CN103025782A - Conductive resin composition - Google Patents
Conductive resin composition Download PDFInfo
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- CN103025782A CN103025782A CN2011800359305A CN201180035930A CN103025782A CN 103025782 A CN103025782 A CN 103025782A CN 2011800359305 A CN2011800359305 A CN 2011800359305A CN 201180035930 A CN201180035930 A CN 201180035930A CN 103025782 A CN103025782 A CN 103025782A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Disclosed is a conductive resin composition that includes a conductive powder, a resol-type phenolic resin, and an isocyanate compound and can obtain a cured product with stable properties. The conductive resin composition is characterized by including a resol-type phenolic resin (A), a pyrazole compound (B), an isocyanate compound (C), and a conductive powder (D). It is desirable that the pyrazole compound (B) is a 3,5-dimethylpyrazole. Alternatively, the conductive resin composition is characterized by including (A) a resol-type phenolic resin, an isocyanate compound blocked by the pyrazole (F), and a conductive powder (D). It is desirable that the isocyanate compound blocked by the pyrazole (F) is a 3,5-dimethylpyrazole-blocked 1,6-hexamethylene diisocyanate trimer.
Description
Technical field
The present invention relates to conductive resin composition, specifically, relate to the conductive resin composition of the cured article that can access resistance value, stable on heating excellent in stability.
Background technology
Carry out silk screen printing and form the conductive paste of conductor circuit pattern at tellite as being used for, use in the resin glue that is formed by thermosetting resin, thermoplastic resin compounding to be dispersed with the conductive paste of the carbonaceous conductive powder of metal powder, carbon black, the graphite and so on such as silver, copper all the time.For conductive paste, require the characteristics such as electroconductibility, printing, adaptation, anti-welding heat performance, high heat resistance, wet fastness, resistance to sudden heating, wear resistant, in order to satisfy these characteristic requirements, various resinous principles, conducting powder have been proposed.
As the thermosetting resin of binding agent, for example known have a resol type phenol resin.The excellent heat resistance of resol type phenol resin in addition, when being used for conductive paste, can cause volumetric shrinkage from condensation, and the conducting powder of as a result institute's compounding contact area each other increases, and can expect that resistance value reduces and electroconductibility becomes good.And then price is relatively low, and except thermotolerance, the excellences such as cementability, mechanical characteristics, electrical characteristic not only are used as binding agent, and is widely used as formed material, caking agent, the coating agent of various base materials.Disclose in the patent documentation 1 to use and contained the resin combination of resol type phenol resin as the scheme of the resin glue of conductive paste.
On the other hand, for resol type phenol resin, require further to improve printing, the fragility of improving cured coating film, package stability etc.
In addition, as the conductive paste of cementability, flexibility, wear resistant excellence, also proposed to make compound with hydroxyl and polyisocyanate compound to carry out addition reaction and the resin glue that obtains.For example, in the patent documentation 2,3 conductive paste that comprises polyester polyol, isocyanate compound and conducting powder is disclosed.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 5-194822 communique
Patent documentation 2: TOHKEMY 2006-100081 communique
Patent documentation 3: TOHKEMY 2006-302825 communique
Summary of the invention
The problem that invention will solve
In recent years, for the thermotolerance that further improves the resin glue that uses resol type phenol resin, improve resin properties, development of new resin glue, attempted making resol type phenol resin and isocyanate compound to carry out addition.
Yet, at this moment, have following problem: the condensation reaction of resol type phenol resin self and with the coexistence of the addition reaction system of isocyanate compound, becoming is difficult to control reaction system, it is large that the deviation of the physical property of the cured article that resistance value, anti-welding heat performance etc. obtains becomes.
Therefore, the object of the invention is to, a kind of conductive resin composition is provided, it comprises conducting powder, resol type phenol resin and isocyanate compound, and it can access the fixed cured article of physical stability.
For the scheme of dealing with problems
The inventor etc. are conceived to give reaction with selectivity under specific temperature condition, a reaction is preferentially carried out, thereby address the above problem, and conduct in-depth research, and then find, when the condensation reaction of resol type phenol resin is preponderated, the resin properties such as characteristic that resistant to cook is boiled exert an influence, and the addition reaction that makes isocyanic ester can not produce detrimentally affect to resin properties when preponderating, and can seek the stabilization of physical property.And, find can suppress the condensation reaction of resol type phenol resin by pyrazole compound, and then finished the present invention.
That is, conductive resin composition of the present invention is characterised in that, it comprises (A) resol type phenol resin, (B) pyrazole compound, (C) isocyanate compound and (D) conducting powder.
About conductive resin composition of the present invention, aforementioned (B) pyrazole compound is preferably 3，5-dimethylpyrazole.Aforementioned (C) isocyanate compound is preferably the end-blocking isocyanic ester.
In addition, conductive resin composition of the present invention is characterised in that, its comprise (A) resol type phenol resin, (F) with the pyrazoles end-blocking isocyanate compound and (D) conducting powder.Aforementioned (F) with the pyrazoles end-blocking isocyanate compound be preferably the 3，5-dimethylpyrazole end-blocking thing of 1,6-hexamethylene diisocyanate trimer.
Conductive resin composition of the present invention preferably also comprises (E) polyvinyl acetal resin.
And then about conductive resin composition of the present invention, aforementioned (D) conducting powder is preferably more than one in carbon black and the graphite.
Electroconductive resin cured article of the present invention is characterised in that it solidifies aforesaid conductive resin composition and obtains.
In addition, conductor circuit pattern of the present invention is characterised in that it uses aforementioned electroconductive resin cured article.
The effect of invention
According to the present invention, a kind of conductive resin composition can be provided, it comprises conducting powder, pyrazole compound, resol type phenol resin and isocyanate compound, and it can access the fixed cured article of physical stability.
Description of drawings
Fig. 1 illustrates the solids component ratio of resol type phenol resin and 3，5-dimethylpyrazole and the chart of the relation of gelation time.
Embodiment
Conductive resin composition of the present invention be comprise (A) resol type phenol resin, (B) pyrazole compound, (C) isocyanate compound and (D) conducting powder be the conductive resin composition of feature, or take comprise (A) resol type phenol resin, (F) with the pyrazoles end-blocking isocyanate compound and (D) conducting powder as the conductive resin composition of feature.
Below, each composition is specifically described.
Need to prove that in the present invention, resin refers to (A), (B), (C), (E) and (F).
＜(A) resol type phenol resin＞
In the present invention, (A) resol type phenol resin is so long as the material that can use in the resin glue of conductive paste, and then known resol type phenol resin all can use.In addition, also can utilize alkoxyl group etc. to carry out modification.Molecular weight to (A) resol type phenol resin has no particular limits, and weight-average molecular weight Mw is preferably 500 ~ 5000.
Resol type phenol resin for example can obtain the phenolic compound methylolation with formaldehydes in the presence of alkali, places under acidic conditions or heats and can cause condensation reaction, causes gelation, curing.
For the phenolic compound as the raw material of resol type phenol resin, for example can list phenol, meta-cresol, ortho-cresol, p-cresol, p-tert-butylphenol, p-ethyl phenol, 2,3-xylenol, 2,5-xylenol, m-ethylphenol, 3,5-xylenol, meta-methoxy phenol, dihydroxyphenyl propane, Bisphenol F etc.From solidified nature and stable on heating aspect, preferred dihydroxyphenyl propane, phenol, meta-cresol, m-ethylphenol, 3,5-xylenol, meta-methoxy phenol.
As aforementioned formaldehydes, can list formaldehyde, Paraformaldehyde 96 Huo trioxane etc., they can be a kind of, also can be two or more.It is desirable to, average per 1 aromatic nucleus, resulting methylol is more than 1.0.
With respect to the resin solid composition in the composition, (A) the compounding amount of resol type phenol resin converts in solids component and is preferably 10 ~ 55 quality %, more preferably 20 ~ 45 quality %.During the compounding quantity not sufficient 10 quality % of resol type phenol resin, sometimes the characteristics such as the necessary anti-welding heat performance of conductor circuit pattern, high heat resistance reduce, on the other hand, and when surpassing 55 quality %, sometimes boiling property of resistant to cook, flexibility, printing etc. are caused detrimentally affect, so not preferred.In addition, (A) formaldehyde content of resol type phenol resin is 0.1% when following, because environmental performance is excellent, is preferred therefore.
＜(B) pyrazole compound＞
Although its reason is also unclear, if but pyrazole compound is present in the resin combination, then the condensation reaction of resol type phenol resin is suppressed, and can control the reaction of the resin combination that comprises resol type phenol resin and isocyanate compound, seeks the stabilization of the physical property of cured article.Pyrazole compound can be included in separately in the resin combination, in addition, also can comprise by the end-capping reagent as isocyanate compound as described below.
Among the present invention; as (B) pyrazole compound; for example can list without the pyrazoles, 3-methylpyrazole, 4-methylpyrazole, 5-methylpyrazole, the 3-amyl group pyrazoles, 3 that replace; 5-dimethyl pyrazole, 3-chlorine pyrazoles, 3, any one above pyrazoles that is replaced by the alkyl of carbonatoms 1 ~ 5, halogen atom, phenyl or ethanoyl of 3,4,5 of the pyrazole rings such as 4-dibromo pyrazoles.Substituting group on these pyrazole rings can be for a kind of, also can be for two or more.Pyrazole compound is preferably more than one the pyrazole compound that is selected from without in substituted pyrazolecarboxylic, alkyl substituted pyrazolecarboxylic and their derivative, from as the thermal dissociation of end-capping reagent and the balance of thermostability, is particularly preferably 3，5-dimethylpyrazole.
With respect to the solids component of resol type phenol resin, the compounding amount of pyrazole compound converts in solids component and is preferably 1 ~ 35 quality %, more preferably 10 ~ 30 quality %.When the compounding amount of pyrazole compound is lower than 1 quality %, for condensation, be inadequate for what under condition of cure of the present invention, suppress resole, on the other hand, if surpass 35 quality %, then surpass necessarily inhibited reaction, can cause the reduction of coating characteristic, so not preferred.
＜(C) isocyanate compound＞
Among the present invention, as (C) isocyanate compound, so long as be used for the material of the resin glue of conductive paste, then known isocyanate compound all can use.As such isocyanate compound, the terminal isocyanate prepolymer that can list aliphatic isocyanates compound, aromatic isocyanate compound, is obtained by isocyanate compound and polyol or polyamine compounds or high molecular contain isocyanate-based polymer etc.
With respect to the resin solid composition in the composition, the preferred compounding amount of isocyanate compound converts with solids component and counts 20 ~ 80 quality %, more preferably 35 ~ 75 quality %.When the compounding amount of isocyanate compound is lower than 20 quality %, cause the reduction of boiling property of resistant to cook, and if surpass 80 quality %, cause that then the characteristics such as anti-welding heat performance, high heat resistance reduce, so not preferred.
As above-mentioned aliphatic isocyanates compound, for example have 1,6-hexamethylene diisocyanate (HDI or HMDI), isophorone diisocyanate (IPDI), methylcyclohexane 2,4-(2,6)-vulcabond (hydrogenation TDI), 4,4 '-methylene-bis (cyclohexyl isocyanate) (hydrogenation MDI), 1,3-(isocyanato-methyl) hexanaphthene (hydrogenation XDI), norbornylene vulcabond (NDI), lysinediisocyanate (LDI), trimethyl hexamethylene diisocyanate (TMDI), dimer acid diisocyanate (DDI), N, N ', N "-three (6-isocyanato-hexa-methylene) biuret etc.
As above-mentioned aromatic isocyanate compound, for example can list tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), Xylene Diisocyanate (XDI) etc.
As the low-molecular-weight polyhydroxylated compound that is used for obtaining above-mentioned end isocyanate prepolymer and polymkeric substance, can list ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, 1,4-butyleneglycol, 1,3 butylene glycol, hexylene glycol, neopentyl glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, polyoxyethylene glycol, polypropylene glycol, polyethylene glycol adipate, polypropylene adipate (PPA) etc.
In addition, from the viewpoint of single dose quality guaranteed period, isocyanate compound preferably use end-capping reagent (encapsulant) end-blocking that is known the end-blocking isocyanic ester.As end-capping reagent, for example can list ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, the alcohols such as isopropylcarbinol, phenol, chlorophenol, cresols, xylenol, the phenols such as p-NP, p-tert-butylphenol, to sec-butyl phenol, to secondary amino group phenol, paraoctyl phenol, the induced by alkyl hydroxybenzene such as nonylphenol, the 3-pyridone, oxine, the basic nitrogen compounds such as 8-hydroxyl quinaldine red, diethyl malonate, methyl aceto acetate, methyl ethyl diketone isoreactivity methylene compound, ethanamide, acrylamide, the amidess such as Acetanilide, succinimide, the acid imides such as maleimide, the 2-ethyl imidazol(e), the imidazoles such as 2-ethyl-4-methylimidazole, 2-Pyrrolidone, the lactams such as ε-caprolactam, acetoxime, methyl ethyl ketoxime, cyclohexanone-oxime, the oximes of the ketone such as ethylidenehydroxylamine or aldehyde, ethyleneimine, hydrosulphite etc.Above-mentioned end-capping reagent can use a kind of, also can be used in combination two or more.
＜(D) conducting powder＞
Among the present invention, as (D) conducting powder, so long as be used for the material of the resin glue of conductive paste, then known conducting powder all can be used.As conducting powder, carbon dusts such as the mixture that can list the carbon blacks such as the metal powders such as gold and silver, copper, platinum, palldium alloy, furnace treated black, thermal black, thermally oxidized black, acetylene black, Ketjen black, graphite, carbon black and graphite, carbon nanotube, the mixture of preferred carbon black, graphite, carbon black and graphite.
Content about (D) conducting powder, in the situation of metal powder, convert in the solids component in the composition, be preferably 70 ~ 95 quality %, more preferably 75 ~ 90 quality % in the situation of carbon dust, convert in the solids component in the composition, be preferably 35 ~ 65 quality %, more preferably 45 ~ 55 quality %.When the compounding amount is less than above-mentioned scope, can not get sufficient electroconductibility, and during more than above-mentioned scope, the physical strength of cured film reduces, so not preferred.
＜(E) polyvinyl acetal resin＞
Among the present invention, from viewpoints such as the dispersiveness of conducting powder, printing characteristics, comprise (A) resol type phenol resin, (B) pyrazole compound, (C) isocyanate compound and (D) conducting powder conductive resin composition or comprise (A) resol type phenol resin, (F) with the pyrazoles end-blocking isocyanate compound and (D) any of conductive resin composition of conducting powder all preferably further contain (E) polyvinyl acetal resin.As (E) polyvinyl acetal resin, so long as be used for the material of the resin glue of conductive paste, then known polyvinyl acetal resin all can use.(E) polyvinyl acetal resin for example can be by obtaining the polyvinyl alcohol resin acetalation with aldehyde.
As above-mentioned aldehyde, be not particularly limited, such as listing formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, 2-ethyl hexanal, hexamethylene aldehyde, furfural, phenyl aldehyde, 2-tolyl aldehyde, 3-tolyl aldehyde, 4-tolyl aldehyde, p-Hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenyl acetaldehyde, beta-phenyl propionic aldehyde etc., preferred butyraldehyde.These aldehyde can be used alone, and also can be used in combination more than two kinds.
As the ProductName of commercially available polyvinyl acetal resin, such as listing S-LEC BL-1, BL-1H, BL-2, BL-2H, BL-5, BL-10, BL-S, BM-1, BM-2, BM-S, BH-3, BX-1, BX-2, BX-5, BX-55, BX-L, BH-3, BH-S, BM-S, KS-3Z, KS-5, KS-5Z, KS-8, KS-23Z (above is Sekisui Chemical Co., Ltd's system), Denka Butyral4000-2,5000A, 6000C, 6000EP (above is Deuki Kagaku Kogyo Co., Ltd's system) etc.In addition, these resins can use a kind of, also can be used in combination two or more.
With respect to the resin solid composition in the composition, the compounding amount of polyvinyl acetal resin converts in solids component and is preferably 1.5 ~ 20 quality %, more preferably 3 ~ 15 quality %.When the compounding amount was lower than 1.5 quality %, the dispersiveness of conducting powder, printing characteristic etc. be can not see additive effect, if the compounding amount surpasses 20 quality %, the thermotolerance that anti-welding heat performance etc. is filmed reduces, so not preferred.
＜(F) with the pyrazoles end-blocking isocyanate compound＞
In the conductive resin composition of the present invention, (F) with the pyrazoles end-blocking isocyanate compound be the material that isocyanate compound obtains with the pyrazole compound end-blocking.Illustrative compound is same in isocyanate compound and above-mentioned (C) isocyanate compound, and illustrative compound is same in pyrazole compound and above-mentioned (B) pyrazole compound.Conductive resin composition of the present invention comprise (F) with the pyrazoles end-blocking isocyanate compound the time, can comprise (B) pyrazole compound, can not comprise (B) pyrazole compound yet.
With respect to the resin solid composition in the composition, (F) with the pyrazoles end-blocking the compounding amount of isocyanate compound convert in solids component and be preferably 25 ~ 85 quality %, more preferably 40 ~ 80 quality %.
＜other composition＞
In the conductive resin composition of the present invention, except above-mentioned each composition, can also contain other composition.As other composition, can list solvent, defoamer, thixotropic agent, coupling agent, antioxidant, dispersion agent, flow agent etc., known material all can use.
＜electroconductive resin cured article＞
Electroconductive resin cured article of the present invention obtains by above-mentioned conductive resin composition is solidified.The preferred thermofixation of curing.Solidification value is preferably 100 ~ 200 ℃, more preferably 120 ~ 180 ℃.In addition, conductor circuit pattern of the present invention has electroconductive resin cured article of the present invention at tellite.Conductor circuit pattern of the present invention can be by utilizing the coating conductive resin compositions of the present invention such as silk screen printing and its curing being obtained at known tellite.
The manufacture method of＜electroconductive resin cured article＞
As the manufacture method of electroconductibility cured article of the present invention, preferably will comprise (A) resol type phenol resin, (B) pyrazole compound, (C) isocyanate compound and (D) conductive resin composition of conducting powder make the methods of its curing 100 ~ 200 ℃ of lower heating.Each composition of conductive resin composition as mentioned above.In addition, also can contain other above-mentioned composition.More preferably 120 ~ 180 ℃ of solidification values.Heating means are not particularly limited, and the known methods such as conveyor type baking oven of intermittent type baking oven, heated air circulation type drying oven, far infrared rays all can adopt.
Embodiment
Below, more specifically the present invention will be described by embodiment.Need to prove that " part " just refers to mass parts unless otherwise specified.
(reference example 1)
Add the basic catalyst shown in the following table 1 of 8.8 mass parts with respect to solids component 100 mass parts of resol type phenol resin, measure it 150 ℃ of lower heating times (gelation time) till gelation.Gelation is confirmed by visual.Show the result in following table 1.
[table 1]
(reference example 2)
As described in Table 2, to the 3，5-dimethylpyrazole of resol type phenol resin adding as one of (B) of the present invention composition, measure it 150 ℃ of lower heating times (gelation time) till gelation.Gelation is confirmed by visual.Show the result in following table 2.In addition, the solids component of expression resol type phenol resin and 3，5-dimethylpyrazole is shown in Fig. 1 than the figure with the relation of gelation time.
[table 2]
(embodiment 1 ~ 6, comparative example 1 ~ 5)
As described in Table 3, each composition with 3 rollers mill blending dispersion, is made conductive resin composition (conductive paste) (embodiment 1 ~ 6 and comparative example 1 ~ 5).Wherein, the unit in the table 3 is mass parts.
[table 3]
※ 1: the flourish KCC of group makes RE SITOP PL-5208 (NV=60%)
※ 2: Sekisui Chemical Co., Ltd makes the acetate of butyl carbitol dilution varnish (NV=20%) of S-LEC BM-S
※ 3:1, the trimerical methyl ethyl ketoxime affixture of 6-hexamethylene diisocyanate (HDI) (NV=70%)
※ 4:Baxenden company makes BI-7982 (NV=70%)
※ 5:3, the 5-dimethyl pyrazole
※ 6:Lion Corporation makes Ketjen Black EC-300J
※ 7: the Japanese blacklead manufacturing SP-20 of Co., Ltd.
※ 8:Kyowa Hakko Chemical Co., Ltd. makes Butycenol20acetate (acetate of butyl carbitol)
Use the printed circuit board (PCB) that utilizes the conductive paste making that obtains, carry out volume resistance value, adaptation, resistance to tape peeling, anti-welding heat performance, boil patience, pencil hardness test by following evaluation test method.Show the result in following table 4.
(1) volume resistance value
In the copper circuit section of the glass epoxy substrate that is formed with electrode, be coated with respectively the conductive paste of above-described embodiment 1 ~ 6 and comparative example 1 ~ 5 by silk screen print method, form the pattern epithelium of wide 1mm * long 100mm.Then in the heated air circulation type drying oven, under 150 ℃, be heating and curing 30 minutes.Then, to resulting cured film, measure resistance value (R) by milliohm tester (Milliohm HiTester) (HIOKI company makes 3540m Ω HiTESTER), calculate volume specific resistance.Mensuration about the volume resistance value, use surface profiler to measure the thickness (t) of conductive molded body, use light microscope determining based on accurately live width (w) and the length (l) of catoptrical conductive molded body, based on these measured values, " ρ=Rwt/l " calculates the volume resistance value by formula.Herein, ρ represents volume specific resistance (Ω cm), and R represents resistance value (Ω), and w represents width (cm), and t represents thickness (cm), and l represents length (cm).Wherein, volume resistance value numerical value is more little more preferred.
(2) adaptation resistance to tape peeling
Similarly form the pattern epithelium of 15mm * 15mm by silk screen print method at the copper-clad surface of glass epoxide copper-clad laminated board with above-mentioned (1), be heating and curing.On resulting cured film, make the grid of 100 1mm * 1mm of cutters, investigate the number of grid residual on the substrate the when side is with the glass ribbon release coated film from it, estimate adaptation (JIS K5400-8.5).The preferred result of the residual more expression of grid.In addition, about the evaluation of resistance to tape peeling, glass ribbon is sticked on the cured film, to peel off band with respect to the angle of filming as 90 °, by the dirt settling of Visual Confirmation band.Metewand is as follows.
Zero: do not have dirt settling on the glass ribbon fully
*: there is dirt settling on the glass ribbon
(3) anti-welding heat performance
After will in 260 ℃ solder bath, flooding 10 seconds with the printed circuit board (PCB) that above-mentioned (1) similarly makes, to the cured film after processing, measure resistance value by milliohm tester (MilliohmHiTester) (HIOKI company makes, 3540m Ω HiTESTER).By the volume resistance value that calculates, the volume resistance value before to process goes out velocity of variation as benchmark.Wherein, the velocity of variation absolute value after scolder is processed is more little more preferred.
(4) boil patience
To in boiling water, flood with the printed circuit board (PCB) that above-mentioned (1) similarly makes and boil in 2 hours.For the cured film of boiling after the processing, measure resistance value by milliohm tester (MilliohmHiTester) (HIOKI company makes, 3540m Ω HiTESTER), calculate velocity of variation.Wherein, the velocity of variation absolute value that boils after the processing is more little more preferred.
(5) pencil hardness
For the printed circuit board (PCB) of similarly making with (1), according to the test method of JIS K5600-5-6, filming with pencil scratching tester applied load 1kg the time does not have the maximum hardness of damage to represent.The pencil that uses is the Hi-uni of Mitsubishi (Mitsubishi Pencil K. K's manufacturing).
[table 4]
As above, can be confirmed by comparative example 1,2, by adding pyrazole compound, suppress the condensation of resole, coating characteristic is exerted an influence.In addition, as can be known, in comparative example 3 ~ 5, mix in the system that exists at resole resin and isocyanate compound, the ratio of components of isocyanate compound is higher, boils patience and more improves, and on the other hand, the resistance change rate after scolder is processed becomes large.Can envision, this may be because during thermofixation with the addition reaction of isocyanate compound the time, carry out resole from condensation, so required hydroxyl minimizing of addition reaction, isocyanate compound is residual, exerts an influence when scolder is processed.And then, can infer, in part because of resole from condensation, the network concentration of the crosslinking structure that forms during thermofixation becomes sparse, thermotolerance reduces.Resistance change rate after scolder is processed when on the other hand, confirming to add 3，5-dimethylpyrazole in embodiment 1 ~ 3 diminishes.Inferred that by previous reference example 1,2 this is because because 3，5-dimethylpyrazole and resole are coexisted, gelation time latens, thereby being suppressed from condensation of resole during thermofixation.And then, confirm, even using the embodiment 4 ~ 6 that 3，5-dimethylpyrazole is used for the isocyanate compound of end-capping reagent, demonstrate similarly excellent anti-welding heat performance.Thus, the cured film of using conductive resin composition of the present invention (conductive paste) to form demonstrates excellent anti-welding heat performance, boils patience, have high conductivity, to the adaptation of base material, thereby the circuit that can be used in aptly printed circuit board (PCB) forms.
Claims (11)
1. a conductive resin composition is characterized in that, it comprises (A) resol type phenol resin, (B) pyrazole compound, (C) isocyanate compound and (D) conducting powder.
2. conductive resin composition according to claim 1, wherein, described (B) pyrazole compound is 3，5-dimethylpyrazole.
3. conductive resin composition according to claim 1 and 2, wherein, described (C) isocyanate compound is the end-blocking isocyanate compound.
4. conductive resin composition according to claim 1 wherein, also comprises (E) polyvinyl acetal resin.
5. conductive resin composition according to claim 1, wherein, described (D) conducting powder is more than one in carbon black and the graphite.
6. a conductive resin composition is characterized in that, its comprise (A) resol type phenol resin, (F) with the pyrazoles end-blocking isocyanate compound and (D) conducting powder.
7. conductive resin composition according to claim 6, wherein, described (F) with the pyrazoles end-blocking isocyanate compound be the 3，5-dimethylpyrazole end-blocking thing of 1,6-hexamethylene diisocyanate trimer.
8. conductive resin composition according to claim 6 wherein, also comprises (E) polyvinyl acetal resin.
9. conductive resin composition according to claim 6, wherein, described (D) conducting powder is more than one in carbon black and the graphite.
10. an electroconductive resin cured article is characterized in that, it obtains each the described conductive resin composition curing in the claim 1 ~ 9.
11. a conductor circuit pattern is characterized in that, its right to use requires 10 described electroconductive resin cured articles.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010166493 | 2010-07-23 | ||
| JP2010-166493 | 2010-07-23 | ||
| JP2010209267A JP5650477B2 (en) | 2010-07-23 | 2010-09-17 | Conductive resin composition |
| JP2010-209267 | 2010-09-17 | ||
| PCT/JP2011/065725 WO2012011398A1 (en) | 2010-07-23 | 2011-07-08 | Conductive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103025782A true CN103025782A (en) | 2013-04-03 |
| CN103025782B CN103025782B (en) | 2015-09-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201180035930.5A Active CN103025782B (en) | 2010-07-23 | 2011-07-08 | Conductive resin composition |
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| Country | Link |
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| JP (1) | JP5650477B2 (en) |
| KR (1) | KR101979034B1 (en) |
| CN (1) | CN103025782B (en) |
| TW (1) | TWI478979B (en) |
| WO (1) | WO2012011398A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104620684A (en) * | 2013-01-30 | 2015-05-13 | Dic株式会社 | Conductive paste, method for forming conductive pattern, and object with printed conductive pattern |
| CN105981472A (en) * | 2014-02-13 | 2016-09-28 | 电子部品研究院 | Heating paste composition, surface type heating element using same, and potable low-power heater |
| CN107667449A (en) * | 2015-05-14 | 2018-02-06 | 大华合成技术株式会社 | Hybrid vehicle battery preheating apparatus and its control method |
| CN108495878A (en) * | 2016-01-20 | 2018-09-04 | 三菱瓦斯化学株式会社 | Resin combination, the resin sheet with supporter, multilayer board and semiconductor device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5771042B2 (en) * | 2011-03-31 | 2015-08-26 | 太陽ホールディングス株式会社 | Conductive resin composition |
| KR101689289B1 (en) * | 2015-05-14 | 2016-12-23 | 주식회사 대화알로이테크 | Method for manufacturing heating coating thread by using heating paste composition |
| JP6151742B2 (en) * | 2015-06-09 | 2017-06-21 | タツタ電線株式会社 | Conductive paste |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06145291A (en) * | 1992-11-09 | 1994-05-24 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| JP2000094620A (en) * | 1998-09-22 | 2000-04-04 | Asahi Chem Ind Co Ltd | Phenol resin foam |
| CN1280156A (en) * | 2000-07-11 | 2001-01-17 | 湖北省化学研究所 | Anisotyopic conductive adhesive and its preparing method |
| JP2001064779A (en) * | 1999-08-25 | 2001-03-13 | Kansai Paint Co Ltd | Surface treating composition for galvanized steel sheet |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5953717B2 (en) * | 1981-07-27 | 1984-12-26 | 日本黒鉛工業株式会社 | Method for manufacturing contact terminals for heat seal connectors on printed circuit boards |
| JPS60254144A (en) * | 1984-05-31 | 1985-12-14 | Canon Inc | Electrophotographic sensitive body |
| JPS61235417A (en) * | 1985-04-11 | 1986-10-20 | Bridgestone Corp | Electromagnetic wave absorbing material |
| JPS61255925A (en) * | 1985-05-09 | 1986-11-13 | Hitachi Chem Co Ltd | Blocked isocyanate for foundry and foundry resin-coated sand prepared by using same |
| JPH083066B2 (en) * | 1987-12-24 | 1996-01-17 | 東レ株式会社 | Transparent conductive ink composition |
| JP2619289B2 (en) * | 1989-06-20 | 1997-06-11 | 三井金属鉱業株式会社 | Copper conductive composition |
| JPH05194822A (en) | 1992-01-20 | 1993-08-03 | Taiyo Ink Seizo Kk | Conductive paste |
| JPH0644819A (en) * | 1992-07-24 | 1994-02-18 | Kao Corp | Conductive paste and conductive paint film |
| JPH08218006A (en) * | 1995-02-17 | 1996-08-27 | Hitachi Chem Co Ltd | Electroconductive paste |
| DE19736920A1 (en) * | 1997-08-25 | 1999-03-04 | Bayer Ag | Aqueous coating composition for stove enamelling and process for its production |
| JP3969080B2 (en) * | 2001-01-31 | 2007-08-29 | 東海ゴム工業株式会社 | Endless belt |
| US6916537B2 (en) * | 2001-11-01 | 2005-07-12 | Transitions Optical Inc. | Articles having a photochromic polymeric coating |
| JP2003281935A (en) * | 2002-03-22 | 2003-10-03 | Dainippon Printing Co Ltd | Photosensitive conductive paste using polyvinyl acetal, electrode forming method, and electrode formed thereby |
| JP4467439B2 (en) * | 2003-03-18 | 2010-05-26 | ダウ・コーニング・コーポレイション | Conductive composition and method of using the conductive composition |
| JP2006100081A (en) | 2004-09-29 | 2006-04-13 | Toyobo Co Ltd | Conductive paste |
| JP4547623B2 (en) | 2005-04-25 | 2010-09-22 | 東洋紡績株式会社 | Conductive paste |
| MY149267A (en) * | 2006-12-26 | 2013-08-15 | Sumitomo Bakelite Co | Conductive paste |
| WO2009037960A1 (en) * | 2007-09-19 | 2009-03-26 | Konica Minolta Medical & Graphic, Inc. | Lithographic printing plate material, and phenolic resin having cyclic ureide compound residue |
-
2010
- 2010-09-17 JP JP2010209267A patent/JP5650477B2/en active Active
-
2011
- 2011-07-08 KR KR1020137001637A patent/KR101979034B1/en active IP Right Grant
- 2011-07-08 WO PCT/JP2011/065725 patent/WO2012011398A1/en active Application Filing
- 2011-07-08 CN CN201180035930.5A patent/CN103025782B/en active Active
- 2011-07-21 TW TW100125788A patent/TWI478979B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06145291A (en) * | 1992-11-09 | 1994-05-24 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| JP2000094620A (en) * | 1998-09-22 | 2000-04-04 | Asahi Chem Ind Co Ltd | Phenol resin foam |
| JP2001064779A (en) * | 1999-08-25 | 2001-03-13 | Kansai Paint Co Ltd | Surface treating composition for galvanized steel sheet |
| CN1280156A (en) * | 2000-07-11 | 2001-01-17 | 湖北省化学研究所 | Anisotyopic conductive adhesive and its preparing method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104620684A (en) * | 2013-01-30 | 2015-05-13 | Dic株式会社 | Conductive paste, method for forming conductive pattern, and object with printed conductive pattern |
| CN104620684B (en) * | 2013-01-30 | 2017-11-14 | Dic株式会社 | Conductive paste, the forming method of conductive pattern and conductive pattern printed article |
| CN105981472A (en) * | 2014-02-13 | 2016-09-28 | 电子部品研究院 | Heating paste composition, surface type heating element using same, and potable low-power heater |
| CN107667449A (en) * | 2015-05-14 | 2018-02-06 | 大华合成技术株式会社 | Hybrid vehicle battery preheating apparatus and its control method |
| CN108495878A (en) * | 2016-01-20 | 2018-09-04 | 三菱瓦斯化学株式会社 | Resin combination, the resin sheet with supporter, multilayer board and semiconductor device |
| CN108495878B (en) * | 2016-01-20 | 2020-12-22 | 三菱瓦斯化学株式会社 | Resin composition, resin sheet with support, multilayer printed wiring board, and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012041517A (en) | 2012-03-01 |
| JP5650477B2 (en) | 2015-01-07 |
| KR20140003370A (en) | 2014-01-09 |
| TWI478979B (en) | 2015-04-01 |
| CN103025782B (en) | 2015-09-23 |
| KR101979034B1 (en) | 2019-05-15 |
| TW201219483A (en) | 2012-05-16 |
| WO2012011398A1 (en) | 2012-01-26 |
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