Prepolymer, encapsulating resin containing said prepolymer, and use of encapsulating resin

Abstract

The present invention discloses a prepolymer, the raw materials for which include (A) a compound having a structure represented by Formula 1, (B) an organosiloxane containing phenyl and Si-H groups, and (C) a platinum catalyst. The prepolymer improves the compatibility between the silicone and the epoxy resin by combining a specific compound with the silicone. This prepolymer allows for a simple process, easy operation, and high yield, making it advantageous for producing high-performance encapsulating resins. The present invention also provides an encapsulating resin containing an epoxy resin, the prepolymer, a curing agent, an adhesion promoter, and a catalyst. The encapsulating resin is a thermosetting epoxy resin produced by reacting an epoxy component with a curing agent. It has excellent resistance to aging caused by light in the 450-470 nm blue light band, excellent heat resistance, ease of encapsulation, and good transparency, making it a promising material. [Formula 1] JPEG2023512890000007.jpg4562 (wherein R1, R2, and R3 are each independently selected from vinyl or epoxy.)

Description

[Technical field]

[0001] The present invention relates to the technical field of thermosetting encapsulating molding materials, and in particular to a prepolymer, an encapsulating resin containing the prepolymer, and the use of the encapsulating resin. [Background technology]

[0002] As a light-emitting semiconductor, LED (Light Emitting Diode) has become an essential photoelectric component in the fields of lighting, active RGB display, LCD backlight, and in-vehicle lighting. In most cases, LED lighting and RGB display devices are sealed by pre-injecting a reflector onto a resin substrate or a metal support, injecting or dispensing a liquid sealing material into the reflector, and then heat-curing the sealing material to form an LED sealing structure that is integrated with the reflector. The reflector is a carrier for the liquid sealing material, and at the same time, it reflects the light emitted from the LED chip and forms a one-sided light structure that shines directly upward (Top View). White lighting devices are sealed using a white reflector to increase the light extraction efficiency, and RGB display devices use a black reflector to increase the contrast of the display.

[0003] White light LED uses a blue light chip with an emission wavelength of 450nm to 470nm as a light source, excites the yellow phosphor mixed in the sealing resin to emit yellow light, and finally combines the yellow light and blue light to produce white light. The reflector of the white light device first uses PPA (polyphthalamide resin) material, which is a thermoplastic material, so it has obvious advantages such as easy injection molding, strong flexibility, and low cost, and is very suitable for sealing low-power white light LEDs of 0.5 to 1W. However, for LED white lamp beads higher than 1W, the blue light chip has a strong photodecomposition effect on the PPA resin, which causes yellowing of the material, reduces the reflectance of the reflector material, and impairs the light emission of the LED chip. In addition, when applied to lamps, white light LED chips require a high-temperature reflow surface mounting process of up to 260℃, and the thermoplastic PPA is prone to deformation and thermal expansion stress at high temperatures, which results in damage to the LED lamp beads.

[0004] Later, thermosetting epoxy resin reflector materials mainly composed of triazine derivative epoxy resins and alicyclic epoxy resins appeared on the market and became known as "EMC holders". Since such epoxy resins do not contain a benzene ring structure, the blue light resistance of EMC holders is significantly improved compared to PPA materials, and since they are thermosetting materials, they also have excellent resistance to reflow heat deformation. In the industry, white light chips sealed using this material are called EMC lamp beads. EMC reflector holders are more resistant to blue light than PPA thermoplastic materials and have obvious advantages in heat resistance, but LED products with relatively high output (2-3W) still have problems with blue light resistance, and the yellowing of epoxy resins due to long-term high temperature and blue light exposure remains a major problem. Summary of the Invention

[0005] In order to solve the above problems, the first aspect of the present invention is to provide a manufacturing material comprising: (A) a compound having a structure represented by formula 1; (B) an organosiloxane containing phenyl and Si-H groups; and (C) a platinum catalyst. [ka] (where R 1 , R 2 , R 3 are each independently selected from vinyl or epoxy.

[0006] As a preferred technical solution, the raw material for producing the prepolymer further includes (D) an inhibitor.

[0007] A second aspect of the present invention provides a method for producing the prepolymer, comprising the steps of melting (A) 100 parts by weight of a compound having a structure represented by Formula 1, (B) an organosiloxane containing phenyl and Si-H groups, and (D) an inhibitor at 60 to 150°C, mixing them uniformly, lowering the temperature to 60 to 120°C, adding (C) a platinum catalyst, and stirring for 5 to 15 hours to obtain a prepolymer.

[0008] A third aspect of the present invention provides an encapsulating resin comprising an epoxy resin, the prepolymer, a curing agent, an adhesion promoter, and a catalyst.

[0009] A fourth aspect of the present invention provides a method for producing the encapsulating resin, comprising the steps of stirring an epoxy resin and a prepolymer at 100 to 150° C., adding a curing agent, an adhesion promoter, and a catalyst, stirring and discharging the mixture, cooling, pulverizing the mixture, and forming a cake to obtain the encapsulating resin.

[0010] A fifth aspect of the present invention provides a sealing resin for a white reflector, comprising, as production raw materials, 100 parts by weight of the sealing resin and 50 to 400 parts by weight of titanium dioxide.

[0011] A sixth aspect of the present invention provides use of the sealing resin for a white reflector used in a white light LED device having an output of 1 to 3 W.

[0012] A seventh aspect of the present invention provides a sealing resin for a black reflector, which contains, as production raw materials, 100 parts by weight of the sealing resin and 1 to 30 parts by weight of carbon black.

[0013] An eighth aspect of the present invention provides a use of the above-mentioned encapsulating resin for a black reflector used in a surface-mount SMT light-emitting device of an outdoor RGB display.

[0014] A ninth aspect of the present invention provides an LED device having a reflector structure obtained by injection molding a metal frame or a resin substrate and the sealing resin. Effect of the Invention

[0015] Beneficial effects The present invention provides a prepolymer that improves the compatibility between silicone and epoxy resin by combining a specific compound with silicone, and has a simple process, easy operation, high yield, and is advantageous for producing a high-performance encapsulating resin. The encapsulating resin of the present invention is a thermosetting epoxy resin produced by reacting an epoxy component with a curing agent, and has excellent performance such as resistance to aging caused by light in the blue light band of 450 nm to 470 nm, excellent heat resistance, easy encapsulation, good transparency, and is promising. [Brief description of the drawings]

[0016] In order to further interpret and explain the beneficial effects of the prepolymer provided in the present invention, the encapsulating resin containing the prepolymer, and the use of the encapsulating resin, corresponding drawings are provided, and it should be noted that the drawings provided in the present invention are merely individual examples selected from all the drawings and are not intended to limit the claims, and all other corresponding maps obtained from the drawings provided in this application are within the patent scope of this application. [Figure 1] 1 shows the UV resistance test results of Example 9 of the present invention and Comparative Example 1. [Diagram 2] 1 shows the UV resistance test results of Example 16 of the present invention and Comparative Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The contents of the present invention can be easily understood by referring to the following detailed description of the preferred embodiment of the present invention and the included examples. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall control.

[0018] When a parameter herein is expressed as a range, a preferred range, or a range limited by a series of upper preferred values ​​and lower preferred values, all ranges formed by any combination of any upper or preferred value of the range with any lower or preferred value of the range are considered to be specifically disclosed, even if the ranges are disclosed individually. For example, if a range of "1 to 5" is disclosed, the range described should be understood as a range of "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a range of numerical values ​​is described herein, unless otherwise specified, it is intended that the range includes the endpoints thereof and all integers and fractions within the range.

[0019] Unless the context clearly dictates otherwise, the singular forms include plural referents. "Optionally" or "any one" means that the subsequently described matter or event may or may not occur, and the description includes instances where the event occurs as well as instances where the event does not occur.

[0020] In the specification and claims, when a number is modified with approximation, the invention is not limited to this specific number, but includes permissible modifications that are close to this number and do not change the basic function involved. In such cases, when a numerical value is modified with "approximately," "about," or the like, it is meant that the invention is not limited to this specific numerical value. In some instances, the approximation may correspond to the precision of an instrument for measuring the numerical value. In the specification and claims of this application, the ranges defined can be combined and / or interchanged, and unless otherwise stated, these ranges include all subranges contained within the range.

[0021] Furthermore, the indefinite articles "a" and "one" preceding an element or component of the invention do not limit the number (i.e., the number of times it occurs) of the element or component, and thus "a" or "one" should be understood as including one or at least one, and singular elements or components also include the plural, unless the number clearly refers to the singular.

[0022] Hereinafter, the present invention will be described through specific embodiments, but is not limited to the following specific embodiments.

[0023] In order to solve the above problems, the first aspect of the present invention is to provide a manufacturing material comprising: (A) a compound having a structure represented by formula 1; (B) an organosiloxane containing phenyl and Si-H groups; (C) a platinum catalyst. [ka] (where R 1 , R 2 , R 3 are each independently selected from vinyl or epoxy.

[0024] In some preferred embodiments, R 1 , R 2 , R 3At least one of R is vinyl, and more preferably, 1 , R 2 , R 3 At least one of the layers is vinyl and at least one is epoxy.

[0025] (A) Specific examples of the compound having the structure represented by formula 1 include DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9).

[0026] In some preferred embodiments, in the (B) organosiloxane containing phenyl and Si-H groups, the phenyl is present in a side chain of the organosiloxane.

[0027] In some preferred embodiments, in the (B) organosiloxane containing phenyl and Si—H groups, the Si—H groups are present in the side chains and / or terminal groups of the organosiloxane.

[0028] In the present invention, the organosiloxane may be a commercially available product, such as RH-309 manufactured by Ningbo Runhe High-Tech Materials Co., Ltd., or the phenyl crosslinker series products manufactured by Anvil Special Organosiloxane (Nantong) Co., Ltd.

[0029] In some preferred embodiments, the molar ratio of the Si-H group content in the organosiloxane containing phenyl and Si-H groups (B) to the vinyl content in the compound having a structure represented by formula 1 (A) is (0.2 to 1):1, and more preferably, the molar ratio of the Si-H group content in the organosiloxane containing phenyl and Si-H groups (B) to the vinyl content in the compound having a structure represented by formula 1 (A) is (0.25 to 0.95):1.

[0030] In order to solve the problem that the encapsulating epoxy resin in LED products is prone to yellowing, the inventors introduced a siloxane structure into the material, and since the bond energy of the Si-O-Si siloxane structure of silicone is greater than the C-C bond of epoxy resin, it can effectively improve the heat resistance of the material while improving yellowing, but the properties of organosiloxane and epoxy resin are significantly different, and as a result, the compatibility between them is poor. After further investigation, the inventors found that by producing a prepolymer using a specific epoxy compound and organosiloxane and introducing the prepolymer into the encapsulating resin, the compatibility of organosiloxane with the epoxy resin system can be greatly improved, and the handling and UV resistance of the encapsulating resin can be improved. The inventors also unexpectedly discovered that the use of phenyl-containing silicone is advantageous in reducing the processing viscosity of the encapsulating resin, making the encapsulating operation easier to carry out; generally, phenyl is easily oxidized to quinone, which causes yellowing of the material; however, the steric hindrance effect of phenyl can reduce the interaction force between molecular chains and improve the mobility of molecular chains; therefore, in order to achieve both ease of handling of the material and UV resistance, it is necessary to keep the proportion of the prepolymer raw material used within a specified range.

[0031] In the present invention, the platinum catalyst catalyzes the addition reaction of silicon hydrogen bonds with double bonds and may be a commercially available product such as, for example, KARSTEDT platinum catalyst.

[0032] In some preferred embodiments, the amount of the platinum catalyst (C) used is 0.05 to 1 wt % of the compound having the structure represented by formula (A) 1, and more preferably, the amount of the platinum catalyst (C) used is 0.1 to 0.5 wt % of the compound having the structure represented by formula (A) 1.

[0033] In order to adjust the degree of reaction, in some preferred embodiments, the raw materials for producing the prepolymer further contain an inhibitor (D).

[0034] The inhibitor in the present invention reduces the rate of a chemical reaction. There is no particular limitation on the type of inhibitor, and it may be any inhibitor known to those skilled in the art, such as maleate inhibitors, fumarate inhibitors, organophosphine inhibitors, alkyne inhibitors, etc.

[0035] In some preferred embodiments, the inhibitor is one or a mixture of more selected from 3,7,11-trimethyldodecin-3-ol (CAS number: 1604-35-9, abbreviation TMDO), 3,5-dimethyl-1-hexin-3-ol, 3,6-dimethyl-1-heptin-3-ol, diethyl fumarate, acetylenecyclohexanol (CAS number: 78-27-3), methylbutinol (CAS number: 115-19-5), methyl maleate.

[0036] In some preferred embodiments, the amount of the inhibitor (D) used is 0 to 0.1 wt % (excluding 0) of the compound having the structure represented by formula (A) 1, and more preferably, the amount of the inhibitor (D) used is 0.01 to 0.05 wt % of the compound having the structure represented by formula (A) 1.

[0037] A second aspect of the present invention provides a method for producing the above prepolymer, comprising the steps of melting (A) 100 parts by weight of a compound having a structure represented by Formula 1, (B) an organosiloxane containing phenyl and Si-H groups, and (D) an inhibitor at 60 to 150°C, mixing them uniformly, lowering the temperature to 60 to 120°C, adding (C) a platinum catalyst, and stirring for 5 to 15 hours to obtain a prepolymer.

[0038] A third aspect of the present invention provides an encapsulating resin, which includes, as production raw materials, an epoxy resin, the prepolymer, a curing agent, an adhesion promoter, and a catalyst.

[0039] In consideration of improving the compatibility between the epoxy resin and the prepolymer, in some preferred embodiments, the epoxy resin is one or a mixture of two or more selected from triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), alicyclic epoxy resin (CAS number: 3130-19-6), and hydrogenated bisphenol A epoxy resin, and more preferably, the epoxy resin is triepoxypropyl isocyanurate and / or alicyclic epoxy resin.

[0040] In consideration of achieving both ease of handling and UV resistance of the encapsulating resin, in some preferred embodiments, the weight ratio of the epoxy resin to the prepolymer is (3 to 20):1, and more preferably, the weight ratio of the epoxy resin to the prepolymer is (4 to 10):1.

[0041] In some preferred embodiments, the curing agent is an anhydride curing agent, more preferably, the anhydride curing agent is one or a mixture of more than one selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, hydrogenated pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, eleostearic anhydride, dodecenylsuccinic anhydride, nadic anhydride, methylnadic anhydride, glutaric anhydride, hydrogenated methylnadic anhydride, methylcyclohexenetetracarboxylic dianhydride, polyazelanic anhydride, polysebacic anhydride, 1,4,5,6-tetrabromophthalic anhydride.

[0042] In some preferred embodiments, the amount of the anhydride hardener used is calculated so that the molar ratio of the anhydride group content to the epoxy content of the system is (0.8-1): 1. In this specification, the epoxy content of the system is the sum of the epoxy resin and the epoxy content in the prepolymer.

[0043] In some preferred embodiments, the adhesion promoter is selected from the group consisting of γ-methylacryloyloxypropyltrimethoxysilane, γ-methylacryloyloxypropylmethyldimethoxysilane, γ-methylacryloyloxypropylmethyldiethoxysilane, γ-(2,3-epoxypropoxy)propyltriethoxysilane, γ-(2,3-epoxypropoxy)propylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2,4,6,8-tetrakis[2-(3,4-epoxycyclohexylethyl)tetrakis(ethyl)phenyl]phenyl]phenyl]phenyl] The compound may be one or a mixture of two or more compounds selected from the group consisting of methylcyclotetrasiloxane, 2,4,6-tris[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane, di[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethyl-[2-(3,4-epoxycyclohexylethyl)]cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[3-(epoxyethylmethoxy)propyl]cyclotetrasiloxane, and 2,4,6,8-tetramethyl-2-[3-(epoxyethylmethoxy)propyl]cyclotetrasiloxane.

[0044] In some preferred embodiments, the amount of the adhesion promoter used is 0.01 to 5 wt % of the total amount of the epoxy resin and prepolymer, and more preferably, the amount of the adhesion promoter used is 0.05 to 3 wt % of the total amount of the epoxy resin and prepolymer.

[0045] In some preferred embodiments, the catalyst is one or a mixture of more selected from triphenylphosphine, methyltrioctylphosphonium dimethylphosphate, tetrabutylphosphonium acetate, methyltributylphosphonium dimethylphosphate, benzyltriphenylphosphonium chloride, tetrabutylphosphonium chloride, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole.

[0046] In some preferred embodiments, the amount of the catalyst used is 0.01 to 5 wt % of the total amount of the epoxy resin, prepolymer, and curing agent, and more preferably, the amount of the catalyst used is 0.1 to 1 wt % of the total amount of the epoxy resin, prepolymer, and curing agent.

[0047] In some preferred embodiments, the raw materials for producing the encapsulating resin further contain at least one of a pigment, an inorganic filler, an antioxidant, and an anti-ultraviolet absorbing agent.

[0048] Examples of pigments include titanium dioxide and carbon black, and the amount added may be 1 to 400 wt% of the total amount of the epoxy resin, prepolymer, and hardener. Examples of inorganic fillers include silica, alumina, calcium carbonate, and kaolin, and the amount added may be 50 to 800 wt% of the total amount of the epoxy resin, prepolymer, and hardener. Examples of antioxidants include 2,6-di-tert-butyl-4-methylphenol, antioxidant 1010, and antioxidant 1076, and the amount added may be 0.01 to 5 wt% of the total amount of the epoxy resin, prepolymer, and hardener. Examples of ultraviolet absorbing agents include UV-326, UV-531, UV-234, and UV-320, and the amount added may be 0.01 to 5 wt% of the total amount of the epoxy resin, prepolymer, and hardener.

[0049] A fourth aspect of the present invention provides a method for producing the above-mentioned encapsulating resin, comprising the steps of stirring an epoxy resin and the prepolymer at 150 to 200°C, lowering the temperature to 100 to 150°C, adding a curing agent, an adhesion promoter and a catalyst, stirring and discharging the mixture, cooling, pulverizing the mixture, and forming a cake to obtain the encapsulating resin.

[0050] A fifth aspect of the present invention provides a sealing resin for a white reflector, which contains, as production raw materials, 100 parts by weight of the above sealing resin and 50 to 400 parts by weight of titanium dioxide.

[0051] A sixth aspect of the present invention provides use of the sealing resin for a white reflector used in a white light LED device having an output of 1 to 3 W.

[0052] A seventh aspect of the present invention provides a sealing resin for a black reflector, which contains, as production raw materials, 100 parts by weight of the above sealing resin and 1 to 30 parts by weight of carbon black.

[0053] An eighth aspect of the present invention provides a use of the above-mentioned encapsulating resin for a black reflector used in a surface-mount SMT light-emitting device of an outdoor RGB display.

[0054] The ninth aspect of the present invention provides an LED device having a reflector structure obtained by injection molding a metal frame or a resin substrate and the above-mentioned sealing resin. In the present invention, the reflector is a carrier for sealing the LED by injecting a liquid potting adhesive, and is also a reflective material that realizes one-sided light emission from the LED. The reflector is molded with the above-mentioned sealing resin, which improves the heat resistance and light aging resistance of the LED device.

[0055] Working Example The present invention will be described in detail below with reference to examples. Note that the following examples are merely for further explanation of the present invention and cannot be understood as limiting the scope of the present invention, and any non-essential improvements or adjustments made by those skilled in the art based on the above content of the present invention are included in the scope of the present invention.

[0056] Example 1 Example 1 provides a prepolymer. 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8), RH-SH309 (phenylhydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-Technology Co., Ltd.), and 0.05 parts by weight of 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) were melted at 100°C for 0.5 hours and mixed uniformly. The temperature was then lowered to 90°C, and 0.5 parts by weight of PT5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) were added, and the mixture was stirred for 10 hours to obtain a prepolymer. In this example, the amount of RH-SH309 used was calculated so that the molar ratio of the SiH content in RH-SH309 to the vinyl content in DA-MGIC was 0.95:1.

[0057] Example 2 Example 2 provides a prepolymer. 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9), RH-SH309 (phenylhydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-Tech Materials Co., Ltd.), and 0.05 parts by weight of 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) were melted at 100°C for 0.5 hours, mixed uniformly, and then cooled to 90°C. 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) were added and stirred for 10 hours to obtain a prepolymer. In this example, the amount of RH-SH309 used was calculated so that the molar ratio of the SiH content in RH-SH309 to the vinyl content in MA-DGIC was 0.95:1.

[0058] Example 3 Example 3 provides a prepolymer. 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9), RH-SH309 (phenylhydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-Tech Materials Co., Ltd.), and 0.05 parts by weight of 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) were melted at 90°C for 0.5 hours, mixed uniformly, and then cooled to 80°C. 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) were added and stirred for 8 hours to obtain a prepolymer. In this example, the amount of RH-SH309 used was calculated so that the molar ratio of the SiH content in RH-SH309 to the vinyl content in MA-DGIC was 0.5:1.

[0059] Example 4 Example 4 provides a prepolymer. DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) 100 parts by weight, RH-SH309 (phenylhydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-Tech Materials Co., Ltd.), 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) 0.05 parts by weight were melted at 90°C for 0.5 hours, mixed uniformly, and then cooled to 80°C. PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) 0.5 parts by weight was added and stirred for 8 hours to obtain a prepolymer. In this example, the amount of RH-SH309 used was calculated so that the molar ratio of the SiH content in RH-SH309 to the vinyl content in DA-MGIC was 0.25:1.

[0060] Example 5 Example 5 provides a prepolymer. 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8), XL-2460 (phenylhydrogen organosiloxane, SiH content: 3.85 mmol / g, purchased from Anbi Special Organosiloxane (Nantong) Co., Ltd.), and 0.05 parts by weight of 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) were melted at 90°C for 0.5 hours, mixed uniformly, and then cooled to 80°C. 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000 ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) were added and stirred for 6 hours to obtain a prepolymer. In this example, the amount of XL-2460 used was calculated so that the molar ratio of the SiH content in XL-2460 to the vinyl content in DA-MGIC was 0.5:1.

[0061] Example 6 Example 6 provides a prepolymer. 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8), XL-2460 (phenylhydrogen organosiloxane, SiH content: 3.85 mmol / g, purchased from Anbi Special Organosiloxane (Nantong) Co., Ltd.), and 0.05 parts by weight of 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) were melted at 90°C for 0.5 hours and mixed uniformly. The temperature was then lowered to 80°C, and 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000 ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) were added and stirred for 6 hours to obtain a prepolymer. In this example, the amount of XL-2460 used was calculated so that the molar ratio of the SiH content in XL-2460 to the vinyl content in DA-MGIC was 0.95:1.

[0062] Example 7 Example 7 provides a prepolymer. 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8), XL-2460 (phenylhydrogen organosiloxane, SiH content: 3.85 mmol / g, purchased from Anbi Special Organosiloxane (Nantong) Co., Ltd.), and 0.05 parts by weight of 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) were melted at 90°C for 0.5 hours, mixed uniformly, and then cooled to 80°C. 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000 ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) were added and stirred for 6 hours to obtain a prepolymer. In this example, the amount of XL-2460 used was calculated so that the molar ratio of the SiH content in XL-2460 to the vinyl content in DA-MGIC was 0.25:1.

[0063] Example 8 Example 8 provides a prepolymer. 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9), XL-2460 (organosiloxane, SiH content: 3.85 mmol / g, purchased from Anbi Special Organosiloxane (Nantong) Co., Ltd.), and 0.05 parts by weight of 3,7,11-trimethyldodecyl-3-ol (CAS number: 1604-35-9, abbreviation TMDO) were melted at 90°C for 0.5 hours, mixed uniformly, and then cooled to 80°C. 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000 ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) were added and stirred for 6 hours to obtain a prepolymer. In this example, the amount of XL-2460 used was calculated so that the molar ratio of the SiH content in XL-2460 to the vinyl content in MA-DGIC was 0.5:1. The inventors compared Examples 1 to 8 and found that under the same experimental conditions, the reaction between DA-MGIC and organosiloxane proceeds more easily than the reaction between MA-DGIC and silicone, and the reaction involving XL-2460 proceeds more easily than the reaction involving RH309. The difficulty of the above reactions is judged according to the reaction time and reaction temperature, and when the reaction time is long and the reaction temperature is high, the handling is poor. The evaluation results of the handling are excellent, good, and poor, in order from the most easily reacted. The handling and yield (epoxy equivalent was tested using the titration method) of Examples 1 to 8 are shown in Table 1. [Table 1]

[0064] Example 9 Example 9 provides an encapsulating resin. 90 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 10 parts by weight of the prepolymer in Example 2 are stirred at 180°C for 0.5 hours, cooled to 130°C, and 150 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS number: 4420-74-0), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) are added, stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin.

[0065] Example 10 Example 10 provides a sealing resin. 90 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 10 parts by weight of the prepolymer in Example 4 are stirred at 180° C. for 0.5 hours, cooled to 130° C., and mixed with 150 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7). parts by weight, 0.25 parts by weight of γ-methylacryloyloxypropylmethyldimethoxysilane (CAS number: 14513-34-9), 0.25 parts by weight of γ-(2,3-epoxypropoxy)propylmethyldimethoxysilane (CAS number: 65799-47-5), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were stirred and discharged, cooled, pulverized, and formed into a cake to obtain a sealing resin.

[0066] Example 11 Example 11 provides a sealing resin. 90 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 10 parts by weight of the prepolymer in Example 6 are stirred at 150° C. for 0.5 hours, cooled to 130° C., and mixed with 150 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7). parts by weight, 0.25 parts by weight of γ-(2,3-epoxypropoxy)propyltriethoxysilane (CAS number: 2602-34-8), 0.25 parts by weight of γ-methylacryloyloxypropylmethyldiethoxysilane (CAS number: 65100-04-1), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were added, stirred, discharged, cooled, pulverized, and formed into a cake to obtain a sealing resin.

[0067] Example 12 Example 12 provides a sealing resin, which is prepared by stirring 90 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 10 parts by weight of the prepolymer in Example 7 at 180°C for 0.5 hours, and then cooling to 130°C. The mixture is mixed with 150 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, and the mixture is cooled to 130°C. 1 part by weight of silane (CAS number: 3388-04-3), 1 part by weight of 2,4,6,8-tetrakis[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane (CAS number: 121225-98-7), 1 part by weight of 3-mercaptopropyltriethoxysilane (CAS number: 14814-09-6), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were added, stirred, discharged, cooled, pulverized, and formed into a cake to obtain a sealing resin.

[0068] Example 13 Example 13 provides a sealing resin. 90 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 10 parts by weight of the prepolymer in Example 8 are stirred at 180°C for 0.5 hours, cooled to 130°C, and mixed with 150 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), γ-methyl acrylate, and 10 parts by weight of the prepolymer in Example 8. Add 0.05 parts by weight of propyloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.05 parts by weight of 2,4,6,8-tetrakis[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane (CAS number: 121225-98-7), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stir, discharge, cool, pulverize, and form into a cake to obtain a sealing resin.

[0069] Example 14 Example 14 provides a sealing resin. 85 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 15 parts by weight of the prepolymer in Example 7 are stirred at 180°C for 0.5 hours, cooled to 130°C, and mixed with 130 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), γ-methylacryloyl 0.025 parts by weight of oxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.05 parts by weight of 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[3-(epoxyethylmethoxy)propyl]cyclotetrasiloxane (CAS number: 60665-85-2), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were added, stirred, discharged, cooled, pulverized, and formed into a cake to obtain a sealing resin.

[0070] Example 15 Example 15 provides a sealing resin. 80 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 20 parts by weight of the prepolymer in Example 7 are stirred at 180°C for 0.5 hours, cooled to 130°C, and mixed with 110 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), γ-methyl 0.05 parts by weight of acryloyloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.05 parts by weight of 2,4,6,8-tetramethyl-2-[3-(epoxyethylmethoxy)propyl]cyclotetrasiloxane (CAS number: 61614-55-9), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were added, stirred, discharged, cooled, pulverized, and formed into a cake to obtain a sealing resin.

[0071] Example 16 Example 16 provides a sealing resin. 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 number: 2409-55-4), and 10 parts by weight of the prepolymer in Example 2 are stirred at 180° C. for 0.5 hours, cooled to 130° C., and mixed with hexahydrophthalic dianhydride (CAS number: 85-42- 7) 110 parts by weight of γ-methylacryloyloxypropyltrimethoxysilane (CAS number: 2530-85-0) 0.025 parts by weight of γ-methylacryloyloxypropylmethyldiethoxysilane (CAS number: 65100-04-1) and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were stirred, discharged, cooled, pulverized, and formed into a cake to obtain a sealing resin.

[0072] Example 17 Example 17 provides an encapsulating resin. 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), and 10 parts by weight of the prepolymer in Example 4 are stirred at 180°C for 0.5h, cooled to 130°C, and then 110 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.025 parts by weight of γ-methylacryloyloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of γ-methylacryloyloxypropylmethyldiethoxysilane (CAS number: 65100-04-1), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) are added, stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin.

[0073] Example 18 Example 18 provides an encapsulating resin. 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), and 10 parts by weight of the prepolymer in Example 7 are stirred at 180°C for 0.5 hours, cooled to 130°C, and 110 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.025 parts by weight of γ-methylacryloyloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of γ-methylacryloyloxypropylmethyldiethoxysilane (CAS number: 65100-04-1), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) are added, stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin.

[0074] Example 19 Example 19 provides an encapsulating resin. 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), and 10 parts by weight of the prepolymer in Example 8 are stirred at 180°C for 0.5 hours, cooled to 130°C, and 110 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.025 parts by weight of γ-methylacryloyloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of γ-methylacryloyloxypropylmethyldiethoxysilane (CAS number: 65100-04-1), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) are added, stirred, discharged, cooled, pulverized, and caked to obtain an encapsulating resin.

[0075] Comparative Example 1 Comparative Example 1 provides a sealing resin. 90 parts by weight of triepoxypropyl isocyanurate (TGIC, CAS number: 2451-62-9) and 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4) were stirred at 180°C for 0.5 hours, cooled to 130°C, and 150 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS number: 4420-74-0), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were added, stirred, discharged, cooled, pulverized, and caked to obtain a sealing resin.

[0076] Comparative Example 2 Comparative Example 2 provides an encapsulating resin. 90 parts by weight of alicyclic epoxy resin A and 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4) were stirred at 180°C for 0.5 hours, cooled to 130°C, and 110 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.025 parts by weight of γ-methylacryloyloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of γ-methylacryloyloxypropylmethyldiethoxysilane (CAS number: 65100-04-1), and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2) were added, stirred, discharged, cooled, pulverized, and formed into a cake to obtain an encapsulating resin.

[0077] The handleability of Examples 9 to 19 and Comparative Examples 1 to 2 was evaluated, and a chip was packaged using the sealing resin in each Example. If the sealing resin was unable to package the chip or had too high a melt viscosity, the handleability was poor. The evaluation results of the handleability were ranked from good to excellent, relatively good, and poor, and the handleability of Examples 9 to 19 and Comparative Examples 1 to 2 is shown in Table 2.

[0078] The transparency of Examples 9 to 19 and Comparative Examples 1 and 2 was evaluated. The sealing resin was preheated, pushed into the cavity, and mold-pressed at 160°C for 300 seconds to form the resin. The resin was then molded at 150 to 170°C for 2 to 4 hours to obtain a test piece with a uniform thickness (200±10 um). The mold-pressed sample was observed to determine whether it was transparent or milky. The transparency evaluation results were rated as excellent, relatively good, and poor in the order of transparent, semi-transparent, and milky, and the transparency of Examples 9 to 19 and Comparative Examples 1 to 2 are shown in Table 2. The UV resistance of Examples 9 to 19 and Comparative Examples 1 to 2 was evaluated. The above mold pressed samples were put into a UV irradiation device as test samples, and the color after 1 hour of irradiation was tested using a colorimeter and compared with the aging state. The larger the b value, the worse the UV light attenuation resistance. The results are shown in Table 2. [Table 2]

[0079] A test was carried out on the blue light attenuation resistance of a UV lamp for Example 9, Comparative Example 1, Example 16 and Comparative Example 2. The encapsulating resin obtained by adding the prepolymer of the present invention had better UV light attenuation resistance, and this effect can be seen from Figures 1 and 2.

[0080] As a result of a large amount of experiments conducted in the research, the inventors found that, in the triepoxypropyl isocyanurate system, by selecting any one of Examples 1 to 8 and following the conditions of Example 9, a sealing resin with excellent performance can be obtained, and by sealing an LED chip with this sealing resin, a white LED chip with blue light resistance can be obtained.

[0081] As a result of a large amount of experiments conducted in the course of research, the inventors found that, for an alicyclic epoxy resin system, by selecting any one of Examples 1 to 8 and following the conditions of Example 16, a sealing resin with excellent performance can be obtained, and by sealing an LED chip with this sealing resin, a white light LED chip with blue light resistance can be obtained. The above examples are merely illustrative and are intended to illustrate some features of the method of the present invention. The appended claims are intended to claim the broadest possible scope, and the examples described herein are merely illustrative of embodiments by selecting all possible example combinations. Thus, the applicants do not intend the appended claims to be limited by the selection of examples illustrating features of the present invention. Some numerical ranges used in the claims include subranges therein, and variations of these ranges, where possible, are also covered by the appended claims.

Claims

1. As a manufacturing raw material, (A) a compound having a structure represented by formula 1; (B) an organosiloxane containing phenyl and Si—H groups; (C) a platinum catalyst; (D) an inhibitor, The method for producing the prepolymer comprises the steps of melting (A) 100 parts by weight of a compound having a structure represented by formula 1, (B) an organosiloxane containing phenyl and Si-H groups, and (D) an inhibitor at 60 to 150°C, mixing the mixture uniformly, lowering the temperature to 60 to 120°C, adding (C) a platinum catalyst, and stirring for 5 to 15 hours to obtain a prepolymer. 【Chemistry 1】 (Here, R １ , R ２ , R ３ are each independently selected from vinyl or epoxy.

2. The manufacturing raw materials include epoxy resins, prepolymers, hardeners, adhesion promoters, and catalysts. The prepolymer is used as a manufacturing raw material. (A) Formula 1 【Chemistry 2】 wherein R 1 , R 2 , and R 3 are each independently selected from vinyl or epoxy. and a compound having a structure represented by (B) an organosiloxane containing phenyl and Si—H groups; (C) a platinum catalyst; (D) an inhibitor; The sealing resin is characterized by the above.

3. The method for producing an encapsulating resin according to claim 2, further comprising the steps of: stirring the epoxy resin and prepolymer at 150 to 200° C., lowering the temperature to 100 to 150° C., adding a curing agent, an adhesion promoter, and a catalyst, stirring and discharging the mixture, cooling, pulverizing, and forming a cake, thereby obtaining the encapsulating resin.

4. A sealing resin for a white reflector, comprising, as production raw materials, 100 parts by weight of the sealing resin according to claim 2 and 50 to 400 parts by weight of titanium dioxide.

5. 5. Use of the sealing resin for white reflector according to claim 4, which is used for a white light LED device with an output of 1 to 3 W.

6. A sealing resin for a black reflector, comprising, as production raw materials, 100 parts by weight of the sealing resin according to claim 2 and 1 to 30 parts by weight of carbon black.

7. 7. Use of the encapsulating resin for black reflectors according to claim 6, which is used for surface-mount SMT light-emitting devices in outdoor RGB displays.

8. 3. An LED device comprising: a metal frame or a resin substrate and the sealing resin according to claim 2, which are injection molded to obtain a reflector structure.

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