CN105980599B - Copper film formation composition and the manufacture method using its copper film - Google Patents
Copper film formation composition and the manufacture method using its copper film Download PDFInfo
- Publication number
- CN105980599B CN105980599B CN201580007860.0A CN201580007860A CN105980599B CN 105980599 B CN105980599 B CN 105980599B CN 201580007860 A CN201580007860 A CN 201580007860A CN 105980599 B CN105980599 B CN 105980599B
- Authority
- CN
- China
- Prior art keywords
- copper film
- copper
- compound
- film formation
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/145—Radiation by charged particles, e.g. electron beams or ion irradiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Thermal Sciences (AREA)
- Chemically Coating (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
Abstract
The present invention provides：It is coated on matrix, is handled by using the flash-light method of xenon lamp, so as to obtains the copper film formation composition with sufficient electric conductivity and copper film, without solid phases such as particulates the solution shape high with the adaptation of matrix with low temperature and low energy.A kind of copper film formation composition, it contains：Copper formate or its hydrate；At least one kind of diol compound in the group being made of the compound shown in the compound and the following general formula (1 ') shown in the following general formula (1)；Specific dye compound；With for dissolving the organic solvent of these components, when the total of the content and copper acetate of copper formate or its hydrate or the content of its hydrate is set to 1 mole/kg, diol compound is contained with the scope of 0.1~6.0 mole/kg.
Description
Technical field
The present invention relates to for forming the copper film formation composition of copper film on various matrixes and using its copper film
Manufacture method.
Background technology
It has been reported that largely by being used as the coating thermal decomposition method (MOD methods) of liquid process, particle dispersion liquid is coated with
Method is formed using copper as the conductive layer of electric conductor, the technology of wiring.
For example, the manufacture method that a series of copper film forms article is proposed in patent document 1~4, it is characterised in that
Coating is using Kocide SD or copper organic acid and polyalcohol as the mixed liquor of essential component on various matrixes, in non-oxidizing atmosphere
In be heated to more than 165 DEG C of temperature.Moreover, as the copper organic acid used in the liquid process, copper formate is disclosed, as
Polyalcohol, discloses diethanol amine, triethanolamine.
Proposed in patent document 5, can be formed on basal electrode soft solder excellent heat resistance it is metal film, contain
The metal paste of the organic compound of silver particles and copper.As the organic compound of the copper used in the paste, formic acid is disclosed
Copper, as the amino-compound for reacting with it simultaneously paste, discloses diethanol amine.
The metal salt mixture of the metal pattern formation used in circuit is proposed in patent document 6.Should moreover, forming
In the ingredients of a mixture, as metal salt, disclose copper formate, as organic principle, disclose organic solvent i.e. diethanol amine,
N methyldiethanol amine, N- ethyldiethanolamines, morpholine, as metal ligand, disclose pyridine.
Patent Document 7 discloses, after, printing useful to formation etc. of electronic equipment wiring can at low temperature into
The copper precursors combination of the low-temperature decomposition containing copper formate and 3- dialkyl amido propane -1,2- diol compounds of row thermal decomposition
Thing.
Patent Document 8 discloses the Copper thin film shape containing copper formate and alkanolamine useful to aforementioned liquids technique
Into with composition.Moreover, as alkanolamine, monoethanolamine, diethanol amine and triethanolamine are listed.In addition, patent document 9
In disclose, using the fluid composition containing organo-metallic compound, by flash lamp to the fluid composition carry out illumination
The method penetrated and manufacture metal film.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 1-168865 publications
Patent document 2：Japanese Unexamined Patent Publication 1-168866 publications
Patent document 3：Japanese Unexamined Patent Publication 1-168867 publications
Patent document 4：Japanese Unexamined Patent Publication 1-168868 publications
Patent document 5：Japanese Unexamined Patent Publication 2007-35353 publications
Patent document 6：Japanese Unexamined Patent Publication 2008-205430 publications
Patent document 7：Japanese Unexamined Patent Publication 2009-256218 publications
Patent document 8：Japanese Unexamined Patent Publication 2010-242118 publications
Patent document 9：International Publication No. 2013/145953
The content of the invention
Problems to be solved by the invention
In order to, with fine wiring, film is manufactured inexpensively in the liquid process of composition, be intended to provide using copper film formation
Meet the composition of following characteristics.I.e. it is desired to following feature：For the solution-type without solid phases such as particulates, provide excellent electric conductivity
Copper film, can be converted into that copper film, coating are good, storage stability is good, are obtained by 1 coating with low temperature and low energy
Thickness control easily, the adaptation of gained film and matrix it is high.
Especially as the method that copper film formation is converted into copper film with composition at low temperature, it is known to：Based on use
The copper film manufacture method of the flash-light method of xenon lamp.However, with polyethylene terephthalate (following, to be denoted as " PET ") tree
When fat is forms copper film on the organic resin matrix of representative, for conventional copper film formation composition, exist to make its turn
The problem of turning to the height of the energy needed for copper film, deteriorating organic resin matrix.Therefore, it is desirable to strongly with organic resin matrix
The low energy for the degree not deteriorated is converted into copper film and can obtain the copper film formation group of the copper film high with the adaptation of matrix
Compound.However, fully meet that the copper film formation composition of these requirements is not known.
Therefore, it is an object of the present invention to provide：It is coated on matrix, at the flash-light method of xenon lamp
Reason, so as to low temperature and low energy obtain having sufficient electric conductivity and with the adaptation of matrix it is high it is copper film, be free of
The copper film formation composition of the solution shape of the solid phases such as particulate.
The solution used to solve the problem
The inventors of the present invention study repeatedly in view of above-mentioned actual conditions, it turns out that：With specific ratio contain copper formate or
The copper film formation group of its hydrate, the diol compound with specific structure and the dye compound with specific structure
Compound meets above-mentioned requirements performance, so as to complete the present invention.
That is, the present invention provides a kind of copper film formation composition, it contains：Copper formate or its hydrate 0.01~3.0 rub
That/kg；0~3.0 mole/kg of copper acetate or its hydrate；Selected from as the compound and the following general formula shown in the following general formula (1)
At least one kind of diol compound in the group of compound composition shown in (1 ')；Selected from as the chemical combination shown in the following general formula (A-I)
Compound, thymol blue shown in thing, the following general formula (A-II) and at least one kind of dye compound in the group of Quercetin composition
0.001~20 mass %；With, for dissolving the organic solvent of these components, by the content of foregoing copper formate or its hydrate and
When the total of the content of foregoing copper acetate or its hydrate is set to 1 mole/kg, before being contained with the scope of 0.1~6.0 mole/kg
State diol compound.
(in aforementioned formula (1), X represents hydrogen atom, methyl, ethyl or 3- aminopropyls.In aforementioned formula (1 '), R1And R2
Separately represent the alkyl of hydrogen or carbon number 1~4, R1And R2It is optionally mutually bonded to be formed together with adjacent nitrogen-atoms
Five-membered ring or hexatomic ring)
(in aforementioned formula (A-I), Ar1And Ar2Separately represent optionally by the alkyl of carbon number 1~4, alcoxyl
The phenyl ring or naphthalene nucleus that base, carboxyl, halogen atom, cyano group or vinyl are substituted, RaRepresent hydroxyl, amino, alkyl amino or dioxane
Base amino, in Ar2P represents 1~5 integer, in Ar in the case of for substituted or unsubstituted phenyl ring2To be substituted or unsubstituted
P represents 1~7 integer in the case of naphthalene nucleus.RaAnd Ar2Optionally mutually bonded formation ring structure, p are the situation of 2~7 integer
Under, multiple RaIt is optionally mutually different.In aforementioned formula (A-II), Ar3~Ar5Separately represent optionally by carbon number 1~
The phenyl ring or naphthalene nucleus that 4 alkyl, alkoxy, carboxyl, halogen atom, cyano group or vinyl is substituted, RbRepresent hydroxyl, amino, alkane
Base amino or dialkyl amido, in Ar5Q represents 1~5 integer, in Ar in the case of for substituted or unsubstituted phenyl ring5To take
Q represents 1~7 integer in the case of generation or unsubstituted naphthalene nucleus.RbAnd Ar5Optionally mutually bonded formation ring structure, q are 2~7
Integer in the case of, multiple RbIt is optionally mutually different)
In addition, the present invention provides a kind of manufacture method of copper film, it possesses following process：Painting process, by above-mentioned copper film
Formation is coated on matrix with composition；With irradiation film formation process, using xenon lamp to the foregoing copper film formation group by coating
At least a portion of compound carries out light irradiation.
The effect of invention
According to the present invention, there is provided：It is coated on matrix, is handled by using the flash-light method of xenon lamp, so as to
With low temperature and low energy obtain having sufficient electric conductivity and with high copper film, without the solid phases such as particulates of the adaptation of matrix
The copper film formation composition of solution shape.
Embodiment
The copper film formation of the present invention is the precursor for using copper formate as copper film by the use of one of feature of composition
(Precursor).The copper film formation of the present invention can be that anhydrous compound can also be hydration with the copper formate used in composition
Thing.Specifically, anhydrous copper formate (II), copper formate (II) dihydrate, copper formate (II) tetrahydrate etc. can be used.This
A little copper formates can directly be mixed and can also mixed in the form of aqueous solution, organic solvent solution or organic solvent suspension.
The content of copper formate in the copper film formation composition of the present invention is 0.01~3.0 mole/kg, is preferably 1.0
~2.5 moles/kg.When the content of copper formate is less than 0.01 mole/kg, film can not be obtained sometimes.On the other hand, copper formate
When content is more than 3.0 moles/kg, the stability of solution reduces.Herein, in the present invention " mole (mol)/kg " refers to, " solution
The amount (mole) of the solute dissolved in 1kg ".For example, the molecular weight of copper formate (II) is 153.58, and therefore, copper film of the invention
Formed and be changed into 1.0 moles/kg with when containing copper formate (II) 153.58g in composition 1kg.
The copper film formation of the present invention is used as the controlling agent of copper concentration by the use of that can also contain together with copper formate in composition
Copper acetate.Copper acetate can be that anhydrous compound can also be hydrate.Specifically, anhydrous cupric acetate (II), second can be used
Sour copper (II) monohydrate etc..In addition, these copper acetates can directly be mixed in the same manner as copper formate can also with aqueous solution, have
The form mixing of solvent solution, organic solvent suspension.It should be noted that the molecular weight of copper acetate (II) monohydrate is
199.65, therefore, copper film of the invention is formed and is changed into when containing copper acetate (II) monohydrate 199.65g in composition 1kg
1.0 moles/kg.
The copper film formation of the present invention is preferably 0~3.0 mole/kg with the content of the copper acetate in composition, further excellent
Elect 0.01~2.5 mole/kg as.In addition, the concentration ratio of the copper formate and copper acetate in the copper film formation composition of the present invention
Rate is not particularly limited, and preferably 40 mass % of whole copper in copper film formation composition are above is addition band by copper formate
Come.In addition, the concentration of copper formate and copper acetate (mole/kg) than about 1：When 1, the excellent film of electrical characteristics can be obtained, therefore
Particularly preferably.
In addition, by the way that copper acetate and copper formate are applied in combination, the copper film shape with only preparing identical copper concentration with copper formate
Compared into the situation of composition, the copper film formation composition of low viscosity can be obtained.In general, by copper film formation group
Compound as using ink-jet method, the coating fluid that spin-coating method is the rubbing method of representative in use, viscosity is high sometimes, coating reduces.
Therefore, by the way that copper acetate and copper formate are applied in combination, viscosity can also be kept in the case of copper concentration height to be relatively low,
It can maintain coating.
In addition, dissolubility of the copper acetate in copper film formation composition is very high, therefore, with only controlling copper with copper formate
Film formation is compared with the situation of the copper concentration in composition, can improve copper concentration.Copper concentration in copper film formation composition
The thickness of copper film to being formed a film by rubbing method has considerable influence.On the other hand, for the present invention copper film formation composition,
Even if copper concentration is high, stability is also excellent and coating is also good, can easily control the thickness of gained copper film.It is for example, logical
When crossing rubbing method manufacture copper film, in the wide scope with tens of~1000nm, appropriate film can also be formed with 1 coating
Thick smooth conducting film, that is, copper film.
Component, that is, the diol compound for forming the copper film formation composition of the present invention is selected from by the following general formula (1) Suo Shi
Compound and the following general formula (1 ') shown in compound composition group in it is at least one kind of, there is the ammonia of more than 1 in its molecule
Base.Such diol compound is shown as the effect to copper formate or the solubilizer of Cu formate hydrate.In addition, show
Improve the storage stability of copper film formation composition and the effect of electric conductivity is improved when being converted into film.
In general formula (1), X represents hydrogen atom, methyl, ethyl or 3- aminopropyls.In addition, in general formula (1 '), R1And R2Respectively
Independently represent the alkyl of hydrogen atom or carbon number 1~4.It should be noted that R1And R2Optionally mutually bonded and adjacent nitrogen
Atom forms five-membered ring or hexatomic ring together.As the concrete example of the alkyl of carbon number 1~4, can enumerate：Methyl, ethyl,
Propyl group, 2- propyl group, butyl, 2- butyl, isobutyl group, the tert-butyl group.As R1And R2It is mutually bonded and is formed together with adjacent nitrogen-atoms
Five-membered ring or hexatomic ring concrete example, can enumerate：Pyrroles, pyrrolidines, crassitude, pyridine, 2- picolines, 3- first
Yl pyridines, 4- picolines, 2,4- lutidines, 2,6- lutidines, piperidines, pipecoline, 3- methyl piperidines, 4-
Methyl piperidine.
As the diol compound shown in general formula (1), for example, following compound Ns o.1~No.4.
In addition, the diol compound shown in as general formula (1 '), for example,：Following compound Ns o.5~No.13.
In the above-mentioned diol compound enumerated, diethanol amine (compound N is o.1), N methyldiethanol amine (compound
No.2), N- ethyldiethanolamines (compound N is o.3), N- aminopropyldiethanolamines (compound N is o.4) and 3- dimethylaminos
Base -1,2-PD (compound N is o.8) provides especially good storage stability to copper film formation with composition, therefore it is preferred that.
And then in the above-mentioned diol compound enumerated, use N methyldiethanol amine (compound N is o.2) and 3- dimethyl
During amino -1,2-PD (compound N is o.8), the electric conductivity of gained copper film becomes good, therefore particularly preferably.
For the content of the above-mentioned diol compound in the copper film formation composition of the present invention, by copper formate or its hydration
It is the scope of 0.1~6.0 mole/kg when the total of the content and copper acetate of thing or the content of its hydrate is set to 1 mole/kg.
During less than 0.1 mole/kg, the electric conductivity of gained copper film becomes inadequate.When on the other hand, more than 6.0 moles/kg, coating
Deteriorate, uniform copper film can not be obtained.Preferred scope is 0.2~5.0 mole/kg.In addition, above-mentioned diol compound can be with
Exclusive use can also mix two or more use.
Component, that is, dye compound of the copper film formation composition of the present invention is formed as selected from by the following general formula (A-I) institute
Compound, thymol blue shown in the compound shown, the following general formula (A-II) and at least one kind of in the group of Quercetin composition.Root
According to the research of the inventors of the present invention, if judging with copper formate or its hydrate and diol compound to combine the dye compound simultaneously
It is contained in copper film formation composition, then can reduce energy required when being converted into copper film by using the flash-light method of xenon lamp
Amount.
In aforementioned formula (A-I), Ar1And Ar2Separately represent optionally by the alkyl of carbon number 1~4, alkoxy,
The phenyl ring or naphthalene nucleus that carboxyl, halogen atom, cyano group or vinyl are substituted, RaRepresent hydroxyl, amino, alkyl amino or dialkyl amino
Base, in Ar2P represents 1~5 integer, in Ar in the case of for substituted or unsubstituted phenyl ring2For substituted or unsubstituted naphthalene nucleus
In the case of p represent 1~7 integer.RaAnd Ar2Optionally mutually bonded formation ring structure is more in the case that p is 2~7 integer
A RaIt is optionally mutually different.In aforementioned formula (A-II), Ar3~Ar5Separately represent optionally by the alkane of carbon number 1~4
The phenyl ring or naphthalene nucleus that base, alkoxy, carboxyl, halogen atom, cyano group or vinyl are substituted, RbRepresent hydroxyl, amino, alkyl amino
Or dialkyl amido, in Ar5Q represents 1~5 integer, in Ar in the case of for substituted or unsubstituted phenyl ring5For substitution or nothing
Q represents 1~7 integer in the case of substituted naphthalene nucleus.RbAnd Ar5Optionally mutually bonded formation ring structure, q are 2~7 integer
In the case of, multiple RbIt is optionally mutually different.
As the dye compound shown in general formula (A-I), for example,：Following compound Ns o.14~No.17.
In addition, the dye compound shown in as general formula (A-II), for example,：Following compound Ns o.18~
No.20。
The content of above-mentioned dye compound in copper film the is formationed composition of the present invention is 0.001~20 mass %, excellent
Elect 0.005~15 mass % as, more preferably 0.01~5 mass %.During less than 0.001 mass %, it can not confirm and match somebody with somebody
The effect of mixed dye compound.When on the other hand, more than 20 mass %, by the effect saturation for being compounded and being produced.On in addition,
Two or more use can also be mixed by stating dye compound and can be used alone.
In the above-mentioned dye compound enumerated, 4- phenylazos phenol (compound N is o.14), Solvent Black3 (change
Compound No.18), the Sudan 3 (compound N is o.19), the Sudan R (compound N is o.15), methyl red (compound N is o.16), thymol blue
In the case of combining and be contained in copper film formation composition with copper formate or its hydrate and diol compound with Quercetin, drop
The effect that the low flash-light method by using xenon lamp is converted into energy required during copper film is big, therefore it is preferred that.And then above-mentioned enumerate
In dye compound, 4- phenylazos phenol (compound N is o.14), solvent black (Solvent Black) 3 (compound N is o.18)
The effect of reduction with the Sudan 3 (compound N is o.19) energy required when being converted into copper film by using the flash-light method of xenon lamp
It is especially big, therefore it is preferred that.
As long as form the present invention copper film formation with the organic solvent of composition can stably dissolve above-mentioned copper formate (or
Its hydrate), diol compound, dye compound and other compositions.The organic solvent can be that single composition can also
For mixture.Copper film formation as the present invention can be enumerated with the concrete example of the organic solvent used in composition：Alcohol system is molten
Agent, two alcohol series solvents (wherein, excluding the compound shown in general formula (1) and (1 ')), ketone series solvent, ester series solvent, ether series solvent,
Aliphatic or clicyclic hydrocarbon series solvent, aromatic hydrocarbon series solvent, the hydrocarbon solvent with cyano group, other solvents etc..
As alcohol series solvent, for example,：Methanol, ethanol, propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, 2- butanol,
The tert-butyl alcohol, amylalcohol, isoamyl alcohol, 2- amylalcohols, neopentyl alcohol, tert-pentyl alcohol, hexanol, 2- hexanols, enanthol, 2- enanthol, octanol, 2- ethyl hexyls
Alcohol, sec-n-octyl alcohol, cyclopentanol, cyclohexanol, suberol, methylcyclopentanol, methyl cyclohexanol, methyl cycloheptanol, benzylalcohol, ethylene glycol list
Acetic acid esters, ethylene glycol monoethyl ether, ethyleneglycol monophenylether, ethylene glycol monobutyl ether, glycol monoethyl ether, propylene glycol monomethyl ether, the third two
Alcohol list ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol
Monobutyl ether, 2- (2- methoxy ethoxies) ethanol, 2- (N, N- dimethylamino) ethanol, 3- (N, N- dimethylamino) propyl alcohol
Deng.
As two alcohol series solvents, for example,：Ethylene glycol, propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4-
Butanediol, 1,5- pentanediols, neopentyl glycol, isoprene (3- methyl isophthalic acids, 3- butanediols), 1,2- hexylene glycols, 1,6-HD,
3- methyl isophthalic acids, 5- pentanediols, 1,2- ethohexadiols, ethohexadiol (2- ethyl -1,3- hexylene glycols), 2- butyl -2- ethyls -1,3- the third two
Alcohol, 2,5- dimethyl -2,5-HD, 1,2- cyclohexanediols, 1,4- cyclohexanediols, 1,4 cyclohexane dimethanol etc..
As ketone series solvent, for example,：Acetone, methyl ethyl ketone, espeleton, methylisobutylketone, ethyl butyl ketone, two
Acetone, diisobutyl ketone, methylpentanone, cyclohexanone, methyl cyclohexanone etc..
As ester series solvent, for example,：Methyl formate, Ethyl formate, methyl acetate, ethyl acetate, acetic acid are different
Propyl ester, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, pentyl acetate, isoamyl acetate, acetic acid uncle penta
Ester, phenylacetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, sec-butyl propionate, propionic acid
The tert-butyl ester, amyl propionate, isoamyl propionate, propionic acid tert-pentyl ester, phenyl propionate, 2 ethyl hexanoic acid methyl esters, 2 ethyl hexanoic acid ethyl ester,
2 ethyl hexanoic acid propyl ester, 2 ethyl hexanoic acid isopropyl ester, 2 ethyl hexanoic acid butyl ester, methyl lactate, ethyl lactate, methoxypropionic acid first
Ester, ethoxypropanoate, methoxypropionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether acetate, diethylene glycol list
Methyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol ether acetic acid esters, ethyleneglycol monopropylether acetic acid esters, ethylene glycol
The secondary butyl ether acetic acid esters of monobutyl ether-acetate, ethylene glycol list, ethylene glycol list isobutyl ether acetic acid esters, the tertiary butyl ether acetic acid esters of ethylene glycol list,
Propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, monoisopropyl ether acetic acid
The secondary butyl ether acetic acid esters of ester, propylene glycol monobutyl ether acetic acid esters, propane diols list, propane diols list isobutyl ether acetic acid esters, the tertiary fourth of propane diols list
Ether acetic acid ester, butanediol methyl ether acetate, butanediol monoethyl ether acetate, butanediol list propyl ether acetic acid esters, butanediol Dan Yi
The secondary butyl ether acetic acid esters of propyl ether acetic acid esters, butanediol monobutyl ether-acetate, butanediol list, butanediol list isobutyl ether acetic acid esters, fourth two
The tertiary butyl ether acetic acid esters of alcohol list, methyl acetoacetate, ethyl acetoacetate, oxobutyrate, oxobutyric, gamma lactone,
Delta-lactone etc..
As ether series solvent, for example,：Tetrahydrofuran, oxinane, morpholine, glycol dimethyl ether, diethyl two
Diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, butyl oxide, Anaesthetie Ether, dioxane etc..
As aliphatic or clicyclic hydrocarbon series solvent, for example,：Pentane, hexane, hexamethylene, hexahydrotoluene,
Dimethyl cyclohexane, ethyl cyclohexane, heptane, octane, naphthalane, solvent naphtha etc..
As aromatic hydrocarbon series solvent, for example,：Benzene, toluene, ethylo benzene, dimethylbenzene, mesitylene, diethyl
Benzene, isopropylbenzene, isobutyl-benzene, cymol, tetrahydronaphthalene etc..
As the hydrocarbon solvent with cyano group, for example,：1- dicyanopropanes, 1- cyanobutanes, 1- cyanohexanes, cyanogen
Butylcyclohexane, cyano group benzene, 1,3- dicyanos propane, 1,4- dicyanobutanes, 1,6- dicyanos hexane, 1,4- dicyano hexamethylenes
Alkane, 1,4- dicyanobenzenes etc..
As other organic solvents, for example,：N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl formyl
Amine etc..
In the present invention, in above-mentioned organic solvent, alcohol series solvent, two alcohol series solvents and ester series solvent are cheap, and solute is shown
Sufficient dissolubility is shown, and then the various matrixes such as silicon substrate, metallic matrix, ceramic matrix, glass matrix, resin matrix are shown
It is shown as the good coating of coating solvent, therefore it is preferred that.Wherein, there is hydroxyl in the structure such as alcohol series solvent and two alcohol series solvents
The solvent of base is high to the dissolubility of solute, is particularly preferred.
The present invention copper film formation be not particularly limited with the content of the above-mentioned organic solvent in composition, can according to will
The thickness of the copper film of formation, the manufacture method of copper film and suitably adjust.For example, in the case of manufacturing copper film by rubbing method, phase
(also converted for copper formate in the case of Cu formate hydrate with copper formate, below equally) 100 mass parts, preferably using 0.01~
The organic solvent of 5000 mass parts.When the amount of organic solvent is less than 0.01 mass parts, produces and cracked in gained copper film sometimes,
Or a problem that coating deterioration.Got thinner in addition, the ratio of organic solvent more increases gained copper film, therefore, from production
Set out in terms of rate, preferably more than 5000 mass parts.More specifically, in the case of manufacturing copper film by spin-coating method, relatively
In 100 mass parts of copper formate, preferably using the organic solvent of 20~1000 mass parts.In addition, copper is manufactured by silk screen print method
In the case of film, relative to 100 mass parts of copper formate, preferably using the organic solvent of 0.01~20 mass parts.
The piperidine compounds shown in the following general formula (2) can be contained in the copper film formation composition of the present invention.By containing
There are the piperidine compounds, the coating of copper film formation composition can be made good, and improve storage stability, and can carry
The electric conductivity of high gained copper film.
As the piperidine compounds shown in above-mentioned general formula (2), for example,：Following compound Ns o.21~No.27.
In piperidine compounds listed above, particularly preferably using pipecoline (compound N is o.22).By using 2-
Methyl piperidine, can obtain showing the copper film formation composition of especially good coating and storage stability.
For the content of the above-mentioned piperidine compounds in the copper film formation composition of the present invention, by copper formate or its hydration
It is preferably 0.1~6.0 mole/kg's when the total of the content and copper acetate of thing or the content of its hydrate is set to 1 mole/kg
Scope, more preferably 0.2~5.0 mole/kg.During less than 0.1 mole/kg, coating reduces, and can not obtain sometimes uniformly
Copper film.When on the other hand, more than 6.0 moles/kg, the electric conductivity of gained copper film becomes inadequate sometimes.Preferred scope
For 0.2~5.0 mole/kg.
In addition, for the present invention copper film formation composition in diol compound and piperidine compounds content it is total
Meter, when the total of the content and copper acetate of copper formate or its hydrate or the content of its hydrate is set to 1 mole/kg, preferably
For the scope of the scope of 0.5~2.0 mole/kg, more preferably 1.0~1.5 moles/kg.Thus, copper film formation is combined
The electric conductivity of the coating of thing, storage stability and gained copper film becomes good, therefore it is preferred that.During less than 0.5 mole/kg, produce sometimes
Raw sediment.When on the other hand, more than 2.0 moles/kg, coating reduces sometimes.
The concentration rate of diol compound and piperidine compounds in the copper film formation composition of the present invention is not special
Limit, when diol compound is set to 1 mole/kg, piperidine compounds are preferably the scope of 0.5~1.5 mole/kg.Piperidines
When compound is 1 mole/kg (with the basic equivalent of diol compound), solution has good stability, and it is excellent can to obtain electrical characteristics
Copper film, therefore particularly preferably.
The present invention copper film formation composition can with without prejudice to the present invention effect scope contain essential component with
Outer any condition.As any condition, can enumerate：Dyestuff, pigment, color developing agent, sensitizer, antigelling agent, stabilizer etc.
For assigning the additive of stability to coating fluid composition；Defoamer, thickener, thixotropic agent, levelling agent etc., which are used to improve, to be applied
The additive of the coating of cloth liquid composition；Coalescents such as comburant, crosslinking coagent etc..During using these any conditions
Content is preferably below 50 mass %, more preferably 20 matter in terms of ratio shared in the entirety of copper film formation composition
Measure below %.
As dyestuff, for example,：Double (to the dimethylaminophenyl) -6- dimethylaminos phthalides of 3,3-, 3- are (right
Dimethylaminophenyl) -3- (2- phenyl -3- indyls) phthalide, 3- (to dimethylaminophenyl) -3- (1,2- dimethyl -3-
Indyl) phthalide, double (9- ethyl -3- the carbazyls) -5- dimethylaminos phthalides of 3,3-, 3,3- double (2- phenyl -3- indyls) -
5- dimethylaminos phthalide, 3- (4- diethylaminos phenyl) -3- (1- Ethyl-2-Methyls indol-3-yl) phthalide, 3,3- are double
The triarylmethane systems such as (2- (4- dimethylaminophenyls) -2- (4- methoxyphenyls) vinyl) -4,5,6,7- Rabcides
Compound；The diphenyl methane based compounds such as the colourless auramine of N-2,4,5- trichlorophenyls；(3) rhodamine-β-aniline lactams, 3-
(N- methyl-N-cyclohexyls amino) -6- methyl -7- anilino-s fluorane, 3- diethylamino -7- octyl aminos fluorane, 3- diethyls
Base amino -7- (2- chloroanilinos) fluorane, 3- diethylaminos -7- (2- fluoroanilinos) fluorane, 3- diethylamino -6- first
Base -7- anilino-s fluorane, 3- diethylamino -6- methyl -7- (2,4- accelerine bases) fluorane, 3- diethylaminos -7-
Dibenzyl amino fluorane, the chloro- 7- of 3- diethylaminos -6- (β-ethoxyethyl group amino) fluorane, 3- diethylaminos -6- are chloro-
7- (γ-chloropropyl amino) fluorane, 3- (N- ethyl-M-isoamylaminos) -6- methyl -7- anilino-s fluorane, 3- (N- ethyls -
N- ethoxyethyl groups amino) -6- methyl -7- anilino-s fluorane, 3- (N- ethyl-N- tetrahydrofurfuryls amino) -6- methyl -7- aniline
Base fluorane, 3- dibutylaminos -7- (2- chloroanilinos) fluorane, 3- (N- ethyl-N- Tolylaminos) -6- methyl -7- aniline
Base fluorane, 3- (N, N- dibutylamino) -6- methyl -7- anilino-s fluorane, 3- dipentylamino -6- methyl -7- anilino- fireflies
The xanthene systems such as alkane, 3- piperidyl -6- methyl -7- anilino-s fluorane, 3- (4- anilino-s) anilino- -6- methyl -7- chlorine fluorane
Compound；Benzyl acyl group leucomethylene blue, to thiazine based compounds such as nitrobenzyl acyl group leucomethylene blues；3- methylspiro dinaphthyls
And pyrans, 3- ethyl spiral shells dinaphthopyran, 3- benzyl spiral shells dinaphthopyran, 3- methyl naphtho--(3- methoxyl groups benzo) spiro-pyrans
Deng spiral shell based compound；And 3,5 ', 6- tri- (dimethylamino)-spiral shell (9H- fluorenes -9,1 '-(3 ' H)-isobenzofuran) -3 ' -
Double (2- (4- dimethylaminophenyls) -2- (4- methoxyphenyls) vinyl) -4,5,6,7- tetrachloros (3H) the different benzos of ketone, 1,1-
Furans -3- ketone, 3- (4- diethylamino -2- ethoxyl phenenyls) -3- (1- Ethyl-2-Methyls indol-3-yl) -4- pyridines
Phthalein, 3- (4- diethylamino -2- aminomethyl phenyls) -3- (1- Ethyl-2-Methyls indol-3-yl) -4- azepine phthalides etc..These dyes
Material can be used alone or combine two kinds it is used above.
As pigment, for example,：Iron oxide pigment, titanium pigment, indigo plant, green system's inorganic pigment, carbon pigment, idol
Nitrogen series pigments, phthalocyanine system, fused polycycle pigment etc..As iron oxide pigment, for example,：Iron oxide black, di-iron trioxide,
Zn ferrite pigment etc..As titanium pigment, for example,：Titanium oxide, nickel antimony titan yellow, chromium antimony titan yellow etc..As blue, green
It is inorganic pigment, for example,：Ultramarine, cobalt blue, chromium oxide, spinelle are green etc..As azo pigment, such as can lift
Go out：The azo lake pigments such as lake red C, Wo Qiuge be red, bright fuchsin 6B；Hostaperm Huang H4G, Novaperm Huangs H2G,
The red HFT of Novaperm, PV Fast Huangs HG, PV Fast Huangs H3R, PV Bordeaux HF3R, PV Carmine HF4C, PV are red
The benzimidazolone pigments such as HF2B, PV Fast maroon HMF01, PV Fast palm fibres HFR；Benzidine yellow, benzidine orange, pyrazolone
The benzidine pigment such as red, PV Fast Huangs HR；Cromophtal Huang 8GN, Cromophtal Huang 6G, Cromophtal Huangs 3G,
The red G of Cromophtal Huang GR, Cromophtal orange 4R, Cromophtal orange GP, Cromophtal bright red RN, Cromophtal,
Red 2B, Cromophtal palm fibre 5R of Cromophtal red BRN, Cromophtal red BG, Cromophtal etc. condense azo pigment
Deng.As phthualocyanine pigment, for example,：Phthalocyanine blue, phthalocyanine green etc..As fused polycycle pigment, for example,：
The quinacridone pigments such as the red Y of PV Fast powder E, Cinquacia red B, Cinquacia；Irgazin Huangs 2GLT, Irgazin are yellow
The isoindolinone pigments such as 3RLTN, Cromophtal orange 2G；The series pigments such as red, maroon, bright red；Purple cyclic ketones orange
Deng purple cyclic ketones series pigments；Dioxazine violet Deng dioxazine series pigments；The anthraquinone systems such as the red A3B of Fiesta Huangs RN, Cromophtal, anthracene indigo plant
Pigment；Quinophthalone series pigments such as Paliotol Huangs L0960HG etc..In addition, these pigment can be used alone or combine two
Kind is used above.The additive amount of dyestuff and pigment is preferably 0.02~20 matter with the amount of the copper in composition relative to copper film formation
Measure %, more preferably 0.1~15 mass %.
Then, the manufacture method of the copper film of the present invention is illustrated.The manufacture method of the copper film of the present invention possesses as follows
Process：Painting process, the copper film formation of the invention so far illustrated is coated on matrix with composition；With irradiation film forming work
Sequence, light irradiation is carried out using xenon lamp to the copper film formation by coating with least a portion of composition.As needed, irradiating
Following drying process can be further equipped with before film formation process：Matrix is maintained at 50~200 DEG C, makes the low boiling points such as organic solvent
Component volatilizees.In addition, following annealing operation can be further equipped with after film formation process is irradiated：Matrix is maintained at 200~500
DEG C, improve the electric conductivity of copper film.
As the coating method in above-mentioned painting process, can enumerate：Spin-coating method, infusion process, spraying process, levelling Lacquer finish apply
Method (Mist coat methods), flow coat method, curtain coating method, rolling method, scraper for coating method, stick coating method, slot coated method, screen printing
Brush method, woodburytype, flexographic printing process, ink-jet method, bristle coating etc..
Irradiation condition in above-mentioned irradiation film formation process is not particularly limited, for example,：Irradiation time 0.1~
100 milliseconds, 400~4000V of voltage, 0.1~10J/cm of irradiation energy2Such irradiation condition.
In addition, required thickness in order to obtain, can be repeatedly from above-mentioned painting process to any process.For example, can be with
, can also repeatedly painting process and drying process repeatedly from painting process to whole processes of irradiation film formation process.
The atmosphere of above-mentioned drying process and irradiation film formation process is usually in air, in reducibility gas and non-active gas
Any one, be air in the case of be economical.In addition, the atmosphere of annealing operation is usually reducibility gas and nonactive
Any one of gas.When being annealed under reducibility gas atmosphere, the more excellent copper film of electric conductivity can be obtained, thus it is excellent
Choosing.As reducibility gas, hydrogen can be enumerated.In addition, as non-active gas, can enumerate：Helium, nitrogen and argon gas.
Non-active gas can be used in the form of the diluent gas of reducibility gas.In addition, in each operation, it can apply or irradiate
Gas ions；The discharge lamps such as laser；Energy beyond the heat such as various radiation.
Embodiment
Hereinafter, enumerate embodiment and the present invention is described in more detail.However, any limit of the present invention from following embodiments etc.
System.
1 ＞ of preparation of ＜ copper film formation compositions
[embodiment 1~20]
By the compound described in table 1 in a manner of the concentration (mol/kg, quality %) for the numerical value being changed into respectively in bracket into
Row compounding obtains copper film formation composition 1~20.Specifically, as shown in table 1 like that, formic acid copper compound, glycol are changed
The species and dosage of compound and dye compound, the copper film of 20 kinds of manufacture, which is formed, uses composition 1~20.It should be noted that
The all ethanol of surplus.In addition, the concentration (mol/kg) of each compound described in table 1 is the amount in manufactured composition 1kg.
Table 1
[comparative example 1~3]
Compound described in table 2 is compounded in a manner of the numerical value (mol/kg) being changed into respectively in bracket and is compared
Composition 1~3.It should be noted that surplus is all set to ethanol.In addition, the concentration (mol/kg) of each compound described in table 2
For the amount in manufactured composition 1kg.
Table 2
1 ＞ of manufacture of ＜ copper films
[copper film 1~22 is used in evaluation]
Copper film formation is cast on pet substrate (50mm × 50mm, thickness 0.1mm) respectively with composition 1~20.With
500rpm 5 seconds and each copper film formation composition is coated with conditions of 20 seconds by spin-coating method with 2000rpm.Then, use
Hot plate, carries out drying in 30 seconds in an atmosphere, in 100 DEG C.Use xenon flash lamp device (trade name " SUS686 ", USHIO INC.
Manufacture), in an atmosphere, with the condition shown in table 3 dried pet substrate progress light is irradiated to form Copper thin film (evaluation copper
Film 1~22).It should be noted that the pet substrate that light irradiation has been carried out with xenon flash lamp does not produce discoloration and deformation.
[comparing with copper film 1~12]
Comparative composition 1~3 is cast on pet substrate (50mm × 50mm, thickness 0.1mm) respectively.With 500rpm
5 seconds and each comparative composition is coated with conditions of 20 seconds by spin-coating method with 2000rpm.Then, using hot plate, in an atmosphere,
Drying in 30 seconds is carried out in 100 DEG C.Using xenon flash lamp device (trade name " SUS686 ", USHIO INC. manufacture), in an atmosphere,
Light is carried out with the condition shown in table 3 to dried pet substrate to irradiate to form Copper thin film (comparing with copper film 1~12).Need
Bright, the pet substrate that light irradiation has been carried out with xenon flash lamp does not produce discoloration and deformation.
＜ evaluates 1 ＞
[measure of sheet resistance value]
Use resistrivity meter (Loresta GP：Mitsubishi Chemical Analytech Co., Ltd.s manufacture),
Evaluation of measuring copper film 1~22 and compare the sheet resistance value with copper film 1~12.The sheet resistance value measured is shown in table 3.
Table 3
※1：Do not show electric conductivity.
As shown in table 3 like that, all films with good electric conductivity of copper film 1~22 are used in evaluation, but are compared with copper film 2
~12 be the film without electric conductivity.It follows that the copper film formation of the present invention can be converted into copper with composition with low energy
Film.In addition, to evaluation with copper film 1 compared with comparing the sheet resistance value with copper film 1 when, although irradiation energy is identical,
It is that evaluation copper film 1 is compared compared with the sheet resistance value low 20% with copper film 1, it is known that be the Copper thin film with excellent electric conductivity.
2 ＞ of preparation of ＜ copper film formation compositions
[embodiment 21~24]
As shown in the following, by defined compound with concentration (mol/kg, the matter of the numerical value being changed into respectively in bracket
Amount %) mode be compounded to obtain copper film formation composition 21~24.It should be noted that all ethanol of surplus.Separately
Outside, the concentration (mol/kg) of each compound as shown below is the amount in manufactured composition 1kg.
Copper film forms and uses composition 21
Copper formate tetrahydrate (1.0mol/kg)
Compound N is o.2 (1.0mol/kg)
Compound N is o.14 (5 mass %)
Compound N is o.22 (1.0mol/kg)
Copper film forms and uses composition 22
Copper formate tetrahydrate (1.0mol/kg)
Compound N is o.2 (1.0mol/kg)
Thymol blue (5 mass %)
Compound N is o.22 (1.0mol/kg)
Copper film forms and uses composition 23
Copper formate tetrahydrate (1.0mol/kg)
Compound N is o.2 (1.0mol/kg)
Quercetin (5 mass %)
Compound N is o.22 (1.0mol/kg)
Copper film forms and uses composition 24
Copper formate tetrahydrate (0.5mol/kg)
Copper acetate tetrahydrate (0.5mol/kg)
Compound N is o.2 (1.0mol/kg)
Compound N is o.14 (5 mass %)
Compound N is o.22 (1.0mol/kg)
Thymol blue (5 mass %)
Compound N is o.18 (5 mass %)
[comparative example 4]
As shown in the following, by defined compound with concentration (mol/kg and the matter of the numerical value being changed into respectively in bracket
Amount %) mode be compounded to obtain comparative composition 4.It should be noted that all ethanol of surplus.It is in addition, as shown below
Each compound concentration (mol/kg) be manufactured composition 1kg in amount.
Comparative composition 4
Copper formate tetrahydrate (0.5mol/kg)
Copper acetate tetrahydrate (0.5mol/kg)
Compound N is o.2 (1.0mol/kg)
Compound N is o.22 (1.0mol/kg)
Alizarinopurpurin (5 mass %)
2 ＞ of manufacture of ＜ copper films
[copper film 23~26 is used in evaluation]
Copper film formation is cast on pet substrate (50mm × 50mm, thickness 0.1mm) respectively with composition 21~24.
Each copper film formation composition is coated with by spin-coating method under conditions of 20 seconds with 500rpm 5 seconds and with 2000rpm.Then, make
With hot plate, drying in 30 seconds is carried out in an atmosphere, in 100 DEG C.Use xenon flash lamp device (trade name " SUS686 ", USHIO
INC. manufacture), in an atmosphere, with the condition shown in table 4 dried pet substrate progress light is irradiated to form Copper thin film (evaluation
With copper film 23~26).It should be noted that the pet substrate that light irradiation has been carried out with xenon flash lamp does not produce discoloration and deformation.
[comparing with copper film 13]
Comparative composition 4 is cast on pet substrate (50mm × 50mm, thickness 0.1mm).With 500rpm 5 seconds and with
2000rpm is coated with comparative composition 4 under conditions of 20 seconds by spin-coating method.Then, using hot plate, in an atmosphere, with 100 DEG C
Carry out drying in 30 seconds.Using xenon flash lamp device (trade name " SUS686 ", USHIO INC. manufactures), in an atmosphere, with the institute of table 4
The condition shown carries out light to dried pet substrate and irradiates to form Copper thin film (comparing with copper film 13).It should be noted that use xenon
The pet substrate that flash lamp has carried out light irradiation does not produce discoloration and deformation.
＜ evaluates 2 ＞
[measure of sheet resistance value]
Use resistrivity meter (Loresta GP：Mitsubishi Chemical Analytech Co., Ltd.s manufacture),
Evaluation of measuring copper film example 23~26 and compare the sheet resistance value with copper film 13.The sheet resistance value measured is shown in table 4.
Table 4
※2：Do not show electric conductivity.
As shown in table 4 like that, all films with very good electric conductivity of copper film 23~26 are used in evaluation, but compare use
Copper film 13 is the film without electric conductivity.In addition, the result shown in investigation table 4 and understand in the lump during the result shown in table 3, evaluation
It is lower than the sheet resistance value of evaluation copper film 1~22 with copper film 23~26, it is the more excellent copper film of electric conductivity.
＜ evaluates 3 ＞
[evaluation of adaptation]
By evaluation with copper film 1~26 and compare with copper film 1 respectively with 1mm intervals with 10 × 10 clathrate carry out draw a lattice system
Judge and use sample.For made evaluation sample, implement disbonded test according to JIS K-5600, according to as shown below
Metewand evaluates adaptation.Show the result in table 5.
○：The area for the part peeled off is entire area 0% less than 10%.
×：The area for the part peeled off is more than the 10% of entire area.
Table 5
| Adaptation | |
| Copper film 1 is used in evaluation | ○ |
| Copper film 2 is used in evaluation | ○ |
| Copper film 3 is used in evaluation | ○ |
| Copper film 4 is used in evaluation | ○ |
| Copper film 5 is used in evaluation | ○ |
| Copper film 6 is used in evaluation | ○ |
| Copper film 7 is used in evaluation | ○ |
| Copper film 8 is used in evaluation | ○ |
| Copper film 9 is used in evaluation | ○ |
| Copper film 10 is used in evaluation | ○ |
| Copper film 11 is used in evaluation | ○ |
| Copper film 12 is used in evaluation | ○ |
| Copper film 13 is used in evaluation | ○ |
| Copper film 14 is used in evaluation | ○ |
| Copper film 15 is used in evaluation | ○ |
| Copper film 16 is used in evaluation | ○ |
| Copper film 17 is used in evaluation | ○ |
| Copper film 18 is used in evaluation | ○ |
| Copper film 19 is used in evaluation | ○ |
| Copper film 20 is used in evaluation | ○ |
| Copper film 21 is used in evaluation | ○ |
| Copper film 22 is used in evaluation | ○ |
| Copper film 23 is used in evaluation | ○ |
| Copper film 24 is used in evaluation | ○ |
| Copper film 25 is used in evaluation | ○ |
| Copper film 26 is used in evaluation | ○ |
| Compare and use copper film 1 | × |
Understand like that as shown in table 5, all films with high adhesion of copper film 1~26 are used in evaluation.On the other hand understand,
It is the low film of adaptation to compare with copper film 1.
Claims (6)
1. a kind of copper film formation composition, it contains：
0.01~3.0 mole/kg of copper formate or its hydrate；
0~3.0 mole/kg of copper acetate or its hydrate；
At least 1 in the group being made of the compound shown in the compound and the following general formula (1 ') shown in the following general formula (1)
Kind diol compound；
Selected from as the compound shown in the following general formula (A-I), compound, thymol blue and quercitrin shown in the following general formula (A-II)
0.001~20 mass % of at least one kind of dye compound in the group of element composition；With,
For dissolving the organic solvent of these components,
By the total of the content and the content of the copper acetate or its hydrate of the copper formate or its hydrate be set to 1 mole/
During kg, the diol compound is contained with the scope of 0.1~6.0 mole/kg,
In the general formula (1), X represents hydrogen atom, methyl, ethyl or 3- aminopropyls, in the general formula (1 '), R1And R2Respectively
Independently represent the alkyl of hydrogen atom or carbon number 1~4, R1And R2It is optionally mutually bonded to be formed together with adjacent nitrogen-atoms
Five-membered ring or hexatomic ring,
In the general formula (A-I), Ar1And Ar2Separately represent optionally by the alkyl, alkoxy, carboxylic of carbon number 1~4
The phenyl ring or naphthalene nucleus that base, halogen atom, cyano group or vinyl are substituted, RaRepresent hydroxyl, amino, alkyl amino or dialkyl amino
Base, in Ar2P represents 1~5 integer, in Ar in the case of for substituted or unsubstituted phenyl ring2For substituted or unsubstituted naphthalene nucleus
In the case of p represent 1~7 integer, RaAnd Ar2Optionally mutually bonded formation ring structure is more in the case that p is 2~7 integer
A RaIt is optionally mutually different；In the general formula (A-II), Ar3~Ar5Separately represent optionally by the alkane of carbon number 1~4
The phenyl ring or naphthalene nucleus that base, alkoxy, carboxyl, halogen atom, cyano group or vinyl are substituted, RbRepresent hydroxyl, amino, alkyl amino
Or dialkyl amido, in Ar5Q represents 1~5 integer, in Ar in the case of for substituted or unsubstituted phenyl ring5For substitution or nothing
Q represents 1~7 integer, R in the case of substituted naphthalene nucleusbAnd Ar5Optionally mutually bonded formation ring structure, q are 2~7 integer
In the case of, multiple RbIt is optionally mutually different.
2. copper film formation composition according to claim 1, wherein, the diol compound is selected from by diethanol
It is at least one kind of in the group of amine, N methyldiethanol amine and 3- dimethylamino -1,2- propane diols composition.
3. copper film formation composition according to claim 1 or 2, wherein, the dye compound is selected from by 4- benzene
It is at least one kind of in the group that base azophenol, solvent black 3, the Sudan 3, the Sudan R, methyl red, thymol blue and Quercetin form.
4. copper film formation composition according to claim 1 or 2, wherein, by containing for the copper formate or its hydrate
When the total of amount and the content of the copper acetate or its hydrate is set to 1 mole/kg, with the scope of 0.1~6.0 mole/kg also
Containing the piperidine compounds shown in the following general formula (2),
In the general formula (2), R represents methyl or ethyl, and m represents 0 or 1.
5. copper film formation composition according to claim 4, wherein, the piperidine compounds are pipecoline.
6. a kind of manufacture method of copper film, it possesses following process：
Painting process, copper film formation according to any one of claims 1 to 5 is coated on matrix with composition；With,
Film formation process is irradiated, illumination is carried out with least a portion of composition to the copper film formation by coating using xenon lamp
Penetrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014048578A JP6254025B2 (en) | 2014-03-12 | 2014-03-12 | Composition for forming copper film and method for producing copper film using the same |
| JP2014-048578 | 2014-03-12 | ||
| PCT/JP2015/053068 WO2015137013A1 (en) | 2014-03-12 | 2015-02-04 | Copper film forming composition and process for manufacturing copper film using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105980599A CN105980599A (en) | 2016-09-28 |
| CN105980599B true CN105980599B (en) | 2018-05-15 |
Family
ID=54071465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580007860.0A Active CN105980599B (en) | 2014-03-12 | 2015-02-04 | Copper film formation composition and the manufacture method using its copper film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6254025B2 (en) |
| KR (1) | KR101779734B1 (en) |
| CN (1) | CN105980599B (en) |
| TW (1) | TWI617698B (en) |
| WO (1) | WO2015137013A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6387280B2 (en) * | 2014-10-03 | 2018-09-05 | 株式会社Adeka | Composition for forming copper film and method for producing copper film using the same |
| TW201920515A (en) | 2017-08-01 | 2019-06-01 | 加拿大國家研究委員會 | Copper ink |
| US11891532B2 (en) | 2017-12-22 | 2024-02-06 | National Research Council Of Canada | Copper ink for high conductivity fine printing |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01168866A (en) | 1987-12-24 | 1989-07-04 | Mitsubishi Gas Chem Co Inc | Production of article coated with copper film |
| JPH01168867A (en) | 1987-12-24 | 1989-07-04 | Mitsubishi Gas Chem Co Inc | Production of article coated with copper film |
| JPH01168865A (en) | 1987-12-24 | 1989-07-04 | Mitsubishi Gas Chem Co Inc | Production of article coated with copper film |
| JPH01168868A (en) | 1987-12-24 | 1989-07-04 | Mitsubishi Gas Chem Co Inc | Production of article coated with copper film |
| JP3333302B2 (en) * | 1994-02-28 | 2002-10-15 | 哲夫 佐治 | Thin film manufacturing method |
| JP2000328252A (en) * | 1999-05-24 | 2000-11-28 | Hyper Photon System:Kk | Formation of metallic pattern |
| JP4852272B2 (en) | 2005-07-25 | 2012-01-11 | ナミックス株式会社 | Metal paste |
| JP2008205430A (en) | 2007-01-26 | 2008-09-04 | Konica Minolta Holdings Inc | Method of forming metallic pattern and metal salt mixture |
| JP2009256218A (en) * | 2008-04-14 | 2009-11-05 | Toray Ind Inc | Copper precursor composition, and method of preparing copper film using the same |
| JP2010242118A (en) * | 2009-04-01 | 2010-10-28 | Adeka Corp | Composition for forming copper thin film, and method for manufacturing copper thin film using the composition |
| JP5620795B2 (en) * | 2010-11-26 | 2014-11-05 | 株式会社Adeka | Composition for forming copper film and method for producing copper film using the composition |
| JP5923351B2 (en) * | 2012-03-16 | 2016-05-24 | 株式会社Adeka | Composition for forming copper film and method for producing copper film using the composition |
| JP2013206721A (en) | 2012-03-28 | 2013-10-07 | Fujifilm Corp | Liquid composition, metal film, conductor wiring, and method for manufacturing metal film |
-
2014
- 2014-03-12 JP JP2014048578A patent/JP6254025B2/en active Active
-
2015
- 2015-02-04 KR KR1020167023849A patent/KR101779734B1/en active IP Right Grant
- 2015-02-04 CN CN201580007860.0A patent/CN105980599B/en active Active
- 2015-02-04 WO PCT/JP2015/053068 patent/WO2015137013A1/en active Application Filing
- 2015-03-09 TW TW104107387A patent/TWI617698B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015172226A (en) | 2015-10-01 |
| TWI617698B (en) | 2018-03-11 |
| CN105980599A (en) | 2016-09-28 |
| WO2015137013A1 (en) | 2015-09-17 |
| KR101779734B1 (en) | 2017-09-18 |
| TW201542871A (en) | 2015-11-16 |
| JP6254025B2 (en) | 2017-12-27 |
| KR20160114175A (en) | 2016-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104169463B (en) | The manufacture method of the copper film of copper film formation compositions and use said composition | |
| TWI320796B (en) | Pixel to barrier uneveness controllable ink | |
| CN105408517B (en) | Copper film formation composition and the manufacture method using its copper film | |
| CN105980599B (en) | Copper film formation composition and the manufacture method using its copper film | |
| TWI548640B (en) | A zinc oxide film forming composition, and a method for producing a zinc oxide film | |
| JP6117457B1 (en) | Resist ink for low temperature baking | |
| EP3323858B1 (en) | Process for producing quinacridone pigment composition | |
| JP5946657B2 (en) | Solvent or solvent composition for producing photoresist, and composition for producing photoresist | |
| JP6420191B2 (en) | Nickel film forming composition and method for producing nickel film using the same | |
| JP6815219B2 (en) | Composition for forming a nickel film and a method for producing a nickel film | |
| CN107075681B (en) | Copper film forms the manufacturing method of the copper film with composition and using it | |
| EP4166532A1 (en) | Ink for inkjet printers | |
| TWI574964B (en) | A multiplier, a pigment composition containing the same, and a colorant | |
| DE102012019495A1 (en) | New substituted imidazolo-perylene bisanhydride compounds useful e.g. as reference materials for fluorescence measurements, as pigments and dyes for dyeing purposes, and as pigments in lacquers, preferably synthetic resin lacquers | |
| JP2023174824A (en) | Quinacridone pigment and method for producing the same | |
| KR20170063929A (en) | Composition for forming copper film and method for producing copper film using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |