CN110016302A - Conductive adhesive compositions and the isotropism conductive film formed by it - Google Patents
Conductive adhesive compositions and the isotropism conductive film formed by it Download PDFInfo
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- CN110016302A CN110016302A CN201811552236.0A CN201811552236A CN110016302A CN 110016302 A CN110016302 A CN 110016302A CN 201811552236 A CN201811552236 A CN 201811552236A CN 110016302 A CN110016302 A CN 110016302A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
Abstract
The present invention relates to a kind of conductive adhesive compositions, more specifically, it is excellent to the bonding force of sticky surface, heat resistance and flexibility are good, excellent electric conductivity can simultaneously be such that uniform filling disperses, so as to the isotropism conductive film that the conductive adhesive compositions of uniform electric conductivity are presented and are formed by it.
Description
Technical field
The present invention relates to a kind of conductive adhesive compositions, more specifically, excellent to the bonding force of sticky surface, heat resistance
Good with flexibility, excellent electric conductivity can simultaneously be such that uniform filling disperses, and glue so as to which the conduction of uniform electric conductivity is presented
Mixture composite and the isotropism conductive film formed by it.
Background technique
In recent years, the miniaturization that component connection is accelerated due to the miniaturization of electronic equipment and multifunction, because
This in Electronic Packaging field, have the various film-form adhesives that can easily connect these terminals be used in IC chip and
The bonding of flexible printing wiring board (FPC), IC chip and the glass substrate that is formed with indium tin oxide (ITO) telegraph circuit etc.
Trend.
In particular, flexible printed circuit board (FPCB) has been used for various fields recently.Flexible printed circuit board is with electronics
The electronic component that the miniaturization and lightweight of product is developed has excellent machinability, heat resistance, bending resistance and chemically-resistant
Drug, also, the higher flexible printed circuit board of heat resistance properly uses.Specifically, as all electronic products
Core component, above-mentioned flexible printed circuit board is widely used in camera, computer and peripheral equipment, mobile phone, video and audio set
Device, video camera, printer, DVD, TFT LCD, satellite equipment, military equipment, Medical Devices etc..Flexible print circuit
Plate can individually carry out three dimensional wiring, and the miniaturization and lightweight of equipment may be implemented.In addition, flexible printed circuit board pair
Alternating bending has high-durability, can be realized high-density wiring, and without wiring error, assembling is good, has high reliability.And
And flexible printed circuit board has the advantages that manufacture in a manner of continuously generating.
In the case where flexible printed circuit board, the circuit for being electrically connected such as flexible printing wiring board (FPC) is needed
The conductive adhesion piece of the circuit element of plate ontology and such as reinforcing plate etc. and for circuit board body and circuit element etc. mutually
The electroconductive binder of the circuit board of electrical connection.
Main feature required by this adhesive is as follows, that is, can be in a relatively short period of time in relatively low temperature
Lower solidification so that thermal damage will not be caused to circuit substrate, and provides electrical connection between the substrates.
On the other hand, existing electroconductive binder is in the presence of the holding that cannot be played to the bonding force and adhesiveness of sticky surface
The problem of all excellent effect such as power, heat resistance, flexibility, electric conductivity and filler dispersibility.
In this regard, there is an urgent need to research and develop following electroconductive binder, that is, heat resistance excellent to the bonding force of sticky surface
Good with flexibility, excellent electric conductivity can simultaneously be such that uniform filling disperses, and glue so as to which the conduction of uniform electric conductivity is presented
Mixture.
Existing technical literature
Patent document
(patent document 1) KR 10-2005-0051089 A
Summary of the invention
Problems to be solved by the invention
The present invention be develop to solve the above-mentioned problems, it is intended that provide it is excellent to the bonding force of sticky surface,
Heat resistance and flexibility are good, and excellent electric conductivity can simultaneously be such that uniform filling disperses, so as to which uniform electric conductivity is presented
Conductive adhesive compositions and the isotropism conductive film formed by it.
The solution to the problem
In order to achieve the above object, the present invention provides a kind of conductive adhesive compositions characterized by comprising main tree
Rouge includes glass transition temperature different the first polyurethane based resin and the second polyurethane based resin；And conductive filler.
An embodiment according to the present invention, the glass transition temperature of first polyurethane based resin can for 30 DEG C~
60 DEG C, the glass transition temperature of second polyurethane based resin can be -5 DEG C~20 DEG C.
Also, the main resin can include the first polyurethane based resin and the second poly- ammonia with 1: 0.2~0.6 weight ratio
Esters resin.
Also, the acid value of first polyurethane based resin can be 15~27mgKOH/g, the second polyurethanes tree
The acid value of rouge can be 29~41mgKOH/g.
Also, the main resin may also include third polyurethane based resin, the vitrifying of the third polyurethane based resin
Transition temperature is -35 DEG C~-10 DEG C.
Also, the main resin can include that the first polyurethane based resin and third are poly- with 1: 0.04~0.2 weight ratio
Urethane resinoid.
Also, the acid value of the third polyurethane based resin can be 2.5mgKOH/g or smaller.
Also, the conductive adhesive compositions may also include epoxylite, the epoxide equivalent of the epoxylite
For 80~300g/eq.
Also, the conductive adhesive compositions may also include 0.1~1 weight relative to the main resin of 100 parts by weight
Measure the defoaming agent of part.
Also, relative to the main resin of 100 parts by weight, the content of the conductive filler can be 60~140 weight
Part.
On the other hand, the present invention provides a kind of conductive adhesive compositions characterized by comprising main resin, including extremely
A kind of few polyurethane based resin；And conductive filler, with 3~20 μm of average grain diameter.
An embodiment according to the present invention, the conductive filler can satisfy following conditions (1) and (2):
(1)
(2)
Wherein, described a, b and c are respectively the D10 (μm), D50 (μm) and D90 (μm) of conductive filler.
Also, the D10 of the conductive filler can for 1~5 μm, D50 can be 5~20 μm, D90 can be 20~35 μ
m。
Also, relative to the main resin of 100 parts by weight, the content of conductive filler can be 60~140 parts by weight.
Also, the apparent density (Apparent Density, AD) of the conductive filler can be 0.4~1, tap density
(Tap Density, TD) can be able to be 3000~5000cm for 0.8~2, specific surface area2/g。
Also, the conductive filler may include the copper particle for being coated with silver on the surface, the weight of the copper and the silver
Amount is than that can be 1: 0.02~0.2.
Also, relative to the main resin of 100 parts by weight, the conductive adhesive compositions may also include 0.1~1 weight
Measure the defoaming agent of part.
On the other hand, the present invention provides a kind of isotropism conductive film characterized by comprising conductive adhesive, by upper
The conductive adhesive compositions stated are formed；And release film, the one side of the conductive adhesive is set.
The effect of invention
Conductive adhesive compositions of the invention and the isotropism conductive film formed by it have the following effects that, that is,
Excellent to the bonding force of sticky surface, heat resistance and flexibility are good, and excellent electric conductivity can simultaneously be such that uniform filling disperses, so as to
Uniform electric conductivity is enough presented.
Detailed description of the invention
Fig. 1 be include one embodiment of the invention conductive adhesive compositions isotropism conductive film sectional view.
Symbol description
100: isotropism conductive film
110: conductive adhesive
111: conductive filler
120: release film
Specific embodiment
In the following, the embodiment of the present invention will be described in detail with reference to the attached drawings, so that those skilled in the art can be easy reality
Existing concept of the present invention.It is to be noted, however, that the present invention is not limited to exemplary embodiment but can be with various other sides
Formula is realized.
The conductive adhesive compositions of an embodiment according to the present invention include: main resin, include glass transition temperature
First polyurethane based resin and the second polyurethane based resin different from each other；And conductive filler.
Firstly, being illustrated to main resin.
As the main resin, as long as being that typically in workable main resin in the conductive adhesive compositions of this field,
It just uses without restriction, it is preferable that may include polyurethane based resin, it is highly preferred that may include glass transition temperature
Two kinds of polyurethane based resins different from each other, it is highly preferred that including glass transition temperature three kinds of polyurethanes different from each other
Bonding force, bonding retentivity, flexibility and the heat resistance aspect for the conductive film that resin is described below may be advantageous.
Glass transition temperature (the Tg of first polyurethane based resin1) it can be 30 DEG C~60 DEG C, it is preferable that it can be with
It is 30 DEG C~50 DEG C, the glass transition temperature (Tg of second polyurethane based resin2) it can be -5 DEG C~20 DEG C, preferably
Ground can be 0 DEG C~20 DEG C.If the glass transition temperature of first polyurethane based resin, can be in warm less than 30 DEG C
It presses and resin flowing occurs in process, if the glass transition temperature of first polyurethane based resin is greater than 60 DEG C,
Adhesive force may reduce in automatic positioning weldering (pre-fixing) step.If also, the vitrifying of second polyurethane based resin
Transition temperature is less than -5 DEG C, then resin flowing can occur in hot pressing process, if second polyurethane based resin
Glass transition temperature is greater than 20 DEG C, then adhesive force may reduce in automatic positioning weldering (pre-fixing) step.
The main resin of an embodiment according to the present invention can include the first poly- ammonia with 1: 0.2~0.6 weight ratio
Esters resin and the second polyurethane based resin, it is preferable that the first polyurethane based resin is included with 1: 0.25~0.55 weight ratio
With the second polyurethane based resin.If the weight ratio of first polyurethane based resin and the second polyurethane based resin less than 1: 0.2,
Bonding force deficiency problem then may occur in automatic positioning weldering (/ 120 DEG C being pre-fixed, less than 1 second) process, if described first is poly-
The weight ratio of urethane resinoid and the second polyurethane based resin is greater than 1: 0.6, then can be processed in hot pressing (150 DEG C, 30Kgf/
cm2, 60 minutes) and resin flow field problem that is resin melting and flowing out occurs in process.
Moreover, the acid value of first polyurethane based resin can be 15~27mgKOH/g, it is preferable that acid value can be
17~25mgKOH/g.If the acid value of first polyurethane based resin is less than the bonding force between 15mgKOH/g, with substrate
It may be decreased, if the acid value of first polyurethane based resin is greater than 27mgKOH/g, the oxidation that conductive filler may occur is asked
The problem of inscribing, and increasing in constant temperature and humidity evaluation and PCT evaluation there may be average resistance.
Also, the acid value of second polyurethane based resin can be 29~41mgKOH/g, it is preferable that acid value can be
31~39mgKOH/g.If the acid value of second polyurethane based resin is less than the bonding force between 29mgKOH/g, with substrate
It may be decreased, if the acid value of second polyurethane based resin is greater than 41mgKOH/g, the oxidation that conductive filler may occur is asked
The problem of inscribing, and increasing in constant temperature and humidity evaluation and PCT evaluation there may be average resistance.
Also, the weight average molecular weight of first polyurethane based resin can be 16,000~23,000, it is preferable that can be with
It is 16,500~22,000, the weight average molecular weight of second polyurethane based resin can be 8,000~15,000, it is preferable that
It can be 8,500~14,000.If the weight average molecular weight of first polyurethane based resin is less than 16,000 or second polyurethane
The weight average molecular weight of resinoid is less than 8,000, then bonding force may reduce between sticky surface or flexibility may decline,
If the weight average molecular weight of the first polyurethane based resin be greater than 23,000 or second polyurethane based resin weight average molecular weight be greater than 15,
000, then heat resistance may reduce.
On the other hand, the main resin of an embodiment according to the present invention may also include third polyurethane based resin, institute
The glass transition temperature for stating third polyurethane based resin is -35 DEG C~-10 DEG C, it is preferable that the third polyurethane based resin
Glass transition temperature be -30 DEG C~-10 DEG C.If the glass transition temperature of the third polyurethane based resin is less than -35
DEG C, then the bubble removal in conductive adhesive compositions may be not easy, and heat resistance can be poor, if the third polyurethane based resin
Glass transition temperature be greater than -10 DEG C, the flexibility for the isotropism conductive film being described below may be decreased, adhesion
It may be decreased.
The main resin of an embodiment according to the present invention can include the first poly- ammonia with 1: 0.04~0.2 weight ratio
Esters resin and third polyurethane based resin, it is preferable that can include the first polyurethanes with 1: 0.06~0.18 weight ratio
Resin and third polyurethane based resin.If the weight ratio of first polyurethane based resin and third polyurethane based resin is less than 1:
0.04, then tack welding and adhesion reduce, flexibility decline.If first polyurethane based resin and third polyurethane based resin
Weight ratio be greater than 1: 0.2, then there may be the viscosity of dry coating to increase, heat resistance reduces, resin flows increased problem.
Also, the acid value of the third polyurethane based resin can be 2.5mgKOH/g or smaller, it is preferable that acid value can be with
For 2.0mgKOH/g or smaller.If the acid value of the third polyurethane based resin is greater than 2.5mgKOH/g, then there may be in PCT
The problem of average circuit resistance increase of evaluation front and back or reduction of pliability.
Moreover, the weight average molecular weight of the third polyurethane based resin can be 24,000~32,000, it is preferable that can be with
It is 25,000~31,000.If the weight average molecular weight of the third polyurethane based resin is less than 24,000, then between sticky surface
Bonding force may be decreased or flexibility may decline, if the weight average molecular weight of third polyurethane based resin is greater than 32,000, then
Heat resistance may be decreased.
It on the other hand, include glass transition temperature in the conductive adhesive compositions of an embodiment according to the present invention
In the case where first polyurethane based resin different from each other, the second polyurethane based resin and third polyurethane based resin, described
One polyurethane based resin, the second polyurethane based resin and third polyurethane based resin can all meet following conditions (3) and condition
(4)。
As condition (3), Ke YiweiPreferably, Ke YiweiAs condition (4), Ke YiweiIt preferably, can be with
For
If in the condition (3),Greater than 70, then the bubble in conductive adhesive compositions is gone
Except the flexibility for the isotropism conductive film that may be not easy, and be described below may be decreased.If also, in the condition
(4) in,
Greater than 1.2, then the bubble removal in conductive adhesive compositions may be not easy, and below will
The flexibility of the isotropism conductive film of description may be decreased.
It is 80~300g/eq's that the conductive adhesive compositions of an embodiment according to the present invention, which may also include epoxide equivalent,
Epoxylite, it is preferable that may also include the epoxylite that epoxide equivalent is 100~280g/eq.If the epoxylite
Epoxide equivalent be less than 80g/eq, then clinging force reduces, and sheet resistance gets higher, and problem is likely to occur in terms of heat resistance, if institute
The epoxide equivalent for stating epoxylite is greater than 300g/eq, then adhesion and clinging force may be decreased.
Wherein, the content of the epoxylite can be 5~30 parts by weight relative to the main resin of 100 parts by weight, excellent
Selection of land can be 10~25 parts by weight.If the content of the epoxylite relative to 100 parts by weight main resin less than 5 weights
The problem of measuring part, being then likely to occur in the heat resistance reduction for the isotropism conductive film being described below.If the epoxies tree
The content of rouge is greater than 30 parts by weight relative to the main resin of 100 parts by weight, then the bonding force between plastic basis material may occur
The problem of reduction.
The conductive adhesive compositions of an embodiment according to the present invention may also include solvent.As the solvent, as long as
Be that typically in workable solvent in adhesive composition, just use without restriction, furthermore, it is possible to using selected from by toluene,
Dimethylformamide, dimethylbenzene, benzene, n- methyl pyrrolidone, n- octylpyrrolidone, dimethyl sulfoxide, ethyl carbitol, fourth
Base carbitol, ethyl cellosolve, butyl cellosolve, dimethyl pyrazole, dipropylene glycol, n-butyl ether, methyl ethyl ketone, methyl-isobutyl
One of group of ketone, cyclohexanone, ethyl acetate, methanol, ethyl alcohol, isopropanol, normal propyl alcohol and butanol composition or multi-solvents, more
Preferably, one of group selected from toluene and dimethylformamide composition or multi-solvents can be used.
Wherein, the content of the solvent can be 10~70 parts by weight relative to the main resin of 100 parts by weight, it is preferable that
It can be 15~65 parts by weight, however, the present invention is not limited thereto.
The conductive adhesive compositions of an embodiment according to the present invention may also include defoaming agent, to remove in composition
In bubble.
As the defoaming agent, as long as this field workable defoaming agent usually in binding compositions, just unrestricted
System ground uses, it is preferable that may include polysiloxanes.
Also, the content of the defoaming agent can be 0.1~1 parts by weight relative to the main resin of 100 parts by weight, preferably
Ground can be 0.2~0.8 parts by weight, however, the present invention is not limited thereto.
Secondly, being illustrated to the conductive filler.
The content of an embodiment according to the present invention, the conductive filler can be relative to the main resin of 100 parts by weight
60~140 parts by weight, it is preferable that can be 65~135 parts by weight.If the content of the conductive filler is relative to 100 parts by weight
Main resin less than 60 parts by weight, then heat resistance reduction may occur, the problem of sheet resistance and circuitous resistance increase.If described
The content of conductive filler is greater than 140 parts by weight relative to the main resin of 100 parts by weight, then there may be what clinging force reduced to ask
Topic.
Conductive adhesive compositions according to another embodiment of the present invention include: main resin, including at least one poly- ammonia
Esters resin；And conductive filler, with 3~20 μm of average grain diameter.
Hereinafter, conductive adhesive compositions according to another embodiment of the present invention will be described, but will omit to it is upper
State the description of the identical part of conductive adhesive compositions.
The average grain diameter of the conductive filler can be 3~20 μm, it is preferable that average grain diameter can be 5~15 μm.If institute
The average grain diameter of conductive filler is stated less than 3 μm, then there may be resins to flow increased problem, if the conductive filler is averaged
Partial size is greater than 20 μm, then since the surface of conductive adhesive is unevenly and there may be bonding force reduction, surface roughness increases
The problem of.
Also, the conductive filler according to another embodiment of the present invention can satisfy following conditions (1) and (2).
As condition (1), Ke YiweiPreferably, Ke YiweiAs condition
(2), Ke YiweiPreferably, Ke Yiwei
Wherein, described a, b and c are respectively the D10 (μm), D50 (μm) and D90 (μm) of conductive filler.
If in the condition (1),Greater than 56, then it is stained with out in the surface for the conductive adhesive being described below
The amount of conductive filler can increase, and may cause surface roughness since the surface of conductive adhesive is uneven and increase,
Tack welding, adhesion and clinging force reduce.If also, in the condition (2),Greater than 8, then the conduction that is described below
The amount that conductive filler out is stained in the surface of adhesive layer can increase, and may lead since the surface of conductive adhesive is uneven
Surface roughness is caused to increase, tack welding, adhesion and clinging force reduce.
On the other hand, the D10 of the conductive filler can be 1~5 μm, it is preferable that D10 can be 1.5~4.5 μm, D50
It can be 5~20 μm, it is preferable that D50 can be 5.5~19 μm, and D90 can be 20~35 μm, it is preferable that D90 can be 21
~33 μm.
If the D10 of the conductive filler is less than 1 μm, due to being stained with out in the surface for the conductive adhesive being described below
Conductive filler amount increase and may cause tack welding, adhesion and clinging force reduce, if the D10 of the conductive filler is greater than
5 μm, then it may cause surface roughness because the surface of conductive adhesive is uneven and increase, tack welding, adhesion and abutting
Power reduces.If also, the D50 of the conductive filler is less than 5 μm, due in the surface for the conductive adhesive being described below
The amount for being stained with conductive filler out increases and may cause tack welding, adhesion and clinging force reduces, if the D50 of the conductive filler
Greater than 20 μm, then may cause surface roughness since the surface of conductive adhesive is uneven and increase, tack welding, adhesion and
Clinging force reduces.If also, the D90 of the conductive filler is less than 20 μm, due to the conductive adhesive that is described below
The amount that conductive filler out is stained in surface increases and may cause tack welding, adhesion and clinging force reduces, if the conduction is filled out
The D90 of material is greater than 35 μm, then may cause surface roughness since the surface of conductive adhesive is uneven and increase, tack welding,
Adhesion and clinging force reduce.
The apparent density (Apparent Density, AD) of conductive filler according to another embodiment of the present invention can be
0.4~1.0, it is preferable that apparent density can be 0.5~0.8, tap density (Tap Density, TD) can for 0.8~
2.0, it is preferable that tap density can be 0.9~1.5, if the apparent density of the conductive filler less than 0.4, there may be
The problem of specific surface area increases, and dispersibility reduces, and adhesion declines.It, may if the apparent density of the conductive filler is greater than 1
Conductivity is caused to reduce in the presence of volume is reduced compared with same amount, and the problem of sheet resistance increase.If also, described leading
The tap density of electric filler is less than 0.8, then the specific surface area of conductive filler increases, and the oil absorption of resin is caused to increase, thus viscous
Resultant force reduces, and thickness greatly reduces in hot pressing.It, may hair if the tap density of the conductive filler is greater than 2.0
The settlement issues of raw conductive filler, and there is resin flow field problem since the oil absorption of resin is less.
Also, the specific surface area of the conductive filler can be 3000~5000cm2/ g, it is preferable that can for 3200~
4800cm2/g.If the specific surface area of the conductive filler is less than 3000cm2/ g, then there may be the settlement issues of conductive filler and
The problem of reducing volume compared with same amount and conductivity caused to reduce, thereby increases and it is possible to there are problems that resin flows increase.If institute
The specific surface area for stating conductive filler is greater than 5000cm2/ g, then increase there may be the oil absorption due to resin and viscosity increases, point
The problem of dissipating property reduces, and bonding force declines.
On the other hand, as conductive filler according to another embodiment of the present invention, as long as this field usually can be used
Material, just use without restriction, it is preferable that using on the surface be coated with silver copper particle just in terms of electric conductivity possibility
It is advantageous.
Wherein, in the copper particle for being coated with silver on the surface, the weight ratio of the copper and the silver is 1: 0.02
~0.2, preferably 1: 0.05~0.15, this is from the perspective of electric conductivity, it may be possible to advantageous.
As the shape of the conductive filler, as long as the shape for the filler that this field usually can be used, just unrestricted
System, it is preferable that can be used has in the group being made of slice-shaped, spherical shape, dendroid shape, granulated and fiber shape extremely
The conductive filler of few a kind of shape, it is highly preferred that can be used with selected from being made of dendroid shape, slice-shaped and fiber shape
The conductive filler of at least one of group shape.
On the other hand, as shown in Figure 1, isotropism conductive film 100 according to the present invention includes: conductive adhesive 110, by
Above-mentioned conductive adhesive compositions are formed；And release film 120, the one side of the conductive adhesive 110 is set.
Firstly, being illustrated to conductive adhesive 110.
The conductive adhesive 110 can be different according to required type of purposes and sticky surface etc., therefore, in this hair
This is not particularly limited in bright.As an example, conductive adhesion included in isotropism conductive film 100 according to the present invention
The thickness of layer 110 can be 20~100 μm, it is preferable that thickness can be 30~80 μm, however, the present invention is not limited thereto.
Also, the conductive adhesive 110 may include evenly dispersed conductive filler 111 in this layer.
Secondly, being illustrated to release film 120.
As the release film 120, as long as being that typically in the release film that can be used in isotropism conductive film, not by
Limitation ground uses, it is preferable that PET film can be used, it is highly preferred that can be used coated in silicone resin, fluorine and acrylic acid
At least one PET film, however, the present invention is not limited thereto.
Also, the thickness of the release film 120 can be different according to the thickness of conductive adhesive 110, it is preferable that thickness
It can be 20~100 μm, it is highly preferred that thickness can be 30~80 μm, however, the present invention is not limited thereto.
Moreover, the off-type force as the release film 120, as long as the release film for being generally arranged at bonding film have from
Type power, it is just unrestricted, it is preferable that off-type force can be 100~300gf/inch, it is highly preferred that can be 150~250gf/
Inch, however, the present invention is not limited thereto.
On the other hand, the residual adhesive rate of the release film 120 can be 93% or bigger, it is preferable that can be 95%
Or it is bigger.Wherein, residual adhesive rate refers to when Initial adhesion is 100, to the ratio by the bonding force after 24 hours
Rate.As an example, when Initial adhesion is 100, the bonding force after passing through 24 hours relative to Initial adhesion is 95
In the case where, residual adhesive rate can be 95%.
On the other hand, conductive adhesive compositions of the invention and the isotropism conductive film formed by it are with as follows
Effect, that is, excellent to the bonding force of sticky surface, heat resistance and flexibility are good, and excellent electric conductivity simultaneously can make uniform filling point
It dissipates, so as to which uniform electric conductivity is presented.
The present invention is more specifically described below with reference to embodiment, but the following example is not necessarily to be construed as limiting this hair
Bright range, and should be interpreted to promote the understanding of the present invention.
<embodiment 1>
(1) prepared by conductive adhesive compositions
Firstly, in the solvent made of through the weight ratio mixed toluene and dimethylformamide with 1: 0.14, as leading
Electric filler, mixing apparent density be 0.7, tap density 1.1, specific surface area 4,100cm2/ g, oxygen are equal to or less than
0.07% and average grain diameter be 8 μm be coated with silver copper particle.Wherein, the weight ratio of copper and silver is 1: 0.11, and the conduction is filled out
The size distribution D10 of material is 2.7 μm, and D50 is 8.6 μm, and D90 is 21.5 μm.
Main resin is mixed in the solvent for being mixed with conductive filler mixture is made, the main resin passes through with 1: 0.4
Weight ratio mixing weight average molecular weight be 18,000, glass transition temperature (Tg1) be that 40 DEG C and acid value are 21mgKOH/g the
One polyurethane based resin and weight average molecular weight are 13,000, glass transition temperature (Tg2) it be 10 DEG C and acid value is 35mgKOH/g
The second polyurethane based resin form.
Wherein, in the mixture, relative to the main resin of 100 parts by weight, the content of the solvent is 42 parts by weight, described
The content of conductive filler is 114 parts by weight.
In the mixture, hybrid epoxidized equivalent is 190g/eq as the bisphenol-A of epoxylite and as defoaming
The polysiloxanes of agent, so that the main resin relative to 100 parts by weight, the content of bisphenol-A is 20 parts by weight, the content of polysiloxanes
For 0.6 parts by weight, then by using bubble is removed in vacuo to prepare conductive adhesive compositions.
(2) isotropism conduction film preparation
As release film, surface be coated with silicone resin, with a thickness of 50 μm, off-type force be 200gf/inch and residual adhesive
In the one side for the PET film that rate is 97%, the conductive adhesive compositions of the preparation are applied, are then dried, to make
At the isotropism conductive film with the conductive adhesive with a thickness of 50 μm.
<embodiment 2~42 and comparative example 1~4>
Glass transition temperature, weight ratio, quantity, acid in addition to changing polyurethane based resin as shown in the following table 1 to table 7
Value, the epoxide equivalent of epoxylite, the average grain diameter of conductive filler and size distribution (D10, D50 and D90), filer content,
Except apparent density and tap density, it is conductive that the isotropism as shown in table 1 to table 7 is prepared in the same manner as example 1
Film.
<experimental example 1>
Physical property below the isotropism conductive film prepared according to examples and comparative examples is evaluated, is tied
Fruit is shown in the following table 1 into table 7.
1. surface finish measurement
For the isotropism conductive film prepared according to examples and comparative examples, measured using the surface roughometer
Surface roughness Ra value is shown in the following table 1 into table 7.
2. tack welding and adhesion evaluation
For the isotropism conductive film prepared according to examples and comparative examples, judge in the circuitous resistance sample preparation
Whether by positioning Welding in technique, so that adhesion evaluation result is shown in the following table 1 into table 7.
3. sheet resistance measures
For the isotropism conductive film prepared according to examples and comparative examples, surface electricity is measured using surface resistivity meter
Resistance, measures at 9 points to obtain average resistance, is as a result shown in the following table 1 into table 7.
<experimental example 2>
By the isotropism conductive film prepared according to examples and comparative examples and stiffening plate (SUS) hot laminating (120 DEG C, 0.5
Second), release film is removed, then tack welding (120 DEG C, 0.5 second, pre-fix) are carried out on flexible printed circuit board, by hot pressing
(150℃30Kgf/cm2, 60 minutes) process and baking (160 DEG C, 60 minutes), to prepare circuitous resistance sample.It evaluates following
Physical property, result is shown in the following table 1 into table 7.
1. circuitous resistance measures
Foregoing circuit resistance sample system is based on to the isotropism conductive film prepared according to examples and comparative examples is used
The resistance of the sample of Preparation Method preparation measures, and obtains circuitous resistance by measuring the average resistance of 10 samples, ties
Fruit is shown in table 1 into table 7.
2. reflux evaluation
Foregoing circuit resistance sample preparation is based on using the isotropism conductive film prepared according to examples and comparative examples
Method prepares sample, to make 10 prepared circuitous resistance samples by 260 DEG C of peak backflow testers twice before and it
Average circuit resistance afterwards measures, as the result is shown in table 1 into table 7.
3. floating weldering evaluation
Foregoing circuit resistance sample preparation is based on using the isotropism conductive film prepared according to examples and comparative examples
Method prepares sample, for making 10 prepared circuitous resistance samples, to using lead bath by solder at a temperature of 260 ± 5 DEG C
Fusing and immerse within every 10 seconds the sample it is primary before and after average circuit resistance measure, as the result is shown in table 1
Into table 7.
4. constant temperature and humidity is evaluated
Foregoing circuit resistance sample preparation is based on using the isotropism conductive film prepared according to examples and comparative examples
Method prepares sample, to before placing 10 prepared circuitous resistance samples 96 hours at 85 DEG C of temperature and 85% humidity
Average circuit resistance later measures, as the result is shown in table 1 into table 7.
5.PCT evaluation
Foregoing circuit resistance sample preparation is based on using the isotropism conductive film prepared according to examples and comparative examples
Method prepares sample, places under 121 DEG C of temperature, 2 atmospheric pressure and 100% humidity to by 10 prepared circuitous resistance samples
Average circuit resistance before and after 12 hours measures, as the result is shown in table 1 into table 7.
6. thermal shock is evaluated
Foregoing circuit resistance sample preparation is based on using the isotropism conductive film prepared according to examples and comparative examples
Method prepares sample, withIt is recycled for one, measurement passes through the sample
Average circuit resistance before and after 100 circulations, as the result is shown in table 1 into table 7.
7. resin flowing evaluation
Foregoing circuit resistance sample preparation is based on using the isotropism conductive film prepared according to examples and comparative examples
Method prepares sample, in 10 prepared circuitous resistance samples, to the tree revealed between SUS and flexible printed circuit board
The average value of rouge measures, as the result is shown in table 1 into table 7.
<experimental example 3>
By the isotropism conductive film prepared according to examples and comparative examples and stiffening plate (SUS) hot laminating (120 DEG C, 0.5
Second), release film is removed, then carries out tack welding (120 DEG C, 0.5 second, pre-fix) on polyimides portion (cover film), is passed through
Hot pressing (150 DEG C of 30Kgf/cm2, 60 minutes) process and baking (condition: 160 DEG C, 60 minutes), thus prepare length be 150mm
And width is the polyimides clinging force sample of 10mm.
By isotropism conductive film and stiffening plate (SUS) hot laminating (120 DEG C, 0.5 second), release film is removed, is then being plated
Tack welding (120 DEG C, 0.5 second, pre-fix) are carried out in golden portion (Au), by hot pressing (150 DEG C of 30Kgf/cm2, 60 minutes) and process
With baking (160 DEG C, 60 minutes), to prepare the golden clinging force sample that length is 150mm and width is 10mm.
Then, the physical property below polyimides clinging force sample and golden clinging force sample is evaluated.It is tied
Fruit is shown in table 1 into table 7.
1. clinging force measures
For the isotropism conductive film prepared according to examples and comparative examples, measurement passes through the polyimides clinging force
The clinging force of sample and the sample of golden clinging force sample preparation methods preparation, wherein clinging force 180 ° peel angle and
The average value of 10 samples is measured under conditions of the peeling rate of 50mm/min to obtain, result is shown in the following table 1 to table 7
In.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
By the table 1 to table 7 it is found that being all satisfied the glass transition temperature of preferred polyurethane based resin according to the present invention
Degree, weight ratio, quantity, acid value, epoxylite epoxide equivalent etc. embodiment 1,3,4,7,8,16,18 and 19 be unsatisfactory for
The embodiment 2,5,6,9~15,17,20~26 of wherein at least one is compared with comparative example 1 and 2, and adhesion is good, rough surface
Degree, sheet resistance and circuitous resistance are lower, reflux evaluation, floating weldering evaluation, constant-humidity constant-temperature evaluation, PCT evaluation and thermal shock evaluation
As a result excellent, resin flowing is lower, and clinging force is good.
Also, know average grain diameter, size distribution (D10, D50 for being all satisfied preferred conductive filler according to the present invention
And D90), filer content, apparent density and tap density etc. embodiment 27,28,30 and 32 and be unsatisfactory for wherein at least one
Embodiment 29,31,33~42, comparative example 3 compared with 4, adhesion is good, surface roughness, sheet resistance and circuitous resistance
Lower, reflux evaluation, floating weldering evaluation, constant-humidity constant-temperature evaluation, PCT evaluation and thermal shock evaluation result are excellent, resin flow value compared with
Low, clinging force is good.
As above one embodiment of the invention is illustrated, but purport of the invention is not limited to the implementation in the present invention
Example, those skilled in the art, can be by holding the additional of constitutive requirements, modification, deletion, increase etc. in identical main scope
It changes places and proposes other embodiments, and these belong to main scope of the invention.
Claims (18)
1. a kind of conductive adhesive compositions characterized by comprising
Main resin includes glass transition temperature different the first polyurethane based resin and the second polyurethane based resin；And
Conductive filler.
2. conductive adhesive compositions according to claim 1, which is characterized in that
The glass transition temperature of first polyurethane based resin is 30 DEG C~60 DEG C, the glass of second polyurethane based resin
Glass transition temperature is -5 DEG C~20 DEG C.
3. conductive adhesive compositions according to claim 1, which is characterized in that
The main resin includes the first polyurethane based resin and the second polyurethane based resin with 1: 0.2~0.6 weight ratio.
4. conductive adhesive compositions according to claim 1, which is characterized in that
The acid value of first polyurethane based resin is 15~27mgKOH/g, and the acid value of second polyurethane based resin is 29
~41mgKOH/g.
5. conductive adhesive compositions according to claim 1, which is characterized in that
The main resin further includes third polyurethane based resin, and the glass transition temperature of the third polyurethane based resin is-
35 DEG C~-10 DEG C.
6. conductive adhesive compositions according to claim 5, which is characterized in that
The main resin includes the first polyurethane based resin and third polyurethane based resin with 1: 0.04~0.2 weight ratio.
7. conductive adhesive compositions according to claim 5, which is characterized in that
The acid value of the third polyurethane based resin is 2.5mgKOH/g or smaller.
8. conductive adhesive compositions according to claim 1, which is characterized in that it further include epoxylite, the ring
The epoxide equivalent of oxygen resinoid is 80~300g/eq.
9. conductive adhesive compositions according to claim 1, which is characterized in that the master relative to 100 parts by weight
Resin further includes the defoaming agent of 0.1~1 parts by weight.
10. conductive adhesive compositions according to claim 1, which is characterized in that the master relative to 100 parts by weight
Resin, the content of the conductive filler are 60~140 parts by weight.
11. a kind of conductive adhesive compositions characterized by comprising
Main resin, including at least one polyurethane based resin；And
Conductive filler, with 3~20 μm of average grain diameter.
12. conductive adhesive compositions according to claim 11, which is characterized in that
The conductive filler is all satisfied following conditions (1) and (2):
(1)
(2)
Wherein, described a, b and c are respectively the D10 (μm), D50 (μm) and D90 (μm) of conductive filler.
13. conductive adhesive compositions according to claim 11, which is characterized in that the D10 of the conductive filler be 1~
5 μm, D50 be 5~20 μm, D90 is 20~35 μm.
14. conductive adhesive compositions according to claim 11, which is characterized in that relative to described in 100 parts by weight
Main resin, the content of conductive filler are 60~140 parts by weight.
15. conductive adhesive compositions according to claim 11, which is characterized in that the apparent density of the conductive filler
For 0.4~1, tap density be 0.8~2, specific surface area is 3000~5000cm2/g。
16. conductive adhesive compositions according to claim 11, which is characterized in that
The conductive filler includes the copper particle for being coated with silver on the surface, the weight ratio of the copper and the silver for 1: 0.02~
0.2。
17. conductive adhesive compositions according to claim 11, which is characterized in that relative to described in 100 parts by weight
Main resin further includes the defoaming agent of 0.1~1 parts by weight.
18. a kind of isotropism conductive film characterized by comprising
Conductive adhesive, as being formed according to claim 1 to conductive adhesive compositions described in any one of 17；And
The one side of the conductive adhesive is arranged in release film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0175562 | 2017-12-19 | ||
| KR1020170175562A KR102066206B1 (en) | 2017-12-19 | 2017-12-19 | Conductive adhesive composition and isotropic conductive film formed with the same |
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| Publication Number | Publication Date |
|---|---|
| CN110016302A true CN110016302A (en) | 2019-07-16 |
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| CN201811552236.0A Pending CN110016302A (en) | 2017-12-19 | 2018-12-18 | Conductive adhesive compositions and the isotropism conductive film formed by it |
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| Country | Link |
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| KR (1) | KR102066206B1 (en) |
| CN (1) | CN110016302A (en) |
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| CN113529432A (en) * | 2020-04-22 | 2021-10-22 | 财团法人纺织产业综合研究所 | Conductive fabric and preparation method thereof |
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| KR102258039B1 (en) * | 2020-12-21 | 2021-05-28 | 주식회사 에스아이피 | Conductive ink composition for discharging electrostatic charges |
| KR102255284B1 (en) * | 2021-01-25 | 2021-05-25 | 주식회사 에스아이피 | Conductive ink composition for discharging electrostatic charges |
| KR102311044B1 (en) * | 2021-05-12 | 2021-10-12 | 주식회사 에스아이피 | Conductive ink composition for discharging electrostatic charges |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106068317A (en) * | 2014-06-30 | 2016-11-02 | 大自达电线股份有限公司 | Electric conductivity plastering agent constituent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8810701D0 (en) * | 1988-05-06 | 1988-06-08 | Bostik Ltd | Hot-melt polyurethane adhesive compositions |
| KR20050051089A (en) | 2003-11-27 | 2005-06-01 | 나노캠텍주식회사 | Manufacture of conductive pressure sensitive adhesion protective film |
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2017
- 2017-12-19 KR KR1020170175562A patent/KR102066206B1/en active IP Right Grant
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2018
- 2018-12-18 TW TW107145681A patent/TW201927970A/en unknown
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|---|---|---|---|---|
| CN106068317A (en) * | 2014-06-30 | 2016-11-02 | 大自达电线股份有限公司 | Electric conductivity plastering agent constituent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113529432A (en) * | 2020-04-22 | 2021-10-22 | 财团法人纺织产业综合研究所 | Conductive fabric and preparation method thereof |
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| TW201927970A (en) | 2019-07-16 |
| KR20190074151A (en) | 2019-06-27 |
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