TW201723033A - Dielectric film and making method thereof, display and making method thereof, composition, and touch panel - Google Patents

Abstract

A dielectric film and making method thereof, a display and making method thereof, a composition and a touch panel are provided. The method for making a dielectric film includes providing a substrate on which is deposited a siloxane starting material and particles, wherein the siloxane starting material has a siloxane polymer, a siloxane oligomer and/or silane monomers, and wherein the particles have an average particle size of less than 400 nm. After deposition, heat and/or electromagnetic energy is applied to the siloxane particle layer so as to cure the layer and form a dielectric film on the substrate. The formed film is optically transmissive to visible light and transmits at least 80% of the visible light incident thereon, and is electrically insulating and has a sheet resistance of 1000 [Omega]/sq or more.

Description

Dielectric siloxane oxide particle film and device having the same

This invention relates to dielectric films. In particular, the present invention relates to a membrane-containing alkane membrane, a method of producing such a membrane, a display comprising the membrane, and a method of producing such a display.

LEDs and LCDs appear in a variety of products, from lighting fixtures (LEDs) to displays (both LEDs and LCDs), such as consumer products and smart phones, tablets, laptops, computer monitors in homes or businesses. TV, monitor, and touch screen.

Both the LED device and the LCD device may include a dielectric layer. Such dielectric layers can be in the form of passivation layers, encapsulants, thick films or thin film dielectrics in LED devices or LCD devices. One area that appears is between the two conductive layers in the touch screen portion of the display.

Dielectric film materials are disclosed in US 2011051064, US 5645901, and KR 20120119020. Improved materials with stability and extended shelf life characteristics are still needed.

It is an object of the present invention to address at least some of the problems associated with known materials.

It is an object of the present invention to provide a dielectric film comprising a siloxane polymer and particles in a siloxane polymer.

Another object of the present invention is to provide a method of producing a silicone polymer film.

A third object of the invention is to provide a display.

A fourth object of the present invention is to provide a method of manufacturing a display.

A fifth object of the present invention is to provide a composition comprising a pyrithione polymer having a [-Si-O-Si-O]n repeating main chain and particles.

A sixth object of the present invention is to provide a touch panel.

According to the present invention, there is provided a dielectric film comprising a dielectric layer formed on a support substrate, the dielectric layer comprising a siloxane polymer and particles having an average particle size of less than 1 micron in the siloxane polymer; The dielectric layer is optically transmissive to visible light and transmits at least 75% of the light incident thereon; and wherein the dielectric layer is electrically insulating and has a sheet resistance of 1000 Ω/sq or greater.

Typically, the molecular weight of the siloxane polymer is from 300 gram per mole to 10,000 gram per mole; and wherein the composition has a viscosity of from 5 MPa to 75,000 MPa-second at a viscosity of 5 rpm and at 25 ° C; And wherein it is substantially free of -OH groups.

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

Achieve considerable advantages. Thus, optically transparent, electrically insulating, nanoparticle-heloxane composite dielectrics are disclosed, along with devices containing the same. The non-conductive particles can be spherical, branched, flake or wire deposited within or surrounded by the oxoxane composite. In all cases, high optical transmission was achieved at a refractive index between 1.2 and 2.0.

The coating can also be patterned according to various patterning methods disclosed herein. The formed transparent electrically insulating dielectric preferably comprises at least one type of electrically insulating particles, such as high aspect ratio particles, such as flakes, and at least one type of hafoxygen polymer. Additional low aspect ratio particles (eg, nanoparticles) may be included as necessary to adjust the refractive index, thermal conductivity, electrical conductivity, mechanical properties, thermal stability, or chemical resistance of the film.

As disclosed herein, the transparent insulating dielectric can be a touch sensor, a display, an OLED device, a vertical emitter InGaN LED, a portion of an IME mask, or any other device that can benefit from an electrically insulating film and a transparent film. Part of it.

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

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 term "comprising", when used in the specification, is intended to mean the existence of the stated features, steps, operations, components and/or components, but does not exclude the addition of one or more other features, steps, operations, components And / or its ethnic groups.

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

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.

As disclosed herein, novel siloxane oxide particle compositions that are optically transmissive and electrically insulating in the visible spectrum can be used in semiconductor devices utilizing electrically insulating layers and in microelectronic and optoelectronic devices, such as displays (eg, LED displays, such as OLED/ In AMOLED or LCD display). Specifically, but not limited to, touch screen displays, such as resistive or capacitive touch screens for smart phones, tablets, laptops and notebooks, computer monitors, and digital cameras, Touch screens for video recorders, portable gaming devices, personal media players, e-book readers, printing presses, car displays, GPS/PND navigation devices, and touch screens in retail, commercial and industrial environments.

However, non-touch screen versions of such products may also benefit from the siloxane oxide insulating and light transmissive materials as disclosed herein.

As discussed above, both the LED device and the LCD device can comprise a dielectric layer. Such dielectric layers may be present in the LED device or LCD device in the form of a passivation layer, encapsulant, thick film or thin film dielectric. One area that appears is between the two conductive layers in the touch screen portion of the display. The following examples are directed to touch screen displays, however, dielectric materials as disclosed herein can be used anywhere in a region where a dielectric material is desired, and in particular, in photovoltaic devices that require a transparent insulating material.

In a resistive touch screen, a flexible transparent top substrate (eg, a plastic film, such as polyester) is placed spaced apart from a more rigid bottom substrate (eg, a glass substrate) with an air gap therebetween. When the user's finger touches the flexible top substrate, it bends to make contact with the bottom substrate. The voltage at the contact point can be measured and the position of the contact point calculated. In a capacitive touch panel, an additional one or more substrates are attached to a display (eg, an array of LCDs or LED pixels), which may be any suitable material, such as glass, polyester, acrylic, and the like. The substrate has a matrix of conductive lines with a dielectric layer therebetween. The cap lens is bonded to enclose the entire assembly. When the user's finger touches the substrate, it increases the measurement capacitance of the electrode closest to the touch point, wherein the change of the capacitance can be measured and used to calculate the touch position. Examples of surface capacitance or projected capacitance can include conductive materials as disclosed herein. The various substrates are part of a display, such as a substrate on which a color filter is formed, a substrate on which a TFT array is formed, a cover substrate, etc., and are bonded together by an adhesive which is preferably insulated and highly transparent to visible light. Regardless of whether the layer serves as a capacitor, a passivation layer or a sealing layer, an adhesive, or the like, the dielectric between the two conductive layers, a transparent and insulating film of a siloxane oxide particle as disclosed herein is applicable.

Figure 1 is a cross-sectional view of a touch screen capacitive display on a unit. As can be seen in this figure, the substrate 2 (which may be suitable for a transparent substrate such as glass or polymer) has a polarizer layer 1 thereon. A thin film transistor array 3 and a liquid crystal cell array 4 are formed on the glass. A VCOM layer 5 (common electrode) and a color filter 6 are placed on the glass substrate 7. The touch sensitive portion of the device is formed from a patterned conductive layer 8, an insulating layer 9, and a patterned conductive layer 10. In the patterned layer 10, the pattern lines emerge from the page, and in layer 8, the pattern runs orthogonally to the lines in layer 10 (i.e., horizontally in the left-right direction on the page). Disposed between the two conductive layers 8 and 10 is a dielectric layer 9. The second polarizer is shown as layer 11, and cover glass 13 is bonded to the remainder of the structure via adhesive layer 12.

In FIG. 1, dielectric layer 9 and adhesive layer 12 can be transparent and insulating layers of siloxane oxide particles as disclosed herein having the same or different formulations. Although the dielectric layer may be free of particles, it preferably includes particles such as ceramic particles having an average particle size of less than 1 micron. The transparency and refractive index can be tuned depending on the selected alkane material and the particle material and size (as discussed below). It is also possible that the conductive portions of the device, such as patterned layer 8 and patterned layer 10, are also made of a siloxane oxide material, as will be discussed in greater depth below. The use of the same or similar materials for multiple layers of electrical insulation and electrical conduction in the device helps match the CTE and refractive index and can improve the overall optical and end-of-life quality of the device.

2 is a cross-sectional view of a touch screen capacitive display in a cell. As can be seen in FIG. 2, a polarizing layer 21 and a thin film transistor array 23 are provided on the glass substrate 22. A capacitive touch screen portion of the display is provided thereon with an insulating layer 25 between the conductive layer 24 and the conductive layer 26. In this example, the patterned wires in layer 26 protrude from the page, while the patterned lines of layer 24 run horizontally from left to right on the page. The LCD unit layer 27 and the color filter 28 on the transparent substrate 29 are also explained. Further, a polarizing layer 30 and an adhesive layer 31 are provided for bonding the additional transparent substrate 32 on the top. The transparent substrate of Figures 1 and 2 can be independently made of glass or polymer (polyester/polyethylene terephthalate, acrylic/polymethyl methacrylate, etc.) or other suitable light transmissive substrate. As with FIG. 1, the adhesive layer 31 and the insulating layer 25 may be made of an insulating and light-transmitting aluminoxane particle material. Additionally, conductive layer 24 and conductive layer 26 may also be made of a material that is electrically conductive and highly transparent to visible light, as will be discussed further below.

As seen in Figure 3, the cross-section of an exemplary capacitive touch display 1 is illustrated in an enlarged form. A simplified view of the liquid crystal display layer (liquid crystal material, color filter, support substrate, etc.) is shown in FIGS. 3 and 9. A light transmissive substrate 8 is disposed thereon, which may be any suitable material such as glass, polyester, acrylic, or the like. On the substrate 8 is a conductive pattern 7, which is a line extending from the plane of Figure 3 and optionally made of a conductive siloxane oxide particle material as described above. These conductive strips extend across the length of the display. Formed on the conductive strip is a capacitor layer-insulating layer 6, which can be deposited to fill the space between the conductive strips 7 and form an insulating layer thereon. The insulating layer is preferably a siloxane oxide material as described above, preferably having selected particles to provide an electrically insulating layer, such as ceramic particles (e.g., oxide particles or nitride particles) and optical clarity in the visible spectrum. Both the conductive strip 7 and the dielectric layer 6 should be transmissive to visible light, preferably each having at least 70%, but more preferably at least 80%, and more preferably at least 90%, at least 92.5% or at least 95% incident thereon. Visible light.

As further seen in Figure 3, an additional patterned conductive strip layer 5 is provided. In this case, the conductive strips are formed as strips that are perpendicular (or otherwise non-parallel) to the strips 7 on opposite sides of the dielectric layer 5. The conductive line 5 can be the drive line of the display and the conductive line 7 can be the sense line. Also shown is an upper light transmissive substrate 3 which may be glass, polyester, acrylic or other suitable material that transmits light in the visible spectrum. Substrate 3 is then passed through an adhesive 4 which should also transmit visible light, and which may be made by a oxoxane material (with or without particles) as disclosed herein. The use of the same or similar materials for multiple layers in the device helps match the CTE and refractive index and can improve the overall optical and end-of-life quality of the device.

The region between the conductive strips 5 (and/or the conductive strips 7) may be an electrically insulating and optically transmissive paraxane material having particles as disclosed herein. It should be noted that the area 9 may be a display pixel (plasma, LED, etc.) other than the LCD pixels, and the conductive area may be incorporated into the liquid crystal display 9, such as in the case of a touch display in the unit as described above. The on-cell, in-cell, and out-cell touch displays may all use an electrically insulating siloxane particle material as disclosed herein, or a non-touch screen display in which a dielectric film is utilized.

The touch screen display on the glass is illustrated in the cross section of Figure 4. As shown in FIG. 4, a transparent conductive layer 51, a conductive jumper 52, and a dielectric layer 53 (for example, a UV-curable insulating layer) are disposed on the light-transmitting substrate 50. Metal traces 54, conductive patterns 55, passivation layer 56, and an additional dielectric overcoat 57 are also illustrated. Layer 52 can be deposited at elevated temperatures and layer 55 can be deposited at low temperatures. The conductive layer can be provided as a siloxane polymer as disclosed herein, but having metal particles to form a conductive layer after thermal curing, and the dielectric layer can be provided as a siloxane material as disclosed herein, having a ceramic Particles, such as oxide or nitride particles, are cured by heat treatment or UV treatment.

Although the use of a decane composition does not require a solvent, if a very thin layer is required, it may be necessary to add a non-polar or polar (protic or aprotic) organic solvent to provide the siloxane material in a low viscosity liquid form. Minimize the thickness of the deposited layer. Lowering the molecular weight of the oxirane polymer as part of the composition, or using a monomer (eg, the first compound, the second compound, and/or the third compound) in place of the siloxane polymer in the composition reduces viscosity and Helps minimize film thickness (and therefore light transmission) if necessary. A surfactant and a UV-sensitive additive capable of reacting the oxoxane composition upon exposure to UV light may be added. The choice of a functional reactive group as an acrylate helps to polymerize under UV light.

As can be seen in Figures 5a to 5d, a UV patternable deposition method is illustrated. In Figure 5a, a substrate 70 can be provided that is any suitable substrate, such as glass, quartz, sapphire, polymer, semiconductor, ceramic, metal, and the like. A oxoxane composition as disclosed herein and preferably comprising particles as disclosed above is deposited on substrate 70. The oxoxane particle composition can be deposited as a fluid, such as a liquid or gel, preferably by a method such as syringe deposition or screen printing. Other deposition methods can be used, such as spin coating, dipping, ink jet, curtain coating, drip, gravure, reverse offset, extrusion coating, slit coating, spray coating, flexographic, and the like. Additionally, the substrate 70 may be singulated from the wafer or may not have been singulated from the wafer, but may alternatively be the entire wafer, or from a large sheet such as a large glass for a display panel, solar cell or the like. Piece) the part of the cut. It is possible to deposit on a large sheet in a roll to roll process. Further, the substrate 70 may be wafer level followed by a support substrate, and the two substrates are singulated into individual crystal grains together. For displays or photovoltaic cells, a deposition process that can be incorporated into a roll-to-roll process is preferred.

As can be seen in Figure 5b, a mask 75 is placed adjacent to the siloxane layer and UV light is provided to the oxane layer via the holes in the mask. The UV light cures and hardens the siloxane layer in the exposed zone 72a while the unexposed zone 72b remains soft, as illustrated in Figure 5c. As can be seen in Figure 5d, the developer is used to remove the unexposed regions 72b leaving the pattern 72a in place. Various baking or drying steps can be used, such as soft bake after initial application of the decane material 72, and hard bake after removal of the unexposed regions 72b.

As an alternative to using a mask to directly pattern the siloxane material as discussed above, it is also possible to pattern the siloxane material via the photoresist layer deposited thereon. In such a method, a photoresist layer is deposited thereon after deposition and soft baking of the siloxane layer. The photoresist can be any suitable photoresist material, including a positive photoresist, wherein the portion of the photoresist exposed to light becomes soluble to the photoresist developer, And the photoresist portion which is not exposed to light is still insoluble to the developer. Alternatively, a negative photoresist can be used in which the portion of the photoresist exposed to light becomes insoluble to the developer and the unexposed portion of the photoresist is soluble to the developer. Any suitable photoresist can be used, such as SU-8, PMMA, DNQ/phenolic, PMGI, and the like. Regardless of the type of photoresist used, when the pattern is formed within the photoresist material, the pattern acts as a UV mask that selectively exposes the underlying siloxane material to form a patterned siloxane layer. .

As mentioned above, the layer of siloxane oxide particles is preferably electrically insulating, optically transmissive and patternable. However, in view of the general problems of heat accumulation in consumer devices and other devices, it is also possible to provide a layer of aerobicane particles for heat dissipation. The siloxane layer can thus be provided as a thermally conductive layer, such as a thermally transmissive, patterned or unpatterned and electrically or non-electrically insulating thermally conductive layer. The particles may be selected based on thermal conduction characteristics rather than electrical insulation properties, the particles being electrically insulating materials (such as the various nitrides, oxides, etc. mentioned herein). Of course, if the substrate is not optically transmissive, or where the position within the device does not require high optical transmittance in the visible spectrum, the thermally conductive and electrically insulating layer may be light reflected or light depending on the selected particles (type, amount, and size). Absorbed.

Additionally, the dielectric siloxane layer can be provided as a solid film, without patterning, but only exposed to UV light to cure into a continuous film. The film can be cured only by UV without applying any heat, or it can be cured by a combination of UV and heat, such as where the heat is below 120 ° C or even below 100 ° C for heat sensitive devices. In some cases, it may be desirable for the UV-induced free radical or photoacid generator to move laterally into the non-exposed regions in the dielectric film to cause cross-linking and curing in the non-exposed regions, such as in a non-UV transparent cover glass frame. under.

The oxoxane composition can include a coupling agent, a curing agent, an antioxidant, an adhesion promoter, and the like as disclosed herein. In particular, the oxoxane material includes a reactive group on the Si-O backbone that is reactive when incident UV light is applied. The developer can be any suitable developer such as TMAH, KOH, NaOH, and the like. It is also possible to pattern the siloxane material by laser patterning instead of UV light.

As seen in Figure 6, an alternative method of providing a pattern of electrically insulating material is illustrated. A conductive layer 82 is deposited on the substrate 80 as shown in Figure 6a. The conductive layer can be any suitable conductive film, but is preferably a oxoxane material as disclosed herein having particles therein. If particles are present, they should be particles that provide electrically conductive properties - such as metal particles. As shown in Figure 6b, layer 82 is patterned, such as by UV light. Patterning can also be by laser patterning or other suitable methods, such as hot stamping. Once layer 82 is exposed to UV light 86 via mask 85 (as shown in Figure 6c), the unexposed portions are removed to leave empty areas or grooves 82b and conductive portions 82a on substrate 80 (Fig. 6d). Thereafter, an electrically insulating material as disclosed herein is provided to the void region to provide an electrically insulating pattern on the substrate 80.

For Figure 6, the electrically insulating material deposited in the formed grooves or lines is preferably a siloxane oxide material as disclosed herein, and wherein the particles are preferably ceramic particles such as cerium oxide, quartz, alumina. Aluminum nitride, aluminum nitride coated with cerium oxide, barium sulfate, alumina trihydrate, boron nitride, or an oxide of titanium, lanthanum, aluminum, zirconium, hafnium or selenium. The siloxane oxide material can be used for both the conductive portion and the electrically insulating portion. In one example, the two oxoxanes have similar or preferably identical organic substituents, such as the first compound SiR ¹ _a R ² _4-a R ² group, wherein a is 1 to 3, R ¹ is a reactive group, and R ² is an alkyl group or an aryl group, as mentioned above, or the same monomer SiR ¹ _a R ² _{4-a is} used for A siloxane polymer is produced for both conductive materials and electrically insulating materials. This contributes to the film stability of the conductive portion and the insulating portion and is closer to the CTE value. Additionally, in instances where the electrically insulating material is disposed in a different layer than the electrically conductive material, such as for a capacitor portion between patterned conductive layers in a capacitive touch screen display, the same R ² groups and/or the same can be used Starting monomer.

Instead of forming a patterned conductive layer, it is possible to first deposit particles onto the substrate separately from the siloxane material. In this case, the particles may be deposited in an organic solvent or aqueous solvent solution or other carrier to form a "matrix" of nanowires on the substrate. The particle "film" is retained after drying or removing other suitable methods of solvent. A oxoxane material as disclosed herein is deposited thereon. The decane material can be deposited with a solvent, additionally dried and polymerized (e.g., with heat and/or UV light) to form a combined final cured layer of siloxane. Alternatively, the decane can be deposited with the desired molecular weight to provide the desired viscosity without the addition of any solvent, followed by application of heat or UV light to harden and cure the siloxane material. It is also possible to provide a halogen-containing monomer at this stage (for example, a first compound, a second compound or other optional components, such as a third compound, a coupling agent, etc., optionally used), followed by application of heat and/or UV. Light to a layer comprising particles and a polymeric alkane.

The electrically insulating layer as disclosed herein can be provided as a plurality of layers within the device, such as a first patterned electrically insulating siloxane layer, and a second electrically insulating layer (patterned or unpatterned). It is also possible to have regions of the same or similar helium oxide material but with particles providing conductivity between the electrically insulating portions within the same layer. Additionally, an intervening conductive layer can be provided between the plurality of electrically insulating siloxane layers. In the case where the conductive portion and the electrically insulating portion are made of the same or similar siloxane materials as disclosed herein, the problem of CTE mismatch can be reduced.

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 of the formula SiR ¹ _a R ² _4-a is provided wherein a is 1 to 3, R ¹ is a reactive group, and R ² is an alkyl group or an aryl group. A second compound having the formula SiR ³ _b R ⁴ _c R ⁵ _4-(b+c) wherein R ³ is a crosslinking functional group, R ⁴ is a reactive group, and R ⁵ is an alkyl group or an aryl group is also provided. 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 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 produced 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 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. 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 can be, for example, any epoxide, oxetane, acrylate, alkenyl or alkynyl group.

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 wherein 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 a weight ratio of less than 0.5% by weight relative to the first compound and the second compound together, or in a lower amount, such as less than 0.1% by weight.

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, ethanol or other by-products of the polymerization (depending on the selected compound) after polymerization is preferably carried out in a 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. 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 thermally activatable, especially preferred borane compounds 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, which may be combined with the first compound, the second compound, and the The tri 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, the oxoxane monomer R ¹ _a R ² _b R ³ _3-(a+b) Si-O-SiR ² ₂ -O-Si R ¹ _a R ² _b R ³ _{3 - (a + b)} wherein R ¹ is 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.

For a patterned or unpatterned dielectric layer, the particles added to the decane composition may be made of a non-conductive material such as cerium oxide coated with cerium oxide, cerium sulfate, alumina trihydrate, boron nitride, Quartz, alumina, aluminum nitride, aluminum nitride, etc. are formed. The filler may be in the form of particles or flakes and may be in micron size or nanometer 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, cerium, nickel, nickel cobalt, molybdenum, magnesium, manganese, lanthanides, Ceramic particles of iron, indium tin, copper, cobalt aluminum, chromium, barium or calcium oxides. 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.

The particle filler may also be made of a conductive material (such as a conductive layer or other layer used in the same device) such as carbon black, graphite, graphene, gold, silver, copper, platinum, palladium, nickel, aluminum, silver plated copper, plated. Silver aluminum, tantalum, tin, antimony-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 gold-plated, silver-gold, silver, nickel, A polymer of tin, platinum, or 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.

Alternatively, the filler for, for example, a conductive layer 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, Niobium, zinc, molybdenum, titanium, tungsten, silver plated copper, silver plated aluminum, tantalum, tin, bismuth-tin alloy, silver plated fiber or alloys or combinations 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-metallic or non-metallic particles such as arsenic, antimony, bismuth, antimony, bismuth and antimony are envisioned.

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.

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. However, in order to achieve higher optical transmittance, submicron particles are also envisioned, such as less than 1 micron, or such as 1 nanometer to 500 nanometers, such as less than 200 nanometers, such as 1 nanometer to 100 nanometers, or even less than 10 Nano particles. 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. Desirable are nanoparticles having an average particle size of less than 50 nanometers, such as less than 25 nanometers. In general, for improved optical transmission, it may be desirable to provide particles having an average particle size that is less than the wavelength of the electromagnetic radiation passing therethrough. For visible light devices (displays, lamps, etc.) having visible light in the range of 400 nm to 700 nm, it is preferred that the particles have an average particle size of less than 700 nm and more preferably less than 400 nm.

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, such as nanowires and nanotubes having extremely high aspect ratios, are also possible, but for optical transmission purposes, a maximum average size of less than 400 nm is preferred. The high aspect ratio of the H 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.

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 group or an aryl group, and R ¹⁵ is a functional group containing 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 in the preparation of the final product, or the filler particles can be treated with a coupling agent before it is mixed with the particles.

The particles can be provided to the oxoxane material with or without surface treatment. If the surface is first treated, the surface may be coated with an organic material such as a carboxylic acid, PVP or PVA, and may be an amine, a thiol, a decane or a combination thereof.

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 can be a thermally conductive layer or film, such as having a kelvin of greater than 0.5 watts per meter after final thermal or UV curing (W/( m·K)) 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. However, in other applications, the particles may be selected to produce a material having a low thermal conductivity, such as for a transparent dielectric layer as disclosed herein, if desired.

For a dielectric layer having a high resistivity, for example, greater than the sheet resistance. Further, if necessary, the final cured product may have a high electrical resistivity such as greater than 1 × 10 ³ Ω/sq, preferably greater than 1 × 10 ³ Ω/sq, such as greater than 1 × 10 ⁵ Ω/sq, or even higher, For example, it is larger than 1 × 10 ⁵ Ω/sq. As mentioned herein, the insulating layer may also be used in combination with a conductive layer of a siloxane oxide particle, in which case such layer will preferably have 200 Ω/sq or less, preferably 100 Ω/sq, such as 50. Ω/sq sheet resistance.

In some cases, in an LED or LCD device such as a display or in the case where an insulating siloxane composition will be applied to a device that requires optical features, although in some cases it may be desirable to have a final curing siloxane having optical Absorptive or optically reflective properties, and more likely the material will desirably be highly transmissive to light in the visible spectrum (or within the spectrum of the final 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 stabilizers or antioxidants which may be used 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 the stretching frequency and correspondingly retard its reactivity; this steric hindrance thus provides a phenolic compound having its stabilizing 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 in electronics or optoelectronic packaging, LED and OLED front-end and back-end processing, 3D, photovoltaic and display passivation and insulation in the adhesive or sealant and for packaging, printed electronics, power electronics and EMI, Touch sensors and other displays as well as thermal or UV curable sealants or dielectrics.

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/mole, and more preferably About 500 grams / mole to 2000 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. However, if the average particle size of the particles is less than the wavelength of visible light, for example preferably less than 400 nanometers (eg less than 200 nanometers, or even smaller, such as less than 100 nanometers or less than 50 nanometer average particle size), then a higher weight percentage The load is possible, such as 20% to 50%, or greater than 50%, greater than 75%, or even greater than 90%, while still achieving the desired optical transparency (eg, even at 75% load, optical transmittance for visible light) Can be greater than 90% or even greater than 95%).

Polymerization of the first and second compounds is carried out, and the particles are mixed therewith to form a viscosity of from 50 MPa to 2,000 MPa, preferably from 1,000 MPa to 5,000 MPa to 5,000 MPa. Viscous fluid from seconds to 50,000 MPa-sec. 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, since it may sometimes be necessary to transport the substantially solvent-free composition to the customer and subsequently to the customer 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. However, as mentioned above, although the application of the decane composition does not require a solvent, if a very thin layer is required, it may be necessary to add a non-polar or polar (protic or aprotic) organic solvent with a low viscosity. The liquid form provides a siloxane material to minimize the thickness of the deposited layer.

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. Example:

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 is 1087 mPas and the Mw is 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. Example of a capping material: Example 1

Will contain diphenylnonanediol (100.0 grams, 0.46 moles), 3-(trimethoxydecyl)propyl methacrylate (62.6 grams, 0.25 moles), methyltrimethoxydecane (17.2 grams, Methanol (0.13 mol) and BaO (0.1 g) were placed in a 500 ml flask and refluxed for 1 hour. The volatiles were evaporated under reduced pressure and a transparent resin was obtained.

The weight average molecular weight (Mw) of the polymer was measured by Agilent GPC. The Mw of polyoxyalkylene E1 was 1530 g/mole. FTIR analysis was performed to detect the OH-group and the methoxy group. The polyoxyalkylene E1 was substantially free of -OH groups (no peak was observed at the Si-OH band of 3390 cm ^-1 ). The remaining alkoxy groups were observed to be in the Si-OCH ₃ band at 2840 cm ^-1 . Example 2

25 grams of the polymer resin obtained from Example 1 was dissolved in 50 grams of acetone. Add 0.01 M HCl until the solution is cloudy. Stirring was continued for 8 hours at room temperature. Excess water is added to precipitate the polymer and the obtained polymer is thereafter separated and dried. The polymer was dissolved in 30 g of methyl tert-butyl ether (MTBE) and 5 g of hexamethyldioxane was added followed by 0.05 g of pyridine hydrochloride. Stirring was continued for 24 hours at room temperature. The non-reactive components were evaporated under reduced pressure and the obtained resin was washed by using MTBE-water extraction. The solvent was evaporated under reduced pressure and a transparent resin (22.9 g) was obtained.

The Mw of polyoxyalkylene E2 was 1670 g/mole. FTIR analysis was performed to detect the OH-group and the methoxy group. In the FTIR analysis, the polyoxyalkylene E2 was substantially free of -OH groups, and the Si-OCH ₃ peak at 2840 cm ^-1 had disappeared. 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 necessary, the refractive index can be selected based on the selected alkane particle material. 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, 1.5 to 1.65, etc.) may be provided, and 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 a metal-containing monomer may be used in place of the first compound, the second compound or the third compound as mentioned above, or may be additionally used.

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, the coupling agent has the formula (R ¹⁶ Ar) _i SiR ¹ _j , wherein i=1 or 2, and j=4-i, wherein R ₁₆ is an experience with the siloxane polymer when heat or UV light is applied A cross-linked functional crosslinking group wherein 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 and the R ₁₆ functional crosslinking group may be an epoxy group, an acrylate, a vinyl group, an allyl group, an acetylene, an alcohol, an amine, a thiol, a decyl alcohol 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 7, 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 7, 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 8, 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 a high percentage of particles is extremely transparent and suitable for a variety of optical applications.

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 a group, and another portion being particles mixed with a decane material, wherein the particles have an average particle size of less than 100 microns, and the particles are any suitable particles, but are preferably ceramic particles, such as nitride or oxide particles, and are preferably. It is a nanoparticle having an average particle size smaller than the range of visible light, for example, less than 400 nm. 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 over 2 weeks Less than 15%, and more preferably less than 10%. In addition, storage, shipping and subsequent application by the customer can all be carried out in the absence of solvent (except for possible traces of residue remaining after drying to remove the solvent), avoiding solvent trapping subsequently formed in the layer of the final product. (solvent capture), shrinkage during polymerization, loss of quality over time during use of the device, etc. No substantial cross-linking occurs during shipping and storage without the application of heat or UV light preferably above 100 °C. The composition and finally the Si-H bond is substantially absent.

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 9, 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 9, 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 less than 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 10, 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 10, 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 10. Similar results were observed by heating the polymeric material for only 1 hour at 200 ° C or 300 ° C. It is possible to result in less than 1% mass loss by heating the polymeric deposition material at 375 ° C or above 375 ° C for at least 1 hour. As can be seen in Figure 10, a mass loss of 5% or less was observed even at temperatures above 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 The thermally stable material as disclosed herein is polymerized by UV light.

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 compositions of the present invention are useful in semiconductor devices and microelectronic and optoelectronic devices, such as displays, such as LED displays, such as OLED/AMOLED and LCD displays. Examples include touch screen displays, such as resistive or capacitive touch screens for smartphones, tablets, laptops and laptops, computer monitors, and digital cameras, camcorders, portable gaming devices Touch screens on personal media players, e-book readers, printers, car displays, GPS/PND navigation devices, and touch screens in retail, commercial and industrial environments. However, the non-touch screen type benefits from the siloxane oxide insulating and light transmissive materials as disclosed herein. Citation List Patent Literature US 2011051064 US 5645901 KR 20120119020

1‧‧‧ polarizer layer
2, 70, 80‧‧‧ substrate
3‧‧‧Thin-film array
4‧‧‧Liquid Crystal Cell Array
5‧‧‧VCOM layer
6‧‧‧ color filter
7, 22‧‧‧ glass substrate
8, 10‧‧‧ patterned conductive layer
9, 25‧‧‧ insulation
11 ‧ ‧ layer
12, 31‧‧‧ adhesive layer
13‧‧‧ Cover glass
21, 30‧‧‧ polarizing layer
23‧‧‧Thin Film Array
24, 26, 82‧‧‧ conductive layer
27‧‧‧LCD unit
28‧‧‧ color filter
29‧‧‧Transparent substrate
32‧‧‧Additional transparent substrate
50‧‧‧Transparent substrate
51‧‧‧Transparent conductive layer
52‧‧‧Electrical jumper
53‧‧‧ dielectric layer
54‧‧‧Metal traces
55‧‧‧ conductive pattern
56‧‧‧ Passivation layer
57‧‧‧Additional dielectric top coat
72‧‧‧Oxysiloxane materials
72a‧‧‧ Exposure area
72b‧‧‧Unexposed areas
75, 85‧‧‧ mask
82a‧‧‧Electrical part
82b‧‧‧ Groove
86‧‧‧UV light

1 is a cross-sectional view of an on-cell touch capacitive panel display device. 2 is a cross-sectional view of an in-cell capacitive touch panel display device. 3 is a simplified view of a touch panel display device. 4 is a cross-sectional view of an on-glass capacitive touch panel display device. Figures 5a through 5d illustrate a method of patterning an insulating aluminoxane particle film. Figures 6a through 6d illustrate an alternative method of patterning an insulating aluminoxane particle film. Figure 7 shows a plot of refractive index versus wavelength for different particle loadings. Figure 8 is a graph of transmittance versus particle loading. Figure 9 illustrates the mass change of the siloxane polymer during the thermally induced polymerization. Figure 10 illustrates the thermal stability of the siloxane material after deposition and polymerization.

1‧‧‧ polarizer layer

2‧‧‧Substrate

3‧‧‧Thin-film array

4‧‧‧Liquid Crystal Cell Array

5‧‧‧VCOM layer

6‧‧‧ color filter

7‧‧‧ glass substrate

8, 10‧‧‧ patterned conductive layer

9‧‧‧Insulation

11 ‧ ‧ layer

12‧‧‧ adhesive layer

13‧‧‧ Cover glass

Claims (20)

A dielectric film comprising: a dielectric layer formed on a support substrate, comprising a siloxane polymer and particles having an average particle size of less than 1 micrometer in the siloxane polymer, wherein the dielectric layer is visible light Light that is optically transmissive and transmits at least 75% of the light incident thereon, and wherein the dielectric layer is electrically insulating and has a sheet resistance of 1000 Ω/sq or greater. The dielectric film of claim 1, wherein the ceramic particles are nitride particles. The dielectric film according to any one of the preceding claims, wherein the particles are aluminum nitride, tantalum nitride, boron nitride, titanium nitride, copper nitride, molybdenum nitride, tungsten nitride, nitrogen. Iron, tantalum nitride, indium nitride, gallium nitride or carbon nitride. A dielectric film according to any one of the preceding claims, wherein the siloxane polymer comprises an organic aryl group. A method of fabricating a dielectric film, comprising: providing a substrate; and depositing on the substrate a composition having a siloxane starting material and particles, wherein the siloxane starting material comprises a siloxane polymer, ruthenium An oxane oligomer and/or a decane monomer, and wherein said particles have an average particle size of less than 400 nm; wherein thermal energy and/or electromagnetic energy is applied to said layer of siloxane oxide to cure said layer and Forming a dielectric film on the substrate; wherein the film is optically transmissive to visible light and transmits at least 80% of visible light incident thereon; and wherein the film is electrically insulating and has a sheet resistance of 1000 Ω/sq or Bigger. The method of producing a dielectric film according to claim 5, wherein the particles have an average particle size of less than 50 nm, and in particular, the particles have an average particle size of less than 25 nm. The method of producing a dielectric film according to claim 5, wherein the oxane starting material comprises a phenyl group and a methacrylate functional reactive group, and wherein the particles are It is a ceramic oxide nanoparticle and has an average particle size of less than 400 nm. A display comprising: a plurality of pixels in a matrix, each of the pixels comprising: a liquid crystal layer and/or a light emitting diode layer; a plurality of substrates that are optically transmissive to visible light; and an adhesive that bonds the first substrate to the first a second substrate and forming a conductive material, the conductive material having a sheet resistance greater than 1000 Ω/sq and comprising a siloxane material and particles having an average particle size of less than 400 nm, wherein the electrically insulating material is thermally stable, Wherein if heated to at least 200 ° C, there will be a mass loss of less than 2%. The display of claim 8, wherein the particles are nitride particles selected from the group consisting of aluminum nitride, tantalum nitride, boron nitride, titanium nitride, copper nitride, molybdenum nitride, and nitrogen. Tungsten, iron nitride, tantalum nitride, indium nitride, gallium nitride or carbon nitride; or the particles are oxide nanoparticles, including bismuth, zinc, aluminum, lanthanum, cerium, tungsten, titanium, Titanium, niobium, tantalum, nickel, nickel cobalt, molybdenum, magnesium, manganese, lanthanide, iron, indium tin, copper, cobalt aluminum, chromium, niobium or calcium oxide; or the particles include titanium, tantalum, aluminum An oxide of zirconium, hafnium or selenium with a refractive index of 1.6 to 1.9. The display of claim 8 or 9, wherein the siloxane material is a siloxane or an alkyl group comprising a siloxane or an alkyl group, the particles comprising a transition metal oxide and having an average particle size of less than 100 Nano. The display of any one of the preceding claims, wherein the plurality of substrates comprises a first substrate having a liquid crystal element thereon, a second substrate including a capacitive touch sensor thereon, and a third substrate, the third substrate being a cover substrate. A method of manufacturing a display, comprising: providing a first substrate having an array of pixel elements thereon, wherein the pixel elements each comprise a liquid crystal material and/or a light emitting diode material; providing a second substrate, the second substrate being covered Substrate; and bonding the first substrate and the second substrate together by an adhesive, wherein the adhesive comprises an electrically insulating material having a resistivity greater than 1000 Ω/sq and including xenon oxide An alkane material and particles having an average particle size of less than 400 nm; wherein the siloxane material between the first substrate and the second substrate is cured and hardened by applying heat and/or UV light to The first substrate and the second substrate are bonded together. The method of manufacturing a display of claim 12, wherein curing comprises soft baking the siloxane oxide particle material, UV patterning the siloxane oxide particle material, and selectively removing a portion of the method The siloxane oxide material leaves an electrically insulating pattern. The method of producing a display according to any one of claims 12 to 13, wherein the oxirane starting material is substantially free of -OH groups. A method of manufacturing a display according to any one of claims 12 to 14, wherein the siloxane starting material is substantially free of Si-H bonds. The method of manufacturing a display according to any one of claims 12 to 15, wherein the siloxane material comprises an organic aryl group or an alkyl group. The method of manufacturing a display according to any one of claims 12 to 16, wherein the decyl alkane material comprises an aryl group but does not include an alkyl group. The method of manufacturing a display according to any one of claims 12 to 17, wherein the aryl group is a phenyl group directly bonded to the oxime in the oxoxane material. A composition comprising: a hafnoxy polymer having a repeating backbone of [-Si-O-Si-O]n having a) an alkyl or aryl group on the repeating backbone, and the repeating backbone Having b) a functional crosslinking group; and particles which are oxide nanoparticles or nitride nanoparticles having an average particle size of less than 400 nm, wherein the molecular weight of the siloxane polymer is 300 gram / Mohr to 10,000 g/mole, and wherein the composition has a viscosity of 5 MPa to 75,000 MPa-sec at a 5 rpm viscometer and at 25 ° C, and wherein the siloxane polymer is substantially There is no -OH group on it. A touch panel comprising: a transparent substrate; a first conductive layer; a dielectric layer comprising a siloxane polymer and particles having an average particle size of 400 nm or less; and a second conductive layer, wherein the cesium oxide The alkane polymer comprises an aryl group and is substantially free of -OH groups, and wherein the siloxane polymer has a mass loss of less than 1% when heated to 200 ° C, and wherein the dielectric layer has a resistivity of 1000 Ω/sq or greater, and wherein the dielectric layer has an optical transmittance of at least 85% for visible light.