CN113667306B - Photodiffusion type organic silicon composite material and preparation method thereof - Google Patents

Photodiffusion type organic silicon composite material and preparation method thereof Download PDF

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CN113667306B
CN113667306B CN202010412035.1A CN202010412035A CN113667306B CN 113667306 B CN113667306 B CN 113667306B CN 202010412035 A CN202010412035 A CN 202010412035A CN 113667306 B CN113667306 B CN 113667306B
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谭奎
何丹丹
谢晓芳
魏道胜
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Jiangxi Bluestar Xinghuo Silicone Co Ltd
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
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    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract

A photodiffusion type organic silicon composite material and a preparation method thereof, wherein the composite material comprises a component A and a component B, and the component A and the component B comprise the following raw materials: the component A comprises base rubber and reinforcing filler; the component B comprises a crosslinking agent, a catalyst and a light diffusing agent, wherein the light diffusing agent is liquid and contains groups with high molar refractivity, such as ether bonds, aromatic rings and alkoxy groups which can be hydrolyzed to generate ester bonds with high molar refractivity. According to the invention, the liquid light diffusant is added into the organic silicon material, and the liquid light diffusant can not shield light, so that the loss of transmission light is reduced, and the organic silicon material can keep higher transmittance; meanwhile, because the refractive index of the light diffusants is larger than 1.45, and the refractive index of the used base glue is generally 1.39-1.40, after the potting glue is cured, the light diffusants and the polydimethylsiloxane are separated in a microscopic phase, so that the potting glue is endowed with higher haze.

Description

Photodiffusion type organic silicon composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of organic silicon materials, and particularly relates to a light diffusion type organic silicon composite material and a preparation method thereof.
Background
The LED lamp is widely loved by people due to the advantages of green, environment-friendly, high-efficiency, energy-saving and the like, is mainly applied to the fields of screen display systems, indicator lamps, mobile phones and the like, and is also actively developed in the field of power illumination in recent years. However, the LED lamp has a limited area for illuminating a point light source, has strong light intensity, contains a large amount of blue light components, and is vulnerable to eye injury, and people often use a packaging material with light diffusion performance to solve the problems of soft light and high brightness from the point light source to the area light source. The most widely used LED lamps are lens materials, including polycarbonate, polymethyl methacrylate, glass and the like, which can obtain the advantages of higher transparency, light intensity suitable for human eyes and the like by mixing with some light diffusant, but with technological progress, the strength, linear expansion coefficient and the like of the materials are more and more unsatisfied, and particularly for long, thin, soft and wide LED lamps, the bending performance, shrinkage or expansion performance of the materials are far from the standard, so that another soft and elastic encapsulating material-potting material is favored by the market for the long, thin, soft and wide LED lamps.
The encapsulating material mainly comprises epoxy resin and an organic silicon material, the epoxy resin can change color and cannot bear a high-temperature welding process, and the application of the encapsulating material has certain limitation, so that the organic silicon material has the development prospect at present, the organic silicon material can absorb heat and prevent color change, particularly has higher refractive index per se, and the defect in beauty is that the haze of the organic silicon material is generally lower, for example, patent CN201410568860.5 discloses preparation of two-component condensation type LED organic silicon encapsulating glue, patent CN201310346458.8 discloses two-component organic silicon encapsulating glue, and patent CN201410685155.3 discloses single-component dealcoholization type room-temperature vulcanization organic silicon encapsulating glue and a preparation method thereof. The organic silicon pouring sealant prepared by the patents has the characteristics of good light transmittance, high refractive index, good thermal stability, small stress cracking and the like, and has the defect that although the light transmittance is high, the haze and the diffusion are small and cannot meet the actual requirement. Generally, in order to seek higher light transmittance in the preparation process, the haze of the obtained potting adhesive is correspondingly reduced, and a light diffuser is generally directly added, so that the haze is improved, but the light transmittance is lost, and patents such as patent CN201710545923.9 which are beneficial to improving the haze by the light diffuser disclose an LED surface light source, wherein the potting adhesive is silica gel, and the light diffuser is organic silicon with the particle size of 2-4 μm. CN201610219317.3 discloses a polyester resin-based light diffusion composite material, which is prepared by mixing polycarbonate, polyterephthalate, a light diffusion agent, an antioxidant and a mold release agent, wherein the light diffusion agent is selected from one or more of silicone resin microspheres, silica gel microspheres and crosslinked PMMA microspheres; CN201711188327.6 discloses a light diffuser for LEDs, a preparation method thereof and a light diffuser material containing the light diffuser, the light diffuser is an organic silicon microcapsule, a capsule material is composed of methyltrimethoxysilane and phenyltrimethoxysilane, the particle size of the microcapsule is 1-5 μm, although the light diffuser in the patent can make a base material obtain higher haze and avoid dizziness, they all have common disadvantages: the solid light diffusant with high cost is used, has a certain shielding effect on light, and can certainly cause the reduction of light transmittance and diffusion angle, so that the LED lamp beads are obviously visible to the naked eye, and therefore, the development of a pouring sealant material with low light transmittance loss or even no light transmittance loss under the condition of improving the haze is urgently needed.
Disclosure of Invention
The invention aims to overcome the defect that the haze and the light transmittance of an organic silicon encapsulating material of an LED lamp in the prior art cannot meet the requirements at the same time, and provides a light diffusion type organic silicon composite material.
In order to achieve the purpose, the invention provides the following technical scheme:
the light diffusion type organic silicon composite material comprises a component A and a component B, and is characterized in that the component A and the component B comprise the following raw materials: the component A comprises base rubber and reinforcing filler; the component B comprises a crosslinking agent, a catalyst and a light diffusant, wherein the light diffusant is a compound of a formula (I) and/or a formula (II):
Figure BDA0002493583820000021
wherein R is 1 Is composed of
Figure BDA0002493583820000022
R 11 Is C2-C16 alkane;
R 2 is composed of
Figure BDA0002493583820000023
R 21 Is C2-C16 alkane;
R 3 is phenyl, -H or C2-C16 alkane;
Figure BDA0002493583820000024
wherein R is 4 is-H, an alkoxysilane containing an imido group (-CONH-), an alkoxysilane containing an alkylene group- (CH) 2 ) x -alkoxy silane, alkenyl; m in the formula (II) is an integer between 0 and 12, preferably an integer between 0 and 6; n in the formula (II) is an integer of 20-400, preferably an integer of 50-200.
Specifically, the compound of the formula (I) is selected from at least one of dioctyl phthalate, dibutyl phthalate and dihexyl phthalate.
The inventor unexpectedly finds that the compound of the formula (I) can be used as a light diffusant of an organic silicon pouring sealant material, not only can improve the haze, but also can not cause too much reduction of light transmittance.
The light diffusant is liquid at room temperature, and when the light diffusant is a compound shown as a formula (I), the kinematic viscosity v is less than 150mPa & s; when the light diffuser is a compound of formula (II), the kinematic viscosity v is < 10000 mPas.
The refractive index of the light diffusant is larger than 1.45.
The component A and the component B comprise the following raw materials in parts by weight: the component A comprises 100 parts of base rubber and 1-30 parts of reinforcing filler; the component B comprises 10-20 parts of cross-linking agent, 0.2-5 parts of catalyst and 20-50 parts of light diffusant.
In order to make the light diffusion type organic silicon composite material cheaper to use, the light diffusing agent in the component B in the scheme can be separated and marked as the component C, namely, the light diffusion type organic silicon composite material further comprises the component A, the component B and the component C, wherein the component A, the component B and the component C comprise the following raw materials in parts by weight: wherein the component A comprises 100 parts of base adhesive, 0-50 parts of plasticizer, 1-30 parts of reinforcing filler and 0-1 part of pigment, the component B comprises 2-20 parts of cross-linking agent and 0.1-10 parts of catalyst, and the component C comprises 20-50 parts of light diffusant.
The base adhesive is alpha, omega-dihydroxy polydimethylsiloxane, and the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 400-80000 mPas, preferably 400-10000 mPas.
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane determines the construction performance and the mechanical performance of the composite material to a great extent, and the lower the viscosity value is, the better the construction performance of the composite material is, but the lower the elongation at break is; the higher the viscosity value, the poorer the workability of the composite material, but the higher the elongation at break.
The plasticizer is polydimethylsiloxane, and the viscosity range is 50-500 mPas, preferably 100-350 mPas.
The reinforcing filler is white carbon black or methyl MQ resin, and the specific surface area of the white carbon black is 100-300m 2 The white carbon black comprises gas-phase white carbon black or precipitation white carbon black.
The pigment is selected from at least one of cinnabar, realgar, malachite green, wollastonite, mica powder, titanium dioxide, cochineal red, natural fish scale powder, gamboge, alizarin red, indigo, lithopone, lead chrome yellow, iron blue, scarlet powder, bipale yellow, phthalocyanine blue and quinacridone.
The catalyst is at least one of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, n-butyl titanate, isopropyl titanate and titanate chelate.
The cross-linking agent includes but is not limited to at least one of methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, propylorthosilicate, polymethyltriethoxysilane, and polyethylorthosilicate.
The component A of the composite material also can comprise 5-50 parts of plasticizer and 0.01-1 part of pigment.
The invention also provides a preparation method of the double-component light diffusion type organic silicon composite material, which comprises the following steps:
1) Adding the base adhesive, the plasticizer, the reinforcing filler and the pigment into a reaction container, and uniformly stirring under negative pressure to obtain a component A;
2) Adding a cross-linking agent, a catalyst and a light diffusant into a reaction vessel, and uniformly stirring under negative pressure to obtain a component B;
3) Before use, uniformly mixing the component A obtained in the step 1) and the component B obtained in the step 2) to obtain the light diffusion type organic silicon composite material which can be directly encapsulated for use;
step 1), the negative pressure is-0.05- (-0.10) MPa, and the stirring time is 15-60min;
the negative pressure in the step 2) is-0.05- (-0.10) MPa, and the stirring time is 15-60min.
If the light diffusion type organic silicon composite material comprises the components A, B and C, the light diffusion agent is not added in the step 2), and the components A, B and C are mixed before being used in the step 3), so that the light diffusion type organic silicon composite material is obtained and can be directly encapsulated for use.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the liquid light diffusant is added into the organic silicon material, and the liquid light diffusant can not shield light, so that the transmission light loss is reduced, and the prepared organic silicon material can keep higher transmittance; meanwhile, because the molecules of the light diffusant contain groups with high molar refraction degree, such as ether bonds, aromatic rings and alkoxy groups which can be hydrolyzed to generate ester bonds with high molar refraction degree, the refractive index of the used base glue is 1.39-1.40, after the potting glue is cured, the light diffusant and the polydimethylsiloxane are separated at microscopic phase, and the potting glue is endowed with high haze.
2. The invention has the advantages of low price of each component, low production cost, simple and environment-friendly preparation process, flexible and various product forms, double-component or three-component type and convenient construction.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, the parts of the reagents are parts by weight. All reagents used are commercially available in the art.
Example 1
1) 100 parts of alpha, omega-dihydroxy polydimethylsiloxane having a viscosity of 1500mPa · s, 10 parts of polydimethylsiloxane having a viscosity of 350mPa · s, and 10 parts of fumed silica (trade name: wake V-15) and 0.03 part of phthalocyanine blue are added into a reaction vessel and stirred for 30min under the negative pressure of-0.085 MPa; obtaining a component A;
2) Adding 8 parts of ethyl orthosilicate, 30 parts of dioctyl phthalate (a light diffusant with a structure of a formula I) and 1 part of dibutyltin dilaurate into a reaction vessel, and stirring for 15min under the negative pressure of-0.085 MPa to obtain a component B;
3) Mixing the component A obtained in the step 1) and the component B obtained in the step 2) to obtain the light diffusion type organic silicon composite material.
Example 2
The procedure was repeated except for using 20 parts of dioctyl phthalate, a light diffusing agent, as in example 1.
Example 3
The procedure of example 1 was repeated, except that 50 parts of dioctyl phthalate as a light diffusing agent was used.
Example 4
The procedure of example 1 was repeated, except that the amount of dioctyl phthalate as the light diffusing agent was 10 parts.
Example 5
The procedure of example 1 was repeated, except that the amount of dioctyl phthalate as the light diffusing agent was 80 parts.
Example 6
The procedure was repeated as in example 1 except that the light diffusing agent was dibutyl phthalate (a light diffusing agent having a structure represented by formula I).
Example 7
The procedure was repeated as in example 1 except that the light diffusing agent was a silane-modified polyether (trade name: dollouin S203H, a light diffusing agent having a structure of the formula II, kinematic viscosity: 6000 to 8000mPa. S).
Example 8
The rest is the same as example 1, except that the light diffusing agent is polyether (trade name: dow DL-4000D, light diffusing agent with structure of formula II, kinematic viscosity is 800-1000mPa.s).
Example 9
1) 100 parts of alpha, omega-dihydroxy polydimethylsiloxane having a viscosity of 1500mPa · s, 10 parts of polydimethylsiloxane having a viscosity of 350mPa · s, 10 parts of fumed silica (trade name: wake V-15) and 0.03 part of phthalocyanine blue are added into a reaction vessel and stirred for 30min under the negative pressure of-0.085 MPa; obtaining a component A;
2) Adding 8 parts of ethyl orthosilicate and 1 part of dibutyltin dilaurate into a reaction vessel, and stirring for 15min under the negative pressure of-0.085 MPa to obtain a component B;
3) And (2) adding 30 parts of component C (dioctyl phthalate) (the light diffusant with the structure of the formula I) into the component A obtained in the step 1) and the component B obtained in the step 2) and uniformly mixing to obtain the light diffusion type organic silicon composite material.
Example 10
The process is the same as example 1 except that the reinforcing filler is a methyl MQ resin (Shenzhen Jipeng silicon fluoride materials Co., ltd.) with the designation of 5201P.
Comparative example 1
The rest is the same as the embodiment 1, except that the light diffusing agent used is Shenzhen Haiyang powder HY-690, the average grain diameter is 2 μm, and the dosage is 2 parts (2 parts is the recommended dosage by the manufacturer).
Comparative example 2
The rest is the same as the embodiment 1, except that the light diffusing agent used is Shenzhen Haiyang powder HY-690, the average grain diameter is 2 μm, and the using amount is 10 parts (2 parts is the manufacturer recommended using amount).
Comparative example 3
The rest is the same as the embodiment 10, except that the light diffusing agent used is Shenzhen Haiyang powder HY-690, the average grain diameter is 2 μm, and the using amount is 2 parts (2 parts is the manufacturer suggested using amount).
The cured light-diffusing organic silicon composite material prepared in the above examples and comparative examples was subjected to optical performance test and mechanical performance test by preparing sample pieces according to the following steps and specifications, and the results are shown in table 1 below.
1. The composite materials of the examples and the comparative examples are respectively prepared into flat and uniform sample wafers with the thickness of 0.3mm, and optical performance tests are carried out.
2. The composite materials of the examples and the comparative examples are respectively prepared into flat and uniform sample wafers with the thickness of 0.5mm, and optical performance tests are carried out.
3. Preparing a plurality of wedge-shaped grooves with the same size, fixing LED lamp strips with the models of 2835-120P-12V, 24-26LM/PCS in lumen and 10W/M in the bottoms of the wedge-shaped grooves, then respectively coating (encapsulating) the composite materials of the embodiment and the comparative example in the wedge-shaped grooves, flattening the upper surfaces, and curing for 7 days at room temperature; then light LED lamp strip, see through the wedge groove and observe the lamp pearl that lights, do the sign in the position that every sample just can't see the lamp pearl totally respectively to measure the thickness of this sign position. This thickness is referred to as the critical thickness A. Then preparing a sample wafer with the critical thickness A of each sample, and testing the optical performance.
4. And (3) performing mechanical property test according to the standard GB/T528-2009 (determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber).
TABLE 1
Figure BDA0002493583820000061
Figure BDA0002493583820000071
As can be seen from the above table, in the embodiment, the light-diffusing type organic silicon composite material prepared by using the liquid low-molecular light-diffusing agent can obtain higher haze with lower thickness, has higher transmittance without great loss of transmitted light, and has a composite material coverage thickness of less than 7.5mm, and the LED lamp beads are completely invisible to naked eyes. Whereas comparative examples 1 and 2 show a greater loss of light transmittance under the same conditions.
As can be further found from the above table, the reinforcing filler white carbon black itself can also provide a certain haze, but has a certain influence on the light transmittance, so that in example 10, after the white carbon black is replaced by the methyl MQ resin, compared with examples 1 to 9, the light transmittance is greatly improved, and the haze is slightly reduced.
Comparative example 3 was replaced with methyl MQ resin, but the haze was not as good as in example 10 due to insufficient light diffusion, the critical thickness was high, and the mechanical properties of the powder light diffusion powder were greatly affected.
The invention has the advantages of low price of each component, low production cost, simple and environment-friendly preparation process, flexible and various product forms, double-component or three-component type and convenient construction.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.

Claims (8)

1. The application of the compound shown in the formula (I) as a light diffusion type organic silicon composite material light diffusion agent is characterized in that the light diffusion type organic silicon composite material comprises a component A and a component B, the raw materials of the component A comprise 100 parts of base glue, 1-30 parts of reinforcing filler and 5-50 parts of plasticizer, the plasticizer is polydimethylsiloxane, and the viscosity range is 50-500mPa & s; the raw materials of the component B comprise 10-20 parts of cross-linking agent, 0.2-5 parts of catalyst and 20-50 parts of compound shown in the formula (I), wherein the compound shown in the formula (I) is as follows:
Figure FDA0003929634350000011
wherein R is 1 Is composed of
Figure FDA0003929634350000012
R 11 Is C2-C16 alkane;
R 2 is composed of
Figure FDA0003929634350000013
R 21 Is a C2-C16 alkane;
R 3 is phenyl, -H or C2-C16 alkane.
2. Use according to claim 1, wherein the light diffuser is liquid at room temperature and has a kinematic viscosity v < 150 mPa-s.
3. The use according to claim 1, wherein the light diffuser has a refractive index > 1.45.
4. Use according to claim 1, wherein the base gum is an α, ω -dihydroxy polydimethylsiloxane having a viscosity in the range of 400 to 80000 mPa-s.
5. Use according to claim 1, wherein the plasticizer has a viscosity in the range of 100 to 350 mPa-s.
6. The use according to claim 1, wherein the reinforcing filler is white carbon black or methyl MQ resin, the specific surface area of the white carbon black is 100-300m 2/g, and the white carbon black comprises fumed silica or precipitated silica.
7. The use of claim 1, wherein the catalyst comprises at least one of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, n-butyl titanate, isopropyl titanate, titanate chelate.
8. The use according to claim 1, wherein the cross-linking agent comprises at least one of methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethylorthosilicate, propylorthosilicate, polymethyltriethoxysilane, polyethylorthosilicate.
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