CN107615408B - The manufacturing method and conductive film of conductive film - Google Patents
The manufacturing method and conductive film of conductive film Download PDFInfo
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- CN107615408B CN107615408B CN201680030108.2A CN201680030108A CN107615408B CN 107615408 B CN107615408 B CN 107615408B CN 201680030108 A CN201680030108 A CN 201680030108A CN 107615408 B CN107615408 B CN 107615408B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
Abstract
The issue of the present invention is to provide the manufacturing method of the conductive film high with the adaptation, environmental resistance and marresistance of substrate and conductive films.Include the following steps: to form the 1st resin layer (S1) on substrate using the 1st resin combination comprising the 1st functional group, it is not fallen into conductive material to the degree of the inside of layer the 1st resin layer is dry (S2), then the conductive pattern (S3, S4) with opening portion when forming vertical view on the 1st resin layer, using comprising can with the 2nd resin combination of the 2nd functional group of the 1st functional group's co-curing of above-mentioned 1st resin layer by be coated conductive pattern it is at least part of in a manner of form the 2nd resin layer, make the 1st resin layer and the 2nd resin layer co-curing (S5).
Description
Technical field
The present invention relates to the manufacturing method of conductive film and conductive films.
Background technique
According to the purposes applied into various electronic components, develops, produced various conductive films.For example, electrically conducting transparent
Film is in liquid crystal display (LCD), plasm display panel (PDP), organic electroluminescence type display, solar battery
(PV) and in the various fields such as the transparent electrode of touch panel (TP), antistatic (ESD) film and electromagnetic wave shielding (EMI) film make
With.As these transparent conductive films, in the past, the transparent conductive film that ITO (tin indium oxide) is utilized is used, but there are following
Such problems: the supply stability of indium is low, and manufacturing cost is high, lacks flexibility, and, when film forming, needs high temperature.Therefore, generation
Exploration for the transparent conductive film of ITO actively carries out.Wherein, the transparent conductive film containing metal nanometer line due to electric conductivity,
Optical characteristics and flexibility are excellent, form a film using wet process, and manufacturing cost is low, and when film forming does not need high temperature, etc., because
It and is suitable as the transparent conductive film for replacing ITO.
For example, as it is known that comprising silver nanowires, with high conductivity, optical characteristics, the transparent conductive film of flexibility (referring to
Patent document 1).In addition, disclose in following patent documents 2 has the electrically conducting transparent containing metal nanometer line over the transparent substrate
The manufacturing method of the transparent conductive film of layer.
In such transparent conductive film, the adaptation height of conductive layer and substrate is necessary, in addition, especially for containing
For the transparent conductive film of metal nanometer line, since the surface area of the unit mass of the metals such as silver is big, it is easy and various compounds
Reaction, accordingly, there exist shortcoming environmental resistance such problems.Therefore, because the various medicaments used in process, cleaning solution
Oxygen, the influence of moisture etc. in air influence, being exposed by long-term preservation, nanostructure easily corrodes, and electric conductivity is held
It tends to decrease.In addition, microgranular impurity, dust, dust etc. adhere to, are mixed in order to prevent especially in electronic material etc. on the way
Enter the surface of substrate, usually carry out physics washing procedure using brush etc., but by the process, also surface can be caused to damage,
This becomes problem.
To solve the above-mentioned problems, it has carried out a variety of in the stacking protection of the surface of the transparent conductive film comprising silver nanowires
Film, the trial that environmental resistance and marresistance are assigned to the transparent conductive film.(referring to patent document 3~4).
As described previously for transparent conductive film, it is desirable that the adaptation of conductive layer and substrate, environmental resistance and marresistance
It is high.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application Publication 2010-507199 bulletin
Patent document 2: No. 5609008 bulletins of Japanese Patent No.
Patent document 3: Japanese Unexamined Patent Publication 2014-191894 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2013-200943 bulletin
Summary of the invention
Problems to be solved by the invention
The purpose of the present invention is to provide the adaptation of conductive layer and substrate, environmental resistance and the high conductive films of marresistance
Manufacturing method and conductive film.
Means for solving the problems
In order to achieve the above objectives, an embodiment of the invention is a kind of manufacturing method of conductive film, the method
Including following processes: the process that the 1st resin layer is formed on substrate using the 1st resin combination comprising the 1st functional group, preceding
The process that the conductive pattern with opening portion when overlooking is formed on the 1st resin layer is stated, using comprising can be with aforementioned 1st resin layer
2nd resin combination of the 2nd functional group of the 1st functional group's co-curing by be coated aforesaid conductive pattern it is at least part of in a manner of
The process for forming the 2nd resin layer, and make the process of aforementioned 1st resin layer and the 2nd resin layer co-curing.
Preferably, after the surface of aforementioned 1st resin layer becomes inviscid, above-mentioned conductive pattern is formed.
In addition, above-mentioned 1st functional group includes carboxyl, hydroxyl, epoxy group, (methyl) acryloyl group, vinyl, allyl etc.
In subsequent handling have reactive position, it is preferred that the 1st resin combination include the polyurethane containing carboxyl,
Phenol novolak type epoxy resin, phenoxy resin, the polyurethane containing carboxyl and the ring for being lower than 1 equivalent in terms of carboxyl benchmark
It is any number of in the mixture of oxygen compound, dially phthalate resin.
It is further preferred, that above-mentioned 2nd resin combination includes the mixing of the polyurethane containing carboxyl and epoxide
Object, phenol novolak type epoxy resin, phenoxy resin, the polyurethane containing carboxyl with carboxyl benchmark be calculated as 1 equivalent with
On the mixture of epoxide, dially phthalate resin and acrylate monomer mixture in it is any number of.
It is further preferred, that aforesaid substrate, the 1st resin layer, conductive pattern and the 2nd resin layer are transparent.
In addition, other embodiments of the invention are a kind of conductive films, which is characterized in that have on substrate and include the 1st
1st resin layer of functional group, the conductive pattern with opening portion when on the 1st resin layer with vertical view, to be coated the conduction
At least part of mode of pattern is formed with the 2nd resin layer comprising the 2nd functional group, also, in aforesaid conductive pattern openings
The curing reaction part of 2nd functional group of the 1st functional group and the 2nd resin layer in portion with the 1st resin layer.
Preferably, the total light transmittance of above-mentioned conductive film is 70% or more.
Above-mentioned conductive pattern may include the metal nanometer line with unordered cross-contact portion.
Above-mentioned conductive pattern may include the metal fine pattern regularly or irregularly formed.
The effect of invention
Through the invention, it is possible to provide adaptation, environmental resistance, marresistance and the good conduction of optical characteristics with substrate
Film.
Detailed description of the invention
Fig. 1 is the process chart of the manufacturing method for the conductive film that embodiment is related to.
Fig. 2 is the concept map for amplifying conductive pattern portions that embodiment is related to.
Fig. 3 is the figure for indicating the environmental resistance evaluation result of conductive film of embodiment 1 and comparative example 7.
Specific embodiment
Hereinafter, being illustrated to a specific embodiment of the invention (hereinafter referred to as embodiment).
The manufacturing method for the conductive film that embodiment is related to is characterised by comprising following processes: use includes the 1st function
The process that 1st resin combination of group forms the 1st resin layer on substrate has opening when being formed and being overlooked on the 1st resin layer
The process of the conductive pattern in portion, using comprising can be with the 2nd of the 2nd functional group of the 1st functional group's co-curing of above-mentioned 1st resin layer the
Resin combination by be coated conductive pattern it is at least part of in a manner of form the process of the 2nd resin layer, and make the 1st resin layer with
The process of 2nd resin layer co-curing.
The process chart of the manufacturing method of conductive film of the present embodiment is shown in Fig. 1.In Fig. 1, firstly, in substrate 10
The 1st resin layer (priming coat) 12 (the S1: the 1 resin layer formation process) of upper formation.Herein, for the 1st resin layer 12, as long as
It is that can be used with the resin of the excellent adhesion of substrate 10.
The method for implementing above-mentioned S1 (the 1st resin layer formation process) is not particularly limited, and can enumerate such as silk-screen printing, recessed
The contacts such as version printing and their hectographic printing, bar coater, die coating machine, gravure coater printing, ink jet printing, spraying, spreading
The off-contact printings such as device (dispenser).
It as the substrate for constituting substrate 10, is not particularly limited, glass substrate, PET (poly terephthalic acid second two can be used
Alcohol ester) resin films such as film, PEN (polyethylene naphthalate) film etc..
In addition, the 1st resin layer 12 is made of the 1st resin combination comprising the 1st functional group, the 1st functional group is in base
Formed on the surface of plate 10 after the 1st resin layer 12 can with constitute aftermentioned 2nd resin layer the 2nd resin combination in include the
2 functional group's co-curings.
Next, for above-mentioned 1st resin layer 12, it is preferred that on the surface of the substrate 10 by the 1st resin combination
It after object is formed as stratiform, is heated at normal temperature or at temperature appropriate, is used for its solidification or drying to aftermentioned
The conductive material for forming conductive pattern does not fall into degree (the S2: the 1 resin combination back tender of the inside to the 1st resin layer 12
Sequence).Solidify or dry degree can be judged by following manner: according to JIS K 5701, utilizing parallel plate viscometer
(spreadometer) result of the test carried out is 0mm, becomes the state of no mobility, if solid using being formed at normal temperature
The resin combination of the resin layer of body, then in aftermentioned conductive pattern formation process, conductive material will not be fallen into completely to the 1st
In 12 layers of resin layer, thus preferably.After the formation (S1), solidification or dry (S2) of the 1st resin layer 12, in the 1st resin layer 12
Conductive pattern 14 with opening portion when upper formation is overlooked." conductive pattern " is also included the case where to be paved with whole face shape and be formed.Afterwards
The conductive pattern 14 with opening portion for example can be by will dispersed metal in a dispersion medium when overlooking shown in the Fig. 2 (a) stated
Ink made of nano wire (ink) (hereinafter, sometimes referred to as " metal nanometer line ink ") is printed on the 1st resin layer 12 and forms pattern
(S3: printing process), by the metal nanometer line ink irradiation light or and carry out heating to be burnt into (S4: firing process)
It obtains.Surface through the conductive pattern comprising metal nanometer line being burnt into becomes the shape exposed upwards from 12 surface of the 1st resin layer
State.
So-called herein " opening portion " refers to that aftermentioned 2nd resin combination can contact such thickness with the 1st resin combination
The through portion for spending direction has gap as shown in Fig. 2 (a), (b) between metal nanometer line 18 or metal fine 19.It needs
Bright, Fig. 2 (a), (b) are the concept maps for partly amplifying conductive pattern 14.
In the case where using metal nanometer line ink, by being printed, to make metal nanometer line 18 disorderly to have
The mode in cross-contact portion is accumulated on substrate, and in the cross-contact portion, electrical connection (including connects metal nanometer line 18 each other
The case where touching), electric conductivity (Fig. 2 (a)) thus is presented.In addition, opening portion 20 at this time passes through the metal nano disorderly accumulated
Line 18 and become irregular shape.Even if can also obtain having in thickness direction using metal nanometer line ink print whole face film
The conductive pattern of the opening portion 20 of upper perforation.So-called herein " metal nanometer line ", refer to diameter be tens of nm~hundreds of nm,
The metal nanometer line for the shape that length is several μm~tens of μm.
In addition, foring opening for shape (rectangle) of rule by metal fine 19 in the example shown in Fig. 2 (b)
Oral area 20.Metal foil or aftermentioned metal nanoparticle ink can be used to be formed for metal fine 19.It should be noted that Fig. 2 (b)
Example in, metal fine 19 is arranged in clathrate, has cross part, but for example can also be according to row parallel in a certain direction
Column, the mode without cross part are formed.In addition, metal fine 19 can also be configured irregularly, keep opening portion 20 random
Shape.
The printing process implemented in above-mentioned S3 (printing process) is not particularly limited, as long as can be by metal nanometer line ink
It is printed as the printing process of pattern, can be used.Such as silk-screen printing, intaglio printing and their hectographic printing, stick can be enumerated
The off-contact printings such as the contacts such as painting machine, die coating machine, gravure coater printing, ink jet printing, spraying, dispenser.It is above-mentioned in progress
In the case where contact printing, preferably the 1st resin layer 12 is formed by the way that such as the 1st resin combination is coated on substrate 10
Afterwards, become dry to touch state (without tackiness), i.e. state of the surface without sticky (without tackiness).Even if printing dress as a result,
It sets and is contacted with the 1st resin layer 12, also can be carried out good printing.It should be noted that in order to constitute the 2nd resin layer 16
2nd resin combination carry out co-curing when, shorten curing time, can constitute the 1st resin layer 12 the 1st resin combination in mix
Close curing accelerator.In the case where the 1st resin combination includes aftermentioned epoxide, preferably it is pre-mixed solidification and promotes
Agent.
On the other hand, it in the case where carrying out the off-contact printing of ink-jet mode etc, does not need to make the 1st resin layer 12
Dry to touch state does not fall into the degree of the inside of the 1st resin layer 12 for conductive material completely, becomes the surface of conductive material
The state exposed on 12 surface of the 1st resin layer.
It should be noted that the ink as the printing that can be used for conductive pattern 14, is not limited to above-mentioned metal nanometer line ink,
Such as metal nanoparticle ink can be used.But in the case where black using metal nanoparticle, in order to which electric conductivity is presented, it is necessary at
For the state that conducting particles densely contacts each other, when forming whole face film, when vertical view, there's almost no opening portion 20.Therefore,
In order to form the pattern with opening portion 20, the filament figure for example as shown in Fig. 2 (b), with opening portion 20 is needed to form
Case (pattern of metal fine 19).Thread pattern can be regularly formed, and can also irregularly be formed, can also be according to such as network diagramming
There is case the mode of cross part to be formed like that.So-called herein " metal nanoparticle ", refer to have the partial size with nm grades it is spherical,
The particle of horn shape, flat [plate] shape etc., preferably spherical shape.
When the total light transmittance of the substrate of conductive pattern 14 after foring printing is 80% or more, it can be ensured that for making
The sufficient gap that 1st resin layer 12 is contacted with aftermentioned 2nd resin layer 16, thus preferably.
Next, by cover conductive pattern it is at least part of in a manner of form the 2nd resin layer (coating) 16 (S5: the 2
Resin layer formation process).The available method same as S1 above-mentioned (the 1st resin layer formation process) of the process is implemented.It is so-called
"at least a portion", including whole.For example, in order to turned on outside and in the case where expose a part as electrode portion,
The part is not coated.In this case, become the state for being coated a part.Herein, the 2nd resin layer 16 by comprising can with constitute
2nd resin combination of the 2nd functional group of the 1st functional group's co-curing for including in the 1st resin combination of above-mentioned 1st resin layer 12
Object is constituted.After the 2nd resin layer formation process (S5), the 1st resin layer 12 is made based on above-mentioned 1st functional group and the 2nd functional group
With 16 co-curing of the 2nd resin layer (S6: co-curing process (illustration omitted)).That is, making the 1st function for including in the 1st resin layer 12
Group is cured with the 2nd functional group for including in the 2nd resin layer 16 reacts.Conductive pattern 14 has opening portion in thickness direction
20, the 2nd resin combination for constituting the 2nd resin layer 16 enters the opening portion 20, occurs admittedly with the interface of the 1st resin layer 12
Change reaction.That is, in the opening portion of conductive pattern 14 20, the 1st functional group and the 2nd resin layer 16 with the 1st resin layer 12
The curing reaction part of 2nd functional group.As a result, conductive pattern 14 is clamped by the 1st resin layer 12 with the 2nd resin layer 16
(sandwich), it and in the opening portion of conductive pattern 14 20 is kept, can be obtained has good adaptation with substrate 10
Conductive pattern 14.The combination of 2nd functional group of the 1st functional group and the 2nd resin layer 16 as the 1st resin layer 12, can enumerate example
Such as carboxyl/epoxy, epoxy group/carboxyl, hydroxyl/carboxyl, (methyl) acryloyl group/vinyl, vinyl/(methyl) acryloyl
Base, allyl/(methyl) acryloyl group etc., but it is not limited to these.
2nd resin combination of the 2nd resin layer 16 of the 1st resin combination and composition as above-mentioned the 1st resin layer 12 of composition
The combination of object can be enumerated according to the sequence of (the 1st resin layer: the 2nd resin layer): ((the 1st functional group is for polyurethane containing carboxyl
Carboxyl): the mixture of polyurethane and epoxide containing carboxyl (the 2nd functional group is epoxy group)), (phenol novolacs
Type epoxy resin (the 1st functional group is epoxy group): phenol novolak type epoxy resin (the 2nd functional group is epoxy group)), (benzene
Oxygroup resin (the 1st functional group is epoxy group): phenoxy resin (the 2nd functional group is epoxy group)), (polyurethane containing carboxyl
(the 1st functional group is carboxyl): phenoxy resin (the 2nd functional group is epoxy group)), (polyurethane containing carboxyl with carboxyl base
Mixture (1st functional group be carboxyl) of the quasi- meter lower than the epoxide of 1 equivalent: the polyurethane containing carboxyl with carboxyl base
Standard is calculated as the mixture (the 2nd functional group be epoxy group) of the epoxide of 1 equivalent or more), (dially phthalate resin
(the 1st functional group is allyl): (the 2nd functional group is alkene to the mixture of dially phthalate resin and acrylate monomer
Propyl and acryloyl group)) etc..
In said combination, contain in the 1st resin combination comprising the polyurethane containing carboxyl, the 2nd resin combination
In the case where the combination of the polyurethane and epoxide of carboxyl, by adding to the 1st resin layer 12 and the 2nd resin layer 16
Heat, thus make the carboxyl (the 1st functional group) of the polyurethane containing carboxyl for including in the 1st resin layer 12 and the 2nd resin layer 16 with
The epoxy group (the 2nd functional group) of epoxide is bonded and co-curing occurs.1st resin combination includes the poly- ammonia containing carboxyl
Ester and lower than the epoxide of 1 equivalent, the 2nd resin combination include the polyurethane containing carboxyl and with carboxylic in terms of carboxyl benchmark
Base benchmark is calculated as the case where combination of the epoxide of 1 equivalent or more and co-curing similarly occurs.In addition, in phenol novolac
Type epoxy resin combination is each other, in the case where phenoxy resin composition combination with one another, pass through addition ring appropriate
Oxygen resin curing agent simultaneously carries out heating to which co-curing occur.In this case, the 1st functional group and the 2nd functional group become
Epoxy group.In addition, including phenoxy resin comprising the polyurethane containing carboxyl, the 2nd resin combination in the 1st resin combination
In the case where combination, by being heated to the 1st resin layer 12 and the 2nd resin layer 16, thus carboxyl (the 1st functional group) and epoxy
Base (the 2nd functional group) is bonded and co-curing occurs.In addition, including dially phthalate resin (the in the 1st resin combination
1 functional group be allyl), the 2nd resin combination include dially phthalate resin and acrylate monomer (the 2nd function
Group is allyl and acryloyl group) combination in the case where, by carrying out light irradiation to carry out addition polymerization occur it is solid altogether
Change.
Herein, aforesaid substrate 10, the 1st resin layer 12, conductive pattern 14 and the 2nd resin layer 16 are preferably transparent.As a result,
It can be applied to the transparent elements such as touch panel.It is so-called transparent herein, refer to that total light transmittance is 80% or more.Comprising them
At the total light transmittance of conductive film of the invention of composition be preferably 70% or more, more preferably 75% or more, further
Preferably 80% or more.
Embodiment
Hereinafter, illustrating the embodiment of the present invention.It should be noted that embodiment below is for will be readily understood that this
Invention, the present invention are not restricted by the embodiments.
In the present embodiment, the molecular weight and acid value of resin and the total light transmittance of conductive pattern and sheet resistance according to
Following manner measurement.
< molecular weight >
The value by weight of polystyrene measured using gel permeation chromatography (hereinafter referred to as GPC).
The determination condition of GPC is as described below.
Device name: Japan Spectroscopy Corporation HPLC unit HSS-2000
Column: Shodex column LF-804
Mobile phase: tetrahydrofuran
Flow velocity: 1.0mL/min
Detector: Japan Spectroscopy Corporation RI-2031Plus
Temperature: 40.0 DEG C
Sample size: 100 μ L of sample loop
Sample solution concentration: it is prepared into about 0.1 mass %
< acid value >
With precision balance precise about 0.2g sample to 100ml conical flask, ethanol/toluene=1/2 (matter is added thereto
Amount ratio) mixed solvent 10ml dissolved.In turn, into the container 1~3 drop ethanolic phenolphthalein solution of addition as indicator,
It is sufficiently stirred until sample becomes uniform.It is titrated with 0.1N potassium hydroxide-ethanol solution, by the blush of indicator
Terminal when continuing 30 seconds as neutralization.Using by its result, the value for using following calculating formulas to obtain as the acid value of resin.
Acid value (mg-KOH/g)=(B × f × 5.611)/S
The usage amount (ml) of B:0.1N potassium hydroxide-ethanol solution
The factor of f:0.1N potassium hydroxide-ethanol solution
S: the collection capacity (g) of sample
< total light transmittance >
It is that the conductive pattern formed on substrate is cut with 50mm square, uses nephelometer (NDH2000, Japan's electricity color work
Industry system) be measured obtained from value.
< sheet resistance >
Use resistrivity meter ロ レ ス タ (registered trademark) GP MCP-T610 type (Mitsubishi Chemical ア Na リ テ ッ Network system), benefit
It is measured with 4 terminal methods.Mode determination and ESP mode has been used using terminal.
< contains the synthesis example > of the polyurethane of carboxyl
[synthesis example 1]
To with agitating device, thermometer, condenser 2L three-necked bottle in, be loaded as the C- of polyol compound
(Co., Ltd.'s Network ラ レ system, polycarbonate glycol, raw material glycol molar ratio are 1,9- nonanediol: 2- methyl-1,8- are pungent by 1015N
Glycol=15:85, molecular weight 964) 143.6g, 2, the 2- dimethylolpropionic acid (day as the dihydroxy compounds with carboxyl
This chemical conversion Co. Ltd. system) 27.32g and the propylene glycol monomethyl ether (trade name: acetic acid methoxy propyl as solvent
Ester, ダ イ セ Le Co. Ltd. system) 259g, dissolve above-mentioned 2,2- dimethylolpropionic acid in 90 DEG C.
The temperature of reaction solution is reduced to 70 DEG C, using dropping funel, the デ being added dropwise through 30 minutes as polyisocyanates
(di-2-ethylhexylphosphine oxide (4- cyclohexyl isocyanate) firmly changes バ イ エ Le ウ レ タ Application strain formula to ス モ ジ ュ ー Le (registered trademark)-W
Commercial firm's system) 87.5g.After completion of dropwise addition, 120 DEG C are warming up to, carries out reacting for 6 hours in 120 DEG C, isocyanates confirmed by IR
After basic disappearance, isobutanol 0.5g is added, and then react within 6 hours in 120 DEG C.The weight of the obtained polyurethane containing carboxyl
Average molecular weight is 32300, and the acid value of the resin is 40mgKOH/g.
[synthesis example 2]
In addition to having used C-1015N (Co., Ltd.'s Network ラ レ system) 44.8g, 2,2- dimethylolpropionic acid (Japanization strain
Formula commercial firm system) 16.1g and propylene glycol monomethyl ether (ダ イ セ Le Co. Ltd. system) 100.3g, デ as solvent
It is same with synthesis example 1 except ス モ ジ ュ ー Le (registered trademark)-W (firmly changing バ イ エ Le ウ レ タ Application Co. Ltd. system) 40.7g
It operates to sample, obtains the polyurethane containing carboxyl.The weight average molecular weight of the obtained polyurethane containing carboxyl is 29200, the tree
The acid value of rouge is 60mgKOH/g.
[embodiment 1]
As shown in table 1 like that, in (eastern レ (strain) the Le ミ ラ ー processed (registration of PET (polyethylene terephthalate) substrate
Trade mark) 125T60) on, using bar coater printer's ink, the ink is to cooperate the polyurethane tree containing carboxyl synthesized in synthesis example 1
Rouge and キ ュ ア ゾ ー Le (registered trademark) 2P4MHZ-PW (2- phenyl -4- methyl -5- hydroxymethyl as curing accelerator
Imidazoles adds 1 mass parts relative to 100 mass parts of resin) and become 30 with the resin component concentration comprising curing accelerator
The mode of quality % is diluted with propylene glycol monomethyl ether and is formed and (be equivalent to the 1st resin combination), in 100
DEG C carry out drying in 1 hour, is formed film thickness for 10 μm (using ミ Star ト ヨ high-precision digital-display micrometer (digimatic
Micrometer) MDH-25M 293-100, measurement arbitrary 5 at obtained from average value) priming coat (be equivalent to the 1st resin
Layer).The thickness of priming coat passes through the thickness including substrate after measurement forms priming coat and is dried and subtracts the thickness of substrate
It spends and finds out.
After drying, implement tackiness evaluation based on JIS Z0237.The case where all balls are not stopped is as no hair
It is viscous, the state table that any ball stops is shown with tacky.
After it confirmed without tacky (without tackiness), silver nanowires dispersion liquid is made, and (by silver nanowires 0.125g, (line is average
Diameter is about 40nm, and average length is about 10 μm, is the number mean value by SEM 100 silver nanowiress arbitrarily observed) point
Dissipate in ethyl alcohol 50g (preparation 0.25 mass % dispersion liquid of silver nanowires)), using dispersion liquid 0.05g, using bar coater, with not
The mode overflowed from priming coat is coated.The coating of silver nanowires dispersion liquid has been carried out well.It is coated with silver nanowires dispersion
It after liquid, carries out being burnt into for 1 hour in 100 DEG C, forms the conductive pattern of whole face shape.Sheet resistance after firing is 80 Ω/, Quan Guang
Line transmitance is 89%.
Then, as coating (being equivalent to the 2nd resin layer), using bar coater, to cover the substantially entire surface of conductive pattern
Mode printer's ink, in 140 DEG C of progress, 1 hour co-curing, the ink is the polyurethane containing carboxyl synthesized in synthesis example 1
In resin 10g and epoxide (Mitsubishi Chemical jER (registered trademark) 828) 0.69g, cooperate relative to poly- containing carboxyl
It is 1 mass parts for 100 mass parts of total amount of urethane resin and epoxide (Mitsubishi Chemical jER (registered trademark) 828)
Curing accelerator (four countries be melted into processed キ ュ ア ゾ ー Le (registered trademark) 2P4MHZ-PW) and what is formed (be equivalent to the 2nd resin
Composition uses propylene glycol monomethyl ether in such a way that the resin component concentration comprising curing accelerator becomes 30 mass %
Dilution).Whole film thickness until including priming coat is 20 μm.If relative to the poly- ammonia containing carboxyl synthesized in synthesis example 1
100 mass parts of ester resin cooperate the epoxide (Mitsubishi Chemical jER (registered trademark) 828) of 6 mass parts, then synthesis example 1
The carboxyl of the polyurethane resin containing carboxyl of middle synthesis and epoxide (Mitsubishi Chemical jER (registered trademark) 828)
Epoxy group becomes 1 equivalent.For the coating (being equivalent to the 2nd resin layer) of embodiment 1, as shown in Table 1, make to synthesize
The cooperation of the polyurethane resin containing carboxyl and epoxide (Mitsubishi Chemical jER (registered trademark) 828) that are synthesized in example 1
It is 100 to 7 (being recorded as 100/7 in table 1) than (mass ratio), therefore, becomes following compositions: relative to what is synthesized in synthesis example 1
For the carboxyl of polyurethane resin containing carboxyl, the epoxy group of epoxide (Mitsubishi Chemical jER (registered trademark) 828)
Slightly excessively exist.
For obtained conductive film, evaluating characteristics below are carried out.Show the result in table 1.
(adaptation evaluates (disbonded test))
It for cured film, is evaluated as adaptation, carries out cross cut test (cross cut test) JIS K5600.It will knot
Fruit is recorded in table 1,2 as " disbonded test ".It should be noted that the numerical value of test result is smaller, adaptation (resistance to stripping is indicated
From property) higher (most preferably 0).In table 1, the disbonded test result of embodiment 1 is 0, it is known that adaptation (peel resistance) is high.
(marresistance test)
It tests, is simply determined by paper friction scratch resistance as marresistance.For the paper used, JK is used
ワ イ パ ー, reciprocal 5 times on the cover layer.By visual observation and microscope, confirmation have not damaged, scratch.Using result as " anti-scratch
Wound property is tested " and it is recorded in table 1,2.
◎: by visual observation and microscope does not observe damage, scratch.
Zero: not observing damage by visual observation, but Slight abrasion marks are observed by microscope.
△: it does not observe damage by visual observation, but damage, scratch is observed by microscope.
×: damage, scratch can be differentiated by visual observation.
(environmental resistance)
As environmental resistance, using Constant Temperature and Humidity Chambers (ETAC TH402A), in 85 DEG C, 85%RH (relative humidity) atmosphere
Lower preservation is changed with the ratio relative to initial surface resistivity to measure the sheet resistance until after about 1100 hours.It will knot
Fruit is shown in Fig. 3.
(optical characteristics)
As optical characteristics, obtained conductive film is measured using Haze meter NDH 2000 (Japan's electricity color system)
HAZE (mist degree) and determination of light transmittance.Table 1,2 is recorded in using result as " optical characteristics ".
Zero: total light transmittance is 80% or more and HAZE is 20% or less
×: total light transmittance is that 80% or more and HAZE is higher than 20%
[embodiment 2~6]
Using the ink prepared similarly to Example 1 other than being changed to material shown in table 1 and constituting, by same
Thickness is constituted, same process forms priming coat, conductive pattern and coating.Carry out adaptation evaluation similarly to Example 1
The test of (disbonded test), marresistance, optical characteristics evaluation, show the result in table 1.If in the coating relative to embodiment 2
100 mass parts of polyurethane resin containing carboxyl synthesized in the synthesis example 2 used cooperate epoxide (Mitsubishi Chemical's system
JER (registered trademark) 828) 9 mass parts, then the carboxyl and epoxidation of the polyurethane resin containing carboxyl synthesized in synthesis example 2
The epoxy group for closing object (Mitsubishi Chemical jER (registered trademark) 828) becomes 1 equivalent.The coating of embodiment 2 (is equivalent to
2nd resin layer) for, as shown in Table 1, make the polyurethane resin and epoxy compound containing carboxyl synthesized in synthesis example 2
The match ratio (mass ratio) of object (Mitsubishi Chemical jER (registered trademark) 828) is 100 to 10 (being recorded as 100/10 in table 1), because
This, becomes following compositions: for the carboxyl of the polyurethane resin containing carboxyl synthesized in synthesis example 2, epoxy compound
The epoxy group of object (Mitsubishi Chemical jER (registered trademark) 828) slightly excessively exists.
In addition, for the priming coat (being equivalent to the 1st resin layer) of embodiment 6, as shown in Table 1, make synthesis example 1
The polyurethane resin containing carboxyl of middle synthesis and the match ratio of epoxide (Mitsubishi Chemical jER (registered trademark) 828)
(mass ratio) is 100 to 3 (being recorded as 100/3 in table 1), and therefore, become following compositions: what is synthesized in synthesis example 1 contains carboxyl
Polyurethane resin carboxyl remain half.It should be noted that the coating (being equivalent to the 2nd resin layer) of embodiment 6 and reality
It is same to apply example 1.
[embodiment 7]
Using the ink prepared similarly to Example 1 other than being changed to material shown in table 1 and constituting, by same
Thickness is constituted, same process forms priming coat, conductive pattern and coating.At this point, the curing accelerator as coating, generation
For キ ュ ア ゾ ー Le (registered trademark) 2P4MHZ-PW (four countries' chemical conversion system), IRGACURE (registered trademark) 184 has been used
(BASF AG's system).It should be noted that using small-sized UV irradiation unit QRU-2161- instead of 140 DEG C of solidifications in 1 hour
Z11-00 (Co., Ltd.'s オ ー Network makes institute), carries out about 40mW/cm2Exposure, thus carries out co-curing.It carries out and embodiment 1
Same adaptation evaluation (disbonded test), marresistance test, optical characteristics evaluation, show the result in table 1.
[comparative example 1]
Material shown in table 2 is changed to constitute and form priming coat.Priming coat is liquid state, tacky serious, even if sharp
With other print processes such as ink-jet, the printing for carrying out silver nanowires ink is also failed to.Think that reason is: molecular weight in other examples
It is 10,000 or more, in contrast, the molecular weight of the resin of comparative example 1 is small, is 4100.
[comparative example 2~5]
Using the ink prepared similarly to Example 1 other than being changed to material shown in table 2 and constituting, by same
Thickness is constituted, same process forms priming coat, conductive pattern and coating.Wherein, comparative example 4 carries out about 40mW/cm2UV
Light exposure, carries out and the comparable processing of co-curing.The adaptation carried out similarly to Example 1 evaluates (disbonded test), scratch resistance
Property test, optical characteristics evaluation, show the result in table 2.
In Examples 1 to 4, passed through using identical resin component when carrying out co-curing in priming coat and coating
The chemical bonding of priming coat and coating and it is closely sealed, it is not peeling-off.
In embodiment 5, different resin components are used in priming coat and coating, but due to co-curable
Functional group, thus, there is no the removings after solidification between priming coat and coating.In contrast, in comparative example 4,5, the bottom of at
The resin that have used curing mechanism in coating and coating different implements UV solidification, real in comparative example 5 in comparative example 4
In the case where having applied heat cure, co-curing does not occur for priming coat and coating, peeling-off between priming coat and coating.
In addition, in embodiment 6, as priming coat, with the ratio of functional group (carboxyl) residual half to poly- containing carboxyl
Epoxide (Mitsubishi Chemical jER (registered trademark) 828) is added in urethane, under 100 DEG C of 1 hour drying conditions, at
It is also closely sealed with coating by chemical bonding by residual functionality for appropriate state as semi-solid preparation, thus, there is no
Removing between priming coat and coating.It in contrast, is used in priming coat and coating for comparative example 2 and 3
The condition that resin can be fully cured, at the time point for foring priming coat (100 DEG C, drying in 1 hour), that reacts with coating is residual
Remaining functional group disappears in priming coat, therefore, peeling-off between priming coat and coating (disbonded test result is 5).
According to Examples 1 to 6 and comparative example 2~5 it is found that carrying out the superiority of co-curing.
[table 1]
[table 2]
[comparative example 6]
Other than being not provided with priming coat, for composition similarly to Example 1.Similarly to Example 1 closely sealed is carried out
Property evaluation (disbonded test), marresistance test, optical characteristics evaluation, show the result in table 2.Disbonded test, scratch resistance test
Well, but due to base coat, thus when heating to the pet substrate after silver coating nanowire dispersion, full light is saturating
Crossing rate reduces by 5% or more, but is 80% or more.However, HAZE is 2% before heating, but after the heating more than 50%, optics is special
Property is substantially damaged.By heating, oligomer is precipitated from pet substrate, and surface roughness increases, and therefore, damages optical characteristics.
[comparative example 7]
For a comparative example for being not provided with coating.Carried out similarly to Example 1 adaptation evaluation (disbonded test),
Marresistance test, optical characteristics evaluation, show the result in table 2.Since there is no coating, therefore, tried by marresistance
It tests, damage is generated in metal portion, in addition, the result of environmental resistance similarly to Example 1 as shown in Figure 3 is it is found that passing through
After about 700 hours, resistance starts to significantly rise, and environmental resistance is low.
Description of symbols
10 substrates, 12 the 1st resin layers, 14 conductive patterns, 16 the 2nd resin layers, 18 metal nanometer lines, 19 metal fines, 20
Opening portion.
Claims (10)
1. a kind of manufacturing method of conductive film comprising following processes:
The process that the 1st resin layer is formed on substrate using the 1st resin combination comprising the 1st functional group,
The process of the conductive pattern with opening portion when forming vertical view on aforementioned 1st resin layer,
Using comprising can be with the 2nd resin combination of the 2nd functional group of the 1st functional group's co-curing of aforementioned 1st resin layer with quilt
The process that at least part of mode of aforesaid conductive pattern forms the 2nd resin layer is covered, and
Make the process of aforementioned 1st resin layer and the 2nd resin layer co-curing.
2. the manufacturing method of conductive film according to claim 1, wherein become on the surface of aforementioned 1st resin layer without viscous
Property after, formed aforesaid conductive pattern.
3. the manufacturing method of conductive film according to claim 1 or 2, wherein aforementioned 1st functional group include carboxyl, hydroxyl,
It is epoxy group, (methyl) acryloyl group, vinyl, any number of in allyl.
4. the manufacturing method of conductive film according to claim 1 or 2, wherein aforementioned 1st resin combination contains carboxylic
Polyurethane, phenol novolak type epoxy resin, phenoxy resin, the polyurethane containing carboxyl of base are low in terms of carboxyl benchmark
It is any number of in the mixture, dially phthalate resin of the epoxide of 1 equivalent.
5. the manufacturing method of conductive film according to claim 1 or 2, wherein aforementioned 2nd resin combination contains carboxylic
The polyurethane of base and the mixture of epoxide, phenol novolak type epoxy resin, phenoxy resin, gathering containing carboxyl
Mixture, dially phthalate resin and the propylene of urethane and the epoxide that 1 equivalent or more is calculated as with carboxyl benchmark
It is any number of in the mixture of acid ester monomer.
6. the manufacturing method of conductive film according to claim 1 or 2, wherein aforesaid base plate, the 1st resin layer, conductive pattern
And the 2nd resin layer be transparent.
7. a kind of conductive film, wherein there is the 1st resin layer comprising the 1st functional group on substrate, have on the 1st resin layer
Conductive pattern with opening portion when having vertical view, by be coated the conductive pattern it is at least part of in a manner of be formed with comprising the 2nd
2nd resin layer of functional group, also, the 1st functional group in aforesaid conductive pattern openings portion with aforementioned 1st resin layer and the
The curing reaction part of 2nd functional group of 2 resin layers.
8. conductive film according to claim 7, wherein total light transmittance is 70% or more.
9. conductive film according to claim 7 or 8, wherein aforesaid conductive pattern includes to have unordered cross-contact portion
Metal nanometer line.
10. conductive film according to claim 7 or 8, wherein aforesaid conductive pattern includes regularly or irregularly to be formed
Metal fine pattern.
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| JP2015-150490 | 2015-07-30 | ||
| JP2015150490 | 2015-07-30 | ||
| PCT/JP2016/071920 WO2017018427A1 (en) | 2015-07-30 | 2016-07-26 | Method for producing conductive film, and conductive film |
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| JP (1) | JP6664396B2 (en) |
| KR (1) | KR102000956B1 (en) |
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| JP2019206738A (en) * | 2018-05-30 | 2019-12-05 | Ｄｏｗａエレクトロニクス株式会社 | Silver nanowire ink, transparent conductive film producing method and transparent conductive film |
| JPWO2020137144A1 (en) * | 2018-12-27 | 2021-10-21 | 富士フイルム株式会社 | Photosensitive transfer material, laminate, touch panel, patterned substrate manufacturing method, circuit board manufacturing method, and touch panel manufacturing method |
| CN113316743A (en) * | 2018-12-27 | 2021-08-27 | 富士胶片株式会社 | Conductive transfer material, method for manufacturing substrate having pattern, method for manufacturing circuit substrate, laminate, and touch panel |
| US11590746B2 (en) * | 2019-07-18 | 2023-02-28 | The Boeing Company | Elimination of surfacing film and primer from composite substrates |
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| WO2010082428A1 (en) * | 2009-01-19 | 2010-07-22 | コニカミノルタホールディングス株式会社 | Transparent electrode, method for producing same, and organic electroluminescent element |
| CN104073178A (en) * | 2013-03-29 | 2014-10-01 | 第一毛织株式会社 | Anisotropic conductive film including conductive adhesive layer and semiconductor device connected by the same |
| JP2015131429A (en) * | 2014-01-14 | 2015-07-23 | 東レ株式会社 | Conductive laminate, and touch panel and electronic paper using the same |
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| JPS569008B2 (en) | 1973-06-25 | 1981-02-26 | ||
| JP2002164247A (en) * | 2000-11-24 | 2002-06-07 | Murata Mfg Co Ltd | Dielectric ceramic composition and layered ceramic capacitor |
| CN102324462B (en) | 2006-10-12 | 2015-07-01 | 凯博瑞奥斯技术公司 | Nanowire-based transparent conductors and applications thereof |
| KR20110103835A (en) * | 2008-12-02 | 2011-09-21 | 다이니폰 인사츠 가부시키가이샤 | Electromagnetic wave shielding material, and method for manufacturing same |
| JP2013200943A (en) | 2012-03-23 | 2013-10-03 | Toray Advanced Film Co Ltd | Transparent conductive film and manufacturing method of the same, and touch panel |
| JP2014075215A (en) * | 2012-10-03 | 2014-04-24 | Sekisui Chem Co Ltd | Insulation material, multilayer film, laminate, connection structure, production method of laminate, and production method of connection structure |
| JP2014191894A (en) | 2013-03-26 | 2014-10-06 | Dic Corp | Transparent electroconductive film and touch panel |
| KR20150084689A (en) * | 2014-01-14 | 2015-07-22 | 주식회사 동진쎄미켐 | Transparent conductive electrode and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010082428A1 (en) * | 2009-01-19 | 2010-07-22 | コニカミノルタホールディングス株式会社 | Transparent electrode, method for producing same, and organic electroluminescent element |
| CN104073178A (en) * | 2013-03-29 | 2014-10-01 | 第一毛织株式会社 | Anisotropic conductive film including conductive adhesive layer and semiconductor device connected by the same |
| JP2015131429A (en) * | 2014-01-14 | 2015-07-23 | 東レ株式会社 | Conductive laminate, and touch panel and electronic paper using the same |
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| TW201718247A (en) | 2017-06-01 |
| JPWO2017018427A1 (en) | 2018-05-24 |
| WO2017018427A1 (en) | 2017-02-02 |
| KR20170133483A (en) | 2017-12-05 |
| CN107615408A (en) | 2018-01-19 |
| TWI693160B (en) | 2020-05-11 |
| JP6664396B2 (en) | 2020-03-13 |
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