WO2017018427A1 - Method for producing conductive film, and conductive film - Google Patents
Method for producing conductive film, and conductive film Download PDFInfo
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- 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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- 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
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- 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
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.
Abstract
Description
ゲルパーミエーションクロマトグラフィー(以下GPCと表記)で測定したポリスチレン換算の値である。 <Molecular weight>
It is a value in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC).
装置名:日本分光株式会社製HPLCユニット HSS-2000
カラム:ShodexカラムLF-804
移動相:テトラヒドロフラン
流速 :1.0mL/min
検出器:日本分光株式会社製 RI-2031Plus
温度 :40.0℃
試料量:サンプルル-プ 100μリットル
試料濃度:約0.1質量%に調製 The measurement conditions for GPC are as follows.
Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Shodex column LF-804
Mobile phase: Tetrahydrofuran flow rate: 1.0 mL / min
Detector: RI-2031Plus manufactured by JASCO Corporation
Temperature: 40.0 ° C
Sample volume:
100ml三角フラスコに試料約0.2gを精密天秤にて精秤し、これにエタノール/トルエン=1/2(質量比)の混合溶媒10mlを加えて溶解する。更に、この容器に指示薬としてフェノールフタレインエタノール溶液を1~3滴添加し、試料が均一になるまで十分に攪拌する。これを、0.1N水酸化カリウム-エタノール溶液で滴定し、指示薬の微紅色が30秒間続いたときを、中和の終点とする。その結果から下記の計算式を用いて得た値を、樹脂の酸価とする。
酸価(mg-KOH/g)=〔B×f×5.611〕/S
B:0.1N水酸化カリウム-エタノール溶液の使用量(ml)
f:0.1N水酸化カリウム-エタノール溶液のファクター
S:試料の採取量(g) <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)
基板上に形成した導電パターンを50mm角でカットし、濁度計(NDH2000、日本電色工業製)を使用して測定した値である。 <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.
抵抗率計ロレスタ(登録商標)GP MCP-T610型(三菱化学アナリテック製)により4端子法で測定した。測定モードおよび使用端子はESPモードを用いた。
<カルボキシ基含有ポリウレタンの合成例> <Surface resistance>
The resistivity was measured with a Loresta (registered trademark) GP MCP-T610 type (manufactured by Mitsubishi Chemical Analytech) by the 4-terminal method. The ESP mode was used for the measurement mode and the terminals used.
<Synthesis example of carboxy group-containing polyurethane>
攪拌装置、温度計、コンデンサーを備えた2L三口フラスコに、ポリオール化合物としてC-1015N(株式会社クラレ製、ポリカーボネートジオール、原料ジオールモル比が1,9-ノナンジオール:2-メチル-1,8-オクタンジオール=15:85、分子量964)143.6g、カルボキシ基を有するジヒドロキシル化合物として2,2-ジメチロールブタン酸(日本化成株式会社製)27.32g、および溶媒としてプロピレングリコールモノメチルエーテルアセテート(商品名:メトキシプロピルアセテート、ダイセル株式会社製)259gを仕込み、90℃で上記2,2-ジメチロールブタン酸を溶解させた。 [Synthesis Example 1]
C-1015N (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio: 1,9-nonanediol: 2-methyl-1,8-octane was added to a 2 L three-necked flask equipped with a stirrer, thermometer and condenser. 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.
C-1015N(株式会社クラレ製)44.8g、2,2-ジメチロールブタン酸(日本化成株式会社製)16.1g、および溶媒としてプロピレングリコールモノメチルエーテルアセテート(ダイセル株式会社製)100.3g、デスモジュール(登録商標)-W(住化バイエルウレタン株式会社製)40.7gを用いた以外は、合成例1と同様に操作し、カルボキシ基含有ポリウレタンを得た。得られたカルボキシ基含有ポリウレタンの重量平均分子量は29200、その樹脂の酸価は60mgKOH/gであった。 [Synthesis Example 2]
C-1015N (manufactured by Kuraray Co., Ltd.) 44.8 g, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 16.1 g, and propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation) 100.3 g as a solvent, A carboxy group-containing polyurethane was obtained in the same manner as in Synthesis Example 1 except that 40.7 g of Desmodule (registered trademark) -W (manufactured by Sumika Bayer Urethane Co., Ltd.) was used. The weight average molecular weight of the obtained carboxy group-containing polyurethane was 29200, and the acid value of the resin was 60 mgKOH / g.
表1に示されるように、PET(ポリエチレンテレフタレート)基板(東レ(株)製ルミラー(登録商標)125T60)上に、合成例1で合成したカルボキシ基含有ポリウレタン樹脂と硬化促進剤であるキュアゾール(登録商標)2P4MHZ-PW(2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール、樹脂100質量部に対して1質量部添加)とを配合し、硬化促進剤を含む樹脂分濃度が30質量%となるようにプロピレングリコールモノメチルエーテルアセテートで希釈したインク(第1の樹脂組成物に相当)をバーコーターにて印刷し、100℃、1時間で乾燥して膜厚10μm(ミツトヨ製 高精度デジマチックマイクロメータ MDH-25M 293-100を用いて任意に5か所測定したその平均値)のアンダーコート層(第1の樹脂層に相当)を形成した。アンダーコート層の厚みはアンダーコート層形成、乾燥後の基板込みの厚みを測定し、基板の厚みを差し引くことにより求めた。 [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. for 1 hour, and a film thickness of 10 μm (Mitutoyo high precision Digimatic Micro Meter MDH-25M 293-100, measured arbitrarily at 5 points, the average value) under) 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.
硬化膜に対し、密着性評価としてクロスカット試験JIS K5600を行った。結果を表1、2に「剥離試験」として記載する。なお、試験結果の数値は小さいほど密着性(耐剥離性)が高い(0が最もよい)ことを意味する。表1において、実施例1の剥離試験結果が0となっており、密着性(耐剥離性)が高いことがわかる。 [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.
耐擦傷性試験として、紙摩擦により簡易的に擦傷性を判定した。使用した紙は、JKワイパーを用い、オーバーコート層上を5回往復させた。目視および顕微鏡により傷・擦り痕の有無を確認した。結果を表1、2に「耐擦傷性試験」として記載する。
◎:目視および顕微鏡にて傷・擦り痕がない。
○:目視では傷が見えないが、顕微鏡でわずかに擦り痕が見える。
△:目視では傷が見えないが、顕微鏡で傷・擦り痕が見える。
×:目視で傷・擦り痕が判別できる。 [Abrasion 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.
Δ: 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.
環境耐性として、恒温恒湿器(ETAC製TH402A)にて85℃、85%RH(相対湿度)雰囲気下で保管し、約1100時間後までの表面抵抗変化を初期表面抵抗からの比で測定した。結果を図3に示す。 [Environmental resistance]
As environmental resistance, it was stored in a constant temperature and humidity chamber (TH402A manufactured by ETAC) in an atmosphere of 85 ° C. and 85% RH (relative humidity), and the surface resistance change until after about 1100 hours was measured as a ratio from the initial surface resistance. . The results are shown in FIG.
光学特性として、得られた導電フィルムのHAZE(ヘーズ)及び光線透過率測定をHaze meter NDH 2000(日本電色製)を用い測定した。結果を表1、2に「光学特性」として記載する。
○:全光線透過率80%以上かつHAZE20%以下
×:全光線透過率80%以上かつHAZE20%を超える 〔optical properties〕
As an optical characteristic, HAZE (haze) and 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
表1に示す材料構成に変更した以外は実施例1と同様に調製したインクを用い、同様の厚み構成、同様の工程によりアンダーコート層、導電パターン及びオーバーコート層を形成した。実施例1同様の密着性評価(剥離試験)、耐擦傷性試験、光学特性評価を行った結果を表1に示す。実施例2のオーバーコート層に使用している合成例2で合成したカルボキシ基含有ポリウレタン樹脂100質量部に対してエポキシ化合物(三菱化学製jER(登録商標)828)9質量部を配合すると、合成例2で合成したカルボキシ基含有ポリウレタン樹脂のカルボキシ基とエポキシ化合物(三菱化学製jER(登録商標)828)のエポキシ基が当量となる。実施例2のオーバーコート層(第2の樹脂層に相当)は、表1に示されるように、合成例2で合成したカルボキシ基含有ポリウレタン樹脂とエポキシ化合物(三菱化学製jER(登録商標)828)との配合比(質量比)が100対10(表1では100/10と記載)とされているので、合成例2で合成したカルボキシ基含有ポリウレタン樹脂のカルボキシ基に対してエポキシ化合物(三菱化学製jER(登録商標)828)のエポキシ基が小過剰存在する組成となっている。 [Examples 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. When 9 parts by mass of an epoxy compound (JER (registered trademark) 828 manufactured by Mitsubishi Chemical) was blended with 100 parts by mass of the carboxy group-containing polyurethane resin synthesized in Synthesis Example 2 used in the overcoat layer of Example 2, synthesis was performed. 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). As shown in Table 1, 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). )) To 100: 10 (described as 100/10 in Table 1), 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).
表1に示す材料構成に変更した以外は実施例1と同様に調製したインクを用い、同様の厚み構成、同様の工程によりアンダーコート層、導電パターン及びオーバーコート層を形成した。その際にオーバーコート層の硬化促進剤としてキュアゾール(登録商標)2P4MHZ-PW(四国化成製)に代わりIRGACURE(登録商標)184(BASF社製)を用いた。なお、140℃1時間の硬化に変えて、小型UV照射装置 QRU-2161-Z11-00(株式会社オーク製作所)を用い、約40mW/cm2を露光する事により共硬化させた。実施例1同様の密着性評価(剥離試験)、耐擦傷性試験、光学特性評価を行った結果を表1に示す。 [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. In this case, IRGACURE (registered trademark) 184 (manufactured by BASF) was used as a curing accelerator for the overcoat layer instead of Curesol (registered trademark) 2P4MHZ-PW (manufactured by Shikoku Kasei). Note that, instead of curing at 140 ° C. for 1 hour, co-curing was performed by exposing about 40 mW / cm 2 using a small UV irradiation apparatus QRU-2161-Z11-00 (Oak Manufacturing Co., Ltd.). Table 1 shows the results of the same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1.
表2に示す材料構成に変更しアンダーコート層を形成した。アンダーコート層が液状状態でベタつきが酷く、インクジェット等の他の印刷法でも銀ナノワイヤインクの印刷ができなかった。他の例では、分子量が1万以上であるのに対し、比較例1の樹脂は分子量が4100と小さい事が原因であると考えられる。 [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. In other examples, 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.
表2に示す材料構成に変更した以外は実施例1と同様に調製したインクを用い、同様の厚み構成、同様の工程によりアンダーコート層、導電パターン及びオーバーコート層を形成した。但し、比較例4は約40mW/cm2のUV光を露光させ、共硬化相当の処理をした。実施例1同様の密着性評価(剥離試験)、耐擦傷性試験、光学特性評価を行った結果を表2に示す。 [Comparative Examples 2 to 5]
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 2 was changed. However, in Comparative Example 4, UV light of about 40 mW / cm 2 was exposed and a treatment corresponding to co-curing was performed. Table 2 shows the results of the same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1.
アンダーコート層を設けない以外は実施例1と同様の構成である。実施例1同様の密着性評価(剥離試験)、耐擦傷性試験、光学特性評価を行った結果を表2に示す。剥離試験、耐擦傷試験は良好であるもののアンダーコート層が無いため銀ナノワイヤ分散液塗布後のPET基板を加熱すると、全光線透過率が5%以上低下したが、80%以上ではあった。しかしながら、HAZEは、加熱前は、2%であったものが、加熱後50%を超え、光学特性が大幅に損なわれている。加熱により、PET基板からオリゴマーが析出して表面粗さが増大したために、光学特性が損なわれている。 [Comparative 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.
オーバーコート層を設けない一比較例である。実施例1同様の密着性評価(剥離試験)、耐擦傷性試験、光学特性評価を行った結果を表2に示す。オーバーコート層が無いため、耐擦傷性試験により金属部に傷が生じ、また図3に示した実施例1同様の環境耐性の結果から、約700時間経過後、抵抗が顕著に上昇し始め、環境耐性が低い事が分かる。 [Comparative 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.
DESCRIPTION OF
Claims (10)
- 基板上に第1の官能基を含む第1の樹脂組成物を用いて第1の樹脂層を形成する工程と、
前記第1の樹脂層上に平面視において開口部を有する導電パターンを形成する工程と、
前記導電パターンの少なくとも一部を被覆するように前記第1の樹脂層の第1の官能基と共硬化可能な第2の官能基を含む第2の樹脂組成物を用いて第2の樹脂層を形成する工程と、
前記第1の樹脂層と第2の樹脂層とを共硬化させる工程と、
を含む導電フィルムの製造方法。 Forming a first resin layer using a first resin composition containing a first functional group on a substrate;
Forming a conductive pattern having an opening in a plan view on the first resin layer;
A second resin layer using a second resin composition containing a second functional group that can be co-cured with the first functional group of the first resin layer so as to cover at least a part of the conductive pattern Forming a step;
Co-curing the first resin layer and the second resin layer;
The manufacturing method of the conductive film containing this. - 前記導電パターンは、前記第1の樹脂層の表面に粘性がなくなった後に形成する、請求項1に記載の導電フィルムの製造方法。 The method for producing a conductive film according to claim 1, wherein the conductive pattern is formed after the surface of the first resin layer is no longer viscous.
- 前記第1の官能基が、カルボキシ基、ヒドロキシ基、エポキシ基、(メタ)アクリロイル基、ビニル基、アリル基のいずれかを含む、請求項1または2に記載の導電フィルムの製造方法。 The method for producing a conductive film according to claim 1 or 2, wherein the first functional group includes any of a carboxy group, a hydroxy group, an epoxy group, a (meth) acryloyl group, a vinyl group, and an allyl group.
- 前記第1の樹脂組成物が、カルボキシ含有ポリウレタン、フェノールノボラック型エポキシ樹脂、フェノキシ樹脂、カルボキシ含有ポリウレタンとカルボキシ基基準で当量未満のエポキシ化合物との混合物、ジアリルフタレート樹脂のいずれかを含む、請求項1から3のいずれか一項に記載の導電フィルムの製造方法。 The first resin composition includes any one 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 manufacturing method of the electrically conductive film as described in any one of 1-3.
- 前記第2の樹脂組成物が、カルボキシ含有ポリウレタンとエポキシ化合物との混合物、フェノールノボラック型エポキシ樹脂、フェノキシ樹脂、カルボキシ含有ポリウレタンとカルボキシ基基準で当量以上のエポキシ化合物との混合物、ジアリルフタレート樹脂とアクリレートモノマーとの混合物のいずれを含む、請求項1から4のいずれか一項に記載の導電フィルムの製造方法。 The second resin composition is 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, a diallyl phthalate resin and an acrylate The manufacturing method of the electrically conductive film as described in any one of Claim 1 to 4 containing any of a mixture with a monomer.
- 前記基板、第1の樹脂層、導電パターン及び第2の樹脂層が各々透明である、請求項1から5のいずれか一項に記載の導電フィルムの製造方法。 The method for producing a conductive film according to any one of claims 1 to 5, wherein the substrate, the first resin layer, the conductive pattern, and the second resin layer are each transparent.
- 基板上に、第1の官能基を含む第1の樹脂層を有し、該第1の樹脂層上に平面視において開口部を有する導電パターンを有し、該導電パターンの少なくとも一部を被覆するように第2の官能基を含む第2の樹脂層が形成されており、かつ、前記導電パターン開口部において前記第1の樹脂層の第1の官能基と第2の樹脂層の第2の官能基との硬化反応部分を有する導電フィルム。 The substrate has a first resin layer containing a first functional group, and has a conductive pattern having an opening in a plan view on the first resin layer, and covers at least a part of the conductive pattern. The second resin layer containing the second functional group is formed, and the first functional group of the first resin layer and the second resin layer of the second resin layer are formed in the opening portion of the conductive pattern. The conductive film which has a hardening reaction part with the functional group of.
- 全光線透過率が、70%以上である、請求項7に記載の導電フィルム。 The conductive film according to claim 7, wherein the total light transmittance is 70% or more.
- 前記導電パターンが無秩序な交差接触部を有する金属ナノワイヤを含む請求項7または8に記載の導電フィルム。 The conductive film according to claim 7 or 8, wherein the conductive pattern includes metal nanowires having disordered cross contact portions.
- 前記導電パターンが規則的または不規則的に形成された金属細線パターンを含む請求項7または8に記載の導電フィルム。
The conductive film according to claim 7 or 8, wherein the conductive pattern includes a fine metal wire pattern formed regularly or irregularly.
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JP (1) | JP6664396B2 (en) |
KR (1) | KR102000956B1 (en) |
CN (1) | CN107615408B (en) |
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Cited By (2)
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WO2019230633A1 (en) * | 2018-05-30 | 2019-12-05 | Dowaエレクトロニクス株式会社 | Silver nanowire ink, method for producing transparent conductive film, and transparent conductive film |
WO2020137144A1 (en) * | 2018-12-27 | 2020-07-02 | 富士フイルム株式会社 | Photosensitive transfer material, laminate, touch panel, method for producing patterned substrate, method for producing circuit board, and method for producing touch panel |
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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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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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JP2002164247A (en) * | 2000-11-24 | 2002-06-07 | Murata Mfg Co Ltd | Dielectric ceramic composition and layered ceramic capacitor |
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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 |
KR101568659B1 (en) * | 2013-03-29 | 2015-11-12 | 제일모직주식회사 | Anisotropic conducting film comprising conductive adhesive layer and a semiconductor device connected by the film |
KR20150084689A (en) * | 2014-01-14 | 2015-07-22 | 주식회사 동진쎄미켐 | Transparent conductive electrode and method for producing the same |
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- 2016-07-26 KR KR1020177031866A patent/KR102000956B1/en active IP Right Grant
- 2016-07-26 JP JP2017530888A patent/JP6664396B2/en active Active
- 2016-07-26 CN CN201680030108.2A patent/CN107615408B/en active Active
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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 |
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 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2019230633A1 (en) * | 2018-05-30 | 2019-12-05 | Dowaエレクトロニクス株式会社 | Silver nanowire ink, method for producing transparent conductive film, and transparent conductive film |
WO2020137144A1 (en) * | 2018-12-27 | 2020-07-02 | 富士フイルム株式会社 | Photosensitive transfer material, laminate, touch panel, method for producing patterned substrate, method for producing circuit board, and method for producing touch panel |
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 |
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KR102000956B1 (en) | 2019-07-17 |
TW201718247A (en) | 2017-06-01 |
JPWO2017018427A1 (en) | 2018-05-24 |
KR20170133483A (en) | 2017-12-05 |
CN107615408A (en) | 2018-01-19 |
TWI693160B (en) | 2020-05-11 |
JP6664396B2 (en) | 2020-03-13 |
CN107615408B (en) | 2019-07-02 |
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