CN109651425B

CN109651425B - Isocyanate compound containing multiple silicon-hydrogen bonds and application thereof

Info

Publication number: CN109651425B
Application number: CN201710946416.6A
Authority: CN
Inventors: 张汝志; 万小欢
Original assignee: Flory Photoelectric Materials Suzhou Co ltd
Current assignee: Lin Shangyu
Priority date: 2017-10-12
Filing date: 2017-10-12
Publication date: 2021-02-26
Anticipated expiration: 2037-10-12
Also published as: CN109651425A

Abstract

The invention discloses an isocyanate compound containing a plurality of silicon-hydrogen bonds, which has a typical structure shown as the following formula:

Description

Isocyanate compound containing multiple silicon-hydrogen bonds and application thereof

Technical Field

The invention particularly relates to an isocyanate compound containing a plurality of silicon hydrogen bonds, a curable organic silicon composition containing the isocyanate compound containing the plurality of silicon hydrogen bonds and the like, which can be applied to the field of packaging of semiconductor devices and electronic devices such as Light Emitting Diodes (LEDs).

Background

LEDs (semiconductor light emitting diodes) are widely used in the fields of illumination, backlight, and the like, because they have advantages of low power consumption, long life, small size, and the like. The packaging process is a very important process in the LED manufacturing process, and has a very significant influence on the working performance, cost, and the like of the LED.

With the development of semiconductor devices, the performance requirements for packaging adhesives have been gradually increased. For example, as the power and brightness of Light Emitting Diodes (LEDs) are continuously increased, higher requirements are made on the optical properties, physical properties, chemical properties, and the like of silicone compositions, and the conventional epoxy resin encapsulating materials have not been able to meet the actual requirements.

At present, it has become a conventional way in the industry to package a white LED with high power and high brightness by using a polysiloxane compound formed by thermally curing a polysiloxane component containing an unsaturated bond and a component containing a silicon hydrogen bond as a crosslinking agent through a hydrosilylation reaction in the presence of a catalyst. However, the existing crosslinking agents still have some insurmountable defects. For example, the silicone encapsulant using the existing cross-linking agent generally has the defects of low curing speed, long curing time, small hardness, low refractive index, poor toughness (low hardness), large volume shrinkage during curing, and the like of the cured silicone encapsulant, and thus when the silicone encapsulant is applied to encapsulation of LEDs and the like, the light emitting efficiency, the light quality, the uniformity of light color, the reliability of devices, and the like of the LEDs and the like are often affected.

Disclosure of Invention

The invention mainly aims to provide an isocyanate compound containing a plurality of silicon-hydrogen bonds and application thereof, so as to overcome the defects in the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides an isocyanate compound containing a plurality of silicon-hydrogen bonds, which has a structure shown as the following formula:

the embodiment of the invention also provides application of the isocyanate compound containing a plurality of silicon-hydrogen bonds as a cross-linking agent in hydrosilylation reaction.

The embodiment of the invention also provides a method for preparing the isocyanate compound containing a plurality of silicon-hydrogen bonds, which comprises the following steps: the isocyanate compound having a plurality of silicon-hydrogen bonds according to claim 1 is produced by subjecting a cyclic compound having a plurality of vinyl groups and a silicon-hydrogen bond compound to hydrosilylation in the presence of a catalyst.

Preferably, the cyclic compound having a plurality of vinyl groups has a structure represented by the following formula:

preferably, the silicon hydrogen bond compound has a structure represented by the following formula:

embodiments of the present invention also provide a curable silicone composition including a vinyl-containing polysiloxane component, a silicon-hydrogen bond-containing component, and a hydrosilylation catalyst; the component containing the silicon-hydrogen bonds comprises the isocyanate compound containing a plurality of silicon-hydrogen bonds.

The embodiment of the invention also provides application of the curable organosilicon composition in article bonding, preparation of article surface coating or article packaging.

When the isocyanate compound containing a plurality of silicon hydrogen bonds is applied as a cross-linking agent for hydrosilylation, compared with the existing cross-linking agent, the isocyanate compound has the advantages of higher refractive index, higher viscosity, higher cross-linking density and the like, and the organic silicon composition containing the isocyanate compound containing a plurality of silicon hydrogen bonds also has the characteristics of high curing efficiency, higher hardness and refractive index after curing, low heat weight loss, better toughness, small volume shrinkage during curing and the like.

The technical solution of the present invention is explained in more detail with reference to the following examples, but the present invention is not limited thereto.

Detailed Description

An aspect of an embodiment of the present invention provides an isocyanate compound having a plurality of silicon-hydrogen bonds, which has a structure represented by the following formula:

when the isocyanate compound containing a plurality of silicon hydrogen bonds is applied as a cross-linking agent for hydrosilylation, compared with the existing cross-linking agent, the isocyanate compound has the advantages of higher refractive index, higher viscosity, higher cross-linking density and the like, and the organic silicon composition containing the isocyanate compound containing a plurality of silicon hydrogen bonds also has the characteristics of high curing efficiency, high curing speed, higher hardness and refractive index after curing, low heat weight loss, suitability for industrial application of viscosity and the like.

In another aspect of the embodiments of the present invention, there is provided a use of the isocyanate compound containing a plurality of silicon-hydrogen bonds as a cross-linking agent in a hydrosilylation reaction.

An aspect of an embodiment of the present invention provides a method of preparing the isocyanate compound having a plurality of silicon-hydrogen bonds, which includes: and (2) carrying out hydrosilylation reaction on a cyclic compound containing a plurality of vinyl groups and a silicon hydrogen bond compound in the presence of a catalyst to generate the isocyanate compound containing a plurality of silicon hydrogen bonds. It should be noted that addition products reflecting the March's rule and the March's rule due to the Silicon hydrogenation reaction (see: Silicon in Organic, Organometallic, and Polymer Chemistry by Michael A. Brook, Wiley Interscience, pp 401-458) result in the presence of multiple isomers, which are also within the scope of the present application.

in some more specific embodiments, the preparation method specifically comprises: mixing a cyclic compound containing a plurality of vinyl groups, a silicon-hydrogen bond compound, a catalyst and an organic solvent, heating and refluxing to perform hydrosilylation reaction, and generating the isocyanate compound containing a plurality of silicon-hydrogen bonds.

The organic solvent may be selected from organic solvents which can dissolve the cyclic compound containing a plurality of vinyl groups and the silicon hydrogen bond compound, but do not react with any of the cyclic compound containing a plurality of vinyl groups, the silicon hydrogen bond compound and the catalyst, and may be, for example, common organic solvents such as benzene and toluene.

Further, the conditions of the hydrosilylation reaction can be referred to in the literature "hydrosilylation reaction and research" (Schedule, 2 nd 1998, p 82-84).

Another aspect of an embodiment of the present invention provides a curable silicone composition including a silicone-based component including vinyl groups, a component including silicon-hydrogen bonds, and a hydrosilylation catalyst; the component containing the silicon-hydrogen bonds comprises the isocyanate compound containing a plurality of silicon-hydrogen bonds.

In some preferred embodiments, the vinyl-containing polysiloxane component contains at least two silicon-bonded alkenyl groups and at least one silicon-bonded aromatic group.

Preferably, the refractive index of the vinyl-containing polysiloxane component is not less than 1.5, and particularly preferably 1.50 to 1.65.

Preferably, the vinyl group-containing polysiloxane component has a viscosity of 10 to 10,000cPs, and particularly preferably 50 to 5000cPs at 25 ℃.

Preferably, the vinyl group-containing silicone based component is selected from one or more of a linear polymer, a branched polymer or a network polymer.

Further preferably, the vinyl group-containing silicone-based component is selected from linear polymers.

Still more preferably, the vinyl group-containing silicone component has a structure represented by the following formula:

wherein D is 1-500, M is 1-500, and N is 1-500; more preferably, D is 1 to 50, M is 1 to 500, and N is 1 to 50. In some preferred embodiments, the molar ratio of the vinyl group contained in the vinyl group-containing polysiloxane component to the silicon-hydrogen bond contained in the silicon-hydrogen bond-containing component is 10:1 to 1:10, preferably 2:1 to 1: 2.

In the present invention, the aforementioned hydrosilylation catalyst should be used in an amount sufficient to promote curing of the silicone composition of the present invention. These hydrosilylation catalysts are known in the art and are commercially available, and may be selected, for example, from, but not limited to, the following: platinum group metals: platinum, rhodium, ruthenium, palladium, osmium or iridium metal or organometallic compounds thereof, and combinations thereof. More specifically, it may be chosen from platinum black, the reaction products of compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, and monoalcohols, platinum bis (ethylacetoacetate), platinum bis (acetylacetonate), platinum dichloride and complexes of said compounds with olefins or low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core-shell type structure. Complexes of platinum with low molecular weight organopolysiloxanes, including complexes of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane with platinum. These complexes can be microencapsulated in a resin matrix. Alternatively, the catalyst may comprise 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex with platinum. These hydrosilylation catalysts can be referred to CN1863875A (paragraph 0020-0021 of the specification), US3,159,601, US3,220,972, US3,296,291, US3,419,593, US3,516,946, US3,814,730, US3,989,668, US4,784,879, US5,036,117, US5,175,325, EP 0347895B, US4,766,176, US5,017,654, etc. And/or, at least one UV active Pt catalyst, see US8,314,200. More specifically, the hydrosilylation catalyst may be selected from a catalytic amount of a platinum catalyst, a rhodium catalyst, or a palladium catalyst; preferably, the platinum catalyst is selected from one or more of platinum micropowder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum/alkenylsiloxane complex, platinum/olefin complex, and platinum/carbonyl complex. Preferably, the hydrosilylation catalyst is present in the silicone composition in an amount of 0.1ppm to 1,0000 ppm.

In some embodiments, the amount of the aforementioned hydrosilylation catalyst can be in the following ranges of platinum group metals based on the weight of the silicone composition of the present invention: 0.1ppm to 1,0000ppm, alternatively 1ppm to 1000ppm, and alternatively 10ppm to 100 ppm.

In some embodiments, the silicone composition may further comprise a solvent or diluent. Preferably, the solvent or diluent is used in an amount sufficient to complex with the components of the silicone composition to form a homogeneous solution. In the present invention, the aforementioned solvent or diluent may be of any type suitable for use, such as water, organic solvent or a mixture of both, preferably from an organic solvent, such as one selected from, but not limited to, n-hexane, toluene, chloroform, dichloromethane, ethanol, acetone, 2-butanone, 4-methyl-2-pentanone, a lipid, a solvent for photoresist (e.g., PGME, PGMEA), etc., for combination with the remaining materials in the composition as a liquid with good fluidity, especially a homogeneous solution.

In some embodiments, the silicone composition may further comprise an inhibitor. The inhibitor, i.e., hydrosilylation reaction inhibitor, refers to a substance that can cause poor hydrosilylation reaction, and is selected from alkynol compounds, ene-alkyne compounds, siloxane or benzotriazole, and other hydrosilane reaction inhibitors, as referenced in CN1863875A (paragraph 0025), etc. For example, the alkynol-based compound inhibitor may be selected from 2-phenyl-3-butyn-2-ol, 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol, and the like; the ene-yne compound may be selected from, for example, 3-methyl-3-penten-1-yne, and the siloxane may be selected from, for example, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetrahexenylcyclotetrasiloxane, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasiloxane, and the like. Among them, alkynols are preferred, and 2-phenyl-3-butyn-2-ol is particularly preferred.

In some embodiments, the silicone composition may further comprise other additives, such as any one or a combination of two or more of small molecule silanes (which may or may not contain ethylene or Si-H functional groups), adhesion promoters, thermally or UV cured epoxy/acrylic/polyurethane/bismaleimide resins, inorganic fillers, rheology modifiers, adhesion promoters, wetting agents, defoamers, leveling agents, dyes, and phosphor anti-settling agents (e.g., shin DM-30, Sanwell SH series LED phosphor anti-settling agents, etc.).

Wherein the adhesion promoter or adhesion promoter may be selected from ethyl orthosilicate, vinyl trimethoxy silane, n-butyl borate, isopropyl borate, titanium isooctanoate, zirconium isooctanoate, n-butyl titanate, isopropyl titanate, KH-171, KH-560, KH-570, vinylmethoxysiloxane homopolymer, 3-glycidyloxypropyltrimethoxysilane, etc. (refer to paragraph 0026 of the CN1863875A description), and commercially available adhesion promoters may be JCR6101, JCR6101UP, EG6301, OE6336, JCR6175, JCR6109, Hipec4939, Hipec 1-9224, OE6250, SR7010, SE9207, SE1740, SE9187L, etc., but not limited thereto.

Wherein the inorganic filler may be known in the art and commercially available, for example, may include inorganic fillers such as silica, e.g., colloidal silica, fumed silica, quartz powder, titanium oxide, glass, alumina, zinc oxide, or combinations thereof, the fillers may be micro-or nano-sized particles, preferably having an average particle size of 5000 nanometers or less and not reducing the percent transmittance by scattering or absorption.

While the definitions thereof with respect to, for example, rheology modifiers, wetting agents, defoamers, leveling agents, dyes, etc., are well known in the art and can be freely chosen from within the corresponding materials commonly used in the art.

Preferably, the amount of additive in the curable silicone composition is no greater than 50 wt%, particularly preferably 10 wt% or less, more preferably 5 wt% or less.

In addition, in some possible embodiments, other one or more silicon-hydrogen bond-containing components, such as tris (dimethylsiloxy) phenylsilane, and the like, in addition to the multiple silicon-hydrogen bond-containing isocyanate compound of the present invention, may also be included in the silicone composition of the present invention. Of course, the effect of these embodiments may be inferior to those embodiments in which only the isocyanate compound containing multiple silicon hydrogen bonds of the present invention is added to the silicone composition of the present invention.

In some more specific preferred embodiments, the silicone composition comprises: 10-95 parts by weight of a vinyl-containing polysiloxane component, 5-90 parts by weight of a silicon-hydrogen bond-containing component, 0.1-10000 ppm of a hydrosilylation catalyst, 0.001-1.0 part by weight of a hydrosilylation inhibitor, 0.001-5 parts by weight of an additive, and 0.001-90 parts by weight of a diluent.

Furthermore, the refractive index of the organic silicon composition is 1.35-2.0, and preferably 1.50-1.60.

Further, the viscosity of the organic silicon composition is 1-10,000,000 cPs, and preferably 1,000-100,000 cPs.

The silicone composition of the present invention can be formulated with reference to the formulation of silicone gel mixtures widely used in the industry, for example, the components can be divided into component a (mainly comprising vinyl group-containing silicone component, platinum catalyst, additive, etc.) and component B ((mainly comprising silicon-hydrogen bond-containing component, additive, etc.), and A, B is mixed in a certain ratio at the time of use, compared to the silicone gel currently used for semiconductor encapsulation, the silicone composition of the present invention also has advantages including, but not limited to, longer lifetime (more than 8h without significant viscosity change) at room temperature, simplified encapsulation process of semiconductor devices (such as LED) to improve yield, and better storage stability (more than 1 month, preferably 3 months at 0-5 c, more preferably 6 months).

Another aspect of embodiments of the present invention also provides a complete cure of the curable silicone composition.

Another aspect of embodiments of the present invention also provides a method of making a complete cure of the curable silicone composition, which may include: the silicone composition is fully cured by heating or electromagnetic radiation (e.g., UV light irradiation).

In some embodiments of the present invention, a method of preparing a complete cure of the curable silicone composition may comprise:

adding the components according to the composition of the curable silicone composition in a plastic cup special for a planetary stirrer and uniformly mixing;

and thermally curing the uniformly stirred fluid (preferably liquid) at 25-300 ℃ for 1-5,000 min.

Preferably, the hardness of the fully cured product is shore a20 to shore D95, and particularly preferably shore a20 to shore D65.

Preferably, the fully cured product has a light transmittance of 80% to 100%, particularly preferably 95% to 100%, with respect to visible light.

By means of the silicone composition of the present invention, good isolation, including physical and chemical isolation, between devices or from the outside can be maintained, and/or good light output or uptake efficiency of the devices can be maintained.

Meanwhile, the complete condensate of the organic silicon composition also shows good bonding force and flexibility, and the performances of dielectric constant, heat conduction efficiency, ageing resistance and the like are also ideal.

In addition, compared with the prior organic silica gel products, the organic silicon composition of the invention also has the advantages including but not limited to the following list, including: long service life at room temperature (more than 8h without significant viscosity change), better gap filling performance, simplified packaging process of semiconductor devices (such as LED) to improve yield, and better storage stability (more than 1 month, preferably 3 months, more preferably 6 months at 0-5 ℃).

Accordingly, another aspect of embodiments of the present invention also provides the use of the curable silicone composition for article bonding, for preparing a surface coating for an article, or for encapsulating an article.

In the present invention, the term "packaging" is understood to include at least the meaning that two or more articles are bonded (adhered) by the silicone composition, or a protective layer (coating) is formed by curing the silicone composition in some regions of the surface of the article, or a part of one or more articles is immersed in a cured product formed from the silicone composition, or one or more articles are entirely embedded and sealed (encapsulated) in a cured product formed from the silicone composition, and the aforementioned functions of bonding, coating, sealing, and the like can be achieved at the same time.

Another aspect of the embodiments of the present invention also provides a bonding method, including:

applying the curable silicone composition on the surface of the first article and/or the second article and/or between the first article and the second article,

curing the silicone composition to achieve bonding of the first article to the second article;

preferably, the curing conditions include: the silicone composition is fully cured by heating or electromagnetic irradiation.

Another aspect of embodiments of the present invention also provides a semiconductor device encapsulating material comprising the curable silicone composition and/or a cured product of the silicone composition.

Another aspect of embodiments of the present invention also provides a class of films or coatings that are primarily formed from the curing of the curable silicone composition.

Another aspect of the embodiments of the present invention also provides a semiconductor light emitting device including: a semiconductor light emitting chip, and said film or coating; and the semiconductor light emitting chip is arranged at a distance from the film or coating.

Another aspect of the embodiments of the present invention also provides a packaging method, including:

an article to be packaged is provided and,

applying the curable silicone composition onto the article to be encapsulated and effecting encapsulation of the article by curing the silicone composition by radiation and/or heat.

Preferably, the article to be packaged includes a semiconductor device or an electronic device. Further preferably, the semiconductor device comprises a semiconductor optoelectronic device. Still further preferably, the semiconductor optoelectronic device comprises a semiconductor light emitting device such as an LED or the like. Another aspect of the embodiments of the present invention also provides a device including a package structure formed by the foregoing packaging method.

Preferably, the encapsulating structure is mainly composed of a cured product of the curable silicone composition and an article encapsulated by the cured product, wherein the encapsulated article includes a semiconductor device or an electronic device.

Preferably, the semiconductor device comprises a semiconductor optoelectronic device. Further preferably, the semiconductor optoelectronic device comprises a semiconductor light emitting device such as an LED, in particular a chip scale package semiconductor device or a wafer level semiconductor device or the like.

In addition, the organic silicon composition of the present invention can be used in combination with fluorescent materials such as phosphor, fluorescent quantum dots, etc. when applied, for example, the aforementioned fluorescent materials can be incorporated into the organic silicon composition, and then used to encapsulate articles. In the process, the inventors have also found that the organic silicon composition of the present invention can greatly reduce or even eliminate the sedimentation of the fluorescent material, especially the fluorescent powder, which occurs over time, for example, when various fluorescent materials commonly used in the industry are mixed with the composition of the present invention, no sedimentation occurs for more than 8 hours, preferably more than 24 hours, at room temperature, so that a more uniform packaging effect can be generated, and the light emitting uniformity of semiconductor light emitting devices can be improved.

For example, in some embodiments of the present disclosure, one type of fluorescent encapsulation composition may include the silicone composition and a fluorescent material uniformly dispersed within the silicone composition, the fluorescent material including a phosphor and/or fluorescent quantum dots, and the like.

Preferably, the fluorescent material in the fluorescent packaging composition accounts for 0.01 wt% to 90 wt%, more preferably 1 wt% to 80 wt%, and even more preferably 3 wt% to 70 wt% of the non-solvent component.

The fluorescent powder comprises the combination of any one or more than two of rare earth fluorescent powder, rare earth garnet fluorescent powder, alkaline earth metal gallium sulfide, alkaline earth metal sulfide, zinc sulfide, alkaline earth metal aluminate, phosphate, borate, silicate, fluorine arsenate, fluorine germanate, rare earth sulfide, rare earth oxide, vanadate and nitride fluorescent powder. The content of the fluorescent powder in the fluorescent packaging composition in the non-solvent component is preferably 1.0 wt% to 90 wt%, and more preferably 1.0 wt% to 70 wt%.

More preferably, the phosphor may be a nano phosphor.

The constituent material of the fluorescent quantum dot includes II-VI or III-V elements, and may be a composite material of two or more of ZnSe, CdS, CdSe and CdSe, for example. The content of the fluorescent quantum dots in the fluorescent packaging composition in the non-solvent component is preferably 0.01-50 wt%, and more preferably 0.01-5.0 wt%.

The foregoing fluorescent encapsulating composition is particularly useful for applications in semiconductor light emitting device encapsulation, including: wafer Level Packaging (WLP), Chip Scale Packaging (CSP), LED filament packaging, and the like.

The technical solution of the present invention is explained in more detail below with reference to several more specific examples and corresponding comparative examples. It should be emphasized that these examples are not to be considered as limiting the scope of the invention in any way. Also, unless otherwise indicated, all parts, percentages, ratios, and the like in this specification are by weight.

The components of the silicone compositions in the following examples and comparative examples can be seen in table 1. The components used in the examples and comparative examples are specifically as follows:

resin: the mass ratio is about 0.833: 13, wherein the equivalent weight (equivalent weight) of the vinyl group contained in the mixture of the resin 1 and the resin 2 is about 1.66 mmol/g.

Resin 1: 50 wt% diphenyldimethylmethylvinylpolysiloxane, vinyl terminated, refractive index 1.541, viscosity 10700 cPs.

Resin 2: silsesquioxane with methyl (Me), phenyl (Ph), vinyl groups, refractive index of 1.550, viscosity of 55000 cPs.

Crosslinking agent 1: refractive index 1.5028, viscosity 6.0 cPs.

Crosslinking agent 2: 30% by weight of diphenyldimethylmethylhydrogenpolysiloxane, refractive index 1.4630, viscosity 400.0 cPs.

Crosslinking agent 3: refractive index 1.460, viscosity 2.5 cPs.

Crosslinking agent 4: refractive index 1.5451, viscosity 1500 cPs.

Adhesion Promoter (Adhesion Promoter): 3-glycidoxypropyltrimethoxysilane.

Inhibitor (hydrosilylation inhibitor): 2-phenyl-3-butyn-2-ol.

Catalyst (hydrosilylation catalyst): a platinum catalyst.

The resin 1, the crosslinking agent 2, the crosslinking agent 3, and the crosslinking agent 4 are as follows.

The resin, resin 1, resin 2, crosslinking agent 1, crosslinking agent 2, crosslinking agent 3, adhesion promoter, inhibitor (hydrosilylation inhibitor), catalyst (hydrosilylation catalyst), and the like can be obtained by a commercially available method or the like.

The aforementioned crosslinking agent 4 can be synthesized by the following steps:

(1) taking 0.5g of hydrosilylation catalyst platinum, adding 5mL of toluene for dilution, and then adding the diluted platinum into a 250mL three-neck flask;

(2) taking 2.49g of 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione (1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione with the molecular weight MW of 249.27g/mol), adding 20mL of toluene for dilution, and adding the mixture into a three-neck flask;

(3) taking 15.00g of 1,1,5,5-tetramethyl-3,3-diphenyl trisiloxane (1,1,5,5-tetramethyl-3,3-diphenyl trisiloxane with the molecular weight of 333), adding 25mL of toluene for dilution, and adding into a three-neck flask;

(4) setting the oil bath temperature at 130 ℃, starting stirring, starting condensed water, and starting refluxing the reaction mixture when the temperature in the three-neck flask is 119 ℃;

(5) after a period of reflux, a small amount of the reaction mixture was aspirated for IR testing to determine if the reaction was complete.

(6) After 48 hours, the reaction was terminated as indicated by an IR result showing no absorption peak of carbon-carbon double bond and the reaction mixture was transferred to a rotary evaporator to evaporate the solvent to precipitate the product crosslinking agent 4 (FT-IR: 3075 to 2920,2126,1691,1516,1253,1119,1053,901,836 to 626 cm-1; 1H NMR. delta. 7.58 to 7.18,4.32 to 4.27,2.50 to 2.00,1.00 to-0.50).

It is noted that the product is a mixture formed by a hydrosilylation reaction.

Characterization and testing: further, the inventors examined the change in properties, the state of cure, and the properties of the cured product, including light transmittance and hardness, of the silicone compositions according to the foregoing examples and comparative examples in a room temperature environment in a manner conventionally known in the art, and the results are shown in table 2 below (note that each test data therein is an average value of the test results of a plurality of samples).

TABLE 1

TABLE 2

Similarly, the inventor also uses other compounds and proportions mentioned in the specification as raw materials to form other groups of organic silicon compositions, tests various performances of the compositions one by one, and the test result is also very suitable for industrial application.

It can be seen that the isocyanate compound containing a plurality of silicon-hydrogen bonds of the invention is used as a cross-linking agent for hydrosilylation reaction, which not only has the advantages of higher refractive index, higher viscosity, higher cross-linking density and the like, but also can ensure that the organic silicon composition containing the isocyanate compound also has the characteristics of high curing efficiency, high curing speed, higher hardness after curing, higher refractive index, low heat weight loss, better toughness, small volume shrinkage during curing, suitability for industrial application of viscosity and the like. Therefore, the material is suitable for being used as a packaging material of a high-power LED, and can also be used for packaging other semiconductor photoelectric devices and electronic devices such as optical switches, photoelectric couplers, solid-state image pickup elements and the like; in addition, the silicone composition can also be used for optical adhesives, surface protection of photoelectric devices, and the like.

It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. An isocyanate compound containing a plurality of silicon-hydrogen bonds, wherein the isocyanate compound containing a plurality of silicon-hydrogen bonds has a structure shown in the following formula:

2. use of an isocyanate compound containing a plurality of silicon-hydrogen bonds as claimed in claim 1 as a cross-linking agent in a hydrosilylation reaction.

3. A method for preparing an isocyanate compound containing a plurality of silicon-hydrogen bonds, which is characterized by comprising the following steps: carrying out hydrosilylation reaction of a cyclic compound containing a plurality of vinyl groups and a silicon hydrogen bond compound in the presence of a catalyst to produce an isocyanate compound containing a plurality of silicon hydrogen bonds according to claim 1;

the cyclic compound having a plurality of vinyl groups has a structure represented by the following formula:

the silicon-hydrogen bond compound has a structure represented by the following formula:

4. the method according to claim 3, comprising in particular: mixing a cyclic compound containing a plurality of vinyl groups, a silicon-hydrogen bond compound, an organic solvent and a catalyst, heating and refluxing to perform hydrosilylation reaction, and generating the isocyanate compound containing a plurality of silicon-hydrogen bonds.

5. A curable silicone composition comprising a vinyl group-containing polysiloxane component, a silicon-hydrogen bond-containing component, and a hydrosilylation catalyst; the method is characterized in that: the silicon-hydrogen bond-containing component comprises the isocyanate compound containing a plurality of silicon-hydrogen bonds as set forth in claim 1.

6. The curable silicone composition of claim 5, wherein: the vinyl-containing polysiloxane component contains at least two silicon-bonded alkenyl groups and at least one silicon-bonded aromatic group.

7. The curable silicone composition of claim 5, wherein: the refractive index of the vinyl group-containing polysiloxane component is not less than 1.5.

8. The curable silicone composition of claim 7, wherein: the refractive index of the vinyl-containing polysiloxane component is 1.50-1.65.

9. The curable silicone composition of claim 5, wherein: the viscosity of the vinyl-containing polysiloxane component at 25 ℃ is 10-10000 cPs.

10. The curable silicone composition of claim 9, wherein: the viscosity of the vinyl-containing polysiloxane component at 25 ℃ is 50-5000 cPs.

11. The curable silicone composition of claim 5, wherein: the vinyl-containing polysiloxane component is selected from one or more of linear polymer, branched polymer or reticular polymer.

12. The curable silicone composition of claim 11, wherein: the vinyl-containing silicone-based component is selected from linear polymers.

13. The curable silicone composition of claim 12, wherein: the vinyl group-containing polysiloxane component has a structure represented by the following formula:

wherein D is 1-500, M is 1-500, and N is 1-500.

14. The curable silicone composition of claim 13, wherein: d is 1-50, M is 1-500, and N is 1-50.

15. The curable silicone composition of claim 12, wherein: the hydrosilylation catalyst is selected from a catalytic amount of a platinum catalyst, a rhodium catalyst, or a palladium catalyst.

16. The curable silicone composition of claim 15, wherein: the platinum catalyst is selected from one or more of platinum micropowder, chloroplatinic acid, platinum/alkenylsiloxane complexes, platinum/olefin complexes, and platinum/carbonyl complexes.

17. The curable silicone composition of claim 5, wherein: the hydrosilylation catalyst is used in the silicone composition in an amount of 0.1ppm to 10000 ppm.

18. The curable silicone composition of claim 5, wherein: the molar ratio of the vinyl contained in the vinyl-containing polysiloxane component to the silicon-hydrogen bond contained in the silicon-hydrogen bond-containing component is 10: 1-1: 10.

19. The curable silicone composition of claim 18, wherein: the molar ratio of the vinyl contained in the vinyl-containing polysiloxane component to the silicon-hydrogen bond contained in the silicon-hydrogen bond-containing component is 2: 1-1: 2.

20. The curable silicone composition of claim 5, wherein: the curable silicone composition further includes a hydrosilane reaction inhibitor and/or an additive and/or a diluent.

21. The curable silicone composition of claim 20, wherein: the hydrosilane reaction inhibitor is selected from an alkynol compound, an ene-alkyne compound, a siloxane or a benzotriazole.

22. The curable silicone composition of claim 20, wherein: the amount of additive in the curable silicone composition is no greater than 50 wt%.

23. The curable silicone composition of claim 22, wherein: the curable silicone composition has an additive content of less than 5 wt%.

24. The curable silicone composition of claim 20, wherein: the diluent is used in an amount sufficient to complex with the components of the silicone composition to form a homogeneous solution.

25. The curable silicone composition according to claim 5, characterized by comprising: 10-95 parts by weight of a vinyl-containing polysiloxane component, 5-90 parts by weight of a silicon-hydrogen bond-containing component, 0.1-10000 ppm of a hydrosilylation catalyst, 0.001-1.0 part by weight of a hydrosilylation inhibitor, 0.001-5 parts by weight of an additive, and 0.001-90 parts by weight of a diluent.

26. The curable silicone composition of claim 25, wherein: the refractive index of the organic silicon composition is 1.35-2.0.

27. The curable silicone composition of claim 26, wherein: the refractive index of the organic silicon composition is 1.50-1.60.

28. The curable silicone composition of claim 25, wherein: the viscosity of the organic silicon composition is 1-10000000 cPs.

29. The curable silicone composition of claim 28, wherein: the viscosity of the organic silicon composition is 1000-100000 cPs.

30. A complete cure of the curable silicone composition of any one of claims 5-29.

31. The fully cured product according to claim 30, wherein: the hardness of the complete condensate is Shore A20-Shore D95.

32. The fully cured product according to claim 31, wherein: the hardness of the complete condensate is Shore A20-Shore D65.

33. The fully cured product according to claim 30, wherein: the light transmittance of the completely cured product to visible light is 80-100%.

34. The fully cured product according to claim 33, wherein: the light transmittance of the completely cured product to visible light is 95-100%.

35. The fully cured product according to claim 30, wherein the method for producing a fully cured product comprises: the silicone composition is fully cured by heating or electromagnetic irradiation.

36. A fluorescent encapsulating composition characterized by comprising the curable silicone composition of any one of claims 5-29 and a fluorescent material uniformly dispersed within the silicone composition, the fluorescent material comprising a phosphor and/or a fluorescent quantum dot.

37. The fluorescent packaging composition of claim 36, wherein: the content of the fluorescent material in the fluorescent packaging composition accounts for 0.01 wt% -90 wt% of the non-solvent component.

38. The fluorescent packaging composition of claim 37, wherein: the fluorescent material in the fluorescent packaging composition accounts for 1-80 wt% of the non-solvent component.

39. The fluorescent packaging composition of claim 38, wherein: the content of the fluorescent material in the fluorescent packaging composition accounts for 3 wt% -70 wt% of the non-solvent component.

40. The fluorescent packaging composition of claim 36, wherein: the fluorescent powder comprises the combination of more than two of rare earth fluorescent powder, rare earth garnet fluorescent powder, alkaline earth metal gallium sulfide, alkaline earth metal sulfide, zinc sulfide, alkaline earth metal aluminate, phosphate, borate, silicate, fluorine arsenate, fluorine germanate, rare earth sulfide, rare earth oxide, vanadate and nitride fluorescent powder.

41. The fluorescent packaging composition of claim 36, wherein: the content of the fluorescent powder in the fluorescent packaging composition accounts for 1.0-90 wt% of the non-solvent component.

42. The fluorescent packaging composition of claim 41, wherein: the content of the fluorescent powder in the fluorescent packaging composition accounts for 1.0-70 wt% of the non-solvent component.

43. The fluorescent packaging composition of claim 36, wherein: the fluorescent powder is nano fluorescent powder.

44. The fluorescent packaging composition of claim 36, wherein: the constituent material of the fluorescent quantum dot contains II-VI group or III-V group elements.

45. The fluorescent packaging composition of claim 44, wherein: the fluorescent quantum dots are made of a combination of more than two of ZnSe, CdS, CdSe and CdSe.

46. The fluorescent packaging composition of claim 36, wherein: the content of the fluorescent quantum dots in the fluorescent packaging composition accounts for 0.01-50 wt% of the non-solvent component.

47. The fluorescent packaging composition of claim 46, wherein: the content of the fluorescent quantum dots in the fluorescent packaging composition accounts for 0.01-5.0 wt% of the non-solvent component.

48. Use of the curable silicone composition of any one of claims 5-29 or the fluorescent encapsulating composition of any one of claims 30-47 in article bonding.

49. Use of the curable silicone composition of any one of claims 5-29 or the fluorescent encapsulating composition of any one of claims 30-47 in the preparation of a surface coating for an article.

50. Use of the curable silicone composition of any one of claims 5-29 or the fluorescent encapsulating composition of any one of claims 30-47 in the encapsulation of an article.

51. A bonding method characterized by comprising:

applying the curable silicone composition of any one of claims 5-29 on a surface of a first article and/or a second article and/or between the first article and the second article,

and curing the silicone composition to achieve bonding of the first article to the second article.

52. A bonding method according to claim 51, wherein the curing conditions include: the silicone composition is fully cured by heating or electromagnetic irradiation.

53. A semiconductor device encapsulating material comprising the curable silicone composition and/or the cured product of the silicone composition according to any one of claims 5 to 29 or the fluorescent encapsulating composition and/or the cured product of the fluorescent encapsulating composition according to any one of claims 30 to 47.

54. A film formed primarily from the curable silicone composition of any one of claims 5-29 or the fluorescent packaging composition of any one of claims 30-47 cured.

55. A coating formed primarily from the curable silicone composition of any one of claims 5-29 or the fluorescent encapsulating composition of any one of claims 30-47 cured.

56. A semiconductor light emitting device, characterized by comprising: a semiconductor light emitting chip, and the thin film of claim 54 or the coating of claim 55; and the semiconductor light emitting chip is arranged at a distance from the film or coating.

57. A method of packaging, comprising:

an article to be packaged is provided and,

applying the curable silicone composition of any one of claims 5-29 or the fluorescent encapsulating composition of any one of claims 30-47 to the article to be encapsulated and effecting encapsulation of the article by curing the silicone composition by radiation and/or heat.

58. The packaging method of claim 57, wherein: the article to be packaged includes a semiconductor device or an electronic device.

59. The packaging method of claim 58, wherein: the semiconductor device is a semiconductor photoelectric device.

60. The packaging method of claim 59, wherein: the semiconductor photoelectric device is a semiconductor light-emitting device.

61. The method of packaging of claim 60, wherein: the semiconductor light emitting device is an LED.

62. An apparatus comprising an encapsulated structure formed by the method of any of claims 57-61, the encapsulated structure consisting essentially of a cured product of a curable silicone composition or a fluorescent encapsulating composition, and an article encapsulated by the cured product, wherein the article being encapsulated comprises a semiconductor device or an electronic device.

63. The apparatus of claim 62, wherein: the semiconductor device is a semiconductor photoelectric device.

64. The apparatus of claim 63, wherein: the semiconductor photoelectric device is a semiconductor light emitting device which comprises an LED.

65. The apparatus of claim 62, wherein: the semiconductor device is a chip-scale package semiconductor device or a wafer-level semiconductor device.