TWI694112B - Composition having siloxane polymer and process for producing siloxane particulate composition - Google Patents

Abstract

A composition having siloxane polymer and a process for producing siloxane particulate composition are provided. The composition has a siloxane material and a filler material that comprises particles preferably with a particle size of less than 100 microns. The siloxane material can have a [-Si-O-Si-O]n repeating backbone, with preferably alkyl or aryl groups thereon, and b) as well as functional cross-linking groups thereon. The composition also has a filler material that includes particles that can be metal, semi- metal or ceramic particles. The composition may also include coupling agents, a catalyst, antioxidants, etc. The composition can be used in a wide variety of areas, such as an adhesive, encapsulant, solder or other layer in a semiconductor package or the like.

Description

Composition with siloxane polymer and production of siloxane particles Composition method

The present invention relates to a composition of silicone material and filler material.

US 2009258216 discloses a method of producing a siloxane composition which is mixed with particles having an average particle size in the range of 0.26 microns to 4 microns.

The prior art is also disclosed in Jean, J (Jin, J), et al., Organic Electronic, 2012, Volume 13, pages 53-57 and WO 2008046142.

Known compositions, when used as single-component adhesives, need to be transported and stored at low temperatures to avoid premature crosslinking. It will be necessary to have a composition that can be transported and stored at room temperature without substantial polymerization or other undesirable reactions.

The object of the present invention is to solve at least a part of the problems in the art.

The object of the present invention is to provide a novel material for manufacturing silicone polymer materials Manufacturing method.

The composition has a siloxane polymer having a repeating main chain of [-Si-O-Si-O]n, the repeating main chain has an alkyl group or an aryl group, and the repeating main chain has a functional crosslink Group. Part of the composition is particles with an average particle size of less than 100 microns, and the particles are metal, semi-metal, or ceramic particles or other suitable particles. The molecular weight of the silicone polymer is 400 g/mol to 200,000 g/mol, specifically 300 g/mol to 10,000 g/mol. The viscosity of the composition with the combined siloxane polymer and particles is 500 mPa-s to 500,000 mPa-s at 5 rpm, specifically 1000 mPa-s to 75,000 mPa-s, such as (eg ) Measured on a viscometer at 5 rpm at 25°C.

In one embodiment, the product is obtained by a method including the steps of: polymerizing silanol and alkoxysilane in the presence of an alkali catalyst to form a viscous and transparent silicone material; providing particles with an average particle size of less than 100 microns ; Mix the coupling agent and the siloxane polymer in the solvent; remove the solvent by drying; and place the composition of the siloxane polymer, particles, and coupling agent in the container.

The present invention provides a silicone composition having a siloxane polymers, including silicon by a method for manufacturing the alumoxane: providing a ^'first compound of a first monomer of _4-a, as a chemical formula SiR ¹ _a R ^2, where a From 1 to 3, R ¹ is a reactive group, and R ^2′ is an alkyl or aryl group, or an oligomer with a molecular weight of less than 1000 g/mol; provides the chemical formula SiR ³ _b R ⁴ _c R ⁵ ₄ -a second compound of _(b+c) , wherein R ³ is a cross-linking 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 an oligomer with a molecular weight of less than 1000 g/mol; and polymerizing the first compound and the second compound together to form a siloxane polymer; and the composition further includes an average particle size of less than 100 Micron particles; wherein the molecular weight of the silicone polymer is 300 g/mol to 10,000 g/mol; the viscosity of the composition at a 5 rpm viscometer is 1000 mPa-s to 75000 mPa-s; and The silicone polymer is substantially free of -OH groups.

The composition of the present invention can be used in various fields, such as adhesives, sealants, solder layers or other layers in semiconductor packages or the like.

The composition of the present invention can be transported and stored as a one-component adhesive at room temperature without substantial polymerization or other undesirable reactions.

100, 102, 104, 106, 108: steps

The following embodiments obtained from the accompanying drawings will understand the example embodiments more clearly. In the accompanying drawings: FIG. 1 is an illustration of an example of manufacturing a silicone polymer and a particle composition.

Figure 2 illustrates the change in mass of the silicone polymer during thermally induced polymerization.

Figure 3 illustrates the thermal stability of the silicone material after deposition and polymerization.

The accompanying drawings illustrating some example embodiments will be referred to hereinafter 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. Rather, these example embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art. In the diagram, for clarity For the sake of clarity, the size and relative size of layers and regions may be exaggerated.

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 to 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 present. Similar symbols throughout the text refer to similar elements. 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, such 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 teachings of the inventive concept, the first element, component, region, layer, or section discussed below may be referred to as the second element, component, region, layer, or section.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, unless the context clearly indicates otherwise, the singular forms "a" and "said" are intended to include the plural forms as well. It should be further understood that the term "comprising" or "including" when used in this specification specifies the presence of stated features, regions, integers, steps, operations, elements and/or components, but does not exclude one or more other features, The presence or addition of regions, integers, steps, operations, elements, components, and/or groups thereof.

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 figure. It will be understood that the relative terms are intended to cover different orientations of the device than those depicted in the drawings. For example, if the device in one drawing is turned over, the element described as being located on the "lower" side of the other element will then be oriented on the "upper" side of the other element. Therefore, the exemplary term "lower portion" may therefore cover the orientation of "lower portion" and "upper portion" depending on the particular orientation of the drawing. Similarly, if the device in one of the figures is turned over, elements described as "below" or "beneath" other elements will be oriented "above" the other elements. Therefore, the exemplary terms "below" or "below" can encompass both upper and lower orientations.

It should be noted that unless the context clearly dictates otherwise, as used herein, the singular forms "a" and "said" include plural indicators. It should also be understood that the term "comprising", when used in this specification, specifies the presence 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, all terms (including technical and scientific terms) used herein have the same meaning as 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 a meaning consistent with their meaning in the context of the relevant technology and the present invention, and unless expressly defined as such herein, will not be ideal Explain in a formal or over-formal sense.

The lower case letters used in the formulas of the following monomers and polymers especially represent integers.

Compositions with silicone polymers and granular materials are provided as viscous materials, optionally with catalysts and coupling agents (used to assist the subsequent thermal or UV polymerization of the composition), as well as stabilizers, antioxidants, and dispersants , Surfactant, etc. composition The material has a suitable viscosity and is easy to coat and eventually polymerize, without requiring a solvent. The silicone-granular composition can be used as a die attach agent, preferably a die attach agent with thermal conductivity characteristics, or as a sealant or other layer in a semiconductor package, such as a thermally conductive but electrically Insulating optical transmission layer. Of course, depending on the selected silicone and particles, various characteristics (density, CTE, thermal conductivity, electrical conductivity, optical transmittance, etc.) are possible.

Referring to FIG. 1, a composition is manufactured in which a silicone polymer is provided at step 100. Preferably, the polymer has a silica main chain, which has an aryl (or alkyl) substituent and a functional crosslinking substituent. At step 102 in FIG. 1, the filler material is mixed with the silicone polymer. The filler material is preferably a granular material including particles having an average particle size of 100 microns or less, preferably 10 microns or less. At step 104, a catalyst is added, and when heat or UV light (or other activation method) is provided to the composition, the catalyst reacts with the functional crosslinking group in the silicone polymer. At step 106, the monomer (or oligomer) coupling agent preferably has a functional crosslinking group that is also reactive when heat or light is applied to the siloxane polymer. Finally, at step 108, depending on the end use of the composition, additional materials such as stabilizers, antioxidants, dispersants, subsequent accelerators, plasticizers, softeners, and other possible components are added. Although a solvent can be added, in a preferred embodiment, the composition is solvent-free and is a viscous fluid stored in a light-tight container for subsequent use or transportation.

As noted above, the composition made as disclosed herein includes a silicone polymer. In order to manufacture the siloxane polymer, _a first compound having the chemical formula SiR ¹ _a R ^2′ _4-a is provided, wherein a is 1 to 3, R ¹ is a reactive group, and R ^2′ is an alkyl or aryl group . A second compound with the chemical formula SiR ³ _b R ⁴ _c R ⁵ _4-(b+c) is also provided, where R ³ is a cross-linking functional group, R ⁴ 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). Together with the first compound and the second compound, a third compound is optionally selected to polymerize with it. The third compound may have the 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 or aryl group and g=4-f. The first compound, the second compound, and the third compound may be provided in any order, and the oligomeric partial polymerization pattern of any of these compounds may be provided instead of the monomers mentioned above.

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

Catalysts are also 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 the compound and the catalyst may be any desired order. The various components provided together are polymerized to produce a siloxane polymer material having the desired molecular weight and viscosity. After polymerization, particles, such as microparticles, nanoparticles, or other desired particles, are added, along with other optional components such as coupling agents, catalysts, stabilizers followed by accelerators, and the like. The components of the composition can be combined in any desired order.

More specific words, 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

Where a is 1 to 3, R ¹ is a reactive group, and R ^2'is an alkyl or aryl group, and the second compound has the following chemical formula: SiR ³ _b R ⁴ _c R ⁵ _4-(b+c)

Where R ³ is a cross-linking 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).

The first compound may have 1 to 3 alkyl or aryl groups (R ^2' ) incorporated into the silicon in the compound. Combinations of different alkyl groups, different aryl groups, or 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 particularly preferably 1 to 12 carbon atoms. Shorter alkyl groups are envisioned, such as 1 to 6 carbons (eg, 2 to 6 carbon atoms). The alkyl group may branch with one or more, preferably two C1 to C6 alkyl groups at the α position or β position. In particular, 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 tertiary butyl are especially 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 groups on the ring, or naphthyl, which may optionally be in the ring structure It carries 1 to 11 substituents selected from halogen alkyl or alkenyl, which 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, naphthacene, which may carry 1-8 substituents as appropriate or may contain 1 to 12 as appropriate Carbon alkyl, alkenyl, alkynyl or aryl groups are "spaced" from the silicon atom. Single-ring structures such as phenyl can also be spaced from silicon atoms in this way.

Siloxane polymers are prepared by performing a polymerization reaction (preferably an alkali-catalyzed polymerization reaction) between the first compound and the second compound. The optional additional compounds as described below may be included as part of the polymerization reaction.

The first compound may have any suitable reactive group R ¹ , such as hydroxy, halogen, alkoxy, carboxy, amine or acetyloxy. If, for example, the reactive group in the first compound is an -OH group, a more specific example of the first compound may include silane diol, especially such as diphenyl silane diol, dimethyl silane diol , Diisopropylsilanediol, di-n-propylsilanediol, di-n-butylsilanediol, di-third butylsilanediol, diisobutylsilanediol, phenylmethylsilanediol And dicyclohexylsilanediol.

The second compound may have any suitable reactive group R ⁴ , such as hydroxy, halogen, alkoxy, carboxy, amine or acetyl, 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 either the first compound or the second compound (or any compound that participates in the polymerization reaction to form a siloxane polymer-such as a third compound, etc.), so that the resulting siloxane The alkane polymer does not have any or substantially any H groups directly bonded to the Si in the silicone polymer. If the group R ^{5 is} completely present in the second compound, it is independently an alkyl or aryl group, such as for the group R ^2′ in the first compound. The alkyl or aryl group R ⁵ may be the same as or different from the group R ^2′ in the first compound.

The crosslinking reactive group R ^{3 of the} second compound may be any functional group that can be crosslinked by an acid, base, free radical, or thermally catalyzed reaction. Such functional groups may for example be any epoxide, 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 epoxide-containing crosslinking groups are glycidoxypropyl and (3,4-epoxycyclohexyl)ethyl (to name a few).

In the case of a propylene oxide group, 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 propylene oxide-containing silanes 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 trimethoxy silane (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 the double bond) group is preferably located at 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 reference bond) is preferably located at position 2 or higher relative to the Si atom or M atom in the molecule. The branched alkynyl group is preferably in the α position or β position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl groups, optionally perfluorinated alkyl groups, alkenyl groups Or alkynyl branch.

In the case of a mercapto group, it can be any organic sulfur 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 may be linear or branched. Preferably, the alkoxy group is composed of a low-carbon alkoxy group having 1 to 6 carbon atoms (such as methoxy, ethoxy, propoxy, and third butoxy). A specific example of the second compound is silane, especially such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane , 3-(trimethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl acrylate, (3-glycidoxypropyl)trimethoxysilane or 3-glycidoxy Propylpropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane.

The third compound may be provided together with the first compound and the second compound to polymerize therewith. The third compound may have the following 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.

One such example is tetramethoxysilane. Other examples include, inter alia, phenylmethyldimethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, methyltrimethyl Oxysilicon Alkane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane.

Although the polymerization of the first compound and the second compound can be performed using an acid catalyst, an alkali catalyst is preferred. The base catalyst used for 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 amines, such as triethylamine, and any barium hydroxides, 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 at less than 0.5% by weight relative to the first compound and the second compound together, or at a lower amount, such as less than 0.1% by weight.

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 at 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 groups) in the second compound, and is preferably less than that in the second compound ( Or second The total number of reactive groups of the compound plus any other compounds added together with the alkoxy group, such as added tetramethoxysilane or other third compounds involved in the polymerization reaction (as mentioned herein). In the case where the number of alkoxy groups exceeds the hydroxyl groups, 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 alkoxy group The base silane is ethoxy silane). 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, the reactivity in the second compound is preferred The total number of groups exceeds the number of -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 first compound-OH group by 40% or more, or even 60% or more, 75% or more, or up to 100% or more . After the polymerization, methanol, ethanol or other by-products of the polymerization reaction (depending on the selected compound) are removed, preferably evaporated in the drying chamber.

The obtained siloxane polymer has any desired (weight average) molecular weight, such as 500 g/mol to 100,000 g/mol. The molecular weight may be at the lower end of this range (e.g., 500 g/mole to 10,000 g/mole or more preferably 500 g/mole to 8,000 g/mole) or the molecular weight of the organosiloxane material may be at the upper end of this range ( (Such as 10,000 g/mole to 100,000 g/mole or more preferably 15,000 g/mole to 50,000 g/mole). It may be necessary to mix polymer organosiloxane materials with lower molecular weight with organosiloxane materials with higher molecular weight.

The composition of the polymer obtained 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 adhesion, silanes with good adhesion properties are used during polymer manufacturing. Have polar groups (such as hydroxyl, epoxy, carboxyl, anhydride or Amino groups) are examples of silanes with good adhesion properties on various substrates.

Depending on the ultimate desired use of the polymer, the obtained siloxane polymer 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, adhesion promoters, and/or other desired components, depending on the silicone material The final required use. In one example, a reducing agent that can reduce the oxidized surface to its metal 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, for example, metal bonding pads or other metals or conductive regions that have been oxidized, to improve the siloxane particle material and The electrical connection between the deposited or subsequent 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, ethanediol Aldehyde, acetaldehyde, glutaraldehyde, aliphatic dialdehyde family, paraformaldehyde, tin powder, zinc powder, formic acid. Additives such as stabilizers, such as antioxidants, such as Irganox (as mentioned below) or diazine derivatives can also be added.

Cross-linked silicone or non-silicone 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 the siloxane polymer, epoxy-functional oligomers or resins can be used. The epoxy oligomer or resin may be any difunctional, trifunctional, tetrafunctional or higher functional epoxy Oligomer or resin. Examples of such epoxy oligomers or resins can be 1,3-bis 2-(3,4-epoxycyclohexyl) ethyl 1,1,3,3-tetramethyl disilaxane, 1, 3-bisglycidoxypropyl 1,1,3,3-tetramethyldisilaxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy 3,4-epoxycyclohexyl methyl cyclohexanecarboxylate, 1,4-cyclohexane dimethanol diglycidyl ether, bisphenol A diglycidyl ether, 1,2-cyclohexane dicarboxylic acid diglycidyl ether Ester (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 (e.g., thermal acid in the case where the polymerization reaction is thermally activated or photoinitiator in the case of UV activation). The crosslinking group in the above-mentioned silicone polymer is preferably an epoxide, propylene oxide, acrylate, alkenyl or alkynyl group. The curing agent is selected based on the crosslinking group in the silicone polymer.

In one embodiment, the curing agent for epoxy groups and glycidyl groups can be selected from nitrogen-containing curing agents that exhibit blocked or reduced activity, such as primary amines and/or secondary amines. The definition "a primary or secondary amine showing blocked or reduced reactivity" shall mean that it cannot react with the resin component due to chemical or physical blockage or only has a very low ability to react with the resin component, but may Regenerate the reactivity after releasing the amine, for example by melting it at an increased temperature, by removing the sheath or coating, by pressure or ultrasound or other energy types to start the curing of the resin component Reaction of other amines.

Examples of heat-activatable curing agents include at least one organoborane or a complex of borane and at least one amine. The amine may be a compound organoborane and/or borane and may be decomplexed as necessary to release organoborane or any type of borane. The amine may include various structures, for example, any primary or secondary amine or a polyamine containing primary and/or secondary amines. The organoborane can be selected from alkylborane. An example of a particularly preferred borane for such heat 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 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 epoxides and/or propylene oxide containing polymers, curing agents, co-curing agents, catalysts, initiators, or other additives designed to participate in or promote the curing of adhesive formulations, such as Anhydride, amine, imidazole, thiol, carboxylic acid, phenol, dicyandiamide, urea, hydrazine, hydrazine, amino-formaldehyde resin, melamine-formaldehyde resin, quaternary ammonium salt, quaternary phosphonium salt, triarylsulfide Onium salts, diaryliodonium salts, diazonium salts and the like.

For acrylates, alkenyl and alkynyl crosslinking group curing agents can be thermally or UV activated. Examples of thermal activation are peroxides and azo compounds. Peroxides are compounds containing unstable oxygen-oxygen single bonds that 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 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-di( (Third butylperoxy)-2,5-dimethyl-3-hexyne, dicumyl peroxide, benzoyl peroxide, di-third pentyl peroxide, peroxybenzoic acid Third butyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-carboxamidopropane) dihydrochloride, diphenyl di Azene, diethyl azodicarboxylate, and 1,1'-azobis (cyclohexanecarbonitrile) (to name a few).

A 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, Yanjiagu 184, Yanjiagu 369, Yanjiagu 500, Yanjiagu 651, Yanjiagu 784, Yanjia made by BASF Jiagu 819, Yanjiagu 907, Yanjiagu 1700, Yanjiagu 1800, Yanjiagu 1850, Yanjiagu 2959, Yanjiagu 1173, Yanjiagu 4265.

One method of incorporating a 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 such kinds 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-aminopropyltrimethoxy Silane and 3-aminopropyltriethoxysilane (to name a few).

The accelerator may then be part of the composition and may 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 the adhesion promoter used in the die attach product may be octyltriethoxysilane, mercaptopropyltriethoxysilane, cyanopropyltrimethoxysilane, 2-(3,4-cyclo Oxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(trimethoxysilyl)propyl methacrylate, 3-(trimethyl Oxysilyl) propyl acrylate, (3-glycidyloxypropyl) trimethoxysilane or 3-glycidoxypropyl triethoxysilane, 3-methacryloxypropyl trimethyl Oxysilane and 3-propane Enyloxypropyltrimethoxysilane.

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

In order to obtain the [Si-O-Si-C] main chain, a chemical with the following formula: R ² _3-a R ¹ _a SiR ¹¹ SiR ¹ _b R ² _3-b

Where a is 1 to 3, b is 1 to 3, R ¹ is a reactive group as explained above, R ² is alkyl, alkenyl, alkynyl, alcohol, carboxylic acid, dicarboxylic acid, aryl, poly The aryl group, polycyclic alkyl group, heterocyclic aliphatic group, heterocyclic aromatic group and R ^{11 are} independently an alkyl group or an aryl group, or an oligomer with a molecular weight of less than 1000 g/mole, as described above The first compound, the second compound and the third compound or any combination thereof are polymerized together.

Examples of such compounds are 1,2-bis(dimethylhydroxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(dimethoxymethylsilane) Group) ethane, 1,2-bis(methoxydimethylsilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3-bis(dimethylhydroxysilane) Group) 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(trimethoxyl) Silyl)phenanthrene, bis(trimethoxysilyl) norbornene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis(methoxydimethylsilyl)benzene and 1,4-bis(triethoxysilyl)benzene (to name a few).

In one embodiment, in order to obtain the [Si-O-Si-C] main chain, the compound having the formula 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, polyaryl group, polycyclic alkyl group , Heterocyclic aliphatic group, heterocyclic aromatic group, R ^{11 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 whose molecular weight is less than 1000 g/mole, polymerized together with the first compound, second compound, third compound, or any combination of these as mentioned herein .

Examples of such 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)ethyldimethoxy Silane-based) ethane, 1,2-bis (propyl methacrylate dimethoxysilyl) ethane, 1,4-bis (vinyl dimethoxysilyl) benzene, 1,4-bis (Ethynyldimethoxysilyl)benzene, 1,4-bis(ethynyldimethoxysilyl)benzene, 1,4-bis(3-glycidoxypropyldimethoxysilyl) Benzene, 1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethoxysilyl]benzene, 1,4-bis(propylmethacrylate dimethoxysilyl)benzene (To name just a few).

In one embodiment, the 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)

Where R ¹ is a reactive group as explained above, R ^2′ is an alkyl or aryl group as explained above, R ³ is a cross-linked functional group as explained above, and a=0 to 3, b=0 to 3. Polymerize with the previously mentioned silane or add it 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 Yl-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 Oxane, 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 Alkanes, 1,1,5,5-tetramethoxy-3,3-dimethyltrisiloxane, 1,1,7,7-tetraethoxy-3,3,5,5-tetramethyl Tetrasiloxane, 1,1,5,5-tetraethoxy-3,3-dimethyltrisiloxane, 1,1,5,5-tetramethoxy-1,5-[2 -(3,4-epoxycyclohexyl)ethyl]-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy-1,5-(3-glycidoxy Propyl)-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-glycidoxypropyl)-3, 3-Diphenyltrisiloxane (to name a few).

Additive added to the composition (after the polymerization silicon alumoxane of material as noted above) may be of the formula of Silane ^{_{compound: R 1 a R 2 'b}} SiR 3 4- (a + b) w

Where R ¹ is a reactive group, such as hydroxy, alkoxy or acetoxy, R ^2′ is an alkyl or aryl group, and R ³ is a cross-linking compound, such as epoxy, propylene oxide, alkenyl, Acrylate or alkynyl, a=0 to 1 and b=0 to 1.

Examples of such additives are tri-(3-glycidoxypropyl) phenyl silane, tri-[2-(3,4-epoxycyclohexyl) ethyl] phenyl silane, tri-(3-methyl Acrylic Acryloyloxy)phenyl Silane, Tri-(3-Acryloyloxy)phenyl Silane, Tetra-(3-Glycidoxypropyl) Silane, Tetra-(2-(3,4-Epoxy (Cyclohexyl) ethyl) silane, tetra-(3-methacryloxy) silane, tetra-(3-propenyl oxy) silane, tri-(3-glycidoxypropyl) p-tolyl silane , Tri-[2-(3,4-epoxycyclohexyl)ethyl] p-tolyl silane, tri-(3-methacryl acetyloxy) p-tolyl silane, tri-(3-propenyl oxy) ) P-tolyl silane, tri-(3-glycidoxypropyl) hydroxy silane, tri-[2-(3,4-epoxycyclohexyl) ethyl] hydroxy silane Alkane, tri-(3-methacryloxy)hydroxysilane, tri-(3-propenyloxy)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 may also be inorganic polycondensates such as SiOx, TiOx, AlOx, TaOx, HfOx, ZrOx, SnOx, polysilazane.

The particulate filler may be a conductive material such as carbon black, graphite, graphene, gold, silver, copper, platinum, palladium, nickel, aluminum, silver-plated copper, silver-plated aluminum, bismuth, tin, bismuth-tin alloy, plated Silver fiber, nickel-plated copper, silver-plated and nickel-plated copper, gold-plated copper, gold-plated and nickel-plated copper, or it may be a polymer of gold-plated, silver-gold, silver, nickel, tin, platinum, titanium, such as polyacrylate , Polystyrene or silicone, but not limited to this. The filler may 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 may 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. The metal particles envisioned as transition metal particles (whether before or after transition metals) are like semi-metals and metalloids. It is envisioned that semi-metallic or metalloid particles, such as arsenic, antimony, tellurium, germanium, silicon and bismuth.

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 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. Fillers can include nitrides, oxynitrides, carbides and carbons that are metals or semi-metals Oxide ceramic compound particles. Specifically, the filler may be particles, and the particles are silicon, zinc, aluminum, yttrium, ytterbium, tungsten, titanium silicon, titanium, antimony, samarium, nickel, nickel cobalt, molybdenum, magnesium, manganese, lanthanide, Ceramic particles of oxides of iron, indium tin, copper, cobalt aluminum, chromium, cesium or calcium.

It is also possible that the particles include carbon and are selected from carbon black, graphite, graphene, diamond, silicon carbonitride, titanium carbonitride, carbon nanobuds, and carbon nanotubes. The particles of the filler may 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, particles of any suitable size 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, 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 less than 10 nanometers are also envisioned. In other examples, particles having an average particle size of 5 nm to 50 nm, or 15 nm to 75 nm, less than 100 nm, or 50 nm to 500 nm are provided. Not elongated, such as particles that are generally spherical or square, or flakes with a flat disc-shaped appearance (with smooth or rough edges) are possible, like elongated whiskers, cylinders, wires, and other elongated particles, such as having 5: Particles with an aspect ratio of 1 or larger, or 10:1 or larger. Very elongated particles with extremely high aspect ratio, 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 smallest 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 50 volumes % Of the particles have a diameter smaller than the D50 value at the cumulative volume distribution curve of the value.

The particles may be a mixture of particles as mentioned elsewhere herein, wherein the first group of particles having an average particle size greater than 200 nanometers and the second group of particles having an average particle size less than 200 nanometers are provided together, for example where the average 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 (eg, the average particle size of the first group is greater than 1 micrometer 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 are melted or sintered at a temperature smaller than the particles or mass of the same material with an enlarged micron size. In one example, the smaller particles have an average particle size of less than 1 micrometer and are melted or sintered at a temperature less than the overall temperature of the same material. Depending on the selected particulate 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 may be equal to or lower than the polymer curing temperature to form a melting or sintering linking the larger particles together before the silicone polymer material is completely crosslinked and solidified The web of particles. In one example, the smaller particles are melted or sintered with the larger particles at a temperature below 130°C, for example below 120°C, or even sintered below 110°C, while the siloxane material is at a higher temperature Undergoes substantial cross-linking, such as substantially sintering or melting below 110°C, but substantially polymerizing above 110°C (or, for example, substantially sintering or melting below 120°C (or 130°C), but (Substantially polymerized above 120°C (or 130°C)). The sintering or melting of the smaller particles before the substantial polymerization of the silicone material allows the formed metal "mesh" to have greater interconnectivity, which increases the final conductivity of the cured layer. The substantial polymerization of the smaller particles before substantial sintering or melting reduces the amount of metal "grid" formed and reduces the conductivity of the final cured layer. when However, it is also possible to provide only particles with a smaller average particle size (e.g. sub-micron size) which can still achieve the benefit of a lower sintering point and melting point compared to the same bulk (or the same particles with an average particle size greater than 1 micron) .

In order to enhance 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, hydroxy, alkoxy, acetyl or ethoxy, R ¹⁴ is an alkyl or aryl group, and R ¹⁵ is comprised of, for example, epoxy, anhydride, cyano , Propylene oxide, amine, mercapto, allyl, alkenyl or alkynyl functional 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, the silicone polymer, the curing agent, and the 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 alcohol solutions, deposition from aqueous solutions, bulk deposition onto fillers, and anhydrous liquid phase deposition. In deposition from an alcohol solution, an alcohol/water solution is prepared and the pH of the solution is adjusted to be slightly acidic (pH 4.5-5.5). Silane was added to this solution and mixed for a few minutes to allow partial hydrolysis. Next, filler particles are added and the solution is mixed from room temperature to reflux temperature for different periods of time. After mixing, the particles are filtered, rinsed with ethanol and Dry in an oven to obtain surface-treated particles with a 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.

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

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

Examples of such silane coupling agents are bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, allyltrimethoxysilane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropylmethyl diethoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, (N-trimethoxysilylpropyl) polyethyleneimine, trimethoxysilylpropyl diethylidene tris Amine, phenyltriethoxysilane, phenyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 1-trimethoxysilyl-2 (p, m-chloromethyl) styrene, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, propyl isocyanate triethoxysilane, 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-(triethoxysilyl Propyl)urea, 1,3-divinyltetramethyldisilazane, vinyltriethoxysilane and vinyltrimethoxysilane (to name a few).

Depending on the type of particles added, the final product of the silicone-particle curing may be a thermally conductive layer or film, such as after final thermal curing or UV curing with greater than 0.5 W/m. The thermal conductivity of kelvin (W/(m.K)). Depending on the type of particles 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. Creven's cured 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, particles can be selected to produce materials with low thermal conductivity when 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 ^-5 Ω. m, and better 1×10 ^-7 Ω. m. In addition, the sheet resistance of the deposited film is preferably less than 100,000, and more preferably less than 10,000. However, the various 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 features, although in some cases it may be required that the final cured silicone has optical absorption properties, it is more likely that the material will desirably be highly transmissive within the visible spectrum (Or within the spectrum of the operating device), or will desirably highly reflect light within the visible spectrum (or within the spectrum of the operating device). As an example of a transparent material, the final cured layer with a thickness of 1 micrometer to 50 micrometers will transmit at least 85% of normal light incident on it, or preferably at least 90%, more preferably at least 92.5%, and most preferably at least 95%.

As an example of a reflective layer, the final cured layer can reflect at least 85% of light incident on it, preferably at least 95% of 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 reactions with oxygen induced by substances such as heat, light, or residual catalyst from raw materials.

Stabilizers or antioxidants suitable for use herein are high molecular weight hindered phenols and polyfunctional phenols, such as sulfur and phosphorus containing phenols. 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. In particular, the third butyl group is generally substituted on the benzene ring in at least one ortho position relative to the phenolic hydroxyl group. The presence of these three-dimensional large-scale substituted free radicals near the hydroxyl group serves to delay its stretching frequency and accordingly its reactivity; this steric hindrance thus provides phenolic compounds with their stable properties. Representative hindered phenols include: 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene; tetra-3( 3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid isopentitol ester; 3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid n-decyl Octane; 4,4'-methylenebis(2,6-tert-butyl-phenol); 4,4'-thiobis(6-tert-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 4-hydroxy-benzoic acid di-n-octylthio) ethyl ester; and sorbitol hexa[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate]. Commercial examples of antioxidants are, for example, Yanjia Nox 1035, Yanjia Nox 1010, Yanjia Nox 1076, Yana Nox 1098, Yana Nox 3114, Yana Nox PS800, Yana Nox made by BASF. PS802, Yanjia Nuoxi 168.

Depending on the end use of the product, the weight ratio between the silicone polymer and the filler is between 100:0 and 5:95. The ratio between the silicone polymer and the cross-linked silicone or non-silicone 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%. Promotion based on the total amount of formulation The amount of agent is 0 to 10%. The amount of antioxidant based on the total weight of the formulation is 0 to 5%.

The silicone-particle composition can be used in many fields. It can be used as electronics or optoelectronics packaging, LED and OLED front-end and back-end processing, 3D, photovoltaic and display metallization, solder replacement for solder bumps in semiconductor packages, printed electronic devices, OLED low work function cathodes, for example Inks, ITO replacement inks, metal grids and other electrodes, high-resolution photovoltaic pastes, LMO cathode pastes, photovoltaic pastes, power electronics and EMI, touch sensors and other displays, thermal or UV curable sealants or Adhesives or sealants in dielectrics (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 hot acid generator is used, the material is placed in an oven for a certain period of time. It is also possible to cure by electromagnetic radiation, such as UV light.

The molecular weight of the siloxane 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 g/mole to 2000 g/mole. The combination of the polymer and particles of any desired size has an average particle size of 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% by weight. If conductivity is required, such as the use of silicone materials in semiconductor packaging, the particles can be metal particles added at 60% to 95% by weight.

The first compound and the second compound are polymerized, and the particles are mixed with it To form a viscous fluid having a viscosity of 50 mPa-s to 100,000 mPa-s, preferably 1000 mPa-s to 75,000 mPa-s and more preferably 5000 mPa-s to 50,000 mPa-s. Viscosity can be measured with a viscometer, such as a Brookfield viscometer or Cole-Parmer viscometer, which rotates a disc or cylinder in a fluid sample and measures to overcome The torque required to induce the viscous resistance of movement. It can be rotated at any desired speed, such as 1 rpm to 30 rpm, preferably 5 rpm, and preferably with the material measured at 25°C.

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

The composition as disclosed herein is preferably free of any substantial solvent. Solvents may be added temporarily, such as for mixing curing agents or other additives with polymeric viscous materials. In this case, for example, a curing agent is mixed with a solvent to form a fluid material that can be subsequently mixed with a viscous siloxane polymer. However, due to the need to deliver the substantially solvent-free composition to the customer and subsequent application to the customer's device, the temporarily added solvent is removed in the drying chamber. However, although the composition is substantially free of solvents, there may be traces of residual solvent that cannot be removed during the drying process. Removal of this solvent by reducing shrinkage during the final curing process facilitates the deposition of the compositions disclosed herein, minimizes shrinkage over time during the lifetime of the device, and helps during the lifetime of the device Due to 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 Degree, etc.), so that when incorporated into a composition with particles and other components, the desired final characteristics in terms of subsequent delivery to the customer are achieved. Due to the stability of the composition, it is possible to ship the composition at ambient temperature without any substantial change in molecular weight or viscosity, even within a week or even a month after manufacturing until the customer's final use.

Examples

The following silicone polymer examples are given by way of illustration and are not intended to be limiting.

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

Siloxane polymer i: with diphenylsilanediol (60 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (55.67 g, 36.7 mol %) and tetramethoxysilane (17.20 g, 18.3 mol%) were filled in a 500 ml round bottom flask with a stir bar and 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 diphenylsilanediol and 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.

Siloxane polymer ii: with diphenylsilanediol (30 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (28.1 g, 37 mol) %) and dimethyldimethoxysilane (6.67 g, 18 mol%) filled a 250 ml round bottom flask with a stir bar and 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 reaction of diphenylsilanediol and alkoxysilane During this period, the silane mixture was stirred at 80°C for 30 minutes. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 2750 mPas and the Mw is 896.

Siloxane polymer iii: with diphenylsilanediol (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%) filled a 250 ml round bottom flask with a 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 diphenylsilanediol and 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.

Siloxane polymer iv: with diphenylsilanediol (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 %) filled a 250 ml round bottom flask with a stir bar and 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 diphenylsilanediol and 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.

Siloxane polymer v: with diphenylsilanediol (15 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (13.29 g, 35 mol) %) and vinyl trimethoxysilane (4.57 g, 20 mol%) filled with stir 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 diphenylsilanediol and 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.

Siloxane polymer vi: with diisopropylsilanediol (20.05 g, 55.55 mole %), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (20.0 g, 33.33 mole Ear%) and bis(trimethoxysilyl)ethane (7.3 g, 11.11 mol%) filled a 250 ml round bottom flask with a stir bar and 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 diphenylsilanediol and 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: with diisobutylsilanediol (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 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 diphenylsilanediol and 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.

Composition example:

The following composition examples are given by way of illustration and are not intended to be limiting.

Comparative Example 1, silver-filled adhesive: using a high-shear mixer, a silver polymer (18.3 g, 18.3%), silver sheet (81 g, 81%) with an average size (D50) of 4 microns, 3- Methacrylate propyltrimethoxysilane (0.5 g, 0.5%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.2%) were mixed together.

Comparative Example 2: Alumina filled adhesive: Alumina (53 g, 53%) with a silicone polymer (44.55 g, 44.45%), average size (D50) of 0.9 μm, 3-roll grinder, 3- Methacrylate propyltrimethoxysilane (1 g, 1%), Yanjia Nuoxi Division 1173 (1 g, 1%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.45 g, 0.45 %)Mix together.

Comparative Example 3, BN filled adhesive: A three-roll mill was used to combine a boron nitride flake (35 g, 35%), a silicone polymer (60 g, 60%) with an average size (D50) of 15 microns, Ganox Division 1173 (1.3 g, 1.3%), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (3.4 g, 3.4%), and K-PURE CXC-1612 thermal acid generation from Kings Industries Agents (0.3 g, 0.3%) are mixed together.

Comparative Example 4, translucent material: using a three-roll grinder, aerosol silica (52.5 g, 5%), cyanosiloxane polymer (92.5 g, 92.5%), average size (D50) of 0.007 micron, bright Canox 1173 (2g, 2%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.5g, 0.5%) were mixed together.

Comparative Example 5, diamond filling: using a three-roll grinder, submicron diamond particles (18 g, 18%) with a silicone polymer (97.5 g, 97.5%), an average size (D50) of 0.500 μm, and Yanjia Nuo Kex 1173 (2 grams, 2%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.5 g, 0.5%) is mixed together.

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 crosslink Group, and another part is particles mixed with siloxane material, wherein the average particle size of the particles is less than 100 microns, the particles are any suitable particles, such as metal, semi-metal, semiconductor or ceramic particles. The composition delivered to the customer may have a molecular weight of 300 g/mol to 10,000 g/mol, and a viscosity of 1000 mPa-s to 75000 mPa-s at a 5 rpm viscometer.

Viscous (or liquid) silicone polymers are substantially free of -OH groups, thus providing extended shelf life and allowing storage or transportation at ambient temperature if necessary. Preferably, the silicone material does not have a -OH peak detectable from FTIR analysis. The stability of the formed siloxane material is increased to allow storage before use, where the increase in viscosity (crosslinking) during storage is minimal, such as storage at room temperature for less than 25% for 2 weeks, preferably over 2 weeks Less than 15%, and more preferably less than 10%. In addition, storage, shipping, and subsequent application by the customer can all be carried out in the absence of solvent (except for possible trace residues remaining after drying to remove the solvent), avoiding subsequent solvent traps formed in the layer of the final product (solvent capture), shrinkage during polymerization, and quality loss over time during device usage. Without the application of heat or UV light preferably above 100°C, no substantial crosslinking occurs during transportation and storage.

As disclosed herein, compositions with silicone polymers, particles, and other possible additives (such as coupling agents, adhesion promoters, etc.) can be shipped as a one-component adhesive at room temperature. Generally speaking, single-component adhesives are shipped at -40°C, Or each component is shipped separately ("two-component" adhesive), where the purchaser must mix the different components together, and generally should preferably be within 24 hours or 48 hours of bonding. In general, a one-component adhesive may not involve mixing multiple components, however, once the adhesive is brought from, for example, -40°C to room temperature, then it should preferably be performed within 24 hours or 48 hours. In contrast, the composition disclosed herein can be shipped as a single-component adhesive and it can be shipped and stored at room temperature, for example, 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% of the initial mass, and the right y-axis is the temperature in degrees Celsius. As can be seen in Figure 2, the mixture of siloxane particles as disclosed herein is rapidly heated to 150°C and then held at 150°C for approximately 30 minutes. In this example, the siloxane particles have a Si-O backbone with phenyl and epoxy groups, and the particles are silver particles. After this period of thermal curing, the mass loss is less than 1%. Desirably, the mass loss is usually less than 4%, and generally less than 2%. However, in many cases, the mass difference between the silicone particle composition before and after curing is less than 1%. The curing temperature is generally below 175°C, although higher curing temperatures are possible. Typically, the curing temperature will be 160°C or lower, more usually 150°C or lower. However, lower curing temperatures are possible, such as 125°C or lower.

As can be seen in FIG. 3, regardless of whether the composition disclosed above is used as an adhesive, a thermally 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 Polymerization and, if necessary, hardening, the layer or quality of the siloxane particles is quite thermally stable. For example, after hardening 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, at Less than 4.0%, preferably less than 2.0% is observed at both 200°C and 300°C, for example less than 1.0% mass loss (usually less than 0.5% mass loss is observed at 200°C, or as in the example of Figure 3, in A mass loss of less than 0.2% was 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 of FIG. 3. Similar results can be observed by heating the polymeric material only at 200°C or 300°C for 1 hour. The result of mass loss of less than 1% by heating the polymer deposited material at or above 375°C for at least 1 hour is possible. As can be seen in Figure 3, a mass loss of 5% or less was observed even at temperatures above 500°C. Such thermally stable materials are desired, in particular, they can be deposited at low temperatures (eg, below 175°C, preferably below 150°C, or below 130°C, 30 minutes curing/baking time), or Thermally stable materials as disclosed herein polymerized by UV light.

The foregoing description illustrates 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 materially departing from the novel teaching content and advantages. Therefore, all such modifications are intended to be included within the scope of the invention as defined in the scope of the patent application. Therefore, it should be understood that the foregoing description illustrates that 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 within the scope of the patent scope of the accompanying application.

Citation list

Patent Literature

US 2009258216

WO 2008046142

Non-patent literature

Gene, J (Jin, J), et al. Silica nanoparticle-embedded sol-gel organic/inorganic hybrid nanocomposite for transparent OLED encapsulation). Organic Electronic (Organic Electronic), 2012, Volume 13, pages 53-57.

100, 102, 104, 106, 108: steps

Claims (20)

A composition having a siloxane polymer, including: a siloxane polymer having a repeating main chain of [-Si-O-Si-O]n, the repeating main chain having a) an alkyl group or an aryl group And b) a functional crosslinking group, where n is an integer; and particles mixed with the siloxane polymer, wherein the particles include a first group of particles having an average particle size greater than 200 nm and an average particle size less than 200 nm The second group of particles, and the average particle size of the particles is less than 100 microns, wherein the molecular weight of the siloxane polymer is 400 g/mole to 200,000 g/mole, and wherein the composition is viscometer at 5 rpm The viscosity at 25°C is 500 mPa-s to 500,000 mPa-s. The composition having a siloxane polymer as described in item 1 of the scope of the patent application contains substantially no -OH group in the siloxane polymer. The composition having a siloxane polymer as described in item 1 of the patent application scope has a viscosity increase of less than 25% after 2 weeks at room temperature. The composition having a siloxane polymer as described in item 1 of the patent application scope has the molecular weight and the viscosity in the absence of a solvent. The composition having a siloxane polymer as described in item 1 of the scope of the patent application, in which no substantial crosslinking occurs without applying heat or UV light higher than 100°C. The composition having a siloxane polymer as described in item 1 of the patent application scope, wherein the average particle size of the particles is less than 20 microns. Groups with silicone polymers as described in item 1 of the patent application The product further includes an acid catalyst that reacts with the functional crosslinking group of the silicone polymer when heat or light is applied. The composition having a siloxane polymer as described in item 1 of the patent application scope, wherein the functional crosslinking group of the siloxane polymer is selected from olefins, alkynes, amines, allyl groups, acid anhydrides, Epoxy, cyano, propylene oxide, mercapto, Si-H, vinyl and acrylate groups. The composition having a siloxane polymer as described in item 1 of the scope of the patent application, wherein the viscosity of the composition in the absence of added solvent at a 5 rpm viscometer at 25°C is 1000 mPa − Seconds to 100,000 mPa-seconds. The composition having a siloxane polymer as described in item 1 of the patent application range, wherein the particles are metal particles or semi-metal particles. The composition having a siloxane polymer as described in item 1 of the patent scope, wherein the particles are silicon, zinc, aluminum, yttrium, ytterbium, tungsten, titanium silicon, titanium, antimony, samarium, nickel, nickel cobalt , Molybdenum, magnesium, manganese, lanthanide, iron, indium tin, copper, cobalt aluminum, chromium, cesium or calcium oxide ceramic particles. The composition having a siloxane polymer as described in item 1 of the patent application scope, wherein the particles are metal particles selected from the group consisting of gold, silver, copper, platinum, palladium, indium, iron, nickel, aluminum, Cobalt, strontium, zinc, molybdenum, titanium, tungsten, or alloys or multiple layers thereof. The composition having a siloxane polymer as described in item 1 of the patent application scope, wherein the particles are carbide particles selected from the following: iron carbide, silicon carbide, cobalt carbide, tungsten carbide, boron carbide, zirconium carbide , Chromium carbide, titanium carbide or molybdenum carbide. The composition having a siloxane polymer as described in item 1 of the patent application range, wherein the particles are nitride particles selected from the following: aluminum nitride, tantalum nitride, boron nitride, titanium nitride, nitrogen Copper, molybdenum nitride, tungsten nitride, iron nitride, silicon nitride, nitrogen Indium chloride, gallium nitride or carbon nitride. The composition having a siloxane polymer as described in item 1 of the patent application scope, wherein the particles include carbon and are selected from graphite, graphene, diamond, carbon nanotubes, carbon black, and carbon nanobuds. The composition having a siloxane polymer as described in item 1 of the scope of the patent application, wherein if exposed to UV light or heat for curing, the mass loss is less than 4%. The composition having a siloxane polymer as described in item 1 of the patent application scope, wherein the molecular weight of the siloxane polymer is 300 g/mol to 10,000 g/mol; and wherein the composition is The viscosity at 5 rpm and 25°C is 1000 mPa-s to 75,000 mPa-s. A method for manufacturing a siloxane particle composition suitable for use as a die attaching agent, a sealant, and an optical transmission layer in a semiconductor package, including: in the presence of an alkali catalyst Polymerizing silanol and alkoxysilane to form a viscous and transparent silicone polymer; providing particles with an average particle size of less than 100 microns; mixing a coupling agent and the silicone polymer in a solvent; removing by drying The solvent; and placing the composition of the silicone polymer, the particles, and the coupling agent in a container. The method for manufacturing a composition of siloxane particles as described in item 18 of the scope of the patent application further includes depositing the composition on a substrate, and further polymerizing the composition by applying ultraviolet light. A composition having a siloxane polymer, including: a siloxane manufactured by the following method: providing a first compound as a first monomer having the chemical formula SiR ¹ _a R ^2′ _4-a , where a is 1 To 3, R ¹ is a reactive group, and R ^2′ is an alkyl or aryl group, or an oligomer with a molecular weight of less than 1000 g/mol; provides the chemical formula SiR ³ _b R ⁴ _c R ⁵ _4-( The second compound of _b+c) , wherein R ³ is a cross-linking 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 an oligomer with a molecular weight of less than 1000 g/mol; and polymerizing the first compound and the second compound together to form a siloxane polymer; and the composition further includes Particles with an average particle size of less than 100 microns; wherein the molecular weight of the silicone polymer is 300 g/mol to 10,000 g/mol; wherein the viscosity of the composition at a 5 rpm viscometer is 1000 mPa-s to 75000 mPa-s; and wherein the silicone polymer is substantially free of -OH groups.

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