CN1835129A - Conductive slurry-like compsns - Google Patents
Conductive slurry-like compsns Download PDFInfo
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- CN1835129A CN1835129A CN 200510068575 CN200510068575A CN1835129A CN 1835129 A CN1835129 A CN 1835129A CN 200510068575 CN200510068575 CN 200510068575 CN 200510068575 A CN200510068575 A CN 200510068575A CN 1835129 A CN1835129 A CN 1835129A
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Abstract
A composition includes electroconductive powder, organic solvent soluble polyimide resin and solvent. Ratio between conductive powder and organic resin is 80 : 20 to 99 : 1. The polyimide resin contains chemical units selected from above units: unit (1) is as formula I; unit (2) is as formula II; And admixture of these units. In unit (2), mol ratio between m and n is 90: 10 to 10: 90. Symbol A represents compound of diamine, where structure of unit (2) is connected to the unit of resin.
Description
Background of invention
The present invention relates to a kind of conductor composition, it is used for low-temperature setting/drying, but needs high thermal endurance, as the terminal of the electric wire on the plastic plate, resistance device/inductor, or tantalum capacitor conductive coating material.
So-called " slug type " conductive slurry-like preparation is coated on the ceramic substrate, makes the external electrode that circuit element comprises chip resistor, chip capacitor or sheet inductor by printing process.For pliable and tough substrate, be that polymer based type conductive slurry-like thing has substituted the slug type slurry with the organic resin.Generally also use typography that above-mentioned slurry is coated on the substrate.Because the viscosity that conductive slurry-like thing or composition are suitable is essential to implementing typography, therefore both can also can be with the slurry of thermoplastic resin preparation based on polymer with thermosetting resin.Thermosetting resin can be used as monomer or oligomer with suitable viscosity and is used for the slurry coating.Under heating, crosslinked polymer or polymerization provide and solidify the needed characteristic of slurry then.On the other hand, can use thermoplastic resin, it is softening in the coating solvent, and drying becomes hard film after printing.
If use organic resin, thermosetting resin such as epoxy resin or phenolic resins can be used for high heat-resisting application.Normally need to solidify the heating that the conductive slurry-like thing based on thermosetting resin is adopted for the slurry of complete polymerization.Conductive slurry-like thing based on low curing temperature thermosetting resin generally requires slurry itself should leave in refrigerator or the household freezer, thereby can not begin to solidify before the time of needs.Can need higher curing temperature at the slurry that room temperature safety is preserved.If do not select suitable storage temperature, solidify the temperature that beginning temperature and substrate are tolerated, so the application of non-curing slurry and solidifying the quality of slurry and operating characteristic on will go wrong.
Second kind of selection based on the conductive slurry-like preparation of polymer is to use thermoplastic resin such as acrylic resin or mylar.Almost it doesn't matter with baking temperature based on the use of the conductive slurry-like thing of thermoplastic resin.Reason is that thermoplastic resin does not have crosslinked or polymerization in the pulpous state system, because these resins have been long-chain polymers and have carried out chemical polymerization.Remove the evaporation of leaveing no choice but accelerated solvent, otherwise the slurry that unnecessary heating is printed.Because the selection of drying condition comprises low temperature, be used as the resin of slurry and the selection of substrate composition comprises offers additional possibilities, thermoplastic resin is widely used on the conductive slurry-like compositions of preparation based on polymer or resin.
In addition, based on pot-life of the electric conductive polymer of thermoplastic resin than storage life limit for length based on the conductive slurry-like thing of thermosetting resin.Yet, poorer than slurry usually based on thermosetting resin based on the thermal endurance of the slurry of thermoplastic resin.
Summary of the invention
The present invention is a conductive composition, it comprises electroconductive powder, dissolves in the polyimide resin and the solvent of organic solvent, wherein the ratio of electroconductive powder and organic resin be 80: 20 to 99: 1 and also wherein polyimide resin comprise and be selected from following chemical unit:
Unit (1)
With
Unit (2)
With the mixture of said units, and wherein in unit (2), the mol ratio of m and n is 90: 10 to 10: 90, and " A " representative is connected in diamine compound on the resin unit with the structure of unit (2).In one embodiment of the invention, " A " in unit (2) is selected from 2, the mixture of 2-two [4-(amino-benzene oxygen) phenyl] propane, diaminourea silicone compounds and above-mentioned diamines.
Detailed Description Of The Invention
Conductive slurry-like thing based on resin suits the requirements, and it doesn't matter because its resistivity is almost with baking temperature, and the storage life limit for length of thermoplastic resin and the thermal endurance of thermoplastic conductive paste composition are combined.The present inventor has reached above-mentioned purpose by making slurry by prescription, and this slurry contains the selected polyimide resin that dissolves in organic solvent.The polyimide resin that dissolves in organic solvent is known as analog thermoplastic plastics in this area, and the characteristics of this thermoplastics are to have good characteristic, as dissolubility and the thermal endurance in organic solvent commonly used.Usually, under suitable condition, octane tetracarboxylic anhydride and diamines are prepared above-mentioned resin with suitable ratio polymerization.Polyimides and its preparation method with the stereoisomer preparation of dicyclo [2.2.2.] octane tetracarboxylic anhydride have been described among Japan publication (Kokai) 07-304868.
The polyimide resin that is used for the present composition can prepare by the following method, as at first synthesizing polyamides acid under relative low temperature, then under elevated temperature, pass through dicyclo [2.2.2.] suffering-7-alkene-2,3,5,6-tetracarboxylic anhydride and appropriate organic solvent such as DMF or toluene carry out polyimidesization in reactor, and add hot mixt to 60-120 ℃.Then with 2, two (amino methyl) dicyclo [2.2.1] heptane or 2 of 5-, two (amino methyl) dicyclo [2.2.1] heptane of 6-separately or mix and dropwise join in the reactor, and 120-160 ℃ of reaction 10 to 120 minutes down.In order to obtain polyimides, mixture reacted 1 to 10 hours down at 160-200 ℃.After the reaction, in air, cool off reactant, and reactant mixture is transferred in the container that is full of acetone.Solid in the acetone solution is also dry.This solid is a polyimides.
Can be used for polyimide resin of the present invention generally by above-mentioned preparation method's preparation, and the general constitutional repeating unit with following molecular formula:
Wherein n is n=10-300, and preferred n=10-150 repeats, but is not limited to this scope.
Second kind of polyimide resin that is particularly useful can pass through dicyclo [2.2.2.] suffering-7-alkene-2,3,5,6-tetracarboxylic anhydride, 2,2-two [4-(amino-benzene oxygen) phenyl] propane, 2,5 (2.6)-two (amino methyl)-dicyclo [2.2.1] heptane and/or two (3-aminopropyls) poly-(dimethyl siloxane) preparation:
Wherein the mol ratio of m and n is from 90: 10 to 10: 90, and A is the diamine compound that two structural chemistry is connected to form the polyimides unit, and m+n's and be 10 to 300, preferred 10-150.
The electroconductive powder that is used for the conductive slurry-like thing is that noble metal powder is as silver, gold, platinum, alkali metal powder such as copper, nickel, tin, the powder of similar alloy scolding tin, graphite and precious metal plating and alloy powder.
Can be that the mixture of the powder on basis or the electroconductive powder of several the above-mentioned types is as electroconductive powder with a kind of metal.The weight rate of electroconductive powder and polyimide resin should be greater than 80: 20.If the ratio of electroconductive powder is less than 80wt%, restriction that will be serious or lack conductivity on the desciccator diaphragm.
Employed organic solvent can be any solvent that can dissolve polyimide resin in the slurry.The example of useful solvent comprises ester such as ethyl lactate or butyl lactate, ketone such as cyclohexanone, cycloaliphatic solvent such as gamma-butyrolacton or nitrogenous solvent such as N-methyl pyrrolidone.
Can prepare the conductive slurry-like thing of the present invention with known method, stir as spreading or power based on the organosilicon/polyamide 6 imines.
By following example explanation the present invention, but this example is not intended to limit the scope of the invention.
Can obtain the example that the present invention dissolves in the polyimide resin of organic solvent by for example Maruzen Petrochemical such as Pl-100 or Pl-117.
Embodiment 1
20 parts of polyimide resins that dissolve in organic solvent of the present invention are dissolved in 80 parts of butyl lactates, obtain polyimide solution.This polyimide resin is provided by Maruzen Petrochemical, and name is called Pl-117.Use then the spreading method with 71 parts of thin slice shape silver powder (particle mean size: 3 μ m) and 29 parts of above-mentioned polyimide solutions mix the conductive slurry-like thing that to obtain 25 ℃ of viscosity be 29Pa.S.
Use above-mentioned slurry that the conducting wire is applied on the glass substrate, respectively 100 ℃, 130 ℃ and 160 ℃ of dryings 30 minutes.The resistivity that each baking temperature is measured is as follows:
Following 30 minutes of baking temperature
Resistivity
| 100℃ | 2.0×10 -5Ωcm |
| 130℃ | 2.1×10 -5Ωcm |
| 160℃ | 2.1×10 -5Ωcm |
160 ℃ of dryings 60 minutes, the resistivity of slurry was 2.3 * 10
-5Ω cm heated 10 minutes down at 260 ℃ again, and the resistivity of slurry is 1.6 * 10
-5Ω cm (Δ resistivity=70%).Heating after 10 minutes down/the preceding loss in weight is 0.65% to dry slurry at 260 ℃.260 ℃ heating is after 10 minutes down, and the section line/peel adhesion of dry slurry on glass substrate is 100/100, do not observe failure.
Comparative example 1
15 parts of polymethacrylate resins (the acrylic resin #2041 that provides as Elvacite) are dissolved in 85 parts the propylene glycol MEE acetic acid esters, obtain acrylic resin soln.With the spreading method thin slice shape silver powder used among 57 parts of embodiment 1 and 43 parts of acrylic resin solns are mixed then.The conductive slurry-like thing that to obtain 25 ℃ of viscosity be 20Pa.S.
The same with embodiment 1, use above-mentioned slurry that the conducting wire is applied on the glass substrate, 160 ℃ of dryings 60 minutes.The resistivity of dry slurry is 1.5 * 10
-5Ω cm.Heated 10 minutes down at 260 ℃, the resistivity of dry slurry is 0.8 * 10 again
-5Ω cm (Δ resistivity=53%).Heating after 10 minutes down/the preceding loss in weight is 10% to dry slurry at 260 ℃.This shows has almost removed whole resins when heating down for 260 ℃.As a result, heating is after 10 minutes down at 260 ℃ again, and the section line/peel adhesion of dry slurry is 0/100, and desciccator diaphragm breaks fully.
From the comparative example of embodiment and it as can be seen, conductor composition of the present invention provides resistivity much at one, and it doesn't matter with the temperature of drying.After the heating, heat is attacked and is not destroyed dry slurry under 260 ℃.And on the other hand, with acrylic resin, a kind of typical " thermoplasticity " resin is attacked and is destroyed by heat by the conductive slurry-like thing on basis.
Claims (2)
1, a kind of conductor composition comprises electroconductive powder, dissolves in the polyimide resin and the solvent of organic solvent, wherein the ratio of electroconductive powder and organic resin be 80: 20 to 99: 1 and also wherein polyimide resin comprise and be selected from following chemical unit:
Unit (1)
With
Unit (2)
With the mixture of said units, and wherein in unit (2), the mol ratio of m and n is 90: 10 to 10: 90, and " A " representative is connected in diamine compound on the resin unit with the structure of unit (2).
2, according to the conductor composition of claim 1, wherein " A " is selected from 2,2-two [4-(amino-benzene oxygen) phenyl] propane, diaminourea silicone compounds and their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100685758A CN1835129B (en) | 2005-03-16 | 2005-03-16 | Conductive slurry-like compositions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100685758A CN1835129B (en) | 2005-03-16 | 2005-03-16 | Conductive slurry-like compositions |
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| CN1835129A true CN1835129A (en) | 2006-09-20 |
| CN1835129B CN1835129B (en) | 2010-04-28 |
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| CN2005100685758A Expired - Fee Related CN1835129B (en) | 2005-03-16 | 2005-03-16 | Conductive slurry-like compositions |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108140446A (en) * | 2015-08-12 | 2018-06-08 | E.I.内穆尔杜邦公司 | It is used to form the thickener and method of the welding polymer thick film conductor based on polyimides |
| CN108140442A (en) * | 2015-08-13 | 2018-06-08 | E.I.内穆尔杜邦公司 | The photon sintering of polymer thick film copper conductor composition |
| JP2018525494A (en) * | 2015-08-12 | 2018-09-06 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Process for forming solderable polyimide-based polymer thick film conductors |
| JP2018529001A (en) * | 2015-08-13 | 2018-10-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Photosintering of solderable polymer thick film copper conductor composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003006553A1 (en) * | 2001-07-09 | 2003-01-23 | Kaneka Corporation | Resin composition |
| EP1448669B1 (en) * | 2001-09-27 | 2010-04-07 | LG Chem Ltd. | Adhesive composition comprising a polyimide copolymer and method for preparing the same |
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2005
- 2005-03-16 CN CN2005100685758A patent/CN1835129B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108140446A (en) * | 2015-08-12 | 2018-06-08 | E.I.内穆尔杜邦公司 | It is used to form the thickener and method of the welding polymer thick film conductor based on polyimides |
| JP2018525494A (en) * | 2015-08-12 | 2018-09-06 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Process for forming solderable polyimide-based polymer thick film conductors |
| JP2018529802A (en) * | 2015-08-12 | 2018-10-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Paste and process for forming solderable polyimide polymer thick film conductors |
| CN108140446B (en) * | 2015-08-12 | 2020-07-31 | E.I.内穆尔杜邦公司 | Paste and method for forming solderable polyimide-based polymer thick film conductor |
| CN108140442A (en) * | 2015-08-13 | 2018-06-08 | E.I.内穆尔杜邦公司 | The photon sintering of polymer thick film copper conductor composition |
| JP2018525789A (en) * | 2015-08-13 | 2018-09-06 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Photosintering of polymer thick film copper conductor composition |
| JP2018529001A (en) * | 2015-08-13 | 2018-10-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Photosintering of solderable polymer thick film copper conductor composition |
| CN108140442B (en) * | 2015-08-13 | 2020-08-07 | E.I.内穆尔杜邦公司 | Photonic sintering of polymer thick film copper conductor compositions |
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| Publication number | Publication date |
|---|---|
| CN1835129B (en) | 2010-04-28 |
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