CN106057292A - Substrate having a conductive film, a method for producing the same, and a conductive paste for a polyimide substrate - Google Patents
Substrate having a conductive film, a method for producing the same, and a conductive paste for a polyimide substrate Download PDFInfo
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- CN106057292A CN106057292A CN201610204778.3A CN201610204778A CN106057292A CN 106057292 A CN106057292 A CN 106057292A CN 201610204778 A CN201610204778 A CN 201610204778A CN 106057292 A CN106057292 A CN 106057292A
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- conducting film
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- silver powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- Spectroscopy & Molecular Physics (AREA)
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- Non-Insulated Conductors (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The present invention provides a substrate provided with a conductive film having a silver conductive film which is excellent in electrical conductivity and adhesion to a polyimide substrate at a low temperature of 300 DEG C or lower, and a method of manufacturing the same And a conductive paste for the substrate. The conductive paste used as the silver powder is a silver powder coated with a coating agent containing a coating agent of a rosin, a fatty acid or an amine in a range of 2.3 mass% or less with respect to the mass of the silver powder, Therefore, even if the sintering treatment is carried out at a low temperature of 300 DEG C or less, the sintering of the silver powder proceeds sufficiently, so that high electrical conductivity and high adhesion to the polyimide substrate can be obtained. Therefore, in the substrate having the conductive film, the constituent components of the silver conductive film and the polyimide substrate intrude into one another within a range of the thickness of the silver conductive film, and the concavo-convex surface formed therefrom is their interface, The contact area increases, and the electrical conductivity and the adhesion are improved.
Description
Technical field
The present invention relates on polyimide substrate, possess the substrate with conducting film of conducting film, its system
Make method and be suitable for being formed the conductive paste of its conducting film.
Background technology
Such as, the electric conductivity that the distribution of circuit substrate is formed, the electrode formation etc. of electronic component is used
Stick with paste, comprise electroconductive powder, resinoid bond, organic solvent and the frit contained as desired
Deng inorganic filler.This conductive paste is roughly divided into heat cure type and burns till type, described thermosetting
Change type can by substantially 300 (DEG C) below in a low temperature of implement heat treatment and on substrate formation
Electrically conductive film, described in burn till type and formed lead by implementing to burn till process at a temperature of more than 400 (DEG C)
Body film.
In the former heat cure type, employ heat reactive resin as resinoid bond, at heat
Reason makes this heat reactive resin be solidified to form conducting film.The type have owing to treatment temperature is low without
Select substrate material advantage, but electroconductive powder when contacting with each other only by resinoid bond
Fixing, and resin can remaining, therefore its difficult point is that resistance value is high, and thermostability and reliably and with long-term
Property is low.
On the other hand, the latter burns till in type, by burn till process sinter electroconductive powder itself,
Or sintered frit is consequently formed conducting film in addition.The type sinters while burning resin
Electroconductive powder, therefore has resistance value low, thermostability and the high advantage of long-term reliability, but needs
Carry out high temperature burns till process, and therefore its difficult point is to be applicable to resin substrate, and manufacturing cost also becomes
High.
Citation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-310022 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-252140 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2011-065783 publication
Summary of the invention
It addition, the thermostability as a kind of polyimide substrate of resin substrate is high and pliability is excellent,
Therefore the substrate of the electronic equipments such as portable terminal device it is widely used in.Polyimide substrate is formed and joins
The main stream approach of line, is the method pressed attached copper to implement etch processes and form pattern, in order to make conductor join
Line low resistance, once to using silk screen printing etc. to be discussed with thick film formation.As it was previously stated, tree
Aliphatic radical plate cannot use the conductive paste burning till type, therefore from the most just improving heat cure in trial
The conductive paste of type, but do not obtain enough electric conductivity.
Such as, it is proposed that in the conductive paste comprising electroconductive powder, solvent and binding agent, this glues
Mixture comprises one or more (the reference patent documentations in aluminium compound and silane coupler
1).This conductive paste forms conducting film by implementing dried at 200 (DEG C), but than resistance is
2.9×10-5(Ω cm)～6.1 × 10-5(Ω cm) left and right, rests on the value that comparison is high.Think that calorize is closed
Thing and silane coupler can make electric conductivity reduce.
It addition, it is proposed that a kind of electric conductivity is black, it comprises: tap density is 1.0～10.0 (g/cm3)、
D50 particle diameter is 0.3～5 (μm), BET specific surface area 0.3～5.0 (m2/ g) electroconductive particle；Number is all
Molecular weight is 10000～300000, the epoxy resin of hydroxyl value 2～300 (mgKOH/g)；And can be with
Hydroxyl generation alcohol exchange reaction in this epoxy resin, relative to this epoxy resin of 100 weight portions be
The metallo-chelate (with reference to patent documentation 2) of 0.2～20 weight portions.Describe this electric conductivity ink for printing
Forming high-precision conductive pattern, relative to the excellent adhesion of polyimide substrate, but it is with upper
Stating paste is heat cure type equally, and resistivity is up to 5.0 × 10-5(Ω cm) left and right, electric conductivity is insufficient.
On the other hand, such as it is proposed that a kind of conductive paste burning till type, it comprises by the most once
Particle diameter be the following group of metallic 1 of 50 (nm), average primary particle diameter be the gold of more than 100 (nm)
Belong to the metal powder constituent that the group of particle 2 is constituted；Thermoplastic resin；And disperse medium, the matter of metal
Measure and show 94～98 (%) (with reference to patent documentation 3) relative to the ratio of the total quality of metal and resin.
According to this conductive paste, polyimide substrate forms film with silk screen printing etc., in 200 (DEG C) left and right
In a low temperature of burn till, can obtain having taken into account the conducting film of electric conductivity and adaptation.
But, above-mentioned conductive paste not yet replaces copper and presses attached distribution, it is also desirable to further improve.Lead
Though electrically have a certain degree of improvement but and insufficient, and need 50 (nm) metal fine powder below
End, therefore cost is high and operability is poor.In above-mentioned patent documentation 3, describe and only use mean diameter
It is that the conductive paste of metallic of more than 100 (nm) is as the low comparative example of electric conductivity, it is believed that this is
The reason the most fully carried out due to the sintering of metal dust.In order to improve its agglutinating property, it is mixed with
50 (nm) micropowder below.
The present invention completes with above-mentioned condition as background, its object is to provide a kind of electric conductivity and
For polyimide substrate excellent adhesion the substrate with conducting film possessing silver conductive film, its
Manufacture method and can be used in manufactures this and conducts electricity with the polyimide substrate of the substrate of conducting film
Property stick with paste.
In order to reach this purpose, the purport of the 1st invention is, a kind of one side at polyimide substrate
Possess the substrate with conducting film comprising silver as the conducting film of conductor composition, described conducting film and institute
The constituent stating polyimide substrate crosses their interface below the gauge of this conducting film
Scope mutually invades the opposing party, and the male and fomale(M&F) being consequently formed becomes its interface.
It addition, the purport of the 2nd invention for reaching described purpose is, one will be containing silver conduct
The manufacturer of the substrate with conducting film that the conducting film of conductor composition is formed on polyimide substrate
Method, including: (a) will comprise the conductive paste of silver powder, resinoid bond and organic solvent described poly-
With the paste painting process of predetermined pattern coating on acid imide substrate, the surface attachment in described silver powder has
Comprise the smears of the scheduled volume of at least one among Colophonium, fatty acid and amine；(b) pass through
Implement to burn till process under the maximum temperature of 250～300 (DEG C) and make silver sintering, described conductive paste generate
The firing process of conducting film.
It addition, the purport of the 3rd invention for reaching described purpose is, a kind of polyimide substrate
With conductive paste, it is to manufacture the base with conducting film for formation conducting film on polyimide substrate
The polyimide substrate conductive paste of plate, it comprises silver powder, resinoid bond and organic solvent,
Described silver powder is the silver powder of attachment smears, is calculated as with the mass ratio relative to this silver powder
2.3 (%) amount below has in surface attachment and comprises at least one among Colophonium, fatty acid and amine
Smears.
According to described 1st invention, for conducting film and polyimide substrate, their constituent with
Scope below the gauge of conducting film mutually invades the opposing party, and the male and fomale(M&F) being consequently formed becomes it
Interface, therefore along with the increase of contact area, electric conductivity and adaptation improve.Therefore, can obtain
To possess have high conductivity and with the conducting film of the high adhesion of polyimide substrate with conducting film
Substrate.
It addition, according to described 2nd invention, polyimide substrate forms conducting film and manufacture with
During the substrate of conducting film, in sticking with paste painting process, applied conductive paste, as silver powder, uses
The argentum powder of the attachment smears of the smears comprising Colophonium, fatty acid or amine is had in its surface attachment
End, therefore in firing process, even if the low temperature in the range of 250～300 (DEG C) is implemented to burn till process,
Sintering also can be sufficiently carried out, and has high conductivity and for polyimide substrate so can obtain possessing
The substrate with conducting film of conducting film of high adhesion.When firing temperature is less than 250 (DEG C), sintering
Insufficient carrying out, on the other hand, even more than 300 (DEG C), electric conductivity, adaptation also will not carry especially
Height, so only can produce the unfavorable condition that polyimide substrate causes excessive heat.
Furthermore, containing silver powder as the conductive paste of conductor composition, aforesaid if not using
The special paste of 50 (nm) micropowder below, generally would not 300 (DEG C) below in a low temperature of burn
Knot.Therefore, for the resin substrate of polyimide substrate etc., generally use thermohardening type and stick with paste, but this
It is but that silver powder utilizes when contacting with each other heat reactive resin to fix, therefore can not get
High electric conductivity.But, in the present invention, it not by fixing that heat reactive resin brings, but silver-colored
Powder itself sinters.The reason that such agglutinating property improves is still not clear, but is considered along with silver
The carrying out of sintering, the contact area of the surface of polyimide substrate and the film containing silver powder increases,
The smears being attached to silver powder acts on its contact interface as sticker or reaction promoter.
It addition, according to described 3rd invention, in the conductive paste of polyimide substrate, silver powder is
Comprising Colophonium, fat by being attached with the following scope of 2.3 (%) based on the mass ratio of silver powder
The silver powder of the attachment smears of the smears of acid or amine, even if therefore at 300 (DEG C) below, preferably
Be 270 (DEG C) below in a low temperature of implement burn till process, the sintering of silver powder is also sufficiently carried out, so
Available high conductivity and the high adhesion for polyimide substrate.Furthermore, as long as smears has one
Point is attached in silver powder, so that it may with the agglutinating property that its amount correspondingly improves silver powder, but more than 2.3 (%)
Becoming surplus then to become when burning till to be difficult to grill thoroughly, make film density reduce, electric conductivity reduces.
Here, it is preferable that, in described 1st invention, the silver of described conducting film there occurs sintering.
That is, the substrate with conducting film of the 1st invention, is the conductive paste using and burning till type, at polyamides
The substrate of conducting film is defined on imines substrate.Silver hair accordingly, as the conductor composition in conducting film
Give birth to sintering, therefore there is high electric conductivity.
It is further preferred, that in described 2nd invention, be attached to the institute on the surface of described silver powder
State smears, be calculated as 2.3 (%) amount below with the mass ratio relative to this silver powder.If smears
There is some attachment can correspondingly improve the agglutinating property of silver powder with this amount up, but become more than 2.3 (%)
Becoming when burning till to be difficult to grill thoroughly when obtaining superfluous, make film density reduce, electric conductivity reduces.
It is further preferred, that in described conductive paste, the mean diameter of described silver powder is 0.5 (μm)
Below.Silver granuel footpath is the biggest, and agglutinating property more reduces, if becoming more than 1 (μm), sinter substantially be difficult to into
OK, resistance value increases.
It is further preferred, that described conductive paste and described conducting film contain substantially no glass.Again
Person, so-called " containing substantially no glass ", refer to be entirely free of ideally glass, but allow
Effect is not brought to contain the characteristics such as agglutinating property.
It is further preferred, that in described 2nd invention and described 3rd invention, described resin-bonded
The decomposition temperature of agent is at 250 (DEG C) below, i.e. grill thoroughly at a temperature of lower than described firing temperature.As
Like this, then in the conducting film formed, Organic substance, carbide are difficult to remaining to fruit, therefore can get
The electric conductivity of the conducting film higher base with conducting film of higher and for polyimide substrate adaptation
Plate.If being also contemplated for printing and operability, then preferred acrylic resins.Such as, methyl can be enumerated
The polymer of Isobutyl 2-propenoate and the material of mean molecule quantity 160,000.Furthermore, resin need not necessarily be made
The decomposition temperature of binding agent is less than firing temperature.For example, it is also possible to using decomposition temperature is 300 (DEG C)
Above resinoid bond.In such a situation, the burning of silver powder also can be made according to the present application
Knot is fully carried out, though remaining Organic substance, carbide the most in the conductive film, it is possible to compared with the past
Obtain the highest electric conductivity.
Accompanying drawing explanation
Fig. 1 is that the silver conductive film schematically showing one embodiment of the invention is formed at polyimide-based
The figure in the cross section of the substrate with conducting film of plate one side.
Fig. 2 is that the cross section of the near interface of the conducting film of the substrate with conducting film of Fig. 1 and substrate is shone
Sheet.
Fig. 3 is by the photo of a part of enlarged representation in the cross section of Fig. 2.
Fig. 4 is the cross section of the near interface of the conducting film of the substrate with conducting film of comparative example and substrate
Photo.
Fig. 5 is by the photo of a part of enlarged representation in the cross section of Fig. 4.
Fig. 6 is the conduction of the substrate with conducting film representing one embodiment of the invention by firing temperature
The figure of the cross sectional shape of film.
Fig. 7 is the SEM on the conducting film surface of the substrate with conducting film of one embodiment of the invention
Photo.
Description of reference numerals
10: silver conductive film, 12: polyimide substrate, 14: with the substrate of conducting film
Detailed description of the invention
Hereinafter, referring to the drawings one embodiment of the invention is described in detail.Furthermore, following
In embodiment, figure is suitably simplified or is deformed, the not necessarily exact picture such as the size ratio of each several part and shape.
Fig. 1 is the band of the one side representing that the silver conductive film 10 of the present invention is formed at polyimide substrate 12
There is the figure in the cross section of the substrate 14 of conducting film.This wiring substrate is in various electronic equipments etc., as tool
There is flexual internal wiring substrate, connect the terminal of the moving part flexibility with the terminal of standing part
Wiring substrates etc. are used.Silver conductive film 10 is only by the thickness gauge such as possessing 1.0～8.0 (μm) left and right
Very little silver composition, possesses when polyimide substrate 12 deforms, the flexibility deformed therewith.
The above-mentioned substrate 14 with conducting film, such as, prepare to comprise silver powder, resinoid bond and organic
The conductive paste of solvent, on polyimide substrate 12 use silk screen printing, intaglio printing, offset printing or
The suitable printing process such as person's ink jet printing forms film, and implements to burn till process and thus generate silver conductive film
10 manufacture.Above-mentioned silver powder is as the attachment smears of the smears having scheduled volume in surface attachment
Silver powder is added.Smears is any one in Colophonium, fatty acid, amine.As fatty acid
Can enumerate such as, stearic acid, lauric acid, oleic acid, linoleic acid, capric acid etc..It addition, as amine,
Such as lauryl amine can be enumerated.
The silver powder of such attachment smears is made as follows.As silver powder, use by general
The commercially available product that damp process modulates.Prepared mean diameter be 0.07 (μm), 0.10 (μm), 0.5 (μm),
0.8 (μm), 0.9 (μm), 1.0 (μm), 1.4 (μm), the globular powder of 3 (μm).It is such as being burnt
Take respectively about 100 (g) in Bei, then add isopropanol about 1000 (ml) and be sufficiently stirred for.Placed one
Evening, then, discarded supernatant portion.Put in isopropanol about 1000 (ml) again, after stirring, place an evening.
This washing operation is repeated 3～5 times.Thus, the Organic substance that will be attached in silver powder fully removes
Go.
Then, smears is made to be dissolved in isopropanol.Hereinafter, to use Colophonium as the feelings of smears
Illustrate as a example by condition.As Colophonium raw material, such as, the gum rosin of waste river chemical industry is used
WW, is taken 1.0～2.5 (g), adds in the isopropanol of 500 (ml) and be stirred.Then, will
The supernatant of the argentum powder finishing above-mentioned washing operation is discarded, and is added to dissolve the different of Colophonium
Propanol is also sufficiently stirred for.Then, this mixture is transplanted in eggplant type flask, uses vaporizer to utilize
The warm water of 55 (DEG C)～60 (DEG C) carries out heating and makes it reduce pressure simultaneously, thus makes isopropanol gasify.Will so
The argentum powder obtained is placed on pallet, places an evening.Thereafter, use the filter screen of 200 sieve apertures to implement screening,
It is thereby preparing for the argentum powder particle having Colophonium in surface attachment.
Furthermore, the Colophonium amount being attached to, the argentum powder obtained utilize TG-DTA with 10 (DEG C/min)
Programming rate heats up until 900 (DEG C) are measured trying to achieve.That is, with the quality of 50 (DEG C) of TG and
The difference of the quality of 400 (DEG C) is as attachment Colophonium amount.Colophonium adhesion amount is by making the gum rosin of interpolation
The amount change of WW is adjusted.Such as, in the case of the argentum powder of particle diameter 0.1 (μm), relative to
Gum rosin (gum rosin) measures 1.2 (g), 1.7 (g), 2.2 (g), Colophonium amount is 1.0 (%), 1.6 (%),
2.0 (%).
As it has been described above, prepare the argentum powder of attachment Colophonium, resinoid bond and organic solvent are utilized stirring
Machines etc. mix.As resinoid bond, use such as acrylic resin (Rhizoma Sparganii レ ヨ Application system
EMB-002), as organic solvent, use such as methanol.They are modulated scheduled volume, uses three rollers
Grinding machine carries out dispersion process makes its gelatinizing, thus obtains conductive paste.Aforesaid propylene acid resin exists
250 (DEG C) are grilled thoroughly (combustion え け Ru) below, are screen printability and treatability are taken into account flat
The isobutyl methacrylate of average molecular weight about 160,000.When sticking with paste modulation, in order to make printing be equal
Degree, such as, viscosity time 25 (DEG C)-20 (rpm) is adjusted to 180～200 (Pa s).
Use the most ready conductive paste, implement thick film screen printing to polyimide substrate.Print
Brush plate-making is SUS400 system.It addition, set printing condition so that the width dimensions of print film becomes
500(μm).After drying, implement to burn till process at a temperature of in the range of 250～300 (DEG C),
Resinoid bond is grilled thoroughly and silver powder sinters, and obtains described silver conductive film 10.
According to the present embodiment, silver powder as described above uses and is attached with Colophonium, fatty acid or amine
The silver powder of the attachment smears of class, though therefore silver in a low temperature of as described above 250～270 (DEG C)
The sintering of powder is also sufficiently carried out, so such as being had sheet resistance values is 2～8 (m Ω/)
The high conductivity of left and right and the conducting film 10 of high adhesion are present on polyimide substrate 12
Substrate 14 with conducting film.
Fig. 2 is conducting film 10 and the boundary of polyimide substrate 12 of the above-mentioned substrate 14 with conducting film
The SEM picture in the cross section near face, Fig. 3 is the SEM picture being exaggerated further by one part.Figure
The light color part about half that accounts for of 2 is conducting film 10, and being positioned at the heavy colour part on the downside of it is polyamides
Imines substrate 12.As this SEM picture represents, conducting film 10 is disappeared until crystal boundary by fully sintering
Degree.And, it is formed concavo-convex at conducting film 10 with the interface of substrate 12, as should in Fig. 3
As boundary member enlarged representation, become the shape that silver invades the region of the opposing party each other with polyimides
State.
Here, the result of the test formed sticking with paste and film formation condition carries out various change and have rated is entered
Row explanation.Following table 1 summarizes the presence or absence to smears and kind, silver granuel footpath have carried out investigation
Result.In Table 1, No.1, No.2, No.6, No.13 are comparative examples, and other are embodiments.
It addition, " composition " hurdle illustrates the composition of conductive paste with quality percentage, silver amount is 68～75 (%),
Amount of glass is 0～2 (%), and resin-bonded dosage is 5～6 (%), and organic solvent amount is the model of 20～24 (%)
Enclose." resin/silver " is the amount of resin percentage rate relative to silver.It addition, in " material " hurdle, " silver
Particle diameter " represent the particle diameter of silver powder before the attachment of the smears of each paste, " additive types " table
Be shown as the material name that the smears of silver powder uses, " adhesion amount " by the coating dosage that is attached to such as
The upper result utilizing TG-DTA to determine represents with the percentage rate relative to silver powder describedly.Separately
Outward, " glass " hurdle is added to the composition system of the glass powder in sticking with paste.It addition, at " experimental condition knot
Really " in hurdle, " galley " is screen size, and " print thickness " is to print dried thickness.
It addition, " treatment temperature " is the highest holding temperature burning till process, by each treatment temperature, test is shown
Result." burning till thickness " is the thickness after burning till, " resistance value " be burn till after use digital versatile
Table membranaceous is led with what terminal intervals 10 (cm), live width 500 (μm) determined based on 2 general terminal methods
The resistance value of body.It addition, " sheet resistance (m Ω/) " is calculated by following formula by above-mentioned resistance value
Sheet resistance values after burning till.Furthermore, conversion thickness is 10 (μm).
Sheet resistance values (m Ω/ )=mensuration resistance value (Ω) × (conductor width (mm)/conductor length
(mm)) × (conductor thickness (μm)/conversion thickness (μm))
It addition, " belt strength " is after burning till, to the silver conduction being formed on polyimide substrate
The surface of film presses with finger adhesive tape (ニ チ バ Application CT-15153P) makes it adhere to, and peels off glue
The appearance of the silver conductive film of attachment judging on the adhesive tape face that band has been peeled off by visualization.?
Entirely without attachment silver conductive film on the most whole of the adhesive tape of pressing, and at polyimide substrate
What the silver conductive film of upper formation also former state remained is set to "○", attachment silver conduction on the adhesive tape of pressing
A part for film, and the part of silver conductive film that formed on polyimide substrate do not remains
It is set to " △ ", the adhesive tape of pressing adheres to more than 90 (%) of silver conductive film, and sub-at polyamides
What more than 90 (%) of the silver conductive film formed on amido plate did not remain is set to "×", have rated above-mentioned
3 stages.
In above-mentioned table 1, as shown in comparative example No.1, No.2, use the silver powder without smears
Time, polyimide substrate does not sinters, therefore result sheet resistance values is high, and belt strength is the lowest.Especially
It is the use of the No.1 of the silver powder that particle diameter is 1 (μm), even if burning till sheet resistance values also at 270 (DEG C)
It is 32.3 (m Ω/), is significantly high value.It addition, comparative example No.13 employs as smears
It is attached with the silver powder of lauryl mercaptan, but can not get the improvement effect of agglutinating property, even if at 270 (DEG C)
Burning till sheet resistance values is also 65.1 (m Ω/), is still high value, also can not get belt strength.
On the other hand, in embodiment No.3～No.5, No.7～No.12, using as smears Colophonium,
Stearic acid, lauric acid, oleic acid, linoleic acid, capric acid, lauryl amine are respectively with the mass ratio relative to silver
It is that the scope of 0.16～2.3 (%) is adhered to, but all by implementing to burn till under 250～270 (DEG C)
Processing, sinter well, sheet resistance values is 2.4～6.7 (m Ω/), it is possible to obtain high electric conductivity.
It addition, belt strength is the most all the result of "○".Furthermore, No.3, No.4 are except all using
Similarly evaluated beyond Colophonium, and the difference that silver granuel footpath is 0.1 (μm), 0.07 (μm), knot
Fruit be the No.3 that particle diameter is big excellent electric conductivity some.The surface area of the silver powder being considered micropowder is big,
It is thus desirable to increase coating dosage.Furthermore, No.6 is in addition to the addition of the glass dust of 2 (%) in paste
Condition as No.3 beyond end, although result obtains sufficient electric conductivity, but it is strong to can not get adhesive tape
Degree.Silver conductive film itself there occurs sintering, but glass likely hinder with polyimide substrate close
Conjunction property.
Furthermore, Fig. 4, Fig. 5 are in above-described embodiment No.7, and firing temperature is the feelings of 230 (DEG C)
The cross-section photograph of condition, corresponds respectively to described Fig. 2, Fig. 3.Firing temperature is too low when 230 (DEG C),
Therefore, it is difficult to be sintered, silver conductive film 10 is also flat condition with the interface of polyimide substrate 12.
Therefore, sheet resistance values is high, and also can not get belt strength.
It addition, following table 2 summarizes the result that further change condition is evaluated,
No.14～No.16 is the result that the particle diameter to silver powder is discussed.Employing particle diameter is
In No.14, No.15 of the silver powder of 0.5～1 (μm), at the firing temperature bottom sheet electricity of 250～270 (DEG C)
Resistance is 3.5～5.4 (m Ω/), obtains high conductivity, and belt strength is also "○" simultaneously, but makes
With in the No.16 of the silver powder that particle diameter is 3 (μm), become the result of poorly conductive compared with them.
The especially firing temperature sheet resistance values at 250 (DEG C) is up to 10.5 (m Ω/), and belt strength is also
“×”.But, if burnt till at 270 (DEG C), then belt strength fully uprises, simultaneously sheet resistance values
Also it is 7.1 (m Ω/), although high, but is improved to the degree that can use.
Table 2
It addition, in No.17～No.19, make the resin-bonded dosage in paste with the mass ratio relative to silver
Range at 12.9～4.3 (%).In either case, can burning till of 250～270 (DEG C)
Obtain high conductivity that sheet resistance values is 2.7～5.4 (m Ω/) and the high adhesive tape that "○" is evaluated is strong
Degree.Amount of resin in paste is allowed in relatively wide scope.
It addition, in No.20, No.21, the resinoid bond during change is stuck with paste is evaluated, No.20
In, (such as, decomposition temperature is the three of 300 (DEG C) left and right to employ the high acrylic resin of decomposition temperature
The EMB-398 of Pedicellus et Pericarpium Trapae レ ヨ Application), in No.21, employ ethyl cellulose and (such as, decompose temperature
Degree is the EC-45 of ダ ウ ケ ミ カ Le of 450 (DEG C) left and right), any one can be
The firing temperature of 250～270 (DEG C) obtains high conductivity and the height that sheet resistance values is 2.3～2.8 (m Ω/)
Belt strength.Furthermore, it is believed that the decomposition temperature of above-mentioned 2 kinds is high, the therefore silver conductive film after burning till
Can be remaining at least some of as Organic substance or carbide in 10, but according to above-mentioned evaluation result, i.e.
Make under such high decomposition temperature also entirely without problem, it is known that even if resinoid bond is grilled thoroughly completely
Also it doesn't matter.
It addition, in No.22～No.24, change the ratio of the resinoid bond in sticking with paste and organic solvent,
Galley is become #400, #250, #165 simultaneously, make print thickness become between 3.2～10.1 (μm)
Change.If print thickness is thickening, then there is the tendency that agglutinating property is somewhat deteriorated, in the burning of 250～270 (DEG C)
At a temperature of one-tenth, print thickness is the No.22 of 3.2 (μm), in the No.23 of 5.8 (μm), obtained sheet electricity
Resistance is 2.7～3.7 (m Ω/), belt strength is the good result of "○", in contrast, printing
Thickness is in the No.24 of 10.1 (μm), is "×" at 250 (DEG C) belt strength.But, No.24
Also fully sintering at 270 (DEG C), obtaining sheet resistance values is 4.8 (m Ω/), belt strength be "○",
More slightly worse than No.22, No.23 but be good result.It addition, for the examination of these No.22～No.24
Material, even if the firing temperature at 300 (DEG C) is evaluated, sheet resistance values is 2.4～2.5 (m Ω/), glue
Band strength is "○", it is possible to confirm all to obtain good result.
It addition, in No.25, do not adhere to smears to silver powder, but in being added to stick with paste,
At the firing temperature of 250 (DEG C), sheet resistance values is 332 (m Ω/), substantially the biggest, can not get conduction
Property, belt strength is also "×".It is able to confirm that the burning in order to improve the silver powder on polyimide substrate
Knot property, the process making smears be attached to silver powder is necessary.
Here, in the above-described embodiment, to the surface configuration that have rated the silver conductive film after burning till 10
Result illustrate.Fig. 6 is the cross sectional shape figure of silver conductive film 10.This cross sectional shape uses Tokyo
The SURFCOM 480A of accurate system, scanning speed 1.5 (mm/sec), multiplying power is 10K, cutoff value
Be 0.8 (mm), in the width direction by crosscutting for the Wiring pattern of 500 (μm) width defined enter
Row measures.In figure 6, it is longitudinally the thickness direction of silver conductive film 10, is laterally its width,
The concavo-convex part that creates of central part is silver conductive film 10, and the flat of its both sides is polyimides
Substrate 12.It addition, temperature is the firing temperature of each evaluation test portion, in 250 (DEG C), the feelings of 270 (DEG C)
Condition determines described embodiment No.3, and the situation at 300 (DEG C) determines described embodiment No.22
Test portion.Furthermore, the test portion of 325 (DEG C) employs and the conductive paste as them, and this determination data does not has
On the books in described table 1, table 2.
As shown in the cross sectional shape of above-mentioned measurement result, implemented by the temperature range at 250～300 (DEG C)
Burn till process and form silver conductive film 10, as shown in described Fig. 2, Fig. 3, silver conductive film 10 and polyamides
The constituent of imines substrate 12 mutually invades the opposing party and forms the interface of concaveconvex shape, its result, silver
The surface of conducting film 10 as shown in Figure 6, becomes concavo-convex violent cross sectional shape.This concavo-convex size is such as
Shown in scale, below the gauge for silver conductive film 10, i.e. 2 (μm) left and right.
In contrast, in the case of 325 (DEG C) burn till, polyimide substrate 12 is by silver conductive film 10
Notable erosion, forms the recess of the degree of depth of more than the thickness size of silver conductive film 10.Now, presumption exists
Silver conductive film 10 side, the constituent of polyimide substrate 12 is substantially invaded universally throughout film thickness direction
Entering, sheet resistance values also uprises.So, can clearly occur under firing temperature 325 (DEG C) polyimide-based
The unfavorable conditions such as plate 12 is broken, thus cannot use, therefore it is omitted in the note in described table 1, table 2
Carry.
Furthermore, Fig. 7 is the surface SEM photograph of silver conductive film 10.As shown in this photo, lead at silver
The surface of electrolemma 10 creates many apertures.Think that the concavo-convex of appearance is by such in described Fig. 6
Hole causes, but when considering the depth of invasion of thickness, constituent, this hole the concavo-convex quilt caused
Ignore.
As described above, according to the present embodiment, silver conductive film 10 and polyimide substrate 12,
Their constituent scope below the gauge of silver conductive film 10 mutually invades the opposing party, by
This male and fomale(M&F) formed becomes their interface, so along with the increase of contact area, and electric conductivity and close
Conjunction improves.Therefore, can obtain having high conductivity and with the high adhesion of polyimide substrate 12
Possesses the substrate 14 with conducting film of silver conductive film 10.
It addition, according to the present embodiment, silver conductive film 10 is being formed on polyimide substrate 12 system
When making the substrate 14 with conducting film, in sticking with paste painting process, applied conductive paste is as argentum powder
End, employs the smears that comprises Colophonium, fatty acid or amine and is attached to the attachment smears on surface
Silver powder, therefore in firing process, even if implementing in a low temperature of in the range of 250～300 (DEG C) to burn
One-tenth processes, and sintering is the most fully carried out, so can obtain having high conductivity and to polyimide substrate 12
The substrate 14 with conducting film possessing silver conductive film 10 of high adhesion.
It addition, according to the present embodiment, conductive paste, as silver powder, employs with relative to silver powder
Mass ratio be the smears that 2.3 (%) scope below is attached to comprise Colophonium, fatty acid or amine
Attachment smears silver powder, even if therefore 300 (DEG C) below in a low temperature of implement burn till process, silver
The sintering of powder is the most fully carried out, so available high conductivity and the height for polyimide substrate 12
Adaptation.
Above, the present invention is described in detail by reference to the accompanying drawing, but the present invention also is able under other modes
Implement, can in addition various changes in the scope without departing from its purport.
Claims (6)
1., with a substrate for conducting film, it is to possess containing silver conduct in the one side of polyimide substrate
The substrate with conducting film of the conducting film of conductor composition, it is characterised in that
The constituent of described conducting film and described polyimide substrate crosses their interface in this conduction
Scope below the gauge of film mutually invades the opposing party, and the male and fomale(M&F) being consequently formed becomes its interface.
Substrate with conducting film the most according to claim 1, described conducting film is that silver there occurs
The conducting film of sintering.
3., with the manufacture method of substrate for conducting film, it is will be containing silver leading as conductor composition
The manufacture method of the substrate with conducting film that electrolemma is formed on polyimide substrate, it is characterised in that
Including:
The conductive paste of silver powder, resinoid bond and organic solvent will be comprised described polyimide-based
On plate with predetermined pattern coating paste painting process, the surface attachment of described silver powder have comprise Colophonium,
The smears of the scheduled volume of at least one among fatty acid and amine；With
Burn till process by enforcement under the maximum temperature of 250～300 DEG C and make silver sintering, be described lead
Electrically stick with paste the firing process generating conducting film.
The manufacture method of the substrate with conducting film the most according to claim 3, at described argentum powder
The described smears of the surface attachment at end, is calculated as less than 2.3% with the mass ratio relative to this silver powder
Amount.
5. a polyimide substrate conductive paste, it is characterised in that be for polyimide-based
Form conducting film on plate and manufacture the polyimide substrate conductive paste of the substrate with conducting film, its
Comprise silver powder, resinoid bond and organic solvent,
Described silver powder is the silver powder of attachment smears, is calculated as with the mass ratio relative to this silver powder
The amount of less than 2.3% has the painting comprising at least one among Colophonium, fatty acid and amine in surface attachment
Cloth agent.
Polyimide substrate conductive paste the most according to claim 5, putting down of described silver powder
All particle diameters are below 0.5 μm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015078076A JP6263146B2 (en) | 2015-04-06 | 2015-04-06 | Substrate with conductive film, method for producing the same, and conductive paste for polyimide substrate |
| JP2015-078076 | 2015-04-06 |
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| Publication Number | Publication Date |
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| CN106057292A true CN106057292A (en) | 2016-10-26 |
| CN106057292B CN106057292B (en) | 2020-01-10 |
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| JP (1) | JP6263146B2 (en) |
| CN (1) | CN106057292B (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108986986A (en) * | 2018-06-21 | 2018-12-11 | 浙江浙能技术研究院有限公司 | A method of three dimensional thin film electrode is made using abrasive material |
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| JP7498584B2 (en) | 2020-03-30 | 2024-06-12 | 株式会社ノリタケカンパニーリミテド | Metal-resin bonded body and its manufacturing method |
| JP7498585B2 (en) | 2020-03-30 | 2024-06-12 | 株式会社ノリタケカンパニーリミテド | Metal-resin bonded body and its manufacturing method |
| JP7498583B2 (en) | 2020-03-30 | 2024-06-12 | 株式会社ノリタケカンパニーリミテド | Metal-resin bonded body and its manufacturing method |
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| JP2008108569A (en) * | 2006-10-25 | 2008-05-08 | Sekisui Chem Co Ltd | Sintering conductive paste |
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| JP2006310022A (en) * | 2005-04-27 | 2006-11-09 | Mitsui Mining & Smelting Co Ltd | Electrically conductive paste, and flexible printed wiring board obtained using the same |
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| JP4986745B2 (en) * | 2007-07-05 | 2012-07-25 | Ｄｏｗａエレクトロニクス株式会社 | Silver paste |
| KR20100109416A (en) * | 2009-03-31 | 2010-10-08 | 디아이씨 가부시끼가이샤 | Electroconductive paste composition and the method of producing the same |
| JP2010287434A (en) * | 2009-06-11 | 2010-12-24 | Dowa Electronics Materials Co Ltd | Substrate with silver conductive film and method for manufacturing same |
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| KR101725181B1 (en) * | 2011-06-10 | 2017-04-10 | 도와 일렉트로닉스 가부시키가이샤 | Bonding material and bonded object produced using same |
| JP2013139589A (en) * | 2011-12-28 | 2013-07-18 | Toda Kogyo Corp | Silver fine particles, method for producing the same, and conductive paste, conductive film, and electronic device containing the silver fine particles |
| WO2013115339A1 (en) * | 2012-02-02 | 2013-08-08 | 戸田工業株式会社 | Silver microparticles, method for producing same, and electronic device, conductive film, and conductive paste containing said silver microparticles |
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| TW201522071A (en) * | 2013-09-10 | 2015-06-16 | Dainippon Ink & Chemicals | Laminate body, conductive pattern, electrical circuit, and method for producing laminate body |
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| CN101522344A (en) * | 2006-09-27 | 2009-09-02 | 同和电子科技有限公司 | Silver particle composite powder and process for production thereof |
| JP2008108569A (en) * | 2006-10-25 | 2008-05-08 | Sekisui Chem Co Ltd | Sintering conductive paste |
| US20090078915A1 (en) * | 2007-09-21 | 2009-03-26 | Samsung Electro-Mechanics Co. Ltd | Nonaqueous conductive nanoink composition |
| CN103339685A (en) * | 2011-01-26 | 2013-10-02 | 纳美仕有限公司 | Electroconductive paste and method for manufacturing same |
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Also Published As
| Publication number | Publication date |
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| CN106057292B (en) | 2020-01-10 |
| JP6263146B2 (en) | 2018-01-17 |
| JP2016197582A (en) | 2016-11-24 |
| TWI687320B (en) | 2020-03-11 |
| TW201636203A (en) | 2016-10-16 |
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