CN103135352B - Conductive resin composition and conducting channel - Google Patents
Conductive resin composition and conducting channel Download PDFInfo
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- CN103135352B CN103135352B CN201210499883.6A CN201210499883A CN103135352B CN 103135352 B CN103135352 B CN 103135352B CN 201210499883 A CN201210499883 A CN 201210499883A CN 103135352 B CN103135352 B CN 103135352B
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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
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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
- 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
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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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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Abstract
The present invention relates to conductive resin composition and conducting channel.A kind of base material, conductive resin composition of electric conductivity that can ensure that excellence that can apply to resistance to heat differential is provided and uses this conductive resin composition and the conducting channel that formed, described conductive resin composition comprise containing carboxy resin, electroconductive powder, 2 ~ 4 functional groups acrylate monomer at least any one and Photoepolymerizationinitiater initiater.
Description
Technical field
The present invention relates to conductive resin composition and use this conductive resin composition and the conducting channel that formed.
Background technology
As the known document of the conductive paste disclosed for forming conductive pattern (pattern) film on base material, have
Patent documentation 1: Japanese Unexamined Patent Publication 2003-280181 publication and patent documentation 2: No. 4411113 publications of Japanese Patent Publication No..
Patent documentation 1,2 disclose a kind of containing conductive powder, organic binder bond (binder), photopolymerization monomer, with
And the conductive paste of Photoepolymerizationinitiater initiater.
By by these conductive pastes (paste) more than 500 DEG C at a temperature of carry out roasting and remove having in paste
Machine composition, so that it is guaranteed that the electric conductivity of conductive circuit layer.
But, this photosensitive conductive paste, due to roasting at a temperature of more than 500 DEG C, therefore has and is difficult in resistance to heat differential
Base material on apply such problem.
Summary of the invention
The problem that invention is to be solved
The present invention makes to solve the problems referred to above, it is provided that a kind of can apply to the base material of resistance to heat differential, can ensure that
The conductive resin composition of excellent electric conductivity and use this conductive resin composition and the conducting channel that formed.
For solving the scheme of problem
In order to solve the problems referred to above, the present invention provides conductive resin composition, it is characterised in that it comprises containing carboxyl tree
Fat, electroconductive powder, 2 ~ 4 functional groups acrylate monomer at least any one and Photoepolymerizationinitiater initiater, Yi Jiti
The conducting channel formed on base material it is formed at for this conductive resin composition.
The effect of invention
According to the present invention, it is possible to provide a kind of can apply to resistance to heat differential base material, the electric conductivity of electric conductivity that can ensure that excellence
Resin combination and use this conductive resin composition and the conducting channel that formed.
Detailed description of the invention
The conductive resin composition maximum of the present invention is characterised by, the functional group number of acrylate monomer specifically for 2 ~
4.
The functional group number of acrylate monomer is because following reason specifically for 2 ~ 4.By making acrylate monomer
Functional group number be more than 2, thus photoreactivity improve and excellent in resolution.Further, since functional group number is less than 4, at light
During solidification, react with each other compared with the intramolecular functional group of acrylate monomer, with the sense of other acrylate monomers
The intermolecular reaction of group is carried out quickly.Thus, between multiple acrylate monomers, form intermolecular combination, thus electric conductivity
Resin composition shrinks.Further, only carry out heat treatment by low temperature, promote intermolecular reaction, electroconductive resin further
Compositions cures sufficiently contraction.Its result, it is believed that electroconductive powder becomes closely, under the resistivity value of conductive pattern film
Fall.
On the other hand, when the functional group number of acrylate monomer is 1, cannot be differentiated owing to lacking photoreactivity
Rate.On the other hand, when the functional group number of acrylate monomer is more than 5, acrylate monomer intramolecular functional group that
This preferential reaction, it is difficult to form intermolecular combination.Its result, it is believed that conductive resin composition does not cures sufficiently contraction,
Thus electroconductive powder is the tightst, it is difficult to reduce the resistivity value of conductive pattern film.
Therefore, the conductive resin composition of the present invention is without 500 DEG C of these temperature containing carboxy resin generation thermal decomposition
Process under degree, carry out the most at lower temperatures processing the electric conductivity i.e. playing excellence.Therefore, the electric conductivity tree of the present invention
Oil/fat composition can be applicable to the base material of resistance to heat differential.It addition, the conductive resin composition of the present invention also ensures that the resolution of excellence
Rate.
The composition being compounded in conductive resin composition
Containing carboxy resin
As containing carboxy resin, the known conventional resin compound containing carboxyl in molecule can be used.
As containing carboxy resin, can be that bag is double bond containing containing carboxyl photoresist, but the most double bond containing containing carboxylic
Base resin.The most double bond containing containing carboxy resin owing to not reacting with acrylate monomer, be formed without intermolecular combination.Therefore, contain
The molecular weight of carboxy resin will not become big, thus easily removes when development.Its result, can make electroconductive powder compact, fall
The resistivity value of low conductive pattern film.
Wherein, even if containing double bond containing carboxy resin with considerably less ratio, if this ratio is playing identical with the present invention
Effect in the range of, the most this bag is double bond containing is also contained in the " the most double bond containing containing carboxyl tree of the present invention containing carboxy resin
Fat " in.As the most double bond containing containing carboxy resin, include, for example out double bond equivalent be more than 10000 containing carboxy resin.
About containing carboxy resin, the most double bond containing containing carboxy resin in particularly preferably double bond and aromatic rings both of which do not contain
Containing carboxy resin.By being the structure without aromatic rings, the light containing carboxy resin self can be suppressed to absorb, relatively carry
The photoreactivity of high acrylate monomer.
The concrete example containing carboxy resin without double bond and aromatic rings is listed below.
Can list:
(1) be there is the change of unsaturated double-bond by the unsaturated carboxylic acid such as (methyl) acrylic acid and in addition more than one
Compound copolymerization and obtain containing carboxy resin,
(2) be there is anhydride and the chemical combination with unsaturated double-bond in addition of unsaturated double-bond by maleic anhydride etc.
Thing copolymerization and obtain containing carboxy resin,
(3) make to have the compound of hydroxyl with, to have the anhydride of unsaturated double-bond unsaturated double with having in addition
The copolymer reaction of the compound of key and obtain containing carboxy resin,
(4) make saturated carboxylic acid with, there is the compound of epoxy radicals and unsaturated double-bond and there is the chemical combination of unsaturated double-bond
The copolymer reaction of thing, make the secondary hydroxyl of generation react with multi-anhydride and obtain containing carboxy resin,
(5) make hydroxyl polymer-containing react with multi-anhydride and obtain containing carboxy resin,
But it is not limited to these.
It should be noted that in this specification, (methyl) acrylic acid be referred to as acrylic acid, methacrylic acid and they
The term of mixture, about other similar expression too.
Above-mentioned this have multiple free carboxyl on the side chain of trunk polymer containing carboxy resin, therefore can utilize
Dilute alkaline aqueous solution develops.
It addition, for the above-mentioned acid number containing carboxy resin, the scope of preferably 40 ~ 200mgKOH/g, more preferably 45 ~
The scope of 120mgKOH/g.When acid number containing carboxy resin is less than 40mgKOH/g, alkali development can be difficult to, on the other hand, exceed
During 200mgKOH/g, it may occur that the dissolving of the exposure portion caused by developer solution, therefore, line can become thinner than required, has
Time exposure portion and unexposed portion can be dissolved by the developing stripping indistinction, it is difficult to describe normal conductive pattern, therefore the most preferred.
It addition, the above-mentioned matter average molecular weight containing carboxy resin is different according to resin matrix, usually 2000 ~ 150000,
And then be 5000 ~ 100000 scope be preferred.When matter average molecular weight is less than 2000, non-stick (tack free) becomes sometimes
Difference, the moisture-proof of the conductive pattern film after exposure deteriorates sometimes, and film decrement occurs during development, and resolution is significantly deteriorated.The opposing party
Face, when matter average molecular weight is more than 150000, developability significantly deteriorates sometimes, and storage stability is deteriorated sometimes.
This compounding amount containing carboxy resin is preferably 3 ~ 50 mass %, more preferably in whole conductive resin compositions
It is 5 ~ 30 mass %.During less than above-mentioned scope, it may occur that conductive pattern film strength reduction etc., thus the most preferred.On the other hand, many
When above-mentioned scope, viscosity uprises sometimes, and coating etc. reduce sometimes, therefore the most preferred.
Electroconductive powder
First, about the material of electroconductive powder, as long as conductive resin composition electric conductivity can be given, then can use and appoint
Meaning material.As this electroconductive powder, can list Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh,
W, Mo, Ru etc., preferred Ag among these.These electroconductive powders can use with the form of components described above simple substance, it is also possible to
Alloy, the form of oxide use.And then it is used as stannum oxide (SnO2), Indium sesquioxide. (In2O3)、ITO(Indium Tin
Oxide) etc..Additionally, as electroconductive powder, it is also possible to it is white carbon black (carbon black), graphite (graphite), carbon nanometer
The carbon dusts such as pipe (carbon nanotube).But, owing to light transmission reduces, it is therefore desirable to note.
The shape of electroconductive powder has no particular limits, in addition to sheet (flake) shape, especially needle-like, spherical be excellent
Choosing.Thus, light transmission raising, the conductive pattern film of excellent in resolution can be formed.
This electroconductive powder is below 30 μm to form fine lines (line), preferably at most particle diameter.By making
Maximum particle diameter is below 30 μm, and the resolution of conductive pattern film improves.
It addition, about electroconductive powder, be preferably used ultramicroscope (SEM) with 10000 times observe random
(random) mean diameter of 10 electroconductive powders in the range of 0.1 ~ 10 μm below.When mean diameter is less than this scope, by
In contact resistance increase and resistance value uprises, therefore the most preferred.On the other hand, when mean diameter is bigger than above-mentioned scope, screen cloth is used
During (mesh screen) version printed conductor pattern (pattern), due to silk screen mesh blocking and cause operability to deteriorate,
It is difficult to form fine lines, thus the most preferred.Surveyed furthermore it is preferred that use by MacxKerodt rake particle instrument (microtrack)
Fixed mean diameter is the powder of 0.5 ~ 3.5 μ m in size.
About the compounding rate of this electroconductive powder, preferably with respect to 100 mass parts, containing carboxy resin, it is 800 ~ 900 matter
Amount part.When the compounding ratio of electroconductive powder is very few, the resistance value of conductive resin combination uprises, it is impossible to obtain sufficiently
The worry of electric conductivity.On the other hand, when comprising volume electroconductive powder, light transmission deteriorates, and utilizes the conductive pattern film of exposure
Formed and deteriorate, thus the most preferred.
The acrylate monomer of 2 ~ 4 functional groups
As acrylate monomer, use in the acrylate monomer of 2 ~ 4 functional groups at least any one.
The concrete example of the acrylate monomer of 2 ~ 4 functional groups described below.
The acrylate monomer of 2 functional groups
As (methyl) acrylate monomer of 2 functional groups, can list BDO two (methyl) acrylate, 1,
6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, Tricyclodecane Dimethanol (methyl) propylene
Acid esters, bisphenol-A (gathering) ethyoxyl two (methyl) acrylate, bisphenol-A (gathering) propoxyl group two (methyl) acrylate, Bisphenol F
(gathering) ethyoxyl two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate,
Two (methyl) acrylate of the 6-caprolactone addition product of 3-hydroxypivalic acid neopentyl glycol (such as, Japan's chemical medicine (strain) manufactures,
KAYARAD HX-220, HX-620 etc.) etc..
The acrylate monomer of 3 functional groups
As the acrylate monomer of 3 functional groups, trimethylolpropane trimethacrylate, trimethylolpropane can be listed
The three of the polyhydric alcohol that trimethyl acrylic ester, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl etc. are more than 3 yuan
Acrylate or trimethyl acrylic ester class.
The acrylate monomer of 4 functional groups
As the acrylate monomer of 4 functional groups, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl third can be listed
Olefin(e) acid ester etc..
As the acrylate monomer of 4 functional groups, the preferably carbamate of 4 functional groups that chemistry formula (I), (II) record
Acrylate monomer or esters acrylate.
[chemical formula 1]
In formula (I),
X1Represent the group comprising acryloxy.
X2Represent the group comprising methacryloxy.
X3And X4Represent the group comprising acryloxy or the group comprising methacryloxy independently of one another.Its
In, X3And X4At least one represent the group comprising methacryloxy.
L1And L2Represent formula (II) independently of one another.
[chemical formula 2]
* the binding site with Z is represented,
Z represents the linking group of divalent.
It addition, as acrylate monomer, the L in logical formula (I)1And L2It is preferably the carbamate as shown in formula (III)
Acrylate.
[chemical formula 3]
In formula (III), * represents the binding site with Z.
And then, as the monomer shown in logical formula (I), preferably descend the urethane acrylate shown in formula (IV).
[chemical formula 4]
In formula (IV),
Z1Represent alkylidene.
R1Represent hydrogen atom.
R2Represent methyl.
R3And R4Represent hydrogen atom or methyl, wherein, R independently of one another3And R4At least one represent methyl.
And then, as the acrylate monomer of 4 functional groups, particularly preferred acrylic compounds (acrylic) and methacrylic acid
Class (methacrylic) is urethane acrylate or the esters acrylate of 1 to 1.
As urethane acrylate or the esters acrylate of this 4 functional groups, the most such as by metering system
Acid glycidyl ester and acrylic acid addition, make the hydroxyl now generated react, with diisocyanate or dicarboxylic acids, the product obtained.
As the commercially available product of the urethane acrylate of 4 functional groups, include, for example out NK Oligo U-4HA (business
The name of an article, chemical industry Co., Ltd. of Xin Zhong village manufactures) etc..
In the acrylate monomer of these 2 ~ 4 functional groups, the preferably acrylate monomer of 4 functional groups shown in formula (I).Should
The acrylate monomer of 4 functional groups is many due to number of functional groups, therefore photoreactivity excellence, excellent in resolution.
It addition, the X of the acrylate monomer of this 4 functional group1With X2Due to different from each other, when photocuring, intramolecular X1
With X2Reaction slow.But, at the X of acrylate monomer1Or X2X with other acrylate monomers1Or X2Intermolecular, score
In son, reaction is reacted quickly.Thus, between multiple acrylate monomers, form intermolecular combination, thus electroconductive resin
The further cure shrinkage of compositions.Further, carry out heat treatment the most at low temperatures, promote intermolecular reaction, electric conductivity tree further
Oil/fat composition cures sufficiently contraction.Its result, it is believed that electroconductive powder compact, the resistivity value of conductive pattern film enters one
Step reduces.
The compounding amount of the acrylate monomer of this 2 ~ 4 functional groups has no particular limits, aforementioned relative to 100 mass parts
Containing carboxy resin, be 10 ~ 100 mass parts, the more preferably ratio of 20 ~ 80 mass parts be suitable.Aforementioned compounding amount is less than 10
During mass parts, photo-curable reduces, it is difficult to the alkaline development after being irradiated by active energy beam forms the lines of conductive pattern,
Therefore it is the most preferred.On the other hand, during more than 100 mass parts, reducing the dissolubility of aqueous alkali, conductive pattern film becomes fragile, therefore not
Preferably.
Photoepolymerizationinitiater initiater
As Photoepolymerizationinitiater initiater, have no particular limits, can be benzoin system, phosphine oxide system, but tool is preferably used
The oxime ester system having group shown in following logical formula V or the 1-Phenylethanone. system photopolymerization with group shown in following logical formula (VI) cause
Agent.
[chemical formula 5]
In formula (V), R6 represents hydrogen atom, the alkyl of carbon number 1 ~ 6 or phenyl, R7 represent hydrogen atom, carbon number 1 ~
The alkyl of 6.
In formula (VI), R8, R9 represent alkyl or the aralkyl of carbon number 1 ~ 12 independently of one another, and R10, R11 are the most only
On the spot represent hydrogen atom or the alkyl of carbon number 1 ~ 6, or can also 2 combine and form ring-type alkane ether.
In aforementioned oxime ester system Photoepolymerizationinitiater initiater, CGI-325, IRGACURE that preferably BASF Japan Ltd. manufactures
N-1919 that OXE01, IRGACURE OXE02, ADEKA company manufactures, NCI-831, (strain) Japan Chemical Industry company manufacture
TOE-004 etc..It addition, as Photoepolymerizationinitiater initiater, it is also possible to it is IRGACURE 389.Wherein, these Photoepolymerizationinitiater initiaters can
It is used alone or is used in combination of two or more.
As the aforementioned 1-Phenylethanone. system Photoepolymerizationinitiater initiater with group shown in logical formula (VI), can list 2-methyl isophthalic acid-
[4-(methyl mercapto) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1,2-
(dimethylamino)-2-［ (4-aminomethyl phenyl) methyl ］-1-［ 4-(4-morpholinyl) phenyl ］-1-butanone, N, N-dimethylamino benzene
Ethyl ketone etc..As commercially available product, can list IRGACURE 907 that BASF Japan Ltd. manufactures, IRGACURE 369,
IRGACURE 379 etc..
The compounding amount of this Photoepolymerizationinitiater initiater has no particular limits, aforementioned relative to 100 mass parts containing carboxy resin,
Be 0.01 ~ 30 mass parts, be preferably 0.5 ~ 15 mass parts scope be suitable.The compounding amount of Photoepolymerizationinitiater initiater is less than 0.01
During mass parts, photo-curable is not enough, and conductive pattern film is peeled off sometimes, and the characteristic of the conductive pattern films such as chemical proofing is sometimes
Can reduce, thus the most preferred.On the other hand, during more than 30 mass parts, the Photoepolymerizationinitiater initiater light on conductive pattern film surface absorbs
Become acutely, have the tendency that deep curable reduces, thus the most preferred.
About the conductive resin composition of the present invention, in order to improve the effect of the present invention further, or in order to not
Play further other effects in the range of the effect of the infringement present invention, can with above-mentioned containing carboxy resin, electroconductive powder, 2 ~ 4
At least any one and Photoepolymerizationinitiater initiater in the acrylate monomer of functional group comprises other one-tenth illustrated below together
Point.
Organic acid
As organic acid, the most not there is the organic acid of aromatic rings.Not there is by compounding the organic acid of aromatic rings, can press down
The light absorption of organic acid processed self, relatively improve the acrylate monomer of 2 ~ 4 functional groups photoreactivity, obtain excellence point
Resolution.
As the specific example of organic acid, 2 can be listed, 2 '-thiodiglycolic acid, adipic acid, isopropylformic acid., formic acid, lemon
Lemon acid, 1,3-propanedicarboxylic acid, acetic acid, oxalic acid, tartaric acid, lactic acid, acetone acid, malonic acid, butanoic acid, malic acid, salicylic acid, benzoic acid, benzene
The carboxylic acidss such as guanidine-acetic acid, acrylic acid, maleic acid, fumaric acid .beta.-methylacrylic acid；Dibutyl phosphite, phosphorous acid butyl ester, phosphorous acid diformazan
Ester, methyl phosphite, phosphorous acid dipropyl, phosphorous acid propyl ester, diphenyl phosphite, phenyl-phosphite, diisopropyl phosphite,
The monoesters of the phosphorous acid such as phosphorous acid isopropyl ester, phosphorous acid-positive methyl-2-Octyl Nitrite or two esters；Dibutylphosphoric acid ester, phosphoric acid fourth
Ester, dimethyl phosphate, methyl orthophosphoric acid, di(2-ethylhexyl)phosphate propyl ester, phosphoric acid propyl ester, diphenyl phosphate, phenyl phosphate, diisopropyl phosphate,
The monoesters of the phosphoric acid such as p isopropylbenzoic acid ester, phosphoric acid-normal-butyl-2-Octyl Nitrite or two esters etc..As organic acid, preferably 2,2 '-
Thiodiglycolic acid.
As the compounding amount of above-mentioned organic acid, relative to the 100 said conductive powder of mass parts, preferably 0.1 ~ 5 mass
The scope of part.The compounding amount of aforementioned organic acid relative to the 100 said conductive powder of mass parts less than 0.1 mass parts time, aforementioned
Electroconductive powder reacts with containing carboxy resin, and long-term storing stability declines, and on the other hand, aforementioned compounding amount is more than 5 matter
During amount part, the moisture etc. easily absorbed in air becomes tide, therefore the most preferred.
Dispersant
By compounding dispersant, the dispersibility of conductive resin composition, settleability can be improved.
As dispersant, include, for example out ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204,
ANTI-TERRA-205、DISPERBYK-101、DISPERBYK-102、DISPERBYK-103、DISPERBYK-106、
DISPERBYK-108、DISPERBYK-109、DISPERBYK-110、DISPERBYK-111、DISPERBYK-112、
DISPERBYK-116、DISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、
DISPERBYK-161、DISPERBYK-162、DISPERBYK-163、DISPERBYK-164、DISPERBYK-166、
DISPERBYK-167、DISPERBYK-168、DISPERBYK-170、DISPERBYK-171、DISPERBYK-174、
DISPERBYK-180、DISPERBYK-182、DISPERBYK-183、DISPERBYK-185、DISPERBYK-184、
DISPERBYK-191、DISPERBYK-192、DISPERBYK-2000、DISPERBYK-2001、DISPERBYK-2009、
DISPERBYK-2020、DISPERBYK-2025、DISPERBYK-2050、DISPERBYK-2070、DISPERBYK-2095、
DISPERBYK-2096、DISPERBYK-2150、BYK-P104、BYK-P104S、BYK-P105、BYK-9076、BYK-9077、
BYK-220S (BYK-ChemieJapan K.K. manufacture), DISPARLON 2150, DISPARLON 1210, DISPARLON
KS-860、DISPARLON KS-873N、DISPARLON 7004、DISPARLON 1830、DISPARLON 1860、
DISPARLON 1850, DISPARLON DA-400N, DISPARLON PW-36, DISPARLONDA-703-50 (this chemical conversion of nanmu
Co., Ltd. manufacture), FLOWLEN G-450, FLOWLEN G-600, FLOWLEN G-820, FLOWLEN G-700, FLOWLEN
DOPA-44, FLOWLEN DOPA-17 (Kyoeisha Chemical Co., Ltd.'s manufacture).
About the content of dispersant, in order to effectively achieve above-mentioned purpose, relative to 100 mass parts electroconductive powders, for
0.1 ~ 10 mass parts, preferably 0.5 ~ 5 mass parts are preferred.
Light polymerization inhibitor
By adding light polymerization inhibitor, the radical polymerization within conductive resin composition can be betided utilizing exposure
In, suppress a certain amount of radical polymerization of kind based on polymerization inhibitor and addition thereof.Thus can suppress to as scattered light this
The photoreaction of the low light level of sample.Thus, the lines of finer conductive pattern film can be formed shrilly, the most preferably use.Light
As long as polymerization inhibitor can serve as light polymerization inhibitor use material then have no particular limits, include, for example out 1,4-benzoquinone, naphthoquinone,
Ditertbutylparacresol, Hydroquinone monomethylether, alpha-Naphthol, acetic acid ethanamidine (acetamidine acetate), hydrazine hydrochloride, front three
Base benzyl ammonium chloride, dinitro benzene, picric acid, benzoquinone dioxime, 1,2,3,-thrihydroxy-benzene, tannic acid, resorcinol (resorcin), copper ferrum
Reagent (cupferron), phenothiazine etc..
About the addition of light polymerization inhibitor, aforementioned relative to 100 mass parts containing carboxy resin, preferably in 0.001 ~ 3 mass
Part, more preferably in the range of 0.01 ~ 2 mass parts.The effect of inhibition cannot be played time fewer than this scope, due to light scattering
Also solidify under low light exposure, be susceptible to the thicker of stripe shape.It addition, reduce than this scope light sensitivitys of many times, need
More light exposure, it is therefore desirable to note.
Filler
In the conductive resin composition of the present invention, in order to improve the physical strength etc. of its film, can be compounded as required
Filler.As this filler, known conventional inorganic or organic filler can be used, particularly preferably use barium sulfate, silicon dioxide,
Brucite and Talcum.
Thermocurable composition
In the conductive resin composition of the present invention, in order to give thermostability, Thermocurable composition can be added.As being used for
The Thermocurable composition of the present invention, can use the polyimide resin such as melmac, benzoguanamine resin, blocked isocyanate chemical combination
Thing, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin, melamine
The known conventional heat-curing resin such as amine derivative.Particularly preferably molecule have more than 2 cyclic ether group and/or ring
The Thermocurable composition of shape thioether group (hreinafter referred to as ring-type (sulfur) ether).
This molecule has 2 Thermocurable compositions with upper annular (sulfur) ether for having more than 2 in the molecule
The compound of any one or two kinds of groups in three-membered ring, four-membered ring or pentacyclic cyclic ether group or cyclic thioether base, such as
Can list intramolecular and have the compound of more than at least 2 epoxy radicals, i.e. multi-functional epoxy compound, intramolecular has at least
The compound of more than 2 oxetanyls, the most multifunctional oxetane compound, intramolecular has more than 2 thioether groups
Compound, i.e. episulfide resin etc..
As aforementioned multi-functional epoxy compound, include, for example out what Japan EpoxyResins Co., Ltd. manufactured
JER828, JER834, JER1001, JER1004, EPICLON 840, the EPICLON that big Japanese ink chemical industrial company manufactures
850, EPICLON 1050, EPICLON 2055, Epo TohtoYD-011, YD-013, YD-that Dongdu chemical conversion company manufactures
127, YD-128, The Dow Chemical Company manufacture D.E.R.317, D.E.R.331, D.E.R.661,
The Araldite 6071 of D.E.R.664, BASFJapan Ltd., Araldite 6084, Araldite GY250, Araldite
GY260, Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128 that Sumitomo Chemical Co. Ltd. manufactures, Asahi Chemical Industry
A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) the bisphenol A-type ring that industrial group manufactures
Epoxy resins；The JERYL903 that Japan Epoxy Resins Co., Ltd. manufactures, big Japanese ink chemical industrial company manufactures
EPICLON 152, EPICLON 165, Epo Tohto YDB-400, YDB-500 that Dongdu chemical conversion company manufactures, The Dow
The Araldite8011 that D.E.R.542, the BASF Japan Ltd. that ChemicalCompany manufactures manufactures, Sumitomo Chemical
Sumiepoxy ESB-400, the E SB-700 that company manufactures, A.E.R.711, A.E.R.714 that industrial group of Asahi Chemical Industry manufactures
Deng (being trade name) brominated epoxy resin；JER152, JER154 that Japan Epoxy Resins Co., Ltd. manufactures, The
D.E.N.431, D.E.N.438 that Dow Chemical Company manufactures, big Japanese ink chemical industrial company manufactures
EPICLON N-730, EPICLON N-770, EPICLON N-865, the EpoTohto YDCN-that Dongdu chemical conversion company manufactures
701, AralditeECN1235, Araldite ECN1273, Araldite that YDCN-704, BASF Japan Ltd. manufactures
ECN1299, AralditeXPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-that chemical medicine company of Japan manufactures
104S, RE-306, Sumiepoxy ESCN-195X, ESCN-220 that Sumitomo Chemical Co. Ltd. manufactures, industrial group of Asahi Chemical Industry
A.E.R.ECN-235, ECN-299 etc. (the being trade name) phenolic resin varnish type epoxy resin manufactured；Big Japanese ink chemistry work
The JER807 that EPICLON 830, the JapanEpoxy Resins Co., Ltd. that industry company manufactures manufactures, Dongdu chemical conversion company system
The Araldite XPY306 etc. that EpoTohto YDF-170, YDF-175, the YDF-2004 made, BASF Japan Ltd. manufactures
(being trade name) bisphenol f type epoxy resin；Epo Tohto ST-2004, ST-2007, ST-that Dongdu chemical conversion company manufactures
The bisphenol-A epoxy resins such as 3000 (trade names)；The JER604 that Japan Epoxy Resins Co., Ltd. manufactures, east
The Araldite MY720 that Epo Tohto YH-434, the BASF Japan Ltd. that the company that is all melted into manufactures manufactures, Sumitomo Chemical
(the being trade name) glycidyl amine type epoxy resins such as the SumiepoxyELM-120 that industrial group manufactures；BASF
The hydantoin type epoxy resin such as the Araldite CY-350 (trade name) JapanLtd. manufactured；DAICEL CHEMICAL
Araldite CY175, CY179 that CELLOXIDE2021, the BASF Japan Ltd. that INDUSTRIES, LTD. manufacture manufactures
Deng (being trade name) alicyclic epoxy resin；YL-933, the The Dow that Japan Epoxy Resins Co., Ltd. manufactures
T.E.N., EPPN-501, EPPN-502 etc. (being trade name) the trihydroxy benzene methylmethane type that Chemical Company manufactures
Epoxy resin；YL-6056, YX-4000, YL-6121 (being trade name) that JapanEpoxy Resins Co., Ltd. manufacture
In di-cresol type or united phenol-type epoxy resin or they mixture；The EBPS-200 that chemical medicine company of Japan manufactures, the rising sun
The bisphenol S type such as electrochemical industry company manufactures EPX-30, the EXA-1514 (trade name) that big Japanese ink chemical industrial company manufactures
Epoxy resin；The bisphenol A novolac type rings such as the JER157S (trade name) that Japan Epoxy Resins Co., Ltd. manufacture
Epoxy resins；JERYL-931, the BASF Japan Ltd. that Japan EpoxyResins Co., Ltd. manufactures manufactures
Araldite 163 grade (being trade name) four hydroxy phenyl ethane type epoxy resin；The Araldite that BASFJapan Ltd. manufactures
(being trade name) the hetero ring type epoxy resin such as PT810, the TEPIC that Nissan Chemical Industries company manufactures；Nof Corp.'s system
The o-phthalic acid diglycidyl ester resins such as the BLEMMER DGT made；The ZX-1063 that Dongdu chemical conversion company manufactures etc. four shrink
Glyceryl dimethylbenzene acyl group ethane resin；ESN-190, ESN-360 that chemical company of Nippon Steel manufactures, big Japanese ink chemistry work
HP-4032, EXA-4750, the EXA-4700 etc. that industry company the manufactures epoxy resin containing naphthyl；Big Japanese ink chemical industry is public
HP-7200, HP-7200H etc. that department manufactures have the epoxy resin of bicyclopentadiene skeleton；The CP-that Nof Corp. manufactures
The glycidyl methacrylate such as 50S, CP-50M copolymerization system epoxy resin；And N-cyclohexylmaleimide and metering system
The copolymerization epoxy resin of acid glycidyl ester；Epoxide modified polybutadiene rubber derivant (such as DAICEL
The PB-3600 etc. that CHEMICALINDUSTRIES, LTD. manufacture), (such as Dongdu chemical conversion company manufactures CTBN modified epoxy
YR-102, YR-450 etc.) etc.；But it is not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.
Wherein, particularly preferred phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their mixture.
As aforementioned multifunctional oxetane compound, double [(3-methyl-3-oxetanyl methoxy can be listed
Base) methyl] ether, double [(3-ethyl-3-oxetanylmethoxy) methyl] ether, Isosorbide-5-Nitrae-bis-[(3-methyl-3-oxa-ring fourth
Alkyl methoxyl group) methyl] benzene, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanylmethoxy) methyl] benzene, acrylic acid (3-methyl-
3-oxetanyl) methyl ester, acrylic acid (3-ethyl-3-oxetanyl) methyl ester, methacrylic acid (3-methyl-3-oxygen
Azetidinyl) methyl ester, methacrylic acid (3-ethyl-3-oxetanyl) methyl ester, their oligomer or copolymer etc.
Multifunctional oxetanes class；And novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, calixarene kind,
Resorcinol calixarenes (calix resorcin arene) class or silsesquioxane (silsesquioxane) etc. have hydroxyl
The etherate etc. of resin and oxa-cyclobutanol.It addition, the unsaturated monomer with oxetanes ring and (first can be listed
Base) copolymer etc. of alkyl acrylate.
As previous molecular has the compound of more than 2 cyclic thioether bases, include, for example out Japan Epoxy
The bisphenol A-type episulfide resin YL7000 etc. that Resins Co., Ltd. manufacture.Same conjunction is used alternatively, it is also possible to use
The episulfide resin etc. that the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced to sulphur atom and obtains by one-tenth method.
It addition, in the conductive resin composition of the present invention, in order to improve curable and the institute of conductive resin composition
Obtain the obdurability of cured film, 1 intramolecular can be added there is more than 2 NCOs or the chemical combination of end-blockingization NCO
Thing.For this 1 intramolecular, there are more than 2 NCOs or the compound of end-blockingization NCO, 1 can be listed
Intramolecular has the compound of more than 2 NCOs, i.e. polyisocyanate compound, or 1 intramolecular has more than 2 envelopes
The compound of endization NCO, i.e. blocked isocyanate compounds etc..
As polyisocyanate compound, such as, can use aromatic polyisocyanate, aliphatic polyisocyante or fat
Ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, 4 can be listed, 4 '-diphenylmethane diisocyanates
Ester, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), naphthalene-1,5-diisocyanate, o-Dimethylbenzene two Carbimide.
Ester, m xylene diisocyanate and 2,4 tolylene diisoeyanate dimer.Concrete as aliphatic polyisocyante
Example, can list tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl six
Methylene diisocyanate, 4,4-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isophorone diisocyanate.As alicyclic ring
The object lesson of formula polyisocyanates, can list bicycloheptane triisocyanate.And the isocyanide enumerated before can be listed
The adduct of ester compound, biuret body and isocyanuric acid ester body.
The end-blocking NCO that blocked isocyanate compounds is comprised refer to NCO by with end-capping reagent
The group that reaction is temporarily passivated by protection.It is heated to this end-capping reagent during set point of temperature to dissociate and generate NCO.
As blocked isocyanate compounds, the additive reaction of isocyanate compound and isocyanate-terminated dose can be used
Product.As the isocyanate compound that can react with end-capping reagent, isocyanurate type, biuret type, adduct can be listed
Type etc..As this isocyanate compound, such as, can use aromatic polyisocyanate same as described above, aliphatic polyisocyanate
Cyanate or ester ring type polyisocyanates.
As isocyanate-terminated dose, include, for example out phenol, cresol, xylenols, chlorophenol and ethyl-phenol etc.
Phenol system end-capping reagent；The lactams system end-capping reagents such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone；Second
Ethyl acetoacetic acid ethyl ester and acetylacetone,2,4-pentanedione isoreactivity methylene base system end-capping reagent；Methanol, ethanol, propanol, butanol, amylalcohol, ethylene glycol list first
Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl oxide, methyl glycollate, ethanol
The alcohol system end-capping reagents such as acid butyl ester, DAA, methyl lactate and ethyl lactate；Formaldoxime, aldoxime, acetone oxime, butanone
The oxime system end-capping reagents such as oxime, diacetyl monoxime, hexamethylene oxime；Butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, phenylmercaptan., methylbenzene phenyl-sulfhydrate,
The mercaptan system end-capping reagents such as ethyl thiophenol；The amide such as acetamide, benzamide system end-capping reagent；Butanimide and maleimide etc.
Imide series end-capping reagent；The amine system end-capping reagents such as dimethylaniline, aniline, butylamine, dibutylamine；The miaows such as imidazoles, 2-ethyl imidazol(e)
Azoles system end-capping reagent；The imines system end-capping reagents etc. such as methylene imine and propylidene imines.
Blocked isocyanate compounds can also be commercially available material, include, for example out 7950,7951,7960,7961,
7982,7990,7991,7992 (more than, Baxenden company manufactures, trade name), Sumidule BL-3175, BL-4165,
BL-1100、BL-1265、DesmoduleTPLS-2957、TPLS-2062、TPLS-2078、TPLS-2117、
Desmotherm2170, Desmotherm2265 (more than, SumikaBayer Urethane Co., Ltd. manufactures, trade name),
Coronate 2512, Coronate2513, Coronate 2520 (more than, Japanese polyurethane industrial group manufactures, trade name),
(Mitsui TakedaChemical Co., Ltd. manufactures, commodity for B-830, B-815, B-846, B-870, B-874, B-882
Name), TPA-B80E, 17B-60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (Asahi KaseiChemicals
Corporation manufactures, trade name), KARENZ MOI-BM (Showa electrician company manufactures, trade name) etc..Wherein,
Sumidule BL-3175, BL-4265 use Methylethyl oxime to obtain as end-capping reagent.
Above-mentioned 1 intramolecular has the compound of more than 2 NCOs or end-blockingization NCO can individually be made
With a kind or be applied in combination two or more.
There is the compounding of the compound of more than 2 NCOs or end-blockingization NCO about this 1 intramolecular
Amount, is suitable relative to 100 mass parts containing the ratio that carboxy resin is 1 ~ 100 mass parts, more preferably 2 ~ 70 mass parts.Before
When stating compounding amount less than 1 mass parts, it is impossible to obtain sufficient film obdurability, thus the most preferred.On the other hand, more than 100 mass
During part, storage stability declines, therefore the most preferred.
Thermal curing catalyst
The conductive resin composition of the present invention uses in above-mentioned molecule and there are 2 thermosettings with upper annular (sulfur) ether
During the property changed composition, preferably comprise thermal curing catalyst.As such thermal curing catalyst, include, for example out imidazoles, 2-first
Base imidazoles, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl miaow
The imdazole derivatives such as azoles, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole；Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-
N, N-dimethyl benzyl amine, 4-methoxyl group-N, N-dimethyl benzyl amine, 4-methyl-N, the amines such as N-dimethyl benzyl amine,
The hydrazide compound such as adipic dihydrazide, sebacic dihydrazide；The phosphorus compounds etc. such as triphenylphosphine.Additionally, as commercially available product, example
2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ of manufacturing as listed chemical conversion industrial group of four countries (are imidazoles system
The trade name of compound), U-CAT (registered trade mark) 3503N, U-CAT3502T that SAN-APRO company manufactures (are dimethyl amine
Blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (are two ring type amidine compound and salt thereof)
Deng.It is defined in these compounds the most especially, as long as the thermal curing catalyst of epoxy resin, oxetane compound
Thermal curing catalyst or promote the material of epoxy radicals and/or oxetanyl and carboxyl reaction, can be used alone
Or mix two or more use.In addition it is also possible to use guanamines, methyl guanamines, benzoguanamine, tripolycyanamide, 2,4-diaminourea-
6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diaminourea-s-triazine, 2-vinyl-4,6-diaminourea-all
Triazine isocyanuric acid adduct, 2,4-diaminourea-6-methacryloxyethyl-s-triazine isocyanuric acid adduct etc.
Striazine derivative.The compound preferably these also worked as adaptation imparting agent combines with aforementioned thermal curing catalyst
Use.
The ratio that compounding amount is amount commonly of these thermal curing catalysts the most enough, such as, contains carboxylic relative to 100 mass parts
Base resin or molecule have 2 heat curable component with upper annular (sulfur) ether, preferably 0.1 ~ 20 mass parts, is more preferably
0.5 ~ 15 mass parts.
Hot polymerization inhibitor
In order to prevent the conductive resin composition of the present invention thermal polymerization or through time polymerization, hot polymerization inhibitor can be used.Make
For hot polymerization inhibitor, include, for example out 4-methoxyphenol, hydroquinone, alkyl or aryl replacement hydroquinone, tert-butyl catechol, even benzene
Triphenol, 2-dihydroxy benaophenonel, 4-methoxyl group-2-dihydroxy benaophenonel, Cu-lyt., phenothiazine, Spergon, naphthylamines, β-
Naphthols, 2,6-di-t-butyl-4-cresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), pyridine, Nitrobenzol, dinitro
Base benzene, picric acid, 4-toluidines, methylene blue, copper and the reactant of organic sequestering agent, methyl salicylate and phenothiazine, Asia
Nitro compound, nitroso compound and the chelate etc. of Al.
Chain-transferring agent
In the conductive resin composition of the present invention, in order to improve light sensitivitys, it is possible to use as known in chain-transferring agent
N phenylglycine class, phenoxy acetic acids, thio phenyl ethoxyacetic acid class, thyroidan etc..If enumerating the concrete of chain-transferring agent
Example, such as, have mercapto succinic acid, TGA, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivant thereof
Etc. the chain-transferring agent with carboxyl；Mercaptoethanol, mercaprol, Mercaptobutanol., mercapto-propanediol, sulfydryl butanediol, hydroxy benzenes
Mercaptan and derivant etc. thereof have the chain-transferring agent of hydroxyl；1-butyl mercaptan, butyl-3-thiopropionate, methyl-3-mercaptopropionic acid
Ester, 2,2-(ethylene epoxide) diethyl mercaptan, ethyl mercaptan, 4-methylbenzenethiol, lauryl mercaptan, propanethiol, butyl mercaptan, penta sulfur
Alcohol, 1-spicy thioalcohol, cyclopentanethiol, cyclohexylmercaptan, thioglycerin, 4,4-thiobisbenzenethiol etc..
It addition, multi-functional mercaptan based compound can be used, have no particular limits, such as, can use hexane-1,6-bis-
The analiphatic sulphur alcohols such as mercaptan, decane-1,10-two mercaptan, dimercapto diethyl base ether, dimercapto diethyl base thioether；Benzene diformazan two
The aromatic mercaptans classes such as mercaptan, 4,4 '-dimercapto diphenylsulfide, 1,4-dimercaptobenzene；Ethylene glycol bis (TGA) ester, poly-
Ethylene glycol bis (TGA) ester, propylene glycol double (TGA) ester, glycerol three (TGA) ester, trimethylolethane trimethacrylate
(TGA) ester, trimethylolpropane tris (TGA) ester, tetramethylolmethane four (TGA) ester, dipentaerythritol six
Many (TGA) esters of the polyhydric alcohol such as (TGA) ester；Double (the 3-mercapto of ethylene glycol bis (3-mercaptopropionic acid) ester, Polyethylene Glycol
Base propanoic acid) ester, propylene glycol double (3-mercaptopropionic acid) ester, glycerol three (3-mercaptopropionic acid) ester, trimethylolethane trimethacrylate (sulfydryl third
Acid) ester, trimethylolpropane tris (3-mercaptopropionic acid) ester, tetramethylolmethane four (3-mercaptopropionic acid) ester, dipentaerythritol six (3-mercapto
Base propanoic acid) many (3-mercaptopropionic acid) esters of the polyhydric alcohol such as ester；1,4-double (3-sulfydryl butyryl acyloxy) butane, 1,3,5-tri-(3-
Mercaptobutyl epoxide ethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, tetramethylolmethane four (3-mercaptobutyric acid) ester etc.
Many (mercaptobutyric acid) esters.
As their commercially available product, can list such as BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP,
DPMP and TEMPIC (more than, Sakai Chemical Industry Co., Ltd. manufactures), KARENZ MT-PE1,
KARENZ MT-BD1 and KARENZ-NR1 (more than, Showa electrician (strain) manufactures) etc..
And then, the heterocyclic compound with sulfydryl worked as chain-transferring agent, include, for example out in sulfydryl-4-fourth
Ester (another name: 2-sulfydryl-4-butyrolactone), 2-sulfydryl-4-methyl-4-butyrolactone, 2-sulfydryl-4-ethyl-4-butyrolactone, 2-mercapto
Base-4-fourth mercapto lactone, 2-sulfydryl-4-butyrolactam, N-methoxyl group-2-sulfydryl-4-butyrolactam, N-ethyoxyl-2-sulfydryl-4-
Butyrolactam, N-methyl-2-sulfydryl-4-butyrolactam, N-ethyl-2-sulfydryl-4-butyrolactam, N-(2-methoxyl group) ethyl-
2-sulfydryl-4-butyrolactam, N-(2-ethyoxyl) ethyl-2-sulfydryl-4-butyrolactam, 2-sulfydryl-5-valerolactone, 2-sulfydryl-
5-valerolactam, N-methyl-2-sulfydryl-5-valerolactam, N-ethyl-2-sulfydryl-5-valerolactam, N-(2-methoxyl group) second
Base-2-sulfydryl-5-valerolactam, N-(2-ethyoxyl) ethyl-2-sulfydryl-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto
Base-5-methyl mercapto-thiadiazoles, 2-sulfydryl-6-caprolactam, 2,4,6-tri-thiol-s-triazine (three chemical conversion Co., Ltd. of association systems
Make: trade name ZISNET F), 2-dibutylamino-4,6-dimercapto-s-triazine (three association chemical conversion Co., Ltd. manufacture: trade name
ZISNET DB) and (three chemical conversion Co., Ltd. of the association manufacture: trade name ZISNET of 2-anilino--4,6-dimercapto-s-triazine
AF) etc..
As the heterocyclic compound with sulfydryl of the chain-transferring agent of the developability not damaging conductive resin composition, special
Preferably 2-mercaptobenzimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole (chemical industry Co., Ltd. of Kawaguchi manufactures,
Trade name: Accel M), 3-sulfydryl-4-methyl-4H-1,2,4-triazole, 5-methyl isophthalic acid, 3,4-thiadiazoles-2-mercaptan, 1-benzene
Base-5-sulfydryl-1H-TETRAZOLE.These chain-transferring agents can be used alone or in combination of two or more kinds.
Other adding ingredients
In the conductive resin composition of the present invention, certainly also dependent on needing the known conventional composition of suitably compounding, example
Such as thickening agent, froth breaking levelling agent, coupling agent, antioxidant, antirust agent etc..
The formation of conducting channel
Then, an example of the method that the conductive resin composition using the present invention forms conducting channel is said
Bright.
About the conductive resin composition of the present invention, with above-mentioned each required composition and the mixing dispersion of any composition
The machineries such as three rollers, mixer can be used.
It is suitable that the most scattered conductive resin composition can pass through silk screen print method, bar coater, knife type coater etc.
Coating process is applied on base material.Then, in order to obtain dry to touch, by heated air circulation type drying oven, far infrared drying stove
Deng, at a temperature of not thermally decomposing containing carboxy resin, e.g., from about 60 ~ 120 DEG C be dried within about 5 ~ 40 minutes, make organic solvent
Evaporation, the film not glued.
It should be noted that can be also film like by conductive resin composition film forming in advance, now film laminating be existed
On base material.
Then, the negative mask of the exposing patterns with regulation is used to carry out contact exposure or noncontact exposure.As exposure
Radiant, can use Halogen light (halogen lamp), high voltage mercury lamp, laser, metal halide (metal haloid) lamp, black
Light modulation, electrodeless lamp etc..As light exposure, the low light quantity of below accumulated light 200mJ/cm2 can be.In addition it is also possible to
Do not use mask, on film, form pattern by laser direct imaging device.
Then, by the development of nebulization, infusion process etc., making film is pattern-like.As developer solution, can suitably use hydrogen
The metal base aqueous solution of sodium oxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate etc., monoethanolamine, diethanolamine, three ethanol
The dilute alkaline aqueous solution of the concentration below the aqueous solution of the amine such as amine, the most about 1.5 mass %, as long as by conductive resin composition
In the carboxyl saponification (saponification) containing carboxy resin, remove uncured portion (unexposed portion), to above-mentioned aobvious
Shadow liquid does not limit.It addition, in order to remove unwanted developer solution after development, preferably carry out washing, acid neutralizes.
Then, the conductive pattern film of gained is dried at a temperature of not thermally decomposing containing carboxy resin.Thus can shape
Become there is low resistance and the conducting channel of fine conductive pattern film.As baking temperature, preferably less than 150 DEG C, more preferably 140
Below DEG C, further preferred less than 130 DEG C.
In these operations, due to not roasting under 500 DEG C of such high temperature, therefore can use and there is no the resin-made of thermostability
Base material as base material.Specifically, as resinous base material, include, for example out polyimides, polyester based resin, polyethers
Sulfone (PES), polystyrene (PS), polymethyl methacrylate (PMMA), Merlon (PC), polyamide (PA), polypropylene
(PP), polyphenylene oxide (PPO) etc., polyester based resin can be used aptly.In addition it is also possible to be glass substrate etc..
Embodiment
Below based on embodiment, the present invention is specifically illustrated.But, the present invention is not restricted by the embodiments.
Compounding ingredients
Containing carboxy resin
Synthesis example 1
In the flask possessing thermometer, blender, Dropping funnel and reflux condenser with 0.87:0.13 mole
Than putting into methyl methacrylate and methacrylic acid, add the dipropylene glycol monomethyl ether as solvent, the idol as catalyst
Nitrogen bis-isobutyronitrile, stirs 6 hours in blanket of nitrogen, at 80 DEG C, obtains containing carboxy resin solution.This matter containing carboxy resin is divided equally
Son amount about 10000, acid number are 74mgKOH/g.Additionally, the matter average molecular weight containing carboxy resin of gained is by (strain) Shimadzu system
Chromatographic column Shodex (registered trade mark) KF-804, KF-803, KF-that pump LC-6AD manufactured by work and Showa electrician (strain) manufacture
802 3 high performance liquid chromatography connected measure.Hereinafter, this solution Han carboxy resin is referred to as A-1 varnish.Need explanation
It is that this contains carboxy resin and does not contains double bond, and without aromatic rings.
Electroconductive powder
Spherical electroconductive powder: Ag powder (below maximum particle diameter 30 μm, mean diameter 2 μm (SEM))
Needle-like conductive powder: Ag powder (below maximum particle diameter 30 μm, mean diameter 2 μm (SEM))
Acrylate monomer
The acrylate monomer of simple function group: trade name；Phenol EO modification acrylate
The acrylate monomer of 2 functional groups: trade name；KAYARAD HX-220 (chemical medicine company of Japan manufactures)
The acrylate monomer of 3 functional groups: trade name；Aronix M-350 (manufacture of East Asia Synesis Company)
The acrylate monomer of 4 functional groups: trade name；NK Oligo U-4HA (manufacture of company of Xin Zhong village)
The acrylate monomer of 6 functional groups: dipentaerythritol acrylate (Nippon Kayaku K. K's manufacture)
Photoepolymerizationinitiater initiater
Trade name: IRGACURE 379EG (BASF Japan Ltd. manufacture), 2-(dimethylamino)-2-[(4-methyl
Phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone
Organic acid
2,2 '-thiodiglycolic acid
Dispersant
Trade name DISPERBYK-111 (BYK-Chemie Japan K.K. manufacture)
Embodiment and the explanation of comparative example
As shown in table 1 below, embodiment 1 ~ 11 and 18 is the example of the acrylate monomer being compounded with 4 functional groups, real
Executing the example that example 12,14,16 is the acrylate monomer being compounded with 2 functional groups, embodiment 13,15,17 is to be compounded with 3 functional groups
The example of acrylate monomer.In these embodiments, embodiment 1 ~ 3,8 ~ 10,12,13 is to change spherical electroconductive powder
(Ag) example that compounding amount is added.Embodiment 4 ~ 6,11,14,15 is to change the compounding of needle-like conductive powder (Ag)
The example that amount is added.Embodiment 7,16 ~ 18 is the example that the spherical and needle-like conductive powder of mixing carries out being compounded.
Embodiment 8 ~ 11 is the compounding amount of the Photoepolymerizationinitiater initiater relative to embodiment 1 ~ 4, adds Photoepolymerizationinitiater initiater
The example that is added of compounding amount.
On the other hand, as shown in table 2 below, comparative example 1,4,6,8 is that the acrylate monomer using simple function group is made
For acrylate monomer, change the example of its compounding amount.Comparative example 2,3,5,7 is that the acrylate monomer using 6 functional groups is made
For acrylate monomer, change the example of its compounding amount.
Evaluation methodology
Evaluate so obtain embodiment 1 ~ 18, the resolution of each conductive resin composition of comparative example 1 ~ 8, resistivity
Value.Its evaluation methodology is following.
Test film makes:
With the polyester net of 300 mesh, the whole face of each conductive resin composition evaluated is coated on the base of polyester resin
On material, then, it is dried 30 minutes in heated air circulation type drying oven, at 90 DEG C, forms the film that dry to touch is good.So
After, use high voltage mercury lamp is as light source, via negative mask with the accumulated light on conductive resin composition as 200mJ/cm2
Mode carry out pattern exposure, then use 0.4 mass %Na of liquid temperature 30 DEG C2CO3Aqueous solution carries out developing, washing.Finally exist
It is dried under conditions of 130 DEG C × 30 minutes, makes the test film being formed with conductive pattern film.
Resolution: evaluate the minimum feature of the test film made in aforementioned manners.
Resistivity value: form the pattern of 4mm × 10cm in aforementioned manners, measures resistance value and thickness calculates resistivity value.
It is " well " by minimum lines entirely without the evaluation of result of defect.
These embodiments 1 ~ 18, the compounding ingredients of comparative example 1 ~ 5, compounding amount and resolution, resistivity value are shown in the lump
Table 1,2.Wherein, " solid constituent of A-1 varnish " of table 1,2 refers to remove the quality of solvent from A-1 varnish.
[table 1-1]
[table 1-2]
[table 1-3]
[table 2]
Understand the conductive resin composition for embodiment 1 ~ 18, even if being 200mJ/cm2Following low light exposure
Exposure, it is possible to form the conductive pattern film of the high-resolution of below L/S=30/30 μm.Can not make containing carboxy resin it addition, understand
Occurring thermal decomposition ground to form resistivity value (Ω cm) is 5.00 × 10-4Following conductive pattern film.Therefore, it is known that the present invention's
Conductive resin composition can be applicable to the base material of resistance to heat differential, the electric conductivity that can ensure that excellence and resolution.
Claims (8)
1. a non-roasting conductive resin composition, it is characterised in that comprise in the acrylate monomer of 2～4 functional groups
At least any one, containing carboxy resin, electroconductive powder and Photoepolymerizationinitiater initiater, wherein,
Relative to containing carboxy resin described in 100 mass parts, the content of described electroconductive powder is more than 800 mass parts and 900 matter
Below amount part,
Described containing carboxy resin without double bond.
Non-roasting conductive resin composition the most according to claim 1, it is characterised in that described acrylate monomer
For the acrylate monomer of 4 functional groups described in following chemistry formula (I),
In formula (I),
X1Represent the group comprising acryloxy,
X2Represent the group comprising methacryloxy,
X3And X4Represent the group comprising acryloxy or the group that comprises methacryloxy independently of one another, wherein,
X3And X4At least one represent the group comprising methacryloxy,
L1And L2Represent formula (II) independently of one another,
* the binding site with Z is represented,
Z represents the linking group of divalent.
Non-roasting conductive resin composition the most according to claim 2, wherein, the L in logical formula (I)1And L2Such as formula
(III) shown in,
In formula (III), * represents the binding site with Z.
Non-roasting conductive resin composition the most according to claim 3, wherein, logical 4 functional groups shown in formula (I)
Shown in acrylate monomer such as following formula (IV),
In formula (IV),
Z1Represent alkylidene,
R1Represent hydrogen atom,
R2Represent methyl,
R3And R4Represent hydrogen atom or methyl, wherein, R independently of one another3And R4At least one represent methyl.
5. according to the non-roasting conductive resin composition described in any one in Claims 1 to 4, it is characterised in that institute
State containing carboxy resin also without aromatic rings.
6. according to the non-roasting conductive resin composition described in any one in Claims 1 to 4, it is characterised in that institute
Stating Photoepolymerizationinitiater initiater is oxime ester system or 1-Phenylethanone. system.
7. according to the non-roasting conductive resin composition described in any one in Claims 1 to 4, it is characterised in that also
Comprise the organic acid without aromatic rings.
8. a conducting channel, it uses the non-roasting conductive resin composition described in any one in claim 1～4
It is formed on base material and forms.
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| CN103969951A (en) * | 2013-01-30 | 2014-08-06 | 太阳油墨制造株式会社 | Conducting Resin Composition And Conducting Circuit |
| BE1022066B1 (en) * | 2013-06-28 | 2016-02-15 | Chemstream Bvba | SURFACE ACTIVE AND PREPARATION THEREOF |
| JP5409954B1 (en) * | 2013-07-29 | 2014-02-05 | 太陽インキ製造株式会社 | Conductive resin composition and cured product thereof |
| CN104749883B (en) * | 2013-12-30 | 2022-04-01 | 上海飞凯光电材料股份有限公司 | Photoresist |
| CN105785716A (en) * | 2014-12-26 | 2016-07-20 | 上海飞凯光电材料股份有限公司 | Photoresist |
| JP2016194563A (en) * | 2015-03-31 | 2016-11-17 | 太陽インキ製造株式会社 | Conductive resin composition and conductive circuit |
| CN113130113B (en) * | 2019-12-31 | 2022-10-28 | 财团法人工业技术研究院 | Conductive material composition and conductive material prepared from same |
| US11437162B2 (en) | 2019-12-31 | 2022-09-06 | Industrial Technology Research Institute | Conductive material composition and conductive material prepared therefrom |
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| CN1648772A (en) * | 2004-01-29 | 2005-08-03 | 三星Sdi株式会社 | Photosensitive conducting composition for a plasma display panel |
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| JP4323994B2 (en) * | 2004-03-24 | 2009-09-02 | 太陽インキ製造株式会社 | Photosensitive paste composition for baking and baking product pattern using the same |
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| JP5120093B2 (en) * | 2008-06-19 | 2013-01-16 | Ｊｓｒ株式会社 | Photosensitive composition and electrode manufacturing method |
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| KR101451479B1 (en) | 2014-10-15 |
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| TWI499650B (en) | 2015-09-11 |
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