CN107615408B - Manufacturing method of conductive film and conductive film - Google Patents

Abstract

The issue of the present invention is to provide the manufacturing method of the conductive film high with the adaptation, environmental resistance and marresistance of substrate and conductive films.Include the following steps: to form the 1st resin layer (S1) on substrate using the 1st resin combination comprising the 1st functional group, it is not fallen into conductive material to the degree of the inside of layer the 1st resin layer is dry (S2), then the conductive pattern (S3, S4) with opening portion when forming vertical view on the 1st resin layer, using comprising can with the 2nd resin combination of the 2nd functional group of the 1st functional group's co-curing of above-mentioned 1st resin layer by be coated conductive pattern it is at least part of in a manner of form the 2nd resin layer, make the 1st resin layer and the 2nd resin layer co-curing (S5).

Description

Manufacturing method of conductive film and conductive film

technical field

The present invention relates to a method for producing a conductive film and the conductive film.

Background technique

Various conductive films have been developed and produced according to the application to various electronic parts. For example, transparent conductive films have been used in liquid crystal displays (LCDs), plasma display panels (PDPs), organic electroluminescent displays, transparent electrodes for solar cells (PVs) and touch panels (TPs), antistatic (ESD) films, and Electromagnetic wave shielding (EMI) films are used in various fields. As these transparent conductive films, a transparent conductive film using ITO (indium tin oxide) has been used in the past, but there are problems such as low supply stability of indium, high manufacturing cost, lack of flexibility, and poor quality of indium. High temperature is required when filming. Therefore, the search for a transparent conductive film that replaces ITO has been actively carried out. Among them, the transparent conductive film containing metal nanowires has excellent conductivity, optical properties and flexibility, and can be formed by a wet process. The production cost is low, and high temperature is not required for film formation. Membranes are suitable.

For example, a transparent conductive film containing silver nanowires and having high conductivity, optical properties, and flexibility is known (see Patent Document 1). Moreover, the following patent document 2 discloses the manufacturing method of the transparent conductive film which has a transparent conductive layer containing a metal nanowire on a transparent base material.

In such a transparent conductive film, it is necessary to have high adhesion between the conductive layer and the substrate. In addition, especially for a transparent conductive film containing metal nanowires, since the surface area per unit mass of metals such as silver is large, it is easy to interact with each other. Since these compounds react with each other, there is a problem of lack of environmental resistance. Therefore, the nanostructures are easily corroded due to the influence of various chemicals and cleaning solutions used in the process, and the influence of oxygen and moisture in the air exposed due to long-term storage, and the conductivity is likely to decrease. In addition, especially in applications such as electronic materials, in order to prevent particulate impurities, dust, dust, etc. from adhering to and mixing into the surface of the substrate, a physical cleaning process such as a brush is often used, but this process can also cause damage to the surface. This becomes the problem.

In order to solve the above-mentioned problems, various attempts have been made to laminate a protective film on the surface of a transparent conductive film containing silver nanowires, and to impart environmental resistance and scratch resistance to the transparent conductive film. (See Patent Documents 3 to 4).

As described above, the transparent conductive film is required to have high adhesion between the conductive layer and the substrate, environmental resistance, and scratch resistance.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Publication No. 2010-507199

Patent Document 2: Japanese Patent No. 5609008

Patent Document 3: Japanese Patent Laid-Open No. 2014-191894

Patent Document 4: Japanese Patent Laid-Open No. 2013-200943

SUMMARY OF THE INVENTION

The problem to be solved by the invention

An object of the present invention is to provide a method for producing a conductive film with high adhesion between a conductive layer and a substrate, environmental resistance, and scratch resistance, and a conductive film.

means of solving problems

In order to achieve the above object, one embodiment of the present invention is a method for producing a conductive film, the method comprising the steps of forming a first resin layer on a substrate using a first resin composition containing a first functional group, In the step of forming a conductive pattern having openings in a plan view on the first resin layer, a second resin composition containing a second functional group co-curable with the first functional group of the first resin layer is used to cover the conductive pattern. The step of forming the second resin layer in at least a part of the method, and the step of co-curing the first resin layer and the second resin layer.

It is preferable that the said conductive pattern is formed after the surface of the said 1st resin layer becomes tack-free.

In addition, the first functional group may include a moiety having reactivity in subsequent steps, such as a carboxyl group, a hydroxyl group, an epoxy group, a (meth)acryloyl group, a vinyl group, an allyl group, and the like. Preferably, the first resin composition Any of a carboxyl group-containing polyurethane, a phenol novolac epoxy resin, a phenoxy resin, a mixture of a carboxyl group-containing polyurethane and an epoxy compound of less than 1 equivalent on a carboxyl group basis, and a diallyl phthalate resin kind.

Moreover, it is preferable that the said 2nd resin composition contains the mixture of the polyurethane containing a carboxyl group and an epoxy compound, a phenol novolac epoxy resin, a phenoxy resin, a polyurethane containing a carboxyl group, and 1 equivalent or more on the basis of the carboxyl group. Any of the mixture of epoxy compounds, the mixture of diallyl phthalate resin and acrylate monomer.

Moreover, it is preferable that all the said board|substrate, the 1st resin layer, the conductive pattern, and the 2nd resin layer are transparent.

In addition, another embodiment of the present invention is a conductive film comprising a first resin layer containing a first functional group on a substrate, a conductive pattern having an opening in a plan view on the first resin layer, and A second resin layer containing a second functional group is formed so as to cover at least a part of the conductive pattern, and the conductive pattern opening has a curing of the first functional group of the first resin layer and the second functional group of the second resin layer reaction part.

Preferably, the total light transmittance of the conductive film is 70% or more.

The above-described conductive pattern may include metal nanowires having disordered intersecting contacts.

The above-mentioned conductive patterns may include metal thin line patterns formed regularly or randomly.

effect of invention

According to the present invention, it is possible to provide a conductive film having good adhesion to a substrate, environmental resistance, scratch resistance, and optical properties.

Description of drawings

FIG. 1 is a process diagram of a method of manufacturing a conductive film according to an embodiment.

FIG. 2 is a partially enlarged conceptual diagram of the conductive pattern according to the embodiment.

3 is a graph showing the evaluation results of environmental resistance of the conductive films of Example 1 and Comparative Example 7. FIG.

Detailed ways

Hereinafter, specific embodiments (hereinafter referred to as embodiments) of the present invention will be described.

The method for producing a conductive film according to the embodiment is characterized by comprising the step of forming a first resin layer on a substrate using a first resin composition containing a first functional group, wherein the first resin layer is formed on the first resin layer with a The step of forming the conductive pattern of the opening is a step of forming a second resin layer so as to cover at least a part of the conductive pattern using a second resin composition containing a second functional group co-curable with the first functional group of the first resin layer, 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. In FIG. 1 , first, the first resin layer (primer layer) 12 is formed on the substrate 10 ( S1 : first resin layer forming step). Here, the first resin layer 12 can be used as long as it is a resin excellent in adhesiveness with the substrate 10 .

The method for carrying out the above-mentioned S1 (first resin layer forming step) is not particularly limited. Non-contact printing such as ink printing, spray coating, dispenser, etc.

There is no restriction|limiting in particular as a base material which comprises the board|substrate 10, Resin films, such as a glass substrate, a PET (polyethylene terephthalate) film, a PEN (polyethylene naphthalate) film, etc. can be used.

In addition, the first resin layer 12 is composed of a first resin composition containing a first functional group which can be combined with a second resin layer constituting a second resin layer described later after the first resin layer 12 is formed on the surface of the substrate 10 . 2. The second functional group contained in the resin composition is co-cured.

Next, for the above-mentioned first resin layer 12, after forming the first resin composition in a layered form on the surface of the substrate 10, it is preferable to heat it at normal temperature or at an appropriate temperature, so that the This is cured or dried to such an extent that a conductive material for forming a conductive pattern to be described later does not sink into the inside of the first resin layer 12 (S2: first resin composition drying step). The degree of curing or drying can be judged by the following method: According to JIS K 5701, the result of the test using a parallel plate viscometer (spreadometer) is 0 mm, that is, it becomes a state of no fluidity. If a resin that forms a solid at room temperature is used The resin composition of the layer is preferable because the conductive material does not sink into the first resin layer 12 at all in the conductive pattern forming step described later. After the formation of the first resin layer 12 ( S1 ), curing or drying ( S2 ), the conductive pattern 14 having an opening in a plan view is formed on the first resin layer 12 . The "conductive pattern" also includes the case where it is formed in the form of a full surface. The conductive pattern 14 having openings in plan view shown in FIG. 2( a ) to be described later can be prepared by, for example, an ink obtained by dispersing metal nanowires in a dispersion medium (hereinafter, sometimes referred to as “metal nanowire ink”). ”) is printed on the first resin layer 12 to form a pattern (S3: printing step), and is obtained by irradiating light or heating the metal nanowire ink to perform firing (S4: firing step). The fired surface of the conductive pattern including the metal nanowires is in a state of being exposed upward from the surface of the first resin layer 12 .

Here, the term "opening part" refers to a penetration part in the thickness direction such that the second resin composition described later can be brought into contact with the first resin composition, and as shown in FIGS. 2( a ) and ( b ), the metal nanometer There are gaps between the wires 18 or the thin metal wires 19 . In addition, FIG.2(a), (b) is the conceptual diagram which enlarged the conductive pattern 14 partially.

In the case of using the metal nanowire ink, by printing, the metal nanowires 18 are deposited on the substrate in a disorderly manner to have intersecting contacts where the metal nanowires 18 are electrically connected (including contacting each other). ), thereby exhibiting electrical conductivity (Fig. 2(a)). In addition, the opening portion 20 at this time has an irregular shape due to the metal nanowires 18 deposited disorderly. Even if the entire 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 refers to a metal nanowire having a diameter of several tens of nanometers to several hundreds of nanometers and a length of several micrometers to several tens of micrometers.

In addition, in the example shown in FIG.2(b), the opening part 20 of the regular shape (rectangle) is formed by the metal thin wire 19. As shown in FIG. The thin metal wires 19 can be formed using metal foil or metal nanoparticle ink described later. In the example of FIG. 2( b ), the thin metal wires 19 are arranged in a lattice shape and have intersections, but for example, they may be arranged in parallel in a certain direction without having intersections. In addition, the thin metal wires 19 may be arranged randomly, and the openings 20 may have a random shape.

The printing method performed in the above-mentioned S3 (printing step) is not particularly limited, and any printing method can be used as long as the metal nanowire ink can be printed in a pattern. For example, non-contact printing such as screen printing, gravure printing, and their offset printing, contact printing such as a bar coater, die coater, and gravure coater, ink jet printing, spray coating, and spreader can be mentioned. In the case of performing the above-mentioned contact printing, after the first resin layer 12 is formed by applying, for example, the first resin composition to the substrate 10 , it is preferable that the first resin layer 12 be in a dry state to the touch (no tackiness), that is, the surface is not tacky (no tackiness). sticky) state. Thereby, even if a printing apparatus contacts the 1st resin layer 12, favorable printing can be performed. In addition, in order to shorten a hardening time when co-curing with the 2nd resin composition which comprises the 2nd resin layer 16, a hardening accelerator may be mixed with the 1st resin composition which comprises the 1st resin layer 12. When the 1st resin composition contains the epoxy compound mentioned later, it is preferable to mix|blend a hardening accelerator in advance.

On the other hand, in the case of performing non-contact printing such as an inkjet method, the first resin layer 12 does not need to be in a dry state to the touch, and the conductive material does not sink into the inside of the first resin layer 12 at all, that is, It is sufficient that the surface of the conductive material is exposed on the surface of the first resin layer 12 .

In addition, as the ink which can be used for printing the conductive pattern 14, it is not limited to the above-mentioned metal nanowire ink, For example, a metal nanoparticle ink can also be used. However, in the case of using the metal nanoparticle ink, in order to exhibit conductivity, the conductive particles must be in dense contact with each other, and when the entire film is formed, the openings 20 hardly exist in plan view. Therefore, in order to form a pattern having the openings 20, it is necessary to form a thin line pattern (a pattern of the metal thin wires 19) having the openings 20 as shown in FIG. 2(b), for example. The thin line pattern may be formed regularly or randomly, or may be formed so as to have intersections like a mesh pattern. The term "metal nanoparticles" as used herein refers to particles having a spherical shape, an angular shape, a flat [plate] shape, and the like having a particle size of the nm order, preferably a spherical shape.

When the total light transmittance of the substrate on which the printed conductive pattern 14 is formed is 80% or more, it is preferable to secure a sufficient gap for bringing the first resin layer 12 into contact with the second resin layer 16 described later.

Next, the second resin layer (cover layer) 16 is formed so as to cover at least a part of the conductive pattern ( S5 : second resin layer forming step). This process can be implemented by the same method as the above-mentioned S1 (1st resin layer formation process). The so-called "at least a part" includes the whole. For example, when a part is exposed as an electrode part for conducting with the outside, the part is not covered. In this case, it will be in a partially covered state. Here, the 2nd resin layer 16 is comprised from the 2nd resin composition which contains the 2nd functional group which can be co-cured with the 1st functional group contained in the 1st resin composition which comprises the said 1st resin layer 12. After the second resin layer forming step (S5), the first resin layer 12 and the second resin layer 16 are co-cured based on the first and second functional groups (S6: co-curing step (not shown)). That is, the 1st functional group contained in the 1st resin layer 12 and the 2nd functional group contained in the 2nd resin layer 16 are hardened and reacted. The conductive pattern 14 has openings 20 in the thickness direction, and the second resin composition constituting the second resin layer 16 enters the openings 20 and undergoes a curing reaction at the interface with the first resin layer 12 . That is, the opening portion 20 of the conductive pattern 14 has a curing reaction portion of the first functional group of the first resin layer 12 and the second functional group of the second resin layer 16 . As a result, the conductive pattern 14 is sandwiched by the first resin layer 12 and the second resin layer 16, and is held in the opening 20 of the conductive pattern 14, so that the conductive pattern 14 having good adhesion to the substrate 10 can be obtained. . Examples of combinations of the first functional group of the first resin layer 12 and the second functional group of the second resin layer 16 include carboxyl group/epoxy group, epoxy group/carboxyl group, hydroxyl group/carboxyl group, (meth)acryloyl group/ Vinyl, vinyl/(meth)acryloyl, allyl/(meth)acryloyl, etc., but not limited to these.

As a combination of the first resin composition constituting the first resin layer 12 and the second resin composition constituting the second resin layer 16, in the order of (first resin layer: second resin layer), ( Carboxyl group-containing polyurethane (the first functional group is a carboxyl group): a mixture of a carboxyl group-containing polyurethane and an epoxy compound (the second functional group is an epoxy group), (phenol novolac epoxy resin (the first functional group is an epoxy group) : Phenol novolak type epoxy resin (the second functional group is an epoxy group)), (phenoxy resin (the first functional group is an epoxy group): phenoxy resin (the second functional group is an epoxy group)), ( Carboxyl group-containing polyurethane (1st functional group is carboxyl group): phenoxy resin (2nd functional group is epoxy group)), (mixture of carboxyl group-containing polyurethane and less than 1 equivalent of epoxy compound based on carboxyl group (1st The functional group is a carboxyl group): a mixture of a carboxyl group-containing polyurethane and an epoxy compound in an amount of 1 equivalent or more based on the carboxyl group (the second functional group is an epoxy group), (diallyl phthalate resin (the first functional group is an alkene) Propyl): a mixture of diallyl phthalate resin and acrylate monomer (the second functional group is an allyl group and an acryloyl group)) and the like.

In the above-mentioned combination, when the first resin composition contains a carboxyl group-containing polyurethane and the second resin composition contains a combination of a carboxyl group-containing polyurethane and an epoxy compound, the first resin layer 12 and the second resin layer 16 are subjected to By heating, the carboxyl group (first functional group) of the carboxyl group-containing urethane contained in the first resin layer 12 and the second resin layer 16 and the epoxy group (second functional group) of the epoxy compound are bonded and co-cured. The first resin composition contains a carboxyl group-containing polyurethane and an epoxy compound in an amount of less than 1 equivalent on a carboxyl group basis, and the second resin composition contains a combination of a carboxyl group-containing polyurethane and an epoxy compound in an amount of 1 equivalent or more on a carboxyl group basis. Co-curing occurs in the same way. Moreover, in the case of a combination of phenol novolak-type epoxy resin compositions and phenoxy resin compositions, co-curing occurs by adding an appropriate curing agent for epoxy resins and heating. In this case, both the first functional group and the second functional group become epoxy groups. Further, when the first resin composition contains a carboxyl group-containing polyurethane and the second resin composition contains a combination of a phenoxy resin, by heating the first resin layer 12 and the second resin layer 16, the carboxyl group (the first resin layer 16) is heated. 1 functional group) and an epoxy group (2nd functional group) are bonded and co-cured. In addition, the first resin composition contains a diallyl phthalate resin (the first functional group is an allyl group), and the second resin composition contains a diallyl phthalate resin and an acrylate monomer (the second functional group is an allyl group). In the case of a combination of an allyl group and an acryloyl group), co-curing occurs by performing addition polymerization by light irradiation.

Here, the substrate 10 , the first resin layer 12 , the conductive pattern 14 and the second resin layer 16 are preferably transparent. Thereby, it is applicable to transparent elements, such as a touch panel. The term "transparent" here means that the total light transmittance is 80% or more. The total light transmittance of the conductive film of the present invention including these is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more.

Example

Hereinafter, the Example of this invention is demonstrated concretely. It should be noted that the following examples are used to easily understand the present invention, and the present invention is not limited by these examples.

In this example, the molecular weight and acid value of the resin, and the total light transmittance and surface resistance of the conductive pattern were measured as follows.

<Molecular weight>

The value in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC).

The measurement conditions of GPC are as follows.

Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation

Column: Shodex column LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus manufactured by JASCO Corporation

Temperature: 40.0℃

Sample volume: sample loop 100 μL

Sample concentration: prepared to be about 0.1% by mass

＜Acid value＞

About 0.2 g of the sample was accurately weighed into a 100-ml conical flask with a precision balance, and 10 ml of a mixed solvent of ethanol/toluene=1/2 (mass ratio) was added and dissolved. Furthermore, 1 to 3 drops of a phenolphthalein ethanol solution was added to the container as an indicator, and the mixture was sufficiently stirred until the sample became uniform. It was titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization was when the reddish color of the indicator continued for 30 seconds. From the result, the value obtained by using the following calculation formula was made into the acid value of resin.

Acid value (mg-KOH/g)=[B×f×5.611]/S

B: The usage amount of 0.1N potassium hydroxide-ethanol solution (ml)

f: factor for 0.1N potassium hydroxide-ethanol solution

S: Sample collection amount (g)

＜Total light transmittance＞

It is the value obtained by measuring the conductive pattern formed on the board|substrate by 50 mm square cutting and using a turbidity meter (NDH2000, Nippon Denshoku Kogyo).

<Surface Resistance>

The measurement was performed by a 4-terminal method using a resistivity meter, Rolesta (registered trademark) GP MCP-T610 type (manufactured by Mitsubishi Chemical Corporation). The ESP mode is used for the measurement mode and the terminal to be used.

<Synthesis example of carboxyl group-containing polyurethane>

[Synthesis Example 1]

Into a 2L three-necked flask equipped with a stirring device, a thermometer and a condenser, C-1015N (manufactured by Kuraray Co., Ltd., polycarbonate diol, raw material diol molar ratio of 1,9-nonanediol) was charged as a polyol compound. Alcohol: 2-methyl-1,8-octanediol = 15:85, molecular weight 964) 143.6 g, 2,2-dimethylolbutyric acid (manufactured by Nippon Kasei Co., Ltd.) as a dihydroxy compound having a carboxyl group 27.32 g and 259 g of propylene glycol monomethyl ether acetate (trade name: methoxypropyl acetate, manufactured by Daicel Co., Ltd.) as a solvent were dissolved in the above-mentioned 2,2-dimethylolbutyric acid at 90°C.

The temperature of the reaction solution was lowered to 70° C., and using a dropping funnel, Desmjell (registered trademark)-W (methylenebis(4-cyclohexyl isocyanate), a polyisocyanate), was added dropwise over 30 minutes using a dropping funnel, manufactured by Sumina Chemical Co., Ltd. Company system) 87.5g. After completion of the dropwise addition, the temperature was raised to 120° C., and the reaction was performed 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 performed at 120° C. for 6 hours. The weight average molecular weight of the obtained carboxyl group-containing polyurethane was 32,300, and the acid value of the resin was 40 mgKOH/g.

[Synthesis Example 2]

44.8 g of C-1015N (manufactured by Kuraray Co., Ltd.), 16.1 g of 2,2-dimethylolbutyric acid (manufactured by Nippon Kasei Co., Ltd.), and propylene glycol monomethyl ether acetate (Taizel Co., Ltd.) were used as a solvent. A carboxyl group-containing polyurethane was obtained in the same manner as in Synthesis Example 1, except that 100.3 g of the company's product) and 40.7 g of Destroy (registered trademark)-W (manufactured by Sumika Bioltech Co., Ltd.). The weight-average molecular weight of the obtained carboxyl group-containing polyurethane was 29,200, and the acid value of the resin was 60 mgKOH/g.

[Example 1]

As shown in Table 1, on a PET (polyethylene terephthalate) substrate (Lumira (registered trademark) 125T60 manufactured by Toray Co., Ltd.), ink was printed by a bar coater, and the ink is a compounding example. The carboxyl group-containing urethane resin synthesized in 1, and the curing accelerator, 2P4MHZ-PW (2-phenyl-4-methyl-5-hydroxymethylimidazole), as a curing accelerator, were added 1 with respect to 100 parts by mass of the resin. parts by mass), and diluted with propylene glycol monomethyl ether acetate so that the concentration of the resin component containing the curing accelerator becomes 30% by mass (corresponding to the first resin composition), and the treatment was carried out at 100° C. for 1 hour. It was dried to form a primer layer (equivalent to the first resin layer) having a film thickness of 10 μm (average value measured at arbitrary 5 locations using a high-precision digital micrometer MDH-25M 293-100 manufactured by Mitsutoyo). The thickness of the primer layer was determined by measuring the thickness of the substrate including the substrate after forming the primer layer and drying and subtracting the thickness of the substrate.

After drying, evaluation of stickiness was implemented based on JIS Z0237. The state where all the balls did not stop was regarded as non-sticky, and the state where any of the balls stopped was regarded as sticky.

After confirming that there is no stickiness (no stickiness), a silver nanowire dispersion liquid (0.125 g of silver nanowires (the average wire diameter of about 40 nm and the average length of about 10 μm) was randomly observed by SEM was 100 μm. The number average value of each silver nanowire) was dispersed in 50 g of ethanol (preparation of a 0.25 mass % dispersion of silver nanowires), and 0.05 g of the dispersion was used to coat with a bar coater so as not to overflow from the primer layer. The coating of the silver nanowire dispersion liquid was performed well. After the silver nanowire dispersion liquid was applied, it was fired at 100° C. for 1 hour to form a solid conductive pattern. The surface resistance after firing was 80Ω/□, and the total light transmittance was 89%.

Then, as a cover layer (corresponding to the second resin layer), using a bar coater, ink was printed so as to cover substantially the entire surface of the conductive pattern, and co-curing was performed at 140° C. for 1 hour. The ink was in Synthesis Example 1. To 10 g of the synthesized carboxyl group-containing urethane resin and 0.69 g of an epoxy compound (jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation), a carboxyl group-containing urethane resin and an epoxy compound (jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation) were blended. The total amount of 100 parts by mass is 1 part by mass of a curing accelerator (Kipur (registered trademark) 2P4MHZ-PW manufactured by Shikoku Chemicals Co., Ltd.) (corresponding to the second resin composition, at the concentration of the resin component containing the curing accelerator) Diluted with propylene glycol monomethyl ether acetate so that it may become 30 mass %). The entire film thickness including the undercoat layer was 20 μm. When 6 parts by mass of an epoxy compound (jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation) was added to 100 parts by mass of the carboxyl group-containing urethane resin synthesized in Synthesis Example 1, the carboxyl group-containing urethane resin synthesized in Synthesis Example 1 had The carboxyl group and the epoxy group of the epoxy compound (JER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation) were equivalent to 1 equivalent. For the cover layer (corresponding to the second resin layer) of Example 1, as shown in Table 1, the carboxyl group-containing urethane resin synthesized in Synthesis Example 1 was mixed with an epoxy compound (jER (registered trademark) manufactured by Mitsubishi Chemical Corporation) 828) is 100 to 7 (recorded as 100/7 in Table 1), so the following composition is obtained: with respect to the carboxyl group of the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1, the ring The epoxy group of the oxygen compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation) is present in a slight excess.

About the obtained conductive film, the following characteristic evaluation was performed. The results are shown in Table 1.

[Evaluation of Adhesion (Peeling Test)]

About the cured film, the cross cut test (JIS K5600) was performed as adhesiveness evaluation. The results are described in Tables 1 and 2 as "peeling test". In addition, the smaller the numerical value of the test result, the higher the adhesiveness (peeling resistance) (most preferably 0). In Table 1, the peeling test result of Example 1 is 0, and it turns out that the adhesiveness (peeling resistance) is high.

[Scratch resistance test]

As a scratch resistance test, scratch resistance was easily determined by paper rubbing. For the paper used, JKワイパー was used, and the cover was reciprocated 5 times. The presence or absence of damage and scratches was confirmed by visual inspection and a microscope. The results are described in Tables 1 and 2 as "scratch resistance test".

⊚: No damage or scratches were observed by visual inspection and a microscope.

○: No damage was observed by visual observation, but slight scratches were observed by microscope.

Δ: No damage was observed by visual observation, but damage and scratches were observed by a microscope.

×: Damage and scratches can be recognized by visual inspection.

[Environmental Resistance]

The environmental resistance was stored in an atmosphere of 85° C. and 85% RH (relative humidity) using a thermo-hygrostat (TH402A manufactured by ETAC), and the change in surface resistance after about 1100 hours was measured as a ratio to the initial surface resistance. . The results are shown in FIG. 3 .

[Optical Properties]

As optical properties, HAZE (haze) and light transmittance of the obtained conductive film were measured using a Haze meter NDH 2000 (manufactured by Nippon Denshoku). The results are described in Tables 1 and 2 as "optical properties".

○: Total light transmittance is 80% or more and HAZE is 20% or less

×: Total light transmittance is 80% or more and HAZE is more than 20%

[Examples 2 to 6]

Using the ink prepared in the same manner as in Example 1 except that the material composition shown in Table 1 was changed, the primer layer, the conductive pattern, and the cover layer were formed by the same thickness configuration and the same steps. The same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1 were performed, and Table 1 shows the results. With respect to 100 parts by mass of the carboxyl group-containing urethane resin synthesized in Synthesis Example 2 used for the cover layer of Example 2, 9 parts by mass of an epoxy compound (JER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation) was blended, and the result was Synthesis Example 2 The carboxyl group of the carboxyl group-containing urethane resin synthesized in 1 is equivalent to the epoxy group of the epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation). For the cover layer (corresponding to the second resin layer) of Example 2, as shown in Table 1, the carboxyl group-containing urethane resin synthesized in Synthesis Example 2 was mixed with an epoxy compound (jER (registered trademark) manufactured by Mitsubishi Chemical Corporation) 828) is 100 to 10 (recorded as 100/10 in Table 1), so the following composition is obtained: with respect to the carboxyl group of the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 2, the ring The epoxy group of the oxygen compound (JER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation) is present in a slight excess.

In addition, as for the primer layer (corresponding to the first resin layer) of Example 6, as shown in Table 1, the carboxyl group-containing urethane resin synthesized in Synthesis Example 1 was mixed with an epoxy compound (jER (manufactured by Mitsubishi Chemical) The compounding ratio (mass ratio) of registered trademark) 828) was 100 to 3 (represented as 100/3 in Table 1), so the following composition was obtained in which the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1 had half of the carboxyl groups remaining. In addition, the cover layer (corresponding to a 2nd resin layer) of Example 6 is the same as that of Example 1.

[Example 7]

Using the ink prepared in the same manner as in Example 1 except that the material composition shown in Table 1 was changed, the primer layer, the conductive pattern, and the cover layer were formed by the same thickness configuration and the same steps. At this time, as a curing accelerator for the coating layer, IRGACURE (registered trademark) 184 (manufactured by BASF Corporation) was used in place of Kiryaru (registered trademark) 2P4MHZ-PW (manufactured by Shikoku Chemicals). In addition, 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 (Oku Corporation). The same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1 were performed, and Table 1 shows the results.

[Comparative Example 1]

The undercoat layer was formed by changing to the material composition shown in Table 2. The primer layer was in a liquid state and was highly sticky, and the silver nanowire ink could not be printed even by other printing methods such as inkjet. The reason is considered to be that the molecular weight of the resin of Comparative Example 1 was as small as 4,100, while the molecular weight of the other examples was 10,000 or more.

[Comparative Examples 2 to 5]

Using the ink prepared in the same manner as in Example 1 except that the material composition shown in Table 2 was changed, the primer layer, the conductive pattern, and the cover layer were formed by the same thickness configuration and the same steps. Among them, in Comparative Example 4, UV light exposure of about 40 mW/cm ² was performed, and a treatment equivalent to co-curing was performed. The same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1 were performed, and Table 2 shows the results.

In Examples 1 to 4, the same resin component was used for the primer layer and the cover layer, and when co-curing was performed, the primer layer and the cover layer were adhered by chemical bonding, and peeling did not occur.

In Example 5, different resin components were used for the primer layer and the cover layer, but since they had co-curable functional groups, there was no peeling between the primer layer and the cover layer after curing. On the other hand, in Comparative Examples 4 and 5, resins with different curing mechanisms were used for the primer layer and the cover layer, UV curing was performed in Comparative Example 4, and thermal curing was performed in Comparative Example 5. , the undercoat layer and the cover layer do not co-curing, and peeling occurs between the undercoat layer and the cover layer.

In addition, in Example 6, as a primer layer, an epoxy compound (JER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation) was added to the carboxyl group-containing polyurethane at a ratio of half of the functional group (carboxyl group) remaining, followed by drying at 100° C. for 1 hour. Under these conditions, it is in a suitable state such as semi-curing, and the coating layer is adhered to the coating layer by chemical bonding due to the residual functional group, so that there is no peeling between the primer layer and the coating layer. In contrast, in Comparative Examples 2 and 3, the resins used in the primer layer and the cover layer were completely cured, and the primer layer was formed (100° C., 1 hour drying) when the primer layer was formed. The residual functional groups of the layer reaction disappeared in the undercoat layer, and thus, peeling occurred between the undercoat layer and the cover layer (the peel test result was 5).

From Examples 1 to 6 and Comparative Examples 2 to 5, the superiority of co-curing can be seen.

[Table 1]

[Table 2]

[Comparative Example 6]

The structure was the same as that of Example 1 except that the primer layer was not provided. The same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1 were performed, and Table 2 shows the results. The peeling test and the scratch resistance test were good, but since there was no primer layer, the total light transmittance decreased by 5% or more, but was 80% or more, when the PET substrate coated with the silver nanowire dispersion was heated. However, HAZE is 2% before heating, but exceeds 50% after heating, and the optical properties are greatly impaired. By heating, the oligomer is precipitated from the PET substrate, and the surface roughness increases, thereby impairing the optical properties.

[Comparative Example 7]

It is a comparative example without a cover layer. The same adhesion evaluation (peeling test), scratch resistance test, and optical property evaluation as in Example 1 were performed, and Table 2 shows the results. Since there is no coating layer, the scratch resistance test shows that the metal part is damaged, and from the environmental resistance results shown in FIG. 3 , which are similar to those of Example 1, the resistance starts after about 700 hours. Significant increase, low environmental resistance.

Description of reference numerals

10 substrate, 12 first resin layer, 14 conductive pattern, 16 second resin layer, 18 metal nanowires, 19 metal thin wires, 20 openings.

Claims (10)

1. a kind of manufacturing method of conductive film comprising following processes:

The process that the 1st resin layer is formed on substrate using the 1st resin combination comprising the 1st functional group,

The process of the conductive pattern with opening portion when forming vertical view on aforementioned 1st resin layer,

Using comprising can be with the 2nd resin combination of the 2nd functional group of the 1st functional group's co-curing of aforementioned 1st resin layer with quilt The process that at least part of mode of aforesaid conductive pattern forms the 2nd resin layer is covered, and

Make the process of aforementioned 1st resin layer and the 2nd resin layer co-curing.

2. the manufacturing method of conductive film according to claim 1, wherein become on the surface of aforementioned 1st resin layer without viscous Property after, formed aforesaid conductive pattern.

3. the manufacturing method of conductive film according to claim 1 or 2, wherein aforementioned 1st functional group include carboxyl, hydroxyl, It is epoxy group, (methyl) acryloyl group, vinyl, any number of in allyl.

4. the manufacturing method of conductive film according to claim 1 or 2, wherein aforementioned 1st resin combination contains carboxylic Polyurethane, phenol novolak type epoxy resin, phenoxy resin, the polyurethane containing carboxyl of base are low in terms of carboxyl benchmark It is any number of in the mixture, dially phthalate resin of the epoxide of 1 equivalent.

5. the manufacturing method of conductive film according to claim 1 or 2, wherein aforementioned 2nd resin combination contains carboxylic The polyurethane of base and the mixture of epoxide, phenol novolak type epoxy resin, phenoxy resin, gathering containing carboxyl Mixture, dially phthalate resin and the propylene of urethane and the epoxide that 1 equivalent or more is calculated as with carboxyl benchmark It is any number of in the mixture of acid ester monomer.

6. the manufacturing method of conductive film according to claim 1 or 2, wherein aforesaid base plate, the 1st resin layer, conductive pattern And the 2nd resin layer be transparent.

7. a kind of conductive film, wherein there is the 1st resin layer comprising the 1st functional group on substrate, have on the 1st resin layer Conductive pattern with opening portion when having vertical view, by be coated the conductive pattern it is at least part of in a manner of be formed with comprising the 2nd 2nd resin layer of functional group, also, the 1st functional group in aforesaid conductive pattern openings portion with aforementioned 1st resin layer and the The curing reaction part of 2nd functional group of 2 resin layers.

8. conductive film according to claim 7, wherein total light transmittance is 70% or more.

9. conductive film according to claim 7 or 8, wherein aforesaid conductive pattern includes to have unordered cross-contact portion Metal nanometer line.

10. conductive film according to claim 7 or 8, wherein aforesaid conductive pattern includes regularly or irregularly to be formed Metal fine pattern.