WO2017028008A1 - High-refractive-index, high-toughness and vulcanization-resistant led packaging silicone - Google Patents

Abstract

The present invention belongs to the technical field of adhesives, relating to LED packaging silicones, and more particularly to a high-refractive-index LED packaging silicone. A high-refractive-index LED packaging silicone provided by the present invention comprises a component A and a component B, wherein a weight ratio of the component A to the component B is 10:1. The component A comprises the following raw material components in parts by weight: 80-90 parts of a methyl phenyl vinyl silicone resin, 8-18 parts of vinyl dimethyl diphenyl polysiloxane, 0.1-0.3 parts of a platinum-based catalyst, and 1-5 parts of a binder. The component B comprises the following raw material components in parts by weight: 40-60 parts of a methyl phenyl hydrogenated silicone resin, 40-60 parts of hydrogen-terminated diphenyl polysiloxane, and 0.1-0.3 parts of an inhibitor. The high-refractive-index LED packaging silicone in the present invention has the advantageous effects of high hardness, vulcanization resistance, outstanding adhesion, outstanding resistance to cold, heat and impact, etc.

Description

High refractive index and high toughness resistant vulcanized LED package silicone Technical field

The invention relates to a high refractive index LED package silica gel, in particular to a high refractive index, sulfurization resistant, cold and thermal shock resistant LED package silica gel, belonging to the technical field of adhesives.

Background technique

As LED applications become more widespread, the requirements for LED packaging materials are also increasing. The current packaging materials used in LEDs mainly include epoxy resin and silicone materials. The internal stress of epoxy resin is too large, yellowing, poor resistance to high and low temperature, poor aging resistance, and silicone materials, low internal stress, high and low temperature resistance. Good, not yellow, the overall performance is significantly better than epoxy resin, so it quickly replaces epoxy resin and is widely used in the field of LED packaging. The high refractive index organic silica gel having a refractive index higher than 1.50 has an increasing use rate with higher light extraction efficiency.

With the development of industry, the sulfur content in the air is increasing. If the packaging material is improperly selected, the sulfur in the air will pass through the encapsulating material or its bonding interface to corrode the silver layer of the bracket to form black silver sulfide, resulting in Light decay has increased dramatically. Therefore, this brings new challenges to the packaging material, and it is necessary to improve the vulcanization resistance.

At present, the refractive index of high-refractive-index LED packaged silica gel in China can reach between 1.50 and 1.55. However, due to the formulation of silicone resin, vinyl silicone oil and hydrogen-containing silicone oil, the relative content of silicone resin is low and the crosslinking density is low. Low, and the bonding effect is not ideal, so the resistance to vulcanization is poor, the bonding interface is easily broken, and the high-silicone resin content and high cross-linking density of the LED package silica gel have improved resistance to vulcanization, but due to its excessive internal stress. It will lead to a decrease in the toughness of the material, and the reaction may occur in the use of high and low temperature thermal shock lamps, cracking of the encapsulating material, and failure of the bonding interface.

Summary of the invention

The present invention provides a high refractive index LED packaged silica gel with the advantages of the prior art, and has the advantages of high hardness, excellent resistance to vulcanization, excellent adhesion, and excellent cold and thermal shock resistance.

The technical solution to solve the above technical problem is as follows: a high refractive index LED package silica gel, comprising A component and B component, the weight ratio of the A component to the B component is 10:1;

Wherein, the composition and composition of the raw materials of the component A are as follows:

The composition and composition of the raw materials of the B component are as follows:

Methylphenyl hydrogen-containing silicone resin 40 to 60 parts by weight;

Hydrogenated diphenyl polysiloxane 40 to 60 parts by weight;

The inhibitor is 0.1 to 0.3 parts by weight.

Based on the above technical solutions, the present invention can also be improved as follows.

Further, the methylphenylvinyl silicone resin has a molecular formula of (ViMe ₂ SiO _1/2 ) _x (PhSiO _3/2 ) _y , wherein the Me is a methyl group, Vi is a vinyl group, and Ph is a phenyl group. , x: y = 1: 3.5 ~ 5.

The advantageous effect of the above further embodiment is that, as the matrix resin, it is a silicone resin containing vinyl, which improves the strength and hardness of the product and improves the vulcanization resistance.

Further, the vinyl dimethyl diphenyl polysiloxane has a molecular formula of: (ViMe ₂ SiO _1/2 ) _a (ViMePh ₂ SiO _1/2 ) _b , wherein the Me is a methyl group, and Vi is Vinyl, Ph is phenyl, 10 ≤ a ≤ 70, 10 ≤ b ≤ 70, and a: b = 1:1.

The beneficial effect of using the above further solution is that the addition of vinyl dimethyl diphenyl polysiloxane provides a vinyl group which can participate in the reaction, lowers the stress after curing of the system, and improves the resistance to thermal shock.

Further, the structural formula of the adhesive is:

The adhesive of the present invention contains an epoxy group and an alkoxy group, and its structural formula is as shown above. The addition of the adhesive improves the adhesion of the encapsulating material to the plastic and the metal substrate, and the presence of the ring further improves the vulcanization resistance of the polymer.

Further, the platinum-based catalyst is a platinum-methylphenylpolysiloxane complex or a platinum-olefin complex.

Preferably, the platinum-based catalyst is a platinum-methylphenylpolysiloxane complex and has a platinum content of from 3,000 to 10,000 ppm.

Further, the molecular formula of the methylphenyl hydrogen-containing silicone resin is: (HMe ₂ SiO _1/2 ) ₃ (MePhSiO _1/2 ) _n (PhSiO _3/2 ) ₄ , wherein the Me is a methyl group, Ph It is a phenyl group, 4≤n≤6.

The beneficial effect of using the above further embodiment is that the methylphenyl hydrogen-containing silicone resin of the present invention as a crosslinking agent is also a hydrogen-containing silicone resin, which not only provides active hydrogen to participate in the crosslinking reaction, but also increases the crosslinking density. The presence of the D chain link (MePhSiO _1/2 ) improves the toughness of the entire system, improves the thermal shock resistance, and has a low viscosity, which reduces the viscosity, strength and toughness of the entire system.

Further, the terminal hydrogen-containing diphenylpolysiloxane has the formula: (HMe ₂ SiO _1/2 ) ₁ (Ph ₂ SiO _1/2 ) _m , wherein the Me is a methyl group and the Ph is a phenyl group. , 4 ≤ m ≤ 6.

The beneficial effect of using the above further embodiment is that the hydrogen-containing diphenyl polysiloxane of the present invention acts as a chain extender, which not only provides active hydrogen to participate in the chain extension reaction, but also increases the crosslinking density and improves the toughness of the polymer. The cold and thermal shock resistance is improved, and the viscosity is low, which lowers the viscosity, improves the strength and toughness of the entire system.

Further, the inhibitor is selected from the group consisting of ethynylcyclohexanol or 1,1,3-triphenyl-2-propyn-1-ol.

Preferably, the inhibitor is 1,1,3-triphenyl-2-propyn-1-ol, and the structural formula is:

The second aspect of the present invention discloses a method for preparing the foregoing high refractive index LED packaged silica gel, comprising the steps of preparing the component A and the step of preparing the component B;

1) The preparation step of the component A is as follows: 80 to 90 parts of methylphenylvinyl silicone resin, 8 to 18 parts of vinyl dimethyl diphenyl polysiloxane, and 0.1 to 0.3 parts of platinum catalyst. 1 to 5 parts of the binder are sequentially added to the mixer, stirred for 3 to 5 hours, and uniformly mixed to obtain the A component;

2) The preparation step of the B component is as follows: 40 to 60 parts of the methylphenyl hydrogen-containing silicone resin, 40 to 60 parts of the hydrogen diphenyl polysiloxane, and 0.1 to 0.3 parts of the inhibitor are sequentially added to the mixer. The mixture was stirred for 3 to 5 hours, and uniformly mixed to obtain a component B.

A third aspect of the present invention discloses a method for using the high-refractive-index LED packaged silicon, in which the A component and the B component are uniformly mixed in a weight ratio of 10:1, and vacuum defoamed for 20 to 40 minutes. Dispensing or potting on the package to be packaged, first heating at 100 ~ 120 ° C for 0.5 ~ 1.5 hours, then heating at 100 ~ 200 ° C for 3 ~ 5 hours, curing.

The invention has the beneficial effects that the high refractive index LED packaged silica gel of the invention is composed of components A and B, and the component A provides high strength resin, vinyl, catalyst and binder in the reaction, and the B component provides high. Strength resin, crosslinking agent, chain extender and inhibitor, high refractive index LED of the present invention Encapsulated silica gel, in addition to vinyl silicone resin, the curing agent is methyl phenyl hydrosilane resin combined with hydrogen diphenyl polysiloxane, the content of silicone resin increases, and at the same time, the silicone resin is added. The phenyl content; in addition, the crosslink density is further increased, the hardness of the product is improved, the vulcanization resistance is improved, and a binder having a special structure is added, so that the adhesion to the substrate after curing is excellent. The combination of silicone resin and suitable silicone, the combination of crosslinking agent and chain extender reduces the internal stress of the cured material, good interfacial adhesion, and improves the thermal shock resistance and resistance of the product. High temperature performance.

detailed description

The principles and features of the present invention are described below, and the examples are intended to be illustrative only and not to limit the scope of the invention.

Example 1

Raw material

Methylphenyl vinyl silicone resin: (ViMe ₂ SiO _1/2 ) (PhSiO _3/2 ) ₅ ;

Vinyl dimethyl diphenyl polysiloxane: (ViMe ₂ SiO _1/2 ) ₁₀ ( ViMePh ₂ SiO _1/2 ) ₁₀ ;

The platinum-based catalyst is a platinum-methylphenyl polysiloxane complex;

Methylphenyl hydrogen-containing silicone resin: (HMe ₂ SiO _1/2 ) ₃ (MePhSiO _1/2 ) ₅ (PhSiO _3/2 ) ₄ ;

Hydrogenated diphenyl polysiloxane: (HMe ₂ SiO _1/2 ) ₁ (Ph ₂ SiO _1/2 ) ₄ ;

The inhibitor is ethynylcyclohexanol.

2. Preparation method

Preparation of component A: 80 parts of methyl phenyl vinyl silicone resin, 18 parts of vinyl dimethyl diphenyl polysiloxane, 0.1 part of platinum catalyst, and 2.9 parts of binder were added to the mixer for mixing. Stir well for 3h to obtain the A component;

Preparation of component B: Weigh 40 parts of dimethyldiphenyl hydrogen-containing silicone resin, 59.8 parts of hydrogen diphenylpolysiloxane, and inhibitor 1,1,3-triphenyl-2-propyne 1-propanol 0.2 parts. Adding to the mixer in turn, mixing for 3 hours and stirring uniformly, that is, the B component is obtained;

In use, the A component and the B component are uniformly mixed in a weight ratio of 10:1, vacuum defoamed for 20 minutes, dispensed or potted on the package to be packaged, and first heated at 120 ° C for 1 hour. Then, heat at 150 ° C for 4 hours.

Example 2

Raw material

Methylphenyl vinyl silicone resin: (ViMe ₂ SiO _1/2 ) (PhSiO _3/2 ) _3.5 ;

Vinyl dimethyl diphenyl polysiloxane: (ViMe ₂ SiO _1/2 ) ₇₀ ( ViMePh ₂ SiO _1/2 ) ₇₀ ;

The platinum-based catalyst is a platinum-olefin complex;

Methylphenyl hydrogen silicone resin: (HMe ₂ SiO _1/2 ) ₃ (MePhSiO _1/2 ) ₄ (PhSiO _3/2 ) ₄ ;

Hydrogenated diphenyl polysiloxane: (HMe ₂ SiO _1/2 ) ₁ (Ph ₂ SiO _1/2 ) ₅ ;

The inhibitor is 1,1,3-triphenyl-2-propyn-1-ol.

2. Preparation method

Preparation of component A: Weigh 90 parts of methyl phenyl vinyl silicone resin, 8 parts of vinyl dimethyl diphenyl polysiloxane, 0.3 parts of platinum catalyst, and 1.0 part of binder are sequentially added to the mixer for mixing. Stir well for 5h to obtain the A component;

Preparation of component B: 60 parts of dimethyldiphenyl hydrogen-containing silicone resin was weighed, and 39.7 parts of hydrogen diphenylpolysiloxane was contained, and 0.3 parts of inhibitor. Adding to the mixer in turn, mixing for 5 hours and stirring uniformly, that is, the B component is obtained;

In use, the A component and the B component are uniformly mixed in a weight ratio of 10:1, vacuum defoamed for 40 minutes, dispensed or potted on the package to be packaged, and first heated at 100 ° C for 1.5 hours. Then, heat at 100 ° C for 5 hours.

Example 3

Raw material

Methylphenyl vinyl silicone resin: (ViMe ₂ SiO _1/2 ) ₂ (PhSiO _3/2 ) ₈ ;

Vinyl dimethyl diphenyl polysiloxane: (ViMe ₂ SiO _1/2 ) ₄₀ ( ViMePh ₂ SiO _1/2 ) ₄₀ ;

The platinum-based catalyst is a platinum-methylphenyl polysiloxane complex;

Methylphenyl hydrogen-containing silicone resin: (HMe ₂ SiO _1/2 ) ₃ (MePhSiO _1/2 ) ₆ (PhSiO _3/2 ) ₄ ;

Hydrogenated diphenyl polysiloxane: (HMe ₂ SiO _1/2 ) ₁ (Ph ₂ SiO _1/2 ) ₆ ;

The inhibitor is 1,1,3-triphenyl-2-propyn-1-ol.

2. Preparation method

Preparation of component A: 85 parts of methyl phenyl vinyl silicone resin, 9.8 parts of vinyl dimethyl diphenyl polysiloxane, 0.2 parts of platinum catalyst, and 5 parts of binder were sequentially added to a mixer. Mixing for 4 hours and stirring to obtain the A component;

Preparation of component B: 50 parts of dimethyldiphenyl hydrogen-containing silicone resin was weighed, 49.9 parts of hydrogen diphenylpolysiloxane was contained, and 0.1 part of inhibitor was weighed. Adding to the mixer in turn, mixing for 4 hours and stirring evenly, that is, the B component is obtained;

In use, the A component and the B component are uniformly mixed in a weight ratio of 10:1, vacuum defoamed for 20 minutes, dispensed or potted on the package to be packaged, and first heated at 120 ° C for 0.5 hour. Then, heat at 200 ° C for 3 hours.

Comparative example 1

1. Composition of raw materials

Methylphenyl vinyl silicone resin: (ViMe ₂ SiO _1/2 ) (PhSiO _3/2 ) ₅ ;

The platinum-based catalyst is a platinum-methylphenyl polysiloxane complex;

Adhesive (adhesive of the present invention)

Methylphenyl hydrogen-containing silicone resin: (HMe ₂ SiO _1/2 ) ₃ (MePhSiO _1/2 ) ₅ (PhSiO _3/2 ) ₄ ;

The inhibitor is ethynylcyclohexanol.

2. Preparation method

Preparation of component A: Weigh 97 parts of methyl phenyl vinyl silicone resin, 0.2 parts of platinum-based catalyst, and 2.8 parts of binder are sequentially added to the mixer, and mixed and stirred to obtain the A component;

Preparation of component B: 98.8 parts of dimethyldiphenylhydrogensilicone resin and 0.2 parts of inhibitor were weighed. Adding to the mixer in turn, mixing and stirring evenly, that is, the B component;

In use, the A component and the B component are uniformly mixed in a weight ratio of 10:1, vacuum defoamed for 20 minutes, dispensed or potted on the package to be packaged, and first heated at 120 ° C for 1 hour. Then, heat at 150 ° C for 4 hours.

Comparative example 2

1. Composition of raw materials

Vinyl dimethyl diphenyl polysiloxane: (ViMe ₂ SiO _1/2 ) ₇₀ ( ViMePh ₂ SiO _1/2 ) ₇₀ ;

The platinum-based catalyst is a platinum-olefin complex;

Adhesive (adhesive of the present invention)

Hydrogenated diphenyl polysiloxane: (HMe ₂ SiO _1/2 ) ₁ (Ph ₂ SiO _1/2 ) ₅ ;

The inhibitor is 1,1,3-triphenyl-2-propyn-1-ol.

2. Preparation method

Preparation of component A: Weigh 97 parts of vinyl dimethyl diphenyl polysiloxane, 0.2 parts of platinum-based catalyst, and 2.8 parts of binder are sequentially added to the mixer, and the mixture is uniformly stirred to obtain the component A;

Preparation of component B: 98.8 parts of hydrogen diphenylpolysiloxane and 0.2 parts of inhibitor were weighed. Adding to the mixer in turn, mixing and stirring evenly, that is, the B component;

In use, the A component and the B component are uniformly mixed in a weight ratio of 10:1, vacuum defoamed for 20 minutes, dispensed or potted on the package to be packaged, and first heated at 120 ° C for 1 hour. Then, heat at 150 ° C for 4 hours.

Comparative example 3

1. Composition of raw materials

Methylphenyl vinyl silicone resin: (ViMe ₂ SiO _1/2 ) ₂ (PhSiO _3/2 ) ₈ ;

Vinyl dimethyl diphenyl polysiloxane: (ViMe ₂ SiO _1/2 ) ₄₀ ( ViMePh ₂ SiO _1/2 ) ₁₀ ;

The platinum-based catalyst is a platinum-methylphenyl polysiloxane complex;

Methylphenyl hydrogen-containing silicone resin: (HMe ₂ SiO _1/2 ) ₃ (MePhSiO _1/2 ) ₆ (PhSiO _3/2 ) ₄ ;

Hydrogenated diphenyl polysiloxane: (HMe ₂ SiO _1/2 ) ₁ (Ph ₂ SiO _1/2 ) ₆ ;

The inhibitor is 1,1,3-triphenyl-2-propyn-1-ol.

2. Preparation method

Preparation of component A: 85 parts of methyl phenyl vinyl silicone resin, 14.8 parts of vinyl dimethyl diphenyl polysiloxane, 0.2 parts of platinum catalyst were added to the mixer in sequence, and the mixture was stirred and evenly obtained. A component;

Preparation of component B: 50 parts of dimethyldiphenyl hydrogen-containing silicone resin was weighed, 49.8 parts of hydrogen diphenylpolysiloxane was contained, and 0.2 part of inhibitor was weighed. Adding to the mixer in turn, mixing and stirring evenly, that is, the B component;

In use, the A component and the B component are uniformly mixed in a weight ratio of 10:1, vacuum defoamed for 20 minutes, dispensed or potted on the package to be packaged, and first heated at 120 ° C for 1 hour. Then, heat at 150 ° C for 4 hours.

Test method: First, according to GB2411-1980 (1989) plastic Shore hardness test method to make test pieces; Second, package 2835 bracket, keep the color temperature range between 5500 ~ 6000K. Curing conditions: heating at 120 ° C for 1 hour and then heating at 150 ° C for 4 hours. Test 1: According to GB2411-1980 (1989) plastic Shore hardness test method to test the hardness of the test piece; Test 2: use 50% ethanol solution red ink, put into the packaged 2835 stent, placed at 80 ° C for 2 hours, Observe the red ink penetration phenomenon; Test 3: 2g sulfur powder at the bottom of the closed glass bottle, place the 2835 stent in the center of the bottle, test the luminous flux before and after 8 hours at 80 °C, calculate the luminous flux retention rate; Test 4: Pack the cured 2835 stent Into the cold and hot shock box, temperature -40 ~ 125 ° C, 3min / 30min, 1 cycle per hour, test 200 cycles after the dead light rate.

Table 1 performance indicator table

It can be seen from Table 1 that the comparison of Examples 1, 2, and 3 with Comparative Example 1 shows that although the resin content is high, the hardness is improved, and the vulcanization resistance is improved, but the thermal shock resistance is lowered; Examples 1, 2 3, compared with Comparative Example 2, it can be seen that although the pure polysiloxane system is excellent in thermal shock resistance, the vulcanization resistance is poor; and Examples 1, 2, and 3 are compared with Comparative Example 3, Without the adhesive, the sealing material has poor adhesion to the substrate, which causes red ink to leak and resists vulcanization.

The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection of the present invention. Within the scope.

Claims (10)

1. A high refractive index LED packaged silica gel comprising an A component and a B component, wherein the weight ratio of the A component to the B component is 10:1; wherein

   The composition and composition of the raw materials of the component A are as follows:

   

   The composition and composition of the raw materials of the B component are as follows:

   Methylphenyl hydrogen-containing silicone resin 40 to 60 parts by weight;

   Hydrogenated diphenyl polysiloxane 40 to 60 parts by weight;

   The inhibitor is 0.1 to 0.3 parts by weight.
2. The high refractive index LED packaged silica gel according to claim 1, wherein the methylphenylvinyl silicone resin has a molecular formula of (ViMe ₂ SiO _1/2 ) _x (PhSiO _3/2 ) _y , wherein The Me is a methyl group, Vi is a vinyl group, Ph is a phenyl group, and x:y = 1:3.5 to 5.
3. The high refractive index LED packaged silica gel according to claim 1, wherein the vinyl dimethyl diphenyl polysiloxane has the formula: (ViMe ₂ SiO _1/2 ) _a (ViMePh ₂ SiO _{1 /2} ) _b wherein, Me is a methyl group, Vi is a vinyl group, Ph is a phenyl group, 10 ≤ a ≤ 70, 10 ≤ b ≤ 70, and a: b = 1:1.
4. The high refractive index LED packaged silica gel according to claim 1, wherein the platinum-based catalyst is a platinum-methylphenylpolysiloxane complex or a platinum-olefin complex.
5. The high refractive index LED packaged silica gel according to claim 4, wherein the platinum-methylphenylpolysiloxane complex has a platinum content of from 3,000 to 10,000 ppm.
6. The high refractive index LED packaged silica gel according to claim 1, wherein the adhesive has the structural formula:

   
7. The high refractive index LED packaged silica gel according to claim 1, wherein the methylphenyl hydrogen-containing silicone resin has the formula: (HMe ₂ SiO _1/2 ) ₃ (MePhSiO _1/2 ) _n (PhSiO) _3/2 ) ₄ wherein, Me is a methyl group, Ph is a phenyl group, and 4≤n≤6.
8. The high refractive index LED packaged silica gel according to claim 1, wherein the hydrogen diphenyl polysiloxane has a molecular formula of: (HMe ₂ SiO _1/2 ) ₁ (Ph ₂ SiO _{1/2 m} wherein the Me is a methyl group, Ph is a phenyl group, and 4 ≤ m ≤ 6.
9. The high refractive index LED packaged silica gel according to claim 1, wherein the inhibitor is selected from the group consisting of ethynylcyclohexanol or 1,1,3-triphenyl-2-propyn-1-ol.
10. The method for preparing a high refractive index LED packaged silica gel according to any one of claims 1 to 9, comprising a step of preparing a component A and a step of preparing a component B; wherein

    1) Preparation of component A: 80 to 90 parts of methylphenyl vinyl silicone resin, 8 to 18 parts of vinyl dimethyl diphenyl polysiloxane, 0.1 to 0.3 parts of platinum catalyst, adhesive 1 to 5 parts are sequentially added to the mixer, stirred for 3 to 5 hours, and uniformly mixed to obtain the A component;

    2) Preparation of component B: 40-60 parts of methylphenyl-containing silicone resin, 40-60 parts of hydrogen diphenylpolysiloxane at the end, 0.1-0.3 parts of inhibitor are sequentially added to the mixer, and stirred 3 ~5h, mixing uniformly to obtain the B component.