CN107533882A - The manufacture method of nesa coating and nesa coating - Google Patents
The manufacture method of nesa coating and nesa coating Download PDFInfo
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- CN107533882A CN107533882A CN201680023533.9A CN201680023533A CN107533882A CN 107533882 A CN107533882 A CN 107533882A CN 201680023533 A CN201680023533 A CN 201680023533A CN 107533882 A CN107533882 A CN 107533882A
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- Prior art keywords
- base material
- resin base
- nesa coating
- resin
- conductive layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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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
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
Abstract
The problem of the present invention is the excellent adhesion for providing conductive layer and resin base material and nesa coating and the manufacture method of nesa coating with good electric conductivity and the transparency.The nesa coating of the present invention is the nesa coating for having resin base material and conductive layer, it is characterised in that the principal component of above-mentioned resin base material is cyclic olefine resin, and the skin section of above-mentioned resin base material is with 1 × 10‑6~1 × 10‑3Quality % scope contains metal ingredient, and when above-mentioned resin base material is immersed in water, the water content of the per unit volume of the skin section of above-mentioned resin base material is adjusted in the way of turning into relative to the water content of the per unit volume in the middle level portion of above-mentioned resin base material in the range of 120~300%.
Description
Technical field
The present invention relates to the manufacture method of nesa coating and nesa coating.More specifically, it is related to conductive layer and tree
The excellent adhesion of aliphatic radical material and the nesa coating with good electric conductivity and the transparency and the manufacturer of nesa coating
Method.
Background technology
In recent years, use always in liquid crystal display, plasma display, inorganic and organic EL (electroluminescent) displays
The electrically conducting transparent of conductive layer is laminated with the resin base material of the various display devices such as device, touch panel, solar cell (equipment)
Film.
For possessing the equipment of nesa coating, while requiring that large screen is light-duty lightening, there is a perceived need to
Get both higher image quality, operation precision and response speed, and the important ratio ever of high electric conductivity and the transparency is all
Greatly.However, as equipment realizes large screen, user appreciates image from wider array of visual angle, as a result the display device from oblique
When, there is interference fringe, irregular colour in picture, and visual reduce of equipment turns into the problem of important.
In view of the above-mentioned problems, disclose by making the face direction of resin base material postpone (Ro values) as in the range of ± 50nm,
And visual method is improved using cyclic olefine resin (for example, referring to patent document 1).
When forming conductive layer using cyclic olefine resin as resin base material, reduced to suppress to turn into equipment performance
An important factor for the change in size of resin base material, conductive thickness it is uneven, it is desirable to using rubbing method, ink-jet method, cladding process,
The wet processings such as infusion process form conductive layer, it is necessary to improve the water miscible conductive layer coating fluid with being used in wet processing
The adaptation of (ink).
In addition, disclose by implementing sided corona treatment, atmospheric plasma treatment, Excimer uv processing to resin base material
To improve the method for adaptation (for example, referring to patent document 2), but these methods need high machining energy, so expecting one
Kind does not need the method that high machining energy can just form smooth conductive layer.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2014-54760 publications
Patent document 2:Japanese Unexamined Patent Publication 2015-12046 publications
The content of the invention
The present invention in view of the above problems situation and carry out, its solve problem be to provide conductive layer and resin base material
Excellent adhesion and with good electric conductivity and the transparency nesa coating and nesa coating manufacture method.
The present inventor etc. have made intensive studies to solve above-mentioned problem, as a result find by making resin base material
Skin section contains the metal ingredient of specified quantitative, and makes the skin section of above-mentioned resin base material that there is specific moisture content can solve the problem that
Problem is stated, so as to complete the present invention.
That is, above-mentioned problem of the present invention solves by following means.
1. a kind of nesa coating, it is the nesa coating with resin base material and conductive layer, it is characterised in that
The principal component of above-mentioned resin base material is cyclic olefine resin,
The skin section of above-mentioned resin base material is in 1 × 10-6~1 × 10-3Contain metal ingredient in the range of quality %, and,
During according to above-mentioned resin base material is immersed in water, the per unit volume of the skin section of above-mentioned resin base material it is aqueous
Amount turns into the mode in the range of 120~300% relative to the water content of the per unit volume in the middle level portion of above-mentioned resin base material
It is adjusted.
2. according to the nesa coating described in the 1st, it is characterised in that above-mentioned metal ingredient contain gold, silver, copper, iron,
Any of aluminium, nickel, magnesium, zinc and their alloy.
3. according to the nesa coating described in the 1st or the 2nd, it is characterised in that above-mentioned conductive layer is metal conducting layer.
4. a kind of manufacture method of nesa coating, it is to manufacture the nesa coating any one of the 1st~the 3rd
Electrically conducting transparent film manufacturing method, it is characterised in that
Using the resin combination containing cyclic olefine resin, organic polar solvent, organic non-polar solven and water simultaneously
Formed using solution casting method in the process of resin base material, turned into according to the content of the metal ingredient of the skin section of the resin base material
1×10-6~1 × 10-3Mode in the range of quality % is adjusted, and,
During according to above-mentioned resin base material is immersed in water, the per unit volume of the skin section of above-mentioned resin base material it is aqueous
Amount turns into the mode in the range of 120~300% relative to the water content of the per unit volume in the middle level portion of above-mentioned resin base material
It is adjusted.
5. the manufacture method of the nesa coating according to the 4th, it is characterised in that form above-mentioned lead using ink-jet method
Electric layer.
Pass through the above-mentioned means of the present invention, using the teaching of the invention it is possible to provide the excellent adhesion of conductive layer and resin base material and with good
The manufacture method of the nesa coating and nesa coating of electric conductivity and the transparency.
The Mechanism or mechanism of action of the effect of the present invention are still not clear, following to speculate.
Speculate the water content of per unit volume of the skin section by making resin base material relative to above-mentioned resin base material
In the range of the water content of the per unit volume in middle level portion is 120~300%, the permeability of conductive layer coating fluid improves.Separately
Outside, by content 1 × 10-6~1 × 10-3The metal ingredient of skin section containing above-mentioned resin base material in the range of quality %,
So as to which the conductive material contained with conductive layer produces interaction, obtained in resin base material and conductive layer excellent closely sealed
Property, obtain the nesa coating with good electric conductivity and the transparency.
Brief description of the drawings
Fig. 1 is the schematic diagram for representing the example that the layer of the nesa coating of the present invention is formed.
Embodiment
The nesa coating of the present invention is the nesa coating for having resin base material and conductive layer, it is characterised in that above-mentioned
The principal component of resin base material is cyclic olefine resin, and the skin section of above-mentioned resin base material is 1 × 10-6~1 × 10-3Quality %'s
In the range of contain metal ingredient, and, during according to above-mentioned resin base material is immersed in water, the skin section of above-mentioned resin base material it is every
The water content of unit volume turns into 120~300% relative to the water content of the per unit volume in the middle level portion of above-mentioned resin base material
In the range of mode adjust.
This feature is the common technical characteristic of invention that each technical scheme is related to.
As embodiments of the present invention, from the viewpoint of the effect of the present invention shows, i.e., from conductive layer and resin base
From the viewpoint of the adaptation of material, electric conductivity or the transparency, preferably above-mentioned metal ingredient contain gold, silver, copper, iron, aluminium, nickel,
Any of magnesium, zinc and their alloy.
In addition, in the present invention, from the adaptation or electric conductivity of conductive layer and resin base material from the viewpoint of, it is preferably above-mentioned
Conductive layer is metal conducting layer.
As the electrically conducting transparent film manufacturing method of the nesa coating of the manufacture present invention, the sight showed from the effect of the present invention
Point considers, is preferably using the resin combination containing cyclic olefine resin, organic polar solvent, organic non-polar solven and water
And using solution casting method formed resin base material process in, according to the skin section of the resin base material metal ingredient content into
For 1 × 10-6~1 × 10-3Mode in the range of quality % adjusts, and during according to above-mentioned resin base material is immersed in water, on
The water content of the per unit volume of the skin section of resin base material is stated relative to the per unit volume in the middle level portion of above-mentioned resin base material
Water content turn into 120~300% in the range of mode adjust.
In addition, in the present invention, from the viewpoint of the adaptation for improving conductive layer and resin base material is such, preferably by spray
The method of the use of ink and water forms above-mentioned conductive layer.
Hereinafter, the present invention and its inscape and the form mode for implementing the present invention are described in detail.Should
Give explanation, "~" shown in the present invention including being recorded in the numerical value before and after it as the implication of lower limit and higher limit to make
With.
《Nesa coating》
The nesa coating of the present invention has resin base material and conductive layer, and the principal component of above-mentioned resin base material is cyclic olefine
Resin, the skin section of above-mentioned resin base material is in 1 × 10-6~1 × 10-3Contain metal ingredient in the range of quality %, and, according to
When above-mentioned resin base material is immersed in water, the water content of the per unit volume of the skin section of above-mentioned resin base material is relative to above-mentioned
The mode that the water content of the per unit volume in the middle level portion of resin base material turns into the range of 120~300% adjusts.
Fig. 1 represents an example of the embodiment of the nesa coating of the present invention.For the nesa coating of the present invention
1, from the viewpoint of the adaptation for improving conductive layer and resin base material is such, preferred resin base material 2 connects with conductive layer 4.
In addition, with the water content of the per unit volume of the skin section 3 of resin base material 2 relative to the middle level portion 5 of resin base material 2
Per unit volume water content turn into 120~300% in the range of mode adjust.
Here skin section refers to model of the thickness direction from resin base material surface to thickness untill 0.1 μm in resin base material
Enclose.
In addition, two skin sections that the middle level portion of resin base material refers to have compared to above-mentioned resin base material are located at resin base
The region of the private side of material.
It should illustrate, as described above, it is preferred to the resin base material of the nesa coating of the present invention connects with conductive layer, but as long as
Not hinder the layer of adaptation, can also be arranged between resin base material and conductive layer.
＜ resin base materials ＞
For resin base material of the present invention, as long as cyclic olefin resins are principal component, in other words, resin is being formed
Contained in the resin combination of base material with highest ratio, other resin materials, compound can also be contained.In addition,
Can be that individual layer can also have sandwich construction.In the case of sandwich construction, as long as there is at least more than 1 layer by with cycloolefin
The layer that resin is formed for the resin combination of principal component, but seen from improving as the adaptation of conductive layer and resin base material
Point considers that the skin section of preferred resin base material is the layer formed by the resin combination using cyclic olefin resins as principal component.
Be not particularly limited as the material that resin base material uses, for example, can enumerate norbornene resin (such as
The polyester such as ARTON (JSR company systems), polyethylene terephthalate, PEN, polyethylene, polypropylene,
Glassine paper, cellulose acetate, cellulose acetate-butyrate, Cellacefate, cellulose-acetate propionate, triacetic acid are fine
Tie up cellulose esters or their derivatives such as element, nitrocellulose, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl
Alcohol, styrene-based resin, makrolon, ZEONEX, ZEONOR (Nippon Zeon's system)), polymethylpentene, polyethers
Ketone, polyether sulfone, polysulfones system resin, polyethers ketimide, polyamide, acrylic acid or polyacrylate system resin etc..The present invention
In, cellulose esters, makrolon, polyester or the polyacrylic acid such as norbornene resin, cellulose triacetate (TAC) can be enumerated
Deng.
Material, the containing ratio of metal ingredient contained in resin base material as principal component can be asked using nuclear magnetic resonance spectrometry
.
As the water content of resin base material, determine the quality of the resin base material determined in the environment of 23 DEG C 55% and incite somebody to action
The resin base material is immersed in the quality after 48 hours in water, the difference (variable quantity) of two measured values is obtained, by containing for per unit volume
Water is set to the overall water content of resin base material.
Specifically, for the water content in the middle level portion of resin base material, the two sides of resin base material is implemented to splash with copper
Penetrate, after the skin section of resin base material is removed, obtain the quality of the resin base material determined in the environment of 23 DEG C 55% with
Both differences (increase part) for the quality being immersed in water after 48 hours, the water content of per unit volume turns into the aqueous of middle level portion
Amount.In addition, subtract obtained middle level from the water content that the overall per unit volume of the resin base material after 48 hours is immersed in water
Value turns into the water content of the per unit volume of skin section obtained by the water content of the per unit volume in portion.
In the present invention, it is characterised by the water content of per unit volume of the skin section of resin base material relative to resin base material
In the range of the water content of the per unit volume in middle level portion is 120~300%.
In the present invention, the water content of the per unit volume of the skin section by making resin base material is relative in resin base material
The water content of the per unit volume in layer portion is more than 120%, so as to which conductive layer obtains good permeability with coating fluid.By making
Conductive layer penetrates into resin base material with coating fluid, so as to suppress in transmitted light caused by the interface of resin base material and conductive layer
Reflection.In addition, the water content of the per unit volume of skin section by making resin base material is less than 300%, can suppress by
The electrical conductivity caused by membrane of conducting layer is reduced in conductive layer coating fluid excessive permeation to resin base material.In addition, from
Electric conductivity, the transparency from the viewpoint of, more preferably the water content of the per unit volume in the middle level portion of resin base material be 150~
In the range of 250%.
Moisture content can suitably adjust according to the working condition of film, the working condition of the resin base material made, thickness etc..
Changed, from the viewpoint of resistance to bend(ing) from phase difference, resin base material preferably of the present invention 23 DEG C, it is relatively wet
Equilibrium moisture content under degree 80% is less than 3%, more preferably less than 1%.By making equilibrium moisture content be less than 3%, easily
Humidity change is tackled, optical characteristics, size are less susceptible to change, thus preferably.
Equilibrium moisture content is quantitative in the following way：By sample film in 23 DEG C, damping into the room of relative humidity 20%
After placing more than 4 hours, placed 24 hours in room of 23 DEG C of damping into 80%RH, do moisture at 150 DEG C of temperature
After pathogenic dryness, using micro-moisture meter (such as Mitsubishi chemical Co., Ltd's system, CA-20 types) and Karl_Fischer method pair is utilized
Sample is quantified.
It is preferred that metal ingredient of the present invention contains appointing in gold, silver, copper, iron, aluminium, nickel, magnesium, zinc and their alloy
It is a kind of.
The metal ingredient amount that the skin section of above-mentioned resin base material contains is 1 × 10-6~1 × 10-3In the range of quality %,
Preferable scope is 1 × 10-5~5 × 10-4Quality %.By for 1 × 10-3Below quality %, so as to suppress to send out this
When bright nesa coating is used for touch panel, becomes noise inside electrodiffusion to nesa coating and cause transducer sensitivity
Decline.
The assay method of the metal ingredient of skin section is as follows：Nesa coating is immersed in methyl ethyl ketone solution, only dissolved
Skin section.By the complete retarder thinner of obtained liquid, after carrying out ashing processing to it with electric furnace, added with ultra-pure water dilution with nitric acid
After solution obtained by heat of solution partition, the measure of amount of metal is carried out with ICP emission spectrometries (ICP-AES).
Skin section is calculated by the amount of metal obtained by the resin component quality and measure of the skin section obtained from lysate
Metal ingredient amount.
As make above-mentioned metal ingredient be localized in resin base material skin section an embodiment, with solution curtain coating
During legal system molding resins base material, there is the mixing contained using the resin combination used in the present invention (hereinafter also referred to as dopant)
The deliquescent mode of the boiling-point difference of solvent and above-mentioned mixed solvent and metal ingredient.
Specifically, dopant is cast on supporter, when being dried on supporter, waved from the face opposite with supporter
Hair, thus through-thickness produces distribution on supporter.Then volatilized if mixed solvent since low boiling point solvent, therefore
Through-thickness produces the distribution of low boiling point solvent and high boiling solvent.Now, according to the dissolubility of metal ingredient, after the drying
Film in through-thickness produce localization.When dissolubility of the metal ingredient in low boiling point solvent is higher than high boiling solvent, by
The direction (face opposite with supporter) of lower boiling solvent volatilization is inclined in compound, so being localized near surface.
＜ conductive layers ＞
It is preferred that conductive layer of the present invention is the metal conducting layer being made up of metal or metal oxide.As formation
The conductive material contained by conductive layer coating fluid used during conductive layer, is not particularly limited, for instance, it may be preferable to using silver, copper,
The particulate of copper/nickel alloy or its fired body, electroconductive polymer etc., a kind in them can be used or be applied in combination a variety of.
From the viewpoint of hardness, oxidation stability, particularly preferred copper, the particulate of copper/nickel alloy or its fired body.
Conductive layer can be individual layer, it is possible to have stepped construction.
The forming method of conductive layer is preferably wet processing, more preferably ink-jet method.This is due to by controlling conductive layer
Fine rule is able to easily form with the dispensing area of coating fluid, coating weight.In addition, for the fine rule formed with ink-jet method,
In fine rule section, line width has slowly change, therefore can obtain from the contact portion conductive layer surface of resin base material
The nesa coating excellent to the transparency.
(manufacture method of nesa coating)
The manufacture method of the nesa coating of the present invention is characterised by, is being used containing cyclic olefine resin, You Jiji
Property solvent, organic non-polar solven and water resin combination and using solution casting method formed resin base material process in, press
Turn into 1 × 10 according to the content of the metal ingredient of the skin section of the resin base material-6~1 × 10-3Mode in the range of quality % is adjusted
It is whole, and during according to above-mentioned resin base material is immersed in water, the water content of the per unit area of the skin section of resin base material is relative
Adjusted in the mode that the water content of the per unit area in the middle level portion of resin base material turns into the range of 120~300%.
First, the forming method as the resin base material used in nesa coating, for example, can enumerate extrusion by melting,
Method known to solution casting method (solution casting method), rolling process, compression forming methods etc..
(solution casting method)
As the solvent used in solution casting method, preferably using alcohol such as methanol, ethanol, isopropanol, n-butanol, 2- butanol
1 kind in series solvent or be used in mixed way it is a variety of, it can in addition contain which above-mentioned alcohol series solvent and following solvent are used in combination, the solvent
It is the chlorine series solvent such as chloroform, dichloromethane；The fragrant family solvents such as toluene, dimethylbenzene, benzene and their mixed solvent；Methyl is molten
Fine agent, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide (DMSO), twoAlkane, cyclohexanone, tetrahydrofuran, third
Ketone, MEK (MEK), ethyl acetate, diethyl ether, water etc..
As an embodiment of the nesa coating that the present invention is formed with solution casting method, preferably with following work
Sequence：The process for preparing resin combination (dopant), the process that dopant is cast on the supporter of banding or drum type, incite somebody to action
The dopant of curtain coating is dried to the process (the 1st drying process) of basement membrane, enters one from the process of supporter stripping, by the basement membrane of stripping
Process, the process of the resin base material of winding completion for walk dry process (the 2nd drying process), being stretched.
(1) dopant preparation section
Dopant preparation section is by adding mixing cyclic olefin resins and solvent and dissolving to prepare the process of dopant.
Dissolving can use following various dissolving methods：The method carried out at ambient pressure, the method carried out below the boiling point of main solvent,
The method pressurizeed and carried out more than the boiling point of main solvent, Japanese Unexamined Patent Publication 9-95544 publications, Japanese Unexamined Patent Publication 9-95557
The method carried out with hot-cold lysis method described in number publication or Japanese Unexamined Patent Publication 9-95538 publications, Japanese Unexamined Patent Publication
Method carried out under high pressure described in 11-21379 publications etc., but particularly preferably added more than the boiling point of main solvent
The method of pressure.
(2) it is cast process
Curtain coating process is to prolong the dopant prepared in above-mentioned dopant preparation section to for example from pressurization die head narrow slit flow
The process of casting position in the metal support such as stainless steel band or the metal roller of rotation.
In solution casting method, for the concentration of the cyclic polyolefin resin in dopant, as concentration uprises, it can reduce
Drying load after metal support curtain coating, but if the load increase when excessive concentration of cyclic polyolefin resin then filters,
Filtering accuracy is deteriorated.As these the concentration that gets both, preferably 10~35 mass %, more preferably 15~25 mass %.
Metal support in curtain coating (casting) process is preferably that the metal support of mirror finish has been carried out to surface, is made
For metal support, the roller of plating processing has preferably been carried out to surface using stainless steel band or with casting.It is cast (casting)
Width can be 1~4m.
(3) the 1st drying processes
1st drying process be will on curtain coating supporter be cast dopant and formed dopant film (hereinafter also referred to as
Basement membrane) process for evaporating solvent is heated on curtain coating supporter.
Be cast the supporter of process surface temperature be set in more than -50 DEG C and basement membrane do not seethe with excitement foaming temperature below.
As temperature uprises, the rate of drying of basement membrane can be accelerated, thus preferably, but if too high then, basement membrane foams sometimes, flatness
Deterioration, therefore it is set in the temperature not foamed.
As preferable support temperature, suitably determined in the range of 0~100 DEG C, more preferably 5~30 DEG C of model
In enclosing.In addition, basement membrane gelation is made and containing from drum peel being also preferable side in the state of a large amount of solvents by cooling
Method.
Control the method for the temperature of supporter to be not particularly limited, have the method for blowing warm air or cold wind, make supporter
The method that rear side contacts with warm water.Due to effectively being carried out using heat transfer during warm water, so the temperature of supporter becomes one
The time of constant temperature degree is short, thus preferably.
During using warm air, considering the temperature of the basement membrane caused by the evaporation latent heat of solvent reduces, sometimes using the boiling point of solvent
The warm air of the above, and use not only prevents foaming but also the wind of the temperature higher than target temperature.Particularly preferably from being cast to the stripping phase
Between change supporter temperature and dry wind temperature, be effectively dried.
(4) stripping process
Stripping process is the process for peeling off the basement membrane that solvent has been evaporated on supporter in stripping position.The base being stripped
Film is sent to next process.
In order that resin base material shows good flatness, quantity of solvent when peeling off basement membrane from supporter is preferably 10~
In the range of 150 mass %, in the range of more preferably 20~40 mass % or 60~130 mass %, particularly preferably 20
In the range of~30 mass % or 70~120 mass %.
Quantity of solvent is defined by following formula.
Peel off quantity of solvent (quality %)={ (M-N)/N } × 100 during basement membrane
It should illustrate, M is the matter for gathering any time after either manufacturing in the mill sample obtained by basement membrane or film
Amount, N are the quality after M is heated 1 hour at 115 DEG C.
(5) the 2nd drying processes
2nd drying process is the process that the solvent contained by the basement membrane for making to peel off from supporter further evaporates.In the present invention,
Resin base material will be referred to as by the basement membrane of the 2nd drying process.
In the 2nd drying process, (basement membrane is set to make alternately through the multiple rollers configured up and down using in general roller drying mode
Its mode dried), one side described in Japanese Unexamined Patent Publication 2012-13824 publications convey basement membrane while entering with stenter mode
The dry mode of row.
Drying temperature when carrying out stenter is preferably in the range of 30~180 DEG C, more preferably 50~170 DEG C
In the range of.
The thickness of the resin base material that (after drying) is made of the present invention is different according to application target, usually 5~500 μm
In the range of, in the range of preferably 10~150 μm, particularly preferably less than 100 μm if the slimming of equipment is considered.
(6) stretching process
Stretching process is the process for being stretched the resin base material of making.
The resin base material used in present embodiment can be non-stretched base material or the base material of stretching, but from
From the viewpoint of improving intensity, suppressing thermal expansion, the base material that preferably stretches.The method of stretching is not particularly limited.
For example, following method can be enumerated：All speed differences are assigned to multiple rollers, using roller week speed difference in longitudinal stretching between roller
Method；The both ends of basement membrane are fixed with fixture, safety pin, the direct of travel that is spaced in of fixture, safety pin is expanded so as in longitudinal stretching
Method；Similarly in horizontal expansion so as in the method for cross directional stretch；Or expand simultaneously so as in two sides in length and breadth in length and breadth
To the method for stretching；Oblique extension etc..
Multiple methods can be applied in combination in these methods, can also be divided into stretched operation multiple stages to implement.That is,
Relative to film forming direction, can also can be stretched in cross directional stretch in longitudinal stretching in both direction, in addition at two
When direction stretches, it can simultaneously stretch, can also gradually stretch.Alternatively, it is also possible to enter with the 2nd above-mentioned drying process simultaneously
OK.By being divided into for several times, even high magnification stretching also can be stretched more uniformly.Before oblique extension, can horizontal or
Longitudinal feed row prevents the stretching of the degree of the contraction of width.
Resin base material of the present invention length of delay Ro in the face at measure wavelength 589nm is preferably 0~150nm model
In enclosing.Ro is more preferably in the range of 0~20nm or 40~150nm.
In addition, in the range of the thickness direction retardation value Rt at measure wavelength 589nm is preferably 0~400nm, particularly preferably
In the range of Rt is 0~70nm or in the range of Rt is 80~300nm.By making Rt be preferable scope, so as to improve use
Visuality when polarizer.
Formula (i) Ro=(nx-ny)×d
Formula (ii) Rt=((nx+ny)/2-nz)×d
In formula, Ro represents length of delay in film surface, and Rt represents thickness direction retardation value, nxRepresent the slow-axis direction in film surface
Refractive index, nyRepresent the refractive index of the quick shaft direction in film surface, nzThe refractive index of the thickness direction of film is represented, d represents the thickness of film
(nm)。
In the present invention, determine length of delay Ro and thickness direction retardation value Rt in the face at wavelength 589nm and pass through at 23 DEG C
Determined in the environment of 55%RH using measuring difference of phases device " KOBRA-WPR " (prince measures machine Co. Ltd. system).
The length of delay of resin base material can be controlled by stretching ratio when selection, the film forming of resin material etc..It is specific and
Speech, by properly selecting stretching ratio longitudinally, laterally, may be controlled to arbitrarily be worth.
(7) rolling step
Rolling step is by the process of the resin base material formed via above-mentioned operation winding strip web-like.Method for winding can
Using the method typically used, to there is constant calibrated wrench method, constant tension method, taper tension method, internal stress constant program
Force controlling method etc., it can suitably use these methods.
Before winding, end is cut in the width of product and cuts out and goes, in order to prevent adhesion, the scratch between winding,
Both ends can be implemented with annular knurl processing (embossing is processed).The method of annular knurl processing can be that side is had into convex-concave pattern becket
It is processed by heating, pressurizeing.
The structure for the cyclic olefin resins that resin base material of the present invention is used by suitably adjusting, the species of additive
With addition, stretching ratio, peel off when the process conditions such as quantity of solvent so as to realizing desired optical characteristics.It is such as logical
Cross and quantity of solvent when peeling off is being adjusted in the range of 40~85 mass %, also can be in the range of 180~300nm significantly
Control the delay Rt of thickness direction.
Quantity of solvent when in general peeling off is more, and Rt is smaller, and quantity of solvent during stripping is fewer, and Rt is bigger.Such as pass through
Shorten the drying time on metal annular support, quantity of solvent when increase is peeled off, be free to relax planar orientation
And Rt is reduced, it can show various delays according to various uses by adjusting process conditions.
In the present invention, in order to form conductive layer on resin base material, the surface energy of resin base material is preferably more than 40mN/m.
If the surface energy of resin base material is less than 40mN/m, have that the contact angle of conductive material liquid and resin base material uprises becomes
Gesture, because the difference in liquid middle level portion and the evaporation capacity at edge diminishes without promoting conductive material drop extrorse right from middle level portion
Stream.Change in a manner of reducing above-mentioned contact angle the composition of conductive material liquid, but from composition species selection from
By not preferred from the viewpoint of degree.On the other hand, if surface energy is more than 40mN/m, conductive material liquid and resin be present
The trend of the contact angle step-down of base material, promote conductive material drop because the difference of liquid middle level portion and the evaporation capacity at edge becomes greatly
From the extrorse convection current in middle level portion.As a result, promoting the graph thinning of the parallel lines of conductive layer, be further enhanced the transparency
Effect.In addition, from composition species selection the free degree from the viewpoint of it is also preferred that.
The surface energy referred in the present invention refers to represent base using contact angle method measure as titer using water and iodomethane
The value of material wettability of the surface.Specifically, can use consonance interface science Co. Ltd. system DM-500, measure ultra-pure water and
The contact angle of iodomethane, calculate the surface energy of 2 kinds of composition systems and obtain.
It is preferred that form conductive layer in the resin base material that the process more than is formed.
The formation of conductive layer can use various methods, but preferred wet processing, more preferably ink-jet method.Specifically, make
For the forming method of conductive layer, the method that pattern of parallel lines is formed using ink-jet method can be enumerated, such as Japanese Unexamined Patent Publication can be used
Method described in 2014-120353 publications.
Embodiment
Hereinafter, enumerate embodiment the present invention is specifically described, but the invention is not restricted to these embodiments.It should say
It is bright, the expression of " part " or " % " is used in embodiment, unless otherwise specified, represents " mass parts " or " quality % ".
It should illustrate, water content uses the assay method of above-mentioned water content, and " skin section water content/middle level portion water content " is represented per single
The ratio (%) of plane product.
《The making of nesa coating 1》
(preparation of dopant)
Next, mixing following compositions prepares dopant (cyclic olefine resin composition).
Cyclic olefin polymer (JSR company systems " ARTON (registration mark) G7810 ")
Metal nanoparticle (Ag：Average grain diameter 20nm, DOWA Electronics Co. Ltd. system Ag nanometer powders -1)
0.005 mass parts
Using endless belt casting device, in temperature, 33 DEG C are equably cast the dopant of above-mentioned preparation with width 2000mm
(casting) is on stainless steel band supporter.Next, the quantity of solvent in dopant is peeled off in the state of being about 20 mass %, use
Stenter holds the both ends of the width of film, in the state of quantity of solvent is 10 mass %, along width at a temperature of 115 DEG C
Direction stretches 1.05 times (5%) and is dried.
Thereafter, being conveyed through 30 minutes between the roller of 100 DEG C of annealing device is further dried it, makes resin base
Material.
(preparation of conductive layer coating fluid 1)
Metal nanoparticle (Ag：Average grain diameter 20nm, DOWA Electronics Co. Ltd. systems, Ag nanometer powders -1)
0.8 mass parts
Surfactant (silicon systems, BYK Chemie Japan Co. Ltd. systems, BYK348)
0.01 mass parts
The mass parts of 1,3- butadiene 25
The mass parts of water 75
(formation of conductive layer)
The resin base material obtained in will be above-mentioned is cut into 200mm square, the region of the 190mm square on the resin base material
It is interior to use ink-jet method, the grid pattern being made up of fine rule is formed according to following step.
First, using equipped with ink-spraying-head of the filling conductive layer by the use of coating fluid 1 as fine rule formation ink, (Konica is beautiful
Can reach company system " KM512L " (drop volume 42pl)) printer, with the more of 200 μm of spacing formation striateds on above-mentioned film
Bar line.
The metal nanoparticle (Ag) that a plurality of line each contains during drying is gathered in the width of each line
End, as a result, 1 line becomes 2 parallel lines.
Next, being rotated by 90 ° film, describe a plurality of line in a manner of the line with being formed before is orthogonal.This plurality of line also with
The line formed before similarly each becomes 2 parallel lines during drying.
The line being thusly-formed is fired 1 hour at 100 DEG C, so as to form the grid formed with 100 μm of interval layout lines
Pattern, obtain nesa coating 1.
The line width for forming each fine rule of grid pattern is 5 μm, and thickness is 0.02 μm.
《The making of nesa coating 2~19》
Nesa coating 2~19 removes material this point being changed to the ratio for making the material of nesa coating 1 shown in table 1
In addition, made in the same manner as the making step of nesa coating 1.
《The evaluation of nesa coating》
＜ adaptations ＞
For 10mm × 10mm of above-mentioned formation metal pattern, according to JIS K 5600 record, peeled off by adhesive tape
Experiment carries out the evaluation of adaptation.Specifically, drawing for the grid pattern of 25 grids in length and breadth at 2mm intervals is formed with cutter
Trace, cellophane tape is attached from grid pattern.When peeling off the adhesive tape, the number of the section of stripping, root are counted in adhesive tape side
Adaptation is evaluated according to following opinion ratings.
◎：Do not find the metal pattern peeled off
○：It was found that the metal pattern peeled off, produces number and is less than 5.0%
△：It was found that the metal pattern peeled off, it is more than 5.0% and less than 10% to produce number
×：It was found that the metal pattern peeled off, it is more than 10% to produce number
＜ electric conductivity ＞
Make resistrivity meter Loresta GP (DIA Instruments Co. Ltd. systems) four probe PSP with it is above-mentioned
The metal pattern of the wiring of making is connected and determines electrical conductivity, and electric conductivity is evaluated according to following opinion ratings.
◎：Electrical conductivity is less than 5.0 μ Ω cm
○：Electrical conductivity is 5.0 μ Ω cm less than 10 μ Ω cm
△：Electrical conductivity is 10 μ Ω cm less than 20 μ Ω cm
×：Electrical conductivity is more than 20 μ Ω cm
＜ light transmittances ＞
The transparent measure at the initial stage of nesa coating is to use spectrophotometer " U4100 " (Hitachi
Hightech systems), measurement determines 400~800nm of wavelength average transmittance and carried out.
This is determined as follows：It is assumed that for transmission-type capacitive touch panel, in order to react the system of reality, will by supporter,
The nesa coating that high refractive index layer, anti-sulphur layer and transparency conducting layer are formed is with the Immersion used in oil immersion optical system
Oil " TYPE A (n=1.515) " (Nikon Co. Ltd. systems) is attached to glass substrate, determines above-mentioned total light transmittance to comment
Valency.
Above-mentioned average transmittance is to support the normal to a surface on side to tilt from the transparent resin relative to nesa coating
5 ° of angle incident light and determine.
◎：Average transmittance is more than 92%
○：Average transmittance is 90% less than 92%
△：Average transmittance is 85% less than 90%
×：Average transmittance is less than 85%
Evaluation executed as described above.
＜ noises ＞
With obtained conductive film production touch panel, 1MHz frequency is inputted when determining touch panel with electric impedance analyzer
The peak intensity and half-peak breadth of output waveform during square wave, drawn based on the S (output or input) obtained according to following formula
Graduation.
S (output or input)=(peak intensity) × (half-peak breadth)
○：S (output) is more than the 95% of S (input)
△：S (output) is more than the 90% of S (input)
×：S (output) is less than the 90% of S (input)
If adaptation, electric conductivity, the grade of light transmittance and noise are zero or ◎, it is evaluated as good in practicality
Scope.Each evaluation result derived above is shown in table 1.
[table 1]
Think if the water content of the per unit volume of the skin section of the one side for the resin base material being immersed in when in water is relative
In the range of the water content of the per unit volume in the middle level portion of above-mentioned resin base material is 120~300%, then ink is readily permeable
To film skin section, the adaptation with resin base material is obtained, therefore electric conductivity uprises.On the other hand, if water content is excessive,
Ink excessive permeation makes the electric conductivity of skin section reduce to inside resin base material.
Additionally, it is believed that because the amount of metal of resin base material skin section contributes to the adaptation with conductive layer, so amount of metal
More, electric conductivity is higher.On the other hand, if crossing at most base material adaptation height, but circulate in resin base material interior metal amount
Current spread is to inside base material when electric, therefore electric conductivity deteriorates.
For noise similarly, it is believed that the amount of metal of resin base material skin section contributes to the adaptation with conductive layer.
If bad with the adaptation of base material, become strong in the interface scattering reflection of substrate layer and conductive layer, light transmittance
Reduce.Specifically, it is believed that if adaptation is poor, the interface of base material and conductive layer does not bond completely, therefore exists small
Space, it is to cause the principal element that is greatly reduced of the transparency.Therefore, by by the metal of the skin section of above-mentioned resin base material
Composition adjustment is 1 × 10-6~1 × 10-3Small space can be filled in the range of quality %, so as to improve adaptation.
Industrial applicability
Using the present invention, the excellent adhesion of conductive layer and resin base material can be obtained and with good electric conductivity and thoroughly
The nesa coating of bright property, liquid crystal display, plasma display, inorganic and organic el display, touch can be suitably used for
The various display devices such as panel, solar cell.
Symbol description
1 nesa coating
2 resin base materials
3 skin sections
4 conductive layers
5 middle levels portion
Claims (5)
- A kind of 1. nesa coating, it is characterised in that it is the nesa coating with resin base material and conductive layer,The principal component of the resin base material is cyclic olefine resin,The skin section of the resin base material is 1 × 10-6~1 × 10-3Contain metal ingredient in the range of quality %, and,During according to the resin base material is immersed in water, the water content phase of the per unit volume of the skin section of the resin base material The mode turned into for the water content of the per unit volume in the middle level portion of the resin base material in the range of 120~300% is carried out Adjustment.
- 2. nesa coating according to claim 1, it is characterised in that the metal ingredient contain gold, silver, copper, iron, Any of aluminium, nickel, magnesium, zinc and their alloy.
- 3. nesa coating according to claim 1 or 2, it is characterised in that the conductive layer is metal conducting layer.
- 4. a kind of manufacture method of nesa coating, it is characterised in that be saturating any one of manufacturing claims 1~3 The electrically conducting transparent film manufacturing method of bright conducting film,Using resin combination and utilization containing cyclic olefine resin, organic polar solvent, organic non-polar solven and water Solution casting method formed resin base material process in, according to the skin section of the resin base material metal ingredient content turn into 1 × 10-6~1 × 10-3Mode in the range of quality % is adjusted, and,During according to the resin base material is immersed in water, the water content phase of the per unit volume of the skin section of the resin base material The mode turned into for the water content of the per unit volume in the middle level portion of the resin base material in the range of 120~300% is carried out Adjustment.
- 5. the manufacture method of nesa coating according to claim 4, it is characterised in that form described lead using ink-jet method Electric layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015089129 | 2015-04-24 | ||
| JP2015-089129 | 2015-04-24 | ||
| PCT/JP2016/060982 WO2016170957A1 (en) | 2015-04-24 | 2016-04-04 | Transparent conductive film and method for producing transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107533882A true CN107533882A (en) | 2018-01-02 |
Family
ID=57144357
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| Application Number | Title | Priority Date | Filing Date |
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| CN201680023533.9A Pending CN107533882A (en) | 2015-04-24 | 2016-04-04 | The manufacture method of nesa coating and nesa coating |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6693511B2 (en) |
| KR (1) | KR20170129883A (en) |
| CN (1) | CN107533882A (en) |
| WO (1) | WO2016170957A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6870290B2 (en) * | 2016-11-18 | 2021-05-12 | 日本ゼオン株式会社 | Laminated film |
| KR102355283B1 (en) * | 2017-02-22 | 2022-01-25 | 후지필름 가부시키가이샤 | Conductive film, conductive film having a three-dimensional shape and manufacturing method thereof, manufacturing method of stretched film, touch sensor film |
| JP7171229B2 (en) * | 2018-05-10 | 2022-11-15 | トッパン・フォームズ株式会社 | laminate |
| CN112640590A (en) | 2018-08-27 | 2021-04-09 | 柯尼卡美能达株式会社 | Method for forming conductive thin line, method for manufacturing transparent conductor, method for manufacturing device, and combination of conductive ink and substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008226641A (en) * | 2007-03-13 | 2008-09-25 | Kochi Univ Of Technology | Transparent conductive film layered product |
| WO2010024175A1 (en) * | 2008-08-25 | 2010-03-04 | 株式会社関東学院大学表面工学研究所 | Laminate and process for producing the laminate |
| CN102804064A (en) * | 2009-06-09 | 2012-11-28 | 富士胶片株式会社 | Conductive composition, transparent conductive film, display element and integrated solar battery |
| CN103237657A (en) * | 2010-12-06 | 2013-08-07 | 柯尼卡美能达株式会社 | Gas-barrier film, method for producing gas-barrier film, and electronic device |
-
2016
- 2016-04-04 JP JP2017514049A patent/JP6693511B2/en active Active
- 2016-04-04 KR KR1020177030169A patent/KR20170129883A/en not_active Application Discontinuation
- 2016-04-04 CN CN201680023533.9A patent/CN107533882A/en active Pending
- 2016-04-04 WO PCT/JP2016/060982 patent/WO2016170957A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008226641A (en) * | 2007-03-13 | 2008-09-25 | Kochi Univ Of Technology | Transparent conductive film layered product |
| WO2010024175A1 (en) * | 2008-08-25 | 2010-03-04 | 株式会社関東学院大学表面工学研究所 | Laminate and process for producing the laminate |
| CN102804064A (en) * | 2009-06-09 | 2012-11-28 | 富士胶片株式会社 | Conductive composition, transparent conductive film, display element and integrated solar battery |
| CN103237657A (en) * | 2010-12-06 | 2013-08-07 | 柯尼卡美能达株式会社 | Gas-barrier film, method for producing gas-barrier film, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016170957A1 (en) | 2016-10-27 |
| KR20170129883A (en) | 2017-11-27 |
| JP6693511B2 (en) | 2020-05-13 |
| JPWO2016170957A1 (en) | 2018-03-08 |
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