CN104345561A - Electrical-conductive resin composition and cured substance thereof - Google Patents

Electrical-conductive resin composition and cured substance thereof Download PDF

Info

Publication number
CN104345561A
CN104345561A CN201410366813.2A CN201410366813A CN104345561A CN 104345561 A CN104345561 A CN 104345561A CN 201410366813 A CN201410366813 A CN 201410366813A CN 104345561 A CN104345561 A CN 104345561A
Authority
CN
China
Prior art keywords
resin
hydroxyl
aromatic rings
methyl
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410366813.2A
Other languages
Chinese (zh)
Other versions
CN104345561B (en
Inventor
永野琢
吉田贵大
依田健志
青山良朋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of CN104345561A publication Critical patent/CN104345561A/en
Application granted granted Critical
Publication of CN104345561B publication Critical patent/CN104345561B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/22—Esters containing nitrogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Non-Insulated Conductors (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Conductive Materials (AREA)

Abstract

The present invention provides an electrical-conductive resin composition and a cured substance thereof which can improved film strength and sealing performance of a coated film. The conductive resin composition of the present invention comprises: resin containing a hydroxyl group and a carboxyl group and being free of aromatic rings, a conductive powder, a polyfunctional (methyl) acrylate monomer, a photopolymerization initiator, and a blocked isocyanate, wherein the hydroxyl equivalent of the resin is more than 300 and is less than 3000.

Description

Conductive resin composition and solidfied material thereof
Technical field
The solidfied material that the present invention relates to conductive resin composition and use this resin combination and formed.
Background technology
Patent documentation 1 and patent documentation 2 are the known documents of the conductive paste disclosed for forming conductive pattern film on base material.
Patent documentation 1,2 discloses the conductive paste containing conductive powder, organic binder bond, photopolymerization monomer and Photoepolymerizationinitiater initiater.
These conductive pastes remove organic principle in paste by carrying out roasting at temperature more than 500 DEG C, thus guarantee the electric conductivity of solidification nitride layer.
In addition, in the conductive paste of bake kind as described above, usually containing conductive powder and glass dust, by carrying out roasting, thus remove the organic principle in paste, and make glass dust melting, guarantee the electric conductivity of conductive pattern and the adaptation with base material.
But, owing to carrying out roasting at the temperature of such photosensitive conductive paste more than 500 DEG C, therefore there is the problem being difficult to apply on the not resistance to base material be heated.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-280181 publication
Patent documentation 2: Japanese Patent No. 4411113 publication
Summary of the invention
the problem that invention will solve
The present invention makes to solve the problem, the solidfied material being provided in adaptable conductive resin composition on the not resistance to base material be heated and using this conductive resin composition and formed.
And then, the conductive resin composition the invention provides and can make coating strength, all promoting with the adaptation of base substrate and the solidfied material using this conductive resin composition and formed.
for the scheme of dealing with problems
In order to solve the problem, the invention is characterized in, comprise: do not have the resin of the hydroxyl of aromatic rings and carboxyl, electroconductive powder, multifunctional (methyl) acrylate monomer, Photoepolymerizationinitiater initiater and blocked isocyanate, the aforementioned summation without the hydroxyl equivalent of the hydroxyl of aromatic rings and the resin of carboxyl is more than 300 and less than 3000.
In addition, the invention provides a kind of conductive resin composition, it comprises: not there is the hydroxy-containing resin of aromatic rings, do not have aromatic rings containing carboxy resin, electroconductive powder, multifunctional (methyl) acrylate monomer, Photoepolymerizationinitiater initiater and blocked isocyanate, the aforementioned summation without the hydroxyl equivalent of the hydroxyl of aromatic rings and the resin of carboxyl is more than 300 and less than 3000.
In addition, the invention provides a kind of conductive resin composition, it comprises: the resin being selected from hydroxyl and the carboxyl without aromatic rings, the hydroxy-containing resin without aromatic rings and do not have aromatic rings containing carboxy resin group in two or more resins; Electroconductive powder; Multifunctional (methyl) acrylate monomer; Photoepolymerizationinitiater initiater; And blocked isocyanate, the summation of the hydroxyl equivalent of aforementioned two or more resin is more than 300 and less than 3000.
At this, " summation of the hydroxyl equivalent of resin " refers to the value specified as following.
(1) when resin is made up of a kind of resin
The hydroxyl equivalent formula 1 of the resin of " summation of the hydroxyl equivalent of resin "=use
(2) resin is made up of various kinds of resin, when all resins all comprise hydroxyl
The summation formula 2 of " summation of the hydroxyl equivalent of resin "=[hydroxyl equivalent of specific resin × relative to the compounding ratio (quality %)/100 of the specific resin of all resins]
(3) resin is made up of various kinds of resin, when comprising the resin of not hydroxyl
Summation * × 100/ of " summation of the hydroxyl equivalent of resin "=comprise the hydroxyl equivalent of the resin of hydroxyl comprises compounding ratio (quality %) the * * formula 3 of the resin of hydroxyl
* in formula 3, the resin comprising hydroxyl for only a kind time, " comprising the summation of the hydroxyl equivalent of the resin of hydroxyl " is by the value of formula 1 defined, and when the resin comprising hydroxyl is two or more, " comprising the summation of the hydroxyl equivalent of the resin of hydroxyl " is by the value of formula 2 defined.
In * formula 3, when the resin comprising hydroxyl is two or more, mean " comprising the compounding ratio (quality %) of the resin of hydroxyl " summation of compounding ratio (quality %).
Conductive resin composition of the present invention is preferred for forming conducting channel.
In addition, the invention provides and on base material, use this conductive resin composition and the solidfied material formed.
the effect of invention
According to the present invention, can provide and can use on the not resistance to base material be heated and coating strength, the conductive resin composition all excellent with the adaptation of base substrate and the solidfied material that uses this conductive resin composition and formed.
Embodiment
First, composition compounding in composition of the present invention is described.
(not there is the hydroxyl of aromatic rings and the resin of carboxyl, its hydroxyl equivalent be more than 300 and less than 3000)
Containing carboxy resin by making the structure without aromatic rings, thus should can suppress the light absorption containing carboxy resin self, relatively improving the photoreactivity of (methyl) acrylate monomer.
In addition, by there is hydroxyl and the summation of its hydroxyl equivalent being limited to more than 300 and the scope of less than 3000, thus coating strength, excellent especially with the adaptation of base substrate can be made.The summation of hydroxyl equivalent is limited to more than 300 and the reason of less than 3000 is, if be in this scope, then coating strength improves, with the contact resistance value step-down of ITO.
As containing carboxy resin, can for comprise double bond containing carboxyl photoresist, but preferably not double bond containing containing carboxy resin.The not double bond containing carboxy resin that contains can not react with (methyl) acrylate monomer, does not therefore form intermolecular linkage.Therefore, the molecular weight containing carboxy resin can not become large, therefore easily removes during development.Its result, electroconductive powder becomes fine and close.
It should be noted that, even if having double bond containing carboxy resin with few ratio, if its ratio is in the scope playing the effect same with the present invention, then this bag is double bond containing is also included within " not double bond containing containing carboxy resin " of the present invention containing carboxy resin.As not double bond containing containing carboxy resin, such as, can list the material that double bond equivalent is more than 10000.
The resin of this hydroxyl and carboxyl without aromatic rings can use known usual resin compound.List the object lesson of this resin below.
Can list: (1) is by making the resin of the unsaturated carboxylic acids such as (methyl) acrylic acid, more than a kind compound with unsaturated double-bond in addition and the copolymerization such as compound and the hydroxyl that obtains and carboxyl with hydroxyl and (methyl) acryloyl group;
(2) resin of the hydroxyl that the acid anhydrides making to have unsaturated double-bond carries out reacting with the compound with hydroxyl with the multipolymer with the compound of unsaturated double-bond in addition and obtains and carboxyl;
(3) multipolymer of the compound making to have epoxy radicals and unsaturated double-bond and the compound with unsaturated double-bond, to react with saturated carboxylic acid, and the resin of the hydroxyl making the secondary hydroxyl of generation and multi-anhydride carry out reacting and obtain and carboxyl;
(4) make the polymkeric substance of hydroxyl and multi-anhydride carry out reacting and the resin of the hydroxyl obtained and carboxyl, but be not limited to them.
It should be noted that, in this instructions, (methyl) acrylic acid refers to the term being referred to as acrylic acid, methacrylic acid and their potpourri, for other similar expression too.
As described above do not have the hydroxyl of aromatic rings and the resin of carboxyl owing to having a large amount of free carboxyl on the side chain of main chain/polymkeric substance, therefore can utilize dilute alkaline aqueous solution to develop.
In addition, the above-mentioned acid number containing carboxy resin is preferably the scope of 40 ~ 200mgKOH/g, is more preferably the scope of 45 ~ 120mgKOH/g.During containing the acid number of carboxy resin less than 40mgKOH/g, be difficult to alkali development, on the other hand, during more than 200mgKOH/g, the dissolving in the exposure portion caused by developer solution advances, and therefore line becomes thinner than required, is dissolved by the developing stripping the portion of exposure sometimes and unexposed portion indistinction, be difficult to describe normal conductive pattern, thus not preferred.
In addition, the above-mentioned matter average molecular weight containing carboxy resin is different according to resin matrix, be usually preferably in the scope of 20000 ~ 150000, further be preferably in 40000 ~ 100000 scope.When matter average molecular weight is less than 20000, non-adhesion behavior deterioration sometimes, the moisture-proof of the conductive pattern film sometimes after exposure worsens, and produce film during development and reduce, resolution is significantly deteriorated.On the other hand, when matter average molecular weight is more than 150000, developability significantly worsens sometimes, storage-stable deterioration sometimes.
The compounding amount containing carboxy resin is like this preferably 3 ~ 50 quality %, is more preferably 5 ~ 30 quality % in whole conductive resin composition.When being less than above-mentioned scope, the solidification such as conductive pattern film film strength reduces, therefore not preferred.On the other hand, when being greater than above-mentioned scope, viscosity uprises or the reduction such as coating, therefore not preferred.
Above, the compounding situation without the hydroxyl of aromatic rings and the resin of carboxyl is described, but the present invention also can combinationally use the hydroxy-containing resin without aromatic rings and the carboxy resin that contains without aromatic rings replaces above-mentioned containing carboxy resin.Or, can also with above-mentioned containing combinationally use the hydroxy-containing resin without aromatic rings together with carboxy resin and do not have aromatic rings containing at least wantonly a kind in carboxy resin.Now, also in the same manner as the situation of " not there is the hydroxyl of aromatic rings and the resin of carboxyl ", the summation of the hydroxyl equivalent of these resins is set to more than 300 and less than 3000.In addition, during above-mentioned hybrid resin like that, suitable acid number, matter average molecular weight, compounding amount etc. with the situation of above-mentioned " not there is the hydroxyl of aromatic rings and the resin of carboxyl " for benchmark.
This hydroxy-containing resin without aromatic rings also can use known usual resin combination.List the object lesson of this resin below.
The hydroxy-containing resin without aromatic rings that (1) obtains by making to have the compound of hydroxyl and (methyl) acryloyl group etc. and (methyl) lower alkyl acrylate, isobutylene etc. and carrying out copolymerization containing the compound of unsaturated group can be listed, but be not limited thereto.
As the hydroxy-containing resin without aromatic rings, such as, can list East Asia synthesis ARUFONUH-2000 series (UH-2000, UH-2032, UH-2041, UHE-2012 etc.).
In addition, what do not have aromatic rings also can use known usual resin combination containing carboxy resin.List the object lesson of this resin below.
Can list: what (1) obtained by making the unsaturated carboxylic acids such as (methyl) acrylic acid and more than a kind compound with unsaturated double-bond in addition carry out copolymerization do not have aromatic rings containing carboxy resin;
(2) carboxy resin that contains without aromatic rings that the acid anhydrides by making maleic anhydride etc. have unsaturated double-bond carries out copolymerization with the compound with unsaturated double-bond in addition and obtains, but be not limited to these.
As do not have aromatic rings containing carboxy resin, such as can list East Asia synthesis ARUFON UC-3000 series.
(electroconductive powder)
About electroconductive powder, as long as the material of electroconductive powder can give electric conductivity to conductive resin composition, just can use arbitrarily.As such electroconductive powder, can Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru etc. be listed, among them, preferred Ag.These electroconductive powders can use with the form of mentioned component simple substance, also can use with the form of alloy, oxide.And then, also can use tin oxide (SnO 2), indium oxide (In 2o 3), ITO (tin indium oxide; Indium Tin Oxide) etc.It should be noted that, as electroconductive powder, can be the carbon dusts such as carbon black, graphite, carbon nano-tube, but when using them, light transmission reduces, and therefore should be noted that.
The shape of these powder is not particularly limited, is preferably shape except flakey, be particularly preferably needle-like, spherical.Thus, light transmission improves, and can form the pattern film of excellent in resolution.
About such powder, in order to form fine line, maximum particle diameter is preferably less than 30 μm.By maximum particle diameter is set to less than 30 μm, thus the resolution of solidfied material improves.
In addition, for powder, preferably, to use electron microscope (SEM) with the mean grain size of 10000 times of 10 random powder observed, its scope is less than 0.1 ~ 10 μm.When mean grain size is less than this scope, cause the increase of contact resistance, resistance value uprises, therefore not preferred.On the other hand, when mean grain size is greater than above-mentioned scope, when using screen cloth version printed conductor pattern, cause due to the obstruction of half tone operability to worsen, be difficult to form fine line, thus not preferred.It should be noted that, preferably use the mean grain size measured by Microtrac to be the powder of the size of 0.5 ~ 3.5 μm.
The resin of hydroxyl and carboxyl that the compounding rate of electroconductive powder does not have aromatic rings relative to 100 mass parts is preferably set to 800 ~ 900 mass parts.When compounding ratio is very few, worry that the resistance value of conductive resin composition uprises and can not obtain sufficient electric conductivity.On the other hand, when comprising powder in large quantities, the permeability of light is deteriorated, and utilizes the formation of the pattern film of exposure to be deteriorated, therefore not preferred.It should be noted that, compounding " do not have aromatic rings hydroxy-containing resin and do not have aromatic rings containing carboxy resin " time so together with " not there is the hydroxyl of aromatic rings and the resin of carboxyl " in compounding " not there is the hydroxy-containing resin of aromatic rings " and " do not have aromatic rings containing carboxy resin " at least wantonly a kind time, relative to total compounding amount 100 mass parts of these resins, the compounding rate of electroconductive powder is preferably set to 800 ~ 900 mass parts.
Below, about the compounding amount of these resins, with " not there is the hydroxyl of aromatic rings and the resin of carboxyl " for representative illustrates, the compounding amount therefore illustrated also be applied to compounding " do not have aromatic rings hydroxy-containing resin and do not have aromatic rings containing carboxy resin " situation so that at least wantonly a kind of situation together with " not there is the hydroxyl of aromatic rings and the resin of carboxyl " in compounding " not there is the hydroxy-containing resin of aromatic rings " and " do not have aromatic rings containing carboxy resin ".
(multifunctional (methyl) acrylate monomer)
As (methyl) acrylate monomer, use multifunctional (methyl) acrylate monomer (2 officials can (methyl) acrylate monomer) above.The reason of multifunctional (methyl) acrylate monomer is used to be because photoreactivity improves compared with when being 1 with the number of functional group, excellent in resolution.
As (methyl) acrylate monomer, such as, can list usual known polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate etc.Specifically, the hydroxyalkyl acrylates classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate can be listed; The diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The acrylic amides such as N,N-DMAA, N hydroxymethyl acrylamide, N, N-dimethylaminopropylacryl acid amides; The acrylate classes such as acrylic acid N, N-dimethylamino ethyl ester, acrylic acid N, N-dimethylamino propyl ester; The multicomponent methacrylate classes such as the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product; The multicomponent methacrylate classes such as the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct; The multicomponent methacrylate class of the glycidol ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl isocyanurate; Be not limited to aforementioned, can also list by the direct acroleic acid esterifications of polyvalent alcohol such as polyether glycol, PCDL, C-terminal polybutadiene, polyester polyol or the esters of acrylic acid carrying out urethane acrylate by diisocyanate and obtain and melamine acrylate and each methyl acrylic ester corresponding with foregoing acrylates at least any one etc.
Wherein, preferably 4 officials can (methyl) acrylate monomer.As (methyl) acrylate monomer of 4 functional groups, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate etc. can be listed.
As (methyl) acrylate monomer of 4 functional groups, the urethane acrylate monomer of 4 functional groups that preferred chemical formula (I), (II) are recorded or ester acrylate.
In formula (I),
X 1represent the group comprising acryloxy.
X 2represent the group comprising methacryloxy.
X 3and X 4separately represent and comprise the group of acryloxy or comprise the group of methacryloxy.Wherein, X 3and X 4in at least one represent the group comprising methacryloxy.
L 1and L 2separately represent
* the bonding position with Z is represented.
Z represents the link group of divalent.
In addition, as (methyl) acrylate monomer, preferably, the L in general formula (I) 1and L 2for carbamate (methyl) acrylate shown in following formula.
In formula (III), * represents the bonding position with Z.
And then, as the monomer shown in general formula (I), carbamate (methyl) acrylate shown in preferred following formula (IV).
In formula (IV),
Z 1represent alkylidene.
R 1represent hydrogen atom.
R 2represent methyl.
R 3and R 4separately represent hydrogen atom or methyl.Wherein, R 3and R 4in at least one represent methyl.
And then as (methyl) acrylate monomer of 4 functional groups, particularly preferably acryloyl group and methacryl are carbamate (methyl) acrylate or ester (methyl) acrylate of 1 to 1.
As carbamate (methyl) acrylate or ester (methyl) acrylate of 4 such functional groups, such as preferably, make glycidyl methacrylate addition acrylic acid, make the material that the hydroxyl that now produces and diisocyanate or dicarboxylic acid carry out reacting and obtain.
As the commercially available product of carbamate (methyl) acrylate of 4 functional groups, such as, can list NK oligo U-4HA (trade name, Shin-Nakamura Chemical Co., Ltd. manufacture) etc.
Among these multifunctional (methyl) acrylate monomers, (methyl) acrylate monomer of 4 functional groups shown in preferred formula (I).This 4 official can (methyl) acrylate monomer due to functional group number many, therefore photoreactivity is excellent, excellent in resolution.
In addition, the X of (methyl) acrylate monomer of this 4 functional group 1and X 2different from each other, therefore when photocuring, intramolecular X 1with X 2reaction different.But, the X of acrylate monomer 1or X 2with the X of other acrylate monomer 1or X 2intermolecular, compared with inner molecular reaction, react more quickly.Thus, between multiple acrylate monomer, form intermolecular linkage, therefore make the further cure shrinkage of conductive resin composition.So only rely on thermal treatment at low temperatures just can promote intermolecular reaction further, conductive resin composition is cure shrinkage fully.Its result, think that electroconductive powder becomes fine and close, the resistivity value of conductive pattern film reduces further.
The compounding amount of so multifunctional (methyl) acrylate monomer is not particularly limited, aforementioned relative to 100 mass parts " not having the hydroxyl of aromatic rings and the resin of carboxyl " is 10 ~ 100 mass parts, be more preferably the ratio of 20 ~ 80 mass parts is appropriate.During aforementioned compounding quantity not sufficient 10 mass parts, photo-curable reduces sometimes, is difficult to utilize the postradiation alkali development of active energy beam to form the line of conductive pattern, therefore not preferred.On the other hand, during more than 100 mass parts, sometimes reduce the dissolubility of aqueous alkali, conductive pattern film becomes fragile, therefore not preferred.
(Photoepolymerizationinitiater initiater)
As Photoepolymerizationinitiater initiater, be not particularly limited, can be benzoin system, phosphine oxide system, preferably use the oxime ester system with the shown group of following general formula (V) or the acetophenone system Photoepolymerizationinitiater initiater with group shown in following general formula (VI).
In formula (V), R6 represents alkyl or the phenyl of hydrogen atom, carbon number 1 ~ 6, and R7 represents the alkyl of hydrogen atom, carbon number 1 ~ 6.
In formula (VI), R8, R9 separately represent alkyl or the aralkyl of carbon number 1 ~ 12, and R10, R11 separately can represent the alkyl of hydrogen atom or carbon number 1 ~ 6, or also can R10, R11 bonding and form cyclic alkyl ether.
Among aforementioned oxime ester system Photoepolymerizationinitiater initiater, the TOE-004 etc. that N-1919, NCI-831, Nippon Chemical Industrial Co.Ltd. that CGI-325, Irgacure OXE01, Irgacure OXE02, ADEKA Corporation that preferred BASF Japan Ltd. manufactures manufactures manufactures.In addition, as Photoepolymerizationinitiater initiater, can be Irgacure389.It should be noted that, these Photoepolymerizationinitiater initiaters may be used singly or in combin two or more.
As the acetophenone system Photoepolymerizationinitiater initiater with group shown in aforementioned formula (VI), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc. can be listed.As commercially available product, Irgacure 907, Irgacure 369, Irgacure 379 etc. that BASF Japan Ltd. manufactures can be listed.
The compounding amount of such Photoepolymerizationinitiater initiater is not particularly limited, aforementioned relative to 100 mass parts " not there is the hydroxyl of aromatic rings and the resin of carboxyl " or aforementioned " resin being selected from hydroxyl and the carboxyl without aromatic rings, the hydroxy-containing resin without aromatic rings and do not have aromatic rings containing carboxy resin group in two or more resins " (hereinafter referred to as resin.), be 0.01 ~ 30 mass parts, to be preferably the scope of 0.5 ~ 15 mass parts be suitable.During compounding quantity not sufficient 0.01 mass parts of Photoepolymerizationinitiater initiater, photo-curable is not enough sometimes, and conductive pattern film is peeled off, or the characteristic of the conductive pattern film such as chemical proofing, coating strength reduce, therefore not preferred.On the other hand, during more than 30 mass parts, the light absorption sometimes on the conductive pattern film surface of Photoepolymerizationinitiater initiater becomes violent, and deep curability, coating strength reduce, therefore not preferred.
(blocked isocyanate compounds)
In order to improve the obdurability of the cured film obtained by conductive resin composition and there is in compounding 1 molecule with the adaptation of base substrate compound and the blocked isocyanate compounds of end-blocking isocyanate group.In addition, also thermotolerance etc. can be given by compounding blocked isocyanate compounds.
End-blocking isocyanate group contained in blocked isocyanate compounds is isocyanate group by and the group of temporary transient passivation protected with the reaction of end-capping reagent.When being heated to set point of temperature, this end-capping reagent dissociates and generates isocyanate group.
As blocked isocyanate compounds, use the addition reaction product of isocyanate compound and isocyanate-terminated dose.As the isocyanate compound that can react with end-capping reagent, isocyanuric acid ester type, biuret form can be listed, add mould assembly etc.As this isocyanate compound, such as, aromatic polyisocyanate similar to the above, aliphatic polyisocyante or ester ring type polyisocyanates is used.
As isocyanate-terminated dose, such as, can list the phenol system end-capping reagents such as phenol, cresols, xylenols, chlorophenol and ethyl-phenol; The lactams system end-capping reagents such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone; Ethyl acetoacetate and diacetone isoreactivity methylene base system end-capping reagent; The alcohol system end-capping reagents such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzylic ether, methyl glycollate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; The oxime system end-capping reagents such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, hexamethylene oxime; The mercaptan system end-capping reagents such as butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol; The acid amides such as acetamide, benzamide system end-capping reagent; The imide series such as succinimide and maleimide end-capping reagent; The amine system end-capping reagents such as xylidin, aniline, butylamine, dibutylamine; The imidazoles system end-capping reagents such as imidazoles, 2-ethyl imidazol(e); The imines system end-capping reagents etc. such as methylene imine and propylidene imines.
Blocked isocyanate compounds can be also commercially available product, such as, can list 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (more than, Baxenden, Inc. manufacture, trade name), Sumidule BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm2265 (more than, Sumitomo Bayer Urethane Co., Ltd. manufactures, trade name), Coronate 2512, Coronate 2513, Coronate 2520 (more than, Nippon Polyurethane Industry Co., Ltd. manufactures, 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-60B, SBN-70D (Asahi Kasei Chemicals Corporation manufactures, trade name), Karenz MOI-BM (Showa Denko K. K manufactures, trade name) etc.It should be noted that, Sumidule BL-3175, BL-4265 are the materials that use first and second oxime obtains as end-capping reagent.
The above-mentioned compound with end-blocking isocyanate group can be used alone a kind or combinationally use two or more.
The compounding amount with the compound of end-blocking isocyanate group like this relative to 100 mass parts aforementioned resin be 1 ~ 100 mass parts, to be more preferably the ratio of 2 ~ 70 mass parts be suitable.During aforementioned compounding quantity not sufficient 1 mass parts, sometimes can not obtain enough film obdurabilities, not preferably.On the other hand, during more than 100 mass parts, storage stability reduces sometimes, not preferably.
The dissociation temperature of the end-capping reagent of blocked isocyanate is not particularly limited, this end-capping reagent do not react under temporary transient baking temperature (such as 80 ~ 90 DEG C) and in last thermal treatment time reaction be desirable, be therefore preferably higher than temporary transient baking temperature temperature, such as more than 100 DEG C.In addition, as base material, such as, when using polyester based resin, if heat treatment temperature is too high, the easy variable color of base material, therefore the dissociation temperature of the end-capping reagent of blocked isocyanate is set to the temperature such as less than 140 DEG C that can prevent base material variable color, preferably can heat-treats at the non-discoloring temperature of base material.
For conductive resin composition of the present invention, rise further to make effect of the present invention, or in order to play further other effect in the scope not damaging effect of the present invention, can containing following other composition exemplified together with above-mentioned hydroxy-containing resin, electroconductive powder, multifunctional (methyl) acrylate monomer, Photoepolymerizationinitiater initiater and the blocked isocyanate compounds without aromatic rings.
(organic acid)
As organic acid, preferably not there is the organic acid of aromatic rings.By the compounding organic acid without aromatic rings, the light absorption of organic acid self can be suppressed, relatively improve the photoreactivity of (methyl) acrylate monomer of 4 functional groups, obtain excellent resolution.
As the example that organic acid is concrete, can 2 be listed, the carboxylic acidss such as 2 '-thiodiglycolic acid, hexane diacid, isobutyric acid, formic acid, citric acid, glutaric acid, acetic acid, oxalic acid, tartrate, lactic acid, pyruvic acid, malonic acid, butyric acid, malic acid, salicylic acid, benzoic acid, phenylacetic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid; The monoesters of the phosphorous acid such as dibutyl phosphite, phosphorous acid butyl ester, dimethylphosphite, methyl phosphite, phosphorous acid dipropyl, phosphorous acid propyl ester, diphenyl phosphite, phenyl-phosphite, the different phenyl ester of phosphorous acid two, the different phenyl ester of phosphorous acid, phosphorous acid-two-2-Octyl Nitrite or diester class; The monoesters of the phosphoric acid such as dibutylphosphoric acid ester, butylphosphoric acid ester, dimethyl phosphate, methyl orthophosphoric acid, di(2-ethylhexyl)phosphate propyl ester, phosphoric acid propyl ester, diphenyl phosphate, phenyl phosphate, diisopropyl phosphate, p isopropylbenzoic acid ester, phosphoric acid-normal-butyl-2-Octyl Nitrite or diester class etc.As organic acid, preferably 2,2 '-thiodiglycolic acid.
As the compounding amount of above-mentioned organic acid, relative to the said conductive powder of 100 mass parts preferably in the scope of 0.1 ~ 5 mass parts.The compounding amount of aforementioned organic acid relative to the said conductive powder of 100 mass parts less than 0.1 mass parts time, said conductive powder reacts with containing carboxy resin, long-term storing stability is reduced, on the other hand, when aforementioned compounding amount is more than 5 mass parts, moisture etc. in easy absorption air, thus not preferred.
(spreading agent)
By compounding spreading agent, thus dispersiveness, the precipitability of conductive resin composition can be improved.
As spreading agent, such as, ANTI-TERRA-U can be listed, 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 (manufacture of BYK Japan Co., Ltd.), DISPARLON2150, DISPARLON 1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON 1860, DISPARLON1850, DISPARLON DA-400N, DISPARLON PW-36, DISPARLON DA-703-50 (Kusumoto Chemicals, Ltd. manufacture), FLOWLEN G-450, FLOWLEN G-600, FLOWLEN G-820, FLOWLEN G-700, FLOWLEN DOPA-44, FLOWLEN DOPA-17 (manufacture of Kyoeisha Chemical Co., Ltd.).
In order to effectively reach above-mentioned purpose, the content of spreading agent is 0.1 ~ 10 mass parts relative to 100 mass parts electroconductive powders, is preferably 0.5 ~ 5 mass parts.
(photopolymerization inhibitor)
By adding photopolymerization inhibitor, thus in the middle of the free radical polymerization occurred in conductive resin composition inside caused by exposure, a certain amount of free radical polymerization can be suppressed according to the kind of polymerization inhibitor and its addition.Thus, the light reaction that the low light level such with scattered light can be suppressed corresponding.Therefore, can the line of finer conductive pattern film be formed sharply, therefore can preferably use.As long as the material that photopolymerization inhibitor can use as photopolymerization inhibitor is just not particularly limited, such as can list 1,4-benzoquinone, naphthoquinones, BHT, hydroquinone monomethyl ether, alpha-Naphthol, acetic acid ethanamidine (acetamidine acetate), hydrazine hydrochloride, trimethyl benzyl ammonia chloride, dinitro benzene, picric acid, quininie dioxime, 1,2,3,-thrihydroxy-benzene, tannic acid (tannic acid), resorcinol (resorsin), cupferron (cupferron), phenothiazine (phenothiazine) etc.
The resin of the addition hydroxyl and carboxyl that do not have aromatic rings aforementioned relative to 100 mass parts of photopolymerization inhibitor is preferably 0.001 ~ 3 mass parts, is more preferably in the scope of 0.01 ~ 2 mass parts.If be less than this scope, then do not given play to the effect of inhibition, even if also solidify under based on the low exposure of light scattering, wire shaped is easily thicker.In addition, when being greater than this scope, sensitivity decrease, needs a large amount of exposures, therefore should be noted that.
(filler)
In conductive resin composition of the present invention, in order to improve the physical strength etc. of its film, can compounding filler as required.As such filler, known usual inorganic or organic filler can be used, particularly preferably use barium sulphate, silicon dioxide, hydrotalcite and talcum.
(thermal curing catalyst)
Use in conductive resin composition of the present invention in molecule have 2 with the Thermocurable composition of upper annular (sulphur) ether time, preferably containing thermal curing catalyst.As such thermal curing catalyst, such as, can list the imdazole derivatives such as imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzylamine, 4-methoxyl-N, N-dimethyl benzylamine, 4-methyl-N, the hydrazide compounds such as the amines such as N-dimethyl benzylamine, adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds etc. such as triphenylphosphine.In addition, as commercially available product, such as, can list 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound) of Shikoku Chem's manufacture, U-CAT (registered trademark) 3503N, U-CAT3502T (being the trade name of the blocked isocyanate compounds of dimethylamine) of SAN-APRO Ltd. manufacture, DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compounds and its salt) etc.Be not particularly limited to these, as long as the thermal curing catalyst of epoxy resin, oxetane compound or promote in epoxy radicals and oxetanyl at least wantonly a kind with the material of the reaction of carboxyl, can be used alone or mix two or more use.In addition, also guanamines, methyl guanamines, benzoguanamine, melamine, 2 can be used, 4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid adduct, 2, these compounds also worked as adaptation imparting agent and aforementioned hot curing catalysts are preferably combinationally used by the Striazine derivatives such as 4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid adduct.
The compounding amount of these thermal curing catalysts is that the ratio of common amount is namely enough, and such as the resin of the hydroxyl and carboxyl that do not have aromatic rings aforementioned relative to 100 mass parts is preferably 0.1 ~ 20 mass parts, is more preferably 0.5 ~ 15 mass parts.
(thermal polymerization inhibitor)
Thermal polymerization inhibitor may be used for preventing conductive resin composition of the present invention thermal polymerization or through time polymerization.As thermal polymerization inhibitor, such as can list 4-metoxyphenol, quinhydrones, alkyl or aryl replace quinhydrones, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, 2-dihydroxy benaophenonel, 4-methoxyl-2-dihydroxy benaophenonel, cuprous chloride, phenothiazine, chloranil, naphthylamines, betanaphthol, 2, 6-di-t-butyl-4-cresols, 2, 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitro benzene, picric acid, 4-toluidine, methylene blue, the reaction product of copper and organic sequestering agent, gaultherolin, and phenothiazine, nitroso compound, the chelate etc. of nitroso compound and Al.
(chain-transferring agent)
In conductive resin composition of the present invention, in order to improve sensitivity, known N-phenylglycine class, phenoxy acetic acids, sulfo-phenoxy acetic acids, thyroidan etc. can be used as chain-transferring agent.If enumerate the object lesson of chain-transferring agent, then such as mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, halfcystine, thiosalicylic acid and its derivant etc. are had to have the chain-transferring agent of carboxyl; Mercaptoethanol, mercaprol, Mercaptobutanol, mercapto-propanediol, sulfydryl butylene glycol, hydroxythiophenol and its derivant etc. have the chain-transferring agent of hydroxyl; 1-butyl mercaptan, butyl-3-mercaptopropionic acid ester, methyl-3-mercaptopropionic acid ester, 2,2-(ethylidene dioxy base) diethyl mercaptan, ethyl mercaptan, 4-methylbenzene phenyl-sulfhydrate, lauryl mercaptan, propanethiol, butyl mercaptan, amyl hydrosulfide, 1-spicy thioalcohol, cyclopentanethiol, cyclohexylmercaptan, thioglycerol, 4,4-thiobis-benzenethiol etc.
In addition, multi-functional mercaptan based compound can be used, be not particularly limited, such as, analiphatic sulphur alcohols, xylylene two mercaptan, 4 such as hexane-1,6-bis-mercaptan, decane-1,10-bis-mercaptan, dimercapto diethyl ether, dimercapto diethyl base thioether can be used, the aromatic mercaptans classes such as 4 '-dimercapto diphenylsulfide, Isosorbide-5-Nitrae-diphenyl disulfide phenol; Many (mercaptoacetate) class of the polyvalent alcohol such as ethylene glycol bis (mercaptoacetate), polyglycol two (mercaptoacetate), propylene glycol two (mercaptoacetate), glycerine three (mercaptoacetate), trimethylolethane trimethacrylate (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrite four (mercaptoacetate), dipentaerythritol six (mercaptoacetate); Many (3-mercaptopropionic acid ester) class of the polyvalent alcohol such as ethylene glycol bis (3-mercaptopropionic acid ester), polyglycol two (3-mercaptopropionic acid ester), propylene glycol two (3-mercaptopropionic acid ester), glycerine three (3-mercaptopropionic acid ester), trimethylolethane trimethacrylate (mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester); Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane, 1,3,5-tri-(3-mercaptobutyl oxygen base ethyl)-1,3,5-triazine-2,4, many (mercaptobutylate) classes such as 6 (1H, 3H, 5H)-triketones, pentaerythrite four (3-mercaptobutylate).
As their commercially available product, such as can list BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (above is the manufacture of Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1 and Karenz-NR1 (being that Showa Denko K. K manufactures above) etc.
And then, as the heterogeneous ring compound with sulfydryl playing chain-transferring agent effect, such as, can list sulfydryl-4-butyrolactone (another 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-methoxyl-2-sulfydryl-4-butyrolactam, N-ethoxy-2-sulfydryl-4-butyrolactam, N-methyl-2-sulfydryl-4-butyrolactam, N-ethyl-2-sulfydryl-4-butyrolactam, N-(2-methoxyl) ethyl-2-sulfydryl-4-butyrolactam, N-(2-ethoxy) 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) ethyl-2-sulfydryl-5-valerolactam, N-(2-ethoxy) ethyl-2-sulfydryl-5-valerolactam, 2-mercaptobenzothiazole, 2-sulfydryl-5-methyl mercapto-thiadiazoles, 2-sulfydryl-6-caprolactam, (three associations change into Co., Ltd. and manufacture 2,4,6-tri-thiol-s-triazine: trade name Zisnet F), (three associations change into Co., Ltd. and manufacture 2-dibutylamino-4,6-dimercaptos-s-triazine: trade name Zisnet DB), and 2-anilino--4,6-dimercaptos-s-triazine (three association change into Co., Ltd. manufacture: trade name Zisnet AF) etc.
Particularly, about as the heterogeneous ring compound with sulfydryl of chain-transferring agent of developability not damaging conductive resin composition, preferred 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: chemical industry Co., Ltd. of Kawaguchi manufactures 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 may be used singly or in combin two or more.
(other adding ingredient)
Certainly can suitable compounding known usual composition as required in the conductive resin composition of this, such as thickening agent, froth breaking/levelling agent, coupling agent, antioxidant, rust preventive etc.
(formation of solidfied material)
Then, the example forming the method for solidfied material for using conductive resin composition of the present invention is described.
About conductive resin composition of the present invention, respectively mixing dispersion of composition and any composition the equipment such as three-roller or mixer must be used with above-mentioned.
The suitable coating processes such as the conductive resin composition silk screen print method of disperseing so operating, stick coating method, scraper for coating method are applied on base material.Then, in order to obtain dry to touch, at the temperature such as about 60 ~ 120 DEG C of thermal decomposition about dry 5 ~ 40 points of kinds, organic solvent evaporation can not be made, the film do not glued with heated air circulation type drying oven, far infrared drying stove etc. containing carboxy resin.
It should be noted that, can be also film-form by conductive resin composition film forming in advance, now, thin layer is pressed onto on base material.
Then, use the negative mask with the exposing patterns of regulation, carry out contact exposure or noncontact exposure.As exposure light source, use Halogen lamp LED, high-pressure sodium lamp, laser, metal halide lamp, black lamp, electrodeless lamp etc.As exposure, accumulated light can be set to 200mJ/cm 2following low light quantity.It should be noted that, also can not use mask and utilize laser direct imaging device to form pattern on film.
Then, by the development of spray-on process, infusion process etc., film is made pattern-like.As developer solution, the dilute alkaline aqueous solution using amine aqueous solution, the particularly concentration of below about 1.5 quality % such as metal base aqueous solution, monoethanolamine, diethanolamine, triethanolamine such as NaOH, potassium hydroxide, sodium carbonate, sal tartari, sodium silicate can be suitable for, as long as can by conductive resin composition containing carboxy resin carboxyl saponification and remove uncured portion (unexposed portion), be not limited to developer solution as described above.In addition, in order to remove unwanted developer solution after development, preferably carry out washing, acid neutralization.
Then, can not by obtained solidfied material slaking at the temperature of thermal decomposition containing carboxy resin.Curing temperature preferably the scope of 130 DEG C ~ 400 DEG C, be more preferably 150 ~ 400 DEG C.Conductive resin composition of the present invention can obtain solidfied material (such as conductive pattern film) by the slaking of the lower temperature of less than 400 DEG C, therefore can on the substrate that thermotolerance is low, the combination of materials low with thermotolerance make for using.
(base material)
In these operations, not roasting under the high temperature of 500 DEG C, therefore can use the resinous base material without thermotolerance as base material.Specifically, as resinous base material, such as can list polyester based resin, polyethersulfone (PES), polystyrene (PS), polymethylmethacrylate (PMMA), polycarbonate (PC), polyamide (PA), polypropylene (PP), polyphenylene oxide (PPO) etc. that polyimide, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN (PEN) are such, polyester based resin can be used aptly.It should be noted that, also can be glass substrate etc.
Embodiment
Below, the present invention is specifically described according to embodiment.But the present invention is not limited to these embodiments.
(compounding ingredients)
Synthesis example 1 [not there is the hydroxyl of aromatic rings and the resin of carboxyl]
In the flask possessing thermometer, stirring machine, tap funnel and reflux condenser, methyl methacrylate, methacrylic acid and acrylic acid 2-hydroxyl ethyl ester is dropped into the mol ratio of 47:15:38, dipropylene glycol monomethyl ether is dropped into as solvent, azoisobutyronitrile is dropped into as catalyzer, stir 6 hours in a nitrogen atmosphere, at 80 DEG C, obtain " not there is the hydroxyl of aromatic rings and the resin of carboxyl " varnish.Should be 300 containing the hydroxyl equivalent of carboxy resin.
Below, cementing agent A-1 (A-1) is called by being somebody's turn to do " resin of hydroxyl and carboxyl " varnish.
In addition, the compounding amount of each composition of synthesis example is replaced.Make " resin of hydroxyl and carboxyl " varnish of the hydroxyl equivalent different from A-1.Using them as cementing agent A-2 ~ A-5.
Table 1 illustrates the hydroxyl equivalent (rate of charge and calculated value) of cementing agent A-1 ~ A-5, compounding methyl methacrylate, methacrylic acid, acrylic acid 2-hydroxyl ethyl ester, acid number respectively.
Table 1
Table 1 cementing agent A comprises the synthesis example of the resin of hydroxyl and carboxyl
In addition, about the cementing agent A-6 used in comparative example, in " comprising the resin of hydroxyl and the carboxyl " varnish with aromatic rings, dropping into 2200g cresol novolak type epoxy resin, (Nippon Kayaku Company manufactures, EOCN-104S, softening point 92 DEG C, epoxide equivalent 220), 134g dihydromethyl propionic acid, 648.5g acrylic acid, 4.6g methylnaphthohydroquinone, 1131g carbitol acetate and 484.9g solvent naphtha, be heated to 90 DEG C and stir, reaction mixture is dissolved.Then, reactant liquor is cooled to 60 DEG C, drops into 13.8g triphenylphosphine, be heated to 100 DEG C, make it react about 32 hours, obtain the reaction product that acid number is 0.5mgKOH/g.Then, drop into 364.7g tetrabydrophthalic anhydride, 137.5g carbitol acetate and 58.8g solvent naphtha wherein, be heated to 95 DEG C, it is made to react about 6 hours, cooling, obtains " containing carboxyl photoresist " varnish of the acid number 40mgKOH/g of solid matter, nonvolatile component 65%.
Synthesis example 7 [not there is the hydroxy-containing resin of aromatic rings, wherein not containing carboxyl]
In the flask possessing thermometer, stirring machine, tap funnel and reflux condenser, methyl methacrylate, Tert-butyl Methacrylate and acrylic acid 2-hydroxyl ethyl ester is dropped into the mol ratio of 62:15:23, dipropylene glycol monomethyl ether is dropped into as solvent, azoisobutyronitrile is dropped into as catalyzer, stir 6 hours in a nitrogen atmosphere, at 80 DEG C, obtain " not there is the hydroxy-containing resin of aromatic rings " varnish.The hydroxyl equivalent of this hydroxy-containing resin is 500.
Below, cementing agent B-1 (B-1) should be called by " hydroxy-containing resin " varnish.
In addition, replace the compounding amount of each composition of synthesis example, make " the hydroxy-containing resin solution " of the hydroxyl equivalent different from B-1.Using them as cementing agent B-2 (B-2).
The hydroxyl equivalent (rate of charge and calculated value) of cementing agent B-1 ~ B-2, compounding methyl methacrylate, Tert-butyl Methacrylate, acrylic acid 2-hydroxyl ethyl ester, acid number are shown in table 2 respectively.
Table 2
The synthesis example of table 2 cementing agent day hydroxy-containing resin
Synthesis example [do not have aromatic rings containing carboxy resin, wherein not hydroxyl]
In the flask possessing thermometer, stirring machine, tap funnel and reflux condenser, methyl methacrylate, methacrylic acid and Tert-butyl Methacrylate is dropped into the mol ratio of 74:15:11, dipropylene glycol monomethyl ether is dropped into as solvent, azoisobutyronitrile is dropped into as catalyzer, stir 6 hours in a nitrogen atmosphere, at 80 DEG C, obtain " what do not have aromatic rings contains carboxy resin " varnish.Should containing carboxy resin not hydroxyl.
Below, cementing agent C-1 (C-1) should be called by " containing carboxy resin " varnish.
Table 3 illustrates the hydroxyl equivalent (rate of charge and calculated value) of cementing agent C-1, compounding methyl methacrylate, Tert-butyl Methacrylate, acrylic acid 2-hydroxyl ethyl ester, acid number respectively.
Table 3
Table 3
Cementing agent C-1
Rate of charge (mass ratio) Not hydroxyl
Methyl methacrylate 74
Methacrylic acid 15
Tert-butyl Methacrylate 11
Calculated value hydroxyl equivalent -
Acid number (mgKOH/g) dry 98
[electroconductive powder]
Spherical electroconductive powder: Ag powder (maximum particle diameter less than 30 μm, mean grain size 2 μm (SEM)))
[(methyl) acrylate monomer]
4 officials' energy (methyl) acrylate monomers: trade name; NK oligo U-4HA (manufacture of Shin-Nakamura Chemical Co., Ltd.)
[Photoepolymerizationinitiater initiater]
Trade name: Irgacure 379EG (BASF Japan Ltd. manufactures), 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone
[blocked isocyanate]
Trade name BI7982 (Baxenden, Inc. manufacture) isocyanates HDI3 aggressiveness end-capping reagent dimethyl pyrazole (Dimethylpyrazole)
[organic acid]
2,2 '-thiodiglycolic acids
[spreading agent]
Trade name DISPERBYK-111 (manufacture of BYK Japan Co., Ltd.)
(evaluation method)
Test film is made:
The base material of polyester resin uses 300 object polyester half tones be coated with each conductive resin composition evaluated by entire surface, then, in heated air circulation type drying oven at 80 DEG C dry 30 minutes, form the film that dry to touch is good.Then, as light source use high-pressure sodium lamp, across negative mask with the accumulated light on conductive resin composition for 200mJ/cm 2mode carry out pattern exposure, then use 0.4 quality %Na of liquid temperature 30 DEG C 2cO 3aqueous solution is developed, washing.Finally, carried out drying with 140 DEG C × 30 minutes, make the test film being formed with conductive pattern film.
Coating strength: the pattern carrying out L/S=30/30 μm under the condition that above-mentioned test film is made is formed, use the device recorded in JIS K5600-5-4 and pencil scratching tester to apply 750g load, by with line lateral vertical scratch time do not have the sample of the broken string of line to be evaluated as " well ".The sample of existing defects is evaluated as " bad ".The pencil used is Mitsubishi Hi-uni (Mitsubishi Pencil K. K's manufacture, hardness: 3H).
Contact resistance value: under the condition that above-mentioned test film is made, on the ito thin film of sheet resistance values 150 Ω with 5mm interval carry out length 50mm, width 100um I molded line pattern formed, pattern central portion is placed detecting device measure.
Adaptation: the pattern carrying out L/S=30/30 μm is formed, carrying out Cellotape (registered trademark) and peels off, being evaluated as not having the sample of defect completely " well ".The sample that there is defect is evaluated as " bad ".
Resolution: the pattern forming line under the condition that above-mentioned test film is made, evaluates its minimum feature.Live width is evaluated as " well " less than 35 μm, more than 35 μm are evaluated as " bad ".
For embodiment 1 ~ 7 within the scope of the present invention and be in extraneous comparative example 1 ~ 7 of the present invention, the compounding amount of conductive resin composition, hydroxyl equivalent and evaluation result are summarized in following table 4 and table 5 respectively.
Table 4
* the computing method of 1-OH base as described below.
The situation of embodiment 1,2,3,4: the hydroxyl equivalent (with reference to formula 1) of the cementing agent used
The situation of embodiment 6: the summation (with reference to formula 2) of the hydroxyl equivalent × compounding ratio (%) of each cementing agent
The situation of embodiment 5,7: hydroxyl equivalent × 100/ comprising the cementing agent of hydroxyl comprises the compounding ratio (quality %) (with reference to formula 3) of the cementing agent of hydroxyl
* 2 ∞ represent not hydroxyl.
Table 5
* the computing method of 1-OH base as described below.
The situation of comparative example 1,2,5,7: the hydroxyl equivalent (formula 1) of the cementing agent used
The situation of comparative example 4: the summation (with reference to formula 2) of the hydroxyl equivalent × compounding ratio (%) of each cementing agent
The situation of comparative example 3: hydroxyl equivalent × 100/ comprising the cementing agent of hydroxyl comprises the compounding ratio (quality %) (with reference to formula 3) of the cementing agent of hydroxyl
* 2 ∞ represent not hydroxyl.
Confirmed by embodiment 1 ~ 7, for conductive resin composition of the present invention, can apply on the not resistance to base material be heated, excellent electric conductivity and resolution can be guaranteed, and coating strength, the conductive resin composition also all excellent with the adaptation of base substrate under harsh condition can be obtained.

Claims (6)

1. a conductive resin composition, it is characterized in that, comprise: do not have the resin of the hydroxyl of aromatic rings and carboxyl, electroconductive powder, multifunctional (methyl) acrylate monomer, Photoepolymerizationinitiater initiater and blocked isocyanate, the described summation without the hydroxyl equivalent of the hydroxyl of aromatic rings and the resin of carboxyl is more than 300 and less than 3000.
2. a conductive resin composition, is characterized in that, comprises: the resin being selected from hydroxyl and the carboxyl without aromatic rings, the hydroxy-containing resin without aromatic rings and do not have aromatic rings containing carboxy resin group in two or more resins; Electroconductive powder; Multifunctional (methyl) acrylate monomer; Photoepolymerizationinitiater initiater; And blocked isocyanate, the summation of the hydroxyl equivalent of described two or more resin is more than 300 and less than 3000.
3. conductive resin composition according to claim 1, is characterized in that, the resin of the described hydroxyl and carboxyl without aromatic rings is not containing double bond.
4. conductive resin composition according to claim 2, it is characterized in that, described in be selected from hydroxyl and the carboxyl without aromatic rings resin, do not have aromatic rings hydroxy-containing resin and do not have aromatic rings containing the two or more resins in the group of carboxy resin all not containing double bond.
5. the conductive resin composition according to any one of Claims 1 to 4, is characterized in that, described conductive resin composition is for the formation of conducting channel.
6. a solidfied material, it is applied to by the resin combination according to any one of Claims 1 to 4 also dry on base material and is formed.
CN201410366813.2A 2013-07-29 2014-07-29 Conductive resin composition and its solidfied material Active CN104345561B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-156773 2013-07-29
JP2013156773A JP5409954B1 (en) 2013-07-29 2013-07-29 Conductive resin composition and cured product thereof

Publications (2)

Publication Number Publication Date
CN104345561A true CN104345561A (en) 2015-02-11
CN104345561B CN104345561B (en) 2018-04-13

Family

ID=50202671

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410366813.2A Active CN104345561B (en) 2013-07-29 2014-07-29 Conductive resin composition and its solidfied material

Country Status (4)

Country Link
JP (1) JP5409954B1 (en)
KR (1) KR101476108B1 (en)
CN (1) CN104345561B (en)
TW (1) TWI481959B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108700814A (en) * 2016-02-19 2018-10-23 Az电子材料（卢森堡）有限公司 The negative photosensitive composition of low-temperature curable

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015040908A1 (en) * 2013-09-20 2017-03-02 東洋紡株式会社 Photosensitive conductive paste, conductive thin film, electric circuit, and touch panel
TW201539483A (en) * 2014-04-02 2015-10-16 Toyo Boseki Photosensitive conductive paste, conductive thin film, electrical circuit and touch panel
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
JP6795942B2 (en) 2016-09-30 2020-12-02 太陽インキ製造株式会社 Photocurable resin composition, dry film, cured product and printed wiring board

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003162921A (en) * 2001-11-28 2003-06-06 Taiyo Ink Mfg Ltd Photocuring/thermosetting electrically conductive composition and method for forming conductive circuit using the same
JP2003280181A (en) * 2002-03-25 2003-10-02 Taiyo Ink Mfg Ltd Photosensitive electrically conductive paste and electric conductor pattern formed using the same
JP2004341278A (en) * 2003-05-16 2004-12-02 Toyo Ink Mfg Co Ltd Active energy ray-curing color composition
CN1779570A (en) * 2004-10-06 2006-05-31 三星Sdi株式会社 Positive type photosensitive paste composition for PDP electrode, PDP electrode prepared therefrom, and PDP comprising the PDP electrode
JP2012093586A (en) * 2010-10-27 2012-05-17 Jsr Corp Photosensitive paste composition and pattern formation method
JP2013136727A (en) * 2011-11-29 2013-07-11 Taiyo Ink Mfg Ltd Conductive resin composition and conductive circuit

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101241596B1 (en) * 2006-07-28 2013-03-08 코오롱인더스트리 주식회사 Photoresist resin composition for column spacer
KR101231709B1 (en) * 2007-10-11 2013-02-08 주식회사 엘지화학 Cholate-based compound and Negative-type photoresist resin composition comprising the same
KR101451479B1 (en) * 2011-11-29 2014-10-15 다이요 잉키 세이조 가부시키가이샤 Conductive resin composition and conductive circuit
JP5358730B2 (en) * 2011-11-29 2013-12-04 太陽インキ製造株式会社 Conductive resin composition for forming conductive circuit and conductive circuit

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003162921A (en) * 2001-11-28 2003-06-06 Taiyo Ink Mfg Ltd Photocuring/thermosetting electrically conductive composition and method for forming conductive circuit using the same
JP2003280181A (en) * 2002-03-25 2003-10-02 Taiyo Ink Mfg Ltd Photosensitive electrically conductive paste and electric conductor pattern formed using the same
JP2004341278A (en) * 2003-05-16 2004-12-02 Toyo Ink Mfg Co Ltd Active energy ray-curing color composition
CN1779570A (en) * 2004-10-06 2006-05-31 三星Sdi株式会社 Positive type photosensitive paste composition for PDP electrode, PDP electrode prepared therefrom, and PDP comprising the PDP electrode
JP2012093586A (en) * 2010-10-27 2012-05-17 Jsr Corp Photosensitive paste composition and pattern formation method
JP2013136727A (en) * 2011-11-29 2013-07-11 Taiyo Ink Mfg Ltd Conductive resin composition and conductive circuit

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108700814A (en) * 2016-02-19 2018-10-23 Az电子材料（卢森堡）有限公司 The negative photosensitive composition of low-temperature curable

Also Published As

Publication number Publication date
TWI481959B (en) 2015-04-21
KR101476108B1 (en) 2014-12-23
JP5409954B1 (en) 2014-02-05
TW201506543A (en) 2015-02-16
JP2015026013A (en) 2015-02-05
CN104345561B (en) 2018-04-13

Similar Documents

Publication Publication Date Title
CN103823333B (en) Conducting channel formation conductive resin composition and conducting channel
KR101276951B1 (en) Photosensitive electrically conductive paste and electrode pattern
CN103135352B (en) Conductive resin composition and conducting channel
JP5492967B2 (en) Conductive resin composition for forming conductive circuit and conductive circuit
CN104345561A (en) Electrical-conductive resin composition and cured substance thereof
JP5358730B2 (en) Conductive resin composition for forming conductive circuit and conductive circuit
JP5568679B1 (en) Conductive resin composition and conductive circuit
TWI738882B (en) Light-curing resin composition, dry film, cured product, and printed wiring board
JP6097556B2 (en) Conductive resin composition and conductive circuit
CN103969951A (en) Conducting Resin Composition And Conducting Circuit
CN106019834A (en) Conductive resin composition and conductive circuit
JP2015193709A (en) Conductive resin composition and conductive circuit
JP2015125189A (en) Conductive resin composition and cured product thereof
JP6336802B2 (en) Method for manufacturing conductive circuit
JP2014163987A (en) Conductive resin composition and conductive circuit

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20230607

Address after: Saitama Prefecture, Japan

Patentee after: TAIYO HOLDINGS Co.,Ltd.

Address before: Saitama Prefecture, Japan

Patentee before: TAIYO INK MFG. Co.,Ltd.

TR01 Transfer of patent right