CN112812304B - Prepolymer, packaging resin containing prepolymer and application of packaging resin - Google Patents

Abstract

The invention discloses a prepolymer, which is prepared from the following raw materials: (a) a compound having a structure represented by formula 1, formula 1:

wherein R is ₁ 、R ₂ 、R ₃ Each independently selected from vinyl or epoxy; (B) an organosiloxane containing phenyl and Si-H groups; (C) platinum catalyst. The prepolymer adopts specific compound to combine with organic silicon, increases the compatibility of the organic silicon and epoxy resin, has simple and convenient process, is easy to operate, has high yield, and is convenient for further producing high-performance packaging resin. The invention also provides a packaging resin which comprises epoxy resin, the prepolymer, a curing agent, an adhesion promoter and a catalyst. The packaging resin generates thermosetting epoxy resin through the reaction of epoxy components and a curing agent, has excellent performance of resisting light aging in a blue light wave band of 450nm-470nm, and meanwhile, has excellent heat resistance, is easy to package, has good transparency and has wide market prospect.

Description

A kind of prepolymer, encapsulation resin containing the prepolymer and application of encapsulation resin

technical field

The invention relates to the technical field of thermosetting encapsulation and molding materials, in particular to a prepolymer, an encapsulation resin containing the prepolymer and the application of the encapsulation resin.

Background technique

As a light-emitting semiconductor, LED (Light Emitting Diode) has become an irreplaceable optoelectronic component in lighting, active RGB display, LCD backlight, vehicle lighting and other fields. The packaging of LED lighting and RGB display devices mostly uses pre-injection molding of reflective cups on resin substrates and metal brackets, and then pours or dispenses liquid packaging materials into the reflective cups. After thermal curing, the packaging materials are integrated with the reflective cups. LED packaging structure . The reflective cup is not only the carrier of the liquid packaging material, but also responsible for reflecting the light emitted by the LED chip, forming a single-sided light emitting structure that is directed upward (Top View). The white light illuminating device is packaged with a white reflective cup to enhance light extraction efficiency, and the RGB display device uses a black reflective cup to improve the contrast of the display.

The white light LED uses a blue light chip with an emission wavelength of 450-470nm as the light source, and emits yellow light by exciting the yellow phosphor powder mixed in the packaging resin, and finally the yellow light and blue light are synthesized into white light. PPA (polyphthalamide resin) material was first used in white light device reflector cups. As a thermoplastic material, it has obvious advantages such as easy injection molding, strong flexibility, and low cost. It is very suitable for 0.5-1W low-power white light LED packaging. For LED white light beads higher than 1W, the blue light chip has a strong photodegradation effect on the PPA resin, resulting in yellowing of the material, which in turn leads to a decrease in the reflectivity of the reflective cup material and damage to the light emitted by the LED chip. In addition, when white LED chips are applied to lamps, they need to go through the surface mount process of reflow soldering at a high temperature of up to 260°C. Thermoplastic PPA is prone to deformation and thermal expansion stress at high temperatures and damages LED lamp beads.

Later, a thermosetting epoxy reflective cup material with triazine derivative epoxy resin or alicyclic epoxy resin as the core component appeared in the market, which was called "EMC bracket". This type of epoxy resin does not contain a benzene ring structure, which greatly improves the blue light resistance of EMC brackets compared with PPA materials, and because it is a thermosetting material, it has excellent resistance to thermal deformation of reflow soldering. The industry even adopts this material The packaged white light chip is called EMC lamp bead. Although the EMC reflective cup bracket has obvious advantages in blue light resistance and heat resistance compared with PPA thermoplastic materials, there are still blue light tolerance problems in LED products with strong power (2-3W). Yellowing remains a major focus.

Contents of the invention

In order to solve the above problems, the first aspect of the present invention provides a kind of prepolymer, the preparation raw material of described prepolymer comprises:

其中R₁、R₂、R₃分别独立地选自乙烯基或环氧基；(A) a compound having a structure as shown in formula 1, formula 1:

Wherein R ₁ , R ₂ , and R ₃ are independently selected from vinyl or epoxy groups;

(B) organosiloxanes containing phenyl and Si-H groups;

(C) Platinum catalyst.

As a preferred technical solution, the raw materials for the preparation of the prepolymer also include (D) an inhibitor.

A second aspect of the present invention provides a method for preparing a prepolymer as described above, comprising the following steps: mixing 100 parts by weight of (A) a compound having a structure as shown in Formula 1 with (B) a compound containing phenyl and Si -H group organosiloxane and (D) inhibitor are melted at 60-150°C, mixed uniformly and cooled to 60-120°C, (C) platinum catalyst is added, stirred for 5-15 hours to obtain a prepolymer.

The third aspect of the present invention provides an encapsulation resin, the preparation raw materials of the encapsulation resin include epoxy resin, the above-mentioned prepolymer, a curing agent, an adhesion promoter, and a catalyst.

The fourth aspect of the present invention provides a method for preparing the encapsulation resin as described above, comprising the following steps: taking epoxy resin and prepolymer, stirring at 100-150°C, adding a curing agent, promoting adhesion agent, catalyst, stirring, discharging, cooling, crushing, making cakes to obtain encapsulating resin.

A fifth aspect of the present invention provides an encapsulation resin for a white reflective cup, the preparation raw materials of which include 100 parts by weight of the above encapsulation resin and 50-400 parts by weight of titanium dioxide.

The sixth aspect of the present invention provides an application of the above-mentioned encapsulation resin for a white reflective cup, which is used for a white LED device with a power of 1-3W.

The seventh aspect of the present invention provides an encapsulation resin for a black reflective cup, the preparation raw materials of which include 100 parts by weight of the above encapsulation resin and 1-30 parts by weight of carbon black.

The eighth aspect of the present invention provides an application of the packaging resin for the black reflective cup as described above, which is used for surface-mounted SMT light-emitting devices of outdoor RGB display screens.

A ninth aspect of the present invention provides an LED device, which comprises a reflective cup structure obtained by injection molding a metal frame or a resin substrate and the above-mentioned encapsulation resin.

Beneficial effects: the invention provides a prepolymer, which uses a specific compound to combine with silicone, which increases the compatibility between silicone and epoxy resin. The process is simple and easy to operate, and the yield is high, which is convenient for further production of high-performance Encapsulation resin. The encapsulation resin in the present invention generates a thermosetting epoxy resin through the reaction of the epoxy component and the curing agent, which has excellent performance of withstanding photoaging in the blue light band of 450nm-470nm, and at the same time has excellent heat resistance, is easy to encapsulate, has good transparency, and has a wide range of applications. market prospects.

Description of drawings

In order to further explain the beneficial effects of a prepolymer provided in the present invention, the encapsulation resin containing the prepolymer and the application of the encapsulation resin, the corresponding accompanying drawings are provided, and it should be pointed out that the accompanying drawings provided in the present invention They are only individual examples selected from all the drawings, and the purpose is not to limit the claims. All other corresponding maps obtained through the drawings provided in this application should be considered within the scope of protection of this application.

FIG. 1 shows the UV resistance performance test results of Example 9 of the present invention and Comparative Example 1.

Fig. 2 is the UV resistance performance test results of Example 16 of the present invention and Comparative Example 2.

Detailed ways

The invention can be more readily understood by reference to the following detailed description of the preferred practice of the invention and the included examples. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the definitions in this specification shall prevail.

Where a parameter is expressed herein as a range, a preferred range, or a range bounded by a series of upper and lower preferred values, it is to be understood that any range bounded by any upper or preferred range limit and any lower or preferred range limit or preferred value is specifically disclosed. All ranges formed by a pair, whether or not the ranges are disclosed individually. For example, when the range "1 to 5" is disclosed, the recited range should be construed to include the ranges "1 to 4," "1 to 3," "1 to 2," "1 to 2, and 4 to 5" , "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, that range is intended to include its endpoints and all integers and fractions within the range.

Singular forms include plural referents unless the context clearly dictates otherwise. "Optional" or "either" means that the item or event described thereafter may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximate terms in the specification and claims are used to modify the quantity, which means that the present invention is not limited to the specific quantity, but also includes acceptable modifications that are close to the quantity and will not cause changes in the relevant basic functions. Accordingly, a numerical value modified by "about", "about", etc., means that the present invention is not limited to the precise numerical value. In some instances, approximate terms may correspond to the precision of the instrument for measuring the value. Throughout the specification and claims of this application, range limitations may be combined and/or interchanged, unless otherwise stated such ranges include all subranges contained therebetween.

In addition, the indefinite articles "a" and "an" preceding an element or component of the present invention have no limitation on the quantity requirement (ie, the number of occurrences) of the element or component. Thus "a" or "an" should be read to include one or at least one, and elements or components in the singular also include the plural unless the number is clearly intended to be in the singular.

The present invention is described below through specific embodiments, but not limited to the specific embodiments given below.

In order to solve the above problems, the first aspect of the present invention provides a kind of prepolymer, and its preparation raw material comprises:

其中R₁、R₂、R₃分别独立地选自乙烯基或环氧基；(A) a compound having a structure as shown in formula 1, formula 1:

Wherein R ₁ , R ₂ , and R ₃ are independently selected from vinyl or epoxy groups;

(B) organosiloxanes containing phenyl and Si-H groups;

(C) Platinum catalyst.

In some preferred embodiments, at least one of R ₁ , R ₂ , R ₃ is vinyl; more preferably, at least one of R ₁ , R ₂ , R ₃ is vinyl, and at least one for the epoxy group.

As (A) an example of a compound having the structure shown in formula 1, specifically DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8), MA-DGIC (Monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9).

In some preferred embodiments, in the (B) organosiloxane containing phenyl and Si-H groups, the phenyl group is located at the side chain of the organosiloxane.

In some preferred embodiments, in the (B) organosiloxane containing phenyl and Si-H groups, the Si-H groups are located at the side chains and/or terminal groups of the organosiloxane.

The organosiloxane in the present invention can be commercially available, such as RH-309 produced by Ningbo Runhe High-tech Material Technology Co., Ltd., phenyl crosslinking agent series products produced by Ambia Special Organosilicon (Nantong) Co., Ltd., etc. .

In some preferred embodiments, the Si-H group content in the (B) organosiloxane containing phenyl and Si-H groups is the same as that in (A) the compound having the structure shown in formula 1 The molar ratio of vinyl content is (0.2-1):1; further preferably, the content of Si-H groups in (B) organosiloxane containing phenyl and Si-H groups is the same as that of (A) The molar ratio of the vinyl content in the compound having the structure shown in Formula 1 is (0.25-0.95):1.

In order to improve the problem of easy yellowing of the encapsulating epoxy resin in LED products, the inventor introduced a siloxane structure into the material, because the Si-O-Si siloxane structural bond energy of organic silicon is higher than the C-C bond energy of epoxy resin. Larger, can effectively improve the yellowing and improve the heat resistance of the material, but the properties of organosiloxane and epoxy resin are quite different, resulting in poor compatibility between the two. In further exploration, the inventor found that using a specific epoxy compound and organosiloxane to make a prepolymer, and then introducing the prepolymer into the encapsulation resin, can greatly improve the resistance of organosiloxane in the epoxy resin system. Compatibility, thereby improving the handling performance and UV resistance of the encapsulation resin. The inventor also unexpectedly found that the use of silicone containing phenyl group is beneficial to reduce the processing viscosity of the encapsulation resin and make the encapsulation operation easier. Usually, phenyl group is easily oxidized to form quinone, so the material turns yellow. However, phenyl group The steric hindrance effect can reduce the interaction force between molecular chains and increase the migration performance of molecular chains. Therefore, in order to balance the operability and UV resistance of the material, it is necessary to control the proportion of the raw materials of the prepolymer within a certain range.

The platinum catalyst in the present invention is used to catalyze the addition reaction between the silicon-hydrogen bond and the double bond, and can be commercially available, such as Castel platinum catalyst.

In some preferred embodiments, the amount of the (C) platinum catalyst is 0.05 to 1 wt% of the compound (A) having the structure shown in Formula 1; more preferably, the amount of the (C) platinum catalyst is (A) 0.1-0.5 wt% of the compound having the structure shown in formula 1.

From the perspective of adjusting the degree of reaction, in some preferred embodiments, the raw materials for the preparation of the prepolymer further include (D) an inhibitor.

Inhibitors in the present invention are used to reduce the chemical reaction rate, and its type is not particularly limited, it can be any one well known to those skilled in the art, such as maleate inhibitors, fumarate inhibitors, organic phosphine inhibitors agents, alkyne inhibitors, etc.

In some preferred embodiments, the inhibitor is selected from 3,7,11-trimethyldodeyn-3-ol (CAS No.: 1604-35-9, TMDO for short), 3,5-dimethyl Diethyl-1-hexyn-3-ol, 3,6-dimethyl-1-heptyn-3-ol, diethyl fumarate, acetylene cyclohexanol (CAS No.: 78-27-3), A mixture of one or more of methyl butynol (CAS No.: 115-19-5) and methyl maleate.

In some preferred embodiments, the amount of the (D) inhibitor is 0 to 0.1 wt% of the compound (A) having the structure shown in formula 1, excluding 0; more preferably, the (D) inhibitor The dosage of the agent is 0.01-0.05wt% of (A) the compound having the structure shown in formula 1.

The second aspect of the present invention provides the preparation method of the above-mentioned prepolymer, comprising the following steps: 100 parts by weight of (A) a compound having the structure shown in formula 1 and (B) a compound containing phenyl and Si-H groups Melt organosiloxane and (D) inhibitor at 60-150°C, mix well and cool down to 60-120°C, add (C) platinum catalyst, stir for 5-15 hours to obtain prepolymer.

The third aspect of the present invention provides an encapsulation resin, the preparation raw materials of which include: epoxy resin, the above-mentioned prepolymer, a curing agent, an adhesion promoter, and a catalyst.

From the perspective of improving the compatibility of the epoxy resin and the prepolymer, in some preferred embodiments, the epoxy resin is selected from the group consisting of triglycidyl isocyanurate (TGIC, CAS No.: 2451-62 -9), a mixture of one or more of cycloaliphatic epoxy resin (CAS No.: 3130-19-6), hydrogenated bisphenol A epoxy resin; further preferably, the epoxy resin is tricyclic Oxypropyl isocyanurate and/or cycloaliphatic epoxy resins.

From the perspective of balancing the operational performance and UV resistance of the encapsulation resin, in some preferred embodiments, the weight ratio of the epoxy resin to the prepolymer is (3-20):1; more preferably, the ring The weight ratio of oxygen resin to prepolymer is (4-10):1.

In some preferred embodiments, the curing agent is an acid anhydride curing agent; further preferably, the acid anhydride curing agent is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, hydrogenated pyromellitic anhydride Formic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tungoleic anhydride, dodecenylbutane Dianhydride, nadic anhydride, methylnadic anhydride, glutaric anhydride, hydrogenated methylnadic anhydride, methylcyclohexene tetracarboxylic dianhydride, polyazelaic anhydride, polysebacic anhydride, 1,4,5 , A mixture of one or more of 6-tetrabromophthalic anhydride.

In some preferred embodiments, the amount of the acid anhydride curing agent is calculated according to the molar ratio of the content of the acid anhydride group to the content of the epoxy group in the system (0.8-1):1. The epoxy group content of the system described herein is the sum of the epoxy group content in the epoxy resin and the prepolymer.

In some preferred embodiments, the adhesion promoter is selected from γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-Methacryloxypropylmethyldiethoxysilane, γ-(2,3-Glycidoxy)propyltriethoxysilane, γ-(2,3-Glycidoxy) Propylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2,4,6,8-tetra[2-(3,4-epoxycyclohexylethyl)tetramethylcyclotetrasiloxane, 2,4,6-tris[2-(3,4-epoxy Cyclohexylethyl)]tetramethylcyclotetrasiloxane, bis[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane, 2,4,6,8-tetra Methyl-[2-(3,4-epoxycyclohexylethyl)]cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetra[3-( Oxiranylmethoxy)propyl]cyclotetrasiloxane, 2,4,6,8-tetramethyl-2-[3-(oxiranylmethoxy)propyl]cyclotetra A mixture of one or more of siloxanes.

In some preferred embodiments, the amount of the adhesion promoter is 0.01 to 5% by weight of the total amount of epoxy resin and prepolymer; more preferably, the amount of the adhesion promoter is 0.01% to 5% by weight of the epoxy resin 0.05-3wt% of the total amount of prepolymer.

In some preferred embodiments, the catalyst is selected from triphenylphosphine, methyltrioctylphosphonium dimethyl phosphate, tetrabutylphosphonium acetate, methyltributylphosphonium dimethylphosphate, Benzyltriphenylphosphonium chloride, tetrabutylphosphonium chloride, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole A mixture of one or more.

In some preferred embodiments, the amount of the catalyst is 0.01% to 5% by weight of the total amount of the epoxy resin, prepolymer, and curing agent; more preferably, the amount of the catalyst is the epoxy resin, the prepolymer, 0.1-1wt% of the total curing agent.

In some preferred embodiments, the raw materials for preparing the encapsulation resin further include at least one of pigments, inorganic fillers, antioxidants, and anti-ultraviolet absorbers.

As pigments, titanium dioxide, carbon black, etc. can be exemplified, and the addition amount can be 1-400wt% of the total amount of epoxy resin, prepolymer, and curing agent; as inorganic fillers, silica, alumina, calcium carbonate, kaolin can be exemplified etc., the addition amount can be 50-800wt% of the total amount of epoxy resin, prepolymer, and curing agent; as an antioxidant, 2,6-di-tert-butyl-4-methylphenol, antioxidant 1010 , antioxidant 1076, etc., the addition amount can be 0.01-5wt% of the total amount of epoxy resin, prepolymer, and curing agent; as an anti-ultraviolet absorber, UV-326, UV-531, UV-234, UV -320, etc., the addition amount can be 0.01-5wt% of the total amount of epoxy resin, prepolymer, and curing agent.

The fourth aspect of the present invention provides the preparation method of the above-mentioned encapsulation resin, which includes the following steps: take epoxy resin and the above-mentioned prepolymer, stir at 150-200°C, then lower the temperature to 100-150°C, add and solidify agent, adhesion promoter, catalyst, stirring, discharging, cooling, pulverizing, and making cakes to obtain encapsulation resin.

A fifth aspect of the present invention provides an encapsulation resin for a white reflective cup, the preparation raw materials of which include 100 parts by weight of the above encapsulation resin and 50-400 parts by weight of titanium dioxide.

The sixth aspect of the present invention provides an application of the above-mentioned encapsulation resin for a white reflective cup, which is used for a white LED device with a power of 1-3W.

The seventh aspect of the present invention provides an encapsulation resin for a black reflective cup, the preparation raw materials of which include 100 parts by weight of the above encapsulation resin and 1-30 parts by weight of carbon black.

The eighth aspect of the present invention provides an application of the packaging resin for the black reflective cup as described above, which is used for surface-mounted SMT light-emitting devices of outdoor RGB display screens.

A ninth aspect of the present invention provides an LED device, which comprises a metal frame or a resin substrate and the above-mentioned encapsulation resin through injection molding to obtain a reflective cup structure. The reflective cup described in the present invention is not only the carrier when the LED is poured and packaged with liquid potting glue, but also the reflective material that constitutes the light output from one side of the LED. The reflective cup is made of the above-mentioned packaging resin, which can improve the heat resistance of the LED device. and light aging resistance.

Example

The present invention is specifically described below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, some non-essential improvements made by those skilled in the art according to the content of the present invention above And adjustments still belong to the protection scope of the present invention.

Example 1

Embodiment 1 provides a kind of prepolymer, 100 parts by weight DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Material Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodedecyn-3-ol (CAS number: 1604-35 -9, referred to as TMDO) was melted at 100°C for 0.5h, mixed evenly, cooled to 90°C, added 0.5 parts by weight of PT5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 10h, and obtained the prepared Polymer.

In this example, the amount of RH-SH309 used is calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in DA-MGIC of 0.95:1.

Example 2

Example 2 provides a prepolymer, 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Material Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodedecyn-3-ol (CAS number: 1604-35 -9, referred to as TMDO) was melted at 100°C for 0.5h, mixed evenly, cooled to 90°C, added 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 10h, and obtained prepolymer.

In this example, the amount of RH--SH309 is calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in MA-DGIC is 0.95:1.

Example 3

Example 3 provides a prepolymer, 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Material Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodedecyn-3-ol (CAS number: 1604-35 -9, referred to as TMDO) was melted at 90°C for 0.5h, mixed evenly, cooled to 80°C, added 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 8h, and obtained prepolymer.

In this example, the amount of RH-SH309 used is calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in MA-DGIC of 0.5:1.

Example 4

Embodiment 4 provides a kind of prepolymer, 100 parts by weight DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Material Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodedecyn-3-ol (CAS number: 1604-35 -9, referred to as TMDO) was melted at 90°C for 0.5h, mixed evenly, cooled to 80°C, added 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 8h, and obtained prepolymer.

In this example, the amount of RH-SH309 used is calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in DA-MGIC of 0.25:1.

Example 5

Embodiment 5 provides a kind of prepolymer, 100 parts by weight DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl containing Hydrogen organosiloxane, SiH content: 3.85mmol/g, purchased from Ambia Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodeyn-3-ol (CAS No.: 1604-35-9, referred to as TMDO) melted at 90°C for 0.5h, mixed evenly, cooled to 80°C and added 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) , Stir for 6h to obtain prepolymer.

In this example, the amount of XL-2460 used is calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in DA-MGIC of 0.5:1.

Example 6

Embodiment 6 provides a kind of prepolymer, 100 parts by weight DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl containing Hydrogen organosiloxane, SiH content: 3.85mmol/g, purchased from Ambia Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodeyn-3-ol (CAS No.: 1604-35-9, referred to as TMDO) melted at 90°C for 0.5h, mixed evenly, cooled to 80°C and added 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) , Stir for 6h to obtain prepolymer.

In this example, the amount of XL-2460 used is calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in DA-MGIC of 0.95:1.

Example 7

Embodiment 7 provides a kind of prepolymer, 100 parts by weight DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl containing Hydrogen organosiloxane, SiH content: 3.85mmol/g, purchased from Ambia Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodeyn-3-ol (CAS No.: 1604-35-9, referred to as TMDO) melted at 90°C for 0.5h, mixed evenly, cooled to 80°C and added 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) , Stir for 6h to obtain prepolymer.

In this example, the amount of XL-2460 used is calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in DA-MGIC of 0.25:1.

Example 8

Example 8 provides a prepolymer, 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and XL-2460 (organosiloxane Alkane, SiH content: 3.85mmol/g, purchased from Ambia Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodeyn-3-ol (CAS No.: 1604- 35-9, TMDO for short) was melted at 90°C for 0.5h, mixed evenly, cooled to 80°C, added 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 6h, to obtain a prepolymer.

In this example, the amount of XL-2460 used is calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in MA-DGIC of 0.5:1.

In the comparison of Examples 1 to 8, the inventors found that under the same experimental conditions, the reaction of DA-MGIC and organosiloxane was easier than the reaction of MA-DGIC and organosilicon, and the reaction participated by XL-2460 was compared with The reaction involved in RH309 is easier to carry out. The degree of difficulty of the above reaction is judged according to the length of the reaction time and the height of the reaction temperature. If the reaction time is long and the reaction temperature is high, the operability is not good. The evaluation results of the operability are divided into excellent and good according to the order from easy to difficult. , poor, the operability and yield (using titration method to test epoxy equivalent) of Examples 1～8 are shown in Table 1.

Table 1

Example operability yield Example 1 Difference 55% Example 2 Difference 50% Example 3 good 65% Example 4 good 70% Example 5 excellent 95% Example 6 excellent 90% Example 7 excellent 95% Example 8 excellent 85%

Example 9

Embodiment 9 provides a kind of encapsulation resin, takes 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 2, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid di Anhydride (CAS No.: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS No.: 4420-74-0), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, making cakes to obtain encapsulating resin.

Example 10

Embodiment 10 provides a kind of encapsulation resin, takes 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 4, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid di Anhydride (CAS No.: 85-42-7), 0.25 parts by weight of γ-methacryloxypropylmethyldimethoxysilane (CAS No.: 14513-34-9), 0.25 parts by weight of γ-(2 , 3-glycidyloxy)propylmethyldimethoxysilane (CAS No.: 65799-47-5), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2 ), stirring, discharging, cooling, pulverizing, making cakes to obtain encapsulating resin.

Example 11

Embodiment 11 provides a kind of encapsulating resin, take 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 6, stirred at 150°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid di Anhydride (CAS No.: 85-42-7), 0.25 parts by weight γ-(2,3-glycidoxy) propyltriethoxysilane (CAS No.: 2602-34-8), 0.25 parts by weight γ- Methacryloxypropylmethyldiethoxysilane (CAS No.: 65100-04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), Stirring, discharging, cooling, pulverizing, making cakes to obtain encapsulating resin.

Example 12

Embodiment 12 provides a kind of encapsulating resin, take 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 7, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid di Anhydride (CAS No.: 85-42-7), 1 part by weight of β-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (CAS No.: 3388-04-3), 1 part by weight of 2,4 , 6,8-tetra[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane (CAS No.: 121225-98-7), 1 part by weight of 3-mercaptopropyltri Ethoxysilane (CAS No.: 14814-09-6), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, crushing, cake making , to obtain the encapsulation resin.

Example 13

Embodiment 13 provides a kind of encapsulating resin, take 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 8, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid di Anhydride (CAS No.: 85-42-7), 0.05 parts by weight of γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2, 4, 6, 8 -Tetrakis[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane (CAS No.: 121225-98-7), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, and making cakes to obtain encapsulation resin.

Example 14

Embodiment 14 provides a kind of encapsulation resin, take 85 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), 15 parts by weight of the prepolymer in Example 7, stirred at 180°C for 0.5h, cooled to 130°C, added 130 parts by weight of hexahydrophthalic acid di Anhydride (CAS No.: 85-42-7), 0.025 parts by weight of γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2, 4, 6, 8 -Tetramethyl-2,4,6,8-tetrakis[3-(oxiranylmethoxy)propyl]cyclotetrasiloxane (CAS No.: 60665-85-2), 0.5 parts by weight 2 - Ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, and making cakes to obtain an encapsulating resin.

Example 15

Embodiment 15 provides a kind of encapsulation resin, takes 80 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), 20 parts by weight of the prepolymer in Example 7, stirred at 180°C for 0.5h, cooled to 130°C, added 110 parts by weight of hexahydrophthalic acid di Anhydride (CAS No.: 85-42-7), 0.05 parts by weight of γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2, 4, 6, 8 -Tetramethyl-2-[3-(oxiranylmethoxy)propyl]cyclotetrasiloxane (CAS No.: 61614-55-9), 0.5 parts by weight of 2-ethyl-4-methyl Kimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, and making cakes to obtain an encapsulating resin.

Example 16

Embodiment 16 provides a kind of encapsulation resin, takes 90 parts by weight of alicyclic epoxy resin A (bis(7-oxabicyclo[4.1.0]3-heptylmethyl)oxalate), 0.05 parts by weight of 2 , 6-di-tert-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 2, stirred at 180°C for 0.5h, cooled to 130°C, added 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 parts by weight of γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.025 Parts by weight of γ-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100-04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36 -2), stirring, discharging, cooling, pulverizing, making cakes to obtain encapsulating resin.

Example 17

Embodiment 17 provides a kind of encapsulation resin, take 90 parts by weight of alicyclic epoxy resin A, 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), 10 parts by weight of the prepolymer in Example 4, stirred at 180°C for 0.5h, cooled to 130°C, added 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 parts by weight γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.025 parts by weight of γ-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100 -04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin.

Example 18

Embodiment 18 provides a kind of encapsulation resin, take 90 parts by weight of alicyclic epoxy resin A, 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), 10 parts by weight of the prepolymer in Example 7, stirred at 180°C for 0.5h, cooled to 130°C, added 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 parts by weight γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.025 parts by weight of γ-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100 -04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin.

Example 19

Embodiment 19 provides a kind of encapsulating resin, take 90 parts by weight of alicyclic epoxy resin A, 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), 10 parts by weight of the prepolymer in Example 8, stirred at 180°C for 0.5h, cooled to 130°C, added 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 parts by weight γ-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.025 parts by weight of γ-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100 -04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin.

Comparative example 1

Comparative example 1 provides a kind of encapsulation resin, takes 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Methylphenol (CAS No.: 2409-55-4), stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS No.: 4420-74-0), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirred and discharged material, cooled, pulverized, and caked to obtain encapsulating resin.

Comparative example 2

Comparative example 2 provides a kind of encapsulation resin, gets 90 weight parts alicyclic epoxy resin A, 0.05 weight parts 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), Stir at 180°C for 0.5h, cool down to 130°C, add 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 parts by weight of γ-methacryloxypropyl trimethoxy Diethoxysilane (CAS No.: 2530-85-0), 0.025 parts by weight of γ-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100-04-1), 0.5 parts by weight of 2-ethyl Base-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, and making cakes to obtain encapsulating resin.

Evaluate the operability of Examples 9-19 and Comparative Examples 1-2, use the encapsulation resin in each embodiment to encapsulate the chip, if the encapsulation resin cannot encapsulate the chip, or the melt viscosity is too large, the operability No, the operability evaluation results are divided into excellent, good, and poor in order from good to poor. The operability of Examples 9-19 and Comparative Examples 1-2 is shown in Table 2.

To evaluate the transparency of Examples 9-19 and Comparative Examples 1-2, preheat the encapsulating resin, extrude it into the mold cavity, mold and cure at 160°C for 300s, and then cure at 150-170°C for 2-4 hours to obtain the thickness Uniform (200 ± 10um) test sample, observe whether the molded sample is transparent or milky white, and the evaluation results of transparency are divided into excellent, good, and poor according to the order of transparency, translucence, and milky white. Embodiments 9 to 19, for See Table 2 for the transparency of ratios 1-2.

Evaluate the UV resistance performance of Examples 9-19 and Comparative Examples 1-2. Put the above-mentioned molded samples as test samples into the UV irradiation machine uniformly, and use a colorimeter to test the color contrast and aging state after irradiating for 1 hour. The greater the b value , the worse the resistance to UV light decay, the results are shown in Table 2.

Table 2

Example operability transparency UV resistance After UV testb Example 9 excellent Difference excellent 5-6 Example 10 excellent excellent better 6-7 Example 11 excellent excellent better 6-7 Example 12 better better better 6-7 Example 13 better better better 6-7 Example 14 excellent better better 6-7 Example 15 excellent better better 6-7 Example 16 excellent excellent excellent 5-6 Example 17 excellent excellent better 7-9 Example 18 excellent excellent better 7-9 Example 19 excellent excellent better 7-9 Comparative example 1 excellent better good 6-7 Comparative example 2 excellent excellent good 7-8

In Example 9 and Comparative Example 1, Example 16 and Comparative Example 2, it was found through the UV lamp anti-blue light decay test that the encapsulating resin obtained after adding the prepolymer described in the present invention has better UV light decay resistance, This effect can be seen from FIGS. 1 and 2 .

During the research and development process, the inventors found that according to the results of a large number of experiments, in the triglycidyl isocyanurate system, one of the examples 1 to 8 can be selected arbitrarily, and according to the conditions of the example 9, the excellent performance can be obtained. The encapsulation resin, by encapsulating LED chips with it, can obtain LED white light chips with blue light resistance.

In the process of research and development, the inventors found that according to a large number of experimental results, in the cycloaliphatic epoxy resin system, any one of Examples 1 to 8 can be selected arbitrarily, and according to the conditions of Example 16, an encapsulation resin with excellent performance can be obtained. It encapsulates LED chips, and can obtain LED white light chips with anti-blue light performance.

The foregoing examples are illustrative only, and are used to explain some features of the methods described in the present invention. The appended claims are intended to claim the broadest scope conceivable and the embodiments presented herein are merely illustrations of selected implementations according to all possible combinations of embodiments. Accordingly, it is the applicant's intention that the appended claims not be limited by the selection of examples which characterize the invention. Certain numerical ranges used in the claims also include sub-ranges therein, and changes within these ranges should also be construed as being covered by the appended claims where possible.

Claims (4)

1. a kind of encapsulation resin for white reflection cup, it is characterized in that, its preparation raw material comprises the encapsulation resin of 100 parts by weight, 50～400 parts by weight of titanium dioxide, and the preparation method of described encapsulation resin comprises: Get 90 parts by weight of bis(7-oxabicyclo[4.1.0]3-heptylmethyl)oxalate, 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol, 10 parts by weight of prepolymer Stir at 180°C for 0.5h, cool down to 130°C, add 110 parts by weight of hexahydrophthalic dianhydride, 0.025 parts by weight of γ-methacryloxypropyltrimethoxysilane, 0.025 parts by weight of γ- Methacryloyloxypropylmethyldiethoxysilane and 0.5 parts by weight of 2-ethyl-4-methylimidazole are stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin; The preparation method of the prepolymer comprises: mixing 100 parts by weight of monoallyl diglycidyl isocyanurate with phenyl hydrogen-containing organosiloxane with a hydrogen content of 0.87%, 0.05 parts by weight of 3,7, 11-trimethyldodeyn-3-ol was melted at 100°C for 0.5h, mixed uniformly, cooled to 90°C, added 0.5 parts by weight of a platinum catalyst with a concentration of 5000ppm, and stirred for 10h to obtain a prepolymer; The encapsulating resin for the white reflection cup is used for white LED devices with a power of 1-3W. 2. An encapsulating resin for a black reflective cup, characterized in that the raw materials for its preparation include 100 parts by weight of the encapsulating resin as claimed in claim 1, and 1-30 parts by weight of carbon black. 3. An application of the packaging resin for the black reflective cup as claimed in claim 2, characterized in that it is used for surface-mounted SMT light-emitting devices of outdoor RGB display screens. 4 . An LED device, characterized in that it has a reflective cup structure obtained by injection molding a metal frame or a resin substrate and the encapsulating resin as claimed in claim 1 .

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