CN110229648A - A kind of mono-component organic silicone conducting resinl and its preparation method and application - Google Patents
A kind of mono-component organic silicone conducting resinl and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention provides a kind of mono-component organic silicone conducting resinls and its preparation method and application.The raw material composition of the mono-component organic silicone conducting resinl includes: the conducting powder of -85 parts by weight of 50 parts by weight, the matrix resin of -40 parts by weight of 10 parts by weight, the containing hydrogen silicone oil of -5 parts by weight of 0.8 parts by weight, the tackifier of -3 parts by weight of 0.5 parts by weight, the promotor of -3 parts by weight of 0.5 parts by weight, the reinforcing agent of -2 parts by weight of 0.4 parts by weight, the platinum catalyst of the polystyrene cladding of -0.8 parts by weight of 0.1 parts by weight, each raw material total amount of the mono-component organic silicone conducting resinl is 100 parts by weight.The present invention also provides the preparation method of above-mentioned conducting resinl, which is used to prepare solar cell module.The storage time of mono-component organic silicone conducting resinl of the invention is long, without adding inhibitor, does not react at room temperature, fast reaction under high temperature.
Description
Technical field
The present invention relates to a kind of conducting resinl more particularly to a kind of mono-component organic silicone conducting resinls, belong to solar battery skill
Art field.
Background technique
Currently, common commercial electroconductive glue major part matrix is made of epoxy resin, acrylate, organic silicon substrate.
Epoxy resin or acrylate when 260 DEG C or higher temperature are packaged or assemble, ontology can be brought to decompose,
With the integrity problems such as substrate de-lamination.Organosilicon has excellent weatherability (high temperature, low temperature, high humility, ultraviolet etc.), can be in height
It is used under mild most of harsh environments.Solar battery imbrication component will use 25 years or more in an outdoor environment, need height
Reliability conducting resinl carries out the interconnection between cell piece.
The curing mode of organic silicon substrate conducting resinl is mainly that condensed type moisture-curable and add-on type are heating and curing, and is compared
In condensed type moisture-curable organosilicon, the curing rate that add-on type is heating and curing is fast, can greatly improve production efficiency.
Additional organosilicon is (logical in noble metal catalyst using si-h bond and unsaturated carbon carbon bond (usually vinyl)
Often it is platinum complex) under catalysis, carry out Si―H addition reaction and cross-linking reaction.Additional organosilicon be difficult to prepare one-component (silicon hydrogen,
Even if vinyl and catalyst are at room temperature, can also it react).And two-component technique can make troubles to construction: need to grasp
Make personnel accurately to measure；Need mixing apparatus and defoaming device (especially more challenging to high viscosity systems)；The object mixed
If material cannot use up in time, it can solidify and waste is caused to be not easy with what equipment was cleaned.
One-component additional organosilicon conducting resinl needs to be added a large amount of stabilizer (such as alkynol) in the prior art.Stabilizer
It can be vapored away in solidification process, increase the cubical contraction of product, influence the flatness of product surface；In general alkynol class
Closing object has certain toxicity, to limit it in the application in a part of field.And existing organosilicon conductive adhesive needs mostly
Cryo-conservation is wanted, it is larger to the demand of the energy, and make troubles transport and storage, meanwhile, it is shorter to stablize waiting time.
Chinese patent application CN108239520 discloses a kind of one-component additional organosilicon conducting resinl and its preparation side
Method.The one-component additional organosilicon conducting resinl can be stablized by MOLECULE DESIGN introducing in the basis material of conducting resinl and be urged
The cyanuric acid ester group of agent, to obtain the one-component additional organosilicon conducting resinl of room temperature shelf-stable.One-component adds
Molding organosilicon conductive adhesive can stablize storage, and without being additionally added, a large amount of stabilizers such as alkynol, room temperature storage stability are good, solidify
Speed is fast and electric conductivity is good.
But above-mentioned conducting resinl is needed by selecting vinyl modified silicone resin, using in vinyl modified silicone resin
To the complexing of Pt under cyanurate, the activity of catalyst is reduced, catalyst poisoning is avoided, reduces the addition of inhibitor.
It is by modified and chemical action due to inhibiting function monomer though this method is able to suppress the reaction under low temperature to a certain extent
It is connected on matrix resin, the catalytic activity under high temperature can equally be had an impact.
Chinese patent application CN109401724 discloses a kind of solar energy encapsulation one-component electric silica gel and its preparation side
Method.By weight, including following component: silver powder 55-80 parts modified；10-20 parts of add-on type liquid silicone oil；Coupling agent 0.02-1
Part；2-10 parts of reinforcing agent；0.5-4 parts of crosslinking agent；2-5 parts of sp act diluent；0.0002-0.02 parts of platinum catalyst；Solvent
5-20 parts.The electric silica gel can in low-temperature fast-curing and viscosity it is low, can satisfy the quick-setting technique of lamination assembly line and want
Ask, it is low silver additive amount thus there is lower cost, can be with large-scale application in solar energy imbrication component, in addition it is without poison ring
It protects, rapid heat dissipation, high conductivity, good resistance to ag(e)ing can satisfy imbrication component ultra high power, low hot spot effect, outdoor make within 25 years
Demand.
But containing solvent in above-mentioned conducting resinl, no inhibitor, storage time is short, not environmentally.
Summary of the invention
In order to solve problems in the prior art, the purpose of the present invention is to provide one kind can storage-stable, cost is relatively low
Mono-component organic silicone conducting resinl.
In order to achieve the above technical purposes, the present invention provides a kind of mono-component organic silicone conducting resinl, the mono-component organic silicone
Conducting resinl raw material composition include: -85 parts by weight of 50 parts by weight conducting powder, the matrix resin of -40 parts by weight of 10 parts by weight,
The containing hydrogen silicone oil of -5 parts by weight of 0.8 parts by weight, the tackifier of -3 parts by weight of 0.5 parts by weight, the promotion of -3 parts by weight of 0.5 parts by weight
Agent, the reinforcing agent of -2 parts by weight of 0.4 parts by weight, the platinum catalyst of the polystyrene cladding of -0.8 parts by weight of 0.1 parts by weight,
In, each raw material total amount of the mono-component organic silicone conducting resinl is 100 parts by weight.
In a specific embodiment of the invention, the platinum catalyst of polystyrene cladding is through the following steps that preparation
It obtains:
Chloroplatinic acid, silane monomer and isopropanol are mixed, are warming up to 50-60 DEG C, is reacted 0.5-3 hours；
(slow) addition sodium bicarbonate is stirred to react 1-3 hours at 70 DEG C -80 DEG C, filters off precipitating；
It under stirring condition, filtrate is added in polystyrene dispersion liquid, filters, cleaning, obtains polystyrene cladding
Platinum catalyst；
Wherein, the mass ratio of chloroplatinic acid, silane monomer, isopropanol, sodium bicarbonate and sub-polyethylene dispersion liquid is 0.1-10:1-
50:10-300:1-3:50-500.
The platinum for the polystyrene cladding that the preparation method of the platinum catalyst of polystyrene cladding through the invention obtains
Au catalyst has microcapsule structure.The catalyst of the microcapsule structure and the other components of conducting resinl act synergistically, and have one-component
Machine silicon conducting resinl at normal temperature stablize by performance, under high temperature the advantages of rapid curing.Moreover, the mono-component organic silicone conducting resinl passes through
Using the conducting powder of capsule-type platinum catalyst and low-apparent-density, so that the performance of mono-component organic silicone conducting resinl is stablized, room temperature
It stores and cost is relatively low.
Wherein, the concentration of the platinum catalyst of polystyrene cladding can add corresponding polystyrene point according to target
Dispersion liquid is adjusted.
In a specific embodiment of the invention, prepare polystyrene cladding platinum catalyst when stirring revolving speed
For 800rpm-1500rpm.
In a specific embodiment of the invention, silane monomer includes tetramethyl divinyl disiloxane, vinyl
Trimethoxy silane or vinyltriethoxysilane.
Contain conducting powder in mono-component organic silicone conducting resinl of the invention.
In a specific embodiment of the invention, conducting powder includes silver powder, copper powder, bronze, aluminium powder, nickel powder, wicker copper
The combination of one or more of powder.
In a specific embodiment of the invention, partial size≤50 μm (preferably 0.1-50 μm) of the conducting powder of use.
In a specific embodiment of the invention, the apparent density of the conducting powder used is 0.9g/mm3-5g/mm3。
Contain matrix resin in mono-component organic silicone conducting resinl of the invention, matrix resin plays the role of bonding, carrier.
In a specific embodiment of the invention, matrix resin is by methyl vinyl MQ resin and/or phenylethylene
What base MQ resin and vinyl silicone oil were mixed to get with the mass ratio of 1:1.I.e. matrix resin be by methyl vinyl MQ resin with
Vinyl silicone oil 1:1 (mass ratio) is mixed to get；Or it is mixed by phenyl vinyl MQ resin and vinyl silicone oil 1:1 (mass ratio)
What conjunction obtained；Or it is mixed to get by methyl vinyl MQ resin, phenyl vinyl MQ resin and vinyl silicone oil 1:1 (mass ratio)
's.
In a specific embodiment of the invention, the viscosity of matrix resin is 500PaS-5000PaS.The viscosity
Matrix resin facilitate operation, be convenient for silk-screen printing.
Contain containing hydrogen silicone oil in mono-component organic silicone conducting resinl of the invention, containing hydrogen silicone oil is used as crosslinking agent in system.
In a specific embodiment of the invention, containing hydrogen silicone oil is the end hydrogen silicone oil and side hydrogen that molar ratio is 1:1-1:5
Silicone oil.
Contain tackifier in mono-component organic silicone conducting resinl of the invention, there is no particular/special requirement to the optional of tackifier, adopt
With the reagent of this field routine.
Contain promotor in mono-component organic silicone conducting resinl of the invention, wherein promotor is adhesion promoter.
In a specific embodiment of the invention, the promotor used can be vinyltriethoxysilane, ethylene
Base trimethoxy silane, vinyl -3- (2- methoxy ethoxy) silane, vinyl -3- (2- methoxy ethoxy) silane,
γ-methacryloxypropyl trimethoxy silane, epoxy silane oligomer, β-(3,4- epoxycyclohexyl) ethyl trimethoxy
The combination of one or more of base silane.
Contain reinforcing agent in mono-component organic silicone conducting resinl of the invention.Reinforcing agent can promote the intensity after solidifying, and increase
Add the cohesive force of conducting resinl.
In a specific embodiment of the invention, the reinforcing agent used can be fumed silica.
The present invention also provides the preparation method of mono-component organic silicone conducting resinl, the preparation method the following steps are included:
Matrix resin, containing hydrogen silicone oil, tackifier, promotor are mixed, 5min-60min is stirred, reinforcing agent stirring is added
5min-60min obtains mixture；
Conducting powder is added into mixture, stirs 10min-120min, the platinum catalyst of polystyrene cladding is added, stirs
1min-60min is mixed, mono-component organic silicone conducting resinl is obtained.
The present invention provides a kind of solar cell modules, wherein using the present invention when preparing the solar cell module
Mono-component organic silicone conducting resinl as conducting resinl.Here solar components include but is not limited to solar energy imbrication component.
The curing time of mono-component organic silicone conducting resinl of the invention at 140 DEG C -180 DEG C is 0.1min-30min.
The storage time of mono-component organic silicone conducting resinl of the invention is long, (avoids because of inhibitor without adding inhibitor
Yellowing phenomenon caused by addition), it does not react at room temperature, fast reaction under high temperature.
Mono-component organic silicone conducting resinl of the invention is solvent-free, environmental protection, high reliablity.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment
The platinum catalyst of polystyrene cladding is through the following steps that be prepared:
1g chloroplatinic acid, 5g ligand silane monomer (tetramethyl divinyl disiloxane) and 40g isopropanol are mixed, heating
To 55 DEG C, react 3 hours；
It is slowly added to 1.5g sodium bicarbonate (5min addition finishes), at 75 DEG C, is stirred to react 2 hours, it is heavy to be filtered to remove
It forms sediment；
Filtrate is added in 200g resin (polystyrene) solution (toluene) under the conditions of 800-1500rpm, is filtered, is used
Solvent cleans the platinum catalyst (concentration 3000PPM) for obtaining polystyrene cladding for several times.
Catalyst is prepared by the method in subsequent embodiment.
Mono-component organic silicone conducting resinl is prepared by following steps:
By the content of table 1, successively weighing matrix resin, (embodiment 1- embodiment 3 uses Methylethyl MQ resin and ethylene
Base silicone oil mass ratio is 1:1, viscosity 2500Pa.S；Embodiment 4- embodiment 6 is using phenyl vinyl MQ resin and vinyl silicon
The quality of oil is 1:1, viscosity 2000Pa.s), containing hydrogen silicone oil (end hydrogen silicone oil and side hydrogen silicone oil molar ratio be 1:2), tackifier,
Adhesion promoter (γ-methacryloxypropyl trimethoxy silane) stirs 15min, continues to add reinforcing agent (gas phase
Silica), 15min is stirred, mixture is obtained；
Conducting powder is added into mixture, stirs 50min, adds catalyst, stirs 30min, froth in vacuum obtains final
Conducting resinl.
Curing rate is tested under the conditions of 150 DEG C；Room temperature tests its pulling force, and (no professional standard number is enterprises mark
Standard, bonded areas long 1mm are 400 μm wide), the results are shown in Table 1.
Imbrication battery component preparation process:
It will be printed with the finished battery piece of front electrode and back electrode, conducting resinl is imprinted on by designated position by silk-screen printing
On, it then by slice, stacks, solidification (with built-in testing drawing force is stacked after solidification), patch encapsulation obtains imbrication component.
Table 1
Comparative example is as shown in table 2.
Table 2
Above embodiments explanation, the storage time of mono-component organic silicone conducting resinl of the invention is long, without adding inhibitor
(yellowing phenomenon caused by avoiding because of inhibitor addition), does not react, fast reaction under high temperature at room temperature.
Claims (10)
1. a kind of mono-component organic silicone conducting resinl, which is characterized in that the raw material composition of the mono-component organic silicone conducting resinl includes: 50
The conducting powder of -85 parts by weight of parts by weight, the matrix resin of -40 parts by weight of 10 parts by weight, the Silicon Containing Hydrogen of -5 parts by weight of 0.8 parts by weight
Oil, the tackifier of -3 parts by weight of 0.5 parts by weight, the promotor of -3 parts by weight of 0.5 parts by weight, the benefit of -2 parts by weight of 0.4 parts by weight
Strong agent, the platinum catalyst of the polystyrene cladding of -0.8 parts by weight of 0.1 parts by weight, wherein the mono-component organic silicone conducting resinl
Each raw material total amount be 100 parts by weight.
2. mono-component organic silicone conducting resinl according to claim 1, which is characterized in that the platinum of the polystyrene cladding
Catalyst is through the following steps that be prepared:
Chloroplatinic acid, silane monomer and isopropanol are mixed, are warming up to 50 DEG C -60 DEG C, is reacted 0.5-3 hours；
Sodium bicarbonate is added to be stirred to react 1-3 hours at 70 DEG C -80 DEG C, filter off precipitating；
It under stirring condition, filtrate is added in polystyrene dispersion liquid, filters, cleaning obtains the platinum of polystyrene cladding
Catalyst；
Wherein, the mass ratio of chloroplatinic acid, silane monomer, isopropanol, sodium bicarbonate and sub-polyethylene dispersion liquid is 0.1-10:1-50:
10-300:1-3:50-500；
Preferably, the revolving speed of stirring is 800rpm-1500rpm.
3. mono-component organic silicone conducting resinl according to claim 2, which is characterized in that the silane monomer includes tetramethyl
Divinyl disiloxane, vinyltrimethoxysilane or vinyltriethoxysilane.
4. mono-component organic silicone conducting resinl according to claim 1, which is characterized in that the conducting powder includes silver powder, copper
The combination of one or more of powder, bronze, aluminium powder, nickel powder, silver-coated copper powder；
Preferably, partial size≤50 μm of the conducting powder；
Preferably, the apparent density of the conducting powder is 0.9g/mm3-5g/mm3。
5. mono-component organic silicone conducting resinl according to claim 1, which is characterized in that described matrix resin is by methyl second
What alkenyl MQ resin and/or phenyl vinyl MQ resin and vinyl silicone oil were mixed to get with the mass ratio of 1:1；
Preferably, the viscosity of described matrix resin is 500PaS-5000PaS.
6. mono-component organic silicone conducting resinl according to claim 1, which is characterized in that the containing hydrogen silicone oil is that molar ratio is
The end hydrogen silicone oil and side hydrogen silicone oil of 1:1-1:5.
7. mono-component organic silicone conducting resinl according to claim 1, which is characterized in that the promotor is three second of vinyl
Oxysilane, vinyltrimethoxysilane, vinyl -3- (2- methoxy ethoxy) silane, vinyl -3- (2- methoxyl group
Ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silane, epoxy silane oligomer, β-(3,4- epoxy hexamethylene
Base) one or more of ethyl trimethoxy silane combination.
8. mono-component organic silicone conducting resinl according to claim 1, which is characterized in that the reinforcing agent is gas phase titanium dioxide
Silicon.
9. the preparation method of the described in any item mono-component organic silicone conducting resinls of claim 1-8, which is characterized in that the preparation side
Method the following steps are included:
Matrix resin, containing hydrogen silicone oil, tackifier, promotor are mixed, 5min-60min is stirred, reinforcing agent is added and stirs 5min-
60min obtains mixture；
Conducting powder is added into mixture, stirs 10min-120min, the platinum catalyst of polystyrene cladding, stirring is added
1min-60min obtains mono-component organic silicone conducting resinl.
10. a kind of solar cell module, which is characterized in that appointed when preparing the solar cell module using claim 1-8
Mono-component organic silicone conducting resinl described in one is as conducting resinl.
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| CN111394012A (en) * | 2020-04-15 | 2020-07-10 | 苏州世诺新材料科技有限公司 | Self-repairing organic silicon conductive adhesive |
| CN112961646A (en) * | 2021-03-03 | 2021-06-15 | 上海斟众新材料科技股份有限公司 | Fast-curing anti-overflow conductive adhesive and preparation method thereof |
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| CN116496752A (en) * | 2023-04-11 | 2023-07-28 | 上海德朗聚新材料有限公司 | High-toughness organosilicon shingle conductive adhesive and preparation method thereof |
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| CN111394012A (en) * | 2020-04-15 | 2020-07-10 | 苏州世诺新材料科技有限公司 | Self-repairing organic silicon conductive adhesive |
| CN112961646A (en) * | 2021-03-03 | 2021-06-15 | 上海斟众新材料科技股份有限公司 | Fast-curing anti-overflow conductive adhesive and preparation method thereof |
| CN115433541A (en) * | 2022-09-30 | 2022-12-06 | 郑州中原思蓝德高科股份有限公司 | Conductive adhesive and preparation method thereof |
| CN115433541B (en) * | 2022-09-30 | 2023-11-07 | 郑州中原思蓝德高科股份有限公司 | Conductive adhesive and preparation method thereof |
| CN116496752A (en) * | 2023-04-11 | 2023-07-28 | 上海德朗聚新材料有限公司 | High-toughness organosilicon shingle conductive adhesive and preparation method thereof |
| CN116496752B (en) * | 2023-04-11 | 2023-10-03 | 上海德朗聚新材料有限公司 | High-toughness organosilicon shingle conductive adhesive and preparation method thereof |
| CN116618642A (en) * | 2023-07-13 | 2023-08-22 | 长沙立优金属材料有限公司 | Nickel powder with large particles and low apparent density and preparation method and application thereof |
| CN116618642B (en) * | 2023-07-13 | 2023-10-10 | 长沙立优金属材料有限公司 | Nickel powder with large particles and low apparent density and preparation method and application thereof |
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Address after: 215153 No. 100, Zhenbei Road, Tong'an Town, high tech Zone, Suzhou, Jiangsu Patentee after: Suzhou Jingyin New Material Technology Co.,Ltd. Address before: No.88 Zhenbei Road, Tongan town, high tech Zone, Suzhou City, Jiangsu Province Patentee before: SUZHOU ISILVER MATERIALS Co.,Ltd. |