CN106536620A - Resin composition for forming cured film, cured film, electrically conductive member, and method for preventing migration - Google Patents
Resin composition for forming cured film, cured film, electrically conductive member, and method for preventing migration Download PDFInfo
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- CN106536620A CN106536620A CN201580039411.4A CN201580039411A CN106536620A CN 106536620 A CN106536620 A CN 106536620A CN 201580039411 A CN201580039411 A CN 201580039411A CN 106536620 A CN106536620 A CN 106536620A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C08K5/00—Use of organic ingredients
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
Provided is a resin composition for forming a cured film, said resin composition comprising: (A) a (meth)acrylate polymer having a weight average molecular weight of 5,000 to 200,000 (excluding a (meth)acrylate polymer having a silane structure in a side chain thereof); (B) an agent capable of preventing migration and also capable of trapping ions, which comprises a benzotriazole compound; and (C) a solvent.
Description
Technical field
The present invention relates to cured film forms the suppressing method with resin combination, cured film, electroconductive member and migration.
Background technology
So far, for the protecting film needed for touch panel etc., dielectric film etc., photonasty tree has been used by adopting
Photolithographic pattern processing of oil/fat composition forms (patent documentation 1) at necessary position.
But, using the processing of photolithographic pattern is with not only complex procedures but also spends problem as cost.Cause
This, it is desirable to have more easy method can be adopted and protecting film, dielectric film etc. are formed at necessary position with low cost
Compositionss.
In addition, the requirement in carrying, preservation, replaces the utilization of the ilm substrate of glass substrate constantly increasing.Film
Substrate forms web-like etc. when stored and preserves, now, as substrate bends, therefore for the material being coated with ilm substrate
Require and the same flexibility of film.
Further, carried out it is various with use metal nanometer line as the relevant exploitation of the touch panel of the substitute of ITO (specially
Sharp document 2 etc.), but in such touch panel, due to produce metal migration, its become such due to short circuit
Problem, it is therefore desirable to have the external application layer material that can suppress migration, shield electrode, distribution etc..
On the other hand, conventional external application layer material in order to improve hardness, is contained for the purpose of coating on the glass substrate
Inorganic particles (patent documentation 3).But, for containing the conventional method such as inorganic particles, although hardness is improved, but not
With flexibility, for example, the unfavorable situation such as crack in the case of warpage, therefore present situation is not applied for film
The coating of substrate.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2013-064973 publications
Patent documentation 2：Japanese Unexamined Patent Publication 2013-225296 publications
Patent documentation 3：Japanese Unexamined Patent Publication 2012-116975 publications
The content of the invention
Invention problem to be solved
The present invention is completed in view of the above problems, it is therefore intended that offer can be using the method for the simplicity according to print process etc.
Film is formed at necessary position and can be formed with high transmission rate, high adhesion, high rigidity and high flexibility and then also be had
The compositionss for having the cured film of inhibition of metastasis ability, the cured film formed by said composition, the electric conductivity structure with the cured film
Part and inhibition of metastasis method.
Means for solving the problems
The present inventor studies repeatedly with keen determination in order to solve above-mentioned problem, as a result finds by being 5 containing weight average molecular weight,
000～200,000 (methyl) acrylate polymer, the migration inhibitor being made up of benzotriazole cpd and ion trapping
The compositionss of agent and solvent can solve above-mentioned problem, complete the present invention.
That is, the present invention provides following cured film and forms the suppression with resin combination, cured film, electroconductive member and migration
Method processed.
1. cured film formation resin combination, it is characterised in that contain：
(A) weight average molecular weight for 5,000～200,000 (methyl) acrylate polymer (wherein, not included in side chain
(methyl) acrylate polymer with silane structure.)、
(B) comprising benzotriazole cpd migration inhibitor and ion-trapping agent and
(C) solvent.
2. according to 1 cured film formation resin combination, wherein, also containing (D) silane coupler.
3. according to 1 or 2 cured film formation resin combination, wherein, also containing (E) multifunctional (methyl) acrylate
Compound.
4. according to 3 cured film formation resin combination, wherein, also containing (F) radical polymerization initiator.
5. the cured film formation resin combination according to 1～4 any one, wherein, relative to 100 mass of (A) composition
Part, (B) benzotriazole cpd containing 0.1～50 mass parts.
6. the cured film for being formed with resin combination using the cured film formation of 1～5 any one.
7. electroconductive member, which has：Define electrode and/or distribution base material and on the substrate with above-mentioned electricity
The mode that pole and/or distribution connect formed 6 cured film.
8. the suppressing method of migration, the migration come on the comfortable base material for defining electrode and/or distribution with by solidifying
The above-mentioned electrode of the structure of the cured film that film formation is formed with resin combination and/or distribution, it is characterised in that as above-mentioned
Cured film formation resin combination, using the cured film formation resin combination of 1～5 any one.
9. the suppressing method of migration, the migration come on the comfortable base material for defining electrode and/or distribution with by containing
The above-mentioned electrode of the structure of the cured film that the resin combination of (methyl) acrylate polymer and solvent is formed and/or match somebody with somebody
Line, it is characterised in that add benzotriazole cpd in above-mentioned composition.
The effect of invention
The light transmittance of the cured film obtained using the cured film formation resin combination of the present invention, adaptation, hardness are excellent
It is different, and then the also inhibition of metastasis ability with metal.Therefore, can be used as forming the various displays such as organic electroluminescent (EL) element
The material of the cured film such as protecting film, dielectric film in protecting film, planarization film, dielectric film in device etc., touch panel.In addition,
As flexibility is also excellent, therefore the external application layer material of ito film also is suitable as.
In addition, the electroconductive member of the present invention has：Electrode and/or distribution and formed in the way of connecting with which it is upper
State cured film.Above-mentioned cured film not only has the high printing opacity required by the cured film used in the various display such as organic EL element
Characteristic as rate, high adhesion and high rigidity, and have inhibition of metastasis ability, therefore the electroconductive member of the present invention into
For the migration of suppression metal, the electroconductive member of excellent in te pins of durability.Further, since the flexibility of above-mentioned cured film is also excellent, because
This electroconductive member of the invention also can be adapted to adopt in the display with ito film.
Inhibition of metastasis method of the invention, by using benzotriazole cpd, is able to maintain that the printing opacity of cured film
Rate, adaptation and hardness, while suppress the migration of metal.
Description of the drawings
Fig. 1 is the plane graph of embodiment and the resistance to migration sample for evaluation used in comparative example.
Fig. 2 is the sectional drawing of embodiment and the resistance to migration sample for evaluation used in comparative example.
Fig. 3 is the figure of the silver-colored pattern before representing the resistance to test for migrating and evaluating.
Fig. 4 is the figure of the silver-colored pattern after the test of the resistance to migration evaluation for representing relevant with embodiment 1.
Fig. 5 is the figure of the silver-colored pattern after the test of the resistance to migration evaluation for representing relevant with comparative example 1.
Specific embodiment
[cured film formation resin combination]
The cured film formation resin combination of the present invention contains the (first that (A) weight average molecular weight is 5,000～200,000
Base) migration inhibitor that is made up of benzotriazole cpd of acrylate polymer, (B) and ion-trapping agent and (C) solvent.
[(A) (methyl) acrylate polymer]
In the compositionss of the present invention, contained (A) composition is (methyl) propylene that weight average molecular weight is 5,000～200,000
Acid ester polymer.(methyl) acrylate polymer is with by selected from acrylate compounds and methacrylate compound
In at least one monomer derived monomeric unit polymer.But, (methyl) acrylate polymer in the present invention,
From from the viewpoint of storage stability, it is not (methyl) acrylate polymer comprising silane structure in side chain.
In the present invention, as preferred (methyl) acrylate compounds, (methyl) third represented by formula (1) can be included
Enoic acid ester compounds.
[changing 1]
In formula (1), R1Represent hydrogen atom or methyl.R2Represent hydrogen atom or can with hydroxyl, epoxy radicals, acryloyl group,
The alkyl of the carbon number 1～20 that methylacryloyl or NCO replace.
As the alkyl of carbon number 1～20, can be any one of straight-chain, branch-like, ring-type, for example, can include first
It is base, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, just pungent
The straight-chain or branch-like alkyl of the carbon numbers such as base, n-nonyl, positive decyl 1～20；Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl,
It is suberyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclic butyl, Bicvclopentyl, dicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclic
Cyclic alkyl of the carbon numbers such as nonyl, bicyclodecyl 3～20 etc..
As (methyl) acrylate compounds, acrylic acid, methacrylic acid, acrylic acid methyl ester., methyl-prop can be included
E pioic acid methyl ester, ethyl acrylate, ethyl methacrylate, n-propyl, n propyl methacrylate, acrylic acid isopropyl
Ester, isopropyl methacrylate, acrylic acid 2,2,2- trifluoro ethyl esters, methacrylic acid 2,2,2- trifluoro ethyl esters, the tertiary fourth of acrylic acid
Ester, Tert-butyl Methacrylate, acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl esters, first
Base acrylic acid 2- hydroxy propyl esters, acrylic acid 2,3- dihydroxy propyl ester, methacrylic acid 2,3- dihydroxy propyl ester, acrylic acid 4- hydroxyls
Butyl ester, methacrylic acid 4- hydroxybutyls etc..Wherein, if it is considered that the equilibrium of high transmission rate, high adhesion and high rigidity, preferably
Ground, monomer include a kind in methyl methacrylate and ethyl methacrylate.
In the present invention, (methyl) acrylate polymer can be comprising the monomer by derived from acrylate and methacrylate
Other monomers unit beyond unit.As the monomer for giving other monomers unit, typically, styrene chemical combination can be included
Thing, vinyl compound, maleimide compound, acrylonitrile, maleic anhydride.
As distyryl compound, styrene, methyl styrene, chlorostyrene, bromstyrol, 4- tert- fourths can be included
Base styrene etc..
As vinyl compound, can include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene,
Vinyl biphenyl, VCz, 2- hydroxyethyl vinyl ethers, (Ethenyloxy)benzene, propyl vinyl ether etc..
As maleimide compound, for example, can include maleimide, N- methylmaleimidos, N- phenyl horses
Come acid imide, N- N-cyclohexylmaleimides etc..
In these, from from the viewpoint of the hydrophobicity (low water absorbable) of the thin film for obtaining, optimization styrene compound is more excellent
Select styrene.
In the present invention, if it is considered that the equilibrium of high transmission rate, high adhesion and high rigidity, (methyl) acrylate polymer
In the content of monomeric unit by derived from (methyl) acrylate compounds, preferably 50 moles more than %, more preferably 60
Mole more than %, more preferably 70 moles more than %, are still more preferably 80 moles of more than %.
(methyl) acrylate polymer can use commercially available product, it is possible to use by what is manufactured above-mentioned monomer polymerization
Polymer.
As polymerization, can be using radical polymerization, anionic polymerisation, cationic polymerization etc., from can be easier
Ground is manufactured from the viewpoint of having (methyl) acrylate polymer of the weight average molecular weight needed for the present invention, preferably free radical
Polymerization.
As initiator, the peroxidating such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide can be included
Thing；The persulfates such as sodium peroxydisulfate, potassium peroxydisulfate, Ammonium persulfate.；Azodiisobutyronitrile, azo two (methylbutyronitrile), azo two
Azos such as isobutyl cyanide, 2,2'- azos two (isopropylformic acid .) dimethyl ester etc..The usage amount of such initiator is due to because of list
The species of body, amount, reaction temperature and it is different, therefore entirely can not specify, generally, relative to 1 mole of monomer, be 0.005～
0.05 mole or so.Reaction temperature during polymerization can suitably setting into the boiling point of the solvent for using from 0 DEG C, usually 20
～100 DEG C or so.In addition, the response time is 0.1～30 hour or so.
Polymerization is preferably carried out in a solvent, and the solvent used in polyreaction can be using generally using in this reaction
Solvent.Specifically, water outlet can be enumerated；Methanol, ethanol, 1- propanol, 2- propanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1-
Amylalcohol, 2- amylalcohols, 3- amylalcohols, isoamyl alcohol, tert-pentyl alcohol, 1- hexanols, 1-heptanol, 2- enanthol, 3- enanthol, sec-n-octyl alcohol, 2- ethyl -1-
The alcohol such as hexanol, benzylalcohol, Hexalin；Anaesthetie Ether, Di Iso Propyl Ether, dibutyl ethers, cyclopentyl-methyl ether, tetrahydrofuran, 1,4-
The ethers such as dioxane；The halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethanes, carbon tetrachloride；Methyl cellosolve, ethyl cellosolve, isopropyl
The ether alcohols such as base cellosolve, butyl cellosolve, diethylene glycol monobutyl ehter；The ketone such as acetone, butanone, methyl iso-butyl ketone (MIBK), Ketohexamethylene；
The esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate；Pentane, normal hexane, normal heptane, normal octane, positive nonyl
Alkane, n-decane, Pentamethylene., methyl cyclopentane, hexamethylene, hexahydrotoluene, benzene,toluene,xylene, ethylo benzene, methoxybenzene etc.
Aliphatic or aromatic hydrocarbon；The acetals such as methylal, diethylacetal；The fatty acids such as formic acid, acetic acid, propanoic acid；Nitre
Base propane, Nitrobenzol, dimethylamine, monoethanolamine, pyridine, METHYLPYRROLIDONE, N,N-dimethylformamide, dimethyl
Sulfoxide, acetonitrile etc..Consider monomer, the species of initiator, amount, reaction temperature etc., properly select the solvent for using from these.
In the present invention, for the weight average molecular weight (Mw) of (methyl) acrylate polymer, from guaranteeing the molten of polymer
From the viewpoint of Xie Xing, preparation give the compositionss of suitable cured film, it is 5,000～200,000, but if considering suppression group
The excessive of the viscosity of compound adds, and its higher limit is preferably 180,000, more preferably 150,000, more preferably 100,
000, it is still more preferably 80,000, if it is considered that the excessive reduction of the viscosity of composite inhibiting, its lower limit is preferably
10,000, more preferably 15,000, more preferably 30,000, it is still more preferably 40,000.Should illustrate, Mw is to adopt
With the polystyrene conversion measured value of gel permeation chromatography (GPC).
In the case of monomer of more than two kinds manufacture (methyl) acrylate polymer, (methyl) acrylic ester polymerization
Thing can be any one of random copolymer, alternate copolymer, block copolymer.
[(B) migration inhibitor and ion-trapping agent]
In the compositionss of the present invention, contained (B) composition is the migration inhibitor and ion being made up of benzotriazole cpd
Trapping agent.As such benzotriazole cpd, benzotriazole, 4- methylbenzotrazoles, 5- methyl benzo three can be included
The alkyl substituted benzene triazole derivative of the carbon numbers such as azoles 1～3, wherein preferred 5- methylbenzotrazoles.
For the content of (B) composition, relative to 100 mass parts of (A) composition, preferably 0.1～50 mass parts or so, from
High transmission rate, high adhesion and high rigidity is maintained, while repeatability obtains the more excellent solidification of inhibition of metastasis ability well
From the viewpoint of film, more preferably 1～30 mass parts, more preferably 2～25 mass parts.
The compositionss of the present invention, therefore can be in the high transparency for not damaging cured film due to containing benzotriazole cpd
Excellent inhibition of metastasis is realized in the case of property, high adhesion and high rigidity.
[(C) solvent]
The compositionss of the present invention are used with the solution state for being dissolved in solvent.As long as the solvent for now using can dissolve
(A) and (B) composition is stated, also can be molten by these in the case where (D) described later～(H) composition and other additives are also contained
Solution, then be not particularly limited.
As the concrete example of solvent, ethylene glycol, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol can be included
Anaesthetie Ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol bisthioglycolate butyl ether, ethylene glycol mono hexyl ether, ethylene glycol list
Benzylic ether, ethylene glycol list phenyl ether, ethylene glycol acetate, ethylene acetate, ethylene glycol single methyl ether acetass, second two
Alcohol list monoethyl ether acetate, ethylene glycol monobutyl ether acetass, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, two
Glycol ethyl methyl ether, carbiphene, diethylene glycol diethyl ether, diethylene glycol monobutyl ehter, diethylene glycol dibutyl ether, diethylene glycol
It is single hexyl ether, diethyleneglycol monobenzylether, diethylene glycol monophenyl ether, diethylene glycol acetass, diethylene glycol monoethyl ether acetate, two sweet
Alcohol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, Propylene Glycol, propylene glycol monomethyl ether, Propylene Glycol list
Ethylether, glycol monobutyl ether, dipropylene glycol, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol mono butyl
Base ether, tripropylene glycol monomethyl ether, trimethylene, hexanediol, ethohexadiol, methoxymethoxy ethanol, 1- butoxy second
Epoxide propanol, isobutyl acetate, acetic acid methoxybutyl, acetic acid 2- Octyl Nitrites, cyclohexyl acetate, methyl cyclohexanol acetate,
It is benzyl acetate, isoamyl acetate, n-butyl propionate, isobutyl lactate, n-butyl lactate, N_amyl lactate, isoamyl lactate, different
Isoamyl isovalerate, acetobutyric acid ethyl ester, butyl stearate, dibutyl oxalate, diethyl malonate, essence of Niobe, benzoic acid
Ethyl ester, propyl benzoate, methyl salicylate, methyl phenyl ether, ethyl benzyl ether, ethylphenyl ether, Dichloroethyl ether, diisoamyl
Base ether, n-hexyl ether, 1,4- dioxanes, diethylacetal, eucalyptole, butanone, methyl propyl ketone, methyl butyl ketone, methyl
Isobutyl ketone, metacetone, ethyl normal-butyl ketone, diη-propyl ketone, acetonyl acetone, phorone, isophorone, 1-Phenylethanone.,
Glycerol, butanol, 2- butanol, 1,3 butylene glycol, 2,3- butanediols, isoamyl alcohol, 1,5- pentanediols, 2 methyl cyclohexanol, 2- ethyls
Hexanol, 3,5,5- trimethyl hexanols, 1- capryl alcohol, sec-n-octyl alcohol, nonyl alcohol, Decanol, Exxal 12, benzylalcohol, α-terpinol, tetrahydrochysene
Furfuryl alcohol, furfuryl alcohol, abienol, trigly, trichloroacetic acid, lactic acid, valeric acid, isovaleric acid, caproic acid, 2 ethyl hexanoic acid, octanoic acid,
Butyryl oxide., decane, dipentene, terpane, dodecane, 1,1,2- trichloroethanes, 1,1,1,2- sym-tetrachloroethanes, 1,1,2,2- tetrachloros
Ethane, hexachlorethane, toluene, dimethylbenzene, o-dichlorobenzene, m- dichloro-benzenes, o-dichlorobenzene, 1,2,4- trichloro-benzenes, o- dibromo
Benzene, benzonitrile, Nitrobenzol, α-benzyl nitrile (phenylacetonitrile), N-METHYLFORMAMIDE, N- methylacetamides, 2-Pyrrolidone etc..
Above-mentioned solvent can a kind be used alone or two or more be used in mixed way.In addition, it is also possible to which directly using will
(A) solvent used when composition is polymerized.
For above-mentioned solvent, from from the viewpoint of printing, preferably boiling point be more than 150 DEG C, more preferably 180 DEG C with
On, more preferably more than 200 DEG C.As such solvent, particularly preferred diethylene glycol monomethyl ether, diethylene glycol monoethyl
Ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ehter, diethylene glycol monobutyl ehter acetass, diethylene glycol dimethyl ether, two
Glycol Anaesthetie Ether, diethylene glycol dibutyl ether, diethyleneglycol monohexylether, triethylene glycol monobutyl ether, glycol monobutyl ether, dipropyl
Glycol, DPGME, dihydroxypropane single-ethyl ether, diethylene glycol monophenyl ether, ethylene glycol single-benzyl ether, diglycol monotertiary
Benzylic ether etc..
In the case that solvent of more than two kinds is used in mixed way, preferably at least a kind of boiling point is more than 150 DEG C, more preferably
More than 180 DEG C, more preferably more than 200 DEG C.
For the amount of above-mentioned solvent, preferably make the present invention compositionss in solid component concentration become 1～95 matter
The amount of amount %, more preferably makes solid component concentration become the amount of 5～90 mass %, further preferably becomes solid component concentration
The amount of 10～85 mass %.Wherein, after solid constituent is referred to and from whole compositions of the compositionss of the present invention is removed (C) solvent
Composition.
The compositionss of the present invention contain above-mentioned (A)～(C) compositions, from the viewpoint grade for improving external application layer function, can be also
Contain
(D) silane coupler,
(E) multifunctional (methyl) acrylate compounds,
(F) radical polymerization initiator,
(G) polymerization inhibitor,
(H) ion-trapping agent beyond benzotriazole cpd etc..
[(D) silane coupler]
The compositionss of the present invention, from from the viewpoint of improving adaptation, preferably comprise silane coupler as (D) composition.
As preferred one of silane coupler, the silane compound represented by formula (2) can be included.
[changing 2]
In formula (2), R3Represent methyl or ethyl.X represents hydrolization group.Y represents reactive functional groups.M is 0～3
Integer.N is 0～3 integer, preferably 0～2 integer.
As the hydrolization group represented by X, halogen atom, the alkoxyl of carbon number 1～3, carbon number 2～4 can be included
Alkyloxy-alkoxy etc..As above-mentioned halogen atom, chlorine atom, bromine atoms etc. can be included.As the alkoxyl of carbon number 1～3,
It is preferred that the alkoxyl of straight-chain or branch-like, specifically, is methoxyl group, ethyoxyl, positive propoxy and isopropoxy.In addition, making
For the alkyloxy-alkoxy of carbon number 2～4, specifically, be methoxymethoxy, 2- methoxy ethoxy, (ethoxymethyl) epoxide and
2- ethoxy ethoxies.
As the reactive functional groups represented by Y, can include amino, urea groups, (methyl) acryloxy, vinyl,
Epoxy radicals, sulfydryl etc., preferably amino, urea groups, (methyl) acryloxy etc..Particularly preferably amino or urea groups.
As above-mentioned silane coupler, specifically, 3- aminopropyltrichlorosilanes, 3- aminopropyl trimethoxies can be included
Base silane, APTES, 3- amino propyl methyl dimethoxysilanes, 3- amino propyl methyl diethoxies
Base silane, 3- ureido-propyl trimethoxy silanes, 3- ureidopropyltriethoxysilanes, 3- acryloxypropyl trimethoxies
Silane, 3- acryloxypropyl triethoxysilanes, 3- methacryloxypropyl trimethoxy silanes, 3- metering systems
Acryloxypropylethoxysilane triethoxysilane, vinyl trichlorosilane, vinyltrimethoxy silane, VTES,
Allyltrichlorosilane, allyltrimethoxysilanis, allyltriethoxysilane, 3- glycidoxypropyl trimethoxies
Base silane, 3- glycidoxypropyl diethoxy silanes, 3- glycidoxypropyl triethoxysilanes, 3- mercaptos
Base propyl trimethoxy silicane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi methyl dimethoxysilanes, 3- sulfydryls third
Ylmethyl diethoxy silane etc..
In these, particularly preferred 3- TSL 8330s, APTES, 3- urea groups third
Base trimethoxy silane, 3- ureidopropyltriethoxysilanes, 3- methacryloxypropyl trimethoxy silanes, 3- methyl
Acryloxypropyl triethoxysilane etc..
As above-mentioned silane coupler, commercially available product can be used.
In the case that the compositionss of the present invention contain (D) composition, for its content, relative to 100 mass of (A) composition
Part, preferably 0.001～10 mass parts, more preferably 0.01～5 mass parts, further preferred 0.05～1 mass parts.If content is not
0.001 mass parts of foot, cannot obtain the raising effect of adaptation sometimes, if it exceeds 10 mass parts, sometimes hardness reduction.
[(E) multifunctional (methyl) acrylate compounds]
The compositionss of the present invention, from from the viewpoint of improving hardness, preferably comprise multifunctional (methyl) acrylate chemical combination
Thing is used as (E) composition.Multifunctional (methyl) acrylate compounds are in the molecule with least 3 (methyl) acryloxies
Compound, specifically, polyhydric alcohol and (methyl) acrylic acid ester can be included.In addition, (methyl) acryloyl-oxy in 1 molecule
The number of base is 3～6, preferably 3 or 4.
As above-mentioned polyhydric alcohol, glycerol, erithritol, tetramethylolmethane, trimethylolethane, trihydroxy methyl third can be included
Alkane, dipentaerythritol, two (trimethylolpropanes) etc..
As the concrete example of above-mentioned multifunctional (methyl) acrylate compounds, the acid of tetramethylolmethane tetrapropylene can be included
Ester, pentaerythritol tetramethylacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, two seasons penta 4
Six acrylate of alcohol, dipentaerythritol hexamethacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethyl third
Olefin(e) acid ester, methylolethane triacrylate, trimethylolethane trimethacrylate methacrylate, trimethylolpropane tris acrylic acid
Ester, trimethylol-propane trimethacrylate, two (trimethylolpropane) tetraacrylate, two (trimethylolpropane) tetramethyl
Base acrylate etc..
Above-mentioned multifunctional (methyl) acrylate compounds, can be readily available as commercially available product, as its concrete example, example
Can such as include Japanese chemical medicine (strain) KAYARAD (registered trade mark) processed T-1420, DPHA, DPHA-2C, D-310, D-330,
DPCA-20、DPCA-30、DPCA-60、DPCA-120、DN-0075、DN-2475、R-526、NPGDA、PEG400DA、MANDA、
R-167、HX-220、HX620、R-551、R-712、R-604、R-684、GPO-303、TMPTA、THE-330、TPA-320、TPA-
330、PET-30、RP-1040；East Asia synthesizes (strain) ARONIX (registered trade mark) processed M-210, M-240, M-6200, M-309, M-
400、M-402、M-405、M-450、M-7100、M-8030、M-8060、M-1310、M-1600、M-1960、M-8100、M-
8530、M-8560、M-9050；Osaka Organic Chemical Industry (strain) Viscoat 295,300,360, GPT processed, 3PA, 400,260,
312、335HP；Xin Zhong villages chemical industry (strain) NK ESTER A-9300 processed, A-9300-1CL, A-GLY-9E, A-GLY-20E,
A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、AD-TMP、ATM-35E、A-TMMT、A-9550、A-DPH、TMPT
Deng.
In the case that the compositionss of the present invention contain (E) composition, for its content, relative to 100 mass of (A) composition
Part, preferably 10～300 mass parts, more preferably 20～200 mass parts, further preferred 50～150 mass parts.Content is less than 10
The hardness improvement of cured film in the case of mass parts, cannot be obtained sometimes, more than 300 mass parts in the case of, it is sometimes close
The characteristic of conjunction property and flexibility is reduced, and becomes easily to crack.Multifunctional (methyl) acrylate compounds can use a kind
Or two or more is applied in combination.
[(F) radical polymerization initiator]
The compositionss of the present invention, from from the viewpoint of the initiation or promotion of the polymerization of (E) composition, preferably comprise radical polymerization
Initiator is closed as (F) composition.(E) composition is spontaneously polymerized by processing at high temperature, but in substrate degeneration etc. no
In the case of hot setting process being carried out, by adding (F) composition, such that it is able to carry out at low-temperature setting process or photocuring
Reason.
As long as radical polymerization initiator can release the material for causing radical polymerization i.e. by light irradiation and/or heating
Can.For example, as optical free radical polymerization initiator, benzophenone derivates, imdazole derivatives, bisglyoxaline can be included and is derived
Thing, N- aryl glycine derivants, organic azide, titanocenes compound, Alumen complex, organic peroxide, N-
Alkoxy pyridines salt, thioxanthone derivates etc..More specifically, benzophenone, 1,3-, bis- (tert-butyl dioxy carbonyls can be included
Base) benzophenone, 3,3', 4,4'- tetra- (two oxygen carbonyl of tert-butyl) benzophenone, 3- phenyl -5- isoxazole ketone, 2- sulfydryl benzene
And imidazoles, double (2,4,5- triphenyls) imidazoles, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 1- hydroxycyclohexylphenyls
Ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyls) butane -1- ketone, double (η 5-2,4- cyclopentadiene -1- bases) are double
(2,6- bis- fluoro- 3- (1H- pyrroles's -1- bases) phenyl) titanium etc., but it is not limited to these.
As above-mentioned optical free radical polymerization initiator, it is also possible to utilize commercially available product, for example, can include BASF AG
IRGACURE (registered trade mark) 651,184,369,784 etc..In addition, it is also possible to using commercially available product other than the above, specifically, can
Include BASF AG IRGACURE (registered trade mark) 500,907,379,819,127,500,754,250,1800,1870,
OXE01, TPO, DAROCUR (registered trade mark) 1173；Lambson company systems Speedcure (registered trade mark) MBB, PBZ, ITX,
CTX、EDB；Lamberti company systems Esacure (registered trade mark) ONE, KIP150, KTO46；Japanese chemical medicine (strain) makes
KAYACURE (registered trade mark) DETX-S, CTX, BMS, DMBI etc..
In addition, as hot radical polymerization initiator, such as acetyl peroxide, benzoyl peroxide, peroxide can be included
Change butanone, cyclohexanone peroxide, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, mistake
Oxidation dicumyl, dilauroyl peroxide, tert-butyl peroxy acetate, t-butylperoxy pivarate, the tertiary fourth of peroxide -2 ethyl hexanoic acid
The peroxide such as ester (crossing the 2 ethyl hexanoic acid tert-butyl ester)；2,2'- azodiisobutyronitriles, two (2,4- dimethyl-pentens of 2,2'- azos
Nitrile), (1- phenylethyls) azodiphenylmethane, 2,2'- azos two (4- methoxyl group -2,4- methyl pentane nitriles), 2,2'- azos
Two isobutyl dimethyl phthalates, 2,2'- azos two (2- methylbutyronitriles), 1,1'- azos two (1- cyclohexane carbonitriles), 2- (carbamyls
Base azo) isopropyl cyanide, 2,2'- azos two (2,4,4- trimethylpentanes), 2- phenylazo -2,4- dimethyl -4- methoxyl groups penta
The Azos such as nitrile, 2,2'- azos two (2- methylpropanes)；The persulfates such as Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate
Deng, but it is not limited to these.
As commercially available hot radical polymerization initiator, for example, can include day oil (strain) PEROYL (registered trade mark) processed
IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, PERBUTYL (registered trade mark) ND, NHP, MA, PV, 355, A, C, D, E, L,
I, O, P, Z, PERHEXYL (registered trade mark) ND, PV, D, I, O, Z, PEROCTA (registered trade mark) ND, NYPER (registered trade mark)
PMB, BMT, BW, PERTETRA (registered trade mark) A, PERHEXA (registered trade mark) MC, TMH, HC, 250,25B, C, 25Z, 22, V,
PEROCTA (registered trade mark) O, PERCUMYL (registered trade mark) ND, D, PERMENTA (registered trade mark) H, ノ Off マ (registrars
Mark) BC；V-70 processed with Wako Pure Chemical Industries (strain), V-65, V-59, V-40, V-30, VA-044, VA-046B, VA-061, V-50,
VA-057、VA-086、VF-096、VAm-110、V-601、V-501；BASF AG IRGACURE (registered trade mark) 184,369,
651st, 500,819,907,784,2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, DAROCUR (registrar
Mark) 1116,1173；Cytec Surface Specialties company systems UVECRYL (registered trade mark) P36；Lamberti companies
Esacure (registered trade mark) processed KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B etc., but do not limit
Due to these.
In the case that the compositionss of the present invention contain (F) composition, for its content, relative to 100 mass of (A) composition
Part, preferably 1～20 mass parts, more preferably 1～15 mass parts.
[(G) polymerization inhibitor]
The compositionss of the present invention as needed can be containing polymerization inhibitor as (G) composition.As above-mentioned polymerization inhibitor, for example may be used
Include 2,6- diisobutyl phenols, 3,5- di-tert-butylphenols, 3,5- di-tert-butyl cresol, hydroquinone, hydroquinone monomethyl
Ether, pyrogaelol, tert-butyl catechol, 4- methoxyl group -1- naphthols etc..
In the case that the compositionss of the present invention contain (G) composition, its content is preferably 1 mass % in all solids composition
Hereinafter, more preferably below 0.5 mass %.If containing ratio is more than 1 mass %, cause sometimes solidification bad, reaction becomes not
Fully.
[(H) ion-trapping agent beyond benzotriazole cpd]
The compositionss of the present invention can be containing the ion-trapping agent beyond benzotriazole cpd as (H) composition.As
Such ion-trapping agent, for example, can include N, double [3- (3, the 5- di-tert-butyl -4- hydroxy phenyls) propiono] hydrazines of N'-
(Irganox (registered trade mark) MD1024, BASF AG's manufacture), double (benzylidiene hydrazide) (the Eastman Inhibitor of oxalic acid
OABH, Eastman Chemical's manufacture) etc..
In the case that the compositionss of the present invention contain (H) composition, for its content, relative to 100 mass of (A) composition
Part, it is 0.0001～20 mass parts or so, but as noted previously, as benzotriazole cpd also can be played as ion-trapping agent
Function, therefore preferably do not contain other ion-trapping agents.
[other additives]
The compositionss of the present invention, as long as not damaging the effect of the present invention, can further contain surface activity as needed
The dissolution accelerators such as agent, cross-linking agent, defoamer, rheology control agent, pigment, dyestuff, preserving stabilizer, polyhydric phenols, polybasic carboxylic acid
Deng.
As surfactant, it is not particularly limited, for example, can includes fluorine system surfactant, silicon systems surface activity
Agent, nonionic surfactants etc..As this surfactant, for example, can include Mitsubishi General Materials electronization strain
Formula commercial firm エ Off ト ッ プ (registered trade mark) EF301, EF303, EF352；DIC (strain) Megafac (registered trade mark) processed F171,
F173；3M company systems FLUORAD (registered trade mark) FC430, FC431；Asahi Glass (strain) is Asahi Guard (registered trade mark) processed
AG710, AGC SEIMI CHEMICAL CO., LTD. Surflon (registered trade mark) S-382, SC101, SC102, SC103,
SC104, SC105, SC106 etc..
As cross-linking agent, multi-functional epoxy compound, polyfunctional isocyanate compound, multi-functional thiolization can be included
Compound, melamine series cross-linking agent etc., containing (E) composition in the case of, mercaptan compounds more than preferably 3 senses.It is multifunctional
Mercaptan compound can be as polyhydric alcohol with simple function and/or multi-functional thiol's compound addition reaction obtain.As tool
The compound of body, can include 1,3,5- tri- (3- mercaptopropionyl epoxide ethyls) isocyanuric acid ester, 1,3,5- tri- (3- sulfydryl butyryl
Epoxide ethyl) isocyanuric acid ester (Showa electrician (strain) manufacture, Karenz MT (registered trade mark) NR1), trimethylolpropane tris
3 functional thiols's compound such as (3-thiopropionate)；Tetramethylolmethane four (3-thiopropionate), four (3- sulfydryl fourths of tetramethylolmethane
Acid esters) 4 functional thiols's compounds such as (Showa electrician (strain) manufacture, Karenz MT (registered trade mark) PEI)；Dipentaerythritol six
6 functional thiols's compounds such as (3- propionic esters) etc..
As defoamer, acetylenic glycol, silicone fluid and Emulsion, ethoxylation or propoxylation can be included organic
Silicon, hydrocarbon, aliphatic ester derivatives, acetylation polyamide, poly- (oxyalkylene) polymer and copolymer etc., but it is not limited to this
A bit.In the case of carrying out silk screen printing, the compositionss of the present invention preferably comprise defoamer.
For the viscosity at 25 DEG C of the compositionss of the present invention, from from the viewpoint of coating, preferably 1～10,
000mPa s, more preferably 1～5,000mPa s, more preferably 1～1,000mPa s.If viscosity is too low, sometimes
The thickness of target cannot be obtained, if viscosity is too high, coating is reduced sometimes.
In addition, for the viscosity at 25 DEG C of the compositionss of the present invention, from from the viewpoint of printing, preferably 10～
100,000mPa s, more preferably 500～100,000mPa s, more preferably 1,000～100,000mPa s.Such as
Fruit viscosity is too low, and compositionss diffusion after coating, does not form desired pattern, if viscosity is too high, discharge sometimes sometimes
Property reduce etc. producing load to operation, or compositionss are reduced to the transferability of substrate.
Such as the orthogonal part of the X-axis electrode and Y-axis electrode in touch panel constitute bridge structure dielectric film that
In the case that sample forms fine structure using print processes such as silk screen printing, intaglio plate hectographic printings, the 25 of the compositionss of the present invention
Viscosity at DEG C preferably 10～100,000mPa s, more preferably 5,000～100,000mPa s, more preferably
20,000～100,000mPa s.If viscosity is too low, compositionss diffusion after coating, does not form desired figure sometimes
Case, if viscosity is too high, discharge property reduction sometimes etc. produces the load to operation, or compositionss are dropped to the transferability of substrate
It is low.
Should illustrate, in the present invention, viscosity is the measured value using E type viscometers.
[preparation methoies of compositionss]
The preparation method of the compositionss of the present invention is not particularly limited.As one, following methods can be included：Will
(A) composition is dissolved in (C) solvent, and (B) composition is made uniform solution with the ratio mixing for specifying in the solution.In addition,
Can to include in the appropriate stage of the preparation method
The preparation method of row mixing.
During the preparation of the compositionss of the present invention, can be by the solution of (A) composition obtained by the polyreaction in solvent
Directly use.In this case, (B) composition etc. is put in the solution of (A) composition as described above and make uniform molten
Liquid.In addition, in order to adjust concentration, can further add (C) solvent.
The compositionss of the solution state being prepared are being preferably to make after 0.2 μm or so filter etc. is filtered using aperture
With.
[film and cured film]
By using rotary coating, flowing coating, print roll coating, slot coated, slit, then rotary coating, ink-jet are applied
Print processes such as cloth, silk screen printing, aniline printing, intaglio printing, hectographic printing, intaglio plate hectographic printing etc. by the present invention compositionss
In the substrate with electrode and/or distribution, (for example, silicon/silicon dioxide is substrate coated；Silicon nitride board；Be coated to aluminum, molybdenum, chromium,
The metal nanoparticles such as the metal nanometer lines such as the metals such as copper, silver, nano silver wire, Nano silver grain, copper nano-particle, poly- (3,4-
Ethyldioxythiophene)/poly- (styrene sulfonate) (PEDOT/PSS), the base of the electric conductive polymer such as Graphene, CNT
Plate；Glass substrate；Quartz base plate；Ito substrate；Ito film substrate；TAC film, polyester film, acrylic acid mesentery, cycloolefins (COP) film
Deng resin film substrate) etc. it is upper be coated with, then, carry out predrying (prebake) with hot plate or baking oven etc. such that it is able to form film.
The compositionss of the present invention are particularly suitable for the print processes such as ink-jet application, silk screen printing, aniline printing, intaglio plate hectographic printing.
Prebake typically adopts following method：At preferably 60 DEG C～150 DEG C, more preferably 80 DEG C～120 DEG C, make
Processed 0.5～30 minute with the case of hot plate, using baking oven in the case of process 0.5～90 minute.
Next, carrying out the rear baking for heat cure.Specifically, heated using hot plate, baking oven etc..After bakee one
As adopt following method：At preferably 150 DEG C～300 DEG C, more preferably 200 DEG C～250 DEG C, in the case of hot plate
Process 1～30 minute, using baking oven in the case of process 1～90 minute.
In the case that the compositionss of the present invention contain hot radical polymerization initiator, the solidification under low temperature can be carried out.This
In the case of kind, pre-bake conditions are same as described above, but rear stoving temperature is preferably 60 DEG C～200 DEG C, and more preferably 80 DEG C～150
℃.Other conditions are same as described above.
In addition, in the case that the compositionss of the present invention contain optical free radical polymerization initiator, it is right to pass through after prebake
Above-mentioned film irradiation ultraviolet radiation is carrying out photocuring.For ultraviolet, in the range of 200～500nm of wavelength, its light exposure
Preferably 100～5,000mJ/cm2。
The rear baking for heat cure is carried out after photocuring.Specifically, heated using hot plate, baking oven etc..After bakee
Following method is adopted typically：At preferably 60 DEG C～150 DEG C, more preferably 80 DEG C～120 DEG C, in the case of hot plate
Process 1～30 minute, using baking oven in the case of process 1～90 minute.
By it is above-mentioned it is such under the conditions of make the present invention compositionss solidification such that it is able to the step discrepancy in elevation of substrate is filled
Divide ground planarization, the cured film with high transparent can be formed.
The cured film of the present invention is due to the planarization, hardness and the adaptation that at least have required level, therefore also may be used
As the protecting film, planarization that are formed in the various display such as thin film transistor (TFT) (TFT) type liquid crystal display cells, organic EL element
The material of the cured film such as protecting film, dielectric film in film, dielectric film etc., touch panel.Further, since flexibility is also excellent, because
This also is suitable as the external application layer material of ito film.
With being formed in the way of connecting with above-mentioned electrode and/or distribution on the base material for defining electrode and/or distribution
The present invention cured film electroconductive member, due to suppress migration, therefore become be difficult to occur electrode, the short circuit of wiring closet,
The electroconductive member of excellent in te pins of durability.
Inhibition of metastasis method of the invention, due to containing benzotriazole cpd in compositionss, therefore can be not
Excellent inhibition of metastasis is realized in the case of the transparency of infringement cured film, adaptation and hardness.The method of the present invention for silver,
Effectively, especially for suppressing, the migration of silver is effective for the suppression of the migration of copper, gold, aluminum, nickel, stannum, lead, palladium etc..
Embodiment
Hereinafter, synthesis example, embodiment and comparative example are enumerated to illustrate in greater detail the present invention, but the present invention is not limited to
Following embodiments.Should illustrate, the weight average molecular weight (Mw) of the copolymer obtained in synthesis example is being made using Showa electrician (strain)
GPC devices (Shodex GPC-101) (post：Shodex (registered trade mark) KF803l and KF804l (Showa electrician (strain) manufacture)),
Make dissolution solvents tetrahydrofurane with flow 1mL/ point in post (40 DEG C of column temperature) flowing and molten determine under the conditions of such.Should
Explanation, Mw polystyrene conversion values is given to represent.
In addition, reagent and device used in following synthesis examples, embodiment, comparative example are as follows.
DEGMEA (diethylene glycol monoethyl ether acetate), MMA (methyl methacrylate), MAA (methacrylic acid), ST
(styrene)：Tokyo chemical conversion industry (strain) is manufactured
·MAIB：2,2'- azos two (isopropylformic acid .) dimethyl ester, Tokyo chemical conversion industry (strain) manufacture
·PET-30：Tetramethylolmethane (three/tetra-) acrylate, Japanese chemical medicine (strain) manufacture
·5-MBT：5- methylbenzotrazoles, Tokyo chemical conversion industry (strain) manufacture
·IRG184：Photoepolymerizationinitiater initiater, BASF AG IRGACURE (registered trade mark) 184
·APS：APTES, SHIN-ETSU HANTOTAI's chemical industry (strain) LS-3150 processed
·AGITAN771：Defoamer, the manufacture of MUNZING companies
Agitating device：THINKY CORPORATION あ わ と り Taro ARE-310
[1] synthesis of resin
[synthesis example 1]
DEGMEA 532.0g are put in the four-hole boiling flask of 1,000mL, and under nitrogen atmosphere, 70 DEG C (interior temperature) stir below
While last 2 hours lentamente having instilled MMA 280.0g, MAA 30.1g, the mixing of ST 36.5g and MAIB 8.1g thereto
Liquid.After instillation, further at 70 DEG C which is reacted 20 hours, obtained resin solution P1.Should illustrate, in the resin solution
The mol ratio of the monomeric unit in contained resin ((methyl) acrylate polymer) is MMA units：MAA units：ST units
=80：10：10, its Mw are for about 50,000.
[2] making of cured film formation resin combination, the making of cured film and its evaluation
[embodiment 1]
The PET- of resin solution P1,24.3g for obtaining in the synthesis example 1 for loading 55.1g in the plastic containers of 200mL
30th, the DEGMEA of AGITAN771,17.9g of APS, 0.03g of 5-MBT, 0.02g of IRG184,1.3g of 1.3g, is put
Enter in agitating device, stirred 10 minutes with 2,000rpm, make varnish.
[embodiment 2]
The PET- of resin solution P1,25.1g for obtaining in the synthesis example 1 for loading 50.2g in the plastic containers of 200mL
30th, the DEGMEA of AGITAN771,22.6g of APS, 0.03g of 5-MBT, 0.03g of IRG184,0.68g of 1.4g, is put
Enter in agitating device, stirred 10 minutes with 2,000rpm, make varnish.
[embodiment 3]
The PET- of resin solution P1,24.1g for obtaining in the synthesis example 1 for loading 48.3g in the plastic containers of 200mL
30th, the DEGMEA of AGITAN771,23.7g of APS, 0.03g of 5-MBT, 0.02g of IRG184,2.62g of 1.3g, is put
Enter in agitating device, stirred 10 minutes with 2,000rpm, make varnish.
[embodiment 4]
The PET- of resin solution P1,22.9g for obtaining in the synthesis example 1 for loading 45.9g in the plastic containers of 200mL
30th, the DEGMEA of AGITAN771,25.0g of APS, 0.03g of 5-MBT, 0.02g of IRG184,5.00g of 1.2g, is put
Enter in agitating device, stirred 10 minutes with 2,000rpm, make varnish.
[comparative example 1]
The PET- of resin solution P1,24.9g for obtaining in the synthesis example 1 for loading 56.7g in the plastic containers of 200mL
30th, the DEGMEA of AGITAN771,17.0g of APS, 0.03g of IRG184,0.02g of 1.4g, puts it in agitating device,
Stirred 10 minutes with 2,000rpm, make varnish.
The composition of the varnish made in embodiment 1～4 and comparative example 1 is collected and is shown in Table 1.
[table 1]
[3] making and its evaluation of cured film
[making of determination of light transmittance cured film]
The varnish of embodiment 1～4 and comparative example 1 is coated with respectively on the glass substrate by spin coating, first at 110 DEG C
2 minutes prebakes are carried out.Next, carrying out UV irradiation (800mJ/cm2), bakee after then carrying out 30 minutes at 110 DEG C,
Thick about 5 μm cured film is made.For the cured film for obtaining, pencil hardness, adaptation, transparent has been carried out using following methods
The evaluation of property.Show the result in table 2.
[measure of light transmittance]
(strain) Shimadzu Seisakusho Ltd. UV-3100PC is used to determine the ultraviolet-visible absorption spectroscopy of cured film, to wavelength 400nm
Under absorbance evaluated.
[evaluation of pencil hardness]
According to JIS K 5400,1,000g load is used to be determined.
[evaluation of adaptation]
Evaluated using cross cut test method.First, using cutting machine guide, 100 have been made in cured film
Gridiron pattern.Next, on the gridiron pattern bonding NICHIBAN CO., LTD. manufacture adhesive tape, from top erasing rubber
Rub at full tilt so as to fully closely sealed.Then, next adhesive tape is peeled, now, according to having in 100 gridiron patterns
It is several stripping and evaluated.
0B：More than 66 strippings
1B：36～65 strippings
2B：16～35 strippings
3B：6～15 strippings
4B：1～5 stripping
5B：Without stripping
[making of resistance to migration sample for evaluation]
Silver-colored pattern 2 as Fig. 1 has been made on glass substrate 1 by sputtering evaporation.To be implemented using silk screen print method
The varnish of example 1～4 and comparative example 1 is coated with the glass substrate with silver-colored pattern respectively, has carried out 2 first at 110 DEG C
Minute prebake.Next bakee after 30 minutes being carried out at 110 DEG C, make thick about 5 μm cured film 3, obtained evaluating and used
Sample.Will be the sectional drawing for defining the silver-colored pattern substrate of cured film shown in Figure 2.For the sample for obtaining, using following methods
Carry out resistance to migration to evaluate.
[resistance to migration is evaluated]
Under conditions of sample for evaluation is positioned over temperature 60 C, relative humidity 90%RH, enters to be about to anode and negative electrode connects
Connect and apply the voltage of 15 hours 5V to silver-colored pattern ends portion so that the test that electric field is concentrated is produced in pattern top ends, it is thus identified that
Whether there is the generation of the migration that the test causes.Should illustrate, if there occurs and migrate across with before and after microscope viewing test
Pattern is confirming.Pattern before and after test is shown in Fig. 3～5.
[table 2]
| Adaptation | Pencil hardness | Light transmittance (%) | Mist degree (%) | The presence or absence of migration generation | |
| Embodiment 1 | 5B | H | >99 | <1 | Nothing |
| Embodiment 2 | 5B | H | >99 | <1 | Nothing |
| Embodiment 3 | 5B | H | >99 | <1 | Nothing |
| Embodiment 4 | 5B | H | >99 | <1 | Nothing |
| Comparative example 1 | 5B | H | >99 | <1 | Have |
The result by as shown in table 2 understands, obtained by the varnish (cured film is formed and uses resin combination) of embodiment
The pencil hardness of the cured film for arriving is up to more than H, and adaptation is also up to more than 4B, and the transparency is also excellent.In addition, having used these
In the case of cured film, the generation (Fig. 4) for migrating is not found.On the other hand, used by consolidating that the varnish of comparative example is obtained
In the case of changing film, it was found that the generation (Fig. 5) of migration.
The explanation of reference
1 substrate
2 silver medal patterns
3 cured film
Claims (9)
1. cured film formation resin combination, it is characterised in that contain：
(A) weight average molecular weight is 5,000～200,000 (methyl) acrylate polymer, wherein, has not included in side chain
(methyl) acrylate polymer of silane structure,
(B) migration inhibitor being made up of benzotriazole cpd and ion-trapping agent, and
(C) solvent.
2. cured film formation resin combination according to claim 1, wherein, also containing (D) silane coupler.
3. cured film formation resin combination according to claim 1 and 2, wherein, also containing (E) multifunctional (methyl)
Acrylate compounds.
4. cured film formation resin combination according to claim 3, wherein, also causes containing (F) radical polymerization
Agent.
5. the cured film formation resin combination according to any one of Claims 1 to 4, wherein, relative to (A) composition
100 mass parts, (B) benzotriazole cpd containing 0.1～50 mass parts.
6. cured film, its usage right require the cured film formation resin combination described in 1～5 any one and are formed.
7. electroconductive member, which has：Define electrode and/or distribution base material and on the substrate with the electrode and/
Or the cured film described in the claim 6 that formed of the mode that connects of distribution.
8. the suppressing method for migrating, the migration come on the comfortable base material for defining electrode and/or distribution with by cured film shape
Into the electrode and/or distribution of the structure of the cured film formed with resin combination, it is characterised in that as the solidification
Film formation resin combination, usage right require the cured film formation resin combination described in 1～5 any one.
9. the suppressing method for migrating, the migration come on the comfortable base material for defining electrode and/or distribution with by containing (first
Base) acrylate polymer and solvent the electrode of the structure of cured film that formed of resin combination and/or distribution, its
It is characterised by, adds benzotriazole cpd in the composition.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014149946 | 2014-07-23 | ||
| JP2014-149946 | 2014-07-23 | ||
| PCT/JP2015/070691 WO2016013543A1 (en) | 2014-07-23 | 2015-07-21 | Resin composition for forming cured film, cured film, electrically conductive member, and method for preventing migration |
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| JP (1) | JP6787125B2 (en) |
| KR (1) | KR102341781B1 (en) |
| CN (1) | CN106536620A (en) |
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| TW201625730A (en) * | 2014-11-25 | 2016-07-16 | Nissan Chemical Ind Ltd | Resin composition for cured film formation, cured film, electrically conductive member, and corrosion inhibition method for metal electrode and/or metal wiring |
| WO2017170668A1 (en) | 2016-03-31 | 2017-10-05 | 日産化学工業株式会社 | Resin composition for forming high refractive index cured film |
| KR102152634B1 (en) | 2018-10-22 | 2020-09-07 | 현대모비스 주식회사 | Apparatus and method for detecting ionmigration |
| CN117501469A (en) * | 2021-04-27 | 2024-02-02 | 日产化学株式会社 | Composition for forming thin film for electrode of energy storage device |
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- 2015-07-21 WO PCT/JP2015/070691 patent/WO2016013543A1/en active Application Filing
- 2015-07-21 CN CN201580039411.4A patent/CN106536620A/en active Pending
- 2015-07-21 JP JP2016535934A patent/JP6787125B2/en active Active
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- 2015-07-23 TW TW104123891A patent/TWI667274B/en active
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| KR102341781B1 (en) | 2021-12-21 |
| JP6787125B2 (en) | 2020-11-18 |
| KR20170033813A (en) | 2017-03-27 |
| TWI667274B (en) | 2019-08-01 |
| WO2016013543A1 (en) | 2016-01-28 |
| JPWO2016013543A1 (en) | 2017-04-27 |
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