CN110172293A - A kind of UV solidification transparent conductive coating and preparation method thereof - Google Patents

A kind of UV solidification transparent conductive coating and preparation method thereof Download PDF

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Publication number
CN110172293A
CN110172293A CN201910355120.6A CN201910355120A CN110172293A CN 110172293 A CN110172293 A CN 110172293A CN 201910355120 A CN201910355120 A CN 201910355120A CN 110172293 A CN110172293 A CN 110172293A
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transparent conductive
parts
conductive coating
nano
solidifies
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CN201910355120.6A
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Chinese (zh)
Inventor
雷霆
詹振翔
王坤婵
龙翔宇
吕依芮
李丽
杨阳
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10Epoxy resins modified by unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06Unsaturated polyesters having carbon-to-carbon unsaturation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24Electrically-conducting paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20Diluents or solvents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0806Silver
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/085Copper
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a kind of UV to solidify transparent conductive coating, is made of following components by weight: 50-60 parts of base resins, 20-30 parts of double solvents, 10-20 parts of conductive fillers, 1-3 parts of dispersing agents, 0.5-2 parts of polymerization inhibitors and 1-3 parts of photoinitiators;The conductive filler is nano metal powder or the combination of itself and nano-silver thread.The light transmittance that the UV solidifies transparent conductive material may be up to 90%, and for mist degree less than 5%, sheet resistance is suitable with the common electric conductivity of electrically conductive graphite black conducting materials up to 5-15 Ω/sq.

Description

A kind of UV solidification transparent conductive coating and preparation method thereof
Technical field
The present invention relates to functional paint technical fields, and in particular to UV solidifies transparent conductive coating and preparation method thereof.
Background technique
Existing conductive film is mostly opaque, and conductive compositions therein are generally carbon black or graphite, opaque conduction Film application range is smaller.
And existing transparent conductive film is partly led usually using oxides such as indium oxide (indium is at high cost and rare), tin oxide Body needs high temperature sintering or specific process that could form a film on substrate, and film is the brittle film that can not be bent, applicable base Material is also few.It, can not if " progress of transparent conductive film " one ito film described in text is the higher brittle film of hardness Bending, apply it can not on complex shaped substrate surface;Preparation method is more complex, for example, magnetron sputtering method, spray pyrolysis, Chemical vapour deposition technique etc. needs 500 DEG C or so annealing film forming, makes it that can not be applied to plastic basis material surface;The reserves of indium are few, It is expensive, keep its cost high.The sheet resistance of ito film is very big, can not accomplish 100 Ω/sq or less.
In terms of flexible transparent conductive film, existing flexible transparent conductive film forms a film usually using heat cure, solidification temperature Degree 60-150 degree differs, and curing time is also longer, solid in such as " a kind of transparent conductive film-utility model of CN201820082196- " 130 DEG C of temperature of change, the time 3 minutes, or formed a film using specific process, such as magnetron sputtering method, such as " CN201610075929- is a kind of Transparent conductive film and touch screen-application with the transparent conductive film disclose ", applicable substrate is limited.
Summary of the invention
For overcome the deficiencies in the prior art, that one of the objects of the present invention is to provide a kind of translucency is good, electric conductivity is good UV solidify transparent conductive coating.The coating is by using nanoscale conductive powder or conductor wire, so that the coating is preferable Translucency under conditions of have preferable electric conductivity.
The second object of the present invention is to provide the preparation method of the conductive coating.
An object of the present invention adopts the following technical scheme that realization:
A kind of UV solidification transparent conductive coating, is made: 50-60 parts of base resins, 20- of following components by weight 30 parts of double solvents, 10-20 parts of conductive fillers, 1-3 parts of dispersing agents, 0.5-2 parts of polymerization inhibitors and 1-3 parts of photoinitiators;
Conductive filler is nano metal powder or the combination of itself and nano-silver thread;
Double solvents is by alcohols solvent, benzene kind solvent by 10:(3-5) weight ratio form;Alcohols solvent is 4 carbon atoms Alcohol below.
Further, base resin is unsaturated polyester resin, epoxy acrylate, polyester acrylate and polyurethane third One or more of olefin(e) acid ester.
Further, alcohols solvent is one or more of methanol, ethyl alcohol, isopropanol and n-butanol.
Further, benzene kind solvent is one or more of benzene,toluene,xylene and trimethylbenzene.
Further, double solvents presses (2.5-3.5): 1:(0.4-0.6 by ethyl alcohol, n-butanol, toluene, dimethylbenzene): The weight ratio of (0.8-1.2) forms.
Further, nano metal powder be one of nano-silver powder, nanometer aluminium powder, copper nanoparticle and nano-nickel powder or It is two or more.
Further, conductive filler is nano-silver thread and nano-silver powder or the combination with nanometer aluminium powder, the length of nano-silver thread Degree is 5-100 μm.
Further, dispersing agent is BYK-110 dispersing agent.
The second object of the present invention adopts the following technical scheme that realization:
A method of it preparing above-mentioned UV such as and solidifies transparent conductive coating, comprising the following steps:
1) conductive filler, dispersing agent and double solvents are added in high speed disperser and is dispersed, obtain electrocondution slurry;
2) under high speed disperser effect, base resin is gradually added in electrocondution slurry, continues to disperse;
3) polymerization inhibitor and photoinitiator are added in electrocondution slurry, continues to disperse, obtain UV solidification transparent conductive coating.
Further, in step 2), base resin is added dropwise in electrocondution slurry under dispersion machine effect.
Compared with prior art, the beneficial effects of the present invention are:
By the present invention in that with nano metal powder or with the combination of metal wire, formed in base resin almost to light transmission Conductive network of the rate without influence, to obtain transparent conductive coating;
By the present invention in that making nano metal powder with the multiple homogeneous system of alcohols solvent, double solvents and dispersing agent Or be evenly dispersed in base resin with metal wire, to form continuous, uniform conductive network;
The present invention also passes through the alcohols solvent, double solvents and proportion of optimization, and to the carbon chain lengths of alcohols solvent Optimization, make to obtain conductive coating have between dispersibility and VOCs volatile quantity one it is preferably balanced.
The present invention also provides the preparation method of the conductive coating, by first carrying out to conductive nano powder or with nano wire Homogeneous obtains electrocondution slurry, then by way of base resin gradually is added into electrocondution slurry, so that electrocondution slurry is on basis There is preferable dispersing uniformity in resin.
UV provided by the invention solidifies transparent conductive coating, and sheet resistance can reach 5-15 (Ω/sq), and light transmittance is greater than 90%, Mist degree is less than 5%, compared to the conductive coating sheet resistance of common electrically conductive graphite type quite but with the preferable transparency.
Detailed description of the invention
Fig. 1 is the nano-silver thread that embodiment 1-3 is used.
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.This reality Apply employed in example to material be commercially available.
It is specific embodiment of the present invention below, used raw material, equipment etc. remove special limit in the following embodiments It can be obtained by buying pattern outside fixed.
The present invention provides a kind of UV solidification transparent conductive coating, is made of following components by weight: 50-60 parts of bases Plinth resin, 20-30 part double solvents, 10-20 parts of conductive fillers, 1-3 parts of dispersing agents, 0.5-2 parts of polymerization inhibitors and 1-3 parts are light-initiated Agent;
The conductive filler is nano metal powder or the combination of itself and nano-silver thread;
The double solvents is by alcohols solvent, benzene kind solvent by 10:(3-5) weight ratio form;The alcohols solvent is 4 A carbon atom alcohol below.
By the present invention in that with nanoscale conductive powder and conductor wire, and by using alcohols solvent, benzene kind solvent and The mode of dispersing agent make its in base resin have more uniform dispersibility, thus obtain conductive filler be evenly distributed, quality Fine and close conductive coating, substrate surfaces most of for plastics, metal, glass, ceramics etc. all have preferable adhesive ability.It is real Nano-silver thread used in a 1-3 is applied, the draw ratio with 800-1200:1, scanning electron microscope (SEM) photograph is as shown in Figure 1, length is preferably 5-100 μm, more preferably 10-80 μm.
In following specific embodiments, used photoinitiator is that commercially available photoinitiator is diphenyl-(2,4,6- tri- Toluyl) oxygen phosphorus (TPO), molecular formula C22H21PO2, used polymerization inhibitor is commercially available polymerization inhibitor tert-butyl to benzene two Phenol (MTBHQ).
Embodiment 1:
A kind of UV solidification transparent conductive coating, is made: 50 parts of epoxy acrylates, 30 of following components by weight Part double solvents, 15 parts of silver nanowiress, 2 parts of BYK-110 dispersing agents, 0.5 part of polymerization inhibitor and 2 parts of photoinitiators;
The double solvents is mixed by n-butanol and dimethylbenzene by the weight ratio of 7:3.
Prepare the method that the UV solidifies transparent conductive coating, comprising the following steps:
1) silver nanowires, BYK-110 dispersing agent and double solvents are added in high speed disperser and is dispersed, obtain conductive paste Material;
2) under high speed disperser effect, epoxy acrylate is added dropwise into electrocondution slurry, continues to disperse;
3) continue to add to polymerization inhibitor and photoinitiator in electrocondution slurry, continue to disperse, obtain UV solidification electrically conducting transparent and apply Material.
Embodiment 2:
A kind of UV solidification transparent conductive coating, is made: 60 parts of polyester acrylates, 25 of following components by weight Part double solvents, 5 parts of silver nanowiress, 10 parts of nano-silver powders, 3 parts of BYK-110 dispersing agents, 1 part of polymerization inhibitor and 3 parts of photoinitiators;
The double solvents is mixed by ethyl alcohol, n-butanol, toluene, dimethylbenzene by the weight ratio of 3:1:0.5:1.
Prepare the method that the UV solidifies transparent conductive coating, comprising the following steps:
1) silver nanowires, nano-silver powder, BYK-110 dispersing agent and double solvents are added in high speed disperser and is dispersed, obtained To electrocondution slurry;
2) under high speed disperser effect, polyester acrylate is added dropwise into electrocondution slurry, continues to disperse;
3) continue to add to polymerization inhibitor and photoinitiator in electrocondution slurry, continue to disperse, obtain UV solidification electrically conducting transparent and apply Material.
Embodiment 3:
A kind of UV solidification transparent conductive coating, is made of following components by weight: 55 parts of urethane acrylates, 30 parts of double solvents, 5 parts of silver nanowiress, 15 parts of copper nanoparticles, 2 parts of BYK-110 dispersing agents, 2 parts of polymerization inhibitors and 2 parts are light-initiated Agent;
The double solvents is mixed by ethyl alcohol, n-butanol, toluene, dimethylbenzene by the weight ratio of 3.5:1:0.4:1.2.
Prepare the method that the UV solidifies transparent conductive coating, comprising the following steps:
1) silver nanowires, copper nanoparticle, BYK-110 dispersing agent and double solvents are added in high speed disperser and is dispersed, obtained To electrocondution slurry;
2) under high speed disperser effect, urethane acrylate is added dropwise into electrocondution slurry, continues to disperse;
3) continue to add to polymerization inhibitor and photoinitiator in electrocondution slurry, continue to disperse, obtain UV solidification electrically conducting transparent and apply Material.
Comparative example 1:
A kind of a kind of UV curing conductive coating, UV solidification transparent conductive coating, is made of following components by weight: 60 parts of polyester acrylates, 25 parts of double solvents, 15 parts of conductive powdered carbons, 3 parts of BYK-110 dispersing agents, 1 part of polymerization inhibitor and 3 parts of light Initiator;
The double solvents is mixed by ethyl alcohol, n-butanol, toluene, dimethylbenzene by the weight ratio of 3:1:0.5:1.
Prepare the method that the UV solidifies transparent conductive coating, comprising the following steps:
1) conductive powdered carbon, BYK-110 dispersing agent and double solvents are added in high speed disperser and is dispersed, obtain conductive paste Material;
2) under high speed disperser effect, polyester acrylate is added dropwise into electrocondution slurry, continues to disperse;
3) continue to add to polymerization inhibitor and photoinitiator in electrocondution slurry, continue to disperse, obtain UV curing conductive coating.
Performance detection
The conductive coating that embodiment 1-3 and comparative example 1 are obtained is coated on the glazed ceramic surface of 10 × 10cm, is formed The coating of 20-30 μ m thick, it is formed through UV hardening with radiation, detection light transmittance, mist degree simultaneously pass through the test detection attachment of hundred lattice scratches Power, as a result as shown in the table:
As seen from the above table, the conductive coating obtained by embodiment 1-3, sheet resistance and the conductive painting obtained using electrically conductive graphite Layer sheet resistance it is very nearly the same, light transmittance be all larger than 90% and mist degree less than 5%, be good transparent conductive coating.This is transparent Conductive coating is high in glazed ceramic surface adhesion force, can be applied to smooth dielectric surface.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto, The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention Claimed range.

Claims (10)

1. a kind of UV solidifies transparent conductive coating, which is characterized in that be made of following components by weight: 50-60 parts of bases Plinth resin, 20-30 part double solvents, 10-20 parts of conductive fillers, 1-3 parts of dispersing agents, 0.5-2 parts of polymerization inhibitors and 1-3 parts are light-initiated Agent;
The conductive filler is nano metal powder or the combination of itself and nano-silver thread;
The double solvents is by alcohols solvent, benzene kind solvent by 10:(3-5) weight ratio form;The alcohols solvent is 4 carbon Atom alcohol below.
2. UV as described in claim 1 solidifies transparent conductive coating, which is characterized in that the base resin is unsaturated polyester (UP) One or more of resin, epoxy acrylate, polyester acrylate and urethane acrylate.
3. UV as described in claim 1 solidifies transparent conductive coating, which is characterized in that the alcohols solvent be methanol, ethyl alcohol, One or more of isopropanol and n-butanol.
4. UV as described in claim 1 solidifies transparent conductive coating, which is characterized in that the benzene kind solvent is benzene, toluene, two One or more of toluene and trimethylbenzene.
5. UV as described in claim 1 solidifies transparent conductive coating, which is characterized in that the double solvents is by ethyl alcohol, positive fourth Alcohol, toluene, dimethylbenzene press (2.5-3.5): 1:(0.4-0.6): the weight ratio composition of (0.8-1.2).
6. UV as described in claim 1 solidifies transparent conductive coating, which is characterized in that the nano metal powder is nano silver One or more of powder, nanometer aluminium powder, copper nanoparticle and nano-nickel powder.
7. UV as described in claim 1 solidifies transparent conductive coating, which is characterized in that the conductive filler be nano-silver thread with Nano-silver powder or combination with nanometer aluminium powder;The length of the nano-silver thread is 5-100 μm.
8. UV as described in claim 1 solidifies transparent conductive coating, which is characterized in that the dispersing agent is BYK-110 dispersion Agent.
9. a kind of described in any item UV of claim 1-8 such as that prepare solidify the method for transparent conductive coating, which is characterized in that packet Include following steps:
1) conductive filler, dispersing agent and double solvents are added in high speed disperser and is dispersed, obtain electrocondution slurry;
2) under high speed disperser effect, base resin is gradually added in electrocondution slurry, continues to disperse;
3) polymerization inhibitor and photoinitiator are added in electrocondution slurry, continues to disperse, obtain UV solidification transparent conductive coating.
10. method as claimed in claim 9, which is characterized in that in step 2), base resin is added dropwise under dispersion machine effect In electrocondution slurry.
CN201910355120.6A 2019-04-29 2019-04-29 A kind of UV solidification transparent conductive coating and preparation method thereof Pending CN110172293A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3174121B2 (en) * 1992-02-07 2001-06-11 日立化成工業株式会社 Conductive paint
CN102212304A (en) * 2011-03-25 2011-10-12 北京化工大学 Flexible circuit conductive composition, preparation method and using method thereof
CN102527621A (en) * 2011-12-27 2012-07-04 浙江科创新材料科技有限公司 Preparation method for haze-adjustable flexible transparent conductive film
CN103965674A (en) * 2014-05-23 2014-08-06 苏州斯迪克新材料科技股份有限公司 Nano silver conductive coating
CN105754416A (en) * 2016-05-12 2016-07-13 苏州宇希新材料科技有限公司 Preparation method of conductive ink
CN106833353A (en) * 2016-12-21 2017-06-13 华南理工大学 A kind of touch-screen UV curing nano silver wire slurries and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3174121B2 (en) * 1992-02-07 2001-06-11 日立化成工業株式会社 Conductive paint
CN102212304A (en) * 2011-03-25 2011-10-12 北京化工大学 Flexible circuit conductive composition, preparation method and using method thereof
CN102527621A (en) * 2011-12-27 2012-07-04 浙江科创新材料科技有限公司 Preparation method for haze-adjustable flexible transparent conductive film
CN103965674A (en) * 2014-05-23 2014-08-06 苏州斯迪克新材料科技股份有限公司 Nano silver conductive coating
CN105754416A (en) * 2016-05-12 2016-07-13 苏州宇希新材料科技有限公司 Preparation method of conductive ink
CN106833353A (en) * 2016-12-21 2017-06-13 华南理工大学 A kind of touch-screen UV curing nano silver wire slurries and preparation method thereof

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Title
董蔓等: "导电防腐环氧涂料的制备", 《电镀与涂饰》 *

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