TW201723124A - LED lamp, method of making LED lamp, and method for encapsulating LED device - Google Patents

Abstract

An LED lamp, a method of making an LED lamp and a method for encapsulating an LED device are provided. The LED lamp is formed from a die substrate wherein the substrate has formed thereon a semiconductor material, an electrode for the application of a bias across the semiconductor material for causing light to be emitted therefrom, and an adhesive that bonds the die substrate to a support substrate, wherein the adhesive is a polymerized siloxane polymer having a thermal conductivity of greater than 0.1 watts per meter kelvin (W/(m,K)) wherein the adhesive is not light absorbing, wherein the siloxane polymer has silicon and oxygen in the polymer backbone, as well as aryl or alky groups bound thereto, and wherein the adhesive further comprises particles having an average particle size of less than 100 microns.

Description

LED lamp with decane oxygen particle material

This invention relates to LED lamps. In particular, the present invention relates to an LED lamp comprising a die substrate formed on a semiconductor material; an electrode for applying a bias voltage across the semiconductor material to cause light emitted therefrom; and bonding the die substrate to the support substrate The adhesive. The present invention also relates to a method of manufacturing an LED lamp and a method of sealing the LED device.

Light-emitting diode (LED) lighting systems have become more widely used in place of traditional lighting. Light-emitting diode lamps (examples of solid-state lighting) can be tuned to the precise color required due to lower energy usage, increased stability and longer lifespan, the ability to be used in a wider variety of applications than fluorescent lighting, The ability has advantages over traditional lighting such as incandescent bulbs, halogen lighting or fluorescent lighting. In some embodiments, a single LED wafer/die is within the lamp, and in other embodiments, a plurality of LEDs are within the same lamp. The outer casing of the LED lamp can be manufactured to the same specifications as the incandescent bulb, thus allowing use in the case of incandescent bulbs.

A light emitting diode (LED) is a solid state device that converts electrical energy into light, and typically has at least one semiconductor material having an n-doped portion and a p-doped portion. Organic light-emitting diodes are also known. When a bias is applied across the semiconductor material, holes and electrons are ejected into the active layer, where the holes and electrons recombine to produce light. Light is emitted from the active layer and can be oriented primarily in one direction, or in any direction, depending on the type of LED.

The LED can provide white light by a single LED, such as by a blue or violet LED, having a phosphor that shifts the light closer to the perceived white light. The LEDs can be provided in a single color (eg, red, green, or blue), or can be provided as different color LEDs in the same lamp that are combined to provide white light. Examples of the LED may include a red LED using GaAsP and a green LED using GaP, and a nitride semiconductor LED forming green, blue or ultraviolet light. As LEDs become brighter and hotter, heat dissipation becomes more and more of a concern as heat build-up can reduce LED performance.

An LED lamp comprising a crosslinkable polymer composition is disclosed in US 2009221783, US 2012123054, WO 20100267, US 2011171447, and JP 2004225005.

The properties of the polymer composition are known to be insufficient, for example, in terms of thermal stability.

It is an object of the invention to provide an LED lamp.

Another object of the present invention is to provide a method of manufacturing an LED lamp.

A third object of the present invention is to provide a sealing method for an LED device.

The present invention is based on the formation of an LED lamp formed from a die substrate having a semiconductor material formed thereon; an electrode for applying a bias voltage across the semiconductor material to cause light emitted therefrom; and bonding the die substrate Adhesive to the support substrate.

In the present invention, the adhesive is a polymeric siloxane polymer having a thermal conductivity of more than 0.1 watts/meter gram (W/(m·K)), wherein the adhesive does not absorb light, wherein the siloxane is polymerized. The material has rhodium and oxygen in the polymer backbone, and an aryl or alkyl group bonded thereto, and wherein the binder further comprises particles having an average particle size of less than 100 microns.

According to the present invention, a method of fabricating an LED lamp includes the steps of: forming a light emitting diode by providing a semiconductor material and a doped semiconductor material on a first substrate; providing a support substrate; and providing a layer formed of a siloxane polymer The composition of the adhesive further comprises particles and a catalyst having an average particle size of less than 100 microns. The subsequent composition is deposited to bond the first substrate to the support substrate. By applying temperature and/or light, the crosslinking group of the siloxane polymer is activated to further polymerize the siloxane polymer and the hardened polymer while the die substrate and the package substrate are joined together.

In a sealing method of an LED device including a light emitting diode, a semiconductor material is provided on a first substrate and it is doped. Provided includes a sealant composition comprising a siloxane polymer having ruthenium and oxygen in the polymer backbone, and an aryl or alkyl group bonded thereto, and In combination with the functional crosslinking groups, the adhesive composition further comprises particles and catalysts having an average particle size of less than 10 microns. The sealant composition is deposited to encapsulate the light emitting diode and temperature and/or light is applied to activate the crosslinking groups of the siloxane polymer to further polymerize the siloxane polymer and the hardened polymer.

The polymeric and hardened siloxane polymers mentioned above typically have a mass of at least 96% prior to polymerization after polymerization. Typically, the siloxane polymer does not absorb more than 25% of the visible light incident thereon.

More specifically, the invention is characterized by what is stated in the scope of the independent patent application.

Get a considerable advantage. Therefore, the thermal conductivity of the adhesive is high and the adhesive is thermally stable. It also achieves an excellent shelf life, specifically the storage before use. Typically, there is a minimal increase in viscosity (crosslinking) during storage, and storage, shipping, and subsequent application by the customer can all be performed in the absence of solvent, avoiding solvent capture that is subsequently formed in the layer of the final product. The shrinkage during polymerization and the loss of quality over time during use of the device.

Example embodiments will be more clearly understood from the following description taken in conjunction with the drawings.

Various example embodiments will be described more fully hereinafter with reference to the accompanying drawings. However, the inventive concept may be embodied in many different forms and should not be construed as being limited to the example embodiments set forth herein. Rather, the example embodiments are provided so that this description will be thorough and complete, and the scope of the inventive concept will be fully conveyed by those skilled in the art. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity.

It will be understood that when an element or layer is referred to as "on", "connected" or "coupled" to another element or layer, the element or layer can be Layers, directly connected to or coupled to another element or layer, or there may be intervening elements or layers. In contrast, when an element is referred to as "directly on another element or layer" or "directly connected to another element or layer" or "directly coupled to another element or layer," Floor. Like reference numerals refer to like elements throughout. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

It will 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 It should not be limited by these terms. The terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below may be referred to as a second element, component, region, layer or section, without departing from the teachings of the invention.

The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting. As used herein, the singular forms " It is to be understood that the term "comprises" or "comprising", when used in the specification, is used in the context of the specification of the claimed features, regions, integers, steps, operations, components and/or components, but does not exclude one or more other features, The presence or addition of regions, integers, steps, operations, components, components, and/or groups thereof.

In addition, relative terms such as "lower" or "bottom" and "upper" or "top" may be used herein to describe the relationship of one element to another element, as illustrated in the drawings. It will be understood that the relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the drawings. For example, if the device in one of the figures is turned over, the elements described as being located on the "lower" side of the other elements will then be directed to the "upper" side of the other elements. Thus, the exemplary term "lower" may thus encompass the orientation of "lower" and "upper" depending on the particular orientation of the drawings. Similarly, elements that are described as "below" or "beneath" other elements will be "above" the other elements. Thus, the exemplary term "below" or "beneath" can encompass both the top and the bottom.

It should be noted that as used herein, the singular forms "" In addition, it should be understood that the terms "comprises" and / or "includes" are used in the specification to indicate the existence of the stated features, steps, operations, components and/or components, but do not exclude the addition of one or more other features, Steps, operations, component components, and/or their ethnic groups.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning meaning meaning It should be further understood that the 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 related art and the present invention, and will not be ideal unless explicitly defined herein. Interpretation of meaning or over-formalization.

The lower case letters used in the following monomers and polymers are especially integers.

The siloxane oxide material as disclosed herein can be used in any desired LED device, however, as a first example, a GaN LED can be used. GaN-based LEDs are a specific type of illuminating device known as a solid state light source that has many advantages such as tightness, low energy consumption, long life, mercury free, high efficiency, and low service rate. GaN LEDs are available in lighting applications in different forms and combinations, such as a) a combination of three types of monochromatic LEDs (blue, green, red); b) a combination of blue LEDs and yellow phosphor powder; c) UV LEDs Combination with tri-color red-green-blue fluorescent powder, and other combinations and embodiments.

White light can be obtained using a blue LED via a combination of YAG:Ce fluorescent materials of a yttrium-aluminum-garnet structure based on complementary color theory. Since the light emitted from YAG is yellow-green, the white light obtained is characterized by having a high color temperature and a cool hue so that the color rendering is not satisfactory for all uses. Therefore, green, yellow or red fluorescent powders can be added to obtain white light having different color temperatures (cold to warm) and improved color rendering. Other phosphorescent moieties, in particular those based on citrate, sulphate, nitrite and pendant oxy-indolizine, can be used to improve color development.

More specifically, a white LED can use a 450 nm-470 nm blue gallium nitride (GaN) LED covered by a pale yellow phosphor/scintillator coating, which can be treated with YAG:Ce Made of yttrium aluminum garnet crystal. Since the yellow light stimulates the red cone and the green cone of the human eye, the resulting mixture of blue light emitted from the GaN LED and yellow light emitted from the phosphor appears as white light. Other combinations of LEDs and phosphors can also produce a white light appearance. The combination of LEDs can give the appearance of white light, such as ZnSe grown on the ZnSe substrate that simultaneously emits blue light from its active region and emits yellow light from the substrate. Additionally, combinations of red, green, and blue LEDs are known to produce white light with or without a phosphor. Also possible are tungstate, carbonitride, molybdate and selenide phosphors, as well as quantum dots.

The combination of YAG phosphor and blue LED is a common combination for situations where high color rendering index (CRI) and warm color temperature are not required. Alternatively, a phthalate phosphor is possible, such as a citrate phosphor that emits green, yellow, and orange (such as 507 nm to 600 nm) from a UV violet source and a blue source. For LED applications that require warm and saturated red (such as display or residential/retail store lighting), red and/or green phosphors may be required. Nitride phosphors (or oxynitride phosphors) are possible. The red nitride phosphor can emit a color such as between 620 nm and 670 nm. Also possible are, for example, aluminate phosphors that emit light in the green or yellow spectrum, such as from 516 nm to 560 nm.

As seen in FIG. 1, on the sapphire substrate 14, an n-doped gallium nitride region 12 is shown. An n-type semiconductor region can be produced by doping GaN with, for example, germanium or oxygen. A p-doped gallium nitride region 13 is also illustrated. A p-type semiconductor region can be produced by doping GaN with, for example, magnesium. Electrode 10a and electrode 10b are illustrated and used to provide a bias across the GaN semiconductor region to cause LED illumination, in this example, light is emitted in all directions.

Instead of a sapphire substrate, it is possible to use a SiC substrate on which an InGaN semiconductor is formed, such as an LED of Cree, Inc. Alternatively, a GaN substrate having a GaN-doped semiconductor region thereon is also possible, such as an LED of Soraa, Inc., or a Si substrate having a GaN semiconductor thereon, such as Bridgelux (Bridgelux) , Inc.) or LED from Osram, Inc. The use of germanium substrates has the benefit of using large wafer sizes (eg, 6 germanium wafers, 8 germanium wafers, or larger wafers).

As can be seen in Figure 2, a substrate 16 of SiC or Cu is provided having a p-doped GaN region 13 thereon and an n-doped GaN region 12. The electrode 10 is also illustrated. The bias applied between the substrate 16 and the electrode 10 causes the LED to illuminate. As can be seen in Figure 2, the light is oriented primarily in the upward direction. In the example of FIG. 2, the closest to the die substrate provides a p-doped region, while in the example of FIG. 1, the closest die substrate provides an n-doped region.

As illustrated in FIGS. 1 and 2, a die attaching adhesive layer 17 is provided to attach a substrate (sapphire, SiC, Cu, GaN, Si, etc.) to the support substrate or package substrate 19. The LED die attaching agent is preferably, but not necessarily, thermally conductive (e.g., may have greater than 0.5 watts per meter per gram of gram (W/(m·K)), preferably greater than 4.0 watts in the case of optical reflections. /Metal·Kelvin and better than 10.0 W/m·Kelvin thermal conductivity. Depending on the material and concentration chosen, much higher thermal conductivity (such as greater than 25.0 W/m·g It is also possible to have an otogram of more than 50.0 watts/meter gram. However, if the adhesive or sealant is transparent, the thermal conductivity is usually greater than 0.1 watt/meter gram (eg 0.1 watt). / metric gram to 0.5 watt / meter · gram, or such as greater than 0.2 watt / meter · gram, such as greater than 0.5 watt / meter · gram). Whether as an adhesive or seal The rhodium oxide material can be deposited as a fluid, such as a liquid or gel, such as by means of, for example, syringe deposition or screen printing. Other deposition methods can be used, such as spin coating, dipping, ink jet, curtain coating. Cloth, drip, roll coating, gravure printing, reverse offset printing, extrusion coating, slit coating, spray coating, flexography, and the like.

The LED die attaching agent can be electrically insulating or electrically conductive. In the example of FIG. 2, since the die substrate is one of the electrodes, the LED die attaching agent should also be electrically conductive, such as having a resistivity of less than 1×10 ⁻³ Ω∙m, preferably less than 1×10. ^-5 Ω ∙ m, or even less than 1 × 10 ^-7 Ω ∙m resistivity. In the example of Figure 1, the LED die attaching agent can be electrically insulating or electrically conductive. If electrically conductive, the resistivity can be within the ranges as described above with respect to FIG. If electrically insulated, the resistance may be greater than 1 × 10 ³ O. meters, such as greater than 1 × 10 ⁵ O. meters, or even greater than 1 × 10 ⁹ O. meters.

The LED die attach material is preferably not optically absorptive in the visible spectrum (or, for example, in the spectrum of LED illumination - such as ultraviolet light). The die attach layer can transmit visible (or UV) light wherein the transmission is at least 80%, preferably at least 85%, more preferably 90% orthogonal to the visible light incident thereon. It is also possible to transmit 92.5%, or even 95% or more of visible light. If a transparent die attach material is used, a reflective layer on the support substrate or package substrate can be provided as needed to reflect light to improve the brightness of the light output from the LED lamp.

In an alternate example, the LED die attach material is highly reflective. The die attach material is reflective and can help redirect light towards the package substrate or support substrate to direct the package, thus improving the brightness of the LED lamp. Preferably, in this example, 85% or more of the light is reflected by the LED die attach layer, or 90% or more, or even 95% or more of the visible light is reflected. The die attach material may be disposed not only in the lower portion of the die, but also disposed around the sides of the die to reflect light emitted from the sides of the device.

A siloxane oxide particle material as disclosed herein may also be provided on the front side of the LED as a barrier layer or sealant. As seen in FIG. 3, the die 24 is attached to the package substrate 20 via a die attach adhesive 22. In this example, the die attaching agent may be as described above, or may be a conventional die attaching agent such as a die attaching agent prepared from metal welding, frit, polymer epoxide, or the like. . The die 24 is a simplified illustration of an LED device having a layer of semiconductor material on the die substrate that is electrically connected to the package substrate. If desired, a phosphor layer 28 is also provided to shift the wavelength of the light emitted by the LED from the first wavelength of light to the second wavelength of light. Preferably, the second wavelength of light is in the visible spectrum, however, the first wavelength of light may be in the visible spectrum or outside the visible spectrum, such as UV light.

It is also possible that no phosphor is present such that the phosphor layer 28 is not provided. If layer 28 is provided, according to this example, a phosphor is provided within the oxoxane material as disclosed herein, optionally comprising particles, but preferably not. A second encapsulant 29 is provided with or without the encapsulant layer 28 to surround and protect the LED device on the package substrate. If layer 28 is not provided, or if it is provided without a phosphor, it is possible to provide a phosphorescent material within encapsulant layer 29 as necessary. Both layer 28 and layer 29 can be provided with a phosphorescent material, if desired. Encapsulant layer 29 can be made from a oxoxane material as disclosed herein, with or without particles added thereto.

An alternate example is shown in FIG. 4, which illustrates a package substrate 30 having die 32 bonded thereto via bonding layer 34. As mentioned with respect to Figure 3, the tie layer can be a siloxane oxide particle composition as disclosed herein, or another type of die attach material. The die 32 is a simplified view of the LED device, preferably having a p-doped region and an n-doped region, such as a GaN-doped semiconductor material disposed on a substrate such as sapphire, SiC, Cu, Si, GaN, or the like. If necessary, a first sealing layer with phosphorescent material 35 and/or a second sealing layer 37 are provided. Layers 35 and 37 may be as described above with respect to layer 28 and layer 29 of FIG.

Illustrated in Figure 5 is a flip chip package for an LED device in which a semiconductor material 41 (e.g., GaN) is provided on a transparent substrate 40 (e.g., sapphire). In a flip chip package, the semiconductor material 41 and the electrical connection regions 47 are bonded to the substrate 42, which in this case is a germanium substrate having circuitry and electrical connection regions 48 thereon. The electrical connection regions or pad regions on substrate 40 and substrate 42 are connected via a conductive siloxane oxide binder 46 as disclosed herein. If desired, a oxoxane material 49 according to the disclosure herein can be provided that is electrically insulating and that provides improved adhesion and CTE characteristics. The siloxane bottom charge 49 may have no particulate material or may have particles such as oxide or nitride particles that do not provide conductive properties. Conductive material 46 may be provided by screen printing, pin deposition, or other suitable method. The underfill 49 can be a low molecular weight decane or provided in liquid form with the added solvent to fill the area between the substrates via capillary action. Conductive regions 46 may be cured prior to the addition of underfill 49, or both materials may be cured together. Curing can be visualized via UV light or heat.

Additionally, as illustrated in FIG. 5, wire bonds 45 connect the circuitry on the substrate 42 of the crucible to the substrate 44 of the package substrate/support substrate, which may be a ceramic substrate or other desired material. The subsequent agent 43 connects the substrate 42 to the substrate 44 and may be a siloxane oxide particle material as disclosed herein, preferably thermally conductive. The underfill layer 49 can be optically transmissive in the visible (or UV) spectrum or can be optically reflective to visible or UV light. If transmissive, a reflective layer can be provided on substrate 42 to reflect light back in another opposing direction to increase the efficiency of the LED lamp.

More specifically, with respect to the above-mentioned azoxysilane particle composition, a composition is obtained in the case of providing a siloxane polymer. Preferably, the polymer has a ruthenium oxide backbone having an aryl (or alkyl) substituent and a functional crosslinker. The filler material is mixed with the siloxane polymer. The filler material is preferably a particulate material comprising particles having an average particle size of 100 microns or less, preferably 10 microns or less. The catalyst is added, and when heat or UV light (or other activation method) is provided to the composition, the catalyst reacts with a functional crosslinking group in the siloxane polymer. The monomer (or oligomer) coupling agent is included in the composition, preferably having a functional cross-linking group which is also reactive when heat or light is applied, as in the siloxane polymer. Additional materials such as stabilizers, antioxidants, dispersants, adhesion promoters, plasticizers, softeners, and other possible components may also be added depending on the end use of the composition. Although a solvent may be added, in a preferred embodiment, the composition is solvent free and is a solvent free viscous fluid which is stored and transported as such.

As indicated above, the compositions made as disclosed herein include a decane polymer.

To produce a siloxane polymer, a first compound having the 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 group or an aryl group is provided.

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 a aryl group is also provided. Base, and wherein b=1 to 2, and c=1 to (4-b).

A third compound, optionally selected, is used in conjunction with the first compound and the second compound to polymerize therewith. The third compound may have the formula: SiR ⁹ _f R ¹⁰ _g w 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 may be provided in any order, and an oligomeric partial polymerization pattern of any of these compounds may be provided in place of the above-mentioned monomers.

a first compound, a second compound, and a third compound, and any compound described hereinafter, if such a compound has more than one single type of "R" group, such as a plurality of aryl or alkyl groups, or a plurality of reactivity A group, or a plurality of cross-linking functional groups, etc., independently select a plurality of R groups to be the same or different at each occurrence. For example, if the first compound is SiR ¹ ₂ R ² ₂ , a plurality of R ¹ groups are independently selected to be the same or different from each other. Also, a plurality of R ² groups are independently selected to be the same or different from each other. Unless otherwise stated explicitly, any other compounds mentioned herein are the same.

Catalysts are also provided. The catalyst can be a base catalyst or other catalyst as mentioned below. The catalyst provided should be capable of polymerizing the first compound and the second compound together. As noted above, the order in which the compound and catalyst are added can be in any desired order. The various components provided together are polymerized to produce a naphthenic 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, subsequent promoters, and the like. The combination of the components of the composition can be carried out in any desired order.

More specifically, in one example, a siloxane polymer is obtained by polymerizing a first compound and a second compound, wherein the first compound has the 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 group or an aryl group, and the second compound has the following chemical 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).

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

If R ² is aryl, the aryl group may be phenyl, which optionally carries from 1 to 5 substituents selected from halogen, alkyl or alkenyl, or naphthyl, optionally on the ring structure. Carrying from 1 to 11 substituents selected from haloalkyl or alkenyl groups, 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 or tetracene, which may optionally carry 1-8 substituents or, as the case may be, 1 to 12 The alkyl, alkenyl, alkynyl or aryl group of the carbon is "interleaved" from the ruthenium atom. A single ring structure such as a phenyl group may also be spaced apart from the germanium atom in this manner.

The oxirane polymer is obtained by conducting a polymerization reaction between the first compound and the second compound, preferably a base-catalyzed polymerization. Additional compounds, as exemplified below, may be included as part of the polymerization reaction.

The first compound may have any suitable reactive group R ¹ such as a hydroxyl group, a halogen, an alkoxy group, a carboxyl group, an amine or a decyloxy group. By way of example, where the reactive group in the first compound is an -OH group, a more specific example of the first compound may comprise a decane diol, especially such as diphenyl decane diol, dimethyl decane diol. , diisopropyl decanediol, di-n-propyl decane diol, di-n-butyl decane diol, di-tert-butyl decane diol, diisobutyl decane diol, phenyl methyl decane diol And dicyclohexyldecanediol.

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 a decyloxy 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 to form a siloxane polymer, such as a third compound, etc.), such that the resulting oxime The alkane polymer does not have any or substantially any H group that is directly bonded to the Si in the siloxane 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 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 which can be crosslinked by an acid, base, radical or thermal catalyzed reaction. Such functional groups may be selected, for example, from any epoxide, oxetane, acrylate, alkenyl, alkynyl, vinyl, and Si-H groups.

In the case of an epoxy group, it may be a cyclic ether having three ring atoms crosslinkable using an acid, a base, and a thermally catalyzed reaction. Examples of such epoxides containing a crosslinking group 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 having four ring atoms which can be crosslinked using an acid, a base and a thermally catalyzed reaction. Examples of such propylene oxide-containing decanes include 3-(3-ethyl-3-oxetanylmethoxy)propyltriethoxydecane, 3-(3-methyl-3-oxetanylmethyl) Oxy)propyltriethoxydecane, 3-(3-ethyl-3-oxetanylmethoxy)propyltrimethoxydecane or 3-(3-methyl-3-oxetanylmethoxy) Propyltrimethoxydecane (to name a few).

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

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 acetylene group (i.e., the two carbon atoms bonded to the bond) is preferably located at a position 2 or higher relative to the position of the Si atom or the M atom in the molecule. The branched alkynyl group is preferably at the alpha position or the beta position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl groups, optionally a perfluorinated alkyl, alkenyl or alkynyl group.

In the case of a fluorenyl group, it may be any organic sulfur compound containing a carbon-bonded sulfhydryl group. Examples of decyl-containing decanes are 3-mercaptopropyltrimethoxydecane and 3-mercaptopropyltriethoxydecane.

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 consists of a lower alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a third butoxy group. A specific example of the second compound is decane, especially such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane. , 3-(trimethoxydecyl)propyl methacrylate, 3-(trimethoxydecyl)propyl acrylate, (3-glycidyloxypropyl)trimethoxynonane or 3-glycidoxy Propyltriethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane.

The third compound can be provided in conjunction with the first compound and the second compound to polymerize therewith. The third compound may have the formula: SiR ⁹ _f R ¹⁰ _g wherein R ⁹ is a reactive group, and f = 1 to 4, and R ¹⁰ is an alkyl group or an aryl group, and g = 4-f.

One such example is tetramethoxynonane. Other examples include, in particular, phenylmethyldimethoxydecane, trimethylmethoxydecane, dimethyldimethoxydecane, vinyltrimethoxydecane, allyltrimethoxydecane, methyltrimethyl Oxy decane, methyl triethoxy decane, methyl tripropoxy decane, propyl ethyl trimethoxy decane, ethyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy Decane.

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 for base-catalyzed polymerization between the first compound and the second compound may be any suitable basic compound. Examples of such basic compounds are, in particular, 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 particular example, the base catalyst is Ba(OH) ₂ . The base catalyst can be provided in less than 0.5% by weight, or in a lower amount, such as less than 0.1% by weight, relative to the first compound and the second compound.

The polymerization can be carried out in a molten phase or a liquid medium. The temperature is in the range of from about 20 ° C to 200 ° C, usually from about 25 ° C to 160 ° C, especially from about 40 ° C to 120 ° C. In general, 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 range from 95:5 to 5:95, especially from 90:10 to 10:90, preferably from 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 involved in the polymerization - 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, the total number of -OH groups in the amount of the first compound added is not greater than the total number of reactive groups (eg, alkoxy groups) in the second compound, and preferably less than in the second compound (or The total number of reactive groups of the second compound plus any other compound added with the alkoxy group, such as added tetramethoxynonane or other third compound (as referred to herein) involved in the polymerization reaction) . In the case where the number of alkoxy groups exceeds the hydroxyl group, all or substantially all of the -OH groups will be reacted and removed from the oxirane, such as methanol (if the alkoxy decane is methoxy decane), ethanol (if alkoxylated) The decane is ethoxy decane) and the like. Although the number of -OH groups in the first compound and the number of reactive groups in the second compound (preferably other than the -OH group) may be substantially the same, it is preferred that the reactivity in the second compound The total number of groups is more than 10% or more, preferably 25% or more, in number to the -OH group in the first compound. In some embodiments, the number of reactive groups of the second compound exceeds 40% or more of the first compound-OH group, or even 60% or more, 75% or more, or up to 100% or more . Removal of methanol, other by-products of ethanol polymerization (depending on the selected compound) after polymerization, preferably evaporates in the drying chamber.

The obtained alkane polymer has any desired (weight average) molecular weight, such as from 500 g/m to 100,000 g/m. The molecular weight may be at the lower end of the range (for example, 500 g/m to 10,000 g/mole or more preferably 500 g/m to 8,000 g/mole) or the molecular weight of the organosiloxane material may be above the range ( Such as 10,000 gram/mole to 100,000 gram/mole or better 15,000 gram/mole to 50,000 gram/mole. It may be desirable to mix a polymer organic siloxane material having a lower molecular weight with an organic siloxane material having a higher molecular weight.

The naphthenic polymer obtained can then be combined with additional components depending on the final desired use of the polymer. Preferably, the decane polymer is combined with a filler to form a composition, such as a particulate filler having particles having an average particle size of less than 100 microns, preferably less than 50 microns, comprising less than 20 microns. The additional component may be part of a composition such as a catalyst or curing agent, one or more coupling agents, a dispersing agent, an antioxidant, a stabilizer, a subsequent accelerator, and/or other desired components depending on the siloxane material The final desired use. In one example, a reducing agent is included that reduces the oxidized surface to its metallic form. The reducing agent may remove oxidation from the particles if the particles are metal particles having 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 oxide material and Electrical connection between the deposited or subsequent surfaces. The reducing agent or stabilizer may comprise ethylene glycol, β-D-glucose, polyethylene oxide, glycerin, 1,2-propanediol, N,N-dimethylformamide, sodium polyacrylate (PSA), Polyacrylic acid β-cyclodextrin, dihydroxybenzene, polyvinyl alcohol, 1,2-propanediol, hydrazine, barium sulfate, sodium borohydride, ascorbic acid, hydroquinone family, gallic acid, pyrogallol, ethylene Aldehyde, acetaldehyde, glutaraldehyde, aliphatic dialdehyde family, trioxane, tin powder, zinc powder, formic acid. Additives such as stabilizers such as antioxidants such as Irganox (as mentioned below) or diazine derivatives may also be added.

Crosslinked ruthenium or non-ruthenium resins and oligomers can be used to enhance cross-linking between the siloxane polymers. The functionality of the crosslinked oligomer or resin added is selected by the functionality of the siloxane polymer. By way of example, an epoxy-based alkoxysilane may be used during the polymerization of the siloxane polymer, and an epoxy-functional oligomer or resin may be used. The epoxy oligomer or resin can be any difunctional, trifunctional, tetrafunctional or higher functional epoxy oligomer or resin. An example of such an epoxy oligomer or resin may be 1,3-bis 2-(3,4-epoxycyclohexyl)ethyl 1,1,3,3-tetramethyldioxane, 1, 3-diglycidoxypropyl 1,1,3,3-tetramethyldioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy 3,4-epoxycyclohexylmethyl chlorocyclohexane, 1,4-cyclohexanedimethanol diglycidyl ether, bisphenol A diglycidyl ether, 1,2-cyclohexanedicarboxylic acid diglycidyl Ester (to name a few).

The curing agent added to the final formulation is any compound that initiates and/or accelerates the curing process of the functional groups in the siloxane polymer. These curing agents can be thermally and/or UV activated (for example, a thermal acid in the case of thermal activation of a polymerization reaction or a photoinitiator in the case of UV activation). The crosslinking group in the siloxane polymer as described above is preferably an epoxide, propylene oxide, acrylate, alkenyl or alkynyl group. The curing agent is selected based on the crosslinking group in the siloxane polymer.

In one embodiment, the curing agent for the epoxy 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 "displays a blocked or reduced reactivity of a primary amine or a secondary amine" shall mean an extremely low ability to react with a resin component or only react with a resin component due to chemical or physical blocking, but may Regenerating the reactivity after releasing the amine, for example by melting it at elevated temperatures, by removing the outer sheath or coating, by pressure or by ultrasonic or other energy type, starting the resin component The amines of the curing reaction.

Examples of thermally activatable curing agents comprise at least one organoborane or a complex of borane with at least one amine. The amine can be a complex organoborane and/or borane and can be decomposed as necessary to release any type of organoborane or borane. The amine can include a variety of structures, such as any primary or secondary amine or a polyamine containing a primary amine and/or a secondary amine. The organoborane can be selected from the group consisting of alkylboranes. An example of such heat, especially borane, is boron trifluoride. Suitable amine/(organo)borane complexes are commercially available from commercial sources such as King Industries, Air products, and ATO-Tech.

Other heat activated curing agents for epoxy groups are thermal acid generators which release a strong acid at elevated temperatures to catalyze the crosslinking reaction of the 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 Iodine salt. Commercial examples of such thermal acid generators are K-PURE CXC-1612 and K-PURE CXC-1614 manufactured by King's Industrial.

In addition, in the case of epoxides and/or propylene oxide containing polymers, curing agents, co-curing agents, catalysts, initiators or other additives designed to participate in or promote curing of the adhesive formulation may be used, such as Anhydride, amine, imidazole, thiol, carboxylic acid, phenol, dicyandiamide, urea, hydrazine, hydrazine, amine-formaldehyde resin, melamine-formaldehyde resin, quaternary ammonium salt, quaternary phosphonium salt, triaryl sulphur 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 labile oxygen-oxygen single bonds that are readily resolved into reactive free radicals via hemolytic cleavage. The azo compound has an R-N=N-R functional group which is decomposable into nitrogen and two organic radicals. In both cases, the free radicals catalyze the polymerization of acrylate, alkenyl and alkynyl linkages. Examples of peroxides and azo compounds are di-tert-butyl peroxide, 2,2-bis(t-butylperoxy)butane, tert-butyl peracetate, 2,5-di ( Tert-butylperoxy)-2,5-dimethyl-3-hexyne, dicumyl peroxide, benzammonium peroxide, di-third amyl peroxide, peroxybenzoic acid Third butyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylamidinopropane) dihydrochloride, diphenyldiazenene, Diethyl azodicarboxylate and 1,1'-azobis(cyclohexanecarbonitrile), to name a few.

Photoinitiators are compounds which, upon exposure to light, decompose into free radicals and thus promote the polymerization of acrylate, alkenyl and alkynyl compounds. Commercial examples of such photoinitiators are Irgacure 149, Yanjiagu 184, Yanjiagu 369, Yanjiagu 500, Yanjiagu 651, Yanjiagu 784, Yan, manufactured by BASF. Jiagu 819, Yan Jiagu 907, Yan Jiagu 1700, Yan Jiagu 1800, Yan Jiagu 1850, Yan Jiagu 2959, Yan Jiagu 1173, Yan Jiagu 4265.

One method of incorporating a curing agent into the system is to attach a curing agent or a functional group that can act as a curing agent to the decane monomer. Therefore, the curing agent will accelerate the curing of the siloxane polymer. Examples of such types of curing agents attached to decane monomers are γ-imidazolylpropyltriethoxydecane, γ-imidazolylpropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3 - mercaptopropyltriethoxydecane, 3-(triethoxyindolyl)propyl succinic anhydride, 3-(trimethoxyindolyl)propyl succinic anhydride, 3-aminopropyltrimethoxy Decane and 3-aminopropyltriethoxydecane, to name a few.

The promoter can then be part of the composition and can be any suitable compound that enhances the adhesion between the cured product and the surface of the coated product. The most commonly used promoter is a functional decane comprising an alkoxydecane and from 1 to 3 functional groups. Examples of the subsequent promoter for use in the die attach product may be octyltriethoxydecane, mercaptopropyltriethoxydecane, cyanopropyltrimethoxydecane, 2-(3,4-ring) Oxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(trimethoxyindolyl)propyl methacrylate, 3-(trimethyl) Ethyl methoxy) propyl acrylate, (3-glycidyloxypropyl) trimethoxy decane or 3-glycidoxy propyl triethoxy decane, 3-methyl propylene methoxy propyl trimethyl Oxydecane and 3-propenyloxypropyltrimethoxydecane.

The resulting polymeric oxane will have a [Si-O-Si-O]n repeating backbone on which the organic functional groups will depend on the ruthenium 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] backbone, a chemical having the formula: R ² _3-a R ¹ _a SiR ¹¹ SiR ¹ _b R ² _3-b wherein a is 1 to 3 and 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, polyaryl, polycycloalkyl, heterocyclic a group-based, heterocyclic aromatic group, and R ^{11 is} independently an alkyl or aryl group, or an oligomer having a molecular weight of less than 1000 g/mole; and a first compound, a second compound as described above, and The third compound or any combination of these is polymerized together.

Examples of such compounds are 1,2-bis(dimethylhydroxydecyl)ethane, 1,2-bis(trimethoxydecyl)ethane, 1,2-bis(dimethoxymethyldecane). Ethylene, 1,2-bis(methoxydimethyldecyl)ethane, 1,2-bis(triethoxydecyl)ethane, 1,3-bis(dimethylhydroxydecane) Propane, 1,3-bis(trimethoxydecyl)propane, 1,3-bis(dimethoxymethyldecyl)propane, 1,3-bis(methoxydimethyldecyl) Propane, 1,3-bis(triethoxydecyl)propane, 1,4-bis(dimethylhydroxydecyl)butane, 1,4-bis(trimethoxydecyl)butane, 1, 4-bis(dimethoxymethyldecyl)butane, 1,4-bis(methoxydimethyldecyl)butane, 1,4-bis(triethoxydecyl)butane, 1,5-bis(dimethylhydroxydecyl)pentane, 1,5-bis(trimethoxydecyl)pentane, 1,5-bis(dimethoxymethyldecyl)pentane, 1 , 5-bis(methoxydimethylalkylalkyl)pentane, 1,5-bis(triethoxydecyl)pentane, 1,6-bis(dimethylhydroxydecyl)hexane, 1 ,6-bis(trimethoxydecyl)hexane, 1,6-bis(dimethoxymethyldecyl)hexane, 1,6-double (methoxy methoxy decyl) hexane, 1,6-bis(triethoxydecyl) hexane, 1,4-bis(trimethoxydecyl)benzene, bis(trimethoxydecyl) Naphthalene, bis(trimethoxydecyl)phosphonium, bis(trimethoxydecyl)phenanthrene, bis(trimethoxydecyl)norbornene, 1,4-bis(dimethylhydroxydecyl)benzene, 1,4-bis(methoxydimethylalkyl)benzene and 1,4-bis(triethoxyindenyl)benzene, to name a few.

In one embodiment, in order to obtain a [Si-O-Si-C] backbone, a compound of 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) wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, and R ⁵ is an alkyl group, an alkenyl group, an alkynyl group, an alcohol, a carboxylic acid, a dicarboxylic acid, an aryl group, a poly Aryl, polycycloalkyl, heterocycloaliphatic, heterocyclic aromatic, R ^{12 is} independently alkyl or aryl, and wherein c = 1 to 2, d = 1 to (3-c), e =1 to 2, and f=1 to (3-e), or an oligomer having a molecular weight of less than 1000 g/mole, and a first compound, a second compound, a third compound or Any combination of these is aggregated together.

Examples of such compounds are 1,2-bis(vinyldimethoxydecyl)ethane, 1,2-bis(ethynyldimethoxydecyl)ethane, 1,2-bis(ethynyl) Dimethoxy)ethane, 1,2-bis(3-glycidoxypropyldimethoxydecyl)ethane, 1,2-bis[2-(3,4-epoxycyclohexyl) Ethyldimethoxydecyl]ethane, 1,2-bis(propyl methacrylate dimethoxydecyl)ethane, 1,4-bis(vinyldimethoxydecyl)benzene, 1,4-bis(ethynyldimethoxydecyl)benzene, 1,4-bis(ethynyldimethoxydecyl)benzene, 1,4-bis(3-glycidoxypropyldimethyl) Oxyalkylene)benzene, 1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethoxydecyl]benzene, 1,4-bis(propyl methacrylate) Base alkyl) benzene (to name a few).

In one embodiment, having the formula 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) a oxoxane monomer, wherein 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-linking functional group as explained above, and a=0 to 3 , b = 0 to 3, polymerized with the previously mentioned decane or added as an additive to the final formulation. Examples of such compounds are 1,1,5,5-tetramethoxy-1,5-dimethyl-3,3-diphenyltrioxane, 1,1,5,5-tetramethoxy 1,3,3,5-tetraphenyltrioxane, 1,1,5,5-tetraethoxy-3,3-diphenyltrioxane, 1,1,5,5 -tetramethoxy-1,5-divinyl-3,3-diphenyltrioxane, 1,1,5,5-tetramethoxy-1,5-dimethyl-3,3 -diisopropyltrioxane, 1,1,1,5,5,5-hexamethoxy-3,3-diphenyltrioxane, 1,5-dimethyl-1,5- Diethoxy-3,3-diphenyltrioxane, 1,5-bis(mercaptopropyl)-1,1,5,5-tetramethoxy-3,3-diphenyltriazole Oxane, 1,5-divinyl-1,1,5,5-tetramethoxy-3-phenyl-3-methyltrioxane, 1,5-divinyl-1,1, 5,5-tetramethoxy-3-cyclohexyl-3-methyltrioxane, 1,1,7,7-tetramethoxy-1,7-divinyl-3,3,5, 5-tetramethyltetraoxane, 1,1,5,5-tetramethoxy-3,3-dimethyltrioxane, 1,1,7,7-tetraethoxy-3, 3,5,5-tetramethyltetraoxane, 1,1,5,5-tetraethoxy-3,3-dimethyltrioxane, 1,1,5,5-tetramethoxy Base-1,5-[2-(3,4-epoxycyclohexyl)ethyl]-3,3-diphenyltrioxane, 1,1,5,5-tetramethoxy-1, 5-(3-glycidyloxygen Propyl)-3,3-diphenyltrioxane, 1,5-dimethyl-1,5-dimethoxy-1,5-2-(3,4-epoxycyclohexyl) -3,3-diphenyltrioxane, 1,5-dimethyl-1,5-dimethoxy-1,5-(3-glycidoxypropyl)-3,3 - Diphenyltrioxane, to name a few.

The additive added to the composition (after polymerization of the oxoxane material as indicated above) may be a decane compound having the formula: R ¹ _a R ² _b SiR ³ _4-(a+b) wherein R ¹ is reactive a group such as a hydroxyl group, an alkoxy group or an ethoxy group, R ² is an alkyl group or an aryl group, and R ³ is a crosslinking compound such as an epoxy group, a propylene oxide group, an alkenyl group, an acrylate group or an alkynyl group, a =0 to 1 and b=0 to 1.

Examples of such additives are tris-(3-glycidoxypropyl)phenylnonane, tris-[2-(3,4-epoxycyclohexyl)ethyl]phenylnonane, tris-(3-methyl) Propylene oxy)phenyl decane, tris-(3-propenyl oxy)phenyl decane, tetra-(3-glycidoxypropyl) decane, tetra-[2-(3,4-epoxy) Cyclohexyl)ethyl]decane, tetrakis-(3-methylpropenyloxy)decane, tetrakis-(3-propenyloxy)decane, tris-(3-glycidoxypropyl)-p-tolyldecane , tris-[2-(3,4-epoxycyclohexyl)ethyl]p-tolyldecane, tris-(3-methylpropenyloxy)p-tolyldecane, tris-(3-propenyloxyl) P-tolyldecane, tris-(3-glycidoxypropyl)hydroxydecane, tris-[2-(3,4-epoxycyclohexyl)ethyl]hydroxydecane, tris-(3-methylpropene)醯oxy)hydroxydecane, tris-(3-propenyloxy)hydroxydecane.

The additive may also be any organic or fluorenone polymer that may or may not react with the primary polymer matrix and thus act as a plasticizer, softener or matrix modifier such as anthrone. The additive may also be an inorganic polycondensate such as SiOx, TiOx, AlOx, TaOx, HfOx, ZrOx, SnOx, polyazane.

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, tantalum, tin, bismuth-tin alloy, silver plated. Fiber, nickel-plated copper, silver-plated and nickel-copper, gold-plated copper, gold-plated and nickel-copper, or it may be a polymer of gold, silver-gold, silver, nickel, tin, platinum, titanium, such as polyacrylate, Polystyrene or anthrone, but is not limited thereto. The filler may also be a semiconductor material such as germanium, n-type or p-type doped germanium, GaN, InGaN, GaAs, InP, SiC, but is not limited thereto. Further, the filler may be a quantum dot or a surface plasmonic particle or a phosphor particle. 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 a particle which is any suitable metal or semi-metal particle such as selected from the group consisting of gold, silver, copper, platinum, palladium, indium, iron, nickel, aluminum, carbon, cobalt, cerium, zinc, molybdenum, titanium, Tungsten, silver plated copper, silver plated aluminum, tantalum, tin, bismuth-tin alloy, silver plated fiber or alloy or combination thereof. It is expected to be a metal particle of a transition metal particle (whether a front transition metal or a late transition metal), like a semimetal and a metalloid. Semi-metal or metalloid particles such as arsenic, antimony, bismuth, antimony, bismuth and antimony are envisioned.

Alternatively, it may be a non-conductive material such as cerium oxide, quartz, alumina, aluminum nitride, aluminum nitride coated with cerium oxide, cerium sulfate, aluminum trihydrate, boron nitride or the like. The filler can be in the form of particles or flakes and can be micron or nanometer in size. Fillers may include ceramic compound particles which are nitrides of metal or semimetal, nitrogen oxides, carbides, and carbon oxides. In particular, the filler may be particles, which are cerium, zinc, aluminum, lanthanum, cerium, tungsten, titanium lanthanum, titanium, lanthanum, calcium, nickel, nickel cobalt, molybdenum, magnesium, manganese, lanthanides, Ceramic particles of iron, indium tin, copper, cobalt aluminum, chromium, barium or calcium oxides.

It is also possible to include particles of carbon and selected from the group consisting of carbon black, graphite, graphene, diamond, niobium carbonitride, titanium carbonitride, nanobud, and carbon nanotubes. The particles of the filler may be carbide particles such as iron carbide, tantalum 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, tantalum nitride, indium nitride, Gallium nitride or carbon nitride.

Depending on the end application, any suitable size of particles can be used. In many cases, small particles having 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 such as from 1 nanometer to 500 nanometers, such as less than 200 nanometers, such as from 1 nanometer to 100 nanometers, or even less than 10 nanometers. In other examples, particles having an average particle size of from 5 nanometers to 50 nanometers, or from 15 nanometers to 75 nanometers, less than 100 nanometers, or from 50 nanometers to 500 nanometers are provided. Not elongated, such as substantially spherical or square particles, or sheets having a flat disc-like appearance (with smooth edges or rough edges), such as elongated whiskers, cylinders, wires, and other elongated particles, such as having 5: Particles of 1 or greater, or an aspect ratio of 10:1 or greater. Very elongated 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 the nanowire or nanotube is the reference minimum size (width or diameter) because the length can be quite long, even up to several centimeters. As used herein, the term "average particle size" means that the diameter of 50% by volume of the particles is less than the D50 value at the cumulative volume distribution curve of the value.

The particle may be a mixture of particles as referred to elsewhere herein, wherein the first group of particles having an average particle size greater than 200 nanometers is provided with a second group of particles having an average particle size of less than 200 nanometers, such as the average of the first group. The particle size is greater than 500 nanometers and the second group has an average particle size of less than 100 nanometers (eg, the first group has an average particle size greater than 1 micron, the second group has a particle size 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 less than the particles of the same material having an increased micron size. In one example, the smaller particles have an average particle size of less than 1 micron and are melted or sintered at a temperature less than the overall temperature of the same material. The melting and sintering temperatures will vary depending on the selected particle material and the average particle size.

As an example, very small silver nanoparticles can be melted below 120 ° C and sintered at even lower temperatures. Thus, if necessary, the melting or sintering temperature of the smaller particles can be equal to or lower than the curing temperature of the polymer to form a melting or sintering that joins the larger particles together before the complete crosslinking and solidification of the siloxane polymer material. The net of particles. In one example, the smaller particles melt or sinter with larger particles at temperatures below 130 ° C, such as below 120 ° C, or even below 110 ° C, while the decane materials are at higher temperatures Substantially cross-linking, for example substantially sintering or melting below 110 ° C, but substantial polymerization at greater than 110 ° C (or for example sintering or melting below 120 ° C (or 130 ° C), but in Substantial polymerization above 120 ° C (or 130 ° C)). The sintering or melting of the smaller particles prior to substantial polymerization of the siloxane material allows the formed metal "mesh" to have greater interconnectivity which increases the final conductivity of the cured layer. Substantial polymerization prior to substantial sintering or melting of the smaller particles reduces the amount of metal "mesh" formed and reduces the conductivity of the final cured layer. Of course, it is also possible to provide only particles of smaller average particle size (e.g., sub-micron size) which still achieve lower sintering and melting points than the same bulk (or, for example, the same particles having an average particle size greater than 1 micron). benefit.

In order to enhance the coupling with the filler and the siloxane polymer, a coupling agent can be used. This coupling agent will increase the adhesion between the filler and the polymer and thus increase the thermal conductivity and/or conductivity of the final product. The coupling agent may be any decane monomer having the formula: R ¹³ _h R ¹⁴ _i SiR ¹⁵ _j wherein R ¹³ is a reactive group such as a halogen, a hydroxyl group, an alkoxy group, an ethyl fluorenyl group or an ethoxylated group, R ¹⁴ is an alkyl or aryl group, and R ¹⁵ is a functional group such as an epoxy group, an acid anhydride, a cyano group, a propylene oxide, an amine, a decyl group, an allyl group, an alkenyl group or an 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, the siloxane polymer, the curing agent, and the additive when the final product is prepared or the filler particles can be treated with the coupling agent before it is mixed with the particles.

If the particles are treated with a coupling agent prior to use in the final formulation, different methods can be used, such as deposition from an alcohol solution, deposition from aqueous solution, bulk deposition onto a filler, and anhydrous liquid phase deposition. In the deposition from the alcohol solution, an alcohol/water solution was prepared and the pH of the solution was adjusted to be slightly acidic (pH 4.5-5.5). Oxane was added to this solution and mixed for a few minutes to allow partial hydrolysis. Next, the filler particles are added and the solution is mixed from room temperature to reflux temperature for various periods of time. After mixing, the particles were filtered, rinsed with ethanol and dried in an oven to obtain surface treated particles by coupling agent. The deposition from aqueous solution is similar to the deposition from an alcohol solution, but using pure water instead of alcohol as a solvent. If a non-amine functionalization is used, the pH is again adjusted by the acid. After mixing the particles with the water/decane mixture, the particles are filtered, rinsed and dried.

A large number of deposition methods are methods in which the decane coupling agent is mixed with the solvent without any water or pH adjustment. The filler particles are coated with a solution of stanol using different methods such as spraying and then dried in an oven.

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

Examples of such decane coupling agents are bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, allyltrimethoxydecane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropylmethyldiethoxydecane, 3- Aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, (N-trimethoxydecylpropyl)polyethylenediamine, trimethoxydecylpropyldiethylidene Amine, phenyltriethoxydecane, phenyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 1-trimethoxyindolyl-2(p-,i-chloromethyl)phenylethane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, propyl isocyanate triethoxydecane, bis[3-(triethoxy) Mercapto)propyl]tetrasulfide, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 2- (diphenylphosphino)ethyltriethoxydecane, 1,3-divinyltetramethyldiazepine, hexamethyldioxane, 3-(N-phenylethyl) Alkenylmethyl-2-aminoethylamino)propyltrimethoxydecane, N-(triethoxydecylpropyl)urea, 1,3-divinyltetramethyldiazepine, ethylene Triethoxy decane and vinyl trimethoxy decane, to name a few.

Depending on the type of particles added, the siloxane-particle-cured final product may be a thermally conductive layer or film, such as having greater than 0.5 watts/meter gram (W/(m·K) after final thermal or UV curing. )) thermal conductivity. Higher thermal conductivity materials are possible depending on the type of particles selected. The metal particles in the oxane composition can produce a thermal conductivity greater than 2.0 watts per meter per gram, such as greater than 4.0 watts per meter per gram of gram or even greater than 10.0 watts per meter per gram of solidification. The final film. Depending on the end application, a higher thermal conductivity may be required, such as greater than 50.0 watts per meter per gram of gram, or even greater than 100.0 watts per meter per gram. However, in other applications, the particles may be selected to produce a material having a lower thermal conductivity, if necessary, such as where the siloxane oxide material is a transmissive layer as may be present as mentioned above.

Further, if necessary, the final cured product may have a low electrical resistivity such as less than 1 × 10 ^-3 Ω·m, preferably less than 1 × 10 ^-5 Ω·m, and more preferably less than 1 × 10 ^-7 Ω·m. Further, the sheet resistance of the deposited film is preferably less than 100,000, more preferably less than 10,000. However, many of the desired end uses of the material can have high electrical resistivity.

In some cases, particularly where the composition will be applied to a device that requires optical features, although in some cases it may be desirable to have a final cure of the siloxane to have optical absorption characteristics, it is more likely that the material will desirably be highly transmissive in the visible spectrum. Light (or within the spectrum of the operating device), or light that would desirably be highly reflective within the visible spectrum (or within the spectrum of the operating device). As an example of a transparent material, a final cured layer having a thickness of from 1 micron to 50 microns will transmit at least 85% of visible light incident thereto, 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 the light incident thereon, preferably reflecting at least 95% of the light incident thereon at an angle of 90 degrees.

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

Among the suitable stabilizers or antioxidants contained 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 sterically bulky free radical phenolic compounds which also have very close proximity to their phenolic hydroxyl groups. In particular, the third butyl group is typically substituted on the phenyl ring with at least one ortho position relative to the phenolic hydroxyl group. The presence of such three-dimensionally large substituted radicals in the vicinity of the hydroxyl group serves to retard its stretching frequency and correspondingly retard its reactivity; this steric hindrance thus provides a phenolic compound having its stable properties. Representative hindered phenols include: 1,3,5-trimethyl-2,4,6-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-benzene; tetra-3( 3,5-di-t-butyl-4-hydroxyphenyl)-isopretide propionate; 3 (3,5-di-t-butyl-4-hydroxyphenyl)-propionic acid Octacol ester; 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-third 4-hydroxy-benzoic acid di-n-octylthio)ethyl ester; and sorbitol hexa[3-(3,5-di-t-butyl-4-hydroxy-phenyl)-propionate]. Commercial examples of antioxidants are, for example, Yanjia Knox 1035, Yanjia Knox 1010, Yana Knox 1076, Yana Knox 1098, Yana Knox 3114, Yana Knox PS800, Yan Jianuo Kesi PS802, Yan Jianuokesi 168.

The weight ratio between the siloxane polymer and the filler is between 100:0 and 5:95, depending on the end use of the product. The ratio between the siloxane polymer and the crosslinked ruthenium or non-ruthenium resin or oligomer is between 100:0 and 75:25. The amount of the curing agent calculated from the amount of the decane polymer is from 0.1% to 20%. The amount of the adhesion promoter based on the total amount of the formulation is from 0 to 10%. The amount of antioxidant based on the total weight of the formulation is from 0 to 5%.

The decane-particle composition can be used in a variety of fields. It can be used as an electronics or optoelectronics package, LED and OLED front-end and back-end processing, 3D, photovoltaic and display metallization, replacement of solder bumps such as semiconductor bumps, printed electronics, OLED low work function cathodes Ink, ITO replacement inks, metal grids 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 An adhesive or sealant in the dielectric, to name a few.

Depending on the curing mechanism and the type of catalyst activation, the final formulation typically cures 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 alkane polymer formed from the polymerized first compound and the second compound is from about 300 g/m to 10,000 g/mole, preferably from about 400 g/m to 5,000 g/m, and more preferably About 500 grams / mole to 2,000 grams / mole. The polymer is combined with particles of any desired size and preferably has an average particle size of less than 100 microns, more preferably less than 50 microns, or even less than 20 microns. The siloxane polymer is added in an amount of 10% to 90% by weight, and the particles are added in an amount of 1% to 90% by weight. If the end use of the decane material requires optical clarity, the particles can be ceramic particles added at a lower weight percent, such as from 1% to 20% by weight. If conductivity is required, such as when a siloxane material is used in a semiconductor package, the particles may be metal particles added at 60% to 95% by weight.

Polymerization of the first compound and the second compound is carried out, and the particles are mixed therewith to form a viscosity of 50 MPa-sec to 100,000 MPa-sec, preferably 1000 MPa-sec to 75,000 MPa-sec and more preferably 5,000 MPa. - Second to 50,000 MPa-sec viscous fluid. Viscosity can be measured by a viscometer, such as a Brookfield viscometer or Cole-Parmer viscosity meter, which rotates a disk or cylinder in a fluid sample and measures against The torque required to induce viscous resistance to exercise. It can be rotated at any desired rate, such as from 1 rpm to 30 rpm, preferably 5 rpm, and preferably measured at 25 °C.

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

The compositions as disclosed herein are preferably free of any substantial solvent. A solvent may be temporarily added, such as for mixing a curing agent or other additive with a polymeric viscous material. In this case, for example, a curing agent is mixed with a solvent to form a fluid material that can be subsequently mixed with the viscous siloxane polymer. However, due to the need to transport the substantially solvent-free composition to the customer, and subsequently to the customer's device, the temporarily added solvent is removed in the drying chamber. However, although the composition is substantially free of solvent, there may be trace amounts of residual solvent that cannot be removed during the drying process. The removal of this solvent by reducing shrinkage during the final curing process aids in the deposition of the compositions disclosed herein, minimizes shrinkage over time during the life of the device, and aids during the life of the device The thermal stability of the material.

Knowing the final application of the composition, the desired viscosity of the composition, and the particles to be included, it is possible to fine tune the siloxane polymer (starting compound, molecular weight, viscosity, etc.) so that when incorporated with particles and other components In the composition, the final characteristics required for subsequent delivery to the customer are achieved. Due to the stability of the composition, it is possible to transport the composition at ambient temperature without any substantial change in molecular weight or viscosity, even one week after manufacture or even one month until the end of the customer's use. Instance

The following examples of naphthenic polymers are provided to illustrate the invention and are not intended to be limiting.

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

Alkane polymer i: diphenyldecanediol (60 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxydecane (55.67 g, 36.7 mol) %) and tetramethoxynonane (17.20 grams, 18,3 mole %) were filled with 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 cesium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the mixture of decane. The decane mixture was stirred at 80 ° C for 30 minutes during the reaction of diphenyl decanediol with alkoxy decane. After 30 minutes, the formed methanol was evaporated under vacuum. The siloxane polymer has a viscosity of 1000 mPas and a Mw of 1100.

Alkane polymer ii: diphenyldecanediol (30 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxydecane (28.1 g, 37 mol) %) and dimethyldimethoxydecane (6.67 g, 18 mol%) were filled with 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 cesium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the mixture of decane. The decane mixture was stirred at 80 ° C for 30 minutes during the reaction of diphenyl decanediol with alkoxy decane. After 30 minutes, the methanol formed was evaporated under vacuum. The siloxane polymer has a viscosity of 2,750 mPas and a Mw of 896.

Alkoxylate polymer iii: diphenyldecanediol (24.5 g, 50 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxydecane (18.64 g, 33.4 mol) %) and tetramethoxynonane (5.75 g, 16.7 mol%) were filled with 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 cesium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the mixture of decane. The decane mixture was stirred at 80 ° C for 30 minutes during the reaction of diphenyl decanediol with alkoxy decane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the siloxane polymer was 7313 mPas and the Mw was 1328.

Alkane polymer iv: diphenyldecanediol (15 g, 50 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxydecane (13.29 g, 38.9 mol) %) and bis(trimethoxyindenyl)ethane (4.17 g, 11.1 mol%) were filled with 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 cesium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the mixture of decane. The decane mixture was stirred at 80 ° C for 30 minutes during the reaction of diphenyl decanediol with alkoxy decane. After 30 minutes, the methanol formed was evaporated under vacuum. The siloxane polymer has a viscosity of 1788 mPas and a Mw of 1590.

Alkoxysilane polymer v: diphenyldecanediol (15 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxydecane (13.29 g, 35 mol) %) and vinyltrimethoxydecane (4.57 g, 20 mol%) were filled with 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 0.018 g of cesium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the mixture of decane. The decane mixture was stirred at 80 ° C for 30 minutes during the reaction of diphenyl decanediol with alkoxy decane. After 30 minutes, the formed methanol was evaporated under vacuum. The viscosity of the siloxane polymer was 1087 mPas and the Mw was 1004.

The decane polymer vi: diisopropyl decanediol (20.05 g, 55.55 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxydecane (20.0 g, 33.33 Mo) Ear %) and bis(trimethoxydecyl)ethane (7.3 g, 11.11 mol%) were filled with 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 cesium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the mixture of decane. The decane mixture was stirred at 80 ° C for 30 minutes during the reaction of diphenyl decanediol with alkoxy decane. After 30 minutes, the formed methanol was evaporated under vacuum. The siloxane polymer has a viscosity of 150 mPas and a Mw of 781.

The siloxane polymer vii: diisobutyl decanediol (18.6 g, 60 mol%) and 2-(3,4-epoxycyclohexyl)ethyl]trimethoxydecane (17.32 g, 40 mol) Ear %) was filled with 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 cesium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the mixture of decane. The decane mixture was stirred at 80 ° C for 30 minutes during the reaction of diphenyl decanediol with alkoxy decane. After 30 minutes, the formed methanol was evaporated under vacuum. The siloxane polymer has a viscosity of 75 mPas and a Mw of 710. Composition example

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

Comparative Example 1, silver-filled adhesive: a silver plate having a cyclooxy group as a crosslinking functional group (18.3 g, 18.3%) and an average size (D50) of 4 μm using a high shear mixer (81 g, 81%) 3-propyl methacrylate trimethoxy decane (0.5 g, 0.5%) and Jinshi Industrial K-PURE CXC-1612 thermal acid generator (0.2%) were mixed together. The composition has a viscosity of 15,000 mPas.

Comparative Example 2, alumina-filled adhesive: an aluminoxane polymer having an epoxy group as a crosslinking functional group (44.55 g, 44.45%) and an average size (D50) of 0.9 μm using a three-roll mill (53 grams, 53%), 3-propyl methacrylate trimethoxy decane (1 gram, 1%), Yanjia Nokesi 1173 (1 gram, 1%) and Jinshi Industrial K-PURE CXC-1612 heat The acid generator (0.45 grams, 0.45%) was mixed together. The composition has a viscosity of 20,000 mPas.

Comparative Example 3, BN-filled adhesive: boron nitride polymer (60 g, 60%) having an epoxy group as a crosslinking functional group and boron nitride having an average size (D50) of 15 μm using a three-roll mill Sheet (35 g, 35%), Yanka Nok 1173 (1.3 g, 1.3%), 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (3.4 g, 3.4%) and Jinshi Industrial K-PURE CXC-1612 hot acid generator (0.3 g, 0.3%) was mixed together. The composition has a viscosity of 25,000 mPas.

Comparative Example 4, translucent material: a haze-like cerium oxide having a methacrylate-functional oxirane polymer (89 g, 89%) and an average size (D50) of 0.007 μm using a three-roll mill (5 grams, 5%), Yanjia Nokesi 1173 (2 grams, 2%) and Yanjiagu 917 photoinitiator (4 grams, 4%) mixed together. The composition has a viscosity of 25,000 mPas.

Comparative Example 5, transparent material: diphenyldecanediol (20.0 g, 92 mmol), 9-phenanthryl trimethoxydecane (16.6 g, 56 mmol), 3-methylpropene oxime Propyltrimethoxydecane (9.2 g, 37 mmol) and BaO (25 mg) in methanol were placed in a 100 mL flask and refluxed for 1 hour. The volatiles were evaporated under reduced pressure. A clear polymer resin (37 grams) was obtained.

Comparative Example 6, high refractive index material: 8.6 g of a polymer resin having a high refractive index prepared as described in Example X1 in a solution of 5.7 g of ZrO ₂ nanoparticle particles at a solid content of 50% of 1,2-propanediol Blend in methyl ether acetate (PGMEA). 0.26 g of photoinitiator (Darocur 1173), 0.4 g of oligomeric 3-methacryloxypropyltrimethoxydecane as a promoter, and 20 mg of surfactant (Bick Chemical BYK-307) (BYK Chemie) was added to the solution.

The material obtained was spin coated onto a 100 mm tantalum wafer at 2000 rpm. The film was baked on a hot plate at 80 ° C for 5 minutes and UV cured at a dose of 3000 mJ/cm 2 . The refractive index is adjusted by changing the weight ratio of the polymer resin to the ZrO ₂ nanoparticle.

If the oxoxane composition as disclosed herein is disposed within the optical path of the light emitted by the LED and is selected to be optically transmissive to visible (or UV) light, then the selected aluminoxane particle material can be selected To choose the refractive index. A refractive index of 1.25 to 2.0, such as 1.4 to 1.7 or other desired values (1.5 to 1.9, 1.25 to 1.45, etc.) may be provided, wherein the refractive index is measured at a wavelength of 632.8 nm. A higher refractive index can be achieved by providing a metal-containing monomer polymerized into the siloxane polymer, for example, higher than glass, such as a refractive index of 1.6 to 2.0. As described above, it is possible to obtain a [Si-O-Me-O]n (where Me is a metal) main chain. Metal-containing monomers having a metal such as titanium, tantalum, aluminum, zirconium, hafnium or selenium in particular can help increase the refractive index. Such metal-containing monomers may be used in place of the first compound, the second or third compound as mentioned above, or in addition.

In addition, it is possible to increase the refractive index based on the choice of particles (alternatively or in addition to incorporating the metal into the oxoxane polymer as described above). Certain oxide particles, particularly oxides such as titanium, tantalum, aluminum, zirconium, hafnium or selenium, can help increase the refractive index. Additionally, a coupling agent that incorporates particles into the siloxane polymer can be selected to help increase the refractive index. As an example, mention may be made of a coupling agent having the formula: R ¹⁶ Ar) _i SiR ¹ _j wherein i=1 or 2, and j=4-i, R ¹⁶ is a oxoxane when heat or UV light is applied The polymer undergoes a crosslinked functional crosslinking group, Ar is an aryl group, and wherein R ¹ is a reactive group such as a hydroxyl group, a halogen, an alkoxy group, a carboxyl group, an amine or a decyloxy group.

Thus, a compound includes a deuterium atom bonded to one or two aryl groups (the aryl group has a crosslinking substituent) and the deuterium atom is also bonded to two or three reactive groups, preferably an alkoxy group. The aryl group may be phenyl, naphthalene, phenanthrene, anthracene or the like. The R ₁₆ functional crosslinking group can be an epoxy group, an acrylate, a vinyl group, an allyl group, an acetylene, an alcohol, an amine, a thiol, a stanol or the like. The coupling agent may also be selected to have a metal atom such as titanium, ruthenium, aluminum, zirconium, hafnium or selenium instead of ruthenium.

As can be seen in Figure 6, the refractive index of the cured siloxane oxide material as disclosed herein is plotted against the wavelength of the light, and each of the figures has a different amount of particles as part of the decane material, wherein Particles were added to the composition to 75% particle loading. As can be seen in Figure 6, a refractive index of 1.60 or greater in the visible spectrum can be achieved without particles, and in this example a refractive index of 1.70 or greater in the visible spectrum can be achieved with particles. As can be seen in Figure 7, the % transmittance of the siloxane material is plotted against the wavelength of the light. As illustrated in this figure, it is plotted from no particles to 75% different particle loadings and has a % transmittance of visible light greater than 90% (actually greater than 95%) in the visible spectrum. Thus, even a paraxane material loaded with high % particles is extremely transparent and suitable for a variety of optical applications, such as LED lamps.

A stable composition is formed in consideration of the disclosed methods and materials. The composition may have a portion of a siloxane polymer having a [-Si-O-Si-O]n repeating backbone having an alkyl or aryl group and having functional crosslinks on the backbone The group, and another portion, is a particle that is mixed with a oxoxane material, wherein the particles have an average particle size of 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 may have a molecular weight of from 300 gram/mol to 10,000 gram/mol and a viscosity of from 1000 MPa to 75,000 MPa-second at a 5 rpm viscometer.

The viscous (or liquid) siloxane polymer is substantially free of -OH groups, thus providing an extended shelf life and allowing storage or transport at ambient temperatures if necessary. Preferably, the decane material does not have a -OH peak detectable by FTIR analysis. The stability of the formed naphthenic material is increased to allow storage prior to use, wherein the increase in viscosity (crosslinking) during storage is minimal, such as less than 25% during 2 weeks of storage at room temperature, preferably 2 weeks The time period is 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 traces of residue remaining after drying to remove the solvent), avoiding solvent trapping subsequently formed in the layer of the final product. Problems such as shrinkage during polymerization and loss of quality over time during use of the device. Without the application of heat or UV light preferably greater than 100 ° C, substantial cross-linking does not occur during shipping and storage.

When the composition is deposited and polymerized (e.g., by application of heat or UV light), minimal shrinkage or reduction in mass is observed. In Figure 8, the x-axis is time (in minutes), the left y-axis is the mass of the layer in terms of % of the starting mass, and the right y-axis is the temperature in degrees Celsius. As can be seen in Figure 8, the mixture of oxoxane particles as disclosed herein was rapidly heated to 150 °C, followed by holding at 150 °C for approximately 30 minutes. In this example, the siloxane oxide particles have a Si-O backbone having a phenyl group and an epoxy group, and the particles are silver particles. After heat curing over this period, the mass loss is less than 1%. Desirably, the mass loss is typically less than 4%, and typically less than 2%. However, in many cases, the mass difference of the siloxane oxide 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 less, more typically 150 ° C or less. However, lower curing temperatures are possible, such as 125 ° C or lower.

As can be seen in Figure 9, 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 has been deposited and The polymerization and, if desired, hardening, the layer or mass of the siloxane layer is extremely thermally stable. For example, the in-situ material is heated to 600 ° C at a temperature increase rate of 10 ° C per minute after thermal polymerization or UV polymerization hardening, and less than 4.0% is observed at 200 ° C and 300 ° C, preferably. A mass loss of less than 2.0%, such as less than 1.0% (typically a mass loss of less than 0.5% is observed at 200 °C, or as in the example of Figure 9, a mass loss of less than 0.2% 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 of Figure 9. Similar results were observed by heating the polymeric material for only 1 hour at 200 ° C, or 300 ° C. It is possible to heat the polymeric deposition material by less than 1% mass loss at 375 ° C or above 375 ° C for at least one hour. As can be seen in Figure 9, a mass loss of 5% or less was observed even at temperatures greater than 500 °C. Such thermally stable materials are desirable, and in particular may be deposited at low temperatures (eg, below 175 ° C, preferably below 150 ° C, or below 130 ° C, 30 minutes curing / baking time), or may be borrowed A thermally stable material as disclosed herein polymerized by UV light.

There are many alternatives to LED lamps having a oxoxane material as disclosed herein. For example, in Figure 10a, the die 51 can be bonded to the package substrate 50 and covered with the cover substrate 52, with or without particles or phosphors or other wavelength shifts, depending on the desired use of the lamp. The element's helium oxide sealant 53 is filled. Alternatively, as seen in Figure 10b, a conformal layer 55 can be applied which is a decane material (with or without added particles, as desired, with or without a phosphor). The area between the coating 55 and the cover 52 can also be filled with a decyl alkane sealant (with or without added particles). Alternatively, as can be seen in Figure 10c, only the grains 51 are covered with a paraxane material having particles and phosphors as appropriate. In this embodiment, typically, the decane material is added at the wafer level prior to grain singulation. Alternatively, as seen in Figure 10d, a distal phosphor layer 55 can be provided, such as a layer formed on the cover 52 (or alternatively a phosphor embedded within the cover 52). As with other examples, the oxane may or may not have particles, but in such instances from which light from the LED passes, the encapsulant is preferably optically transmissive. In Figures 10a-10d, the grains are in each case the substrate material mentioned with respect to the preceding examples, and may be attached to the package substrate via a siloxane oxide particle as disclosed herein, if necessary.

As can be seen from the above disclosure, the azide particle composition as disclosed above can be used as an adhesive, a protective layer, a portion of a wavelength shifting layer, or a visible light guiding lens (and other embodiments). If used as an adhesive, the material is preferably optically absorptive in the visible spectrum, and preferably transmits or reflects at least 75%, but preferably greater than 80%, or greater than 85% or even higher, such as greater than 90% or 95% of the visible light incident on it. As a wavelength shifting layer, a phosphor, luminophore, scintillator or other chemical element is incorporated therein and absorbs light at one wavelength and emits light at a second, different wavelength. Such a wavelength shifting element can be part of a first oxoxane composition layer proximate to a second lens comprising a decane composition without any wavelength shifting elements. Alternatively, the lens can include both a decane composition and a wavelength shifting element such as a phosphor. It is also possible that the siloxane oxide particle composition is present in the form of a conductive material, such as for flip chip bonding bumps, or for bonding wire bonds between substrates. The electrically conductive regions and patterned regions may also comprise a siloxane material in accordance with the present invention.

The foregoing description illustrates example embodiments and is not to be construed as limiting. Although a few example embodiments have been described, it will be apparent to those skilled in the art that many modifications are possible in the example embodiments without departing from the novel teachings. Accordingly, all such modifications are intended to be included within the scope of the invention as defined in the scope of the claims. Therefore, the present invention is to be understood as being limited to the specific embodiments of the invention, and the modifications of the disclosed embodiments and other embodiments are intended to be included within the scope of the appended claims. Industrial applicability

The disclosed compositions can be used, for example, as an adhesive, a thermally conductive layer, a sealant, a patterned conductive layer, a patterned dielectric layer, a transparent layer, an LED luminaire, and a light reflective layer in a lamp. The LED lamp of the present invention has various uses, for example, as an outdoor sign; an LED pixel array for a flat panel display; an LED backlight for an LCD display; an indoor screen for public events and public transportation; an outdoor screen such as sports or other public events Large screen; indoor and outdoor advertising screens; consumer electronics or LED lights on any equipment, device or mechanism used for the items; infrared LEDs, such as in remote controls; LEDs in traffic signals and road lighting; , headlights and interior lighting; flashlights; greenhouse lighting for indoor growth of agricultural products; and, in general, as an alternative to using incandescent or fluorescent lighting (and other embodiments). LEDs will dominate the lighting sector for the foreseeable future and play an important role in energy conservation, environmental protection and improved quality of life. Citation List Patent Document US 2009221783 US2012123054 WO20100267 US 2011171447 JP 2004225005

10, 10a, 10b‧‧‧ electrodes
12‧‧‧n-doped GaN region
13‧‧‧p-doped GaN region
14‧‧‧Sapphire substrate
16, 40, 42, 44‧‧‧ substrates
17‧‧‧ adhesive layer
19, 20, 30‧‧‧ package substrate
22‧‧‧ die attaching agent
24, 51‧‧‧ grain
25, 45‧‧ ‧ line combination
28‧‧‧phosphor layer
29‧‧‧Sealant layer
35‧‧‧phosphorescent materials
37‧‧‧Second sealing layer
41‧‧‧Semiconductor materials
43‧‧‧Binder
46‧‧‧Oxysiloxane particle adhesive
47, 48‧‧‧Electrical connection area
49‧‧‧Oxysiloxane materials
50‧‧‧Package substrate
52‧‧‧ Covering substrate
53‧‧‧矽Oxygen encapsulant
55‧‧‧Conformal layer

Fig. 1 illustrates an example of a light-emitting diode formed on a light-transmitting substrate. Fig. 2 illustrates an example of a light-emitting diode formed on a light-reflecting substrate. Figure 3 is an illustration of an LED with a front transparent sealant. Figure 4 is an illustration of an LED within a cavity having a sealant encapsulant within the cavity. Figure 5 illustrates an LED flip chip package. Figure 6 shows a plot of refractive index versus wavelength for different particle loadings. Figure 7 is a graph of transmittance versus particle loading. Figure 8 illustrates the mass change of the alkane polymer during the thermally induced polymerization. Figure 9 illustrates the thermal stability of the siloxane material after deposition and polymerization. Figures 10a through 10d illustrate additional examples of LED seals.

10a, 10b‧‧‧ electrodes

12‧‧‧n-doped GaN region

13‧‧‧p-doped GaN region

14‧‧‧Sapphire substrate

17‧‧‧ adhesive layer

19‧‧‧Support substrate or package substrate

Claims (20)

An LED lamp comprising: a die substrate, wherein the substrate is formed with a semiconductor material; an electrode for applying a bias voltage across the semiconductor material to cause light emitted from the semiconductor material; and an adhesive agent The die substrate is bonded to the support substrate, wherein the adhesive is a polymerized siloxane polymer having a thermal conductivity greater than 0.1 watts/meter gram (W/(m·K)), and wherein the The siloxane polymer has ruthenium and oxygen in the polymer backbone, and an aryl or alkyl group bonded to the polymer backbone, and wherein the binder further comprises particles having an average particle size of less than 100 microns; The adhesive does not absorb light and transmits or reflects at least 80% of the visible light incident thereon. The LED lamp of claim 1, wherein the siloxane polymer comprises an aryl group bonded to ruthenium in the oxane backbone. The LED lamp of any of the preceding claims, wherein the adhesive is a light reflecting layer that reflects at least 80% of light incident thereon at a 90 degree angle. The LED lamp of any of the preceding claims, wherein the adhesive is a light reflecting layer that reflects at least 90% of the light incident thereon at a 90 degree angle. An LED lamp according to any one of the preceding claims, wherein the siloxane polymer comprises an aryl group and wherein the particles comprise a transition metal selected from Groups 8 to 11 of the periodic table, and the average The particle size is less than 10 microns. The LED lamp of any of the preceding claims, wherein the adhesive is thermally stable, and the mass loss of the adhesive is less than 1% when heated to at least 200 °C. The LED lamp of any of the preceding claims, wherein the adhesive has a refractive index of 1.4 to 1.6. A method of manufacturing an LED lamp, comprising: forming a light emitting diode by providing a semiconductor material on a first substrate and doping the semiconductor material; providing a support substrate; providing an adhesive composition, the adhesive composition including a oxoxane polymer having hydrazine and oxygen in the polymer backbone, an aryl or alkyl group bonded to the polymer backbone, and a functional group bonded to the polymer backbone a binder group, the binder composition further comprising particles and a catalyst having an average particle size of less than 100 μm; depositing the binder composition to bond the first substrate to the support substrate; and applying temperature and/or light Activating a crosslinking group of the siloxane polymer to further polymerize the siloxane polymer and hardening the polymer while bonding the die substrate and the package substrate together, wherein the polymerized and hardened The siloxane polymer has a mass of at least 96% prior to polymerization after polymerization, and wherein the siloxane polymer does not absorb greater than 25% of visible light incident thereon. The method for producing an LED lamp according to claim 8, wherein the polyoxyalkylene polymer polymerized and hardened has a resistivity of less than 1 × 10 ^-3 Ω·m. The method of manufacturing an LED lamp according to Item 8 or 9, wherein the first particle group is silver-coated copper particles, and the second particle group is silver particles having an average particle size of less than 15 nm. The method for producing an LED lamp according to any one of claims 8 to 10, wherein the polymerized and hardened the siloxane polymer has at least 98% after polymerization after polymerization. quality. A sealing method for an LED device, comprising: forming a light emitting diode by providing a semiconductor material on a first substrate and doping the semiconductor material; providing a sealant composition comprising a siloxane polymerization The siloxane polymer has hydrazine and oxygen in the polymer backbone, an aryl or alkyl group bonded to the polymer backbone, and a functional crosslinking group bonded to the polymer backbone. The adhesive composition further includes particles and a catalyst having an average particle size of less than 10 microns; depositing the sealant composition to seal the light emitting diode; and applying temperature and/or light to activate the germanium oxide polymer a crosslinking group to further polymerize the siloxane polymer and to harden the polymer, wherein the polymerized and hardened oxirane polymer has a mass after polymerization of at least 96% compared to before polymerization And wherein the siloxane polymer does not absorb greater than 25% of visible light incident thereon. A sealing method for an LED device according to the patent application, wherein the phosphor comprises a YAG phosphor, or the phosphor comprises a nitride phosphor. The method of sealing an LED device according to claim 12, wherein the oxide particles are oxides of titanium, hafnium, aluminum, zirconium, hafnium or selenium. The sealing method of the LED device according to any one of claims 12 to 14, wherein the particles are nitride particles selected from the group consisting of aluminum nitride, tantalum nitride, boron nitride, and nitrogen. Titanium, copper nitride, molybdenum nitride, tungsten nitride, iron nitride, tantalum nitride, indium nitride, gallium nitride, and carbon nitride. The method of sealing an LED device according to any one of claims 12 to 15, wherein the particles comprise titanium oxide, aluminum oxide, aluminum nitride or boron nitride. The sealing method of the LED device according to any one of claims 12 to 16, wherein the sealant composition includes a photoinitiator, and ultraviolet light is applied to cure and harden the polymerization of the decane. Things. The sealing method of the LED device according to any one of claims 12 to 17, wherein the sealant composition comprises a heat curing agent, and the composition is cured at a temperature lower than 150 ° C. . The sealing method of the LED device according to any one of claims 12 to 18, wherein the curing temperature is lower than 100 °C. The sealing method of the LED device according to any one of claims 12 to 19, wherein the phosphor is supplied in the oxime at 2 g/cm 3 to 10 g/cm 3 .