WO2017018427A1 - Procédé de production d'un film conducteur, et film conducteur - Google Patents

Procédé de production d'un film conducteur, et film conducteur Download PDF

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Publication number
WO2017018427A1
WO2017018427A1 PCT/JP2016/071920 JP2016071920W WO2017018427A1 WO 2017018427 A1 WO2017018427 A1 WO 2017018427A1 JP 2016071920 W JP2016071920 W JP 2016071920W WO 2017018427 A1 WO2017018427 A1 WO 2017018427A1
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resin layer
resin
group
conductive film
functional group
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PCT/JP2016/071920
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English (en)
Japanese (ja)
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正彦 鳥羽
内田　博
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昭和電工株式会社
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Priority to CN201680030108.2A priority Critical patent/CN107615408B/zh
Priority to KR1020177031866A priority patent/KR102000956B1/ko
Priority to JP2017530888A priority patent/JP6664396B2/ja
Publication of WO2017018427A1 publication Critical patent/WO2017018427A1/fr

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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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing a conductive film and a conductive film.
  • the transparent conductive film may be a liquid crystal display (LCD), a plasma display panel (PDP), an organic electroluminescence display, a transparent electrode of a solar cell (PV) and a touch panel (TP), an antistatic (ESD) film, and an electromagnetic shielding ( It is used in various fields such as EMI) film.
  • LCD liquid crystal display
  • PDP plasma display panel
  • TP touch panel
  • ESD antistatic film
  • EMI electromagnetic shielding
  • ITO indium tin oxide
  • the supply stability of indium is low, the manufacturing cost is high, the flexibility is not high, and the temperature is high during film formation. There was a problem that was necessary. Therefore, a search for a transparent conductive film that replaces ITO has been actively pursued.
  • transparent conductive films containing metal nanowires have excellent conductivity, optical properties, and flexibility, can be formed by wet processes, have low manufacturing costs, and require high temperatures during film formation Therefore, it is suitable as an ITO alternative transparent conductive film.
  • Patent Document 1 discloses a transparent conductive film containing silver nanowires and having high conductivity, optical characteristics, and flexibility.
  • Patent Document 2 discloses a method for producing a transparent conductive film having a transparent conductive layer containing metal nanowires on a transparent substrate.
  • the transparent conductive film containing metal nanowires in particular has a surface area per mass of metal such as silver.
  • the transparent conductive film containing metal nanowires in particular has a surface area per mass of metal such as silver.
  • the transparent conductive film containing metal nanowires since it reacts with various compounds easily, there is a problem that it lacks environmental resistance. For this reason, nanostructures corrode due to the influence of various chemicals and cleaning liquids used in the process, the influence of oxygen and moisture in the air exposed by long-term storage, etc., and the conductivity tends to decrease.
  • a physical cleaning process using a brush or the like is often used in order to prevent adhesion of fine impurities, dust, and dust to the surface of the substrate. The problem is that the surface is also damaged by the process.
  • the transparent conductive film is required to have high adhesion between the conductive layer and the substrate, environmental resistance, and scratch resistance.
  • An object of the present invention is to provide a method for producing a conductive film and a conductive film having high adhesion between the conductive layer and the substrate, environmental resistance, and scratch resistance.
  • an embodiment of the present invention is a method for producing a conductive film, wherein a first resin layer is formed using a first resin composition containing a first functional group on a substrate. Forming a conductive pattern having an opening in plan view on the first resin layer, and forming the first resin layer so as to cover at least part of the conductive pattern. Forming a second resin layer using a second resin composition containing a second functional group co-curable with a functional group; and co-curing the first resin layer and the second resin layer And a step of allowing
  • the conductive pattern is preferably formed after the surface of the first resin layer is no longer viscous.
  • the first functional group only needs to include a site having reactivity in a subsequent process such as a carboxy group, a hydroxy group, an epoxy group, a (meth) acryloyl group, a vinyl group, or an allyl group.
  • the composition preferably contains any of a carboxy-containing polyurethane, a phenol novolac-type epoxy resin, a phenoxy resin, a mixture of a carboxy-containing polyurethane and an epoxy compound having less than an equivalent amount based on a carboxy group, and a diallyl phthalate resin.
  • the second resin composition includes a mixture of a carboxy-containing polyurethane and an epoxy compound, a phenol novolac type epoxy resin, a phenoxy resin, a mixture of a carboxy-containing polyurethane and an epoxy compound having an equivalent amount or more based on a carboxy group, and a diallyl phthalate resin. It is preferred to include any mixture of acrylate monomers.
  • the substrate, the first resin layer, the conductive pattern, and the second resin layer are each transparent.
  • Another embodiment of the present invention is a conductive film having a first resin layer containing a first functional group on a substrate, and an opening in the plan view on the first resin layer.
  • a second resin layer including a second functional group is formed so as to cover at least a part of the conductive pattern, and the first resin is formed in the opening of the conductive pattern. It has a curing reaction portion between the first functional group of the layer and the second functional group of the second resin layer.
  • the total light transmittance of the conductive film is preferably 70% or more.
  • the conductive pattern may include metal nanowires that randomly have cross contact portions.
  • the conductive pattern may include a fine metal line pattern formed regularly or irregularly.
  • the method for producing a conductive film according to the embodiment includes a step of forming a first resin layer using a first resin composition containing a first functional group on a substrate, and a plan view on the first resin layer. A step of forming a conductive pattern having an opening, and a second functional group co-curing with the first functional group of the first resin layer so as to cover at least a part of the conductive pattern. A step of forming a second resin layer using the resin composition, and a step of co-curing the first resin layer and the second resin layer.
  • FIG. 1 shows a process diagram of a method for producing a conductive film according to the present embodiment.
  • a first resin layer (undercoat layer) 12 is formed on a substrate 10 (S1: first resin layer forming step).
  • the first resin layer 12 can be used as long as it has excellent adhesion to the substrate 10.
  • the method for carrying out the above S1 is not limited.
  • screen printing, gravure printing and offset printing thereof, contact printing such as bar coater, die coater, gravure coater, ink jet printing, spray coating And non-contact printing such as a dispenser.
  • Resin films such as a glass substrate, a PET (polyethylene terephthalate) film, a PEN (polyethylene naphthalate) film, etc. can be used.
  • the 1st resin layer 12 is formed on the surface of the board
  • the first resin layer 12 is a conductive material for forming a conductive pattern, which will be described later, by forming the first resin composition on the surface of the substrate 10 in layers and then heating it at room temperature or an appropriate temperature. Is preferably cured or dried to such an extent that it does not sink into the first resin layer 12 (S2: first resin composition drying step).
  • S2 first resin composition drying step.
  • the degree of curing or drying can be determined by the result of a test with a spread meter according to JIS K 5701 being 0 mm, that is, a state where there is no fluidity, but a resin composition that forms a solid resin layer at room temperature is used.
  • a conductive pattern 14 having an opening in plan view is formed on the first resin layer 12.
  • the “conductive pattern” includes a case where the entire surface is formed in a solid shape.
  • a conductive pattern 14 having an opening in a plan view shown in FIG. 2A to be described later is, for example, an ink in which metal nanowires are dispersed in a dispersion medium on the first resin layer 12 (hereinafter referred to as “metal nanowire ink”). May be obtained by pattern printing (S3: printing step) and firing by irradiating or heating the metal nanowire ink (S4: firing step). The surface of the conductive pattern including the fired metal nanowires is exposed above the surface of the first resin layer 12.
  • the “opening” means that there is a gap between the metal nanowires 18 and the fine metal wires 19, and the second resin composition described later is the first resin.
  • the penetration part of the thickness direction which can contact a composition is meant.
  • 2A and 2B are conceptual views in which the conductive pattern 14 is partially enlarged.
  • the metal nanowires 18 are randomly deposited on the substrate to have cross contact portions by printing, and the metal nanowires 18 are electrically connected to each other at the cross contact portions. Conductivity) is exhibited by the inclusion (FIG. 2A). In this case, the opening 20 has an irregular shape due to the metal nanowires 18 deposited randomly. Even when a solid film is printed using metal nanowire ink, a conductive pattern having openings 20 penetrating in the thickness direction can be obtained.
  • the term “metal nanowire” as used herein means one having a shape with a diameter of several tens to several hundreds of nm and a length of several ⁇ m to several tens of ⁇ m.
  • regular-shaped (rectangular) openings 20 are formed by the thin metal wires 19.
  • the fine metal wire 19 can be formed using a metal foil or a metal nanoparticle ink described later.
  • the thin metal wires 19 are arranged in a lattice pattern and have intersecting portions, but may be formed so as to be parallel to a certain direction and have no intersecting portions, for example. Further, the fine metal wires 19 may be irregularly arranged, and the openings 20 may be irregularly shaped.
  • the printing method performed in the above S3 is not limited, and any printing method capable of pattern printing the metal nanowire ink can be adopted.
  • any printing method capable of pattern printing the metal nanowire ink can be adopted.
  • screen printing, gravure printing and offset printing thereof, contact printing such as bar coater, die coater and gravure coater, non-contact printing such as ink jet printing, spray coating, dispenser and the like can be mentioned.
  • the touch-dried state (tack-free) is obtained after the first resin layer 12 is formed on the substrate 10 by, for example, applying the first resin composition.
  • a state having no viscosity (tack-free) is preferable. Thereby, even if the printing apparatus contacts the first resin layer 12, good printing can be performed.
  • a curing accelerator may be mixed.
  • the 1st resin composition contains the epoxy compound mentioned later, it is desirable to mix a hardening accelerator.
  • the first resin layer 12 does not need to be dry to the touch, and the conductive material does not completely sink into the first resin layer 12. It is sufficient that the surface of the conductive material is exposed on the surface of the first resin layer 12.
  • the ink used for printing the conductive pattern 14 is not limited to the metal nanowire ink, and for example, metal nanoparticle ink can be used.
  • metal nanoparticle ink when metal nanoparticle ink is used, the conductive particles must be in close contact with each other in order to exhibit conductivity, and when formed as a solid film, the opening 20 in plan view is There is almost no. Therefore, in order to form a pattern having the opening 20, it is necessary to form a fine line pattern (pattern of the metal fine line 19) having the opening 20 as shown in FIG. 2B, for example.
  • the fine line pattern may be formed regularly or irregularly, and may be formed so as to have an intersection as in a mesh pattern.
  • metal nanoparticles as used herein means those having a spherical shape, preferably a spherical shape, a square shape, a flat [plate] shape or the like having a particle size of the order of nm.
  • the substrate on which the conductive pattern 14 after printing is formed has a total light transmittance of 80% or more, there is a sufficient gap for the first resin layer 12 and the second resin layer 16 described later to contact each other. It is preferable because it is secured.
  • a second resin layer (overcoat layer) 16 is formed so as to cover at least a part of the conductive pattern (S5: second resin layer forming step).
  • This step can be performed by the same method as the above-described S1 (first resin layer forming step).
  • “At least a part” includes all. For example, in the case where a part of the electrode part for electrical connection with the outside is left exposed, the part is not covered. In such a case, a part is covered.
  • the second resin layer 16 includes a second functional group that can be co-cured with the first functional group included in the first resin composition constituting the first resin layer 12. It is comprised with a resin composition.
  • the first resin layer 12 and the second resin layer 16 are co-cured based on the first functional group and the second functional group (S6: co-curing step). (Not shown)). That is, the first functional group contained in the first resin layer 12 and the second functional group contained in the second resin layer 16 are cured and reacted.
  • the conductive pattern 14 has an opening 20 in the thickness direction, and the second resin composition constituting the second resin layer 16 enters the opening 20 and is cured at the interface with the first resin layer 12. react. That is, the opening 20 of the conductive pattern 14 has a curing reaction portion between the first functional group of the first resin layer 12 and the second functional group of the second resin layer 16.
  • the conductive pattern 14 is sandwiched between the first resin layer 12 and the second resin layer 16 and held in the opening 20 of the conductive pattern 14, so that the conductive pattern 14 has good adhesion to the substrate 10.
  • a pattern 14 is obtained.
  • combinations of the first functional group of the first resin layer 12 and the second functional group of the second resin layer 16 include carboxy group / epoxy group, epoxy group / carboxy group, hydroxy group / carboxy group, ( Examples thereof include, but are not limited to, (meth) acryloyl group / vinyl group, vinyl group / (meth) acryloyl group, allyl group / (meth) acryloyl group, and the like.
  • first resin composition constituting the first resin layer 12 and the second resin composition constituting the second resin layer 16 (first resin layer: second resin layer) ) (Carboxy group-containing polyurethane (first functional group is carboxy group): mixture of carboxy group-containing polyurethane and epoxy compound (second functional group is epoxy group)), (phenol novolac type epoxy resin (first 1 functional group is an epoxy group): phenol novolac type epoxy resin (second functional group is an epoxy group)), (phenoxy resin (first functional group is an epoxy group): phenoxy resin (second functional group is an epoxy group) Group)), (carboxy group-containing polyurethane (first functional group is carboxy group): phenoxy resin (second functional group is epoxy group)), (carboxy group-containing polyurethane and Mixture with less than equivalent epoxy compound based on ruxoxy group (first functional group is carboxy group): Mixture of carboxy group-containing polyurethane and more than equivalent epoxy compound based on carboxy group (second functional group is epoxy group)
  • the first resin composition when the first resin composition includes a carboxy group-containing polyurethane and the second resin composition includes a carboxy group-containing polyurethane and an epoxy compound, the first resin layer 12 and the first resin composition
  • the carboxy group (first functional group) of the carboxy group-containing polyurethane contained in the first resin layer 12 and the second resin layer 16 becomes an epoxy group ( 2nd functional group) and co-curing.
  • the first resin composition includes a carboxy group-containing polyurethane and an epoxy compound having an equivalent weight on a carboxy group basis
  • the second resin composition includes a carboxy group-containing polyurethane and an epoxy compound having an equivalent weight or more on a carboxy group basis.
  • co-curing in the same way.
  • co-curing is performed by adding an appropriate curing agent for epoxy resin and heating.
  • both the first functional group and the second functional group are epoxy groups.
  • the first resin composition includes a carboxy group-containing polyurethane
  • the second resin composition includes a phenoxy resin
  • the first resin layer 12 and the second resin layer 16 are heated.
  • the carboxy group (first functional group) and the epoxy group (second functional group) are bonded and co-cured.
  • the first resin composition contains a diallyl phthalate resin (the first functional group is an allyl group)
  • the second resin composition contains a diallyl phthalate resin and an acrylate monomer (the second functional group is an allyl group).
  • the first functional group is an allyl group
  • the second resin composition contains a diallyl phthalate resin and an acrylate monomer (the second functional group is an allyl group).
  • it undergoes addition polymerization and co-curing by light irradiation.
  • the substrate 10, the first resin layer 12, the conductive pattern 14, and the second resin layer 16 are transparent. Thereby, it can apply to transparent elements, such as a touch panel.
  • transparent means that the total light transmittance is 80% or more.
  • the total light transmittance of the conductive film of the present invention having such a constitution is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more.
  • the molecular weight and acid value of the resin, the total light transmittance and the surface resistance of the conductive pattern were measured as follows.
  • GPC gel permeation chromatography
  • ⁇ Acid value> About 0.2 g of a sample is precisely weighed in a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol / toluene 1/2 (mass ratio) is added and dissolved therein. Furthermore, add 1 to 3 drops of phenolphthalein ethanol solution as an indicator to this container and stir well until the sample is uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds. The value obtained from the result using the following calculation formula is defined as the acid value of the resin.
  • Acid value (mg-KOH / g) [B ⁇ f ⁇ 5.611] / S B: Amount of 0.1N potassium hydroxide-ethanol solution used (ml) f: Factor of 0.1N potassium hydroxide-ethanol solution S: Amount of sample collected (g)
  • ⁇ Total light transmittance> It is the value measured using a turbidimeter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) after cutting the conductive pattern formed on the substrate with a 50 mm square.
  • Diol 15: 85, molecular weight 964) 143.6 g, 2,2-dimethylolbutanoic acid (made by Nippon Kasei Co., Ltd.) 27.32 g as a dihydroxyl compound having a carboxy group, and propylene glycol monomethyl ether acetate (product) (Name: methoxypropyl acetate, manufactured by Daicel Corporation) 259 g was charged, and the 2,2-dimethylolbutanoic acid was dissolved at 90 ° C.
  • the temperature of the reaction solution was lowered to 70 ° C., and 87.5 g of Desmodur (registered trademark) -W (methylenebis (4-cyclohexylisocyanate), manufactured by Sumika Bayer Urethane Co., Ltd.) was added as polyisocyanate over 30 minutes with a dropping funnel. It was dripped. After completion of the dropwise addition, the temperature was raised to 120 ° C., and the reaction was carried out at 120 ° C. for 6 hours. After confirming that the isocyanate almost disappeared by IR, 0.5 g of isobutanol was added, and the reaction was further carried out at 120 ° C. for 6 hours. went.
  • the weight average molecular weight of the obtained carboxy group-containing polyurethane was 32300, and the acid value of the resin was 40 mgKOH / g.
  • Example 1 As shown in Table 1, on the PET (polyethylene terephthalate) substrate (Lumilar (registered trademark) 125T60 manufactured by Toray Industries, Inc.), the carboxy group-containing polyurethane resin synthesized in Synthesis Example 1 and cure azole (registered) Trademark) 2P4MHZ-PW (2-phenyl-4-methyl-5-hydroxymethylimidazole, 1 part by mass added to 100 parts by mass of the resin), and the resin content concentration including the curing accelerator is 30% by mass. Ink diluted with propylene glycol monomethyl ether acetate (corresponding to the first resin composition) was printed with a bar coater, dried at 100 ° C.
  • Over coat layer (corresponding to the first resin layer) was formed.
  • the thickness of the undercoat layer was determined by measuring the thickness including the substrate after formation of the undercoat layer and drying, and subtracting the thickness of the substrate.
  • a silver nanowire dispersion (0.125 g of silver nanowire (average diameter of wire: about 40 nm, average length: about 10 ⁇ m, 100 silver nanowires that were arbitrarily observed by SEM) Is dispersed in 50 g of ethanol (preparing a 0.25% by mass silver nanowire dispersion)), and 0.05 g of the dispersion is used so that it does not protrude from the undercoat layer with a bar coater. did.
  • the silver nanowire dispersion was successfully coated. After the silver nanowire dispersion was applied, it was baked at 100 ° C. for 1 hour to form a solid conductive pattern. The surface resistance after firing was 80 ⁇ / ⁇ , and the total light transmittance was 89%.
  • an overcoat layer (corresponding to the second resin layer), 10 g of the carboxy group-containing polyurethane resin synthesized in Synthesis Example 1 and 0.69 g of an epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical) were added to a curing accelerator. (Shikoku Kasei Co., Ltd.
  • Adhesion evaluation (peeling test) A cross-cut test JIS K5600 was performed on the cured film as an adhesion evaluation. The results are shown in Tables 1 and 2 as “Peel Test”. In addition, it means that adhesiveness (peeling resistance) is so high that the numerical value of a test result is small (0 is the best). In Table 1, the peel test result of Example 1 is 0, indicating that the adhesion (peel resistance) is high.
  • scratch resistance test As a scratch resistance test, scratch resistance was simply determined by paper friction. The used paper was reciprocated five times on the overcoat layer using a JK wiper. The presence or absence of scratches or scratches was confirmed visually and under a microscope. The results are shown in Tables 1 and 2 as “scratch resistance test”. A: There are no scratches or scratches visually or under a microscope. ⁇ : Scratches are not visible with visual inspection, but slight scratch marks are visible with a microscope. ⁇ : Scratches are not visible with the naked eye, but scratches / scratches are visible with a microscope. X: Scratches and scuff marks can be identified visually.
  • HAZE haze
  • light transmittance measurement of the obtained conductive film were measured using Haze meter NDH 2000 (manufactured by Nippon Denshoku). The results are listed as “optical properties” in Tables 1 and 2.
  • ⁇ Total light transmittance 80% or more and HAZE 20% or less
  • ⁇ Total light transmittance 80% or more and HAZE 20% or more
  • Example 2 to 6 An undercoat layer, a conductive pattern, and an overcoat layer were formed by the same thickness configuration and the same steps using the ink prepared in the same manner as in Example 1 except that the material configuration shown in Table 1 was changed.
  • Table 1 shows the results of the same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1.
  • JER registered trademark 828 manufactured by Mitsubishi Chemical
  • the carboxy group of the carboxy group-containing polyurethane resin synthesized in Example 2 is equivalent to the epoxy group of the epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical).
  • the overcoat layer of Example 2 (corresponding to the second resin layer) was composed of the carboxy group-containing polyurethane resin synthesized in Synthesis Example 2 and an epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical). ))
  • the epoxy compound (Mitsubishi) with respect to the carboxy group of the carboxy group-containing polyurethane resin synthesized in Synthesis Example 2
  • the composition has a small excess of epoxy group of chemical jER (registered trademark) 828).
  • the undercoat layer of Example 6 (corresponding to the first resin layer) was a carboxy group-containing polyurethane resin synthesized in Synthesis Example 1 and an epoxy compound (JER (registered trademark) manufactured by Mitsubishi Chemical Corporation). ) 828) is 100 to 3 (described as 100/3 in Table 1), so that the carboxy group of the carboxy group-containing polyurethane resin synthesized in Synthesis Example 1 remains in a half amount. It has become.
  • the overcoat layer (corresponding to the second resin layer) of Example 6 is the same as that of Example 1.
  • Example 7 An undercoat layer, a conductive pattern, and an overcoat layer were formed by the same thickness configuration and the same steps using the ink prepared in the same manner as in Example 1 except that the material configuration shown in Table 1 was changed.
  • IRGACURE registered trademark
  • 184 manufactured by BASF
  • Curesol registered trademark
  • 2P4MHZ-PW manufactured by Shikoku Kasei
  • Comparative Example 1 It changed into the material structure shown in Table 2, and formed the undercoat layer.
  • the undercoat layer was in a liquid state and was very sticky, and silver nanowire ink could not be printed by other printing methods such as inkjet.
  • the molecular weight is 10,000 or more, whereas the resin of Comparative Example 1 is considered to be caused by the low molecular weight of 4100.
  • Example 5 different resin components are used for the undercoat layer and the overcoat layer, but since they have a co-curable functional group, there is no separation between the undercoat layer and the overcoat layer after curing.
  • Comparative Examples 4 and 5 resins having different curing mechanisms are used for the undercoat layer and the overcoat layer.
  • Comparative Example 4 when UV curing is performed, and in Comparative Example 5, heat curing is performed, the undercoat is used. The layer and the overcoat layer were not co-cured, and peeling occurred between the undercoat layer and the overcoat layer.
  • Example 6 as an undercoat layer, an epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical) was added at a ratio in which a half amount of the functional group (carboxy group) remained in the carboxy group-containing polyurethane. Under the condition of time drying, it should be in a semi-cured state, and the residual functional group adheres to the overcoat layer by chemical bonding, so there is no peeling between the undercoat layer and the overcoat layer. On the other hand, in Comparative Examples 2 and 3, the resin used for the undercoat layer and the overcoat layer is in a condition that can be completely cured, and the undercoat layer is formed when the undercoat layer is formed (dried at 100 ° C. for 1 hour). Since the residual functional group that reacts with the overcoat layer disappears in the coat layer, peeling occurred between the undercoat layer and the overcoat layer (peeling test result is 5).
  • jER registered trademark 828 manufactured by Mitsubishi Chemical
  • Example 6 The configuration is the same as that of Example 1 except that no undercoat layer is provided.
  • Table 2 shows the results of the same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1. Although the peel test and scratch resistance test were good, but there was no undercoat layer, when the PET substrate after the silver nanowire dispersion was applied was heated, the total light transmittance decreased by 5% or more, but was 80% or more. However, HAZE, which was 2% before heating, exceeds 50% after heating, and the optical properties are greatly impaired. Due to heating, oligomers are precipitated from the PET substrate and the surface roughness is increased, so that the optical properties are impaired.
  • Example 7 This is a comparative example in which no overcoat layer is provided.
  • Table 2 shows the results of the same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1. Since there is no overcoat layer, scratches occur in the metal part by the scratch resistance test, and from the result of environmental resistance similar to Example 1 shown in FIG. 3, after about 700 hours, the resistance starts to increase significantly, It turns out that environmental tolerance is low.

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  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

[Problème] Proposer : un procédé de production d'un film conducteur qui présente une bonne adhésion sur un substrat, une résistance élevée à l'environnement et une résistance élevée aux rayures ; et un film conducteur. [Solution] Une première couche de résine est formée sur un substrat à l'aide d'une première composition de résine contenant un premier groupe fonctionnel (S1) ; après un séchage de la première couche de résine suffisant pour qu'un matériau conducteur ne soit pas immergé dans la couche (S2), un motif conducteur qui, vu dans un plan, présente une ouverture, est formé sur la première couche de résine (S3, S4) ; et une deuxième couche de résine est formée de façon à recouvrir au moins une partie du motif conducteur à l'aide d'une deuxième composition de résine contenant un deuxième groupe fonctionnel qui peut co-polymériser avec le premier groupe fonctionnel de la première couche de résine, et la première couche de résine et la deuxième couche de résine sont co-polymérisées (S5).
PCT/JP2016/071920 2015-07-30 2016-07-26 Procédé de production d'un film conducteur, et film conducteur WO2017018427A1 (fr)

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CN201680030108.2A CN107615408B (zh) 2015-07-30 2016-07-26 导电膜的制造方法及导电膜
KR1020177031866A KR102000956B1 (ko) 2015-07-30 2016-07-26 도전 필름의 제조 방법 및 도전 필름
JP2017530888A JP6664396B2 (ja) 2015-07-30 2016-07-26 導電フィルムの製造方法及び導電フィルム

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KR (1) KR102000956B1 (fr)
CN (1) CN107615408B (fr)
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WO2019230633A1 (fr) * 2018-05-30 2019-12-05 Ｄｏｗａエレクトロニクス株式会社 Encre à base de nanofils d'argent, procédé de production d'un film conducteur transparent, et film conducteur transparent
WO2020137144A1 (fr) * 2018-12-27 2020-07-02 富士フイルム株式会社 Matériau de transfert photosensible, stratifié, panneau tactile, procédé de production de substrat à motifs, procédé de production de carte de circuit imprimé et procédé de production de panneau tactile

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US11590746B2 (en) * 2019-07-18 2023-02-28 The Boeing Company Elimination of surfacing film and primer from composite substrates

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TW201718247A (zh) 2017-06-01
JPWO2017018427A1 (ja) 2018-05-24
CN107615408B (zh) 2019-07-02
TWI693160B (zh) 2020-05-11
JP6664396B2 (ja) 2020-03-13
KR102000956B1 (ko) 2019-07-17
KR20170133483A (ko) 2017-12-05
CN107615408A (zh) 2018-01-19

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