CN103012799B - A kind of LED phenylakenyl silicone resin and preparation method thereof - Google Patents
A kind of LED phenylakenyl silicone resin and preparation method thereof Download PDFInfo
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- CN103012799B CN103012799B CN201210532360.7A CN201210532360A CN103012799B CN 103012799 B CN103012799 B CN 103012799B CN 201210532360 A CN201210532360 A CN 201210532360A CN 103012799 B CN103012799 B CN 103012799B
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Abstract
The present invention relates to organic silica gel Material Field, disclose a kind of LED phenylakenyl web-like silicon resin with high refractive index and preparation method thereof.Described silicone resin is for having cancellated phenylakenyl silicone resin.Described preparation method does not adopt chlorosilane of the prior art, nontoxic extraction agent to replace toluene of the prior art, can not damage human body, can not to environment yet.Phenylakenyl silicone resin provided by the invention not only has the characteristics such as high refractive index, high transmission rate, clear, and this phenylakenyl silicone resin has good consistency and dispersiveness, thus make the excellent properties such as silicon rubber rebound resilience is good, anti tear, anti-impact force, thermotolerance are good, radiation hardness, long service life.
Description
Technical field
The present invention relates to organic silica gel Material Field, is a kind of silicone resin for LED and preparation method thereof specifically.
Background technology
LED(Lighting Emitting Diode) i.e. LED lighting is a kind of light emitting semiconductor device.The light-emitting devices such as photodiode (LED) are emerging environmental protection light sources, and countries in the world are actively promoted the use of.And for the light-emitting element package material of the type, except requiring to possess from the function of outer protection luminous element, for preventing the brightness of luminous element from reducing, also require the transparency possessing height.
At present, LED encapsulation material mainly adopts the epoxy resin with good transparency to be packaged material.Use epoxy resin as the LED of packaged material after life-time service, inevitably xanthochromia can occur due under the UV-irradiation of launching at LED chip, cause its transmittance to decline, reduction brightness.Based on more and more higher to the requirement of LED encapsulation material, epoxy resin can not meet the encapsulation requirement of LED.Through years of researches development, have the organic silica gel material (patent No. is CN101414655) adopting and have high refractive index, optical throughput can improve 5-8%.The LED product of the encapsulation that silicone resin material is made, there is high-clarity (transmittance is greater than 95%), radiation hardness, thermotolerance are good, irradiate without xanthochromia for a long time through high temperature, can not crack, greatly extend the advantage such as work-ing life and superior cementability of LED encapsulation material, its performance is far superior to epoxy resin.Along with development trend now, the energy in short supply, putting before environmental protection and the strategy of sustainable development, increasing epoxy resin will replace by silicone resin.
Organic silica gel material is divided into two types: a kind of is the methylsiloxane glue material of low-refraction, and another kind is the phenyl organosilicon material with high refractive index.The organic silica gel material that market generally uses mainly methylsiloxane glue material, current power-type LED, just in flourish and widespread use, because the specific refractory power of methylsiloxane glue material is low, can not meet power type LED encapsulation completely.Phenyl organic silica gel material has the features such as high refractive index, thermotolerance be good, and the LED encapsulation material being more suitable for power-type than methylsiloxane glue material uses.
The phenylakenyl organic silica gel material of domestic and international report is all use phenylakenyl silicone resin.Phenylakenyl silicone resin is a kind of very unique silicone resin, and it has the excellent properties such as high refractive index, high transmission rate, the good radiation hardness of rebound resilience.Current known aminomethyl phenyl thiazolinyl silicone resin is mainly divided into two kinds: one is methyl chlorosilane, phenyl chlorosilane, methylvinyl-chlorosilanes, toluene etc. is main raw material, as the method described in patent CN101979427A, CN1798810A, CN101343365A, WO2004107458, US20050212008, US0040116640.The speed different skewness that can cause group of aminomethyl phenyl thiazolinyl silicone resin owing to being hydrolyzed of this method synthesis, and produce obnoxious flavour and the material of a large amount of hydrogenchloride, contaminate environment, electronic product.This method cycle is short in addition, efficiency is low, complicated operation, reaction fierceness, product are complicated, the shortcomings such as the specific refractory power of the aminomethyl phenyl thiazolinyl silicone resin finally obtained is low, poor transparency.Another is starting material with the alkoxysilane of different functionality and octadecyloxy phenyl oxosilane, acidic cation-exchange resin etc., as the method described in patent CN101475689A, CN101717512A, CN101109823A, CN101016446A.Long, the difficult control of preparation process, the various complexity of step of this method cycle, efficiency is low, reaction product is more complicated, acidic cation-exchange resin residual color cause product not clear affect the problems such as product performance.
In sum, there is some problem in the existing phenylakenyl silicone resin of technology synthesis and the method for synthesis thereof.Therefore, what this environmental protection light source industry was badly in need of solving is to provide that a kind of specific refractory power is high, the better phenylakenyl silicone resin of transparency, and provide a kind of raw material to be easy to get, simple to operate, reaction conditions is gentle, the time is short, cost is low, environmentally safe, be convenient to the silicone resin synthetic method of suitability for industrialized production.
Summary of the invention
In order to solve the problem, the invention provides and a kind of there is the advantages such as high refractive index, high transmission rate, clear, rebound resilience is good, anti tear, anti-impact force, thermotolerance are good, radiation hardness, long service life etc. are excellent performance and raw material is easy to get, industry preparation is easy phenylakenyl silicone resin.
The present invention is achieved in that
A kind of LED silicone resin, described silicone resin is cancellated containing thiazolinyl active group phenyl polysiloxane for having.
Preferably, described silicone resin is represented by following general formula:
Wherein, R, R 〞, R " ' be the straight or branched alkyl of identical or not identical 1 ~ 6 carbon atom, acyloxy or the straight or branched aryl of 6 ~ 20 carbon atoms or the aralkyl of 7 ~ 20 carbon atoms; R' is the straight or branched thiazolinyl of 2 ~ 6 carbon atoms.
Preferably, described R, R 〞, R " ' be identical or different methyl or ethyl or phenyl or phenmethyl or styroyl.
Preferably, described R ' is vinyl.
Another object of the present invention is to provide a kind of method preparing described LED silicone resin, and described method comprises the steps:
A) under an acid catalysis, drip containing phenyl functional group silane agent, carry out polyreaction containing the silane agent of alkenyl-functional groups;
B) add extraction agent, based target containing phenylakenyl web-like silicon resin, to control temperature of reaction be 50 ~
90 DEG C, 1 ~ 7 hour reaction times;
C) left standstill by product, anhydrate layer, with distilled water, phenylakenyl web-like silicon resin cleaned to neutrality, obtains the phenylakenyl web-like silicon resin solution being dissolved in extraction agent;
D) by neutrality containing phenylakenyl web-like silicon resin solution, be after the membrane filtration of 0.5 ~ 5 μm with aperture, low-boiling-point substance is removed in underpressure distillation, obtains phenylakenyl web-like silicon resin.
Preferably, the structural formula of the described silane agent containing phenyl functional group is: R
1(R
2o)
3si or R
1(R
2o)
2si R
3, wherein, R
1, R
3for the straight or branched alkyl of identical or not identical 2 ~ 6 carbon atoms, acyloxy or the straight or branched aryl of 6 ~ 20 carbon atoms or the aralkyl of 7 ~ 20 carbon atoms, R
2for straight or branched alkyl, the acyloxy of 1-6 carbon atom.The described silane agent containing phenyl functional group can be but be not limited to as follows:
Phenyl triethoxysilane;
Styroyl (trimethoxy) silane;
Phenyltrimethoxysila,e;
Phenylbenzene diethoxy siloxanes.
Preferably, described is R containing alkenyl-functional groups silane agent structural formula
1(R
2o)
2siR
3or R
1(R
2o)
3si, wherein R
1it is the straight or branched thiazolinyl of 2 ~ 6 carbon atoms; R
2, R
3for straight or branched alkyl, the acyloxy of identical or not identical 1 ~ 6 carbon atom.The described alkenyl-functional groups silane agent that contains can be but be not limited to as follows:
Methylvinyldimethoxysilane;
Vinyltrimethoxy silane;
Vinyltriethoxysilane;
Octenyl Trimethoxy silane.
Preferably, described extraction agent is isomeric alkane or methyl oligosiloxane.
Optionally, the in preparation process a) step increases organoalkoxysilane agent, is specially: under an acid catalysis, and the silane agent dripped containing the silane agent of alkenyl-functional groups, organoalkoxysilane agent, phenyl functional group carries out polyreaction.
Preferably, the structural formula of described organoalkoxysilane agent is R
1(R
2o)
2si R
3, wherein R
1, R
2, R
3for straight or branched alkyl, the acyloxy of identical or not identical 1 ~ 6 carbon atom.Described organoalkoxysilane agent agent can be but be not limited to as follows:
Dimethyldiethoxysilane;
Dimethyldimethoxysil,ne;
Phenylakenyl silicone resin provided by the invention not only has the characteristics such as high refractive index, high transmission rate, clear, has the excellent properties such as rebound resilience is good, anti tear, anti-impact force, thermotolerance are good, radiation hardness, long service life.And this phenyl Silicon Containing Hydrogen resin has good consistency and dispersiveness, cause addition reaction with linking agent to be cross-linked, thus produce firmly Chemical bond with silicon rubber, improve the mechanical strength of silicon rubber, and being increased to optimum value along with phenylakenyl web-like silicon resin demand, cross-linking density becomes large, is crosslinkedly tending towards perfect, mechanical property (as tensile strength and tensile yield) can improve gradually, and the cementability of end properties is better, shear bonding strength has significant effect.
The preparation method of phenylakenyl silicone resin provided by the invention does not adopt chlorosilane of the prior art, nontoxic extraction agent to replace toluene of the prior art, can not damage human body, can not to environment yet.Adopt the phenylakenyl silicone resin prepared of present method to have excellent performance, reaction conditions is gentle, the reaction times is short, simple to operate, raw material is easy to get, cost is low, environmentally safe, be convenient to suitability for industrialized production.
Embodiment
Embodiment 1:
With stirring, reflux condensing tube, 140g distilled water is added respectively in the four-hole boiling flask of thermometer and dropping funnel, the hydrochloric acid of 1.0g1N, after being uniformly mixed, drip 360.56g phenyl triethoxysilane, 198.35g methylvinyldimethoxysilane, 180.11g dimethyldimethoxysil,ne, add 100g dehydrated alcohol again, 10g37% hydrochloric acid and 170g isohexadecane extraction agent carry out cohydrolysis-polycondensation, temperature of reaction is 85 DEG C, controlling the reaction times is stratification after 2h, aqueous phase is removed, with distilled water, organic phase is washed neutrality, be by the organic phase of neutrality with aperture after the membrane filtration of 0.5 μm, low-boiling-point substance is removed in underpressure distillation (110 ~ 130 DEG C/-0.096Mpa), obtain the cancellated silicone resin of phenylakenyl of clear.
Embodiment 2:
With stirring, reflux condensing tube, 200g distilled water is added respectively in the four-hole boiling flask of thermometer and dropping funnel, the hydrochloric acid of 1.2g1N, after being uniformly mixed, drip 339.51g styroyl (trimethoxy) silane, 272g diphenyl diethoxy silane, 198.35g methylvinyldimethoxysilane, add 100g dehydrated alcohol again, 10g37% hydrochloric acid and 380g isohexadecane extraction agent carry out cohydrolysis-polycondensation, temperature of reaction is 90 DEG C, controlling the reaction times is stratification after 1h, aqueous phase is removed, with distilled water, organic phase is washed neutrality, be by the organic phase of neutrality with aperture after the membrane filtration of 0.5 μm, low-boiling-point substance is removed in underpressure distillation (110 ~ 130 DEG C/-0.096Mpa), obtain the cancellated silicone resin of phenylakenyl of clear.
Embodiment 3:
With stirring, reflux condensing tube, 140g distilled water is added respectively in the four-hole boiling flask of thermometer and dropping funnel, 1.g1N hydrochloric acid, after being uniformly mixed, drip 408g diphenyl diethoxy silane, 180.11g dimethyldimethoxysil,ne, 285.47g vinyltriethoxysilane, 360.56g phenyl triethoxysilane, add 50g dehydrated alcohol again, 10g37% hydrochloric acid and 250g decamethyl tetrasiloxane extraction agent carry out cohydrolysis-polycondensation, temperature of reaction is 85 DEG C, controlling the reaction times is stratification after 2h, aqueous phase is removed, with distilled water, organic phase is washed neutrality, be by the organic phase of neutrality with aperture after the membrane filtration of 0.5 μm, low-boiling-point substance is removed in underpressure distillation (110 ~ 130 DEG C/-0.096Mpa), obtain the cancellated silicone resin of phenylakenyl of clear.
Embodiment 4:
In the four-hole boiling flask with stirring, reflux condensing tube, thermometer and dropping funnel, add 98g distilled water, 0.5g hydrochloric acid respectively, stirring at room temperature mixes.360.56g phenyl triethoxysilane is dripped under room temperature, 244.36g dimethoxydiphenylsilane, 198.35g methylvinyldimethoxysilane, 180.11g dimethyldimethoxysil,ne, add 70g dehydrated alcohol again, 10g37% hydrochloric acid and 200g hexamethyldisiloxane extraction agent carry out cohydrolysis-polycondensation, temperature of reaction is 50 DEG C, controlling the reaction times is stratification after 7h, aqueous phase is removed, with distilled water, organic phase is washed neutrality, be by the organic phase of neutrality with aperture after the membrane filtration of 0.5 μm, low-boiling-point substance is removed in underpressure distillation (110 ~ 130 DEG C/-0.096Mpa), obtain the cancellated silicone resin of phenylakenyl of clear.
Embodiment 5:
In the four-hole boiling flask with stirring, reflux condensing tube, thermometer and dropping funnel, add 140g distilled water, 1.0g hydrochloric acid respectively, stirring at room temperature mixes.240.37g phenmethyl triethoxyl silane is dripped under room temperature, 232.40g 7-octenyl Trimethoxy silane, 180.11g dimethyldimethoxysil,ne, add 70g dehydrated alcohol again, 10g37% hydrochloric acid and 225g Permethyl 99A. extraction agent carry out cohydrolysis-polycondensation, temperature of reaction is 70 DEG C, controlling the reaction times is stratification after 2h, aqueous phase is removed, with distilled water, organic phase is washed neutrality, be by the organic phase of neutrality with aperture after the membrane filtration of 0.5 μm, low-boiling-point substance is removed in underpressure distillation (110 ~ 130 DEG C/-0.096Mpa), obtain the cancellated silicone resin of phenylakenyl of clear.
Following test is done in the impact of the phenylakenyl web-like silicon resin provided by above-described embodiment 1 ~ 5 on LED (luminous element) organosilicon encapsulating material performance, and test result is in table 1, table 2:
The performance of table 1 phenylakenyl web-like silicon resin
Table 2 phenylakenyl web-like silicon resin is on the impact of LED organosilicon encapsulating material performance
Wherein SP-605, SA34-7A are the phenylakenyl silicone resin of commercial type, and SP-605 is that Run He company produces, and SA34-7A is that Shu Nian company produces.
As can be seen from above-mentioned test result, adopting LED(luminous element prepared by phenylakenyl silicone resin provided by the invention) performance such as encapsulation silica gel material specific refractory power, transparency, rebound resilience, anti tear, anti-impact force is obtained for and effectively improves.
Above the technical scheme that the embodiment of the present invention provides is described in detail, apply specific case herein to set forth the principle of the embodiment of the present invention and embodiment, the explanation of above embodiment is only applicable to the principle helping to understand the embodiment of the present invention; Meanwhile, for one of ordinary skill in the art, according to the embodiment of the present invention, embodiment and range of application all will change, and in sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. a LED silicone resin, is characterized in that: described silicone resin is represented by following general formula:
Wherein, R is the straight or branched aryl of 6 ~ 20 carbon atoms or the aralkyl of 7 ~ 20 carbon atoms, R 〞, R ' " be the straight or branched alkyl of identical or not identical 1 ~ 6 carbon atom, acyloxy or the straight or branched aryl of 6 ~ 20 carbon atoms or the aralkyl of 7 ~ 20 carbon atoms; R' is the straight or branched thiazolinyl of 2 ~ 6 carbon atoms.
2. prepare a method for LED silicone resin according to claim 1, it is characterized in that: described method comprises the steps:
A) under an acid catalysis, drip containing phenyl functional group silane agent, carry out polyreaction containing the silane agent of alkenyl-functional groups;
B) add extraction agent, based target is containing phenylakenyl web-like silicon resin, and controlling temperature of reaction is 50 ~ 90 DEG C, 1 ~ 7 hour reaction times;
C) left standstill by product, anhydrate layer, with distilled water, phenylakenyl web-like silicon resin cleaned to neutrality, obtains the phenylakenyl web-like silicon resin solution being dissolved in extraction agent;
D) by neutrality containing phenylakenyl web-like silicon resin solution, be after the membrane filtration of 0.5 ~ 5 μm with aperture, low-boiling-point substance is removed in underpressure distillation, obtains phenylakenyl web-like silicon resin.
3. prepare the method for LED silicone resin as claimed in claim 2, it is characterized in that: the structural formula of the described silane agent containing phenyl functional group is: R
1(R
2o)
3si or R
1(R
2o)
2si R
3, wherein, R1, R3 are the straight or branched aryl of 6 ~ 20 identical or not identical carbon atoms or the aralkyl of 7 ~ 20 carbon atoms, R
2for straight or branched alkyl, the acyloxy of 1-6 carbon atom.
4. prepare the method for LED silicone resin as claimed in claim 2, it is characterized in that: described is R containing alkenyl-functional groups silane agent structural formula
1(R
2o)
2siR
3or R
1(R
2o)
3si, wherein R
1it is the straight or branched thiazolinyl of 2 ~ 6 carbon atoms; R
2, R
3for straight or branched alkyl, the acyloxy of identical or not identical 1 ~ 6 carbon atom.
5. prepare the method for LED silicone resin as claimed in claim 2, it is characterized in that: described extraction agent is isomeric alkane or methyl oligosiloxane.
6. the method preparing LED silicone resin as described in one of claim 3 ~ 5, it is characterized in that: a) the step increase organoalkoxysilane agent in preparation process, be specially: under an acid catalysis, the silane agent dripped containing the silane agent of alkenyl-functional groups, organoalkoxysilane agent, phenyl functional group carries out polyreaction.
7. prepare the method for LED silicone resin as claimed in claim 6, it is characterized in that: the structural formula of described organoalkoxysilane agent is R
1(R
2o)
2si R
3, wherein R
1, R
2, R
3for straight or branched alkyl or the acyloxy of identical or not identical 1 ~ 6 carbon atom.
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| CN103012799B true CN103012799B (en) | 2015-08-19 |
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| CN104231273B (en) * | 2014-09-16 | 2016-09-14 | 上海应用技术学院 | A kind of high viscosity self-cross linking type LED packaging plastic resin and preparation method thereof |
| CN109694648B (en) * | 2018-12-29 | 2020-11-13 | 中山市聚力有机硅技术有限公司 | Organic fluorine-silicon release emulsion with good stability and preparation method thereof |
| CN109679499B (en) * | 2018-12-29 | 2021-01-15 | 中山市聚力有机硅技术有限公司 | Organic silicon release emulsion with excellent anchoring performance and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
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2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
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Effective date of registration: 20170330 Address after: 528400 Guangdong Torch Development Zone, Zhongshan science and Technology West Wu Song Road, No. 1, No. four, building 8, room Patentee after: Zhongshan cohesion silicone Technology Co., Ltd. Address before: 510630 Guangzhou province high tech Industrial Development Zone, Guangzhou Science City spectrum West Road, No. 108, on the first floor of the workshop on the eastern side of the room, room 69 Patentee before: Cao Jianlin |
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