CN110322985A - A kind of electrocondution slurry and its preparation method and application - Google Patents
A kind of electrocondution slurry and its preparation method and application Download PDFInfo
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- CN110322985A CN110322985A CN201810264578.6A CN201810264578A CN110322985A CN 110322985 A CN110322985 A CN 110322985A CN 201810264578 A CN201810264578 A CN 201810264578A CN 110322985 A CN110322985 A CN 110322985A
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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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
- H05K1/115—Via connections; Lands around holes or via connections
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- Microelectronics & Electronic Packaging (AREA)
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- Parts Printed On Printed Circuit Boards (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
The application provides a kind of electrocondution slurry and its preparation method and application, is counted on the basis of the gross mass of the raw material components of the electrocondution slurry, the electrocondution slurry includes following raw material components and weight percentage: scaling powder 5wt% ~ 20wt%；Electroplating surfaces with tin metal powder 60wt% ~ 90wt%；Low-melting-point metal powder 5wt% ~ 20wt%.The application uses electroplating surfaces with tin copper powder and/or electroplating surfaces with tin copper alloy powder, avoid the generation of copper powder/copper alloy powder surface oxide layer, in addition, tin coating is directly contacted with copper or copper alloy surface, during heating, the low-melting-point metal powder and tin coating melted first forms low-temperature alloy melt, direct invasion copper/copper alloy, so that next step alloying becomes easier to carry out；Due to having used low-melting-point metal, alloying is carried out at a lower temperature, not only accelerates the speed of alloying, also makes alloying reaction more complete, improves the reliability of hole connection.
Description
Technical field
The present invention relates to a kind of conducting mediums, more particularly to a kind of electrocondution slurry and its preparation method and application.
Background technique
Printed circuit board (referred to as PCB circuit board), also known as printed circuit board are the offers of electronic component electrical connection
Person.The history of its existing more than 100 years of development, major advantage is to greatly reduce the mistake of wiring and assembly, is improved certainly
Dynamicization level and productive labor rate.Via hole (English is via) is one of the important component of multi-layer PCB wiring board, each layer
Plank has to first to drill before bonding and copper facing.If can not just be interconnected without the step.In root
Need to carry out copper plating treatment (plated through hole technology, Plated- by machinery equipment according to drilling demand after being drilled, in Kong Bi
Through-Hole technology, PTH).After making metal processing inside Kong Bi, it can allow internal each sandwich circuit can
It is connected to each other.Hole wall copper facing can all be completed in chemical process, need to use a large amount of water, thus there are many heavy metal wastewater thereby and have
The discharge of machine waste water, complicated component, processing difficulty are larger.These be present in waste liquid, the metal in waste water as without processing just discharge,
Not only it causes waste but also polluted environment.
It is increasing for the research of printed circuit plate hole filling electrocondution slurry in recent years, add in scaling powder and resin
Add low-melting-point metal powder and high-melting metal powder, heat under certain condition, low-melting-point metal powder melts first, dissolves high-melting-point
Metal powder realizes conducting in hole to which alloying occur.This new process avoids previous electroless copper bring waste water
Processing problem is one of the hot spot of current multilayer circuit board area research.
At least two metal powders are used in technical solution at present, the metal of low melting point first melts, then infiltration dissolution Gao Rong
Point metal powder is to occur alloying, and therefore, the oxide layer on high-melting metal powder surface will affect low-melting-point metal to its surface
Wetability, thus influence two kinds of metal powder alloyings progress.And the copper alloy powder of silver cladding is used, although inoxidizability has
The problem of improving, but increased costs can be brought.Therefore the inoxidizability that suitable method improves metal powder, Yi Jiru are found
What accelerates the speed for forming alloying after low-temperature metal melts with high-temperature metal, is the technical problem of this field face.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of electrocondution slurry and its preparation sides
Method and purposes, it is at high cost in multilayer circuit board preparation process in the prior art for solving, it is difficult to which that simple and effective formation is stablized
The problem of conducting layer.
In order to achieve the above objects and other related objects, the present invention obtains by the following technical programs.
The present invention provides a kind of electrocondution slurry, is counted on the basis of the gross mass of the raw material components of the electrocondution slurry, described
Electrocondution slurry includes following raw material components and weight percentage:
Scaling powder 5wt%~20wt%
Electroplating surfaces with tin metal powder 60wt%~90wt%.
Low-melting-point metal powder 5wt%~20wt%.
Preferably, the weight percentage of scaling powder is 10wt~20wt%.
Preferably, the weight percentage of electroplating surfaces with tin metal powder is 60wt%~80wt%.
Preferably, the weight percentage of low-melting-point metal powder is 10wt%~20wt%.
Scaling powder is the oxidation film that metal surface formation can be removed in welding procedure, helps and promotes welding process, together
When with protective effect, prevent oxidation reaction chemical substance.
The flux ingredients having been known in solder paste can be used in the scaling powder.In a preferred embodiment,
The scaling powder includes solvent, excipient and activating agent.
Preferably, the scaling powder includes the percentage composition of middle each raw material component are as follows:
Excipient 30wt%-70wt%
Activating agent 5wt%-20wt%
Surplus is solvent.
Preferably, the excipient is 35wt%~50wt%.It is highly preferred that the excipient be 35wt%~
45wt%.
Preferably, the activating agent is 5wt%~15wt%.
Solvent is selected from one of alcohol, ketone, ester, ether, alkane and aromatic solvent or a variety of in the application.Such as, such as
Alcohol is selected from ethylene glycol, isopropanol, terpinol, glycerol；The ester is selected from ethyl acetate etc.；The ether is selected from ethylene glycol ethyl ether, second
Glycol monobutyl ether and diethylene glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, one of dipropylene glycol propyl ether etc. or
It is a variety of.
Excipient is that (such as newtrex, fumaric acid modified rosin, maleic acid change for rosin and its modification derivant in the application
Property rosin, phenol aldehyde modified rosin, glycolic modified rosin, acrylic acid modified rosin, rosin modified phenol), epoxy resin, phenolic aldehyde
Resin, acrylic resin, polyester resin, polyimides, polyamide, celluosic resin, terpene resin, polyvinyl alcohol, poly- second two
One such or a variety of mixing also may be selected in alcohol or polyvinylpyrrolidone etc..
It is organic acid, organic amine or halogen acid salt of amine etc. that activating agent is commonly used in the application, also be can choose many of
Mixing.Such as, organic acid is selected from malic acid, citric acid, and lauric acid, stearic acid, oleic acid, palmitinic acid, glutaric acid, adipic acid is pungent
Diacid, azelaic acid, decanedioic acid and abietic acid, maleic acid, fumaric acid, ascorbic acid it is one or more.Organic amine is selected from monoethanol
Amine, diethanol amine, one of triethanolamine and aniline or a variety of.The halogen acid salt of amine is selected from ethylamine hydrochloride, diethylamine salt
Hydrochlorate, dimethylamine hydrochloride, cyclohexylamine hydrochloride, triethanolamine hydrochloride, in glutamic acid hydrochloride and ethylamine hydrobromide
It is one or more.
In addition, conventional thixotropic agent (paraffin, polyamide-based organic matter, castor oil and its derivative can be added in actual use
Object, such as polyamide wax, rilanit special, polyamide modified rilanit special etc.), corrosion inhibiter (benzotriazole, imidazoles), table
Face activating agent (OP-10), preservative, antioxidant etc. improve the printing and stability of slurry, and additive amount is usually no more than
The 10wt% of solvent, excipient and activating agent total content in scaling powder.
In the application, in the copper alloy powder of copper powder and electroplating surfaces with tin of the electroplating surfaces with tin metal powder selected from electroplating surfaces with tin
It is one or two kinds of.
The copper powder of the electroplating surfaces with tin refers to that the tin with core-shell structure coats copper powder.The electroplating surfaces with tin copper powder has core
The partial size of shell structure, that is, the tin shell for having copper core and being coated on outside same core, the electroplating surfaces with tin copper powder of core-shell structure is no more than 15 μm,
Preferably 1 μm~15 μm, such as can for 1~8 μm, 2~8 μm, 2~10 μm, 3~10 μm, 2~11 μm, 3 μm~15 μm, 9 μm~
15 μm etc.；Preferable particle size is 3 μm~10 μm, such as can be 3 μm~5 μm, 5 μm~7 μm, 4 μm~8 μm, 5 μm~10 μm, 4 μm~
10 μm and 6 μm~10 μm.Wherein, the ratio of the copper nuclear diameter of the copper powder of the electroplating surfaces with tin of core-shell structure and core-shell structure overall diameter
It is 0.60~0.90, such as can is 0.60,0.65,0.70,0.75,0.80,0.85 and 0.90, preferably 0.70~0.88.
The copper alloy powder of electroplating surfaces with tin described herein refers to that the tin with core-shell structure coats copper alloy powder, described
The copper alloy powder of electroplating surfaces with tin has core-shell structure, i.e., with copper alloy core and the tin shell structure being coated on outside copper alloy core, core
The partial size of the copper alloy powder of total partial size, that is, electroplating surfaces with tin of shell structure is no more than 15 μm, and preferably 1 μm~15 μm, such as can be 1 μ
M~8 μm, 2 μm~8 μm, 2 μm~10 μm, 3 μm~10 μm, 2 μm~11 μm, 1 μm~11 μm, 9 μm~12 μm, 2 μm~15 μm,
3 μm~14 μm etc.；3 μm~10 μm of preferable particle size.Wherein the ratio of the diameter of copper alloy core and core-shell structure overall diameter is 0.67
~0.90, such as can be 0.60,0.65,0.70,0.75,0.80,0.85 and 0.90, preferably 0.70~0.88.
Copper alloy described herein can be corronil.Preferably, nickel is 10wt~15wt% in copper alloy.
Copper alloy described herein is also possible to cupromanganese.Preferably, manganese is 10wt%~15wt% in copper alloy.
Copper alloy is preferably corronil in the application.
Low-melting-point metal powder described herein refers to fusing point in 231 DEG C of metal powders below.Preferably, the low melting point
Metal powder is selected from indium, tin-indium alloy, sn-bi alloy, sn-ag alloy, gun-metal, tin bismuth indium alloy, tin bismuth silver alloy, tin bismuth copper
One of alloy and Tin Silver Copper Alloy are a variety of.It is highly preferred that the low-melting-point metal powder is sn-bi alloy.It is highly preferred that
The sn-bi alloy includes the Bi of the Sn and 40wt%~60wt% of 40wt%~50wt%, such as can for 42wt% Sn and
The Bi of 58wt%, eutectic melting point are 138 DEG C.
It is highly preferred that it is preferably 1 μm~12 μm no more than 12 μm that the low-melting-point metal powder, which obtains partial size, more preferably
It is 3 μm~8 μm.
The invention also discloses the preparation methods of electrocondution slurry as described above, the preparation method is that by each raw material component
It obtains after mixing.It preferably, further include milled processed after mixing.The group of metallic in slurry is reduced by milled processed
Poly- phenomenon.
Disclosed herein as well is the purposes of electrocondution slurry as described above in the printed circuit boards.
Preferably, the purposes is using the through hole in electrocondution slurry described above filling printed circuit board, and low temperature dries
It is dry to remove solvent, form using heating fusing and under pressurization the via hole conductor with cementation.Preferably, first
It is warming up between 150 DEG C~230 DEG C, so that flux ingredients work in slurry, removes metallic tin oxide on surface；Then it rises
For temperature to 230 DEG C or more, pressurization is kept for a period of time.During this period, low-melting-point metal powder and electroplating surfaces with tin metal powder are melted and are produced
Intercrescence aurification forms via hole conductor, this via hole conductor can connect the metal foil of insulating layer resin two sides in printed circuit board, together
When under stress, also achieve resin insulating barrier and metal foil and bond.
The invention also discloses a kind of printed circuit board, the printed circuit board includes several metal foil layers and is folded in
Resin insulating barrier between the metal foil layer, the resin insulating barrier are equipped with several perforative through holes；The resin is exhausted
Filled with the via hole conductor formed using electrocondution slurry as described above on through hole in edge layer；The gold of resin insulating barrier two sides
Belong to layers of foil and electrical connection is realized by the via hole conductor.Preferably, the metal foil layer is copper foil, is used as conductive layer.
The thickness of the thickness and resin insulating barrier of metal foil can need to be customized according to product in the application.
The invention also discloses a kind of preparation methods of printed circuit board base board as described above, include the following steps:
A) through hole is formed on resin insulating barrier；
B) electrocondution slurry is filled in through hole；
C) it is then configured using metal foil in the two sides of the resin insulating barrier；
D) heated pressing forms printed wiring board substrate.
In step a), can using the technological means punched in the prior art to resin layer on resin insulating barrier shape
At through hole.Preferably, in step a), the mode for forming through hole can be machine drilling or carbon dioxide gas laser drilling
Hole.The diameter of the through hole can be set according to specific needs.
Preferably, in step b), electrocondution slurry is filled in through hole using half-tone screen printing method.
Preferably, it in step d), is heated up to be warming up to 150 DEG C~300 DEG C.It is highly preferred that being first heated up to 150 DEG C~230
DEG C, so that low-temperature metal powder melts in slurry, the tin layers of electroplating surfaces with tin metal powder surface are melted, form low-melting alloy melt；
Then 230 DEG C or more are warming up to.
Preferably, in step d), pressure is 0.5~5MPa when pressurization.
In step c), the heating bonding processes can carry out in vacuum hotpressing machine.During this period, low-temperature metal powder and
Metallic tin melts first forms low-melting alloy solution, then melts copper/copper alloy and generates intermetallic compound, forms via hole and leads
Body, this via hole conductor can connect the metal foil of insulating layer resin two sides, while under stress, also achieve insulation resin
Layer is bonded with metal foil.
Preferably, the resin insulating barrier is thermoplastic resin of the fusing point at 250 DEG C or more.Such as selected from polyimides (letter
Be written as PI), it is liquid crystal polymer (being abbreviated as LCP), polyether-ether-ketone resin (being abbreviated as PEEK), polyphenylene sulfide (being abbreviated as PPS), poly-
One of phenylate (being abbreviated as PPO) and polytetrafluoroethylene (PTFE) (being abbreviated as PTFE) are a variety of.Preferably liquid crystal polymer (is abbreviated as
LCP)。
The invention also discloses a kind of preparation methods of printed circuit board, include the following steps:
1) surface copper clad patternsization are carried out using the insulation resin laminate that chemical etching is covered with copper foil to single side to handle；
2) resin layer that the insulation resin laminate of copper foil is covered with to single side drills to form blind hole or through-hole；
3) filling such as the described in any item electrocondution slurries of Claims 1 to 4 in blind hole or through-hole；
4) several insulation resin sheets for being covered with copper foil through treated single side are subjected to contraposition stacking, and solid
It is fixed；
5) heated pressing forms printed wiring board.
In the preparation method of printed circuit board, drilling is by passing through laser or mechanical means in designated position in step 2)
It carries out drilling and forms blind hole or through-hole.In step 4), fixation is fixed using rivet.In step 5), heating compressed portion is for example above-mentioned
It is described, i.e., when heating presses, including one of following feature or a variety of: it is first warming up to 150 DEG C~230 under a certain pressure
DEG C, then pressure is kept to be warming up to 230 DEG C or more；Pressure is 0.5~5Mpa.Beneficial effects of the present invention: the application uses surface
Tin plating copper powder and/or electroplating surfaces with tin copper alloy powder, avoid copper powder/copper alloy powder surface oxide layer generation, in addition, there are also with
Lower advantage: 1) tin coating is directly contacted with copper or copper alloy surface, during heating, the low-melting-point metal powder that melts first with
Tin coating forms low-temperature alloy melt, direct invasion copper/copper alloy, so that next step alloying becomes easier to carry out；2) by
In having used low-melting-point metal, alloying is carried out at a lower temperature, not only accelerates the speed of alloying, also make
Alloying reaction is more complete, improves the reliability of hole connection.
Detailed description of the invention
Structural schematic diagram when the not formed via hole conductor of the printed circuit board that Fig. 1 is shown as in the embodiment of the present application 1.
Fig. 2 is shown as the structural schematic diagram when printed circuit board in the embodiment of the present application 1 forms via hole conductor.
Fig. 3 is shown as the configuration schematic diagram when printed circuit board in the embodiment of the present application 3 forms via hole conductor.
Component label instructions in Fig. 1, Fig. 2 and Fig. 3
| 100 | Metal foil layer |
| 200 | Resin insulating barrier |
| 300 | Through hole |
| 400 | The via hole conductor formed by electrocondution slurry |
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily.
Before further describing the specific embodiments of the present invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, rather than limiting the scope of protection of the present invention.The test method of actual conditions is not specified in the following example,
Usually according to normal condition, or according to condition proposed by each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this
Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real
The existing present invention.
Embodiment 1
As depicted in figs. 1 and 2, in the present embodiment, printed circuit board includes LCP resin insulating barrier 200 and is overlaid on respectively
The metal foil layer 100 of its two sides, metal foil layer 100 is specially copper foil, using as conductive layer.In the application the thickness of copper foil and
The thickness of LCP resin insulating barrier can need to be customized according to product.In the application the present embodiment, metal foil layer 100
18 μm of thickness.LCP resin insulating barrier 200 with a thickness of 50 μm.The conductor formed by electrocondution slurry alloying is filled in hole.Specifically
Implementation are as follows:
Prepare the LCP resin sheet with a thickness of 50 μm first, using machine drilling or carbon dioxide gas volumetric laser specified
Position drilling, forms 100 μm of diameter of through-hole, then with resin residue glue in liquor potassic permanganate removal hole.
Electrocondution slurry is filled in hole using half-tone screen printing method, it is 30 minutes dry in 70 DEG C of baking ovens, then in LCP tree
The single side that rouge piece two sides configures 18 μm of thickness is roughened copper foil, rough surface towards LCP resin side, and using vacuum hotpressing machine into
Row high-temperature laminating, bonding processes are as follows: first under 4MPa pressure, be warming up to 180 DEG C and keep the temperature 10 minutes, then pressure reduction is extremely
1MPa is warming up to 290 DEG C, heat-insulation pressure keeping 20 minutes, is then cooled to 60 DEG C again and obtains integrated print hereinafter, die sinking is taken out
Brush wiring board.Also it can according to need and patterned in copper foil surface, obtain printed wire panel products.
The electrocondution slurry is prepared as follows:
80 parts by weight of copper powder for taking electroplating surfaces with tin, are stirred with the scaling powder of 10 parts by weight by 10 parts of sn-bi alloy powder
It is even, it is then ground using three-roller, obtains the electrocondution slurry.The copper powder of the electroplating surfaces with tin is the tin with core-shell structure
Copper powder is coated, 3 μm of average grain diameter, wherein the ratio of copper nuclear diameter and core-shell structure overall diameter is 0.80 or so.The tin bismuth closes
Bronze is Sn 42wt% and Bi 58w%, and average grain diameter is 8 μm.The scaling powder contain 5 parts of polyethylene glycol, 45 parts of rosin, diethyl
5 parts of hydramine；25 parts of ethylene glycol, 20 parts of ethylene glycol ethyl ether.
Electric conductivity test: the resistance of single through-hole inner conductor, respectively less than 20m Ω are measured.
Thermal cycle test: 30min at -55 DEG C /+125 DEG C of sample is subjected to 1000 circulations, tests the electricity in single through-hole
Resistance.Resistance change rate is less than 10%；In the application, sample is placed into 30min at -55 DEG C, then place at 125 DEG C
30min is a circulation；
Flow back soldering resistance: N2Under atmospheric condition, 260 DEG C are heated to, keeps 1min, cools to room temperature, test resistance variation
Less than 20%.
Embodiment 2
As depicted in figs. 1 and 2, in the present embodiment, printed circuit board includes LCP resin insulating barrier 200 and is overlaid on respectively
The metal foil layer 100 of its two sides, metal foil layer 100 is specially copper foil, using as conductive layer.In the application the thickness of copper foil and
The thickness of LCP resin insulating barrier can need to be customized according to product.In the application the present embodiment, metal foil layer 100
18 μm of thickness.LCP resin insulating barrier 200 with a thickness of 50 μm.The conductor formed by electrocondution slurry alloying is filled in hole.Specifically
Implementation are as follows:
Prepare the LCP resin sheet with a thickness of 50 μm first, using machine drilling or carbon dioxide gas volumetric laser specified
Position drilling, forms 100 μm of diameter of through-hole, then with resin residue glue in liquor potassic permanganate removal hole.
Electrocondution slurry is filled in hole using half-tone screen printing method, it is 30 minutes dry in 70 DEG C of baking ovens, then in LCP tree
The single side that rouge piece two sides configures 18 μm of thickness is roughened copper foil, rough surface towards LCP resin side, and using vacuum hotpressing machine into
Row high-temperature laminating, bonding processes are as follows: first under 4MPa pressure, be warming up to 180 DEG C and keep the temperature 10 minutes, then pressure reduction is extremely
1MPa is warming up to 290 DEG C, heat-insulation pressure keeping 20 minutes, is then cooled to 60 DEG C again and obtains integrated print hereinafter, die sinking is taken out
Brush wiring board.Then, it also can according to need and patterned in copper foil surface, obtain printed wire panel products.
The electrocondution slurry is prepared as follows:
80 parts by weight of copper powder for taking electroplating surfaces with tin, are stirred with the scaling powder of 10 parts by weight by 10 parts of sn-bi alloy powder
It is even, it is then ground using three-roller, obtains the electrocondution slurry.The copper powder of the electroplating surfaces with tin is the tin with core-shell structure
Copper powder is coated, 3 μm of average grain diameter, wherein the ratio of copper nuclear diameter and core-shell structure overall diameter is 0.80 or so.The tin bismuth closes
Bronze is Sn 42wt% and Bi 58w%, and average grain diameter is 8 μm.The scaling powder, contain 5 parts of polyethylene glycol, 30 parts of rosin, apple
5 parts of tartaric acid, 10 parts of adipic acid, 35 parts of ethylene glycol, 15 parts of ethylene glycol ethyl ether.
Electric conductivity test: the resistance of single through-hole inner conductor, respectively less than 15m Ω are measured.
Thermal cycle test: 30min at -55 DEG C /+125 DEG C of sample is subjected to 1000 circulations, tests the electricity in single through-hole
Resistance.Resistance change rate is less than 10%；In the application, sample is placed into 30min at -55 DEG C, then place at 125 DEG C
30min is a circulation.
Flow back soldering resistance: N2Under atmospheric condition, 260 DEG C are heated to, keeps 1min, cools to room temperature, test resistance variation
Less than 20%.
Comparative example 1
Electrocondution slurry is prepared as follows:
45 parts by weight of copper powder are taken, 45 parts by weight of pure tin powder are uniformly mixed with the scaling powder of 10 parts by weight, then utilize
Three-roller grinding, obtains the electrocondution slurry.The copper powder with 3 μm of glass putty average grain diameter, the scaling powder be embodiment 2 in
Scaling powder.
Printed wiring board substrate manufacture process is same as Example 1.
Test: measuring the resistance of the via hole conductor in single via hole, does not turn on largely and (is greater than 1000m Ω).
Embodiment 3
In the present embodiment, printed circuit board includes the resin insulating barrier 200 and metal foil layer 100 of PPO material, metal foil layer
100 be specially copper foil.The thickness of the thickness of copper foil and PPO resin insulating barrier can be determined according to product in the application
System.In the application the present embodiment, 18 μm of the thickness of copper foil layer 100.PPO resin insulating barrier 200 with a thickness of 50 μm.It is filled in hole
The conductor formed by electrocondution slurry alloying.Specific implementation as shown in figure 3, are as follows:
Prepare two single sides first and paste the PPO insulation resin sheet of copper foil, the insulation resin sheet of PPO material with a thickness of 50
μm, 18 μm of copper foil layer thickness.It is utilized respectively chemical etching and carries out surface copper clad patterns, resin is face-up, utilize titanium dioxide
Carbon gas laser drills in designated position, forms 100 μm of diameter of blind hole, then residual with resin in plasma process removal hole
Glue.Obtain resin sheet a and b.
Prepare the PPO insulation resin sheet that a single side pastes copper foil again, the insulation resin sheet of PPO material with a thickness of 50 μ
M, 18 μm of copper foil layer thickness.It being utilized respectively chemical etching and carries out surface copper clad patterns, mechanical drilling machine drills in designated position,
100 μm of diameter of through-hole is formed, then with resin residue glue in plasma process removal hole.Obtain resin sheet c.
Electrocondution slurry is filled in hole using half-tone screen printing method, it is 30 minutes dry in 70 DEG C of baking ovens, it is then that this is several
The resin sheet precision contraposition stacking that layer filling perforation finishes, after rivet is fixed, carries out high-temperature laminating, bonding processes using vacuum hotpressing machine
Are as follows: it first under 5MPa pressure, is warming up to 200 DEG C and keeps the temperature 10 minutes, then pressure reduction to 0.5MPa is warming up to 260 DEG C, protects
Then warm pressure maintaining 20 minutes is cooled to 60 DEG C hereinafter, multilayer printed circuit board product is taken out in die sinking again.It is specific as shown in Figure 3.
The electrocondution slurry is prepared as follows:
60 parts by weight of corronil powder of electroplating surfaces with tin are taken, 20 parts of sn-bi alloy powder, are stirred with the scaling powder of 20 parts by weight
It is uniformly mixed, is then ground using three-roller, obtain the electrocondution slurry.The corronil powder of the electroplating surfaces with tin be with
The tin coated copper nickel alloy powder (cupro-nickel weight ratio 9:1 in corronil) of core-shell structure, 8 μm of average grain diameter, wherein corronil
The ratio of nuclear diameter and core-shell structure overall diameter is 0.88 or so.The sn-bi alloy powder is Sn 42wt% and Bi 58w%, is put down
Equal partial size is 3 μm.Scaling powder described in this implementation is the scaling powder containing 5 parts of polyethylene glycol, 35 parts of rosin, 5 parts of malic acid, oneself
5 parts of diacid, 35 parts of ethylene glycol, 15 parts of ethylene glycol ethyl ether.
Electric conductivity test: the resistance of single through-hole inner conductor, respectively less than 20m Ω are measured.
Thermal cycle test: 30min at -55 DEG C /+125 DEG C of sample is subjected to 1000 circulations, tests the electricity in single through-hole
Resistance.Resistance change rate is less than 10%；
Flow back soldering resistance: N2Under atmospheric condition, 260 DEG C are heated to, keeps 1min, cools to room temperature, test resistance variation
Less than 20%.
Embodiment 4
As depicted in figs. 1 and 2, in the present embodiment, printed circuit board includes polyether-ether-ketone resin insulating layer 200 and presses respectively
It is overlying on the metal foil layer 100 of its two sides, metal foil layer 100 is specially copper foil, using as conductive layer.The thickness of copper foil in the application
And the thickness of polyether-ether-ketone resin insulating layer can need to be customized according to product.In the application the present embodiment, metal foil
18 μm of thickness of layer 100.Polyether-ether-ketone resin insulating layer 200 with a thickness of 50 μm.Filling is by electrocondution slurry alloying shape in hole
At conductor.Specific implementation are as follows:
Prepare the polyether-ether-ketone resin piece with a thickness of 50 μm first, is existed using machine drilling or carbon dioxide gas volumetric laser
Designated position drilling, forms 100 μm of diameter of through-hole, then with resin residue glue in liquor potassic permanganate removal hole.
Electrocondution slurry is filled in hole using half-tone screen printing method, it is 30 minutes dry in 70 DEG C of baking ovens, then in polyethers
The single side that ether ketone resin piece two sides configures 18 μm of thickness is roughened copper foil, and rough surface is utilized towards polyether-ether-ketone resin side
Vacuum hotpressing machine carries out high-temperature laminating, bonding processes are as follows: first under 4MPa pressure, is warming up to 170 DEG C and keeps the temperature 10 minutes, then
Pressure reduction is warming up to 330 DEG C, heat-insulation pressure keeping 20 minutes, is then cooled to 60 DEG C again hereinafter, die sinking taking-up obtains to 1MPa
Integrated printed wiring board.Then, it also can according to need and patterned in copper foil surface, obtain printed wiring board production
Product.
The electrocondution slurry is prepared as follows:
70 parts by weight of copper powder for taking electroplating surfaces with tin, are stirred with the scaling powder of 15 parts by weight by 15 parts of sn-bi alloy powder
It is even, it is then ground using three-roller, obtains the electrocondution slurry.The copper powder of the electroplating surfaces with tin is the tin with core-shell structure
Copper powder is coated, 3 μm of average grain diameter, wherein the ratio of copper nuclear diameter and core-shell structure overall diameter is 0.80 or so.The tin bismuth closes
Bronze is Sn 42wt% and Bi 58w%, and average grain diameter is 8 μm.The scaling powder contain 10 parts of polyethylene glycol, 35 parts of rosin, apple
5 parts of tartaric acid；35 parts of ethylene glycol, 15 parts of ethylene glycol ethyl ether.
Electric conductivity test: the resistance of single through-hole inner conductor, respectively less than 20m Ω are measured.
Thermal cycle test: 30min at -55 DEG C /+125 DEG C of sample is subjected to 1000 circulations, tests the electricity in single through-hole
Resistance.Resistance change rate is less than 10%；In the application, sample is placed into 30min at -55 DEG C, then place at 125 DEG C
30min is a circulation；
Flow back soldering resistance: N2Under atmospheric condition, 260 DEG C are heated to, keeps 1min, cools to room temperature, test resistance variation
Less than 20%.
Embodiment 5
As depicted in figs. 1 and 2, in the present embodiment, printed circuit board includes LCP resin insulating barrier 200 and is overlaid on respectively
The metal foil layer 100 of its two sides, metal foil layer 100 is specially copper foil, using as conductive layer.In the application the thickness of copper foil and
The thickness of LCP resin insulating barrier can need to be customized according to product.In the application the present embodiment, metal foil layer 100
18 μm of thickness.LCP resin insulating barrier 200 with a thickness of 50 μm.The conductor formed by electrocondution slurry alloying is filled in hole.Specifically
Implementation are as follows:
Prepare the LCP resin sheet with a thickness of 50 μm first, using machine drilling or carbon dioxide gas volumetric laser specified
Position drilling, forms 100 μm of diameter of through-hole, then with resin residue glue in liquor potassic permanganate removal hole.
Electrocondution slurry is filled in hole using half-tone screen printing method, it is 30 minutes dry in 80 DEG C of baking ovens, then in LCP tree
The single side that rouge piece two sides configures 18 μm of thickness is roughened copper foil, rough surface towards LCP resin side, and using vacuum hotpressing machine into
Row high-temperature laminating, bonding processes are as follows: first under 4MPa pressure, be warming up to 150 DEG C and keep the temperature 10 minutes, then pressure reduction is extremely
1MPa is warming up to 290 DEG C, heat-insulation pressure keeping 50 minutes, is then cooled to 60 DEG C again and obtains integrated print hereinafter, die sinking is taken out
Brush wiring board.Then, it also can according to need and patterned in copper foil surface, obtain printed wire panel products.
The electrocondution slurry is prepared as follows:
65 parts by weight of copper powder for taking electroplating surfaces with tin, are stirred with the scaling powder of 15 parts by weight by 20 parts of sn-bi alloy powder
It is even, it is then ground using three-roller, obtains the electrocondution slurry.The copper powder of the electroplating surfaces with tin is the tin with core-shell structure
Copper powder is coated, 3 μm of average grain diameter, wherein the ratio of copper nuclear diameter and core-shell structure overall diameter is 0.80 or so.The tin bismuth closes
Bronze is Sn 42wt% and Bi 58w%, and average grain diameter is 8 μm.The scaling powder contain 5 parts of polyethylene glycol, 45 parts of rosin, diethyl
5 parts of hydramine；25 parts of ethylene glycol, 20 parts of ethylene glycol ethyl ether.
Electric conductivity test: the resistance of single through-hole inner conductor, respectively less than 20m Ω are measured.
Thermal cycle test: 30min at -55 DEG C /+125 DEG C of sample is subjected to 1000 circulations, tests the electricity in single through-hole
Resistance.Resistance change rate is less than 10%；In the application, sample is placed into 30min at -55 DEG C, then place at 125 DEG C
30min is a circulation；
Flow back soldering resistance: N2Under atmospheric condition, 260 DEG C are heated to, keeps 1min, cools to room temperature, test resistance variation
Less than 20%.
Embodiment 6
As depicted in figs. 1 and 2, in the present embodiment, printed circuit board includes LCP resin insulating barrier 200 and is overlaid on respectively
The metal foil layer 100 of its two sides, metal foil layer 100 is specially copper foil, using as conductive layer.In the application the thickness of copper foil and
The thickness of LCP resin insulating barrier can need to be customized according to product.In the application the present embodiment, metal foil layer 100
18 μm of thickness.LCP resin insulating barrier 200 with a thickness of 50 μm.The conductor formed by electrocondution slurry alloying is filled in hole.Specifically
Implementation are as follows:
Prepare the LCP resin sheet with a thickness of 50 μm first, using machine drilling or carbon dioxide gas volumetric laser specified
Position drilling, forms 100 μm of diameter of through-hole, then with resin residue glue in liquor potassic permanganate removal hole.
Electrocondution slurry is filled in hole using half-tone screen printing method, it is 30 minutes dry in 80 DEG C of baking ovens, then in LCP tree
The single side that rouge piece two sides configures 18 μm of thickness is roughened copper foil, rough surface towards LCP resin side, and using vacuum hotpressing machine into
Row high-temperature laminating, bonding processes are as follows: first under 4MPa pressure, be warming up to 180 DEG C and keep the temperature 10 minutes, then pressure reduction is extremely
1MPa is warming up to 290 DEG C, heat-insulation pressure keeping 50 minutes, is then cooled to 60 DEG C again and obtains integrated print hereinafter, die sinking is taken out
Brush wiring board.Then, it also can according to need and patterned in copper foil surface, obtain printed wire panel products.
The electrocondution slurry is prepared as follows:
75 parts by weight of copper powder for taking electroplating surfaces with tin, are stirred with the scaling powder of 10 parts by weight by 15 parts of sn-bi alloy powder
It is even, it is then ground using three-roller, obtains the electrocondution slurry.The copper powder of the electroplating surfaces with tin is the tin with core-shell structure
Copper powder is coated, 3 μm of average grain diameter, wherein the ratio of copper nuclear diameter and core-shell structure overall diameter is 0.80 or so.The tin bismuth closes
Bronze is Sn 42wt% and Bi 58w%, and average grain diameter is 8 μm.The scaling powder contain 5 parts of polyethylene glycol, 35 parts of rosin, diethyl
5 parts of hydramine；35 parts of ethylene glycol, 20 parts of ethylene glycol ethyl ether.
Electric conductivity test: the resistance of single through-hole inner conductor, respectively less than 20m Ω are measured.
Thermal cycle test: 30min at -55 DEG C /+125 DEG C of sample is subjected to 1000 circulations, tests the electricity in single through-hole
Resistance.Resistance change rate is less than 10%；In the application, sample is placed into 30min at -55 DEG C, then place at 125 DEG C
30min is a circulation；
Flow back soldering resistance: N2Under atmospheric condition, 260 DEG C are heated to, keeps 1min, cools to room temperature, test resistance variation
Less than 20%.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of electrocondution slurry, which is characterized in that it is counted on the basis of the gross mass of the raw material components of the electrocondution slurry, it is described to lead
Plasma-based material includes following raw material components and weight percentage:
Scaling powder 5wt%~20wt%
Electroplating surfaces with tin metal powder 60wt%~90wt%
Low-melting-point metal powder 5wt%~20wt%.
2. electrocondution slurry according to claim 1, which is characterized in that the scaling powder includes solvent, excipient and activity
Agent.
3. electrocondution slurry according to claim 1, which is characterized in that the electroplating surfaces with tin metal powder is selected from electroplating surfaces with tin
One or both of copper powder and the copper alloy powder of electroplating surfaces with tin.
4. according to electrocondution slurry described in claim foot 1, which is characterized in that the low-melting-point metal powder refers to fusing point 231
DEG C metal powder below.
5. such as the preparation method of the described in any item electrocondution slurries of Claims 1 to 4, the preparation method is that by each raw material component
It obtains after mixing.
6. such as the purposes of the described in any item electrocondution slurries of Claims 1 to 4 in the printed circuit boards.
7. purposes according to claim 6, which is characterized in that using such as the described in any item conductive pastes of Claims 1 to 4
Through hole in material filling printed circuit board, low temperature drying remove solvent, have using heating up and being formed under pressurization
The via hole conductor of electrical connection effect.
8. a kind of printed circuit board, which is characterized in that the stamp circuit board includes several metal foil layers and is folded in described
Resin insulating barrier between metal foil layer, the resin insulating barrier are equipped with several perforative through holes；The resin insulating barrier
In through hole on filled with using electrocondution slurry as described above formed via hole conductor；The metal foil of resin insulating barrier two sides
Layer realizes electrical connection by the via hole conductor.
9. a kind of preparation method of printed circuit board base board as claimed in claim 8, includes the following steps:
A) through hole is formed on resin insulating barrier；
B) filling such as the described in any item electrocondution slurries of Claims 1 to 4 in through hole；
C) it is then configured using metal foil in the two sides of the resin insulating barrier；
D) heated pressing forms printed wiring board substrate.
10. a kind of preparation method of printed circuit board, includes the following steps:
1) surface copper clad patternsization are carried out using the insulation resin laminate that chemical etching is covered with copper foil to single side to handle；
2) resin layer that the insulation resin laminate of copper foil is covered with to single side drills to form blind hole or through-hole；
3) filling such as the described in any item electrocondution slurries of Claims 1 to 4 in blind hole or through-hole；
4) several insulation resin sheets for being covered with copper foil through treated single side are subjected to contraposition stacking, and fixed；
5) heated pressing forms printed wiring board.
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| CN110783013A (en) * | 2019-11-06 | 2020-02-11 | 英利能源（中国）有限公司 | Solar cell electrode slurry, cell and preparation method of assembly of cell |
| CN114055007A (en) * | 2021-11-16 | 2022-02-18 | 陕西众森电能科技有限公司 | Superfine low-temperature soldering tin powder, soldering paste, preparation method and application thereof |
| CN115703176A (en) * | 2021-08-06 | 2023-02-17 | 陕西众森电能科技有限公司 | High-electric-conductivity and heat-conduction solder paste and preparation method thereof |
| CN115910423A (en) * | 2021-08-06 | 2023-04-04 | 陕西众森电能科技有限公司 | Industrial low-temperature conductive paste with high conductivity and preparation method thereof |
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