupling agent, adhesion promoter, etc.) as disclosed herein can be delivered as a one-component adhesive at room temperature. Generally speaking, one-component adhesives are shipped at -40°C, or the components are shipped separately ("two-component" adhesives), where the purchaser must mix the different components together, and it is usually better to Follow up within 24 hours or 48 hours. Generally speaking, a one-component adhesive may not involve mixing multiple components. However, once the adhesive is brought from, for example, -40°C to room temperature, the next step should preferably be performed within 24 hours or 48 hours. In contrast, the composition disclosed herein can be shipped in the form of a one-component adhesive and it can be shipped and stored at room temperature, for example, shipped and stored at room temperature for 2 weeks without substantial polymerization or other undesirable reaction.

When the composition is deposited and polymerized (for example, heat or UV light is applied), minimal shrinkage or reduction in mass is observed. In Figure 2, the x-axis is time (in minutes), the left y-axis is the mass of the layer in terms of initial mass%, and the right y-axis is the temperature in Celsius. As can be seen in Figure 2, the silicone particle mixture as disclosed herein is rapidly heated to 150°C and then held at 150°C for approximately 30 minutes. In this example, the silicone particles have a Si-O backbone with phenyl groups and epoxy groups, and the particles are silver particles. After this period of thermal curing, the mass loss is less than 1%. Desirably, the quality loss is generally less than 4%, and generally less than 2%. However, in many cases, the difference in mass of the silicone particle composition between before and after curing is less than 1%. The curing temperature is generally below 175°C, although higher curing temperatures are possible. Generally, the curing temperature will be 160°C or lower, more typically 150°C or lower. However, lower curing temperatures are possible, such as 125°C or lower.

As can be seen in Figure 3, no matter the composition disclosed above is used as an adhesive, a thermal conductive layer, a sealant, a patterned conductive layer, a patterned dielectric layer, a transparent layer, a light reflective layer, etc., once the composition is deposited and Polymerized and optionally hardened, the silicone particle layer or quality is quite thermally stable. For example, after curing by thermal polymerization or UV polymerization, the in-situ material is heated to 600°C at a temperature increase rate of 10°C per minute, and less than 4.0% is observed at both 200°C and 300°C, which is more Preferably less than 2.0%, such as less than 1.0% mass loss (usually less than 0.5% mass loss is observed at 200°C, or as in the example in Figure 3, less than 0.2% mass loss is observed at 200°C). At 300°C, a mass loss of less than 1%, or more specifically less than 0.6%, was observed in the example in Figure 3. Similar results can be observed by only heating the polymeric material at 200°C or 300°C for 1 hour. By heating the polymeric deposition material at 375°C or higher for at least 1 hour, a result of less than 1% mass loss is possible. As can be seen in Figure 3, a mass loss of 5% or less is observed even at temperatures higher than 500°C. Such thermally stable materials are required. In particular, they can be deposited at low temperatures (for example, less than 175°C, preferably less than 150°C, or less than 130°C, 30 minutes curing/baking time), or can be The thermally stable materials as disclosed herein are polymerized by UV light.

The foregoing describes example embodiments and is not to be construed as limiting. Although several example embodiments have been described, those skilled in the art will readily understand that many modifications are possible in the example embodiments without substantially departing from the novel teachings and advantages. Therefore, all such modifications are intended to be included in the scope of the present invention as defined in the scope of the patent application. Therefore, it should be understood that the foregoing description of various example embodiments should not be construed as being limited to the specific embodiments disclosed, and modifications to the disclosed embodiments and other embodiments are intended to be included in the scope of the appended patent application. Industrial applicability

The silicone composition as disclosed herein has a variety of uses. It can be used as a die attaching agent in semiconductor devices, such as for attaching microelectronic devices or optoelectronic devices formed on, for example, silicon substrates to a carrier or packaging substrate. The material can be used for flip chip packaging to connect bonding pads on one substrate to another, as an underfill material or as a protective layer or sealant. Depending on the selected particles, the material can be thermally insulating, and/or can be conductive or electrically insulating. If used in the optical path of a device, such as a display, LED lamp, or photovoltaic cell, the material can be optically transmissive in the visible spectrum. Reference list Patent literature US 201410030 CN 103059573 WO 2006112591 WO 2007001039 WO 2008046142 US 2010178478 US 2005244658 Non-patent literature Jin, J (JIN, J), et al. Examples of silicon dioxide nanoparticles used for transparent OLED sealing are embedded sol-gel organic/inorganic hybrid nanocomposites (Silica nanoparticle-embedded sol-gel organic/inorganic hybrid nanocomposite for transparent OLED encapsulation). Organic Electronic, 2012, Volume 13, Pages 53-57.

16, 18, 20, 22, 24: steps

The example embodiments will be understood more clearly from the following implementations obtained in conjunction with the accompanying drawings, in the accompanying drawings: Figure 1 illustrates an exemplary method of manufacturing a silicone polymer composition. Figure 2 illustrates the mass change of the silicone polymer during the thermally induced polymerization. Figure 3 illustrates the thermal stability of the silicone material after deposition and polymerization.

16, 18, 20, 22, 24: steps

Claims (15)

A method of manufacturing a composition, comprising: providing a ^{first compound having the chemical formula SiR 1} _a R ² _4-a as a first monomer, wherein a is 1 to 3, R ¹ is a reactive group, and R ² is Alkyl or aryl, or oligomers with a molecular weight of less than 1000 g/mol; Provide a ^{second compound with the chemical formula SiR 3} _b R ⁴ _c R ⁵ _4-(b+c) , wherein R ³ is a cross-linking function Group, R ⁴ is a reactive group, R ⁵ is an alkyl group or an aryl group, and wherein b=1 to 2, and c=1 to (4-b), or an oligomer with a molecular weight of less than 1000 g/mol物; The first compound and the second compound are mixed with particles with an average particle size of less than 1 micron, wherein the particles include a mixture of the first group and the second group of silver nanoparticles, all of the silver nanoparticles The first group has a smaller particle size than the second group, wherein the first group of silver nanoparticles is melted or sintered at a first temperature, and the first temperature is lower than that of the first compound and the second group. The second temperature at which the second compound undergoes substantial polymerization of the silicone polymer, so as to form all the larger-sized silver nanoparticles in the silicone polymer before the polymerization of the silicone polymer. The silver post structure of the second group, and the first compound and the second compound are polymerized together to form the silicone polymer having a silver lattice structure formed therein. The method for producing a composition as described in the first item of the patent application, wherein the reactive group in the first compound is a hydroxyl group, a halogen, an alkoxy group, a carboxyl group, an amine, or an acyloxy group, and the second compound The reactive group in it is a hydroxyl group, a halogen, an alkoxy group, a carboxyl group, an amine or an acyloxy group. The method for producing a composition as described in item 2 of the scope of the patent application, wherein the reactive group in the second compound has O and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Group, tert-butyl alkoxy group. The method for producing a composition as described in the first item of the scope of patent application, wherein R ² in the first compound is a polycyclic group, and the polycyclic group is selected from adamantyl and dimethyladamantyl Propyl, norbornyl, or norbornene, and the polycyclic group is directly attached to silicon or separated from the silicon by an alkyl, alkenyl, alkynyl, or aryl group containing 1 to 12 carbons. The method of manufacturing a composition as described in the first item of the scope of patent application, wherein in the first compound, a=2, and in the second compound, b=1. The method for producing a composition as described in the first item of the scope of the patent application, wherein R ² in the first compound is a C1-C6 alkyl group. The method for manufacturing a composition as described in the first item of the patent application, wherein a third compound is provided for polymerization together with the first compound and the second compound, and the third compound is of the chemical formula SiR ⁹ _f R ¹⁰ _g The third monomer, where f=1 to 4, R ¹⁰ is an alkyl group or an aryl group and g=4-f, or is an oligomer which has been polymerized and has a molecular weight of less than 1000 g/mol The third monomer, and wherein R ⁹ is methoxy or ethoxy. The method for producing a composition as described in the first item of the scope of patent application, wherein the first compound is a silane diol selected from the group consisting of diphenyl silane diol, dimethyl silane diol, and diisopropyl silane Glycol, di-n-propyl silane diol, di-n-butyl silane diol, di-tertiary butyl silane diol, diisobutyl silane diol and phenyl methyl silane diol. The method for producing a composition as described in the first item of the patent application, wherein the polymerization of the first compound and the second compound is substantially performed without adding an organic solvent. The method for producing a composition as described in the first item of the patent application, wherein at least one of the reactive groups of the first compound or the second compound is -OH. The method for manufacturing a composition as described in item 1 of the scope of the patent application, wherein the composition does not have a substantial -OH group. The method for producing a composition as described in the first item of the scope of the patent application, wherein the amount of -OH groups in the first compound is less than the amount of reactive groups in other compounds polymerized with the first compound. A method of manufacturing a composition includes: providing a first compound as a first monomer having the following chemical formula: SiR ¹ _a R ² _{4 -a} or R ² _3-a R ¹ _a SiR ¹¹ SiR ¹ _a R ² _{3- a} where a is 1 to 3, R ¹ is a reactive group, R ² is an alkyl group or an aryl group, R ^{11 is} independently an alkyl group or an aryl group, or an oligomer with a molecular weight of less than 2000 g/mol ; Provide a second compound with the following chemical formula: SiR ³ _b R ⁴ _c R ⁵ _4-(b+c) or R ⁵ _3-(b+c) R ⁴ _c R ³ _b SiR ¹² SiR ³ _b R ⁴ _c R ⁵ _3-(b+c) wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, and R ⁵ is an alkyl group or an aryl group, R ^{12 is} independently an alkyl group or an aryl group, and wherein b= 1 to 2, and c=1 to 2, or an oligomer with a molecular weight of less than 2000 g/mol; polymerizing the first compound and the second compound together to form a silicone polymer; and The silicone polymer is mixed with metal, semi-metal or ceramic particles with an average particle size of less than 100 microns. The method for producing a composition as described in the first item of the patent application, wherein in the second compound, R ⁵ is an alkyl group or an aryl group, and wherein b=1 to 2 and c=1 to 2. The method for manufacturing a composition as described in the scope of patent application, wherein the particles include a first group of particles and a second group of particles, and the melting point of the second group of particles is lower than the melting point of the first group of particles.

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