CN102737753A - Conducting paste and conducting pattern - Google Patents

Conducting paste and conducting pattern Download PDF

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Publication number
CN102737753A
CN102737753A CN2012100888659A CN201210088865A CN102737753A CN 102737753 A CN102737753 A CN 102737753A CN 2012100888659 A CN2012100888659 A CN 2012100888659A CN 201210088865 A CN201210088865 A CN 201210088865A CN 102737753 A CN102737753 A CN 102737753A
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resin
paste
conductive paste
pattern
printing
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CN102737753B (en
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佐佐木正树
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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Abstract

The invention provides a conducting paste and a conducting pattern. The conducting paste is excellent in printing adaptability, and can form a fine pattern which is excellent in electrical characteristic without the high temperature process. The conducting paste includes the following components: the silver powder with the tap density of 4.9 to 6.0g/cm3, the specific surface area of 0.7 to 1.3m2/g, and the average grain diameter of 0.6 to 1.0[mu]m, at least one organic binding agent resin from the thermoset resin, the thermoplastic resin, and the thermal drying resin, and the organic solvent.

Description

Conductive paste and conductive pattern
Technical field
The present invention relates to be used to form the for example conductive paste and the conductive pattern of the conductive patterns such as electrode of electronic device.
Background technology
The conductive paste that contains conductive powder and organic binder bond resin as use comes on base material, to form the method for fine conductive pattern, and print processes such as belonging to the intaglio printing of adding the addition process (additive process) of material at required position, intaglio offset is widely used.In this print process,, therefore require to have good transfer printing property owing to China ink is transferred on the base material via version.Therefore, require to have suitable rheological behavior, the excellent paste of printing adaptability that adapts to fine conductive pattern printing.
As the purposes that forms this fine printed patterns, for example, can enumerate out display and use electromagnetic wave shielding mesh.Electromagnetic wave shielding mesh is in order to shield (the Plasmia indicating panel by PDP; Plasma Display Panel), CRT (cathode ray tube; Cathode Ray Tube) electromagnetic wave that produces of display such as, the function film that will be formed with cancellate conductive pattern is configured in the display front.Therefore, need form fine pattern with the mode of the visuality that do not influence display on the gauze screen.And if formed pattern does not show good electrical conductivity (low resistance), then shielding properties is impaired.In addition, the base material of electromagnetic wave shielding mesh is formed by resin film, therefore, also need utilize low temperature process to form conductive pattern.
About can forming the conductive paste of conductive pattern at low temperatures, propose that kinds of schemes is arranged (for example with reference to patent documentation 1 etc.).Yet in formed conductive pattern, being difficult to obtain resistance value is 10 -5Ω cm level can be practical good electrical.Therefore, as conductive powder, consider to use laminar material, but have the problem that is difficult to obtain fine printed patterns.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-355933 communique
Summary of the invention
The problem that invention will solve
Like this, require not use high-temperature technology just can form fine conductive pattern and formed pattern has good electrical characteristics.In addition, when forming the conductive pattern of electronic device, need have good printing adaptability through print process.Yet, have the problem be difficult to obtain satisfy simultaneously the paste of these requirements.
The purpose of this invention is to provide a kind of conductive paste, it has good printing adaptability, and does not use high-temperature technology just can form the fine conductive pattern that can obtain good electrical characteristics.
The scheme that is used to deal with problems
In order to solve this problem, the conductive paste of an embodiment of the invention is characterised in that, contains following composition: tap density is 4.9~6.0g/cm 3, specific area is 0.7~1.3m 2/ g, the average grain diameter of using scanning electron microscope to measure are the silver powder of 0.6~1.0 μ m, at least a organic binder bond resin in heat-curing resin, thermoplastic resin and the heated drying property resin, and organic solvent.
According to this formation, can have good printing adaptability, do not use high-temperature technology just can form the pattern that can obtain good electrical.
In addition, in the conductive paste of an embodiment of the invention, silver powder is preferably spherical.Through being spherical, can make dispersed the raising.
In addition, the formation method of the conductive pattern of an embodiment of the invention comprises: use this conductive paste, form through printing and be coated with film figure, this is coated with film figure 80~200 ℃ of dry down and/or curing.Through forming conductive pattern like this, can be applicable to the low devices of thermal endurance such as flexible devices.
In addition, the conductive pattern of an embodiment of the invention is characterised in that containing tap density is 4.9~6.0g/cm 3, specific area is 0.7~1.3m 2/ g, the average grain diameter of using scanning electron microscope to measure are silver powder and the organic binder bond resin of 0.6~1.0 μ m.According to this formation, the conductive pattern that can obtain the compactness height, have good electrical.
The effect of invention
According to the conductive paste of an embodiment of the invention, have good printing adaptability, and do not use high-temperature technology just can form the conductive pattern that can obtain good electrical.
Embodiment
The conductive paste of an embodiment of the invention below is described.
The conductive paste of this execution mode is characterised in that, contains following composition: tap density is 4.9~6.0g/cm 3, specific area is 0.7~1.3m 2/ g, the average grain diameter of using scanning electron microscope to measure are the silver powder of 0.6~1.0 μ m, organic binder bond resin, and organic solvent.
Silver powder in the conductive paste of this execution mode is used to give formed conductive pattern with conductivity.
In this silver powder, tap density is set at 4.9~6.0g/cm 3Tap density is lower than 4.9g/cm 3The time, the density of the silver powder of formed circuit pattern descends, and therefore is difficult to obtain low-resistance conductive pattern.5.2~6.0g/cm more preferably 3
In addition, specific area is set at 0.7~1.3m 2/ g.Specific area is lower than 0.7m 2During/g, when preserving, cause sedimentation easily, on the other hand, specific area surpasses 1.3m 2During/g, oil absorption increases, paste mobile impaired.0.9~1.1m more preferably 2/ g.
In addition, will be set at 0.6~1.0 μ m with the average grain diameter that scanning electron microscope is measured.Average grain diameter is obtained in the average grain diameter of 10,000 times of 10 silver powder at random of observing down to use SEM (scanning electron microscope).Average grain diameter is difficult to the contact between the silver powder takes place during less than 0.6 μ m, is difficult to obtain sufficient conductivity.On the other hand, when average grain diameter surpassed 1.0 μ m, formed conductive pattern was difficult to obtain compactness.
As its shape, can use different shapes such as spherical, laminar, dendroid, when especially considering printing adaptability, dispersed in paste, preferably using length-width ratio is that 1~1.5 spherical silver powder is as main body.
The compounding rate of this silver powder is benchmark with the nonvolatile component (do not volatilize from paste because of dry, remain in the composition in the film) of conductive paste, is preferably 85~97 quality %.When being lower than 85 quality %, be difficult to obtain sufficient conductivity, on the other hand, when surpassing 97 quality %, paste mobile impaired is difficult to give printing adaptability.88~95 quality % more preferably.
Organic binder bond resin in the conductive paste of this execution mode is used to give printing adaptability, and residual after the coating of conductive paste, drying, curing, is used to obtain conductive pattern to rerum naturas such as the good adaptation of base material, resistance to bend(ing), hardness.
As this organic binder bond resin; As long as can give conductive paste with printing adaptability; To its not special restriction, suitable use just can not form heat-curing resin, thermoplastic resin, the heated drying property resin of pattern (curing) at low temperatures through photocuring.For example; Preferred especially phenoxy resin, acrylic resin, polyvinyl butyral resin; In addition; Can enumerate out various modified polyester resins such as mylar, urethane-modified polyester, epoxy modified polyester resin, acrylic acid modified polyester resin, EU resin, polycarbonate polyurethane resin, acrylated polyurethane resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, phenolic resins, polyamidoimide, polyimides, polyamide, NC Nitroncellulose, cellulose-acetate-butyrate (CAB), cellulose-acetate-propionic ester modified celluloses such as (CAP) class etc.These resins can use separately or two or more combinations are made and be used as the organic binder bond resin.
In order to give formed pattern with characteristics such as solvent resistance, high rigidity, can use resin glue with functional group's (for example carboxyl, hydroxyl etc.) that can be three-dimensional cross-linked.Wherein, preferably include the carboxylic acid resin that contains who has 2 above carboxyls at least in 1 molecule especially.Contain the carboxylic acid resin as this, particularly, can enumerate out following resin, but be not limited to these resins.
(1) through making the carboxy resin that contains that unsaturated carboxylic acid such as (methyl) acrylic acid and in addition more than one copolymerization of the compound with unsaturated double-bond obtain.
(2) contain carboxy resin through what monofunctional epoxy compounds such as addition butyl glycidyl ether, phenyl glycidyl ether on more than one copolymer of unsaturated carboxylic acid such as (methyl) acrylic acid and in addition the compound with unsaturated double-bond obtained.
(3) make (methyl) glycidyl acrylate or (methyl) acrylic acid 3; Saturated carboxylic acid reactions such as the copolymer that 4-epoxycyclohexyl methyl esters etc. contains the compound of epoxy radicals and unsaturated double-bond and in addition the compound with unsaturated double-bond and, propionic acid, make again generation secondary hydroxyl acquisition with the multi-anhydride reaction contain carboxy resin.
(4) make copolymer that maleic anhydride etc. has the acid anhydrides of unsaturated double-bond and a compound with unsaturated double-bond in addition and, butanols etc. have the compound reaction of hydroxyl and obtain contain carboxy resin.
(5) make multi-functional epoxy compound and saturated mono carboxylic acid reaction, make hydroxyl and the saturated or unsaturated multi-anhydride reaction of generation again and obtain contain carboxy resin.
(6) make the reaction of hydroxyl polymer-containing such as polyvinyl alcohol derivative and saturated or unsaturated multi-anhydride and the hydroxyl that obtains and the resin of carboxyl.
(7) make and have at least one alcoholic hydroxyl in multi-functional epoxy compound and saturated mono carboxylic acid and a part and contain carboxy resin with the product of the compound of a reactive group beyond the alcoholic hydroxyl of epoxy reaction obtains with, saturated or unsaturated multi-anhydride reaction.
(8) make multifunctional oxetane compound and the saturated mono carboxylic acid reaction that has at least 2 oxetanes rings in a part, make primary hydroxyl and the saturated or unsaturated multi-anhydride reaction in the gained modification oxetane resin again and obtain contain carboxy resin.
(9) make obtain with the multi-anhydride reaction again after polyfunctional epoxy resin and the saturated mono carboxylic acid reaction contain carboxy resin further with molecule in have the compound reaction of an oxirane ring and obtain contain carboxy resin.
In the middle of these, especially preferably use the carboxy resin that contains of (1), (2) and (3).Utilize them, can at random adjust molecular weight, glass transition temperature etc., and can adjust the printing adaptability of conductive paste, the suitable adaptation of controlling base material.
In addition, this acid number that contains carboxy resin is preferably 40~200mg KOH/g.When the acid number that contains carboxy resin was lower than 40mg KOH/g, the aggregation force of conductive paste descended, and took place to shift bad during printing easily.On the other hand, when surpassing 200mg KOH/g, the viscosity of conductive paste becomes too high, needs a large amount of crosslinking agents of compounding etc., is difficult to give printing adaptability.45~150mg KOH/g more preferably.
In addition; When using resin film as base material; Consider preferred polyester resin, acrylic resin, polyvinyl butyral resin, modified polyester resin, vinyl chloride-vinyl acetate copolymer, copolymer polyester resin etc. from resistance to bend(ing) with to the aspect of the adaptation of base material.
Wherein, Consider from the aspect that can realize high meticulous printing and low resistanceization; The resin that side chain has hydroxyl, a carboxyl is preferred, as object lesson, can enumerate out phenoxy resin, hydroxyl group containing polyester resin, polyvinyl butyral resin, contain the acrylic resin of carboxyl or hydroxyl.
As the organic binder bond resin, number-average molecular weight (Mn) is preferably 3000~50000.Number-average molecular weight is lower than at 3000 o'clock, and it is bad that transfer takes place during printing easily, is difficult to form the favorable conductive pattern.On the other hand, number-average molecular weight surpasses at 50000 o'clock, the beard shape defective that the wire drawing because of paste causes, the bending of lines etc. takes place easily, the printing adaptability deterioration when printing.More preferably 5000~30000.
Wherein, number-average molecular weight is the value that converts through the polystyrene standard that gel permeation chromatography (GPC) is measured.
In addition, as the organic binder bond resin,, can give Thermocurable with thermoplastic resin or heated drying property resin and heat-curing resin combination use.
Particularly; In the conductive paste of this execution mode; In order to form three-dimensional netted chain structure; Improve solvent resistance, the adaptation of formed pattern, can also through further in the organic binder bond resin, comprise have with resin in reactive heat-curing resin of functional group of thermoplastic resin or heated drying property resin as crosslinking agent, thereby give Thermocurable.
As the heat-curing resin of crosslinking agent only otherwise make the printing adaptability deterioration, can be with the functional group reactions of thermoplastic resin in the organic binder bond resin or heated drying property resin, carry out crosslinked getting final product.As this crosslinking agent; So long as the resin that solidifies through heating gets final product; To its not special restriction; For example, can enumerate out epoxy resin, phenolic resins, melmac, alkyd resins, polyurethane resin, mylar, acrylic resin, polyimide resin and their modified resin, they can use separately or two or more combinations are used.In addition, can enumerate out oxetane compound of having at least 2 oxa-cyclobutyl in the molecule etc.
In this heat-curing resin, preferably include the epoxy resin that has 2 above glycidyls at least in 1 molecule as crosslinking agent.As this epoxy resin; For example; Can enumerate out the known epoxy resin such as epoxy resin, alicyclic epoxy resin of phenolic varnish type, xenol type, di-cresols type, tris-phenol type, N-glycidol fundamental mode, the N-glycidol fundamental mode of bisphenol A-type, hydrogenated bisphenol A type, Bisphenol F type, bisphenol S type, phenol phenolic varnish type, cresols phenolic varnish type, bisphenol-A; Be not limited to specific epoxy resin, in addition, can they used separately or two or more combinations are used.Wherein, preferably have as the heat-curing resin of crosslinking agent and be lower than 3000 number-average molecular weight (Mn).
For the compounding rate of these epoxy resin, be that 1~100 mass parts suits with respect to thermoplastic resin in the 100 mass parts organic binder bond resins or heated drying property resin, be preferably 5~40 mass parts.
In addition, can also compounding be used for promoting thermoplastic resin or the heated drying property resin of organic binder bond resin and as the curing catalysts of the reaction of the heat-curing resin of crosslinking agent, for example amines, imdazole derivatives etc.
Organic solvent in the conductive paste of this execution mode is used to give good printing adaptability.As this organic solvent, get final product with regard to the organic solvent that can dissolve so long as do not carry out chemical reaction with above-mentioned organic binder bond resin.Particularly; For example; Can enumerate out toluene, xylenes, ethyl acetate, butyl acetate, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, 1-butanols, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, terpineol, MEK, carbitol, carbitol acetic acid esters, BC etc.; These solvents can use separately, perhaps can two or more mixing be used.
In addition, in order to prevent dry, the maintenance metastatic of paste in the printing process, can make up the high boiling solvent of boiling point in 240 ℃~330 ℃ scopes that uses under the 0.1013MPa.
As this high boiling solvent; Can enumerate out diamyl benzene (260~280 ℃ of boiling points), three amylbenzenes (300~320 ℃ of boiling points), n-dodecane alcohol (255~259 ℃ of boiling points), diethylene glycol (DEG) (245 ℃ of boiling points), diethylene glycol monobutyl ether acetic acid esters (247 ℃ of boiling points), diethylene glycol dibutyl ether (255 ℃ of boiling points), diglycol monotertiary acetic acid esters (250 ℃ of boiling points), triethylene glycol (276 ℃ of boiling points), triethylene glycol monomethyl ether (249 ℃ of boiling points), triethylene glycol list ether (256 ℃ of boiling points), triethylene glycol monobutyl ether (271 ℃ of boiling points), tetraethylene glycol (327 ℃ of boiling points), tetraethylene glycol monobutyl ether (304 ℃ of boiling points), tripropylene glycol (267 ℃ of boiling points), tripropylene glycol monomethyl ether (243 ℃ of boiling points), 2; 2; 4-trimethyl-1,3-pentanediol mono isobutyrate (253 ℃ of boiling points) etc.In addition; As oil is hydro carbons; Can enumerate AF SOLVENT that the Japan National Oil Corp that makes new advances makes No. 4 (240~265 ℃ of boiling points), No. 5 (boiling point=275~306 ℃), No. 6 (296~317 ℃ of boiling points), No. 7 (259~282 ℃ of boiling points) and No. 0 SOLVENTH (245~265 ℃ of boiling points) etc.; As required, can contain the two or more of them.
This organic solvent is suitable to be contained so that conductive paste reaches the mode of the viscosity that is suitable for printing.
In addition, for the conductive paste of this execution mode is painted, can contain colouring agent.The kind of colouring agent, shape etc. are not special to be limited, and can use known colouring agent.The color of colouring agent for example is to be suitable for causing that the color of the reduction of the brightness that is enough to suppress external light reflection gets final product under the situation of display applications.Preferably enumerate out the black of blueness, black, three mixture of colours generation etc.
Especially be preferably black, can use carbon black, solvent black, glossy black etc., from being prone to the acquired consideration that waits, colorant is fit to carbon black.For example, as carbon black, can enumerate out channel black, furnace black or colorant such as dim with carbon black and conductive carbon black, acetylene black etc.
As long as the compounding amount of this colouring agent can obtain good printing adaptability, can be colored as object brightness.Consider from the viewpoint of printing adaptability,, be preferably below 100 mass parts with respect to 100 mass parts organic binder bond resins.When surpassing 100 mass parts, take place that significant viscosity rises, thixotropy became problems such as height.More preferably below 80 mass parts.
In addition, as lower limit, for example under the situation of display applications,, be preferably more than 5 mass parts with respect to 100 mass parts organic binder bond resins.When the compounding amount of colouring agent was lower than 5 mass parts, the brightness of paste was increased, and the visuality of display worsens.More preferably more than 10 mass parts.
This colouring agent can add with powder, dispersion liquid.
In the conductive paste of this execution mode; In order to obtain more excellent printing adaptability and conductivity; Preferably, the compounding amount of silver powder, organic binder bond resin, colouring agent (containing sometimes) is by the compounding amount of satisfied (the compounding amount of the compounding amount+colouring agent of the silver powder)/organic binder bond resin of quality criteria: A is the relation of 10≤A≤26.
The A value was less than 10 o'clock, because the ratio of conducting powder reduces relatively, conductivity reduces; And the powder components in proportions in the paste reduces; Therefore be difficult to obtain the rheological characteristic that is suitable for printing, and surpass at 26 o'clock, it is too much that the ratio of the powder in the paste becomes; Form the high paste of thixotropy, can not reach the rheological characteristic that is suitable for printing.13≤A≤22 more preferably.
In addition, in the scope of not damaging printing adaptability, can the compounding metal dispersion, additive such as thixotropy imparting agent, antifoaming agent, levelling agent, surface tension reducer, plasticizer, oxidation inhibitor, matal deactivator, coupling agent, filler.
For this conductive paste, in order to obtain good printing adaptability, its concentration is preferably 50~1000dPas in the measured value (25 ℃) that is obtained by cone-plate type viscosimeter.When being lower than 50dPas, the ratio of the organic solvent in the paste is too high, and metastatic reduces, and is difficult to carry out good printing.On the other hand, when surpassing 1000dPas, be difficult to be filled on the version, in addition, scraper scrape the deterioration of getting property, dirty version (paste be attached to non-setting-out portion) takes place easily.100~650dPas more preferably.Wherein, during printing, can suitably dilute to reach this concentration.
In addition, the dynamic fusible viscosity value of representing this conductive paste is preferably 5~35.Viscosity value is less than 5 o'clock, the metastatic difference when printing sometimes and press quality is worsened.On the other hand, viscosity value surpasses at 35 o'clock, is printed fluffing (being printed the destruction of thing), the obstruction (being printed thing stops up in printing machine) of thing during printing easily.More preferably 10~30.Wherein, viscosity value is to use rotational viscosity meter (common name: the value of inkometer) under 30 ℃, 400 conditions of changeing, measuring.
Use this conductive paste, for example being described below forms conductive pattern.At first, through being printed on the film figure that is coated with that forms conductive paste on the base material.As printing process, can use known printing processes such as silk screen printing, intaglio printing, intaglio offset.At this moment, as base material, can use flexible substrates such as printed circuit board (PCB), glass substrate and PET film.
With as above operate in form on the base material be coated with film figure at 60~120 ℃ down after dry 1~60 minute, through 100~250 ℃ of following easy fireds 1~60 minute, make the pattern cured of filming, form conductive pattern.
Like this, can obtain good pattern form, and, low resistance, conductive pattern that solvent resistance is high can be obtained.In addition, this conductive pattern does not carry out high temperature and burns till and just can obtain, and therefore, can be used as the electrode use of flexible substrate, device that thermal endurance is low.
Embodiment
Below through embodiment and comparative example this execution mode is described particularly, but the invention is not restricted to these embodiment.Need to prove that except as otherwise noted, following compounding amount is benchmark with the quality.
[preparation of conductive paste]
Use the spherical silver powder shown in the table 1, the conductive paste of preparation embodiment 1~5 and comparative example 1~4.
At first; With 1500 weight portion silver powder, 100 weight portions polyvinyl butyral resin (S-LEC BL-1 as the organic binder bond resin; Ponding chemical industrial company makes), 30 weight portions are as the diethylene glycol monoethyl ether acetic acid esters compounding as organic solvent of the carbon black (MA-100, Mitsubishi Chemical Ind makes) of colouring agent, 200 weight portions.
Then, they are mixed, mixing with triple-roller mill, obtain conductive paste.And then, with an organic solvent, the viscosity of gained conductive paste is adjusted to 500dPas.The silver-colored containing ratio of gained paste is 82 quality % in paste, after making solvent evaporates and drying, is 92 quality %.
Table 1
And then, use the silver powder that uses among the embodiment 1, as shown in table 2, make silver powder containing ratio different conductivity paste.Wherein, organic binder bond resin and colouring agent use the material that uses among the embodiment 1~5, and organic solvent uses the diethylene glycol monoethyl ether acetic acid esters that has added the triethylene glycol monobutyl ether.
Wherein, in the conductive paste of making like this, the silver-colored containing ratio in the paste of embodiment 6 is 82 quality %, and making solvent evaporates is 93 quality % afterwards.Silver-colored containing ratio in the paste of embodiment 7 is 85 quality %, and making solvent evaporates is 94 quality % afterwards.In addition, the silver-colored containing ratio in the paste of embodiment 8 is 74 quality %, and making solvent evaporates is 88 quality % afterwards.
Table 2
* 1: the diethylene glycol monoethyl ether acetic acid esters
* 2: the triethylene glycol monobutyl ether
[mensuration of resistivity value]
Use each conductive paste that obtains like this,, on glass substrate, form the paste pattern of 1mm * 40cm respectively through silk screen printing.Then, the paste pattern 120 ℃ of down dry (low-temperature heat processing) in 30 minutes, is formed the conductive pattern of 1mm * 40cm.
For each conductive pattern of such acquisition, measure resistance value through the four-terminal method that uses Milliohm HiTESTER, calculate resistivity value by its resistance value and thickness.The resistivity value of each conductive pattern is shown in the table 3.
Table 3
As shown in table 3, in the conductive pattern of the conductive paste that uses embodiment 1~7, its resistivity value is 10 -5Ω cm level.In the conductive pattern of the conductive paste that uses embodiment 8, even reduce the silver-colored containing ratio in the paste, also can conducting.On the other hand, in the conductive pattern of the conductive paste that uses comparative example 1~4, be high resistance, especially in the comparative example 2,4, can not conducting.
[printing adaptability evaluation]
Use embodiment 1~5 and comparative example 2,3, carry out the adaptive test of intaglio printing.Use each conductive paste of gained,, go up the cancellate paste pattern of formation at the thick polyester film of 100 μ m (COSMOSHINE A4300, manufactured is spun by Japan) through intaglio printing.The chromium plating intaglio plate that uses this moment has formed the grid pattern of live width 23 μ m, version dark 13 μ m, spacing 250 μ m.
Gained paste pattern 120 ℃ of down dry (low-temperature heat processing) in 30 minutes, is made the light-permeable conductive film that is formed with the clathrate conductive pattern.
For each light-permeable conductive film of such making, observe cancellate conductive pattern, estimate dirty version (paste is attached in the non-setting-out portion), beard shape defective, ambiguous having or not.Evaluation result has been shown in the table 3.Metewand is described below.
Well: dirty version, beard shape defective, smudgy all less than finding.
Bad: as to have found dirty version, beard shape defective, ambiguous any at least.
In addition, use Loresta EP (Mitsubishi Chemical Ind's manufacturing), carry out the mensuration of sheet resistance.
Table 4
As shown in table 4ly know,, can take into account good printing adaptability and low sheet resistance through using the conductive paste of embodiment.On the other hand, in comparative example 2, though printing adaptability is good, sheet resistance value increases, and in comparative example 3, pattern lacks compactness, and it is bad that printing adaptability becomes, and sheet resistance value also significantly increases.
Then, be shown in the embodiment that uses heat-curing resin following.
[synthesizing of organic binder bond resin]
(containing the synthetic of carboxyl polyurethane resin)
In the reaction vessel that is provided with agitating device, thermometer, condenser, add 288g (0.36mol) as polyol component by 1; 5-pentanediol and 1; (Asahi Kasei Chemicals Corporation makes the PCDL that the 6-hexylene glycol is derived; T5650J; Number-average molecular weight 800), 45g (0.09mol) bisphenol type epoxy propane modification addition product glycol (ADEKA manufactured, BPX33, number-average molecular weight 500), 81.4g (0.55mol) as the dimethylolpropionic acid of dimethylolalkanoic acids and 11.8g (0.16mol) as the n-butanol of molecular weight regulator (end-capping reagent), 250g carbitol acetic acid esters (DAICEL CHEMICAL INDUSTRIES as solvent; LTD. make), under 60 ℃, all raw materials are dissolved.
This lysate is stirred on the limit, and the limit drips the trimethylene diisocyanate of 200.9g (1.08mol) as polyisocyanates through dropping funel.Drip end and continue to react in stirring limit under 80 ℃, limit afterwards, the absorption spectra (2280cm of NCO during the affirmation infrared ray absorbing is composed -1) back end reaction disappears.After reaction finishes, add the carbitol acetic acid esters, make that solid constituent is 60wt%, obtain polyurethane resin solution (varnish 1).
The weight average molecular weight of gained polyurethane resin is 18300, and the acid number of solid constituent is 50.3mg KOH/g.Wherein, weight average molecular weight is to use gel carrier liquid chromatograph (HLC-8120GPC, TOSOH CORPORATION makes) to obtain by the polystyrene conversion value.
(containing the synthetic of carboxyl acrylic resin)
In the reaction vessel that is provided with agitating device, thermometer, dropping funel, condenser; Add methyl methacrylate and acrylic acid by 0.80: 0.20 mol ratio; And add triethylene glycol monobutyl ether (boiling point: 271 ℃) as solvent, as the azodiisobutyronitrile of catalyst; Under nitrogen atmosphere, stirred 6 hours down at 80 ℃, obtain the acrylic resin soln (varnish 2) of non-volatile content 40wt%.The number-average molecular weight of gained resin is 15000, and weight average molecular weight is about 40000, and acid number is 97mg KOH/g.Wherein, weight average molecular weight and varnish 1 are likewise obtained.
Use the resin varnish, phenoxy resin and the heat-curing resin that obtain in the above-mentioned synthetic example, mixing according to each composition of proportioning compounding shown in the table 5 with triple-roller mill, the conductive paste of acquisition embodiment 9~11.Wherein, the silver-colored containing ratio in all pastes all is 94 quality % after making solvent evaporates.
Table 5
[remarks]
* 1:InChem manufactured PKHB
* 2: Mitsubishi Chemical Ind makes, and jER828 (bisphenol A type epoxy resin, epoxide equivalent=190g/eq)
* 3: the silver powder that uses among the embodiment 1
* 4: the diethylene glycol monoethyl ether acetic acid esters
* 5: the triethylene glycol monobutyl ether
* 6:2,4-diaminourea-6-[2 '-methylimidazole-(1)]-ethyl-s-triazine isocyanuric acid addition product
(utilizing the evaluation of the printing adaptability of simple and easy intaglio printing)
(making of sample)
Use steel spatula, each conductive paste of gained is filled into be formed with live width/spacing 70/30 μ m, version is dark: the recess of the glass intaglio plate of the candy strip of 10 μ m.
Then, the blanket cylinder that this glass intaglio plate and silicon rubber by 30 ° of rubber hardnesses are formed contacts, and the conductive paste of filling in the recess is transferred on the blanket cylinder surface (shifts (off) operation).And then the pattern transfer of the conductive paste that blanket cylinder is surperficial is (fixing (set) operation) to the soda-lime glass surface of thickness 1.8mm.
As follows the sample that obtains is like this estimated.
(printing adaptability 1: the evaluation of transfer printing property)
After the transfering process, fixing operation after 10 seconds, whether the visual valuation conductive paste is residual on the blanket cylinder surface.Metewand is described below.
Zero: no conductive paste residual (100% transfer printing) on the blanket cylinder surface.
△: residual conductive paste on the part on blanket cylinder surface.
*: residual conductive paste on the whole surface of blanket cylinder.
(printing adaptability 2: the transfer printing property evaluation after placing for 30 seconds on the blanket cylinder)
After the transfering process, fixing operation after 30 seconds, whether the visual valuation conductive paste is residual on the blanket cylinder surface.Metewand is described below.
Zero: no conductive paste residual (100% transfer printing) on the blanket cylinder surface.
△: residual conductive paste on the part on blanket cylinder surface.
*: residual conductive paste on the whole surface of blanket cylinder.
(printing adaptability 3: the shape of formed pattern)
With the observation by light microscope transfer printing glass substrate of the pattern of conductive paste is arranged, estimate the having or not of craspedodrome property, beard shape defective of the pattern of printing.Metewand is described below:
Zero: have craspedodrome property and/or do not find beard shape defective fully.
△: be short of craspedodrome property a little and/or find few beard shape defective.
*: have bending, the broken string of pattern, and/or obviously produce many beard shape defectives.
< mensuration of resistivity value >
The test pattern of printing live width 1mm, length 40cm uses the heated air circulation type drying oven, under 120 ℃, carries out 30 minutes heat treated.Service test appearance (HIOKI manufactured, Milliohm HiTES TER 3540) is measured the resistance value of gained pattern, calculates resistivity value by the thickness of pattern.
Table 6
As shown in table 6ly know,, also can take into account good printing and low-resistance value even used the conductive paste of the embodiment 9~11 of heat-curing resin.Wherein, and crosslinked, therefore, even be immersed in the organic solvent, can dissolvedly not remove yet by pattern through heating for embodiment 9~11.

Claims (5)

1. a conductive paste is characterized in that, contains following composition:
Tap density is 4.9~6.0g/cm 3, specific area is 0.7~1.3m 2/ g, the average grain diameter of using scanning electron microscope to measure be 0.6~1.0 μ m silver powder and
At least a organic binder bond resin in heat-curing resin, thermoplastic resin and the heated drying property resin, and
Organic solvent.
2. conductive paste according to claim 1 is characterized in that, said organic binder bond resin contains hydroxyl or carboxyl in molecule.
3. according to claim 1 or the described conductive paste of claim 2, it is characterized in that said silver powder is spherical.
4. the formation method of a conductive pattern is characterized in that, uses the conductive paste described in claim 1~claim 3, form through printing and be coated with film figure,
Descend dry and/or curing at 80~200 ℃ the said film figure that is coated with.
5. a conductive pattern is characterized in that, contains following composition:
Tap density is 4.9~6.0g/cm 3, specific area is 0.7~1.3m 2/ g, the average grain diameter of using scanning electron microscope to measure be 0.6~1.0 μ m silver powder and
The organic binder bond resin.
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