Boron-containing addition type curing modified organic silicon LED packaging agent and preparation method thereof

Abstract

The invention relates to the field of LED packaging agents, and particularly discloses a boron-containing addition type curing modified organic silicon LED packaging agent and a preparation method thereof. The raw materials of the LED packaging agent comprise the following components in parts by weight: 100 parts of boron-containing vinyl silicone oil, 1-10 parts of boron hydrogen-containing silicone oil, 20-50 parts of MTQ type boron-containing silicone resin, 0.05-0.2 part of an inhibitor and 0.5-2.0 parts of a platinum system catalyst. The boron group is introduced into the system, so that the hardness and the bonding performance of the LED packaging agent can be greatly improved, the LED packaging agent can have excellent ultraviolet aging resistance, and the protection effect of the LED packaging agent on a light-emitting chip is remarkably improved.

Description

Technical Field

[0001] The present application relates to the field of LED encapsulants, and more specifically, to a boron-containing addition-curing modified organic silicon LED encapsulant and a preparation method thereof. Background Art

[0002] Light-emitting diodes (LEDs) are semiconductor components that emit light. Compared to conventional lighting, they offer numerous advantages, such as energy conservation, environmental protection, and a long service life. Known as "green lighting," they hold enormous promise in the lighting and display sectors. With increasing government and public awareness of energy conservation and environmental protection, coupled with technological advancements, LEDs are increasingly being used in general lighting applications, including landscape lighting, traffic signals, interior decorative lights, mining lamps, navigation lights, automotive LED lighting, and interior LED decorative lights.

[0003] LED packaging technology primarily encapsulates the light-emitting chip. As one of the core technologies in LED device manufacturing, this technology not only requires chip protection but also excellent light transmittance. Therefore, LED packaging places certain special requirements on the packaging material. Traditional LED encapsulants are based on epoxy resin. However, due to the poor high temperature and UV resistance of epoxy resin encapsulants, silicone materials are now increasingly used as the matrix.

[0004] Silicone encapsulants offer excellent thermal and UV stability, low ion content, low moisture absorption, minimal internal stress, excellent high and low temperature resistance, and resistance to yellowing. They also exhibit high transmittance in both the UV and visible regions, and their modulus and refractive index can be controlled by modifying their structure. These exceptional properties make them a preferred material for high-power LED packaging. However, certain areas of LED stents require treatment with insulating materials such as polyphthalamide (PPA) sheets. These materials have low surface energy, making them difficult to bond to due to the poor adhesion of existing silicone encapsulants, thus impacting the LED packaging process. Summary of the Invention

[0005] In order to solve the above technical problems, the present application provides a boron-containing addition-curing modified silicone LED encapsulant and a preparation method thereof.

[0006] In the first aspect, the present application provides a boron-containing addition-curing modified silicone 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; Contains 1-10 parts of borohydride silicone oil; 20-50 parts of MTQ type boron-containing polysilicone resin; Inhibitor 0.05-0.2 parts; 0.5-2.0 parts of platinum system catalyst.

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

[0008] Preferably, the preparation method of the boron-containing vinyl silicone oil comprises the following steps: Under the protection of inert gas, 80-100 parts by weight of methylcyclosiloxane, 1-10 parts by weight of vinylcyclosiloxane and 1-3 parts by weight of catalyst are mixed and stirred at a temperature of 60-80°C for 1-3 hours, then 1-10 parts by weight of boric acid or boric ester are added to the reaction system, and the temperature is continuously raised to 90-140°C and the reaction is carried out for 1-6 hours. Thereafter, 1-10 parts by weight of a capping agent is added within 0.5-1.0 hours and the reaction is carried out for 1-2 hours. The temperature is then raised to 175-185°C for desulfurization treatment, and the boron-containing vinyl silicone oil is obtained after cooling.

[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 preparation method of the borohydride-containing silicone oil comprises the following steps: Under the protection of inert gas, 80-100 parts by weight of methylcyclosiloxane, 1-10 parts by weight of hydrogencyclosiloxane and 1-3 parts by weight of catalyst are mixed and stirred at a temperature of 60-80°C for 1-3 hours, then 1-10 parts by weight of boric acid or boric ester are added to the reaction system, and the temperature is continuously raised to 90-140°C and the reaction is carried out for 1-6 hours. Thereafter, 1-10 parts by weight of a capping agent is added within 0.5-1.0 hours and the reaction is carried out for 1-2 hours. The temperature is then raised to 155-165°C for desulfurization treatment, and the boron-containing vinyl silicone oil is obtained after cooling.

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

[0012] Preferably, the vinylcyclosiloxane includes tetramethyltetravinylcyclotetrasiloxane and / or octavinylcyclotetrasiloxane.

[0013] Preferably, the hydrogenated cyclosiloxane 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 includes one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine and anion exchange resin.

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

[0019] Preferably, the boric acid includes one or more of boric acid, phenylboric acid and tetrahydroxyboron.

[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 includes one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane and tetramethyldisiloxane.

[0022] Preferably, the ratio of Q segments to T segments of the MTQ boron-containing polysilicone resin is 0.6-1.2, the molecular weight is 3000-5000, and the molecules of the MTQ boron-containing polysilicone resin contain alkyl groups and / or phenyl groups.

[0023] Preferably, the preparation method of the MTQ type boron-containing polysilicone resin comprises the following steps: After mixing 50-100 parts by weight of Q-linked siloxane and 10-20 parts by weight of T-linked siloxane, 0.1-3.0 parts by weight of a catalyst and 1-10 parts by weight of boric acid or boric acid ester are added under the protection of an inert gas, and the mixture is reacted at a temperature of 50-80°C for 0.5-1.0h. Then, 10-30 parts by weight of a capping agent is added within 0.5-1.0h and the mixture is reacted for 1-2h. After that, xylene is added for liquid separation and extraction, desulfurization treatment is performed, and the MTQ-type boron-containing polysilicone resin is obtained after cooling.

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

[0025] Preferably, the T-linked 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-based catalyst includes one of platinum black, platinum chloride, chloroplatinic acid, an alcohol 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] In a second aspect, the present application provides a method for preparing a boron-containing addition-curing modified silicone LED encapsulant, which adopts the following technical solution: A method for preparing a boron-containing addition-curing modified organic silicon LED encapsulant comprises uniformly mixing boron-containing vinyl silicone oil, boron-hydrogen silicone oil, MTQ-type boron-containing polysilicone resin, an inhibitor and a platinum system catalyst.

[0030] In summary, this application has the following beneficial technical effects: The present application adopts boron-containing vinyl silicone oil as the main glue, and is matched with MTQ-type boron-containing polysilicone resin and boron-hydrogen silicone oil. Under the action of an inhibitor and a platinum system catalyst, the curing is carried out at a certain temperature to obtain a boron-containing addition-type curing modified silicone LED encapsulant. By introducing a boron group into the system, the present application can not only greatly improve the hardness and bonding performance of the LED encapsulant, but also make it have excellent resistance to ultraviolet light aging, significantly improving the protective effect of the LED encapsulant on the light-emitting chip. In addition, the present application introduces a boron group into vinyl silicone oil, MTQ-type polysilicone resin and hydrogen-containing silicone oil, which can not only greatly increase the boron content in the LED encapsulant, but also improve the compatibility between the components in the system, thereby further improving the hardness, bonding performance and ultraviolet light aging resistance of the LED encapsulant. DETAILED DESCRIPTION

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

[0032] In some embodiments of the boron-containing vinyl silicone oil, the methylcyclosiloxane includes one or more of octamethylcyclotetrasiloxane, tetraphenyltetramethylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane; In some embodiments of the boron-containing vinyl silicone oil, the vinyl cyclosiloxane includes tetramethyltetravinylcyclotetrasiloxane and / or octavinylcyclotetrasiloxane; In some specific embodiments of the boron-containing vinyl 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, dodecylbenzenesulfonic acid and a cation exchange resin, and the basic catalyst includes one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine and an anion exchange resin; in some preferred specific embodiments of the boron-containing vinyl silicone oil, the catalyst is a cation exchange resin or an 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 embodiments of the boron-containing vinyl silicone oil, the boric acid comprises one or more of boric acid, phenylboric acid and tetrahydroxyboron; In some embodiments of the boron-containing vinyl silicone oil, the borate ester includes one or more of trimethyl borate, triethyl borate, triethanolamine borate, and triallyl borate; In some embodiments of the boron-containing vinyl silicone oil, 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 ratios and the following steps are performed: under the protection of inert gas, 80-100 parts by weight of methylcyclosiloxane, 1-10 parts by weight of vinylcyclosiloxane and 1-3 parts by weight of a catalyst are mixed and stirred at a temperature of 60-80°C for 1-3 hours, then 1-10 parts by weight of boric acid or boric acid ester are added to the reaction system, the temperature is continuously raised to 90-140°C, the reaction is carried out for 1-6 hours, and then 1-10 parts by weight of a capping agent is added within 0.5-1.0 hours to react for 1-2 hours, and the temperature is then raised to 175-185°C for desulfurization treatment, and cooled to obtain a boron-containing vinyl silicone oil having a viscosity of 2000-10000 mPa·s, an alkenyl content of 0.5-5wt%, and containing alkyl and / or phenyl groups in the molecule.

[0033] In some embodiments containing borohydride silicone oil, the methylcyclosiloxane includes one or more of octamethylcyclotetrasiloxane, tetraphenyltetramethylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane; In some embodiments containing borohydride silicone oil, the hydrogenated cyclosiloxane comprises tetramethylcyclotetrasiloxane; In some embodiments of the borohydride silicone oil, the catalyst comprises an acidic catalyst or a basic catalyst, wherein the acidic catalyst comprises one or more of concentrated hydrochloric acid, concentrated sulfuric acid, dodecylbenzenesulfonic acid and a cation exchange resin, and the basic catalyst comprises one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine and an anion exchange resin; In some preferred embodiments of the borohydride silicone oil, the catalyst is a cation exchange resin or an 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 embodiments containing borohydride silicone oil, the boric acid comprises one or more of boric acid, phenylboric acid and tetrahydroxyboron; in some embodiments containing borohydride silicone oil, the borate ester comprises one or more of trimethyl borate, triethyl borate, triethanolamine borate and triallyl borate; In some embodiments containing borohydride silicone oil, the end-capping agent includes one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, and tetramethyldisiloxane; In some specific embodiments of borohydrogen silicone oil, the above raw materials are used in the following proportions and the following steps are performed: under the protection of inert gas, 80-100 parts by weight of methylcyclosiloxane, 1-10 parts by weight of hydrogencyclosiloxane and 1-3 parts by weight of a catalyst are mixed and stirred at a temperature of 60-80° C. for 1-3 hours, then 1-10 parts by weight of boric acid or boric acid ester are added to the reaction system, the temperature is continuously raised to 90-140° C., the reaction is carried out for 1-6 hours, and then 1-10 parts by weight of a capping agent is added within 0.5-1.0 hours and the reaction is carried out for 1-2 hours, and the temperature is then raised to 155-165° C. for dehydrogenation treatment, and the reaction is cooled to obtain a borohydrogen silicone oil having a hydrogen content of 0.3-1.2wt% and a viscosity of 500-2000 mPa·s.

[0034] In some embodiments of the MTQ-type boron-containing polysilicone resin, the Q-linked siloxane comprises one or more of tetramethyl silicate, tetraethyl silicate, methyl polysilicate, and ethyl polysilicate; In some embodiments of the MTQ-type boron-containing polysiloxane, the T-linked siloxane includes one or more of methyltrimethoxysiloxane, methyltriethoxysiloxane, phenyltrimethoxysiloxane, and phenyltriethoxysilane; In some embodiments of the MTQ-type boron-containing polysilicone 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, dodecylbenzenesulfonic acid and a cation exchange resin, and the basic catalyst includes one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine and an anion exchange resin; In some preferred embodiments of the MTQ-type boron-containing polysilicone resin, the catalyst is a cation exchange resin or an 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 embodiments of the MTQ type boron-containing polysilicone resin, the boric acid comprises one or more of boric acid, phenylboric acid and tetrahydroxyboron; In some embodiments of the MTQ-type boron-containing polysilicone resin, the borate ester includes one or more of trimethyl borate, triethyl borate, triethanolamine borate, and triallyl borate; In some embodiments of the MTQ-type boron-containing polysiloxane, the end-capping agent includes one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, and tetramethyldisiloxane; In some specific embodiments of the MTQ-type boron-containing polysilicone resin, the above raw materials are used in the following proportions and the following steps are performed: 50-100 parts by weight of Q-linked siloxane and 10-20 parts by weight of T-linked siloxane are mixed, and under the protection of an inert gas, 0.1-3.0 parts by weight of a catalyst and 1-10 parts by weight of boric acid or boric acid ester are added, and the mixture is reacted at a temperature of 50-80°C for 0.5-1.0h, and then 10-30 parts by weight of a capping agent are added within 0.5-1.0h to react for 1-2h, and then xylene is added for liquid separation and extraction, desulfurization treatment is performed, and cooling is performed to obtain an MTQ-type boron-containing polysilicone resin having a Q-linked to T-linked 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 embodiments of the boron-containing addition-curing modified silicone LED encapsulant, the inhibitor includes one or more of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylacetylene, and ethynylcyclohexanol; In some embodiments of the boron-containing addition-curing modified silicone LED encapsulant, the platinum-based catalyst includes one of platinum black, platinum chloride, chloroplatinic acid, an alcohol solution of chloroplatinic acid, and a complex of chloroplatinic acid and vinyl siloxane; In some preferred embodiments of the boron-containing addition-curing modified silicone LED encapsulant, the platinum system catalyst is a complex of chloroplatinic acid and vinyl siloxane, wherein the platinum content is 500-2000 ppm; In some specific embodiments of boron-containing addition-curing modified silicone LED encapsulant, 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 polysilicone 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 a temperature of 120-150°C for 3-5 minutes. The boron-containing addition-curing modified silicone LED encapsulant obtained by curing has a Shore hardness of not less than 54, an adhesive strength of not less than 3.1 MPa, and excellent resistance to ultraviolet light aging.

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

[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. Then nitrogen was introduced and 1 kg of anion exchange resin D201 was added and mixed. The mixture was stirred at 60 ° C for 3 hours. Then, 10 kg of 50% by mass boric acid solution was added to the reaction system, and the temperature was continued to rise to 90 ° C and reacted for 6 hours. After that, 1 kg of hexamethyldisiloxane was added within 0.5 hours and reacted for 1 hour. The temperature was then raised to 175 ° C for desulfurization treatment and cooled to obtain boron-containing vinyl silicone oil.

[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. Then nitrogen was introduced and 3 kg of anion exchange resin D201 was added and mixed. The mixture was stirred at 80 ° C for 1 hour. Then, 1 kg of 50% by mass boric acid solution was added to the reaction system, and the temperature was continued to rise to 140 ° C and reacted for 1 hour. After that, 10 kg of hexamethyldisiloxane was added within 1 hour and reacted for 2 hours. The temperature was then raised to 185 ° C for desulfurization treatment and cooled to obtain boron-containing vinyl silicone oil.

[0039] Preparation Example 3 The borohydride-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. Then, nitrogen was introduced, and 1 kg of cation exchange resin D001 was added and mixed. The mixture was stirred at 60 ° C for 3 hours. Then, 10 kg of 50% by mass boric acid solution was added to the reaction system, and the temperature was continued to be raised to 90 ° C. and reacted for 6 hours. After that, 1 kg of tetramethyldisiloxane was added within 0.5 hours and reacted for 1 hour. The temperature was then raised to 155 ° C for desulfurization treatment, and the boron hydrogen silicone oil was obtained after cooling.

[0040] Preparation Example 4 The borohydride-containing silicone 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. Then, nitrogen was introduced, and 3 kg of cation exchange resin D001 was added and mixed. The mixture was stirred at 80 ° C for 1 hour. Then, 1 kg of 50% by mass boric acid solution was added to the reaction system, and the temperature was continued to be raised to 140 ° C. and reacted for 1 hour. After that, 10 kg of tetramethyldisiloxane was added within 1 hour and reacted for 2 hours. The temperature was then raised to 165 ° C for desulfurization treatment, and the boron hydrogen silicone oil was obtained after cooling.

[0041] Preparation Example 5 MTQ type boron-containing polysilicone resin is prepared by the following method: After mixing 50 kg of polyethyl silicate and 20 kg of methyltrimethoxysiloxane, introduce inert gas and stir, add 0.1 kg of cation exchange resin D001 and 10 kg of 50 wt% boric acid solution, react at 50 ° C for 1 hour, then add 10 kg of hexamethyldisiloxane within 0.5 hours and react for 1 hour, then add xylene for liquid separation and extraction, desulfurization treatment, and cooling to obtain MTQ type boron-containing polysilicone resin.

[0042] Preparation Example 6 MTQ type boron-containing polysilicone resin is prepared by the following method: After mixing 100 kg of polyethyl silicate and 10 kg of phenyltrimethoxysiloxane, an inert gas was introduced and 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 reacted for 2 h. After that, xylene was added for liquid separation and extraction, desulfurization treatment was performed, and cooling was performed to obtain MTQ-type boron-containing polysilicone 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. Then nitrogen was introduced and 1 kg of anion exchange resin D201 was added and mixed. The mixture was stirred at 60 ° C for 3 hours, then heated to 90 ° C and reacted for 6 hours. After that, 1 kg of hexamethyldisiloxane was added within 0.5 hours and reacted for 1 hour. The mixture was then heated to 175 ° C for desulfurization and cooled to obtain vinyl silicone oil.

[0044] Comparative Preparation Example 2 Hydrogenated 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. Then, nitrogen was introduced and 1 kg of cation exchange resin D001 was added and mixed. The mixture was stirred at 60 ° C for 3 hours, then heated to 90 ° C and reacted for 6 hours. After that, 1 kg of tetramethyldisiloxane was added within 0.5 hours and reacted for 1 hour. The mixture was then heated to 155 ° C for desulfurization and cooled to obtain hydrogenated silicone oil.

[0045] Comparative Preparation Example 3 MTQ type polysilicone resin is prepared by the following method: After mixing 50 kg of polyethyl silicate and 20 kg of methyltrimethoxysiloxane, introduce inert gas and stir, add 0.1 kg of cation exchange resin D001, react at 50 ° C for 1 hour, then add 10 kg of hexamethyldisiloxane within 0.5 hours and react for 1 hour, then add xylene for liquid separation and extraction, desulfurization treatment, and cooling to obtain MTQ type polysilicone resin.

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

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

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

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

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

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

[0052] Comparative Example 1 The difference from Example 1 is that no boron group is introduced into the reaction system, that is, the boron-containing vinyl silicone oil prepared in Preparation Example 1 is replaced by the vinyl silicone oil prepared in Comparative Preparation Example 1, the boron-hydrogen silicone oil prepared in Preparation Example 3 is replaced by the hydrogen-containing silicone oil prepared in Comparative Preparation Example 2, and the MTQ-type boron-containing polysilicone resin prepared in Preparation Example 5 is replaced by the MTQ-type polysilicone resin prepared in Comparative Preparation Example 3. The rest is the same as Example 1.

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

[0055] Comparative Example 4 The difference from Example 1 is that only the MTQ type boron-containing polysilicone resin prepared in Preparation Example 5 is replaced by the MTQ type polysilicone resin prepared in Comparative Preparation Example 3, and the rest is the same as Example 1.

[0056] Performance testing 1. Adhesive strength: The LED encapsulants prepared in the above examples and comparative examples were tested with reference to 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 measured with reference to GB / T 531.1-2008 "Test method for indentation hardness of vulcanized or thermoplastic rubber - Part 1: Shore hardness"; 3. UV aging resistance: With reference to GB / T 16422.1-2006 "Plastics Laboratory Light Source Exposure Test Methods Part 1: General", 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°C in the light and 40-60°C in the dark. The radiation intensity was 0.25-1.55W / m 2 / nm, the irradiation time is 12h, and the degree of product peeling after light aging test is evaluated; The above test results are shown in Table 1.

[0057] Table 1 project Bond strength (MPa) Shore hardness (D) Product peeling degree (%) 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 boron-containing addition-curing modified silicone LED encapsulants prepared in Examples 1-6 of the present application have a bond strength of 3.1-4.8 MPa, a Shore hardness of 54-77, and a product peeling degree of only 4.9-6.8%. The experimental data show that by introducing boron groups into the system, the LED encapsulants prepared in this application not only have high bonding strength and hardness, but also have excellent resistance to ultraviolet light aging.

[0058] The difference between Comparative Example 1 and Example 1 is that no boron group is introduced into the system. As can be seen from Table 1, the bonding strength of Comparative Example 1 is only 0.5 MPa, which is almost close to 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 the introduction of boron groups into the system in this application can improve the bonding 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 the boron group. 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 the boron group, the bonding strength and hardness of the obtained LED encapsulant are low, and the UV aging resistance is poor.

[0060] The difference between Comparative Examples 3-4 and Example 1 is that no boron group is introduced into any of the components other than the main glue. As can be seen from Table 1, the bonding strength of Comparative Examples 3-4 is only 2.1-2.7 MPa, the Shore hardness is 49-52, and the product peeling degree is 18.5-20.1%. All performance is worse than that of Example 1. The test data show that the present application introduces boron groups into vinyl silicone oil, hydrogenated silicone oil and polysilicone resin, which can greatly improve the compatibility between the three, thereby improving the bonding strength, hardness and UV aging resistance of the LED encapsulant.

[0061] In summary, the applicant has discovered through experiments that if the boron group is introduced via an additive, that is, when the boron content is low, the compatibility with other components is not significantly reduced, and the resulting LED encapsulant exhibits good bonding strength, hardness, and UV aging resistance. However, if the boron group is introduced into the main adhesive, the boron content is significantly increased, thereby reducing the compatibility between the boron-containing vinyl silicone oil and other components. Therefore, the present application utilizes a combination of boron-containing vinyl silicone oil, MTQ-type boron-containing polysilicone resin, and boron hydrogen-containing silicone oil to significantly improve the bonding strength, hardness, and UV aging resistance of the LED encapsulant.

[0062] The embodiments of this specific implementation method are all preferred embodiments of the present application and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A boron-containing addition-curing modified silicone 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; Contains 1-10 parts of borohydride silicone oil; 20-50 parts of MTQ type boron-containing polysilicone resin; Inhibitor 0.05-0.2 parts; 0.5-2.0 parts of platinum system catalyst.

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

3. The boron-containing addition-curing modified silicone LED encapsulant according to claim 2, characterized in that: The preparation method of the boron-containing vinyl silicone oil comprises the following steps: Under the protection of inert gas, 80-100 parts by weight of methylcyclosiloxane, 1-10 parts by weight of vinylcyclosiloxane and 1-3 parts by weight of catalyst are mixed and stirred at a temperature of 60-80°C for 1-3 hours, then 1-10 parts by weight of boric acid or boric ester are added to the reaction system, and the temperature is continuously raised to 90-140°C and the reaction is carried out for 1-6 hours. Thereafter, 1-10 parts by weight of a capping agent is added within 0.5-1.0 hours and the reaction is carried out for 1-2 hours. The temperature is then raised to 175-185°C for desulfurization treatment, and the boron-containing vinyl silicone oil is obtained after cooling.

4. The boron-containing addition-curing modified silicone 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.

5. The boron-containing addition-curing modified silicone LED encapsulant according to claim 4, characterized in that: The preparation method of the boron hydrogen silicone oil comprises the following steps: Under the protection of inert gas, 80-100 parts by weight of methylcyclosiloxane, 1-10 parts by weight of hydrogencyclosiloxane and 1-3 parts by weight of catalyst are mixed and stirred at a temperature of 60-80°C for 1-3 hours, then 1-10 parts by weight of boric acid or boric ester are added to the reaction system, and the temperature is continuously raised to 90-140°C and the reaction is carried out for 1-6 hours. Thereafter, 1-10 parts by weight of a capping agent is added within 0.5-1.0 hours and the reaction is carried out for 1-2 hours. The temperature is then raised to 155-165°C for desulfurization treatment, and the boron-containing vinyl silicone oil is obtained after cooling.

6. The boron-containing addition-curing modified silicone LED encapsulant according to claim 1, characterized in that: The ratio of Q segments to T segments of the MTQ boron-containing polysilicone resin is 0.6-1.2, the molecular weight is 3000-5000, and the molecules of the MTQ boron-containing polysilicone resin contain alkyl groups and / or phenyl groups.

7. The boron-containing addition-curing modified silicone LED encapsulant according to claim 6, characterized in that: The preparation method of the MTQ type boron-containing polysilicone resin comprises the following steps: After mixing 50-100 parts by weight of Q-linked siloxane and 10-20 parts by weight of T-linked siloxane, 0.1-3.0 parts by weight of a catalyst and 1-10 parts by weight of boric acid or boric acid ester are added under the protection of an inert gas, and the mixture is reacted at a temperature of 50-80°C for 0.5-1.0h. Then, 10-30 parts by weight of a capping agent is added within 0.5-1.0h and the mixture is reacted for 1-2h. After that, xylene is added for liquid separation and extraction, desulfurization treatment is performed, and the MTQ-type boron-containing polysilicone resin is obtained after cooling.

8. The boron-containing addition-curing modified silicone LED encapsulant according to claim 1, characterized in that: The inhibitor includes one or more of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylacetylene, and ethynylcyclohexanol.

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

10. A method for preparing the boron-containing addition-curing modified silicone LED encapsulant according to claim 1, characterized in that: The boron-containing vinyl silicone oil, the boron-containing hydrogen silicone oil, the MTQ type boron-containing polysilicone resin, the inhibitor and the platinum system catalyst are mixed evenly.