CN109971133A - A kind of reflectance coating with conductive and heat-conductive surface layer and a kind of preparation method of graphene master batch - Google Patents

A kind of reflectance coating with conductive and heat-conductive surface layer and a kind of preparation method of graphene master batch Download PDF

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Publication number
CN109971133A
CN109971133A CN201711442465.2A CN201711442465A CN109971133A CN 109971133 A CN109971133 A CN 109971133A CN 201711442465 A CN201711442465 A CN 201711442465A CN 109971133 A CN109971133 A CN 109971133A
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conductive
graphene
heat
master batch
surface layer
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金亚东
杨承翰
张强
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Ningbo Solartron Technology Co Ltd
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Ningbo Solartron Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/12—Reflex reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/00—Use of ingredients characterised by shape
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The present invention relates to optical thin film more particularly to a kind of reflectance coating with conductive and heat-conductive surface layer and a kind of preparation methods of graphene master batch.To solve the problems, such as existing reflectance coating there are poor heat radiation, the present invention provides a kind of reflectance coating with conductive and heat-conductive surface layer and a kind of preparation method of graphene master batch.The reflectance coating includes foamed core layer and conductive and heat-conductive surface layer, and the one or both sides of foamed core layer are arranged in the conductive and heat-conductive surface layer；The conductive and heat-conductive surface layer includes graphene.Reflectance coating heat dissipation Quick uniform provided by the invention, can connecing the current reflector plate of solution, there are poor heat radiations, and long-term bright display of putting will lead to reflector plate formation warpage or contraction, to bring the problem of non-uniform of visual effect.

Description

A kind of reflectance coating with conductive and heat-conductive surface layer and a kind of preparation of graphene master batch Method
Technical field
The present invention relates to optical thin film more particularly to a kind of reflectance coating with conductive and heat-conductive surface layer and a kind of graphene are female The preparation method of grain.
Background technique
With economic rapid development, low energy consumption, picture is clear due to having for liquid crystal display (LCD), small in size etc. all More advantages have become current most common display technology.
The framework of the liquid crystal display of mainstream is the backlight for providing area source and the OC (open of display imaging at present Cell) unit, wherein reflector plate is essential optical component in the backlight.As liquid crystal display is constantly to more Greatly, gentlier, brighter, apparent, more Bao Fazhan proposes the heat resistance of reflector plate in large size liquid crystal display higher Requirement, current reflector plate there are poor heat radiation, it is long-term put bright display and will lead to reflector plate form warpage or contraction, from And the taste problem (referring to whether visual effect is uniform) of visual effect is brought, influence display effect.
Summary of the invention
To solve the problems, such as existing reflectance coating there are poor heat radiation, the present invention provides a kind of with the anti-of conductive and heat-conductive surface layer Penetrate film and a kind of preparation method of graphene master batch.Reflectance coating heat dissipation Quick uniform provided by the invention, it is current can to connect solution Reflector plate there are poor heat radiation, it is long-term put bright display and will lead to reflector plate form warpage or contraction, to bring visual effect Problem of non-uniform.
In order to solve the above-mentioned technical problem, the invention adopts the following technical scheme:
The present invention provides a kind of reflectance coating with conductive and heat-conductive surface layer, and the reflectance coating includes that foamed core layer and conduction are led The one or both sides of foamed core layer are arranged in hotlist layer, the conductive and heat-conductive surface layer；The conductive and heat-conductive surface layer includes graphene.
The conductive and heat-conductive surface layer is also known as conductive and heat-conductive functional layer, conductive and heat-conductive coating.
Further, the foamed core layer includes masterbatch resin and polyester.
The reflectance coating is also known as reflector plate.
Further, the content of graphene is 0.07~0.13% in the conductive and heat-conductive surface layer, and the percentage is Weight percent.
Further, the graphene is sheet, and the piece diameter of the graphene is 3~10 μm, graphene with a thickness of 5~ 10nm。
Further, during the preparation process, the graphene is first prepared into graphene master batch, and the graphene master batch includes The graphene of 0.28~0.32wt% and the polyester of 99.68~99.72wt%.
Further, the conductive and heat-conductive surface layer includes the polyester of 60-75wt% and the graphene mother of 25-40wt% Grain.
Further, the conductive and heat-conductive surface layer includes the polyester of 60-65wt% and the graphene mother of 35-40wt% Grain；The graphene master batch includes the graphene of 0.3wt%, and the piece diameter of graphene is 3~10 μm, with a thickness of 5~10nm.It is above-mentioned Technical solution includes embodiment 3 and embodiment 5-6.
Further, the conductive and heat-conductive surface layer includes the polyester of 65wt% and the graphene master batch of 35wt%；It is described Graphene master batch includes the graphene of 0.3wt%, and the piece diameter of graphene is 7~10 μm, with a thickness of 5~10nm.Above-mentioned technical side Case includes embodiment 3.
Further, the conductive and heat-conductive surface layer includes the polyester of 60wt% and the graphene master batch of 40wt%；It is described Graphene master batch includes the graphene of 0.3wt%, and the piece diameter of the graphene in the graphene master batch is 3~7 μm, with a thickness of 5 ~10nm.Above-mentioned technical proposal includes embodiment 6.
Further, the polyester in the conductive and heat-conductive surface layer is selected from polyethylene terephthalate (PET), is poly- to benzene Dioctyl phthalate butanediol ester (PBT), polyethylene naphthalate (PEN) or its co-polymerization modified polyester.
The raw material for preparing graphene master batch includes graphene powder, ethylene glycol, terephthalic acid (TPA), catalyst and stabilizer, The additive amount of the graphene powder is 0.28-0.32wt%, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1.45-1.55: 1, the additive amount of catalyst is 0.024-0.026wt%, the additive amount of heat stabilizer is 0.001wt%.
The present invention also provides a kind of preparation methods of graphene master batch, the described method comprises the following steps:
(1) graphene powder and ethylene glycol are premixed in such a way that ultrasonic wave disperses, graphene dispersing solution is made；
(2) direct esterification technique and situ aggregation method are used: according to the ratio by terephthalic acid (TPA), ethylene glycol, putting into reaction kettle In, while a certain amount of catalyst, stabilizer and graphene dispersing solution is added, whole process carries out under nitrogen protection, setting Nitrogen pressure is 0.3MPa, and mixing speed 70r/min, esterification temperature is 240 DEG C, is gradually warming up to 210 DEG C, and esterification starts, The amount of steaming to water reaches the 90% of theoretical value, pressure release to normal pressure, and esterification terminates.285 DEG C of condensation temperature of setting, normal pressure polycondensation 0.5h, then low vacuum precondensation 0.5h, last high vacuum polycondensation, pressure are less than 60Pa.When reaching preset same stirring function When rate, polycondensation terminates, and discharge simultaneously pelletizing.
Further, the additive amount of graphene is 0.28-0.32wt% in the step (1).
The additive amount refers to that graphene accounts for raw material (the benzene diformazan in graphene and step (2) of graphene master batch preparation Acid, ethylene glycol, catalyst, stabilizer) weight percent.
Further, the molar ratio of ethylene glycol and terephthalic acid (TPA) is 1.45-1.55:1 in the step (2).
The molar ratio of the ethylene glycol and terephthalic acid (TPA) is referred to as acid-alcohol ratio.
Further, the molar ratio of the ethylene glycol and terephthalic acid (TPA) is preferably 1.5:1.
Further, the additive amount of catalyst is 0.024-0.026wt% in the step (2), the heat stabilizer Additive amount is 0.001wt%.
Further, the additive amount of the catalyst is preferably 0.025wt%.
The additive amount refers to that catalyst or heat stabilizer account for raw material (graphene and the step (2) of the preparation of graphene master batch In phthalic acid, ethylene glycol, catalyst, stabilizer) weight percent.
Further, the catalyst in the step (2) is selected from antimony-based catalyst, and the heat stabilizer is phosphoric acid.
Further, the antimony-based catalyst is selected from antimony glycol [Sb2(EG)3]。
The present invention also provides a kind of preparation methods of reflectance coating with conductive and heat-conductive surface layer, and the method includes following steps It is rapid:
(1) graphene master batch is mixed with polyester according to a certain percentage, is melted after dry, obtains the table of reflectance coating Layer melted material
(2) by foamed core layer masterbatch resin and polyester raw material mix, melted after dry, obtain foamed core layer melting material Material；
(3) raw material of step (1) and step (2) is separately added into different extruders, biaxial tension is made and leads with conduction The reflectance coating of hotlist layer.
Further, the foamed core layer includes the masterbatch resin of 5-20% and the polyester raw material of 80-95%；The resin Master batch contains the inorganic particulate of 80-90% and the vector resin of 10-20%；The percentage is weight percentage.It is described inorganic Particle is selected from SiO2,Al2O3TiO2、CaCO3、BaSO4Or CaHPO4One of or at least two combination.The vector resin In polypropylene (PP), polyethylene (PE), 4 monomethyl pentene polymers (TPX), thermoplastic polyurethane elastomer (TPU) It is a kind of.The polyester raw material is selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), and poly- pair (ethylene naphthalate) (PEN) or its co-polymerization modified polyester.
In order to achieve the above object, using primary bright CN201310277344.2, (publication date is 2013 11 to the present invention Months 13 days) on the basis of a kind of reflective film and preparation method thereof, processing again is carried out to assign conductive and heat-conductive function to surface layer Can, foamed core layer still uses primary bright CN201310277344 technology.
Compared with prior art, the reflectance coating provided by the invention with conductive and heat-conductive surface layer can rapidly and uniformly dissipate Heat, can for a long time using and be not easy to cause the non-uniform problem of visual effect.It is provided by the invention anti-with conductive and heat-conductive surface layer The electric conductivity for penetrating film is preferable.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of the reflectance coating with conductive and heat-conductive surface layer provided by the invention；
Fig. 2 is the structural schematic diagram of another reflectance coating with conductive and heat-conductive surface layer provided by the invention.
Specific embodiment
It, hereafter will be of the invention preferable for the functional character and advantage that is more readily understood structure of the invention and can reach Embodiment, and schema is cooperated to be described below in detail:
As shown in Figure 1, the reflectance coating provided by the invention with conductive and heat-conductive surface layer includes foamed core layer 2 and conductive and heat-conductive Apply surface layer 1.
As shown in Fig. 2, the reflectance coating provided by the invention with conductive and heat-conductive surface layer includes conductive and heat-conductive surface layer 11 and 12, Foamed core layer 2.
The producer for preparing raw material for the graphene masterbatch that the embodiment of the present invention and comparative example provide and specification:
Title Specification Producer
Graphene KNG series Xiamen Kai Na graphene technical concern Co., Ltd
Terephthalic acid (TPA) Technical grade Constant force petrochemical industry Co., Ltd
Ethylene glycol Technical grade China PetroChemical Corporation
Catalyst Technical grade Shanghai Mai Ruier chemical technology Co., Ltd
Heat stabilizer Food-grade Bo Yang Chemical Company, Suzhou City
The preparation method of graphene master batch provided by the invention the following steps are included:
(1) a certain proportion of graphene powder and ethylene glycol are carried out premixing obtained graphite in such a way that ultrasonic wave disperses Alkene dispersion liquid；
(2) direct esterification technique and situ aggregation method are used: terephthalic acid (TPA), ethylene glycol being pressed into different ratio, investment is anti- It answers in kettle, while the graphene dispersing solution of a certain amount of catalyst, stabilizer antimony glycol, phosphoric acid and different content is added, it is whole A process carries out under nitrogen protection, sets nitrogen pressure as 0.3MPa, mixing speed 70r/min, esterification temperature 240 DEG C, 210 DEG C are gradually warming up to, esterification starts, and the amount of steaming to water reaches the 90% of theoretical value, pressure release to normal pressure, and esterification terminates. 285 DEG C of condensation temperature, normal pressure polycondensation 0.5h of setting, then low vacuum precondensation 0.5h, last high vacuum polycondensation, pressure are less than 60Pa.When reaching preset same power of agitator, polycondensation terminates, and discharge simultaneously pelletizing.
The preparation method of reflectance coating provided by the invention with conductive and heat-conductive surface layer the following steps are included:
(1) graphene master batch is mixed with polyester according to a certain percentage, is melted after dry, obtains the table of reflectance coating Layer melted material；
(2) by foamed core layer masterbatch resin and polyester raw material mix, melted after dry, obtain foamed core layer melting material Material；
(3) raw material of step (1) and step (2) is separately added into different extruders, biaxial tension is made and leads with conduction The reflectance coating of hotlist layer.
Reflectance coating provided by the invention with conductive and heat-conductive surface layer tests its main performance using following methods:
(1) the reunion test of graphene master batch:
Existed with German zeiss company vltra55 type thermal field emission scanning electron microscope (EDS/EBSD) observation graphene Whether conductive heat conducting material surface layer has agglomeration, occurs reuniting, is formulated failure.
(2) conducting performance test:
By conductive and heat-conductive superficial reflex film obtained, electric conductivity survey is carried out with Japanese SIMCO ST-4 surface impedance meter Examination, it is desirable that measure surface resistivity≤10 in result9Ω/ just shows the conductive energy of material.
(3) heating conduction is tested:
The test of unstable state moment heat-pole method: it according to GB/T5990-1986, is tested on TC3000E type conductometer, sample Product are having a size of 60mm × 60mm × 2mm；(thermal coefficient for not making the reflector plate of thermally conductive treatment is 0.3W. (m.k) -1)；It leads Hot coefficient is bigger to illustrate that heating conduction is better.
Linear thermal conductivity factor instrument, TC3000E, Xi'an Xiatech Electronic Technology Co., Ltd..
(4) reflectance coating appearance is tested
If the appearance of reflectance coating is white, does not show macroscopic grey or black is OK.
(5) display taste test
It draws a design according to the reflection drawing of 55 cun of straight-down negatives and side entering type machine, is then assembled into complete machine and carries out lighting survey Examination, duration 1000hr, then observing display can or can not have that the bad bring taste of reflectance coating heat dissipation (can be right when test Than the display that test group is equipped with the reflectance coating without thermally conductive surface layer, paired observation is assembled with the anti-of conductive and heat-conductive surface layer Penetrate the uniform situation of visual effect of the display of film), the uneven situation of visual effect do not occur then is OK.
Embodiment 1
The present invention provides a kind of reflectance coating with conductive and heat-conductive surface layer and a kind of preparation method of graphene masterbatch, described Reflectance coating includes foamed core layer and conductive and heat-conductive surface layer, and the side of foamed core layer is arranged in the conductive and heat-conductive surface layer；It is described to lead Conductance hotlist layer includes graphene.
During the preparation process, the foamed core layer includes 5% masterbatch resin and 95% PET, the masterbatch resin packet Include 90% TiO2With 10% TPX.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Embodiment 2
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Embodiment 3
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Embodiment 4
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Embodiment 5
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Embodiment 6
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Embodiment 7
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Embodiment 8
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 2.
Comparative example 1
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 2
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 3
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 4
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 5
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.The synthesis material of graphene master batch, which is matched, when to be closed 1 is shown in Table at situation.
Comparative example 6
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 7
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 8
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 9
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 10
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 11
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 12
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 13
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 14
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 15
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 16
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 17
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 18
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 19
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 20
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 21
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 22
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 3.
Comparative example 23
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 3.
Comparative example 24
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 25
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 26
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 27
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 28
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 29
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 3.
Comparative example 30
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 31
The graphene master batch provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Comparative example 32
The reflectance coating with conductive and heat-conductive surface layer provided such as embodiment 1.
The synthesis material of graphene master batch is shown in Table 1 with when synthesis situation.
Reflectance coating, the performance test results with when reflectance coating on conductive and heat-conductive surface layer are prepared with the graphene master batch of preparation It is shown in Table 3.
The synthesis material of graphene master batch, which is matched, in 1 embodiment 1-8 of table, comparative example 1-32 when synthesizes situation
The performance test results with when reflectance coating on the conductive and heat-conductive surface layer that 2 embodiment 1-8 of table is provided
The conductive and heat-conductive surface layer that 3 comparative example 22,23,29,32 of table provides with when reflectance coating and the performance test results
Sb in table 12O3Refer to antimony oxide, Sb (Ac)3Refer to antimony acetate.
From table 1 it follows that the graphene master batch synthesis failure or reunion of comparative example 1-21,24-28,30-31 preparation Seriously, it is not used to the reflectance coating that preparation has conductive and heat-conductive surface layer.
The molar ratio Tai Gaotai of alkyd is low in comparative example 1-3 can all lead to the synthesis failure of graphene master batch；Comparative example 4-31 In different types of antimony class catalyst be lower than from phosphoric acid type thermal stabilizing agent and different additive amounts and graphene additive amount When 0.3wt%, have a significant impact for the synthesis of graphene master batch；It is scanned in comparative example 22-23, comparative example 29 by thermal field formula Electron microscope observation finds that the piece diameter of graphene is too small or content is too low, effectively cannot form conductive mesh on membrane material surface Network cannot be tested by electric conductivity；The thickness of graphene is too big in comparative example 30-31, also will affect the synthesis of graphene master batch； The additive amount of graphene master batch is too high in comparative example 32, and diaphragm is caused to be no longer presented white.
The comprehensive performance of reflectance coating provided by the invention with conductive and heat-conductive surface layer is good.Wherein, embodiment 3 and implementation The comprehensive performance for the reflectance coating with conductive and heat-conductive surface layer that example 5-6 is provided is preferable, and reflectance coating appearance tests OK, surface resistivity It is at most 107.9Ω/, thermal coefficient are at least 1.1W. (m.k)-1, taste test OK.Particularly, embodiment 3 and embodiment 6 The comprehensive performance of the reflectance coating with conductive and heat-conductive surface layer provided is more preferable, and reflectance coating appearance test OK, surface resistivity are 107.7Ω/, thermal coefficient are 1.2W. (m.k)-1, taste test OK.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.It is all The equivalent changes and modifications that content is done according to the present invention are encompassed by the scope of the patents of the invention.

Claims (10)

1. a kind of reflectance coating with conductive and heat-conductive surface layer, which is characterized in that the reflectance coating includes that foamed core layer and conduction are led The one or both sides of foamed core layer are arranged in hotlist layer, the conductive and heat-conductive surface layer；The conductive and heat-conductive surface layer includes graphene.
2. the reflectance coating according to claim 1 with conductive and heat-conductive surface layer, which is characterized in that the conductive and heat-conductive table The content of graphene is 0.07~0.13% in layer, and the percentage is weight percentage.
3. the reflectance coating according to claim 1 with conductive and heat-conductive surface layer, which is characterized in that the graphene is piece Shape, the piece diameter of the graphene are 3~10 μm, graphene with a thickness of 5~10nm.
4. the reflectance coating according to claim 1 with conductive and heat-conductive surface layer, which is characterized in that during the preparation process, institute State graphene and be first prepared into graphene master batch, the graphene master batch include 0.28~0.32wt% graphene and 99.68~ The polyester of 99.72wt%.
5. the reflectance coating according to claim 1 with conductive and heat-conductive surface layer, which is characterized in that the conductive and heat-conductive table The graphene master batch of polyester and 25-40wt% of the layer including 60-75wt%.
6. a kind of method for preparing graphene master batch as claimed in claim 4, which is characterized in that the method includes following steps It is rapid:
(1) graphene powder and ethylene glycol are premixed in such a way that ultrasonic wave disperses, graphene dispersing solution is made；
(2) direct esterification technique and situ aggregation method are used: according to the ratio by terephthalic acid (TPA), ethylene glycol, being put into reaction kettle, together When a certain amount of catalyst, stabilizer and graphene dispersing solution is added, whole process carries out under nitrogen protection, set nitrogen pressure Power is 0.3MPa, and mixing speed 70r/min, esterification temperature is 240 DEG C, is gradually warming up to 210 DEG C, esterification starts, to water The amount of steaming reaches the 90% of theoretical value, pressure release to normal pressure, and esterification terminates.285 DEG C of condensation temperature, normal pressure polycondensation 0.5h of setting, so Low vacuum precondensation 0.5h afterwards, last high vacuum polycondensation, pressure are less than 60Pa.When reaching preset same power of agitator, contracting Beam is coalesced, discharge simultaneously pelletizing.
7. the preparation method of graphene master batch according to claim 6, which is characterized in that graphene in the step (1) Additive amount be 0.28-0.32wt%.
8. the preparation method of graphene master batch according to claim 6, which is characterized in that ethylene glycol in the step (2) Molar ratio with terephthalic acid (TPA) is 1.45-1.55:1.
9. the preparation method of graphene master batch according to claim 6, which is characterized in that catalyst in the step (2) Additive amount be 0.024-0.026wt%, the additive amount of the heat stabilizer is 0.001wt%.
10. the preparation method of graphene master batch according to claim 6, which is characterized in that the catalysis in the step (2) Agent is selected from antimony-based catalyst, and the heat stabilizer is phosphoric acid.
CN201711442465.2A 2017-12-27 2017-12-27 A kind of reflectance coating with conductive and heat-conductive surface layer and a kind of preparation method of graphene master batch Pending CN109971133A (en)

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Application publication date: 20190705