CN106019834A - Conductive resin composition and conductive circuit - Google Patents

Abstract

The invention provides a conductive resin composition and a conductive circuit. More particular, the invention provides a conductive resin composition having low resistance and adhesion which meet requirements of a high-precision conductive circuit, capable of inhibiting developing of residues, and capable of forming a superfine conductive circuit with a high resolution ratio and a conductive circuit formed through the conductive resin composition. The conductive resin composition contains a carboxyl-containing resin, conductive powder, a carboxyl (methyl) acrylate monomer, a photopolymerization initiator and a thermosetting component.

Description

Conductive resin composition and conducting channel

Technical field

The present invention relates to be suitable for forming leading of conducting channel useful in slim touch panel display etc. Electrically resin combination and use its conducting channel formed.

Background technology

In recent years, in touch panel display etc., miniaturization, densification, high-precision refinement etc. require height Rising, the requirement become more meticulous being formed at circuit therein, electrode etc. increases the most than ever.

For such requirement, use the conductive paste for forming conducting channel and with pattern printing Method is compared the photoetching process of the high-precision refinement etc. that can carry out conducting channel and is suitable for (referring for example to patent documentation 1～6).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2014-101412 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2013-137511 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2013-136727 publication

Patent documentation 4: No. 2010/113287 publication of International Publication

Patent documentation 5: Japanese Unexamined Patent Publication 2014-167090 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2015-026013 publication

Summary of the invention

The problem that invention is to be solved

But, due to frame (bezel) narrowing of touch panel display, special requirement are formed at The further high-precision refinement of the spacing of the conducting channel of frame (bezel), when utilizing conventional conductive paste Resolution is insufficient.In as the developing procedure of photoetching technique, development residue is produced so it addition, also have Problem.

The present invention develops in view of such practical situation, and its problem is, it is provided that one meets fine The low resistance required by conducting channel and adaptation and suppression development residue generation and can shape Become to have the conductive resin composition of the fine conducting channel of excellent resolution and use it to be formed Conducting channel.

For solving the scheme of problem

One scheme of the present invention is as described below.

[1] a kind of conductive resin composition, it contains: containing carboxy resin, electroconductive powder, containing carboxylic Base (methyl) acrylate monomer, Photoepolymerizationinitiater initiater and Thermocurable composition.

[2] according to the conductive resin composition described in [1], wherein, aforementioned containing carboxyl (methyl) propylene The acid number of acid ester monomer is the scope of 5～200mgKOH/g.

[3] according to the conductive resin composition described in [1] or [2], wherein, aforementioned containing carboxyl (methyl) Acrylate monomer is the compound shown in following logical formula (I).

In formula,

N is the integer of 0～4；

R is each independently hydrogen atom or methyl；

L₁For-O-base ,-(O-CH₂CH₂)_n1-O-base (wherein, n1 is the integer of 0～8) ,- (O-CH₂CH₂CH₂)_n2-O-base (wherein, n2 is the integer of 0～8)；

L₂For selecting free singly-bound, alkylidene, alkenylene, phenylene, ring alkylidene and ring alkenylene composition Group in group.

[4] according to the conductive resin composition according to any one of [1]～[3], wherein, aforementioned heat cure Property composition is blocked isocyanate.

[5] according to the conductive resin composition according to any one of [1]～[4], wherein, said conductive The mean diameter of powder is 0.1～10 μm.

[6] a kind of conducting channel, its use the conductive resin composition according to any one of [1]～[5] and Formed.

The effect of invention

According to the present invention it is possible to provide the resistive required by a kind of conducting channel meeting fine and close The generation and can being formed of conjunction property and suppression development residue has leading of the fine of excellent resolution The electricity conductive resin composition of circuit and use its conducting channel formed.

Furthermore it is possible to provide a kind of to use Na₂CO₃Concentration is the diluted alkaline developer solution about 0.2 mass % Also can be formed when developing conducting channel without produce development residue conductive resin composition and Use the conducting channel that it is formed.

Detailed description of the invention

Hereinafter, the present invention is described in detail.

The conductive resin composition of the present invention contains: containing carboxy resin, electroconductive powder, containing carboxyl (first Base) acrylate monomer, Photoepolymerizationinitiater initiater and Thermocurable composition.

Hereinafter, also including optional member, can contain in the conductive resin composition of the present invention Each composition illustrate.

<containing carboxyl (methyl) acrylate monomer>

The fisrt feature of the conductive resin composition of the present invention is, containing containing carboxyl (methyl) propylene Acid ester monomer.

The present inventor etc. conduct in-depth research, found that: by using containing carboxyl (methyl) propylene Acid ester monomer, such as, using Na₂CO₃Concentration is that the diluted alkaline developer solution about 0.2 mass % develops Time, also can suppress the generation of development residue, and resolution is also improved.Speculate this is because, logical Cross (methyl) acrylate monomer used in structure containing carboxyl, promote unexposed area based on The developability of alkaline developer, therefore significantly improves development residue.It addition, speculate owing to utilizing diluted alkaline water Solution develops, it is possible to form image when the damage causing exposure portion is few, and then, Exposure area and the unexposed area dissolubility contrast in alkaline developer improves, and result improves resolution Rate.

Herein, " (methyl) acrylate " refers to be referred to as acrylate or methacrylate or third The term of the mixture of olefin(e) acid ester and methacrylate, for other similar performances too.

For containing carboxyl (methyl) acrylate monomer, in an arrangement, acid number is preferably 5～200mgKOH/g, more preferably 10～180mgKOH/g, more preferably 20～150mgKOH/g. By making acid number be less than 5mgKOH/g, the dissolubility step-down in developer solution, developability decline sometimes. During it addition, acid number is more than 200mgKOH/g, the dissolubility in developer solution excessively improves sometimes, causes Resolution declines.

In one scheme of the present invention, it is preferably following logical formula (I) containing carboxyl (methyl) acrylate monomer Shown compound.

In formula,

N is the integer of 0～4；

R is each independently hydrogen atom or methyl；

L₁For-O-base ,-(O-CH₂CH₂)_n1-O-base (wherein, n1 is the integer of 0～8) ,- (O-CH₂CH₂CH₂)_n2-O-base (wherein, n2 is the integer of 0～8)；

L₂For selecting free singly-bound, alkylidene, alkenylene, phenylene, ring alkylidene and ring alkenylene composition Group in group.

In logical formula (I), as L₂Alkylidene can be any number of of straight chain and side chain.As L₂Asia Alkyl is preferably the alkylidene of carbon number 0～8, such as can enumerate methylene, ethylidene, propylidene, three Methylene, tetramethylene, pentamethylene, hexa-methylene etc..As alkylidene, preferably carbon number 1～4 Alkylidene.

As L₂Alkenylene can be any number of of straight chain and side chain.As L₂Alkenylene be preferably carbon The alkenylene of several 2～8, such as, can enumerate vinyl, 1-methene-ethylidene (-C (=CH₂)CH₂-) Deng.

As L₂Ring alkylidene such as can enumerate cyclohexylene etc..

As L₂Ring alkenylene such as can enumerate cycloethylene thiazolinyl etc..

It addition, as L₂Phenylene, ring alkylidene, ring alkenylene can have substituent group, as this Substituent group, such as, can enumerate the alkyl of the carbon number such as methyl, ethyl 1～4, halogen atom, the alkane of carbon number 1～4 Epoxide etc..

And, group L₂It is preferably the alkylidene of carbon number 1～4, more preferably methylene or ethylidene.

As preferably one example of the compound shown in logical formula (I), can enumerate n be 1, R be hydrogen atom (more The most all R are hydrogen atom), L₁For-O-base, L₂Compound for ethylidene.

Molecular weight containing carboxyl (methyl) acrylate monomer is preferably such as 100～5000, more preferably 300～3000.

The conductive resin composition of the present invention can individually contain a kind containing carboxyl (methyl) acrylate Monomer, it is also possible to containing two or more containing carboxyl (methyl) acrylate monomer.

For the containing containing carboxyl (methyl) acrylate monomer in the conductive resin composition of the present invention There is rate, in terms of solid constituent conversion, relative to described later containing carboxy resin 100 mass parts, preferably 5～100 The scope of mass parts, more preferably 10～80 mass parts.See from the viscosity of film, conducting channel formation etc. Point sets out, and preferably comprises rate within the range.

<second comonomer>

The conductive resin composition of the present invention can contain further except containing carboxyl (methyl) acrylate Monomer (hereinafter referred to as " second comonomer ") beyond monomer.As this second comonomer, such as, can enumerate: Usual known polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (first Base) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate etc..Specifically For, that can enumerate in following substances is at least any of etc.: 2-Hydroxy ethyl acrylate, propylene The hydroxyalkyl acrylates classes such as acid-2-hydroxy propyl ester；Ethylene glycol, methoxyl group TEG, Polyethylene Glycol, The diacrylate esters of the glycol such as propylene glycol；N, N-DMAA, N hydroxymethyl acrylamide, The acrylic amides such as N, N-dimethylaminopropylacryl amide；Acrylic acid N, N-dimethylamino ethyl ester, The acrylate classes such as acrylic acid N, N-dimethylamino propyl ester；Hexanediol, trimethylolpropane, The polynary acrylic acid of the polyhydric alcohol such as tetramethylolmethane, Bis(pentaerythritol), three (hydroxyethyl) isocyanuric acid ester Esters or the ethylene oxide adduct of these polyhydric alcohol, propylene oxide adduct or 6-caprolactone addition product Deng multicomponent methacrylate class；Phenoxy group acrylate, bisphenol a diacrylate and these phenols The multicomponent methacrylate class of ethylene oxide adduct or propylene oxide adduct etc.；Glycerol diglycidyl Ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, isocyanuric acid three shrink sweet The multicomponent methacrylate class of the glycidyl ethers such as grease；It is not limited to aforementioned, by polyether polyol, gathers The direct acroleic acid esterifications of polyhydric alcohol such as carbonate diol, C-terminal polybutadiene, PEPA or The esters of acrylic acid of urethane acrylate, tripolycyanamide third is carried out via diisocyanate Olefin(e) acid ester and each methyl acrylic ester corresponding with foregoing acrylates.

And then, it is possible to use make polyfunctional epoxy resin and the acrylic acid such as cresol novolak type epoxy resin Reaction and obtain Epocryl, make this Epocryl hydroxyl further with by The diisocyanate such as hydroxy acrylate and isoflurane chalcone diisocyanate such as pentaerythritol triacrylate The epoxy amino formic acid esters acrylate compounds that half carbamate compounds formed reacts and obtains Deng as reactive diluent.Such epoxy acrylate system resin can improve photo-curable, and not Dry to touch can be reduced.

<containing carboxy resin>

As containing carboxy resin, it is possible to use molecule contains the known usual resin compound of carboxyl.

As containing carboxy resin, can be comprise carbon-to-carbon double bond containing carboxyl photoresist, but preferably Without carbon-to-carbon double bond containing carboxy resin.The most double bond containing containing carboxy resin will not with containing carboxyl (methyl) Acrylate monomer, as optional member second comonomer react, thus without formed intermolecular linkage.Cause This, the molecular weight containing carboxy resin will not become big, so easily removing when development.Its result, conduction Property powder become close, it is possible to reduce conducting channel resistance value.It addition, as containing carboxy resin, Ke Yiwei Comprise aromatic rings containing carboxyl photoresist, but preferably without aromatic rings containing carboxy resin.By setting For the structure without aromatic rings, it is possible to the suppression light containing carboxy resin itself absorbs, it is possible to relatively improve The photoreactivity of (methyl) acrylate monomer, thus promotes cure shrinkage.Its result, electric conductivity powder End becomes close, it is possible to reduce the resistivity of conducting channel.

It is exemplified below the concrete example containing carboxy resin.

(1) unsaturated carboxylic acid such as (methyl) acrylic acid and more than a kind having in addition to it is unsaturated double The compound copolymerization of key and obtain containing carboxy resin；

(2) maleic anhydride etc. have the anhydride of unsaturated double-bond and have unsaturated double-bond in addition to it Compound copolymerization and obtain containing carboxy resin；

(3) anhydride with unsaturated double-bond and the compound with unsaturated double-bond in addition to it are made Copolymer react with the compound with hydroxyl and obtain containing carboxy resin；

(4) make to have the compound of epoxy radicals and unsaturated double-bond and there is the compound of unsaturated double-bond Copolymer react with saturated carboxylic acid, make the secondary hydroxyl of generation react with multi-anhydride and obtain containing carboxyl Resin；

(5) make hydroxyl polymer-containing react with multi-anhydride and obtain containing carboxy resin,

But it is not limited to these resins.

It should be noted that in this specification, (methyl) acrylic acid refers to be referred to as acrylic acid, methyl-prop Olefin(e) acid and the term of their mixture, for other similar expression too.

As described above have multiple free carboxyl, therefore containing carboxy resin at the side chain of trunk polymer Dilute alkaline aqueous solution can be utilized to develop.

It addition, the above-mentioned acid number containing carboxy resin is preferably the scope of 40～200mgKOH/g, more preferably The scope of 45～120mgKOH/g.From the viewpoint of developability, the preferably acid number containing carboxy resin is More than 40mgKOH/g.On the other hand, from prevent exposure portion to be dissolved by the developing and make line carefully to necessity with From the viewpoint of upper or exposure portion and unexposed portion dissolubility contrast deteriorates, preferably 200mgKOH/g Below.

It addition, the above-mentioned matter average molecular weight containing carboxy resin is different according to the difference of resin matrix, the most excellent Be selected in 2000～150000 scope, further preferably 5000～100000 scope.From non-adhesion behavior, The viewpoints such as resolution are set out, and preferably matter average molecular weight is more than 2000.On the other hand, from developability, storage Hiding the viewpoints such as stability to set out, preferably matter average molecular weight is less than 150000.

About the containing ratio containing carboxy resin in conductive resin composition, with conductive resin composition In all solids composition quality as benchmark, preferably 3～50 mass %, more preferably 5～30 mass %. From the viewpoint of the intensity of conducting channel, preferably the containing ratio containing carboxy resin is more than 3 mass %. On the other hand, from the viewpoint of viscosity, coating, preferably the containing ratio containing carboxy resin is 50 mass % Below.

<electroconductive powder>

For the material of electroconductive powder, as long as giving conduction to the conductive resin composition of the present invention Property, then can use any material.As such electroconductive powder, can enumerate Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru etc., wherein, Preferably Ag.These electroconductive powders can use with the form of components described above simple substance, it is also possible to alloy, The form of oxide uses.And then, it is possible to use stannum oxide (SnO₂), Indium sesquioxide. (In₂O₃)、ITO (tin indium oxide, Indium Tin Oxide) etc..It should be noted that as electroconductive powder, permissible For carbon dusts such as white carbon black, graphite, CNTs.But, owing to light transmission can reduce, so should be noted that.

The shape of electroconductive powder is not particularly limited, preferably shape beyond de-scaling sheet (flake) shape, Especially preferably needle-like or spherical.Thus, light transmission improves, and can form the conduction electricity of excellent in resolution Road.

For such electroconductive powder, in order to formed fine line, preferably at most particle diameter be 30 μm with Under.By making maximum particle diameter be below 30 μm, the resolution of conducting channel improves.

It addition, for electroconductive powder, to use ultramicroscope (SEM) to observe under 10000 times The mean diameter meter of random 10 electroconductive powders arrived, it ranges preferably from below 0.1～10 μm.From leading From the viewpoint of electricity Xing, preferably mean diameter is more than 0.1 μm.On the other hand, from the net preventing silk screen From the viewpoint of eye blocking, preferably mean diameter is below 10 μm.It should be noted that be preferably used The mean diameter utilizing Mai Qike Particle Size Analyzer (Microtrac) to measure is leading of the size of 0.5～3.5 μm Electroconductive powder.

For the containing ratio of the electroconductive powder in the conductive resin composition of the present invention, with electric conductivity tree All solids composition quality in oil/fat composition is as benchmark, the scope of preferably 75～90 mass %.From From the viewpoint of electric conductivity, the preferably containing ratio of electroconductive powder is more than 75 mass %.On the other hand, From the viewpoint of the permeability of light, the preferably containing ratio of electroconductive powder is below 90 mass %.

<Photoepolymerizationinitiater initiater>

As Photoepolymerizationinitiater initiater, it is not particularly limited, it is possible to use oxime ester system, 1-Phenylethanone. system, benzene are even In relation by marriage system, phosphine oxide system any number of.

In one scheme of the present invention, Photoepolymerizationinitiater initiater preferably has base shown in following logical formula V The oxime ester system's polymerization initiator rolled into a ball or the 1-Phenylethanone. system photopolymerization with group shown in following logical formula (VI) Initiator.

In logical formula V, R6 represents hydrogen atom, the alkyl of carbon number 1～6 or phenyl, and R7 represents that hydrogen is former Son or the alkyl of carbon number 1～6.

In logical formula (VI), R8 and R9 represents the alkyl of carbon number 1～12 or carbon number 6～12 independently of one another Aralkyl, R10 and R11 represents hydrogen atom or the alkyl of carbon number 1～6 independently of one another.Or, R10 Can be bonded with R11 and form ring together with the nitrogen-atoms in formula, this ring can comprise ehter bond.As tool Style, can enumerate 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone, 2-(diformazan Base amino)-2-[(4-aminomethyl phenyl) methyl)-1-[4-(4-morpholinyl) phenyl]-1-butanone etc..

In aforementioned oxime ester system Photoepolymerizationinitiater initiater, preferably BASF JAPAN Co., Ltd. manufactures CGI-325, IRGACURE OXE01, IRGACURE OXE02, ADEKA Corp. manufacture N-1919, NCI-831, Nippon Chemical Ind manufacture TOE-004 etc..It addition, make For Photoepolymerizationinitiater initiater, can be IRGACURE 369 or IRGACURE 379EG.Need explanation It is that these Photoepolymerizationinitiater initiaters can be used alone or in combination of two or more kinds.

As the aforementioned 1-Phenylethanone. system Photoepolymerizationinitiater initiater with group shown in logical formula (VI), can enumerate 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4- Morpholino phenyl)-1-butanone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4- Morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc..As commercially available product, can enumerate IRGACURE 907 that BASF JAPAN Co., Ltd. manufactures, IRGACURE 369, IRGACURE 379EG etc..

The compounding rate of such Photoepolymerizationinitiater initiater is not particularly limited, relative to aforementioned containing carboxy resin 100 mass parts, the scope of preferably 0.01～30 mass parts, more preferably 0.5～15 mass parts.Solid from light The viewpoints such as the property changed, chemical proofing are set out, and the preferably compounding rate of Photoepolymerizationinitiater initiater is 0.01 mass parts Above.On the other hand, absorb from the light at conductive circuit surface controlling to be caused by Photoepolymerizationinitiater initiater, From the viewpoint of improving deep curable, below preferably 30 mass parts.

<Thermocurable composition>

The conductive resin composition of the present invention contains Thermocurable composition.As the heat used in the present invention Curable composition, it is possible to use the polyimide resin such as melmac, benzoguanamine resin, end-blocking Carbimide. Ester compounds, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, The known usual heat-curing resin such as episulfide resin, melamine derivative.One scheme of the present invention In, preferably molecule has more than 2 in cyclic ether group and cyclic thioether base at least any of (with The most ring-type (sulfur) ether) Thermocurable composition.

Having 2 in such molecule with the Thermocurable composition of upper annular (sulfur) ether is to have in molecule There is any one in 3 rings, 4 rings or the cyclic ether group of 5 rings of more than 2 or cyclic thioether base or two Plant the compound of group, for example, it is possible to enumerate: intramolecular has the chemical combination of more than at least 2 epoxy radicals It is the most that thing i.e. multi-functional epoxy compound, intramolecular have the compound of more than at least 2 oxetanylmethoxy Sense oxetane compound, intramolecular have the compound i.e. episulfide resin etc. of more than 2 thioether groups.

As aforementioned multi-functional epoxy compound, such as, can enumerate: Mitsubishi chemical Co., Ltd manufactures JER828, JER834, JER1001, JER1004, Dainippon Ink Chemicals manufacture EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055, Toto Kasei KK manufacture EPOTOHTO YD-011、YD-013、YD-127、YD-128、Dow Chemical Company D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664, Asahi Chiba Co., Ltd. manufactured The Araldite 6071 of manufacture, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo Chemical industry Co., Ltd. manufacture SUMI-EPOXY ESA-011, ESA-014, ELA-115, ELA-128, Asahi Chemical Industry Co., Ltd manufacture A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin；Mitsubishi chemical Co., Ltd manufactures JERYL903, the EPICLON 152 of Dainippon Ink Chemicals's manufacture, EPICLON 165, Dongdu chemical conversion strain EPOTOHTO YDB-400, YDB-500, Dow Chemical Company system that formula commercial firm manufactures Araldite 8011 that D.E.R.542, Asahi Chiba company made manufactures, Sumitomo Chemical strain formula meeting The SUMI-EPOXY ESB-400 of society's manufacture, ESB-700, Asahi Chemical Industry Co., Ltd manufacture A.E.R.711, A.E.R.714 etc. (being trade name) brominated epoxy resin；Mitsubishi chemical Co., Ltd Manufacture JER152, JER154, Dow Chemical Company manufacture D.E.N.431, D.E.N.438, Dainippon Ink Chemicals manufacture EPICLON N-730, EPICLON N-770, EPICLON N-865, EPOTOHTO YDCN-701, YDCN-704, BASF JAPAN that Toto Kasei KK manufactures Co., Ltd. manufacture Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, Nippon Kayaku K. K manufacture EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Company Ltd manufacture SUMI-EPOXY ESCN-195X, ESCN-220, Asahi Chemical Industry Co., Ltd manufacture A.E.R.ECN-235, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin；DIC strain formula JER807, Dongdu that the EPICLON 830 of commercial firm's manufacture, Mitsubishi chemical Co., Ltd manufacture are melted into strain formula EPOTOHTO YDF-170, YDF-175, YDF-2004, BASF JAPAN strain formula that commercial firm manufactures (the being trade name) bisphenol f type epoxy resins such as the Araldite XPY306 that commercial firm manufactures；Dongdu is melted into The hydrogenations such as EPOTOHTO ST-2004, ST-2007, ST-3000 (trade name) that Co., Ltd. manufactures Bisphenol A type epoxy resin；The JER604 of Mitsubishi chemical Co., Ltd's manufacture, Toto Kasei KK's system Araldite MY720 that the EPOTOHTO YH-434 that makes, Asahi Chiba Co., Ltd. manufacture, live The SUMI-EPOXY ELM-120 that friend chemical industry Co., Ltd. manufactures etc. (being trade name) shrink Glycerol amine type epoxy resin；The Araldite CY-350 (trade name) that Asahi Chiba Japan company manufactures Deng hydantoin type epoxy resin；The CELLOXIDE that Daicel Chemical Industries Ltd. manufactures 2021, Araldite CY175, CY179 that Asahi Chiba Co., Ltd. manufactures etc. (being trade name) Alicyclic epoxy resin；YL-933, Dow Chemical Company that Mitsubishi chemical Co., Ltd manufactures T.E.N., EPPN-501, EPPN-502 etc. (being trade name) the trihydroxy benzene methylmethane type ring manufactured Epoxy resins；YL-6056, YX-4000, YL-6121 that Mitsubishi chemical Co., Ltd manufactures (are commodity Name) etc. di-cresol type or united phenol-type epoxy resin or their mixture；Nippon Kayaku K. K EPX-30, Dainippon Ink Chemicals that the EBPS-200 of manufacture, Asahi Denka Kogyo K. K manufacture manufacture The bisphenol-s epoxy resins such as EXA-1514 (trade name)；The JER157S that Mitsubishi chemical Co., Ltd manufactures Bisphenol A novolac type epoxy resin such as (trade names)；Mitsubishi chemical Co., Ltd manufactures The four of the Araldite 163 that JERYL-931, Asahi Chiba Co., Ltd. manufactures etc. (being trade name) Hydroxy phenyl ethane type epoxy resin；Araldite PT810 that Asahi Chiba Co., Ltd. manufactures, daily outputization (being trade name) the hetero ring type epoxy resin such as the TEPIC that Industrial Co., Ltd manufactures；Japan's oils and fats The o-phthalic acid diglycidyl ester resins such as the BLEMMER DGT that Co., Ltd. manufactures；Dongdu is melted into The four glycidyl group dimethylbenzene acyl group ethane resin such as the ZX-1063 that Co., Ltd. manufactures；Nippon Steel's chemistry Co., Ltd. manufacture ESN-190, ESN-360, Dainippon Ink Chemicals manufacture HP-4032, EXA-4750, EXA-4700 etc. are containing Naphthol-based Epoxy Resin；The tools such as HP-7200, HP-7200H that Dainippon Ink Chemicals manufactures There is the epoxy resin of dicyclopentadiene skeleton；CP-50S, CP-50M that NOF Corp manufactures Etc. glycidyl methacrylate copolymerization system epoxy resin；And N-cyclohexylmaleimide and methyl-prop The copolymerization epoxy resin of olefin(e) acid ethylene oxidic ester；Epoxide modified polybutadiene rubber derivant is (such as DAICEL CHEMICAL INDUSTRIES, LTD. manufacture PB-3600 etc.), CTBN modification ring Epoxy resins (YR-102, YR-450 etc. that such as Toto Kasei KK manufactures) etc., but do not limit Due to these.These epoxy resin can be used alone or in combination of two or more kinds.Wherein, the most excellent Select phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their mixing Thing.

As aforementioned multifunctional oxetane compound, double [(3-methyl-3-oxa-ring fourth can be enumerated Ylmethoxy) methyl] ether, double [(3-ethyl-3-oxetanylmethoxy methoxyl group) methyl] ether, the double [(3-of 1,4- Methyl-3-oxetanylmethoxy methoxyl group) methyl] benzene, 1,4-double [(3-ethyl-3-oxetanylmethoxy methoxyl group) Methyl] benzene, acrylic acid (3-methyl-3-oxetanylmethoxy) methyl ester, acrylic acid (3-ethyl-3-oxa-ring Butyl) methyl ester, methacrylic acid (3-methyl-3-oxetanylmethoxy) methyl ester, methacrylic acid (3-second Base-3-oxetanylmethoxy) methyl ester, the multifunctional oxetanes class such as their oligomer or copolymer, with And oxa-cyclobutanol and novolac resin, poly-(4-Vinyl phenol), Cardo type bisphenols, cup virtue Hydro carbons, resorcinol calixarene kind or silsesquioxane etc. have the etherate etc. of the resin of hydroxyl.Remove Outside this, it is also possible to enumerate the unsaturated monomer with oxetanes ring and (methyl) acrylic acid alkyl The copolymer etc. of ester.

As previous molecular has the compound of more than 2 cyclic thioether bases, such as, can enumerate Rhizoma Sparganii The bisphenol A-type episulfide resin YL7000 etc. that KCC manufactures.Alternatively, it is also possible to use: use Same synthetic method, the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced into sulphur atom and The episulfide resin etc. obtained.

It addition, for the conductive resin composition of the present invention, in order to improve conductive resin composition Curable and the obdurability of gained cured film, can add 1 intramolecular have more than 2 NCOs or The compound of end-blockingization NCO.For such 1 intramolecular have more than 2 NCOs or The compound of end-blockingization NCO, can enumerate 1 intramolecular and have the change of more than 2 NCOs Compound i.e. polyisocyanate compound or 1 intramolecular have the chemical combination of more than 2 end-blockingization NCOs Thing i.e. blocked isocyanate compounds etc..

As polyisocyanate compound, such as, can use aromatic polyisocyanate, aliphatic polyisocyanate Cyanate or ester ring type polyisocyanates.As the concrete example of aromatic polyisocyanate, can enumerate 4,4 '-methyl diphenylene diisocyanate, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), 1,5- Naphthalene diisocyanate, O-phthalic support diisocyanate, an xylylene diisocyanate and 2,4-toluene Diisocyanate dimer.As the concrete example of aliphatic polyisocyante, tetramethylene two can be enumerated Isocyanates, hexamethylene diisocyanate, methylene diisocyanate, tri-methyl hexamethylene two are different Cyanate, 4,4-hexylmethane (4,4-methylene-bis ) and isoflurane chalcone diisocyanate (cyclohexylisocyanate).As ester ring type polyisocyanates Concrete example, can enumerate norbornane triisocyanate.And the isocyanate compound of aforementioned list Adduct, biuret body and isocyanuric acid ester body.

End-blocking NCO contained by blocked isocyanate compounds be NCO by with envelope The reaction of end agent is protected thus the group of temporarily deactivation.When being heated to set point of temperature, its end-capping reagent Dissociate and generate NCO.

As blocked isocyanate compounds, it is possible to use isocyanate compound and isocyanate-terminated dose Additive reaction product.As the isocyanate compound that can react with end-capping reagent, isocyanide can be enumerated Urea acid esters type, biuret form, adduct type etc..As this isocyanate compound, such as, can use Aromatic polyisocyanate similar to the above, aliphatic polyisocyante or ester ring type polyisocyanates.

As isocyanate-terminated dose, such as, can enumerate phenol, cresol, xylenol, chlorophenol and ethyl The phenol system end-capping reagents such as phenol；In epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone etc. Amide system end-capping reagent；Ethyl acetoacetate and acetylacetone,2,4-pentanedione isoreactivity methylene base system end-capping reagent；Methanol, second Alcohol, propanol, butanol, amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, two Glycol monoethyl ether, propylene glycol monomethyl ether, benzylic ether, methyl glycollate, butyl glycolate, diacetone The alcohol system end-capping reagents such as alcohol, methyl lactate and ethyl lactate；Formaldoxime, aldoxime, acetone oxime, butanone The oxime system end-capping reagents such as oxime, biacetyl monoxime, cyclohexanone-oxime；Butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, benzene The mercaptan system end-capping reagents such as thiophenol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol；The amide such as acetamide, Benzoylamide It it is end-capping reagent；The imide series end-capping reagent such as succimide and maleimide；Xylidine, aniline, The amine such as butylamine, dibutyl amine system end-capping reagent；The imidazoles system end-capping reagents such as imidazoles, 2-ethyl imidazol(e)；Methylene is sub- The imines system end-capping reagents etc. such as amine (methylene imine) and propyleneimine (Propylene imine).

Blocked isocyanate compounds can be commercially available product, such as can enumerate 7950,7951,7960, 7961,7982,7990,7991,7992 (above for the manufacture of Baxenden company, trade name), Sumidur BL-3175、BL-4165、BL-1100、BL-1265、Desmodur TPLS-2957、TPLS-2062、 TPLS-2078, TPLS-2117, Desmotherm2170, Desmotherm2265 (are Sumitomo above Bayer Urethane Co, Ltd. manufacture, trade name), CORONATE 2512, CORONATE 2513, CORONATE 2520 (above for Nippon Polyurethane Industry Co., Ltd.'s manufacture, trade name), B-830, B-815、B-846、B-870、B-874、B-882(MITSUI TAKEDA CHEMICALS,INC. Manufacture, trade name), TPA-B80E, 17B-60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (Asahi Kasei Chemicals Corporation manufacture, trade name), Karenz MOI-BM (Showa Denko K. K's manufacture, trade name) etc..It should be noted that Sumidur BL-3175, BL-4265 is the blocked isocyanate compounds using methyl ethyl ketoxime to obtain as end-capping reagent.

Above-mentioned 1 intramolecular has the compound of more than 2 NCOs or end-blockingization NCO can To be used alone or in combination of two or more.

For such 1 intramolecular, there are more than 2 NCOs or the change of end-blockingization NCO The compounding rate of compound, relative to the mass parts containing carboxy resin 100 be 1～100 mass parts, more preferably 2～70 The ratio of mass parts is suitable.From the viewpoint of the obdurability of film, the most aforementioned compounding rate is 1 More than mass parts.On the other hand, from the viewpoint of storage stability, below preferably 100 mass parts.

For the conductive resin composition of the present invention, in order to improve the effect of the present invention further, or In order to play other effects in the range of the effect not hindering the present invention further, can be with mentioned component Together comprise other compositions of the example below.

<organic acid>

As organic acid, the most not there is the organic acid of aromatic rings.By compounding, not there is having of aromatic rings Machine acid, it is possible to the light absorption of suppression organic acid itself, the photoreactivity of carboxylic acrylate monomer Relatively improve, it is possible to obtain excellent resolution.

As the concrete example of organic acid, 2 can be enumerated, 2 '-thiodiglycolic acid, adipic acid, isopropylformic acid., first Acid, citric 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, phenylacetic acid, acrylic acid, maleic acid, fumaric acid .beta.-methylacrylic acid etc. Carboxylic acids；Dibutyl phosphite, phosphorous acid butyl ester, dimethylphosphite, methyl phosphite, phosphorous acid Dipropyl, phosphorous acid propyl ester, diphenyl phosphite, phenyl-phosphite, diisopropyl phosphite, phosphorous The monoesters of the phosphorous acid such as isopropyl propionate, phosphorous acid-2-Octyl Nitrite or two esters；Dibutylphosphoric acid ester, phosphoric acid Butyl ester, dimethyl phosphate, methyl orthophosphoric acid, di(2-ethylhexyl)phosphate propyl ester, phosphoric acid propyl ester, diphenyl phosphate, phosphoric acid The monoesters of the phosphoric acid such as phenyl ester, diisopropyl phosphate, 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 said conductive powder 100 mass parts, it is preferably The scope of 0.1～5 mass parts.The compounding amount of aforementioned organic acid is relative to said conductive powder 100 mass parts During less than 0.1 mass parts, said conductive powder reacts with containing carboxy resin, makes to preserve for a long time and stablizes Property reduce, on the other hand, when aforementioned compounding amount is more than 5 mass parts, become the water easily absorbing in air Grade, the most preferred.

(dispersant)

By compounding dispersant, it is possible to improve the dispersibility of conductive resin composition, settleability.

As dispersant, such as can enumerate 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 Japan KK. 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, DISPARLON DA-703-50 (nanmu This chemical conversion Co., Ltd. manufacture), FLOREN G-450, FLOREN G-600, FLOREN G-820, FLOREN G-700, FLOREN DOPA-44, FLOREN DOPA-17 (common prosperity society chemistry strain formula Commercial firm manufactures).

For the containing ratio of dispersant, in order to effectively achieve above-mentioned purpose, relative to electroconductive powder 100 Mass parts, preferably 0.1～10 mass parts, more preferably 0.5～5 mass parts.

<photopolymerization inhibitor>

By adding photopolymerization inhibitor, can suppress inside the conductive resin composition that caused by exposure Occur radical polymerization in the middle of the kind with polymerization inhibitor and addition corresponding a certain amount of from It is polymerized by base.Thus, it is possible to suppression is for the photoreaction of the low light level as scattered light.Thus, it is possible to it is clear Form the line of trickleer conducting channel clearly, therefore can be preferably used.For photopolymerization inhibitor, As long as the material that can use as photopolymerization inhibitor, just it is not particularly limited, such as, can enumerate The acid of 1,4-benzoquinone, naphthoquinone, ditertbutylparacresol, hydroquinone monomethyl ether, alpha-Naphthol, acetic acid ethanamidine, hydrazonium salt Salt, trimethyl benzyl ammonia chloride, dinitro benzene, picric acid, benzoquinone dioxime, 1,2,3,-thrihydroxy-benzene, tannic acid, Resorcinol, cupferron, phenothiazine etc..

The addition of photopolymerization inhibitor preferably exists relative to the aforementioned mass parts containing carboxy resin 100 In the range of 0.001～3 mass parts, more preferably in the range of 0.01～2 mass parts.If it is fewer than this scope, Then cannot play the effect of inhibition, also can solidify under the low light exposure caused by light scattering, be susceptible to Nemaline thicker.It addition, more than this scope time, sensitivity decline, need more light exposure, because of This should be noted that.

<filler>

In the conductive resin composition of the present invention, in order to improve the physical strength etc. of its film, permissible It is compounded filler as required.As such filler, it is possible to use known usual inorganic or organic filler, Can particularly preferably use barium sulfate, silicon dioxide, brucite and Talcum.

<thermal curing catalyst>

The conductive resin composition of the present invention uses in above-mentioned molecule and there are 2 with upper annular (sulfur) During the Thermocurable composition of ether, preferably comprise thermal curing catalyst.As such thermal curing catalyst, Such as can enumerate imidazoles, 2-methylimidazole, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenyl Imidazoles, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-first The imdazole derivatives such as base imidazoles；Dicyandiamide, benzyldimethylamine, 2,4,4-(dimethylamino)-N, N-diformazan Base benzyl amine, 4-methoxyl group-N, N-dimethyl benzyl amine, 4-methyl-N, the amination such as N-dimethyl benzyl amine The hydrazide compounds such as compound, adipic dihydrazide, sebacic dihydrazide；The phosphorus compounds etc. such as triphenylphosphine. It addition, as commercially available product, such as can enumerate 2MZ-A that Shikoku Chem manufactures, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound), San-Apro Ltd. U-CAT (registered trade mark) 3503N, U-CAT3502T of manufacturing (are the end-blocking of dimethyl amine The trade name of isocyanate compound), DBU, DBN, U-CATSA102, U-CAT5002 (all It is two ring type amidine compound and salt thereof) etc..But it is not particularly limited to these, as long as epoxy resin, The thermal curing catalyst of oxetane compound or promotion are in epoxy radicals and oxetanylmethoxy The material of at least any of reaction with carboxyl, can be used alone or mix two or more use. Alternatively, it is also possible to use guanamines, methyl guanamines, benzoguanamine, tripolycyanamide, 2,4-diaminourea-6-first Base acryloyl-oxyethyl-s-triazine, 2-vinyl-2,4-diaminourea-s-triazine, 2-vinyl-4,6-diamino Base-s-triazine isocyanuric acid adduct, 2,4-diaminourea-6-methacryloxyethyl-s-triazine isocyanide These are preferably also served as the change that adaptation imparting agent plays a role by the Striazine derivatives such as urea acid addition product Compound is applied in combination with aforementioned thermal curing catalyst.

The ratio that compounding amount is common amount of these thermal curing catalysts is the most abundant, such as relative to containing carboxylic Base resin or molecule have 2 Thermocurable composition 100 mass parts with upper annular (sulfur) ether, excellent Elect 0.1～20 mass parts, more preferably 0.5～15 mass parts as.

<thermal polymerization inhibitor>

In order to prevent the conductive resin composition of the present invention thermal polymerization or through time polymerization, it is possible to use heat Polymerization inhibitor.As thermal polymerization inhibitor, such as, can enumerate 4-methoxyphenol, hydroquinone, alkyl Or aryl replaces hydroquinone, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, 2-dihydroxy benaophenonel, 4-methoxyl group -2-dihydroxy benaophenonel, Cu-lyt., chloranil, naphthylamines, betanaphthol, 2,6-di-t-butyl-4-cresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), pyridine, Nitrobenzol, dinitro benzene, picric acid, 4-toluidines, methylene blue, copper and organic sequestering agent reactant, methyl salicylate and nitroso 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 sensitivity, it is possible to use as chain tra nsfer N-phenylglycine class, phenoxy acetic acids, thio phenyl ethoxyacetic acid class, thyroidan etc. known to agent. When enumerating the concrete example of chain-transferring agent, such as, there are mercapto succinic acid, TGA, mercaptopropionic acid, first sulfur Propylhomoserin, cysteine, thiosalicylic acid and derivant thereof etc. have the chain-transferring agent of carboxyl；Mercaptoethanol, Mercaprol, Mercaptobutanol., mercapto-propanediol, sulfydryl butanediol, hydroxythiophenol and derivant thereof etc. There is the chain-transferring agent of hydroxyl；1-butyl mercaptan, 3-mercaptopropionic acid butyl ester, 3-mercapto-propionate, 2,2- (ethylenedioxy) diethyl mercaptan, ethyl mercaptan, 4-methylbenzene phenyl-sulfhydrate, lauryl mercaptan, propanethiol, Butyl mercaptan, amyl hydrosulfide, 1-spicy thioalcohol, cyclopentanethiol, cyclohexylmercaptan, thioglycerol, 4,4-thiobis Phenylmercaptan. etc..

Further, it is possible to use multi-functional mercaptan based compound, it is not particularly limited, such as, can use: The aliphatic such as 1,6-ethanthiol, 1,10-mercaptan in the last of the ten Heavenly stems two, dimercapto diethyl ether, dimercapto diethyl base thioether Thio-alcohol, benzene dimethanethiol (xylylene dimercaptan), 4,4 '-dimercapto diphenylsulfide, 1,4- The aromatic mercaptans classes such as diphenyl disulfide phenol；Double (the sulfydryl second of ethylene glycol bis (mercaptoacetate), Polyethylene Glycol Acid esters), propylene glycol double (mercaptoacetate), glycerol three (mercaptoacetate), trimethylolethane trimethacrylate (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), tetramethylolmethane four (mercaptoacetate), Many (mercaptoacetate) class of the polyhydric alcohol such as dipentaerythritol six (mercaptoacetate)；Ethylene glycol bis (3- Mercaptopropionic acid ester), Polyethylene Glycol double (3-thiopropionate), propylene glycol double (3-thiopropionate), sweet Oil three (3-thiopropionates), trimethylolethane trimethacrylate (mercaptopropionic acid ester), trimethylolpropane tris (3- Mercaptopropionic acid ester), tetramethylolmethane four (3-thiopropionate), dipentaerythritol six (3-thiopropionate) Many (3-thiopropionate) class Deng polyhydric alcohol；1,4-double (3-sulfydryl butoxy) butane, 1,3,5-tri- (3-sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, tetramethylolmethane four (3- Mercaptobutylate) etc. many (mercaptobutylate) class of polyhydric alcohol.

As their commercially available product, such as can enumerate BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (more than, chemical industry Co., Ltd. system Make), Karenz MT-PE1, Karenz MT-BD1 and Karenz-NR1 (more than, Showa electrician's strain formula Commercial firm manufactures) etc..

And then, for the heterocyclic compound with sulfydryl played a role as chain-transferring agent, the most permissible Enumerate: sulfydryl-4-butyrolactone (name: 2-sulfydryl-4-butyrolactone), 2-sulfydryl-4-methyl-4-butyrolactone, 2-sulfydryl-4-ethyl-4-butyrolactone, 2-sulfydryl-4-thiobutryolacatone, 2-sulfydryl-4-butyrolactam, N-methoxy In base-2-sulfydryl-4-butyrolactam, N-ethyoxyl-2-sulfydryl-4-butyrolactam, N-methyl-2-sulfydryl-4-fourth Amide, N-ethyl-2-sulfydryl-4-butyrolactam, N-(2-methoxyl group) ethyl-2-sulfydryl-4-butyrolactam, Acyl in N-(2-ethyoxyl) ethyl-2-sulfydryl-4-butyrolactam, 2-sulfydryl-5-valerolactone, 2-sulfydryl-5-penta Amine, N-methyl-2-sulfydryl-5-valerolactam, N-ethyl-2-sulfydryl-5-valerolactam, N-(2-methoxyl group) Ethyl-2-sulfydryl-5-valerolactam, N-(2-ethyoxyl) ethyl-2-sulfydryl-5-valerolactam, 2-sulfydryl Benzothiazole, 2-sulfydryl-5-methyl mercapto-thiadiazoles, 2-sulfydryl-6-caprolactam, 2,4,6-tri-thiol-equal three Piperazine (three chemical conversion Co., Ltd. of association manufacture: trade name Zisnet F), 2-dibutylamino-4,6-dimercapto-and all Triazine (three chemical conversion Co., Ltd. of association manufacture: trade name Zisnet DB) and 2-anilino--4,6-dimercapto- (three chemical conversion Co., Ltd. of association manufacture s-triazine: trade name Zisnet AF) etc..

Chain-transferring agent particularly as the developability not damaging conductive resin composition i.e. has sulfydryl Heterocyclic compound, preferably 2-mercaptobenzimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole (business The name of an article: chemical industry Co., Ltd. of Kawaguchi manufacture Accel M), 3-sulfydryl-4-methyl-4H-1,2,4-triazole, 5-methyl isophthalic acid, 3,4-thiadiazoles-2-mercaptan, 1-phenyl-5-sulfydryl-1H-TETRAZOLE.These chain-transferring agents can be single Solely use or be applied in combination two or more.

<other adding ingredients>

As required it is of course possible to suitably compounding is known usual in the conductive resin composition of the present invention Composition, such as thickening agent, defoamer/levelling agent, coupling agent, antioxidant, antirust agent etc..

<formation of conducting channel>

Then, an example of the method for conducting channel is formed for the conductive resin composition using the present invention Illustrate.

About the conductive resin composition of the present invention, with above-mentioned each required composition and optional member Mixing dispersion can use the machinery such as triple-roller mill, mixer.

Silk screen print method, stick coating method, scraper is utilized by so having carried out scattered conductive resin composition The suitable coating process such as rubbing method is coated on base material.

After coating, in order to obtain dry to touch, preferably by dried coating film.As drying means, do not have It is particularly limited to.Such as, heated air circulation type drying oven, far infrared drying stove etc. are used, containing carboxyl tree Temperature that fat will not be pyrolyzed, make it be dried about 5～40 minutes at e.g., from about 60～120 DEG C, make organic solvent Evaporation, the film not glued.

Then, use the negative mask of the exposing patterns with regulation, implement contact exposure or noncontact exposes Light.As exposure light source, it is possible to use Halogen light, high voltage mercury lamp, laser, metal halide lamp, black Light modulation, Non-polarized lamp etc..As light exposure, can be set to accumulative light quantity is 200mJ/cm²Following low light Amount.It should be noted that mask can not be used, and utilize laser direct imaging device shape on film Become pattern.

Then, by the development of spraying process, infusion process etc., making film is pattern-like.As developer solution, Can use the metal base aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, The amine aqueous solutions such as monoethanolamine, diethanolamine, triethanolamine.Can particularly preferably use about 1.5 mass % The dilute alkaline aqueous solution of following concentration, but as long as the carboxyl containing carboxy resin in conductive resin composition Be saponified, uncured portion (unexposed portion) is removed, and is not limited to developer solution as described above.

According to the conductive resin composition of the present invention, by use dilute alkaline aqueous solution as developer solution, right The destruction of film is few, and the problem that development residue will not be produced, it is possible to obtain leading of resolution also excellence Electricity circuit.

Therefore, in a scheme of the present invention, for the development used in the forming method of conducting channel Liquid, preferably Na₂CO₃Concentration is the dilute alkaline aqueous solution of 0.05～0.3 mass %, more preferably Na₂CO₃Dense Degree is the dilute alkaline aqueous solution of 0.1～0.2 mass %.

After development, in order to remove unwanted developer solution, preferably carry out washing, acid neutralizes.

Then, the conducting channel obtained is solidified at a temperature of will not being pyrolyzed containing carboxy resin.By This, it is possible to form low resistance and there is the conducting channel of fine pattern.As heat curing temperature, it is preferably Less than 180 DEG C, more preferably less than 150 DEG C, more preferably less than 140 DEG C, particularly preferably 130 DEG C Below.

In these operations, the most at high temperature carry out roasting, accordingly, as base material, it is possible to use do not have There is the resinous base material of thermostability.Specifically, as resinous base material, such as, can enumerate poly- Acid imide, polyester based resin, polyether sulfone (PES), polystyrene (PS), polymethyl methacrylate (PMMA), Merlon (PC), polyamide (PA), polypropylene (PP), polyphenylene oxide (PPO) Deng, it may be preferred to ground uses polyester based resin.It should be noted that can also be glass substrate etc..

[embodiment]

The present invention is specifically described below based on embodiment.But, the present invention is not limited to these and implements Example.

<containing the synthesis of carboxy resin solution>

The synthesis of synthesis example 1:R-1 varnish

In the flask possessing thermometer, blender, Dropping funnel and reflux condenser, by metering system Acid methyl ester and methacrylic acid put into the mol ratio of 0.87:0.13, put into the dipropylene glycol as solvent Monomethyl ether, azodiisobutyronitrile as catalyst, under nitrogen atmosphere, stir 6 hours in 80 DEG C, To containing carboxy resin solution.About this solution Han carboxy resin, matter average molecular weight is about 30000, solid Composition acid number is 100mgKOH/g, and solid constituent is 40 mass %.It should be noted that gained is containing carboxylic The matter average molecular weight of base resin solution has, by connection, the pump LC-6AD that Shimadzu Corporation manufactures Post Shodex (registered trade mark) KF-804 that manufactures with 3 Showa Denko K. K, KF-803, The high performance liquid chromatograph of KF-802 measures.Hereinafter, this solution Han carboxy resin is referred to as R-1 varnish.

<containing carboxyl (methyl) acrylate monomer (A)>

Monomer A-1

As containing carboxyl (methyl) acrylate monomer, Toagosei Co., Ltd is used to manufacture ARONIX M-510 (monomer A-1).This monomer A-1 is logical compound shown in formula (I), its acid number For 100mgKOH/g.

Herein, acid number refers to by according to " JISK2501-2003 petroleum product and lubricating oil-neutralization number are tried Proved recipe method " described in the following method of method and the value that measures.It addition, it is also same about acid number described later Sample.

[assay method of acid number]

The titration mixed with the mass ratio of 1:1 at dimethylbenzene and dimethylformamide by sample dissolution is molten In agent, by potentiometric titration, titrate with 0.1mol/L potassium hydroxide/ethanol solution.Will titration song Flex point on line is set to terminal, potassium hydroxide solution titer till terminal calculate acid number.

Monomer A-2

As containing carboxyl (methyl) acrylate monomer, Toagosei Co., Ltd is used to manufacture ARONIX M-520 (monomer A-2).This monomer A-2 is logical compound shown in formula (I), its acid number For 30mgKOH/g.

Monomer A-3

As containing carboxyl (methyl) acrylate monomer, Toagosei Co., Ltd is used to manufacture ARONIX TO-2359 (monomer A-3).This monomer A-3 is logical compound shown in formula (I), its acid Value is 70mgKOH/g.

<the most carboxylic acrylate monomer (B)>

As the most carboxylic acrylate monomer, chemical industry Co., Ltd. of Xin Zhong village is used to manufacture U-4HA (monomer B-1).

[electroconductive powder]

Use spherical Ag powder.The mean diameter of Ag powder is 0.4 μm.It should be noted that it is average Particle diameter is use ultramicroscope (SEM) random 10 granules of observing under 10000 times average Particle diameter.

[Photoepolymerizationinitiater initiater]

Trade name: IRGACURE OXE02 (BASF JAPAN Co., Ltd. manufacture), 1-[9-ethyl -6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) ethyl ketone

[photopolymerization inhibitor]

Phenothiazine

[organic acid]

2,2 '-thiodiglycolic acid

[dispersant]

Trade name DISPERBYK-111 (BYK Japan KK. manufacture)

[blocked isocyanate]

Trade name BI7982 (manufacture of Baxenden Co., Ltd.) isocyanates HDI trimer end-capping reagent Dimethyl pyrazole (Dimethylpyrazole)

[epoxy resin]

Trade name: jER828 (Mitsubishi chemical Co., Ltd's manufacture) bisphenol A type epoxy resin

[preparation of conductive resin composition]

Use each composition that aftermentioned table 1 records and the carbitol acetate ester as solvent, utilize triple-roller mill, The mixing dispersion of mixer, viscosity adjusts to solid constituent 80～90 mass %.Thus, obtain this table is remembered The each conductive resin composition carried.

<evaluation methodology>

The manufacture of test film

Use the polyester net of 300 mesh, the whole topcoating of each conductive resin composition evaluated is distributed in poly- On the resinous base material of ester, then, it is dried 30 minutes in heated air circulation type drying oven, at 80 DEG C, Form the film that dry to touch is good.Then, use high voltage mercury lamp is as light source, across negative mask 200mJ/cm is become with the accumulative light quantity on conductive resin composition²Mode carry out pattern exposure, so After, use 0.2 mass %Na of liquid temperature 30 DEG C₂CO₃Aqueous solution develops, washing.Finally, at 140 DEG C Solidify under conditions of × 30 minutes, make the test film being formed with conductive pattern film.

(evaluation methodology of performance)

For various performances, proceed as described below evaluation.

(resolution)

In the line of 20 μm/20 μm and space (L/S) of test film, by the situation entirely without defect It is evaluated as A, the situation having defect is evaluated as B.

(development residue)

When observing circuit under optical microscope 100 times, the situation not having residue between circuit is evaluated as A, The situation having residue between circuit is evaluated as B.

(resistivity)

The making of test film: use the polyester net of 300 mesh, by whole for each conductive resin composition topcoating It is distributed on the base material of polyester resin, then, in heated air circulation type drying oven, at 80 DEG C, is dried 30 Minute, form the film that dry to touch is good.Then, use high voltage mercury lamp is as light source, across negative As mask becomes 200mJ/cm with the accumulative light quantity on conductive composition²Mode carry out pattern exposure. Then, liquid temperature 30 DEG C, Na are used₂CO₃Concentration is that the aqueous sodium carbonate of 0.2 mass % develops, Washing.Finally, solidified under conditions of 140 DEG C × 30 minutes, make the test film being formed with conducting channel.

The mensuration of resistivity: utilize said method to form the conductive pattern circuit of 4mm × 10cm, measure electricity Resistance and thickness, calculate resistivity.

(adaptation)

Adaptation: the pattern carrying out L/S=20/20 μm is formed, carries out Cellotape (registered trade mark) stripping From, the situation entirely without defect is evaluated as A, the situation having defect is evaluated as B.

(breakpoint)

Printing film is dried 30 minutes in heated air circulation type drying oven, at 80 DEG C, forms tack After the film that dry property is good, use the Na of liquid temperature 30 DEG C₂CO₃Concentration is the aqueous sodium carbonate of 0.2 mass % Develop, visually measure and come into contact with the developer solution time till film disappears from film.

Table 1 collects and illustrates result of the test.It should be noted that the numerical value that each composition in table 1 relates to does not has During mark unit, represent mass parts.

[table 1]

Claims (6)

1. a conductive resin composition, it contains: containing carboxy resin, electroconductive powder, containing carboxyl (methyl) acrylate monomer, Photoepolymerizationinitiater initiater and Thermocurable composition.

Conductive resin composition the most according to claim 1, wherein, described containing carboxyl (methyl) The acid number of acrylate monomer is the scope of 5～200mgKOH/g.

Conductive resin composition the most according to claim 1 and 2, wherein, described containing carboxyl (first Base) acrylate monomer is the compound shown in following logical formula (I),

In formula (I),

N is the integer of 0～4；

R is each independently hydrogen atom or methyl；

L₁For-O-base ,-(O-CH₂CH₂)_n1-O-base ,-(O-CH₂CH₂CH₂)_n2-O-base, wherein, N1 is the integer of 0～8, and n2 is the integer of 0～8；

L₂For selecting free singly-bound, alkylidene, alkenylene, phenylene, ring alkylidene and ring alkenylene composition Group in group.

4. according to the conductive resin composition according to any one of claims 1 to 3, wherein, described heat Curable composition is blocked isocyanate.

5. lead described according to the conductive resin composition according to any one of Claims 1 to 4, wherein, The mean diameter of electroconductive powder is 0.1～10 μm.

6. a conducting channel, it uses the electroconductive resin combination according to any one of claim 1～5 Thing and formed.