CN106424711B - Electrically conductive microparticle and its manufacturing method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet - Google Patents
Electrically conductive microparticle and its manufacturing method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet Download PDFInfo
- Publication number
- CN106424711B CN106424711B CN201610930540.9A CN201610930540A CN106424711B CN 106424711 B CN106424711 B CN 106424711B CN 201610930540 A CN201610930540 A CN 201610930540A CN 106424711 B CN106424711 B CN 106424711B
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- electrically conductive
- resin
- microparticle
- conductive microparticle
- conductive
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Abstract
The present invention provides a kind of electrically conductive microparticle, can reduce cost, and conductive characteristic is excellent, and can filming when the synthetic made of for example deploying it together with resin forms flake.Electrically conductive microparticle of the invention, it is characterized by: acquiring its diameter degree coefficient with following mathematical expressions (1) as 0.15 or more, 0.4 or less, and at least one shape in outer rim concave mouth and branch leaf be formed with it is multiple, wherein, the internal area of the line of the periphery of the formation electrically conductive microparticle when area refers to two-dimensional projection, the length of the line of the periphery when perimeter refers to two-dimensional projection, but eliminate include conductive material nucleome, and it is coated aforementioned nucleome, and it is made of the conductive material different from the nucleome, and at least part constitutes the electrically conductive microparticle of outermost coating.Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1).
Description
The application be submit on March 5th, 2013 application No. is 201380012622.X and entitled " electric conductivity is micro-
Point of the patent application of grain and its manufacturing method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet "
Case application.
Technical field
The present invention is about electrically conductive microparticle and its manufacturing method.In addition, also about the conduction comprising said conductive particle
Property resin combination.In addition, also about the conductive sheet for having the conductive layer formed by said conductive resin combination
And electromagnetic shielding sheet.
Background technique
Printed circuit board is also and then thinned along with the miniaturization of the e-machines such as mobile phone, digital camera, and is opened
Beginning is often used flexible printed circuit.Would generally be used in printed circuit board conductive sheet, electromagnetic shielding sheet etc. (with
Down also referred to as " conductive sheet etc. ").Conductive sheet etc. requires to include the excellent conductive characteristic of stability at any time, and
The characteristic of electroconductive stuffing contained in thin slice is allowed to become important.
As electroconductive stuffing, silver powder is because conductive characteristic is excellent, therefore conductive sheet containing silver powder etc. is brought at present
Actual use.However, the price of silver powder is high price compared to the resin or other raw materials for being used in conductive sheet etc., and
Cost can be allowed to get higher.Therefore, because recent silver-colored valence is surging, become sternly using the rise in price of the conductive sheet of silver powder etc.
The problem of weight.Although in order to reach the low price of e-machine, there is an urgent need to reduce the use ratio of electroconductive stuffing, if subtracting
The use ratio of few electroconductive stuffing, i.e., be in face of the problem of being unable to maintain that desired electric conductivity.
Therefore, cost effective in order to be realized while meeting conductive characteristic, and have various motions.Such as in patent document
Motion in 1 while reducing the amount of electroconductive stuffing, is promoted by sheet as shown in Figure 2 (flakey) silver powder is used
To by the method for the adhesion of then body.In addition, being disclosed in patent document 2 with by silver-colored plating silver-plated copper made of copper surface
Powder is as the electroconductive particle being used in these thin slices.In addition, being disclosed in patent document 3 to mix dendroid silver-plated copper powder
With conductive paste made of flakey silver powder as electroconductive particle.
Existing technical literature
Patent document
Patent document 1:JP special open 2011-86930 bulletin
Patent document 2:JP special open 2002-75057 bulletin
Patent document 3:JP special open 2009-230952 bulletin
Summary of the invention
Invent the problem of solved
In the market of conductive sheet etc., in order to realize that conductive characteristic is excellent and cost effective, and exploitation is required to cut
Conductive characteristic or excellent thin slice while subtracting the usage amount of the silver powder of high price.In addition, in order to correspond to light and shortization, also
It is required that by the technology of the filmings such as conductive sheet.And by the conductive paste of patent document 3 used as conductive sheet it
Situation, because having deployed dendroid silver-plated copper powder, and the problem of make it difficult for sheet films.This is because dendroid silver-plated copper powder
Some is understood from conductive layer prominent the problem of wearing out other layers, hurting other layers.And among the above, although be using silver
As the example of electroconductive particle, but identical problem is also had in the situation using other electroconductive particles and is generated.Though in addition,
What is so said is the conductive sheet etc. applied to printed circuit board, but conductive sheet integrally also has identical problem and generates.
The present invention is in view of above-mentioned background, and the purpose is to provide that cost can be reduced, and conductive characteristic is excellent, and for example will
Constituent made of it is deployed together with resin is configured to the electrically conductive microparticle of energy filming when flake.
Solve the means of technical problem
Team of the present invention constantly joins hands to study, it is found that following aspect can solve the project of the present invention, of the invention to completing eventually.
That is, the average value of the diameter degree coefficient acquired with following mathematical expressions (1) is 0.15 or more, 0.4 hereinafter, and in outer rim concave mouth
And at least one shape in branch leaf be formed with it is multiple.
Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1)
Wherein, the internal area of the line of the periphery of the formation electrically conductive microparticle when area refers to two-dimensional projection,
The length of the line of the periphery when perimeter refers to two-dimensional projection,
But the nucleome comprising conductive material is eliminated, and is coated aforementioned nucleome, by the electric conductivity object different from the nucleome
Matter is constituted, and at least part constitutes the electrically conductive microparticle of the coating of outermost layer.
The electrically conductive microparticle is made of single conductive material.
The conductive resin composition of the present invention includes the electrically conductive microparticle and resin, and the resin is thermoplasticity
At least one of resin and thermosetting resin.
The electromagnetic shielding sheet of the present invention, which has, is formed by conductive layer by the electroconductive resin constituent.
The conductive sheet of the present invention, which has, is formed by conductive layer by the electroconductive resin constituent.
The preparation method of the electrically conductive microparticle of the present invention the following steps are included:
By allowing aforementioned dendroid particle to collide in closed container with aforesaid solid media, make the dendroid particle by
It is 0.15 or more, 0.4 hereinafter, and allowing outer rim shape distortion as recess using the obtained diameter degree coefficient of following mathematical expressions (1)
And at least one of branch leaf is formed with multiple steps,
Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1),
Wherein, the internal area of the line of the periphery of the formation electrically conductive microparticle when area refers to two-dimensional projection,
The length of the line of the periphery when perimeter refers to two-dimensional projection,
But the nucleome comprising conductive material is eliminated, and is coated aforementioned nucleome, and is the electric conductivity different from the nucleome
Substance is constituted, and at least part constitutes the electrically conductive microparticle of the coating of outermost layer.
The electrically conductive microparticle is made of single conductive material.
Invention effect
According to the present invention of above-mentioned composition, having played, which can provide, can reduce cost, and conductive characteristic is excellent, and for example will
Constituent made of it is deployed together with resin is configured to the excellent effect of the electrically conductive microparticle of energy filming when flake.
Team of the present invention constantly join hands research as a result, having surprisingly found that: by formed diameter degree coefficient average value exist
Above range, and outer rim shape includes the lobate electrically conductive microparticle of at least one of recess and branch leaf, can be allowed conductive special
Property is excellent.And in the equal situation for deploying dendritic electrically conductive microparticle of patent document 3, have a project for being difficult to filming, but according to
According to the electrically conductive microparticle of the present invention, discovery and is configured to above-mentioned outer by allowing the average value of diameter degree coefficient in above range
Edge shape, and being kneaded in constituent can filming when being configured to flake.In addition, because nucleome is led using different from coating
Conductive substances, therefore can increase material selection, and reach the purpose for reducing cost.
Detailed description of the invention
Fig. 1 is the electron micrograph of the example of the electrically conductive microparticle with scaly leaf or branch leaf in the present invention.
Fig. 2 is the electron micrograph of flakey silver powder.
Fig. 3 is the electron micrograph of dendroid silver-plated copper powder.
Fig. 4 is the schematic diagram for connecting the measurement test sample of resistance value.
Specific embodiment
The form to carry out an invention
Hereinafter, illustrating the specific implementation form of the present invention.But as long as meeting the purport of the present invention, other implementation forms are not
It is also contained in the scope of the present invention certainly with saying.It is that will remember in addition, carrying out specific numberical range using "~" in this specification
The numerical value for being loaded in the front and back of "~" is included as the range of lower limit value and upper limit value.In addition, specifically mentioned in this specification
Item other than the implementation present invention necessary to thing, be the prior art based on the field, related dealer can know about it
Design item.In addition, following implementation forms can be appropriately combined each other.
(electrically conductive microparticle)
The electrically conductive microparticle of the present invention is so-called core shell partical, has the nucleome comprising conductive material, and coating
It nucleome and is made of the conductive material different from this nucleome, and at least part constitutes the coating of outermost layer.It is coating
As long as layer is coated at least part of nucleome, and more excellent conductive characteristic in order to obtain, with covering rate, high person is preferable.
From the viewpoint of keeping good conductive characteristic, preferably allow the average covering rate of coating 60% or more, more preferably 70%
More than, then more preferably 80% or more.And the average covering rate in this specification, refer to the method institute identical as aftermentioned embodiment
The value acquired.
Electrically conductive microparticle can be only made of nucleome with coating, also may include other layers.For example, can be formed allow nucleome with
The layer headed by middle layer, bonding layer etc. that engagement between coating consolidates.In addition, nucleome, coating, other layers of energy are respectively
It is independently constituted with single kind, can also be constituted with plural type.In addition, in nucleome, coating, without departing from the present invention
Purport in the range of, the other materials that can also be kneaded other than conductive substance.
The electrically conductive microparticle of the present invention, the average value of the diameter degree coefficient acquired according to following formula (1) is 0.15 or more,
0.4 hereinafter, and at least one shape in outer rim concave mouth and branch leaf be formed with it is multiple.
Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1)
By the diameter degree coefficient of above-mentioned formula (1), the concave-convex degree (fluctuating quantity) of electrically conductive microparticle outer rim will appreciate that.Proper sphere
Be diameter degree coefficient be 1, with the increase of concaveconvex shape, diameter degree coefficient can be reduced.That is, diameter degree coefficient ratio 0 it is big and 1 with
Under.Diameter degree coefficient is read conductive using the analysis software of Mac-View Ver.4 (MOUNTECH company) in this specification
The electron microscope image (1,000 times~10,000 times or so) of property particle, with about 20 electroconductive particles of manual identification model selection.
When selecting lobate or flakey particle, it is the shape of particle of no overlapping on the whole that particle can be confirmed each other by, which selecting out, and by
Surface plate is perpendicular angle from the point of view of observation visual angle.Particle reference data is to be with the equivalent diameter of projected area, distribution
The setting of volume distribution calculates diameter degree coefficient and circle coefficient, seeks 20 average value.Face in above-mentioned mathematical expression (1)
The internal area of product, the line of formation periphery when being two-dimensional projection treats as platen surface, when by this platen surface two-dimensional projection
Treat as the length of perimeter in the periphery of electrically conductive microparticle.
By using: using the average value of the diameter degree coefficient acquired with above-mentioned mathematical expression (1) 0.15 or more, 0.4
Hereinafter, and at least one shape in outer rim concave mouth and branch leaf be formed with multiple hud typed electrically conductive microparticles, can drop
Low cost, and conductive characteristic is excellent, and being capable of filming.The lower limit value of diameter degree coefficient, from preventing conductive filler from penetrating absolutely
From the viewpoint of edge layer, more preferably 0.15 or more, then more preferably 0.20 or more.And the upper limit value of diameter degree coefficient, from conductive layer
Electrical sheet resistance from the viewpoint of, more preferably 0.4 hereinafter, more preferably 0.3 or less.Average value, the circle of above-mentioned diameter degree coefficient
The average value of shape coefficient, preferably every 1cm2The particle defined has about 10 or more.
Also, as shown in figure 3, the diameter degree coefficient of dendroid electrically conductive microparticle is substantially 0.11 hereinafter, and flakey is conductive
Property particle diameter degree coefficient be greater than 0.4, below 0.5 left and right.
The expression that the following mathematical expression of the electrically conductive microparticle of the present invention (2) the acquires closely circle coefficient of circle degree is averaged
Value, preferably 2 or more, 5 or less.
Circle coefficient=(maximum gauge × maximum gauge × π)/(4 × area) ... mathematical expression (2)
Herein, maximum gauge is the length of the maximum length of selected particle.By allow circle coefficient in aforementioned range,
It can obtain the effect that electric conductivity is more promoted.From the viewpoint of preventing conductive filler from penetrating insulating layer, circle coefficient is more preferably
Upper limit value is 4.5 hereinafter, being more preferably 4.0 or less again.In addition, from the point of view of the viewpoint of the electrical sheet resistance of conductive layer, circle coefficient
More preferably lower limit value is 2 or more, then is more preferably 2.4 or more.It may know that the whether close circle (number of shape of particle entirety by circle coefficient
It is worth smaller closer to circle).Also, circle coefficient be the analysis software (Mac-View Ver.4) that is used using diameter degree coefficient it
Form factor 3.
In other words the electrically conductive microparticle of the present invention there is at least one of scaly leaf and branch leaf to be formed with multiple
Lobate electrically conductive microparticle.Fig. 1 shows the electron microscope image of the example of the electrically conductive microparticle of the present invention.The example of same figure
In, nucleome is using copper powder, and coating is using silver.As same as shown in the figure, electrically conductive microparticle is to form recess in its outer rim
And at least one shape in branch leaf be formed with it is multiple.In other words, it is more to be that scaly leaf, branch leaf or such shape are formed with
It is a.Hereinafter, the electrically conductive microparticle of the present invention is also known as " lobate electrically conductive microparticle ".
The thickness of electrically conductive microparticle is preferably 0.1~2 μm, more preferably 0.2~1 μm.By allow thickness 0.1~2 μm it
Range, while maintaining the electric conductivity of conductive sheet, moreover it is possible to more unfertile land manufacture.Wherein, which is based on electronic display
Obtained by micro mirror amplifies 1 dry times~50,000 times or so of image, and signified " thickness " is 10,000 times of figures with electron microscope herein
Picture measures about 10~20 different particles, uses its average value.
In addition, the average grain diameter (D50) of electrically conductive microparticle is preferably 1~100 μm.By average grain diameter (D50) 1~
In 100 μm of range, electric conductivity can be more promoted, in addition, for example deploying the feelings of manufacture electroconductive resin constituent with resin at it
Shape can more promote its solution stability.The average grain diameter (D50) of electrically conductive microparticle is more preferably 3 μm or more, more preferably 50 μm with
Under.Wherein, average grain diameter (D50) is using laser diffraction/13 320 (BECKMAN of scattering method particle size distribution device LS
COULTER corporation), each electrically conductive microparticle institute value is measured with cyclone type dry powder sample module, the aggregate-value of particle is
The average grain diameter of the diameter of 50% granularity.Wherein, the setting of refractive index is set as 1.6.
In addition, the measuring method of the average grain diameter (D50) when allowing electrically conductive microparticle to become the form of conductive sheet, is
With condition identical with the measurement method of diameter degree coefficient, electrically conductive microparticle is observed with SEM, with image analysis software Mac-View
Ver.4 (MOUNTECH company), it is setting for volume distribution that particle reference data, which is with the equivalent diameter of projected area, distribution,
It is fixed, to seek average grain diameter (D50).
The function of nucleome is the kernel portion as electrically conductive microparticle.From the viewpoint of nucleome is by promotion conductive characteristic, preferably
It is only made of conductive material, but also may include non-conducting material.As long as the raw material of nucleome meets these i.e. without special limit
System, Exemplary conductive metal, conductive carbon or electroconductive resin etc..Conductive metal it can be mentioned, for example: gold, platinum, copper, nickel,
Aluminium, iron or its alloy etc. or ITO etc. are preferably copper for the aspect of price and electric conductivity.In addition, conductive carbon is preferably
Such as: acetylene black, Ketjen black, furnace black, nano carbon tubes, carbon nanometer fiber, graphite and graphene etc..In addition, in electroconductive resin
Situation, preferably poly- (3,4-rthylene dioxythiophene), polyacetylene and polythiophene etc..It is conductive that nucleome is preferably itself.
Coating is constituted with the conductive material different from nucleome.It can be used in the conductive material of coating, it can
It is illustrated in the cited substance of nucleome.Wherein, meet the purpose of the present invention using the high substance of conductive characteristic.Specifically, compared with
Good is gold, platinum or silver, wherein being more preferably silver.Also, for present technology, conductive material other than metal, for example (,) it is conductive
It, also can be using electroconductive resin etc. as coating if technological progress promotes electric conductivity from now on although the electric conductivity such as property resin are low
Layer.From take into account cut down cost and promoted conductive characteristic from the viewpoint of, preferably using allow coating conductive characteristic it is excellent it
Conductive material, and allow nucleome advantageous conductive material in cost.And it may also set up and lead in the interlayer of nucleome and coating
Electrical middle layer.
Coating, it is preferably coating with the ratio of 1~40 parts by weight relative to the nucleome of 100 parts by weight, be more preferably 5~
30 parts by weight, then be more preferably 5~20 parts by weight.By the coating in the range for using 1~40 parts by weight, then cut down using work
For the conductive material of coating usage amount while, moreover it is possible to draw conductive characteristic.For example, using copper as nucleome, silver
As the situation of coating, conductive characteristic can be maintained on one side, effectively reduce the price of electrically conductive microparticle on one side.
Electrically conductive microparticle according to the present invention, by allow the average value of diameter degree coefficient in above range, and become outer rim
Shape includes the lobate electrically conductive microparticle of at least one of recess and branch leaf, it is known that conductive characteristic can be allowed excellent.This is considered,
Compared to almost without concave-convex or the sheet (squamous) for fluctuatings electrically conductive microparticle, increase the bumps of particle, and allow particle outside
Edge shape, which becomes the lobed shapes comprising at least one of recess and branch leaf, can increase electric conductivity when being configured to flake
Result caused by the contact point of particle.In addition, having the problem for being difficult to filming, but with dendroid electrically conductive microparticle with this hair
Bright electrically conductive microparticle, can filming easily.Because it is more planarized than dendroid.In addition, because nucleome and coating use
Different conductive materials, and can increase material selection, reaching reduces cost.
Also, the electrically conductive microparticle of this case invention is hud typed particle, with single kind of conductive material, manufacture meets above-mentioned
Diameter degree coefficient, outer rim shape particle situation, also may achieve excellent conductive characteristic and filming.Therefore, silver-colored of equal value
The situation that lattice reduce is also useful for single kind of conductive material if can solve the project for reducing cost.In addition, if making
With copper, though there is the problem of reducing conductive characteristic because of oxidation, if can maintain good with the exploitation of anti-oxidation tech
Conductive characteristic, be also useful for single kind of conductive material.
(manufacturing method of electrically conductive microparticle)
The manufacturing method of the electrically conductive microparticle of the present invention is that have: including the nucleome of conductive material, and is coated this core
Body, and be made of the conductive material different from the nucleome, and at least part constitutes the conduction of the coating of outermost layer
The manufacturing method of property particle.In more detail, be to have following steps: preparing conductive dendroid particle, and for by
By collision dendroid particle, make the step of the solid media of the dendroid particle deformation；By allowing dendroid particle and solid matchmaker
Body collides in closed container, make the diameter degree coefficient 0.15 of the dendroid particle acquired with following mathematical expressions (1) with
It is upper, 0.4 hereinafter, and at least one shape in outer rim concave mouth and branch leaf be formed with multiple steps.
Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1)
Hereinafter, in order to allow the present invention electrically conductive microparticle manufacturing method embody, illustrate an appropriate example.But it is not
It is limited by manufacturing method below, but may have various manufacturing methods.
The manufacturing method of the electrically conductive microparticle of the present invention, which includes, prepares conductive dendroid particle, and for by
By colliding this dendroid particle, make the step (step 1) of the solid media of the dendroid particle deformation, and by making dendroid micro-
Grain collides in closed container with solid media, makes the step (step 2) of the dendroid particle deformation.
In step 1, dendroid particle is preparation so-called dendroid (dendron shape) as shown in Figure 3 with conductive characteristic
Particle.Dendroid particle can suitably using have nucleome and coating into lobate electrically conductive microparticle predecessor it is non-lobate
Electrically conductive microparticle.In addition, can also be the dendroid particle that is only made of nucleome.In this respect, after the processing of step 2,
Carry out the step in nucleome setting coating as step 3.
Solid media in step 1, as long as can by collision dendroid particle, allow dendroid particle by mathematical expression
(1) the diameter degree coefficient acquired is 0.15 or more, 0.4 hereinafter, and obtaining outer rim shape and having in recess and branch leaf at least
A kind of electrically conductive microparticle person of plural number formation, that is, be not particularly limited.
Solid media are preferably the materials such as the metals such as steel, glass, zirconium oxide, aluminium oxide, plastics, titanium oxide and ceramics.
And dispersion machine or pulverizer etc. known to ball mill, sand mill etc. can be used in closed container.In addition, the shape of solid media compared with
The good shape few for the bumps such as spherical, ellipticity.The size of solid media is such as 0.1~3mm or so.In addition, solid media
Specific gravity be such as 1.0~10.0 or so.
Step 2, by dendroid particle and solid media investment closed container, dendroid particle is allowed to touch with solid media
It hits.Dendroid particle touches shape via by solid media, deforms dendroid particle, and can obtain leaf for example as shown in Figure 1
Shape electrically conductive microparticle.When manufacturing electrically conductive microparticle, solid media can also be allowed to collide in the presence of resin.Whereby, it can manufacture
While electrically conductive microparticle, aftermentioned electroconductive resin constituent is manufactured.Jitter time and bump bar of the step 2 for collision
Part, as long as the electrically conductive microparticle that can obtain above-mentioned characteristic is not particularly limited.For example, jitter time can be located to 10 minutes~60
Minute.
When manufacturing electrically conductive microparticle, as the object for being added to electrically conductive microparticle, tackifier, dispersing agent, heavy metal can be used
Inerting agent etc..By tackifier is used, particle excessive settlement can inhibit.Tackifier it can be mentioned, for example silica based compound,
Poly- carbonic acid based compound, polyurethane based compound, urea based compound and polyamide-based etc..It, can by dispersing agent is used
More promote the dispersibility of electrically conductive microparticle.It can be mentioned, for example the acidic dispersion agents that are formed by carbonic acid or phosphate for dispersing agent, or
Alkaline dispersing agent comprising amido, with soda acid base neutralize made of salt form dispersing agent.
By heavy metal inerting agent is used, even if being also not easy to interfere electric conductivity in the situation for being mixed into impurity metal ion.
It can be mentioned, for example acetylacetone,2,4-pentanedione, carboxyl benzotriazole based compound, hindered phenolic compound, hydrazine system chemical combination for heavy metal inerting agent
Object, thiamines formic acid based compound, salicylic acid system imidazoles and thiadiazoles system compound etc..In addition, can enumerate has with chemical formula (1) institute
The compound (hereinafter also referred to " compound A ") of the unit of expression is preferable example.
The additive amount of compound A does not limit in the range of without departing from the purport of the present invention, and from aftermentioned electric conductivity
The viscosity stability of resin combination, the stability at any time of the resistance value of conductive sheet, electromagnetic shielding sheet connect
From the point of view of the viewpoint for the stability at any time puted forth effort, relative to the electrically conductive microparticle of 100 parts by weight, preferably 0.1~30 weight
Part.From the point of view of the viewpoint for promoting stability at any time, more than more preferably 0.5 parts by weight.In addition, coming from the viewpoint for reducing cost
It sees, below more preferably 15 parts by weight.
Compound A has various compounds, is not particularly limited, and preferable example can illustrate for example: N- willow acyl group-N '-acetaldehyde hydrazine, N,
N- dibenzylidene (side oxygroup hydrazides), isophathalic acid bis- (2- phenoxy group propiono hydrazines), 3- (N- willow acyl group) amido -1,2,4- hydroxyl
Phenyl) propiono] hydrazine, chemical formula (2) (two willow hydrazides of decanedioic acid) and chemical formula (3) (N, N '-bis- { 3- [3,5- bis- (three-level fourths
Base) -4- hydroxy phenyl] propiono } hydrazine).Wherein, the more preferably compound of chemical formula (2) and chemical formula (3).By including it
Can provide the high electroconductive resin constituent of reliability.When the opportunity of addition is not limited to manufacture electrically conductive microparticle, manufacture is led
The opportunity of mixed conductivity particle and resin after electrical particle can also wait addition after manufacturing electroconductive resin constituent.
As the example of electrically conductive microparticle, illustrate the Production Example of silver-plated copper powder below.
Production Example 1
Firstly, preparing the dendroid silver-plated copper powder for applying silver-colored plating to copper powder.By this silver-plated copper powder and solid media one
It rises and is put into closed container, allow solid media to collide silver-plated copper powder in closed container, dendroid silver-plated copper powder is made to be deformed into this case
The electrically conductive microparticle of invention.By the branch part for allowing solid media to collide silver-plated copper powder, the squama with this case invention can be obtained
The electrically conductive microparticle of piece leaf or branch leaf.Wherein, in the opportunity point of investment silver-plated copper powder, heavy metal inerting agent etc. can also be put into and added
Add agent, and/or is used in the resin of electroconductive resin constituent.By addition electroconductive resin constituent and additive, making
It makes electrically conductive microparticle simultaneously, can also manufacture aftermentioned electroconductive resin constituent.
Production Example 2
Firstly, preparing dendroid copper powder.This copper powder and solid media are put into togerther closed container, in allowing in closed container
Solid media collide copper powder, dendroid copper powder are deformed into the electrically conductive microparticle shape of this case invention.By allowing solid media to touch
The branch part of shape copper powder can obtain the copper powder with scaly leaf or branch leaf.Next, by being handled with plating that silver is coating
On the acquired copper powder with scaly leaf or branch leaf, the conduction with scaly leaf or branch leaf of this case invention can be obtained
Property particle.
(electroconductive resin constituent)
Next, illustrating the electroconductive resin constituent of the present invention.The electroconductive resin constituent of the present invention is comprising this
The electrically conductive microparticle of invention and the object of resin.And in the electroconductive resin constituent of the present invention, in the purpose without departing from the present invention
In the range of, also may include the present invention electrically conductive microparticle other than electrically conductive microparticle.But come from the viewpoint for promoting reliability
It sees, the electrically conductive microparticle other than the electrically conductive microparticle of the present invention, such as relative to the resin of 100 parts by weight, preferably 3 parts by weight
Left and right below.
It is used in the resin of electroconductive resin constituent, thermoplastic resin or hardening resin can be used.Hardening resin
Preferably thermosetting resin or photocurable resin.
Thermoplastic resin can be enumerated: polyolefin-based resins, vinylite, styrene/acrylic system resin, diene series tree
Rouge, terpene resin, Petropols, cellulose-based resin, polyamide, polyurethane resins, polyester resin, poly- carbonic acid
Ester resin, polyimides system resins, fluororesin etc..
Polyolefin-based resins are preferably homopolymers or the copolymers such as ethylene, propylene, alpha-olefin compound.It can specifically arrange
It illustrates such as: EP rubbers, olefin series thermoplastic elastomer, alpha-olefine polymers.
Vinylite is preferably via polymer and vinyl acetate and second obtained by the vinyl acetates such as polymerization vinyl acetate
The copolymer of the olefin(e) compounds such as alkene.Specifically it can be mentioned, for example vinyl-vinyl acetate copolymers, partly-hydrolysed poly- second
Enol etc..
Styrene/acrylic system resin is preferably by styrene, (methyl) acrylonitrile, acrylic amide, (methyl) propylene
Acid esters, maleimide class etc. are formed by homopolymer or copolymer.Specifically, it can be mentioned, for example: to row polyphenyl second
Alkene, polyacrylonitrile, acrylic copolymer, ethylene methyl methacrylate copolymer etc..
Diolefin resins be preferably butadiene or isoprene equiconjugate diolefin compound homopolymer or copolymer and it
Hydride.Specifically it can be mentioned, for example ethylene-butadiene rubber, styrene-isoprene block copolymers etc..
Terpene resin is preferably the polymer or its hydride formed by terpenes.It can specifically enumerate for example: terpene
Olefine resin, hydrogenated terpene resin.
Petroleum line resin is preferably dicyclopentadiene type Petropols, hydrogenated petroleum resin.
Cellulose-based resin is preferably cellulose acetate butyrate resin.
Polycarbonate resin is preferably bisphenol-a polycarbonate.
It is sub- that polyimides system resins are preferably thermoplastic polyimide, polyamide-imide resin, polyamide acid type polyamides
Polyimide resin.
As long as thermosetting resin in 1 molecule have 1 or more can be used in by heating generation cross-linking reaction it
The resin of functional group, functional group for example have hydroxyl, phenolic hydroxyl group, methoxy, carboxyl, amido, epoxy group, oxa- ring
Butane group, oxazoline group, oxazines base, '-aziridino, sulfydryl, isocyanate group, blocked isocyanate base, enclosed type carboxyl,
Silanol group etc., it can be mentioned, for example: acrylic resin, malein acid ester resin, polybutadiene system resin, polyester resin, polyamine
Carbamate resin, epoxy resin, oxetane resin, phenoxy resin, polyimide resin, polyamide, phenol system
Resin, alkyd resin, amine resin, polylactic resin, oxazoline resin, benzoxazine resin, silica resin, fluororesin etc..
In addition, the thermosetting resin of the present invention, other than above-mentioned resin, preferably comprising optionally reacting to be formed with above-mentioned functional group
The resin or low molecular compound of chemical crosslinking etc. are so-called " curing agent ".
As long as photocurable resin can cause the unsaturated bond of cross-linking reaction in 1 molecule with 1 or more by light
Resin, it can be mentioned, for example acrylic resin, malein acid ester resin, polybutadiene system resins, polyester resin, polyamine
Carbamate resin, epoxy resin, oxetane resin, phenoxy resin, polyimide resin, polyamide, phenol system
Resin, alkyd resin, polyimide resin, polylactic resin, oxazoline resin, benzoxazine resin, silica resin, fluororesin etc..
Electroconductive resin constituent preferably deploys the electric conductivity of 50~500 parts by weight relative to the resin of 100 parts by weight
Particle, more preferably 100~400 parts by weight.By the electrically conductive microparticle of 50~500 parts by weight of allotment, electric conductivity can be more promoted, more
Conductive layer easy to form.
Electroconductive resin constituent is in addition to electrically conductive microparticle and resin, adjustable metal inerting agent above-mentioned, tackifier etc.
It is other for example: dispersing agent, silane coupling agent, antirust agent, copper inhibitor (copper inhibitor), reducing agent, antioxidant,
Pigment, dyestuff, solvent misture, plasticizer, ultraviolet absorbing agent, defoaming agent, leveling agent, filler, fire retardant etc..
The manufacture of electroconductive resin constituent, can be as above, before manufacturing electrically conductive microparticle, by the silver-plated powder of dendroid
It is put into simultaneously with resin, allows the collision of circle media to obtain.Come in addition, can also be mixed after manufacturing electrically conductive microparticle with resin
It arrives.It can be illustrated in when resin is mixed in dispersion, resin is added when being dispersed with stirring body with high speed disperser (Dispermat)
Method.
(conductive sheet)
The conductive sheet of the present invention is that have to be formed by conductive layer by the electroconductive resin constituent of the present invention.It is conductive
The manufacturing method of property thin slice is not particularly restricted, as example, can illustrate electroconductive resin constituent being coated on fissility thin slice
On come the method that forms conductive layer.Conductive sheet can be only conductive layer single layer, can also be other functional layers or support layer etc.
Laminate.As functional layer, can enumerate with insulating properties, thermal conductivity, electromagnetic wave absorbability, hard painting propert, water vapor barrier property,
The layer of oxygen barrier performance, low-k, high dielectric constant, low loss factor, high dissipation factor, heat resistance etc..Its
In, in the situation that the conductive sheet of the present invention is used in art of printed circuit boards, from the viewpoint of heat resistance, preferably wrap
Containing thermosetting resin.
The conductive sheet of the present invention can unlimitedly be used in various uses, and example appropriate can be enumerated: different side is conductive
Property thin slice, electrostatic removal thin slice, earthy thin slice, thin film circuit with, electric conductivity cohere thin slice, thermal conductivity thin slice, bridge circuit
With conductive foil etc..
Aforementioned coating method can be used for example: gravure, contact coating (kiss coating) formula, die coating
Formula, lip mouth cloth of coating-type, unfilled corner wheel cloth of coating-type, scraper type, roller coating formula, cutter painting formula, jet printing type, stick apply formula, spin-coating, dip-coating formula
Deng.
The thickness of conductive layer is preferably 1~100 μm, more preferably 3~50 μm in conductive sheet.By thickness 1~100
μm range, can easily take into account electric conductivity and other physical property.
(electromagnetic shielding sheet)
The electromagnetic shielding sheet of the present invention be have the conductive layer formed by the electroconductive resin constituent of the present invention,
And insulating layer, it can be used in for example shielding the purpose from the electromagnetic wave of circuit generation.The manufacturing method of electromagnetic shielding sheet is not
Especially limitation can illustrate the method that conductive layer manufactured by manner described above and insulating layer fit together as example.Absolutely
Preshaped insulating properties film can be used in edge layer, can also be coated on shape on fissility thin slice by by insulative resin constituent
At insulating layer, it is fit together with the conductive layer with fissility thin slice.Alternatively, directly insulative resin can also be formed
Object is coated on the electrically conductive, to form insulating layer.
The thickness of insulating layer can according to purposes with need to change, such as in the situation for being used in flexible printed circuit, from
Flexibility is maintained on one side, from the viewpoint of the shield effectiveness for improving electromagnetic shielding sheet on one side, preferably 2~10 μm.In addition,
The thickness of insulating layer, when the thickness of conductive layer is set as 100, preferably 50~200 ratio.By become aforementioned ratio,
The balance for obtaining various physical property can be allowed to become easy.
The material of insulating properties film is not particularly restricted, it is possible to use the modeling such as polyester, polycarbonate, polyimides, polyphenylene sulfide
Expect film.In addition, can also be by envelope made of the forming of insulative resin constituent.
Insulative resin constituent is using resin as essential component, and this resin is preferably using the tree that can be used in conductive layer
Rouge.And in insulative resin constituent in addition to the resins, also adjustable silane coupling agent, pigment, dyestuff, divides antioxidant
Powder, solvent misture, plasticizer, ultraviolet absorbing agent, defoaming agent, leveling agent, filler, fire retardant etc..
The electromagnetic shielding sheet of the present invention can also have other layers other than conductive layer and insulating layer.Other layers can
It enumerates for example: having hard painting propert, thermal conductivity, thermal insulation, electromagnetic wave absorbability, water vapor barrier property, oxygen barrier performance, low dielectric normal
The layer of number property, high dielectric constant, low loss factor, high dissipation factor, heat resistance etc..And in the electromagnetism wave screen of the present invention
The situation that thin slice is used in art of printed circuit boards is covered, preferably includes thermosetting resin from the viewpoint of heat resistance.
The electromagnetic shielding sheet of the present invention is by being attached to flexible printed base plate, rigid printed base plate, hardness/pliability
The upper heating pressurization such as substrate then, can be used and be used as electromagnetic wave shielding.In addition, can also be placed directly against on the shell of electronic component
It uses.The printed circuit board of electromagnetic shielding sheet equipped with the present invention can be used in for example: the mobile electricity of smartphone etc.
Words, personal computer, tablet terminal, LED illumination, organic EL illuminating, LCD TV, organic EL TV, digital camera, number are taken the photograph
Automobile-used part of shadow machine, automobile etc. etc..
Embodiment
Hereinafter, the present invention is described in more detail with embodiment, but the present invention is not only restricted to this.Also, " part " below and " % "
It is the value based on " parts by weight " and " weight % " respectively.
Table 1 shows the non-lobate electrically conductive microparticle used as raw material.The dendroid silver-plated copper of electrically conductive microparticle 1~7
Powder is the product using mining company of Mitsui Metal Co., Ltd..In addition, the ball of the dendroid copper powder of electrically conductive microparticle 8, electrically conductive microparticle 9
The flakey silver powder of shape silver-plated copper powder and electrically conductive microparticle 11 is the product using Bo Fen industrial group of FUKUDA METAL.Separately
Outside, the flakey silver-plated copper powder of electrically conductive microparticle 10 is the product using mining company of Mitsui Metal Co., Ltd..And wherein, raw material is led
The average grain diameter (D50) of electrical particle is with laser diffraction/13 320 (BECKMAN of scattering method particle size distribution device LS
COULTER corporation) it seeks.
Table 1
The parts by weight of coating: the value of the nucleome relative to 100 parts by weight
Embodiment A (manufacture electrically conductive microparticle)
Non- 1,400.0 part of electrically conductive microparticle lobate of toluene shown in table 1,10.0 parts of the tackifier of 100 parts of measurement
(Japanese AEROSIL corporation AEROSIL R972) and 1.0 parts of heavy metal inerting agent (two willow hydrazides of decanedioic acid), mixing is stirred
It mixes to uniform.Next, it to be put into Eiger Mill (Eiger Japan corporation together with the zirconium oxide bead of diameter 0.5mm
" Mini-model M-250 MKII ") it carries out decentralized processing 10 minutes.5 decantations are carried out to acquired particle with methyl ethyl ketone.
Further by the drying in 100 DEG C of oven, the lobate electrically conductive microparticle of embodiment A is obtained.Measurement the lobate of embodiment A is led
Average grain diameter (D50), thickness, diameter degree coefficient and the circle coefficient of electrical particle.Average grain diameter (D50), thickness are with aforementioned
Method acquires.And diameter degree coefficient with circle coefficient is maked sample with following methods, manner described above calculates.Acquired leaf
The thickness of shape electrically conductive microparticle, average grain diameter (D50), diameter degree coefficient, circle coefficient and covering rate value be recorded in table 2.
Diameter degree coefficient and circle coefficient
Prepared micro- using corresponding electric conductivity as measurement sample with the production method of aftermentioned electromagnetic shielding sheet
The sample of grain.Then, through conductive adhesive by 1cm2Sample be fixed on the cylindrical sample platform of SEM.Specifically, it is
Remove electromagnetic shielding sheet conductive layer side partition, by conductive layer as upper layer, insulating layer for lower layer in the way of be fixed on examination
Expect on platform.Then, electroconductive paste is filled on the conductive layer of electromagnetic shielding sheet, implements platinum vapor deposition.After vapor deposition, with 1000
Again, under the conditions of acceleration voltage 15kV, the SEM image of electroconductive particle is obtained, is in the above way analyzed.
Covering rate
Double faced adhesive tape is attached on dedicated platform, it, will be extra with air after allowing each metallic powder to fall on double faced adhesive tape
Powder blow away.Then, with x-ray photoelectron spectroscopy instrument (ESC-A AXIS-HS, Shimadzu Seisakusho Ltd.'s corporation) measurement 5 is not
Same point.Then, calculating it to analyze software (Kratos corporation) by the peak area of coating (silver) and nucleome (copper)
Covering rate of the average value of the mass concentration % of coating (silver) as silver.
Embodiment B~K, comparative example δ (manufacture electrically conductive microparticle)
In addition to by the raw material of non-lobate electrically conductive microparticle and using Eiger Mill the decentralized processing time, be changed to as
Other than table 2 is recorded, electrically conductive microparticle is manufactured in the method identical as embodiment A.
Manufacture Examples 1 to 20, comparative example 1~4, reference example 1 (electroconductive resin constituent)
The raw material that will be shown in table 3 is put into container, is stirred 5 minutes with dispersion machine, obtains Examples 1 to 20, comparative example 1
~4, the electroconductive resin constituent of reference example 1.
Wherein, the amido formate of base resin is using polyurethane resins (TOYOCHEM corporation), amide
Be using polyamide-imide resin (TOYOCHEM corporation), polyester be using condensed type polyester (TOYOCHEM corporation) and
Add-on type polyester (TOYOCHEM corporation).To the base resin of 100 parts by weight, 10 parts of curing agent (aziridine chemical combination are used
Object).
Table 3
Additive A: two willow hydrazides of decanedioic acid
Additive B: N, N '-bis- { 3- [3,5- bis- (three-level butyl) -4- hydroxy phenyl] propiono } hydrazines
Blending amount: parts by weight
Manufacture the conductive sheet of embodiment 1
Using rod coater by the electroconductive resin constituent of embodiment 1 by allow dry thickness become 5 μm in a manner of
It is coated on the fissility thin slice of ethylene terephthalate, then 2 minutes dry with 100 DEG C of electric oven, obtains that there is conduction
The conductive sheet C1 of layer.
Manufacture the electromagnetic shielding sheet of embodiment 1
Using rod coater thermosetting amido formate resin (TOYOCHEM corporation) is allowed dry thickness at
It is coated on the fissility thin slice of polyethylene terephthalate for 5 μm of modes, then 2 minutes dry with 100 DEG C of electric oven,
Obtain insulating layer.It allows the conductive layer of conductive sheet C1 and aforementioned dielectric layer to overlap, carries out heat by with the condition of 80 DEG C, 2MPa
It crimps, obtains electromagnetic shielding sheet E1.
Manufacture embodiment 2~20, comparative example 1~4, reference example 1 conductive sheet
In addition to replace embodiment 1 electroconductive resin constituent, using the electroconductive resin constituent of embodiment 2~20 with
Outside, conductive sheet C2~C20 is obtained in method same as Example 1.In addition, the electric conductivity tree in addition to replacing embodiment 1
Fat composition, using comparative example 1~4, reference example 1 electroconductive resin constituent other than, obtained in method same as Example 1
To conductive sheet C21~C25.
Manufacture embodiment 2~20, comparative example 1~4, reference example 1 electromagnetic shielding sheet
In addition to replace conductive sheet 1, using being recorded in other than the conductive sheet of table 4, similarly to Example 1 into
Row, obtains electromagnetic shielding sheet E2~E25.
In addition to replace embodiment 1 electroconductive resin constituent, using the electroconductive resin constituent of embodiment 2~20 with
Outside, electromagnetic shielding sheet E2~E20 is obtained by method same as Example 1.In addition, in addition to replace embodiment 1 it
Electroconductive resin constituent, using comparative example 1~4, reference example 1 electroconductive resin constituent other than, with same as Example 1
Method obtain electromagnetic shielding sheet E21~E25.
Table 4
Measurement connection resistance value
Prepare cut growth 25mm, wide 25mm conductive sheet 10, be fixed on wide 25mm, long 100mm, thickness 0.5mm it
The end of stainless steel plate 11 gives hot pressing then by the condition with 80 DEG C, 2MPa, comes temporarily then.Then, fissility is thin
Piece strips, and after an equal amount of stainless steel plate 12 is overlapped as described above, then is thermally compressed with the condition of 80 DEG C, 2MPa
Come temporarily then.The hot pressing for carrying out 30 minutes to it with the condition of 150 DEG C, 2MPa then, obtains the connection resistance for being shown in Fig. 4
Value measurement testing piece.Using this testing piece, by allowing the BSP of Mitsubishi Chemical's ANALYTECH corporation " Roresuta GP " to visit
Head contacts the side B of stainless steel plate 11 and the side A of stainless steel plate 12, measurement connection resistance value such as Fig. 4.Evaluation criteria system is as follows
It states.
A: less than 1.0 × 10-3
B:1.0 × 10-3Above, less than 1.0 × 10-2
C:1.0 × 10-2Above, less than 1.0 × 10-1
D:1.0 × 10-1More than
Measure sheet resistance value
Electromagnetism obtained by being measured using four probes of Mitsubishi Chemical's ANALYTECH corporation " Roresuta GP "
The sheet resistance value of the conductive layer of wave shield sheet.Evaluation criteria system is for example following.
A: less than 1.0
B:1.0 or more, less than 10.0
C:10.0 or more, less than 50.0
D:50.0 or more
On the other hand, using the cyclic annular probe URS of Mitsubishi Chemical's ANALYTECH corporation " HIRESTA-UP ", measurement electricity
The sheet resistance value of the insulating layer of magnetic wave shield sheet.Evaluation criteria system is for example following.
A:1 × 107More than
B: less than 1 × 107、1×106More than
C: less than 1 × 106、1×104More than
D: less than 1 × 104
Measure adhesion
Prepare the electromagnetic shielding sheet of width 25mm, long 70mm.The fissility film that conductive layer will be close to is peelled off, with
150 DEG C, the condition of 1.0MPa, 30min is by 50 μm of thickness of Kapton (DU PONT-TORAY corporation " Kapton
200EN ") pressurization is attached on the conductive layer of exposing, and hardens conductive layer and insulating layer.In order to for measuring and reinforcement electromagnetism
The purpose of wave shield sheet, the fissility film that will be close to thick 50 μm of insulating layer remove, using having used polyurethane
The then thin slice of polyureas system solid, with the condition of 150 DEG C, 1MPa, 30min, by Kapton, (DU PONT-TORAY is public
Department's system " Kapton 200EN ") it pressurizes and sticks together on the insulating layer of exposing." Kapton/electricity is obtained by these steps
The testing piece of the thin slice/Kapton of magnetic wave shield sheet/then ".By to this testing piece, in 23 DEG C, relative humidity
Under 50% environment, with 90 ° of tensile speed 50mm/min, peel angle, by the interface peel of conductive layer and Kapton,
To measure adhesion.
A:8N/25mm or more
B: less than 8N/25mm, 6N/25mm or more
C: less than 6N/25mm, 3N/25mm or more
D: less than 3N/25mm
Annotation
This specification also discloses the invention of the technical idea shown below understood by above-mentioned implementation form.
Annotation 1
A kind of lobate electrically conductive microparticle is to be subject to the nucleome of electric conductivity with the conductive material different from aforementioned nucleome
It is coating to form, and there is a plurality of scaly leafs or branch leaf.
Annotation 2
A kind of manufacturing method of lobate electrically conductive microparticle, it is characterized in that comprise the steps of: by allow solid media collide
With the dendroid particle that the coating electric conductivity nucleome of silver forms, deform aforementioned dendroid electrically conductive microparticle, to obtain with scale
The lobate step for being formed with multiple particles of leaf or branch leaf.
Annotation 3
A kind of electrically conductive microparticle, the diameter degree coefficient acquired with following mathematical expressions (1) be 0.15 or more, 0.4 hereinafter,
And at least one shape in outer rim concave mouth and branch leaf be formed with it is multiple.
Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1)
Present application advocate based on the Japanese patent application case 2012-49680 that on March 6th, 2012 files an application it
Priority, all is included in this for disclosure.
Utilization in industry
The electrically conductive microparticle of the present invention, which can be used as, needs the filler of conductive characteristic to be used in various uses.Comprising the present invention
The electroconductive resin constituent of electrically conductive microparticle and resin can be suitably in various uses.Such as it can be by electroconductive resin
Constituent forms conductive layer, used as conductive sheet and electromagnetic shielding sheet.Conductive sheet can be used in for example: electricity
The purpose of electrical connection between road.The conductive sheet and electromagnetic shielding sheet of the present invention can be suitably used for for example: bear to repeat
Flexible printed circuit, printed circuit board, metal plate and flexible connector of bending etc..
Symbol description
10 samples
11 stainless steel plates
12 stainless steel plates
Claims (8)
1. a kind of electrically conductive microparticle, which is characterized in that
The diameter degree coefficient acquired with following mathematical expressions (1) is 0.15 or more, 0.4 hereinafter, and in outer rim concave mouth and branch
At least one shape in leaf be formed with it is multiple,
Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1),
Wherein, the internal area of the line of the periphery of the formation electrically conductive microparticle when area refers to two-dimensional projection, it is described
The length of the line of periphery when perimeter refers to two-dimensional projection,
The electrically conductive microparticle is made of single conductive material.
2. electrically conductive microparticle according to claim 1, which is characterized in that
It is with a thickness of 0.1 μm or more, 2 μm hereinafter, 10,000 times of images that the thickness refers to electron microscope, measurement 10~20
A difference particle, uses its average value.
3. a kind of electroconductive resin constituent, which is characterized in that
Comprising electrically conductive microparticle as claimed in claim 1 or 2 and resin,
The resin is at least one of thermoplastic resin and thermosetting resin.
4. electroconductive resin constituent according to claim 3,
It has the compound of the unit indicated with following chemical formula (1) for further allotment:
5. electroconductive resin constituent according to claim 4,
Wherein aforementioned Chemistry Figure (1) is to include at least one of following chemical formula (2) and following chemical formula (3):
6. a kind of conductive sheet, which is characterized in that
Have and conductive layer is formed by as the electroconductive resin constituent according to any one of claim 3-5.
7. a kind of electromagnetic shielding sheet, which is characterized in that
Have and conductive layer, and insulation are formed by as the electroconductive resin constituent according to any one of claim 3-5
Layer.
8. a kind of manufacturing method of electrically conductive microparticle,
The manufacturing method the following steps are included:
Prepare conductive dendroid particle, and for becoming the dendroid particle by aforementioned dendroid particle is collided
The step of the solid media of shape；
By allowing aforementioned dendroid particle to collide in closed container with aforesaid solid media, make the dendroid particle by following
Stating the obtained diameter degree coefficient of mathematical expression (1) is 0.15 or more, 0.4 hereinafter, and outer rim shape distortion is allowed to be recess and divide
At least one of branches and leaves are formed with multiple steps,
Diameter degree coefficient=(area × 4 π)/(perimeter)2... mathematical expression (1),
Wherein, the internal area of the line of the periphery of the formation electrically conductive microparticle when area refers to two-dimensional projection, it is described
The length of the line of periphery when perimeter refers to two-dimensional projection,
The electrically conductive microparticle is made of single conductive material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012049680 | 2012-03-06 | ||
| JP2012-049680 | 2012-03-06 | ||
| CN201380012622.XA CN104170023B (en) | 2012-03-06 | 2013-03-05 | Electrically conductive microparticle and manufacture method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380012622.XA Division CN104170023B (en) | 2012-03-06 | 2013-03-05 | Electrically conductive microparticle and manufacture method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet |
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| Publication Number | Publication Date |
|---|---|
| CN106424711A CN106424711A (en) | 2017-02-22 |
| CN106424711B true CN106424711B (en) | 2019-02-15 |
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| CN201380012622.XA Active CN104170023B (en) | 2012-03-06 | 2013-03-05 | Electrically conductive microparticle and manufacture method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet |
| CN201610930540.9A Active CN106424711B (en) | 2012-03-06 | 2013-03-05 | Electrically conductive microparticle and its manufacturing method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet |
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| JP (2) | JP6264731B2 (en) |
| KR (1) | KR102017121B1 (en) |
| CN (2) | CN104170023B (en) |
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| CN104170023B (en) | 2016-12-28 |
| TWI600033B (en) | 2017-09-21 |
| CN106424711A (en) | 2017-02-22 |
| JP2013214508A (en) | 2013-10-17 |
| TW201344703A (en) | 2013-11-01 |
| CN104170023A (en) | 2014-11-26 |
| WO2013132831A1 (en) | 2013-09-12 |
| KR102017121B1 (en) | 2019-09-02 |
| KR20140138136A (en) | 2014-12-03 |
| TW201705156A (en) | 2017-02-01 |
| JP2018067531A (en) | 2018-04-26 |
| TWI546823B (en) | 2016-08-21 |
| JP6264731B2 (en) | 2018-01-24 |
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