阅读说明：本技术 石墨烯碳油及其制备方法 (Graphene carbon oil and preparation method thereof ) 是由 吴道新 祝文华 邬家康 刘振 姚文娟 彭伟 于 2019-09-27 设计创作，主要内容包括：本发明涉及导电油墨技术领域,公开了一种石墨烯碳油,包括银氨络合物、聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸、石墨烯、羟丙基纤维素、银纳米颗粒和溶剂。本发明还提供一种石墨烯碳油的制备方法。本发明提供的石墨烯碳油的印刷制品具有电阻小、使用寿命长的优点,且该石墨烯碳油具有较好地的均匀性及附着力。(The present invention relates to electrically conductive ink technical fields, disclose a kind of graphene carbon oil, including silver ammonia complex, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid, graphene, hydroxypropyl cellulose, silver nano-grain and solvent.The present invention also provides a kind of preparation methods of graphene carbon oil.The printed matter of graphene carbon oil provided by the invention has the advantages that resistance is small, long service life, and the graphene carbon oil has uniformity and adhesive force preferably.)

1. a kind of graphene carbon oil, which is characterized in that including silver ammonia complex, poly- (3,4-rthylene dioxythiophene)-polystyrene Sulfonic acid, graphene, hydroxypropyl cellulose, silver nano-grain and solvent.

2. graphene carbon oil according to claim 1, which is characterized in that in the graphene carbon oil, in terms of mass parts, silver 8-16 parts of ammino-complex, 6-10 parts of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid, 5-15 parts of graphene, hydroxypropyl is fine 0.1-1 parts of element of dimension, 1-2 parts of silver nano-grain, 20-40 parts of solvent.

3. graphene carbon oil according to claim 2, which is characterized in that in the graphene carbon oil, in terms of mass parts, silver 10-14 parts of ammino-complex, 8-10 parts of poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid, 8-12 parts of graphene, hydroxypropyl is fine 0.1-0.5 parts of element of dimension, 1-1.5 parts of silver nano-grain, 25-35 parts of solvent.

4. graphene carbon oil described in -3 according to claim 1, which is characterized in that the graphene is less equal than three layers Graphene, the silver ammonia complex is silver diamminohydroxide, silver diamminonitrate or chlorination two ammino silver.

5. graphene carbon oil described in -3 according to claim 1, which is characterized in that the solvent is water, ethyl alcohol or propylene glycol.

6. a kind of preparation method of graphene carbon oil, which comprises the following steps:

(1) graphene and solvent supersonic are dispersed, obtains dispersion liquid；

(2) by above-mentioned dispersion liquid and silver ammonia complex, poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid, hydroxy propyl cellulose Element, silver nano-grain mixing, and grind, obtain the graphene carbon oil；

Wherein, in terms of mass parts, silver ammonia complex takes 8-16 parts, and poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid takes 6- 10 parts, graphene takes 5-15 parts, and hydroxypropyl cellulose takes 0.1-1 parts, and silver nano-grain takes 1-2 parts, and solvent takes 20-40 parts.

7. the preparation method of graphene carbon oil according to claim 6, which is characterized in that in terms of mass parts, silver-colored ammonia complexing Object takes 10-14 parts, and poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid takes 8-10 parts, and graphene takes 8-12 parts, and hydroxypropyl is fine Dimension element takes 0.1-0.5 parts, and silver nano-grain takes 1-1.5 parts, and solvent takes 25-35 parts.

8. the preparation method of graphene carbon oil according to claim 7, which is characterized in that in step (2), obtained after grinding Graphene carbon oil in solid particle diameter be less than or equal to 5 μm.

9. the preparation method of graphene carbon oil a method according to any one of claims 6-8, which is characterized in that the graphene For the graphene less equal than three layers, the silver ammonia complex is silver diamminohydroxide, silver diamminonitrate or chlorination two Ammino silver.

10. the preparation method of graphene carbon oil a method according to any one of claims 6-8, which is characterized in that the solvent For water, ethyl alcohol or propylene glycol.

Technical field

The present invention relates to electrically conductive ink technical fields, and in particular to a kind of graphene carbon oil.Furthermore the invention further relates to one The preparation method of kind graphene carbon oil.

Background technique

In order to constantly meet the requirement of the small-sized of electronic product, light weight, high-performance and multifunction this development trend, electricity Subcomponent is more intended to small-sized and ultrathin, and printed circuit board is more intended to high-accuracy figure.It will be in such printing electricity It is more and more difficult to install a large amount of element for arrangement on the plate of road, it is necessary to which printed board itself takes some capacitors or resistance.

Carbon oil is a kind of electronic functionality material, due to its high mechanical strength, abrasion-resistant after film forming, to substrate adhesive force Good, electric conductivity is good to wait superperformances, can replace gold-plated plug, keyboard, production cross-cross skip line resistance and printed resistor, or For perforation material, suitable for making the rigidity or flexibility carbon film printed circuit board of various substrates.

Some silver powder, copper powder or bronze can be added in current carbon oil to reduce its resistance value, thus increase its electric conductivity, But since the chemical activity matter of carbon and metal differs greatly, if the two is exposed in wet air, the change of junction The service life of equipment will be will affect by learning corrosion, limit the use of such product.

In view of this, it is desirable to provide a kind of resistance is low, graphene carbon oil with long service life.

Summary of the invention

It is of the existing technology the technical problem to be solved by the present invention is to overcome the problems, such as, provide a kind of graphene carbon oil and Preparation method, the printed matter of the graphene carbon oil has the advantages that resistance is small, long service life, and the graphene carbon oil has There are uniformity preferably and adhesive force.

To achieve the goals above, first aspect present invention provides a kind of graphene carbon oil, including silver ammonia complex, poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid, graphene, hydroxypropyl cellulose, silver nano-grain and solvent.

Preferably, in the graphene carbon oil, in terms of mass parts, 8-16 parts of silver ammonia complex, poly- (3,4- ethylene dioxy thiophenes Pheno) 6-10 parts of-polystyrolsulfon acid, 5-15 parts of graphene, 0.1-1 parts of hydroxypropyl cellulose, 1-2 parts of silver nano-grain, solvent 20-40 parts.

It is further preferred that in the graphene carbon oil, in terms of mass parts, 10-14 parts of silver ammonia complex, poly- (3,4- second Alkene dioxy thiophene) 8-10 parts of-polystyrolsulfon acid, 8-12 parts of graphene, 0.1-0.5 parts of hydroxypropyl cellulose, silver nano-grain 1-1.5 parts, 25-35 parts of solvent.

Specifically, the graphene is the graphene less equal than three layers, and the silver ammonia complex is hydroxide diamino Close silver, silver diamminonitrate or chlorination two amminos silver.

Specifically, the solvent is water, ethyl alcohol or propylene glycol.

Second aspect, the present invention provide a kind of preparation method of graphene carbon oil, comprising the following steps:

(1) graphene and solvent supersonic are dispersed, obtains dispersion liquid；

(2) by above-mentioned dispersion liquid and silver ammonia complex, poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid, hydroxypropyl Cellulose, silver nano-grain mixing, and grind, obtain the graphene carbon oil；

Wherein, in terms of mass parts, silver ammonia complex takes 8-16 parts, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid 6-10 parts are taken, graphene takes 5-15 parts, and hydroxypropyl cellulose takes 0.1-1 parts, and silver nano-grain takes 1-2 parts, and solvent takes 20-40 Part.

Preferably, in terms of mass parts, silver ammonia complex takes 10-14 parts, poly- (3,4-rthylene dioxythiophene)-polystyrene sulphur Acid takes 8-10 parts, and graphene takes 8-12 parts, and hydroxypropyl cellulose takes 0.1-0.5 parts, and silver nano-grain takes 1-1.5 parts, and solvent takes 25-35 parts.

Preferably, in step (2), the diameter of the solid particle in graphene carbon oil obtained after grinding is less than or equal to 5 μ m。

Preferably, the graphene is the graphene less equal than three layers, and the silver ammonia complex is hydroxide diamino Close silver, silver diamminonitrate or chlorination two amminos silver.

Preferably, the solvent is water, ethyl alcohol or propylene glycol.

Through the above technical solutions, can achieve it is following the utility model has the advantages that

1, graphene carbon oil provided by the invention is by compounding silver nano-grain and hydroxypropyl cellulose, and is added to silver Ammino-complex, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid and graphene, can be effectively reduced the resistance value of carbon oil, Graphene and silver nano-grain can also be wrapped up wherein by poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid simultaneously, Prevent silver nano-grain from chemical attack occurs to influence the service life of equipment.

2, the printed matter of graphene carbon oil provided by the invention is not oxidizable, corrosion-resistant, and silver content is low, has well High temperature resistance, but its electric conductivity is greatly improved, and easily storage and use.

3, the present invention can be effectively reduced the granular size of solid particle in carbon oil by ultrasound, the method for grinding, thus The uniformity for improving carbon oil, improves the stability of printed matter.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Specific embodiment

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

In a first aspect, the present invention provides a kind of graphene carbon oil, including silver ammonia complex, poly- (3,4- ethylene dioxy thiophenes Pheno)-polystyrolsulfon acid, graphene, hydroxypropyl cellulose, silver nano-grain and solvent.

Preferably, in the graphene carbon oil, in terms of mass parts, 8-16 parts of silver ammonia complex, poly- (3,4- ethylene dioxy thiophenes Pheno) 6-10 parts of-polystyrolsulfon acid, 5-15 parts of graphene, 0.1-1 parts of hydroxypropyl cellulose, 1-2 parts of silver nano-grain, solvent 20-40 parts.

It is further preferred that in the graphene carbon oil, in terms of mass parts, 10-14 parts of silver ammonia complex, poly- (3,4- second Alkene dioxy thiophene) 8-10 parts of-polystyrolsulfon acid, 8-12 parts of graphene, 0.1-0.5 parts of hydroxypropyl cellulose, silver nano-grain 1-1.5 parts, 25-35 parts of solvent.

Specifically, the graphene is the graphene less equal than three layers.The graphene can be one layer of graphite Alkene, two layers of graphene or three layers of graphene.The silver ammonia complex be silver diamminohydroxide, silver diamminonitrate or Chlorination two amminos silver.

Specifically, the solvent is water, ethyl alcohol or propylene glycol.

Second aspect, the present invention provide a kind of preparation method of graphene carbon oil, comprising the following steps:

(1) graphene and solvent supersonic are dispersed, obtains dispersion liquid；

(2) by above-mentioned dispersion liquid and silver ammonia complex, poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid, hydroxypropyl Cellulose, silver nano-grain mixing, and grind, obtain the graphene carbon oil；

Wherein, in terms of mass parts, silver ammonia complex takes 8-16 parts, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid 6-10 parts are taken, graphene takes 5-15 parts, and hydroxypropyl cellulose takes 0.1-1 parts, and silver nano-grain takes 1-2 parts, and solvent takes 20-40 Part.

Specifically, in step (1), the graphene in dispersion liquid that ultrasonic disperse obtains needs to be thoroughly dispersed in solvent as far as possible In.Ultrasonic power is generally 1250-1500W, and ultrasonic time can be determined according to the quality of graphene and solvent, generally 30- The amount of 120min, graphene addition are more, and the ultrasonic time is longer, certainly, if it is desired to making the dispersion of graphene in a solvent more To be complete, the time of ultrasound can be increased.In the ultrasonic procedure, graphene and solvent can be placed in beaker or conical flask Or it is ultrasonic in other containers, but in order to prevent during long-time ultrasonic disperse, solvent temperature raising causes solvent to be waved Hair to influence the quality of carbon oil, so, need to provide ice water to the mixture of graphene and solvent during ultrasonic disperse Bath cooling；Also need to be covered with preservative film or other films on the mixing vessel simultaneously to prevent temperature from increasing or being in for a long time Solvent volatilizees and influences the amount of the solvent of addition under opening environment.

Preferably, in terms of mass parts, silver ammonia complex takes 10-14 parts, poly- (3,4-rthylene dioxythiophene)-polystyrene sulphur Acid takes 8-10 parts, and graphene takes 8-12 parts, and hydroxypropyl cellulose takes 0.1-0.5 parts, and silver nano-grain takes 1-1.5 parts, and solvent takes 25-35 parts.

In step (2), the grinding can use hand lapping or mechanical lapping, but whether being using hand lapping Or mechanical lapping, the diameter of the solid particle in graphene carbon oil obtained after grinding need to be less than or equal to 5 μm.Ground The partial size of solid particle in the graphene carbon oil of measurement in journey interval 10 minutes, until Solids Particle Diameter is less than or equal to 5 μ M stops grinding.

Preferably, the graphene is the graphene less equal than three layers, and the silver ammonia complex is hydroxide diamino Close silver, silver diamminonitrate or chlorination two amminos silver.

Preferably, the solvent is water, ethyl alcohol or propylene glycol.

Above-mentioned silver diamminohydroxide, silver diamminonitrate or two ammino silver of chlorination can be made using conventional method.Example Such as: the preparation method of silver diamminohydroxide is by AgNO₃Solution is mixed with NaOH solution, and it is rigid to precipitating that weak aqua ammonia is then added dropwise Good dissolving.

The present invention will be described in detail by way of examples below.

In the present invention, graphene is purchased from Xin Ao graphene Technology Co., Ltd.；Poly- (3,4- ethene dioxythiophene)-polyphenyl second Alkene sulfonic acid dispersion liquid is purchased from German Heraeus company, product type PH1000；It is public that silver nano-grain is purchased from German Sigma Department, particle diameter are less than 100nm；Hydroxypropyl cellulose, ethyl alcohol, propylene glycol are purchased from traditional Chinese medicines group.In graphene carbon oil The partial size of solid particle is measured using nano particle size and zeta potentiometer, and the nano particle size and zeta potentiometer are purchased from american wheat surprise Gram Co., Ltd, model Nanotrac wave II；Resistivity is measured by double digital four-point probes of electrical measurement, should Double digital four-point probes of electrical measurement are purchased from Suzhou Jingge Electronic Co., Ltd., product type ST2263.