A boron-containing addition-cure modified silicone LED encapsulant and a method of making the same

Abstract

The application relates to the field of LED encapsulants, and particularly discloses a boron-containing addition-cured modified silicone LED encapsulant and a preparation method thereof. The raw materials of the LED encapsulant include the following components in parts by weight: boron-containing vinyl silicone oil 100 parts, boron-containing hydrogen silicone oil 1-10 parts, MTQ type boron-containing polysilicon resin 20-50 parts, inhibitor 0.05-0.2 parts and platinum system catalyst 0.5-2.0 parts. By introducing the boron group into the system, the hardness and bonding performance of the LED encapsulant can be greatly improved, the LED encapsulant has excellent ultraviolet light aging resistance, and the protection effect of the LED encapsulant on the light-emitting chip is remarkably improved.

Description

Technical Field

[0001] This application relates to the field of LED encapsulants, and more specifically, it relates to a boron-containing addition-curing modified organosilicon LED encapsulant and its preparation method. Background Technology

[0002] Light-emitting diodes (LEDs) are semiconductor components that emit light. Compared to conventional lighting equipment, they offer many advantages, such as energy saving, environmental protection, and long lifespan, earning them the title of "green lighting." They have enormous application potential in the lighting and display fields. With increasing awareness of energy conservation and environmental protection among governments and the public, as well as technological advancements, LEDs are being used more and more in general lighting applications, including landscape lighting, traffic lights, indoor decorative lights, mining lamps, navigation lights, automotive LED lights, and indoor LED decorative lights.

[0003] LED packaging technology primarily focuses on encapsulating the light-emitting chip. As one of the core technologies in LED device manufacturing, this technology not only requires protection of the chip but also good light transmittance. Therefore, LED packaging places specific requirements on the packaging materials. Traditional LED encapsulants are based on epoxy resin, but due to problems such as poor high-temperature resistance and UV resistance, silicone materials are increasingly being used as the matrix.

[0004] Silicone encapsulants possess excellent thermal and UV stability, low ion content, low moisture absorption, low internal stress, good high and low temperature resistance, and do not yellow. They also exhibit high transmittance in both the UV and visible light regions, and their modulus and refractive index can be controlled by modifying their structure. These superior properties make them the preferred material for high-power LED encapsulation. However, some areas of the LED bracket require insulation materials such as polyphthalamide (PPA) boards. These insulating materials have low surface energy, and existing silicone encapsulants have poor adhesion, making them unsuitable for proper bonding and thus affecting the LED encapsulation effect. Summary of the Invention

[0005] To address the aforementioned technical problems, this application provides a boron-containing addition-curing modified organosilicon LED encapsulant and its preparation method.

[0006] In the first aspect, this application provides a boron-containing addition-curing modified organosilicon LED encapsulant, which adopts the following technical solution: A boron-containing addition-curing modified silicone LED encapsulant, the raw materials used include the following components in parts by weight: 100 parts of boron-containing vinyl silicone oil; 1-10 parts of borohydride silicone oil; 20-50 parts of MTQ type boron-containing polysilicon resin; Inhibitor 0.05-0.2 parts; 0.5-2.0 parts of platinum system catalyst.

[0007] Preferably, the boron-containing vinyl silicone oil has a viscosity of 2000-10000 mPa·s, an alkenyl content of 0.5-5 wt%, and the boron-containing vinyl silicone oil contains alkyl and / or phenyl groups in its molecules.

[0008] Preferably, the method for preparing the boron-containing vinyl silicone oil includes the following steps: Under the protection of an inert gas, 80-100 parts by weight of methylcyclic siloxane, 1-10 parts by weight of vinylcyclic siloxane and 1-3 parts by weight of catalyst are mixed and stirred at 60-80°C for 1-3 hours. Then, 1-10 parts by weight of boric acid or borate ester are added to the reaction system, and the temperature is raised to 90-140°C for 1-6 hours. After that, 1-10 parts by weight of end-capping agent are added within 0.5-1.0 hours and reacted for 1-2 hours. Then, the temperature is raised to 175-185°C for de-lowering treatment. After cooling, boron-containing vinyl silicone oil is obtained.

[0009] Preferably, the borohydride silicone oil has a hydrogen content of 0.3-1.2 wt% and a viscosity of 500-2000 mPa·s.

[0010] Preferably, the method for preparing the borohydride silicone oil includes the following steps: Under the protection of an inert gas, 80-100 parts by weight of methylcyclic siloxane, 1-10 parts by weight of hydrogen-based cyclic siloxane and 1-3 parts by weight of catalyst are mixed and stirred at 60-80°C for 1-3 hours. Then, 1-10 parts by weight of boric acid or borate ester are added to the reaction system, and the temperature is raised to 90-140°C for 1-6 hours. After that, 1-10 parts by weight of end-capping agent are added within 0.5-1.0 hours and reacted for 1-2 hours. Then, the temperature is raised to 155-165°C for de-lowering treatment. After cooling, boron-containing vinyl silicone oil is obtained.

[0011] Preferably, the methylcyclosiloxane includes one or more of octamethylcyclotetrasiloxane, tetraphenyltetramethylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane.

[0012] Preferably, the vinyl cyclosiloxane comprises tetramethyltetravinylcyclotetrasiloxane and / or octavinylcyclotetrasiloxane.

[0013] Preferably, the hydrogen-based cyclic siloxane comprises tetramethylcyclotetrasiloxane.

[0014] Preferably, the catalyst comprises an acidic catalyst or a basic catalyst.

[0015] Preferably, the acidic catalyst includes one or more of concentrated hydrochloric acid, concentrated sulfuric acid, dodecylbenzenesulfonic acid, and cation exchange resin.

[0016] More preferably, the acidic catalyst comprises a cation exchange resin.

[0017] Preferably, the alkaline catalyst comprises one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine, and anion exchange resin.

[0018] More preferably, the alkaline catalyst comprises anion exchange resin.

[0019] Preferably, the boric acid includes one or more of boric acid, phenylboronic acid, and tetrahydroxyboronic acid.

[0020] Preferably, the borate ester includes one or more of trimethyl borate, triethyl borate, triethanolamine borate, and triallyl borate.

[0021] Preferably, the end-capping agent comprises one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, and tetramethyldisiloxane.

[0022] Preferably, the ratio of Q-units to T-units in the MTQ type boron-containing polysilicon resin is 0.6-1.2, the molecular weight is 3000-5000, and the MTQ type boron-containing polysilicon resin molecule contains alkyl and / or phenyl groups.

[0023] Preferably, the preparation method of the MTQ type boron-containing polysilicone resin includes the following steps: After mixing 50-100 parts by weight of Q-chain siloxane and 10-20 parts by weight of T-chain siloxane, 0.1-3.0 parts by weight of catalyst and 1-10 parts by weight of boric acid or borate ester are added under the protection of inert gas. The mixture is reacted at 50-80°C for 0.5-1.0 h. Then, 10-30 parts by weight of end-capping agent are added within 0.5-1.0 h and the mixture is reacted for 1-2 h. After that, xylene is added for liquid-liquid extraction, de-lowering treatment, and cooling to obtain MTQ type boron-containing polysilicon resin.

[0024] Preferably, the Q-linked siloxane includes one or more of tetramethyl silicate, tetraethyl silicate, polymethyl silicate, and polyethyl silicate.

[0025] Preferably, the T-chain siloxane includes one or more of methyltrimethoxysiloxane, methyltriethoxysiloxane, phenyltrimethoxysiloxane, and phenyltriethoxysilane.

[0026] Preferably, the inhibitor comprises one or more of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylacetylene, and ethynylcyclohexanol.

[0027] Preferably, the platinum system catalyst includes one of platinum black, platinum chloride, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, and a complex of chloroplatinic acid and vinylsiloxane.

[0028] More preferably, the platinum system catalyst comprises a complex of chloroplatinic acid and vinylsiloxane, wherein the platinum content is 500-2000 ppm.

[0029] Secondly, this application provides a method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant, which adopts the following technical solution: A method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant involves uniformly mixing boron-containing vinyl silicone oil, boron-containing hydrosilicone oil, MTQ-type boron-containing polysilicon resin, inhibitor, and platinum-based catalyst.

[0030] In summary, this application has the following beneficial technical effects: This application uses boron-containing vinyl silicone oil as the main adhesive, combined with MTQ-type boron-containing polysilicon resin and boron-hydrogen silicone oil. Curing at a specific temperature under the action of inhibitors and a platinum-based catalyst yields a boron-containing addition-type modified organosilicon LED encapsulant. By introducing boron groups into the system, this application not only significantly improves the hardness and adhesion of the LED encapsulant but also endows it with excellent UV aging resistance, significantly enhancing the protective effect of the LED encapsulant on the light-emitting chip. Furthermore, this application introduces boron groups into the vinyl silicone oil, MTQ-type polysilicon resin, and hydrogen-containing silicone oil, which not only substantially increases the boron content in the LED encapsulant but also improves the compatibility between the components in the system, thereby further enhancing the hardness, adhesion, and UV aging resistance of the LED encapsulant. Detailed Implementation

[0031] Unless otherwise specified, all raw materials used in this application are commercially available products.

[0032] In some specific embodiments of boron-containing vinyl silicone oils, the methylcyclosiloxane includes one or more of octamethylcyclotetrasiloxane, tetraphenyltetramethylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane; In some specific embodiments of boron-containing vinyl silicone oils, the vinyl cyclic siloxanes include tetramethyltetravinylcyclotetrasiloxane and / or octavinylcyclotetrasiloxane; In some specific embodiments of boron-containing vinyl silicone oils, the catalyst includes an acidic catalyst or a basic catalyst, wherein the acidic catalyst includes one or more of concentrated hydrochloric acid, concentrated sulfuric acid, dodecylbenzene sulfonic acid, and cation exchange resin, and the basic catalyst includes one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine, and anion exchange resin; in some preferred embodiments of boron-containing vinyl silicone oils, the catalyst is a cation exchange resin or anion exchange resin; wherein the cation exchange resin includes one or more of cation exchange resin 201×7, cation exchange resin D201, and cation exchange resin D204, and the anion exchange resin includes anion exchange resin 001×7 and / or anion exchange resin D001; In some specific embodiments of boron-containing vinyl silicone oils, boric acid includes one or more of boric acid, phenylboronic acid, and tetrahydroxyboronic acid; In some specific embodiments of boron-containing vinyl silicone oils, the borate ester includes one or more of trimethyl borate, triethyl borate, triethanolamine borate, and triallyl borate; In some specific embodiments of boron-containing vinyl silicone oils, the end-capping agent includes one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, and tetramethyldisiloxane; In some specific embodiments of boron-containing vinyl silicone oil, the above raw materials are used in the following proportions and the following steps are performed: Under the protection of an inert gas, 80-100 parts by weight of methyl cyclic siloxane, 1-10 parts by weight of vinyl cyclic siloxane and 1-3 parts by weight of catalyst are mixed and stirred at 60-80°C for 1-3 hours. Then, 1-10 parts by weight of boric acid or borate ester are added to the reaction system, and the temperature is further raised to 90-140°C for 1-6 hours. After that, 1-10 parts by weight of end-capping agent are added within 0.5-1.0 hours and reacted for 1-2 hours. Then, the temperature is raised to 175-185°C for de-lowering treatment, cooled, and a boron-containing vinyl silicone oil with a viscosity of 2000-10000 mPa·s, an alkenyl content of 0.5-5 wt%, and containing alkyl and / or phenyl groups in the molecule is obtained.

[0033] In some specific embodiments of borohydride silicone oil, the methylcyclosiloxane includes one or more of octamethylcyclotetrasiloxane, tetraphenyltetramethylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane; In some specific embodiments of boron-containing silicone oils, the hydrogen-based cyclic siloxane includes tetramethylcyclotetrasiloxane; In some specific embodiments of borohydride silicone oil, the catalyst includes an acidic catalyst or a basic catalyst, wherein the acidic catalyst includes one or more of concentrated hydrochloric acid, concentrated sulfuric acid, dodecylbenzene sulfonic acid and cation exchange resin, and the basic catalyst includes one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine and anion exchange resin. In some preferred embodiments of borohydride silicone oil, the catalyst is a cation exchange resin or anion exchange resin; wherein the cation exchange resin includes one or more of cation exchange resin 201×7, cation exchange resin D201 and cation exchange resin D204, and the anion exchange resin includes anion exchange resin 001×7 and / or anion exchange resin D001. In some specific embodiments of borohydride silicone oil, boric acid includes one or more of boric acid, phenylboronic acid, and tetrahydroxyboronic acid; in some specific embodiments of borohydride silicone oil, borate esters include one or more of trimethyl borate, triethyl borate, triethanolamine borate, and triallyl borate. In some specific embodiments of borohydride silicone oil, the end-capping agent includes one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, and tetramethyldisiloxane; In some specific embodiments of borohydride silicone oil, the above raw materials are used in the following proportions and the following steps are performed: Under the protection of an inert gas, 80-100 parts by weight of methyl cyclic siloxane, 1-10 parts by weight of hydrogen-based cyclic siloxane and 1-3 parts by weight of catalyst are mixed and stirred at 60-80°C for 1-3 hours. Then, 1-10 parts by weight of boric acid or borate ester are added to the reaction system, and the temperature is further raised to 90-140°C for 1-6 hours. After that, 1-10 parts by weight of end-capping agent are added within 0.5-1.0 hours and reacted for 1-2 hours. Then, the temperature is raised to 155-165°C for dehydrogenation treatment, cooled, and a borohydride silicone oil with a hydrogen content of 0.3-1.2 wt% and a viscosity of 500-2000 mPa·s is obtained.

[0034] In some specific embodiments of MTQ type boron-containing polysiloxanes, the Q-linked siloxane includes one or more of tetramethyl silicate, tetraethyl silicate, polymethyl silicate, and polyethyl silicate. In some specific embodiments of MTQ type boron-containing polysiloxane, the T-chain siloxane includes one or more of methyltrimethoxysiloxane, methyltriethoxysiloxane, phenyltrimethoxysiloxane, and phenyltriethoxysilane. In some specific embodiments of MTQ type boron-containing polysilicon resin, the catalyst includes an acidic catalyst or a basic catalyst, wherein the acidic catalyst includes one or more of concentrated hydrochloric acid, concentrated sulfuric acid, dodecylbenzene sulfonic acid and cation exchange resin, and the basic catalyst includes one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine and anion exchange resin. In some preferred embodiments of the MTQ type boron-containing polysilicon resin, the catalyst is a cation exchange resin or anion exchange resin; wherein the cation exchange resin includes one or more of cation exchange resin 201×7, cation exchange resin D201 and cation exchange resin D204, and the anion exchange resin includes anion exchange resin 001×7 and / or anion exchange resin D001. In some specific embodiments of MTQ type boron-containing polysilicone resins, boric acid includes one or more of boric acid, phenylboronic acid and tetrahydroxyboronic acid; In some specific embodiments of MTQ type boron-containing polysilicon resins, the borate ester includes one or more of trimethyl borate, triethyl borate, triethanolamine borate, and triallyl borate; In some specific embodiments of MTQ type boron-containing polysiloxane, the end-capping agent includes one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, and tetramethyldisiloxane; In some specific embodiments of MTQ type boron-containing polysiloxane, the above raw materials are used, and the following steps are performed according to the following ratio: 50-100 parts by weight of Q-chain siloxane and 10-20 parts by weight of T-chain siloxane are mixed, and under the protection of an inert gas, 0.1-3.0 parts by weight of catalyst and 1-10 parts by weight of boric acid or borate ester are added. The mixture is reacted at a temperature of 50-80°C for 0.5-1.0 h. Then, within 0.5-1.0 h, 10-30 parts by weight of end-capping agent are added and reacted for 1-2 h. After that, xylene is added for liquid-liquid extraction, de-lowering treatment, and cooling to obtain MTQ type boron-containing polysiloxane with a Q-chain to T-chain ratio of 0.6-1.2, a molecular weight of 3000-5000, and containing alkyl and / or phenyl groups in the molecule.

[0035] In some specific embodiments of boron-containing addition-curing modified organosilicon LED encapsulants, the inhibitors include one or more of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylacetylene, and ethynylcyclohexanol; In some specific embodiments of boron-containing addition-curing modified organosilicon LED encapsulants, the platinum system catalyst includes one of platinum black, platinum chloride, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, and a complex of chloroplatinic acid and vinylsiloxane. In some preferred embodiments of boron-containing addition-curing modified organosilicon LED encapsulants, the platinum system catalyst is a complex of chloroplatinic acid and vinylsiloxane, wherein the platinum content is 500-2000 ppm; In some specific embodiments of boron-containing addition-curing modified silicone LED encapsulants, the above raw materials are used in the following proportions and the following steps are performed: 100 parts by weight of boron-containing vinyl silicone oil, 1-10 parts by weight of boron-hydrogen silicone oil, 20-50 parts by weight of MTQ type boron-containing polysilicon resin, 0.05-0.2 parts by weight of inhibitor, and 0.5-2.0 parts by weight of platinum system catalyst are mixed evenly and baked at 120-150℃ for 3-5 minutes. The resulting boron-containing addition-curing modified silicone LED encapsulant has a Shore hardness of not less than 54, an adhesive strength of not less than 3.1 MPa, and excellent resistance to ultraviolet aging.

[0036] The applicant further verified the various properties of the boron-containing addition-curing modified organosilicon LED encapsulant prepared in this application using the following six examples and four comparative examples.

[0037] Preparation Example 1 Boron-containing vinyl silicone oil is prepared by the following method: 80 kg of octamethylcyclotetrasiloxane and 10 kg of tetramethyltetravinylcyclotetrasiloxane were treated at 110 °C and then cooled. Nitrogen gas was then introduced, and 1 kg of anion exchange resin D201 was added and mixed. The mixture was stirred at 60 °C for 3 h. Then, 10 kg of 50% boric acid solution was added to the reaction system, and the temperature was raised to 90 °C and reacted for 6 h. After that, 1 kg of hexamethyldisiloxane was added within 0.5 h and reacted for 1 h. The temperature was then raised to 175 °C for de-lowering treatment. After cooling, boron-containing vinyl silicone oil was obtained.

[0038] Preparation Example 2 Boron-containing vinyl silicone oil is prepared by the following method: 100 kg of octamethylcyclotetrasiloxane and 1 kg of tetramethyltetravinylcyclotetrasiloxane were treated at 110 °C and then cooled. Nitrogen gas was then introduced, and 3 kg of anion exchange resin D201 was added and mixed. The mixture was stirred at 80 °C for 1 h. Then, 1 kg of 50% boric acid solution was added to the reaction system, and the temperature was raised to 140 °C and reacted for 1 h. After that, 10 kg of hexamethyldisiloxane was added within 1 h and reacted for 2 h. The temperature was then raised to 185 °C for de-lowering treatment. After cooling, boron-containing vinyl silicone oil was obtained.

[0039] Preparation Example 3 Boron-hydrosilicone oil is prepared by the following method: 80 kg of octamethylcyclotetrasiloxane and 10 kg of tetramethylcyclotetrasiloxane were treated at 110 °C and then cooled. Nitrogen gas was then introduced, and 1 kg of cation exchange resin D001 was added and mixed. The mixture was stirred at 60 °C for 3 h. Then, 10 kg of 50% boric acid solution was added to the reaction system, and the temperature was raised to 90 °C and reacted for 6 h. After that, 1 kg of tetramethyldisiloxane was added within 0.5 h and reacted for 1 h. The temperature was then raised to 155 °C for de-lowering treatment. After cooling, borohydride silicone oil was obtained.

[0040] Preparation Example 4 Boron-hydrosilicone oil is prepared by the following method: 50 kg of octamethylcyclotetrasiloxane, 50 kg of tetraphenyltetramethylcyclotetrasiloxane, and 1 kg of tetramethylcyclotetrasiloxane were treated at 110 °C and then cooled. Nitrogen gas was then introduced, and 3 kg of cation exchange resin D001 was added and mixed. The mixture was stirred at 80 °C for 1 h. Then, 1 kg of 50% boric acid solution was added to the reaction system, and the temperature was raised to 140 °C and reacted for 1 h. After that, 10 kg of tetramethyldisiloxane was added within 1 h and reacted for 2 h. The temperature was then raised to 165 °C for de-lowering treatment, and after cooling, borohydride silicone oil was obtained.

[0041] Preparation Example 5 MTQ type boron-containing polysilicone resin is prepared by the following method: 50 kg of polyethyl silicate and 20 kg of methyltrimethoxysiloxane were mixed, inert gas was introduced and the mixture was stirred, 0.1 kg of cation exchange resin D001 and 10 kg of 50 wt% boric acid solution were added, and the mixture was reacted at 50 °C for 1 h. Then, 10 kg of hexamethyldisiloxane was added within 0.5 h and the mixture was reacted for 1 h. After that, xylene was added for liquid-liquid extraction, de-lowering treatment, and cooling to obtain MTQ type boron-containing polysiloxane resin.

[0042] Preparation Example 6 MTQ type boron-containing polysilicone resin is prepared by the following method: 100 kg of polyethyl silicate and 10 kg of phenyltrimethoxysiloxane were mixed, inert gas was introduced and the mixture was stirred, 3 kg of cation exchange resin D001 and 1 kg of 50 wt% boric acid solution were added, and the mixture was reacted at 80 °C for 0.5 h. Then, 30 kg of hexamethyldisiloxane was added within 1 h and the mixture was reacted for 2 h. After that, xylene was added for liquid-liquid extraction, de-lowering treatment, and cooling to obtain MTQ type boron-containing polysiloxane resin.

[0043] Comparative Preparation Example 1 Vinyl silicone oil is prepared by the following method: 80 kg of octamethylcyclotetrasiloxane and 10 kg of tetramethyltetravinylcyclotetrasiloxane were treated at 110 °C and then cooled. Nitrogen gas was then introduced, and 1 kg of anion exchange resin D201 was added and mixed. The mixture was stirred at 60 °C for 3 h, then heated to 90 °C and reacted for 6 h. After that, 1 kg of hexamethyldisiloxane was added within 0.5 h and reacted for 1 h. The mixture was then heated to 175 °C for de-lowering treatment. After cooling, vinyl silicone oil was obtained.

[0044] Comparative Preparation Example 2 Hydrogen-containing silicone oil is prepared by the following method: 80 kg of octamethylcyclotetrasiloxane and 10 kg of tetramethylcyclotetrasiloxane were treated at 110 °C and then cooled. Nitrogen gas was then introduced, and 1 kg of cation exchange resin D001 was added and mixed. The mixture was stirred at 60 °C for 3 h, then heated to 90 °C and reacted for 6 h. Then, 1 kg of tetramethyldisiloxane was added within 0.5 h and reacted for 1 h. The mixture was then heated to 155 °C for de-lowering treatment. After cooling, hydrogen-containing silicone oil was obtained.

[0045] Comparative preparation example 3 MTQ type polysilicone resin is prepared by the following method: 50 kg of polyethyl silicate and 20 kg of methyltrimethoxysiloxane were mixed, an inert gas was introduced and the mixture was stirred, 0.1 kg of cation exchange resin D001 was added, and the mixture was reacted at 50 °C for 1 h. Then, 10 kg of hexamethyldisiloxane was added within 0.5 h and the mixture was reacted for 1 h. After that, xylene was added for liquid-liquid extraction, de-lowering treatment, and cooling to obtain MTQ type polysiloxane.

[0046] Example 1 A method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant includes the following steps: 100 kg of boron-containing vinyl silicone oil prepared in Preparation Example 1, 1 kg of boron-containing hydrosilicone oil prepared in Preparation Example 3, 30 kg of MTQ-type boron-containing polysilicon resin prepared in Preparation Example 5, 0.05 kg of phenylacetylene and 0.5 kg of chloroplatinic acid were mixed evenly with the complex of vinylsiloxane and baked at 130°C for 5 min to obtain a boron-containing addition-curing modified organosilicon LED encapsulant.

[0047] Example 2 A method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant includes the following steps: 100 kg of boron-containing vinyl silicone oil prepared in Preparation Example 1, 1 kg of boron-containing hydrosilicone oil prepared in Preparation Example 3, 40 kg of MTQ-type boron-containing polysilicon resin prepared in Preparation Example 5, 0.05 kg of phenylacetylene and 0.5 kg of chloroplatinic acid were mixed evenly with the complex of vinylsiloxane and baked at 130°C for 5 min to obtain a boron-containing addition-curing modified organosilicon LED encapsulant.

[0048] Example 3 A method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant includes the following steps: 100 kg of boron-containing vinyl silicone oil prepared in Preparation Example 1, 1 kg of boron-containing hydrosilicone oil prepared in Preparation Example 3, 50 kg of MTQ-type boron-containing polysilicon resin prepared in Preparation Example 5, 0.05 kg of phenylacetylene and 0.5 kg of chloroplatinic acid were mixed evenly with the complex of vinylsiloxane and baked at 130°C for 5 min to obtain a boron-containing addition-curing modified organosilicon LED encapsulant.

[0049] Example 4 A method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant includes the following steps: 100 kg of boron-containing vinyl silicone oil prepared in Preparation Example 2, 1 kg of boron-containing hydrosilicone oil prepared in Preparation Example 4, 30 kg of MTQ-type boron-containing polysilicon resin prepared in Preparation Example 6, 0.05 kg of phenylacetylene and 0.5 kg of chloroplatinic acid were mixed evenly with the complex of vinylsiloxane and baked at 130°C for 5 min to obtain a boron-containing addition-curing modified organosilicon LED encapsulant.

[0050] Example 5 A method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant includes the following steps: 100 kg of boron-containing vinyl silicone oil prepared in Preparation Example 2, 1 kg of boron-containing hydrosilicone oil prepared in Preparation Example 4, 40 kg of MTQ-type boron-containing polysilicon resin prepared in Preparation Example 6, 0.05 kg of phenylacetylene, and 0.5 kg of chloroplatinic acid were mixed evenly with the complex of vinylsiloxane and baked at 130°C for 5 min to obtain a boron-containing addition-curing modified organosilicon LED encapsulant.

[0051] Example 6 A method for preparing a boron-containing addition-curing modified organosilicon LED encapsulant includes the following steps: 100 kg of boron-containing vinyl silicone oil prepared in Preparation Example 2, 1 kg of boron-containing hydrosilicone oil prepared in Preparation Example 4, 50 kg of MTQ-type boron-containing polysilicon resin prepared in Preparation Example 6, 0.05 kg of phenylacetylene and 0.5 kg of chloroplatinic acid were mixed evenly with the complex of vinylsiloxane and baked at 130°C for 5 min to obtain a boron-containing addition-curing modified organosilicon LED encapsulant.

[0052] Comparative Example 1 The difference from Example 1 is that boron groups are not introduced into the reaction system. Specifically, the boron-containing vinyl silicone oil prepared in Preparation Example 1 is replaced with the vinyl silicone oil prepared in Comparative Preparation Example 1, the boron-containing hydrogen silicone oil prepared in Preparation Example 3 is replaced with the hydrogen-containing silicone oil prepared in Comparative Preparation Example 2, and the MTQ-type boron-containing polysilicon resin prepared in Preparation Example 5 is replaced with the MTQ-type polysilicon resin prepared in Comparative Preparation Example 3. All other aspects are the same as in Example 1.

[0053] Comparative Example 2 The difference from Example 1 is that the boron-hydrogen silicone oil prepared in Preparation Example 3 was replaced with the hydrogen-containing silicone oil prepared in Comparative Preparation Example 2, and the MTQ type boron-containing polysilicon resin prepared in Preparation Example 5 was replaced with the MTQ type polysilicon resin prepared in Comparative Preparation Example 3. The rest is the same as Example 1.

[0054] Comparative Example 3 The difference from Example 1 is that only the boron-hydrogen silicone oil prepared in Preparation Example 3 was replaced with the hydrogen-containing silicone oil prepared in Comparative Preparation Example 2, and everything else was the same as in Example 1.

[0055] Comparative Example 4 The difference from Example 1 is that only the MTQ type boron-containing polysilicon resin prepared in Preparation Example 5 was replaced with the MTQ type polysilicon resin prepared in Comparative Preparation Example 3; the rest is the same as in Example 1.

[0056] Performance testing 1. Adhesive strength: The LED encapsulants prepared in the above examples and comparative examples were tested in accordance with GB / T 7124-2008 "Determination of tensile shear strength of adhesives"; 2. Hardness: The LED encapsulants prepared in the above examples and comparative examples were tested according to GB / T 531.1-2008 "Test method for indentation hardness of vulcanized rubber or thermoplastic rubber - Part 1: Shore hardness tester method (Shore hardness)"; 3. UV Aging Resistance: Referring to GB / T 16422.1-2006 "Plastics - Laboratory Light Source Exposure Test Methods - Part 1: General Rules", the LED encapsulants prepared in the above examples and comparative examples were tested using a UV test chamber. The light source used was a UV-340 fluorescent UV lamp. The blackboard temperature was 60-80℃ under illumination and 40-60℃ in darkness, with a radiation intensity of 0.25-1.55 W / m². 2 / nm, irradiation time of 12h, to evaluate the degree of peeling of the product after photoaging test; The test results are shown in Table 1.

[0057] Table 1 Example 1 3.1 54 6.3 Example 2 3.5 61 5.8 Example 3 4.1 68 4.9 Example 4 3.4 70 6.8 Example 5 4.5 75 5.5 Example 6 4.8 77 5.1 Comparative Example 1 0.5 40 35.3 Comparative Example 2 1.8 48 27.4 Comparative Example 3 2.7 52 18.5 Comparative Example 4 2.1 49 20.1 Data Analysis: As can be seen from Table 1, the tensile strength of the boron-containing addition-curing modified organosilicon LED encapsulants prepared in Examples 1-6 of this application is 3.1-4.8 MPa, the Shore hardness is 54-77, and the peeling degree is only 4.9-6.8%. The test data show that by introducing boron into the system, the LED encapsulant prepared in this application not only has high adhesive strength and hardness, but also excellent resistance to ultraviolet aging.

[0058] The difference between Comparative Example 1 and Example 1 is that no boron group was introduced into the system. As can be seen from Table 1, the adhesive strength of Comparative Example 1 is only 0.5 MPa, which is almost zero. The Shore hardness is 40, and the product peeling degree is 35.3%. All performances are significantly worse than those of Example 1. The test data show that introducing boron group into the system in this application can improve the adhesive strength, hardness and UV aging resistance of the LED encapsulant.

[0059] The difference between Comparative Example 2 and Example 1 is that only the main adhesive introduces boron. As can be seen from Table 1, the bonding strength of Comparative Example 2 is only 1.8 MPa, the Shore hardness is 48, and the product peeling degree is 27.4%. All performances are significantly worse than those of Example 1. The test data show that when only the main adhesive introduces boron, the resulting LED encapsulant has lower bonding strength and hardness, and poor resistance to ultraviolet aging.

[0060] The difference between Comparative Examples 3-4 and Example 1 is that boron groups were not introduced into one of the components other than the main adhesive. As can be seen from Table 1, the adhesive strength of Comparative Examples 3-4 is only 2.1-2.7 MPa, the Shore hardness is 49-52, and the peeling degree is 18.5-20.1%. All performances are worse than those of Example 1. The test data show that the introduction of boron groups into vinyl silicone oil, hydrogen-containing silicone oil and polysilicone resin in this application can significantly improve the compatibility between the three, thereby improving the adhesive strength, hardness and UV aging resistance of the LED encapsulant.

[0061] In summary, the applicant's experiments revealed that introducing boron groups as additives, i.e., with a low boron content, does not significantly reduce compatibility with other components, and the resulting LED encapsulant exhibits good adhesive strength, hardness, and UV aging resistance. However, introducing boron groups directly into the main adhesive significantly increases the boron content, thereby reducing the compatibility of the boron-containing vinyl silicone oil with other components. Therefore, this application utilizes a mixture of boron-containing vinyl silicone oil, MTQ-type boron-containing polysiloxane resin, and boron-hydrogen silicone oil to substantially improve the adhesive strength, hardness, and UV aging resistance of the LED encapsulant.

[0062] The embodiments described in this specific implementation are preferred embodiments of this application and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A boron-containing addition-curing modified organosilicon LED encapsulant, characterized in that, The raw materials used include the following components in parts by weight: 100 parts of boron-containing vinyl silicone oil; 1-10 parts of borohydride silicone oil; 20-50 parts of MTQ type boron-containing polysilicon resin; Inhibitor 0.05-0.2 parts; 0.5-2.0 parts of platinum system catalyst; The preparation method of the boron-containing vinyl silicone oil includes the following steps: Under the protection of an inert gas, 80-100 parts by weight of methylcyclic siloxane, 1-10 parts by weight of vinylcyclic siloxane and 1-3 parts by weight of catalyst are mixed and stirred at 60-80°C for 1-3 hours. Then, 1-10 parts by weight of boric acid or borate ester are added to the reaction system, and the temperature is raised to 90-140°C for 1-6 hours. After that, 1-10 parts by weight of end-capping agent are added within 0.5-1.0 hours and reacted for 1-2 hours. Then, the temperature is raised to 175-185°C for de-lowering treatment. After cooling, boron-containing vinyl silicone oil is obtained. The preparation method of the boron-hydrogen silicone oil includes the following steps: Under the protection of an inert gas, 80-100 parts by weight of methylcyclic siloxane, 1-10 parts by weight of hydrocyclic siloxane and 1-3 parts by weight of catalyst are mixed and stirred at 60-80°C for 1-3 hours. Then, 1-10 parts by weight of boric acid or borate ester are added to the reaction system, and the temperature is raised to 90-140°C for 1-6 hours. After that, 1-10 parts by weight of end-capping agent are added within 0.5-1.0 hours and reacted for 1-2 hours. Then, the temperature is raised to 155-165°C for de-lowering treatment. After cooling, borohydride silicone oil is obtained. The preparation method of the MTQ type boron-containing polysilicone resin includes the following steps: After mixing 50-100 parts by weight of Q-chain siloxane and 10-20 parts by weight of T-chain siloxane, 0.1-3.0 parts by weight of catalyst and 1-10 parts by weight of boric acid or borate ester are added under the protection of inert gas. The mixture is reacted at 50-80°C for 0.5-1.0 h. Then, 10-30 parts by weight of end-capping agent are added within 0.5-1.0 h and the mixture is reacted for 1-2 h. After that, xylene is added for liquid-liquid extraction, de-lowering treatment, and cooling to obtain MTQ type boron-containing polysilicon resin.

2. The boron-containing addition-curing modified organosilicon LED encapsulant according to claim 1, characterized in that, The boron-containing vinyl silicone oil has a viscosity of 2000-10000 mPa·s, an alkenyl content of 0.5-5 wt%, and contains alkyl and / or phenyl groups in its molecules.

3. The boron-containing addition-curing modified organosilicon LED encapsulant according to claim 1, characterized in that, The borohydride silicone oil has a hydrogen content of 0.3-1.2 wt% and a viscosity of 500-2000 mPa·s.

4. The boron-containing addition-curing modified organosilicon LED encapsulant according to claim 1, characterized in that, The ratio of Q-units to T-units in the MTQ type boron-containing polysilicon resin is 0.6-1.2, the molecular weight is 3000-5000, and the MTQ type boron-containing polysilicon resin molecule contains alkyl and / or phenyl groups.

5. The boron-containing addition-curing modified organosilicon LED encapsulant according to claim 1, characterized in that, The inhibitors include one or more of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylacetylene, and ethynylcyclohexanol.

6. The boron-containing addition-curing modified organosilicon LED encapsulant according to claim 1, characterized in that, The platinum system catalyst includes one of platinum black, platinum chloride, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, or a complex of chloroplatinic acid and vinylsiloxane.

7. A method for preparing the boron-containing addition-curing modified organosilicon LED encapsulant as described in claim 1, characterized in that, The boron-containing vinyl silicone oil, boron-containing hydrosilicone oil, MTQ type boron-containing polysilicon resin, inhibitor and platinum system catalyst are mixed evenly.