KR102640877B1 - Conductive solution composition and conductive structure using the same - Google Patents

Abstract

A conductive solution composition with excellent adhesion to a crystalline polymer substrate and excellent surface hardness when coated and a conductive structure using the same are disclosed. The conductive solution composition includes a first binder containing a first polyolefin resin containing maleic anhydride; A second binder containing a second polyolefin resin having a glass transition temperature of 20° C. or lower; conductive filler; and a dispersion medium.

Description

Conductive solution composition and conductive structure using the same {Conductive solution composition and conductive structure using the same}

The present invention relates to a conductive solution composition and a conductive structure using the same, and more specifically, to a conductive solution composition with excellent adhesion to a crystalline polymer substrate and excellent surface hardness when coated, and a conductive structure using the same.

Typically, film substrates made of olefin resin (crystalline polymers, such as polypropylene (PP), polyethylene (PE), etc.) have low surface energy, and the conductive composition may not react on the substrate surface itself. Since there are few sites, if only the conductive composition is coated, it does not adhere well. Figure 1 is a diagram showing a method of coating a conductive solution composition on a film substrate made of a typical olefin resin material. As shown in FIG. 1, in order to coat the conductive solution composition, one side of an olefinic resin substrate 12, for example, a polypropylene (PP) substrate, is treated with a primer to modify the surface to form carbonyl groups. Forming an adhesive layer (protrusion layer, 14) having (C=O) and olefin (C=C) bonds, and coating a conductive composition on top of the adhesive layer (14) to form a conductive coating layer (16), 2 It is also manufactured using a coating method. However, in this case, since it is coated using a heat attachment method using thermal lamination, it is impossible to continuously perform the coating process, and since the process goes through two steps, the process cost increases and it is inconvenient.

Figure 2 is a diagram for explaining a manufacturing method of a film made of olefin resin material manufactured by a conventional internal addition method. As shown in Figure 2, in order to compensate for the above shortcomings, a conductive filler is added to the feeder (17, hopper) that supplies the polymer resin composition (18) in the extrusion process, which is a manufacturing process of olefin resin (crystalline polymer) sheet. (22) is supplied together, and then the supplied polymer resin composition (18) and the conductive filler (22) are melted to extrude a film made of olefinic resin in the form of a sheet having a predetermined thickness. Using the extruder 20, a film made of an internally added olefin resin material to which a conductive filler 22 is internally added is manufactured. Here, the front end of the extruder 20 is equipped with a motor 19b that drives the screw 19a to extrude the molten polymer resin composition 18 and the conductive filler 22, and the rear end is equipped with a motor 19b that drives the molten polymer resin composition 18 and the conductive filler 22. It is equipped with an ejector 21 that extrudes the polymer resin composition 18 and the conductive filler 22. However, when carbon black or the like is added as a conductive filler, there is a problem that a sloughing phenomenon may occur. Here, the sloughing phenomenon refers to the phenomenon in which the internally added conductive filler comes out of the film.

Republic of Korea Patent Publication No. 10-2006-0071637 discloses a coating that is coated after corona discharge treatment on one or both sides to increase adhesion to a crystalline polymer sheet. In this case, as described above, lamination Since it is a heat attachment method, a continuous process cannot be performed, and since it is performed by a two-coat coating method, there is a problem of increased manufacturing cost and inconvenience. In Korean Patent Publication No. 10-2000-0075344, A conductive sheet composition capable of crosslinking maleic acid-grafted polyolefin with a conductive carbon material and vinyltrimethoxysilane has been disclosed. However, by adding a conductive filler in the extrusion process to manufacture the sheet, there is a problem that a sloughing phenomenon may occur and There is a problem that manufacturing costs increase because a large amount of conductive filler must be added.

Therefore, the purpose of the present invention is to provide a conductive solution composition that has excellent adhesion to a crystalline polymer substrate, can provide electrical conductivity to the coating surface of the substrate, and has excellent hardness of the coating surface.

Another object of the present invention is to provide a conductive solution composition that simplifies the process, reduces manufacturing costs (fixed costs), and does not cause sloughing, and a conductive structure using the same.

In order to achieve the above object, the present invention includes a first binder containing a first polyolefin resin containing maleic anhydride; A second binder containing a second polyolefin resin having a glass transition temperature of 20° C. or lower; conductive filler; and a dispersion medium. It provides a conductive solution composition comprising a.

In addition, the present invention relates to a substrate; And it is directly adhered to one side of the substrate, and includes a first binder containing a first polyolefin resin containing maleic anhydride, a second binder containing a second polyolefin resin having a glass transition temperature of 20 ° C. or less, and a conductive filler. A conductive structure including a coating film is provided.

The conductive solution composition according to the present invention has excellent adhesion to a crystalline polymer substrate, can provide electrical conductivity to the coated surface of the substrate, and has excellent surface hardness when coated. In addition, since it is manufactured by coating it thinly at 1 degree, the manufacturing cost is reduced, and since no conductive filler is added during the extrusion process, the sloughing phenomenon does not occur.

Figure 1 is a diagram showing a method of coating a conductive solution composition on a film substrate made of a typical olefin resin.
Figure 2 is a diagram for explaining a manufacturing method of a film made of olefin resin material manufactured by a conventional internal addition method.
Figure 3 is a diagram showing an example of a conductive structure according to the present invention.
Figure 4 is a diagram showing the evaluation method of ASTM D3359.
Figure 5 is a photograph (a) of a pencil hardness tester and a diagram showing a method of measuring using it (b).

Hereinafter, the present invention will be described in more detail with reference to the attached drawings.

The conductive solution composition according to the present invention has excellent adhesion and electrical conductivity with a crystalline polymer (substrate), has excellent surface hardness when coated, and includes a first binder, a second binder, a conductive filler, and a dispersion medium. Here, the crystalline polymer refers to a polymer (polyolefin) having a crystallinity of 35% or more, specifically 65% or more, more specifically 65 to 90%, and includes, for example, polyethylene, polypropylene, etc. . Here, the crystallinity is measured by melting enthalpy analysis using a differential scanning calorimeter.

The first binder serves to strengthen the adhesion to the crystalline polymer, and is a first polyolefin (polypropylene, polyethylene, etc., for example, containing) maleic anhydride (MAH). ) It is a resin binder, and as a specific example, it can be represented by the following formula (1), and the maleic anhydride serves to strengthen the adhesion with the crystalline polymer.

[Formula 1]

In Formula 1, m and n are wt% of each repeating unit relative to the total repeating units constituting the first polyolefin containing maleic anhydride, and m is 90 to 99.9 wt%, specifically 90 to 98 wt%. , n is 0.1 to 10 wt%, specifically 2.0 to 10.0 wt%.

With respect to the entire first binder, the content of maleic anhydride is 2 to 30% by weight, specifically 2 to 15% by weight, and more specifically 10 to 15% by weight. If the content of maleic anhydride is too small, the desired adhesion may not be achieved, and if it is too much, sheet resistance and hardness may decrease. In addition, the weight average molecular weight of the first polyolefin resin containing maleic anhydride is 10,000 to 400,000, specifically 50,000 to 200,000. If the weight average molecular weight of the first binder is too small, adhesion may be reduced and efficiency may be poor, and if it is too large, sheet resistance and hardness may be reduced.

The second binder, like the first binder, serves to strengthen the adhesion to the crystalline polymer and strengthen the wetting with the surface of the substrate to be coated. It is used together with the first binder to protect the crystalline polymer. It is a second polyolefin resin (polypropylene, polyethylene, etc.) binder that further improves adhesion and has a glass transition temperature (Tg) of 20 ℃ or less, specifically -15 to 15 ℃. The weight average molecular weight of the second polyolefin resin having a glass transition temperature of 20° C. or lower is 10,000 to 400,000, specifically 50,000 to 200,000. If the glass transition temperature is higher than 20°C, the tackiness of the binder is low and the wettability with the substrate is reduced, which may cause coatingability problems. If the glass transition temperature is too low, the tackiness is high and stickiness occurs. Adhesion and coating properties may be reduced due to residual or reduced wettability. The second binder has improved wettability (liquidity) within the range of the glass transition temperature and can easily penetrate into the surface of the substrate, thereby providing excellent adhesion. The second binder can control wettability according to various substrates by controlling the glass transition temperature and/or molecular weight of the second polyolefin resin. In addition, the glass transition temperature is determined by analyzing the endothermic behavior that occurs when the molecules of a polymer material become active and begin to move due to temperature through differential scanning calorimetry (DSC), or by analyzing the endothermic behavior of a polymer material (Dynamic Mechancal Analyzer, Through DMA), it can be measured by analyzing the tanδ value at the point where molecular movement begins and the elastic modulus rapidly decreases.

The conductive filler serves to provide electrical conductivity and is made of graphite such as graphene, graphene oxide (GO), expanded graphite, and carbon. It may be carbon materials such as carbon black, carbon nanotubes (CNT), poly(3,4-ethylenedioxy thiophene) (PEDOT), and mixtures thereof.

The dispersion medium serves to disperse the conductive filler, and includes water (distilled water), alcohols such as methanol, ethanol, and isopropyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and N-methylpyrrolidone. pyrrolidines, esters such as ethyl acetate, aromatic esters such as benzyl acetate, linear and/or branched hydrocarbons such as dimethoxyethane and 1-chlorobutane, ethyl cellosolve acetate, butyl cellosolve One or more dispersion media selected from the group consisting of glycol ethers (cellosolves) such as acetate and mixtures thereof can be used.

In the conductive solution composition, the content of the first binder is 0.01 to 30% by weight, specifically 0.1 to 20% by weight, and the content of the second binder is 0.01 to 10% by weight, specifically 1.0 to 8% by weight. %, and the content of the conductive filler is 0.001 to 40% by weight, specifically 0.01 to 30% by weight, and more specifically 0.01 to 20% by weight. Additionally, the content of the dispersion medium is 20 to 99% by weight, specifically 48 to 90% by weight. Here, it is more efficient to add the first binder and the second binder in similar or identical amounts (for example, 1:9 to 9:1, specifically 5:5 ratio). If the content of the first binder and the second binder is outside the above range, physical properties such as adhesion to the substrate, sheet resistance, and hardness may decrease, and if the content of the conductive filler is too small, sufficient electrical conductivity may not be provided. If there are too many, it may not be economical. Additionally, if the content of the dispersion medium is outside the above range, the conductive filler may not be sufficiently dissolved or the viscosity may become too low.

The conductive solution composition according to the present invention may further include a crosslinking agent, a dispersing agent, etc., if necessary.

The cross-linking agent (cross-linking enhancer) not only prevents excessive expansion of the hydrophilic polymer, prevents dissolution, and strengthens hardness, but also serves to further improve adhesion together with the first and second binders, and is represented by the following formula (2) The indicated alkoxy silane.

[Formula 2]

In Formula 2, R ₁ is an alkene group containing 0 to 2 oxygen atoms and having 1 to 10 carbon atoms, specifically 1 to 6 carbon atoms, or an aryl group having 4 to 10 carbon atoms, specifically 5 to 8 carbon atoms, R is an alkyl group having 1 to 10 carbon atoms, specifically 1 to 5 carbon atoms. R combines with oxygen (O) to form an alkoxy group (general formula: C _n H _2n+1 O-, abbreviation: RO-). Specific examples of R ₁ include vinyl (-vinyl), aryl (-aryl), and acryl (-acryl), and specific examples of R include methyl, ethyl, propyl, butyl, etc. can be exemplified. The crosslinking agent may be, for example, vinyltrimethoxysilane.

The content of the crosslinking agent is 0.01 to 10% by weight, specifically, 0.01 to 5% by weight. If the content of the cross-linking agent is too small, the degree of cross-linking may not be sufficient, and if it is too much, the cross-linking density may become too high, resulting in difficulty during coating.

The dispersant serves to disperse the conductive filler, and may be polyurethane-based, fatty acid-based, CPT-based, phosphoric acid ester-based, etc., and the content of the dispersant is 0.05 to 10% by weight, specifically 0.1 to 5% by weight. am. If the content of the dispersant is too small, the conductive filler may not be sufficiently dispersed, and if it is too much, more than necessary may be added, making it inefficient.

The conductive composition of the present invention uses the first and second binders to not only strengthen the adhesion to a substrate made of a crystalline polymer with low adhesion, but the second binder strengthens the wettability with the surface of the substrate to form a bond between the substrate and the substrate. Adhesion can be further improved, and hardness can also be improved by using the crosslinking agent.

Figure 3 is a diagram showing an example of a conductive structure according to the present invention. As shown in Figure 3, the conductive solution composition according to the present invention is applied on one side of the substrate 12 made of polyolefin resin (specifically, crystallized polymer), such as polypropylene, polyethylene, etc. (e.g. For example, it is applied to directly contact the substrate 12) and dried to manufacture a conductive structure in which the coating film 24 is formed (directly in contact) on one side of the substrate 12. In this case, the conductive The structure may have a two-layer structure consisting of a substrate 12 and a coating film 24. The conductive solution composition of the present invention has excellent adhesion and does not require a separate coating (14, primer coating) like the conventional process (see FIGS. 1 and 3), so the process cost can be reduced and the surface hardness can also be improved. great. In addition, conventionally manufactured conductive structures are formed in a single-layer structure, which causes a sloughing phenomenon, or are formed in a three-layer or more structure by increasing the number of coatings, increasing the process cost, whereas the conductive structure of the present invention has a two-layer structure. Because it is formed in a structured structure, not only does the sloughing phenomenon not occur, but it also simplifies the process and has the effect of reducing process costs, so it can be applied to a variety of purposes. The thickness of the coating film 24 may be 0.3 to 60 ㎛, specifically 1 to 50 ㎛. If the thickness is less than 0.3 ㎛, conductivity may not be maintained, and if the thickness is more than 60 ㎛, it may be difficult to form a coating film.

In order to prepare the conductive solution composition according to the present invention, first, a first binder and a second binder are prepared. The first binder can be prepared by adding and stirring a first polyolefin resin containing maleic anhydride in the presence of a heated dispersion medium. The amount of the first polyolefin resin used is not particularly limited and may be set as needed, but for example, an amount capable of producing 0.01 to 30% by weight of the first binder is used. The second binder can be manufactured in the same manner, except that a second polyolefin resin having a glass transition temperature of 20° C. or lower is used instead of the first polyolefin resin containing maleic anhydride. The heating temperature of the dispersion medium can be set appropriately as needed, for example, 30 to 150°C, specifically 60 to 120°C. In addition, the dispersion medium serves to disperse the conductive filler, and includes water (distilled water), alcohols such as methanol, ethanol, and isopropyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and N-methylpyrroli. Pyrrolidines such as pigeon, esters such as ethyl acetate, aromatic esters such as benzyl acetate, linear and/or branched hydrocarbons such as dimethoxyethane and 1-chlorobutane, ethyl cellosolve acetate, butylcell. One or more dispersion media selected from the group consisting of glycol ethers (cellosolves) such as Rosolve acetate and mixtures thereof can be used.

Next, in the presence of a dispersion medium, the first binder, the second binder, the conductive filler, and the dispersion medium are mixed to prepare a conductive solution composition. Additionally, the conductive solution composition may further include a crosslinking agent and/or dispersing agent, if necessary. Each of the components is as described in the conductive solution composition.

After the conductive solution composition according to the present invention is applied to one side of a polypropylene sheet or polyethylene film, it is incubated at a predetermined temperature and time, for example, 50 to 150 ° C., specifically, 70 to 100 ° C. for 1 to 10 minutes, Specifically, it can be coated by drying for 2 to 5 minutes. When coating the polypropylene sheet (e.g., Danpla box, etc.), the adhesion is excellent even with 1-coat coating, so the process cost can be reduced compared to the conventional 2-coat coating, and polyethylene film (e.g. For example, when coating on foam slippers, etc., there is an advantage in reducing costs compared to the conventional UV curing type. In addition, the conductive solution composition according to the present invention can be used for various coatings such as ESD (Electrostatic Discharge) coating solutions such as antistatic films, insulator films, heat dissipation coating solutions (coating agents), secondary battery electrode materials, and crystalline polymer plastic sheets or films. It can be used as a material.

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to the following examples.

[Preparation Example 1] Preparation of the first binder

Add 800 g of toluene (Samjeon Pure Pharmaceutical) to the flask, heat the flask until the temperature reaches 70°C, and then add 200 g of the first polyolefin resin in which maleic anhydride is substituted in the polyolefin resin in three portions. and stirred for 2 hours to prepare a binder solution containing 20% by weight of binder and 80% by weight of toluene. The binder content of the binder solution was confirmed by placing a certain amount of the prepared binder in an aluminum dish and measuring the weight before and after drying.

[Preparation Example 2] Preparation of a binder using polyolefin resin with a Tg of 25°C or higher

It was prepared in the same manner as Preparation Example 1, except that a polyolefin resin having a glass transition temperature (Tg) of 25° C. or higher was used instead of the first polyolefin resin.

[Preparation Example 3] Preparation of a second binder using a polyolefin resin with a Tg of 20°C or lower

It was prepared in the same manner as in Preparation Example 1, except that a second polyolefin resin with a glass transition temperature (Tg) of 20° C. or less and a molecular weight of 40,000 was used instead of the first polyolefin resin.

[Preparation Example 4] Preparation of binder using acryl-modified polyolefin resin

It was prepared in the same manner as Preparation Example 1, except that an acryl-modified polyolefin resin was used instead of the first polyolefin resin.

[Examples 1 to 10 and Comparative Examples 1 to 6] Preparation of conductive solution composition

The binder solutions and alkoxy silanes prepared in Preparation Examples 1 to 4 were added in the composition ratios shown in Table 1 below, and 0.1 to 0.1 to 0.1 to 0.1 alkoxy silane was added as an additive for graphene dispersion in methyl ethyl ketone (MEK, Samchun Chemical). A mixed solution was prepared by adding 1% by weight of graphene powder as a conductive filler, and the prepared mixed solution was stirred for 20 minutes, mixed with zirconia beads, and then used a shaker for 40 minutes. and dispersed to prepare a conductive solution composition (Examples 1 to 10 and Comparative Examples 1 to 6).

Binder composition and addition amount Comparative Example 1 MAH modified polyolefin resin 10% (only) Comparative Example 2 10% polyolefin resin with Tg 20℃ or less (exclusive) Comparative Example 3 Acryl modified polyolefin resin 5% + (Tg 20℃) polyolefin resin 5% Comparative Example 4 MAH modified polyolefin resin 5% + (Tg 25℃) polyolefin resin 5% Comparative Example 5 5% MAH modified polyolefin resin + (Tg 30℃) 5% polyolefin resin Comparative Example 6 5% MAH modified polyolefin resin + (Tg 40℃) 5% polyolefin resin Example 1 5% MAH modified polyolefin resin + (Tg 20℃) 5% polyolefin resin Example 2 5% MAH modified polyolefin resin + (Tg 15℃) 5% polyolefin resin Example 3 5% MAH modified polyolefin resin + (Tg 10℃) 5% polyolefin resin Example 4 5% MAH modified polyolefin resin + (Tg 0℃) 5% polyolefin resin Example 5 5% MAH modified polyolefin resin + (Tg -10℃) 5% polyolefin resin Example 6 MAH modified polyolefin resin 5% + (Tg 20℃) polyolefin resin 5% + Alkoxy silane 0.1% Example 7 MAH modified polyolefin resin 5% + (Tg 15℃) polyolefin resin 5% + Alkoxy silane 0.1% Example 8 MAH modified polyolefin resin 5% + (Tg 10℃) polyolefin resin 5% + Alkoxy silane 0.1% Example 9 MAH modified polyolefin resin 5% + (Tg 0℃) polyolefin resin 5% + Alkoxy silane 0.1% Example 10 MAH modified polyolefin resin 5% + (Tg -10℃) polyolefin resin 5% + Alkoxy silane 0.1%

[Experimental Example 1] Evaluation of properties of conductive solution composition

The conductive solution compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were printed on polypropylene (PP) sheets and polyethylene (PE) films using an automatic coating machine and a bar-coater. The coating was dried for 3 minutes in a hot air oven set at 80°C, and the sheet resistance was measured 5 times using a sheet resistance meter (SIMCO, ST-4) and then averaged. The adhesion test was obtained by conducting a cross-cut test according to ASTM D3359 standard and then conducting a tape test using double-sided tape. The hardness of the coating film was obtained by applying a weight of 2 kg. A test was performed by reciprocating 10 cm per film depending on the hardness of the pencil (pencil hardness test), and the results are shown in Table 2 below. Here, Figure 4 is a diagram showing the evaluation method of ASTM D3359. As shown in Figure 4, the ASTM D3359 standard first selects the coating area to be tested, cleans the coating area, and checks whether it is completely dry. Next, when the coating film thickness is 0 to 60 ㎛, cut at 1 mm intervals, at 61 to 120 ㎛ at intervals of 2 mm, and at 121 to 250 ㎛, cut at 3 mm intervals and cross-cut. ) Proceed with the test. In this experimental example, cross-cutting was performed at intervals of 1 mm. Afterwards, tape was applied to the area where peeling did not occur, and the tape was rubbed with an eraser to adhere it to the coating film, and then quickly ripped to check. The evaluation method was divided into six stages: 5B > 4B > 3B > 2B > 1B > 0B. (Adhesion becomes better as you go to 5B). In addition, Figure 5 is a photograph (a) of a pencil hardness tester and a drawing (b) showing a method of measuring using it. As shown in Figure 5, the pencil hardness test is performed using pencils with various hardnesses positioned at an inclination of 45 degrees with respect to the painted surface, using the hardness of the pencil when no scratches are present, and the coating film By measuring the hardness, the hardness is 9H > 8H > 7H > … > 2H > H > F > HB > B > 2B > … It is expressed in 20 levels from > 8B > 9B (hardness becomes superior as it goes to 9H).

Sheet resistance (Log R Ω/sq) Adhesion Coating film hardness Comparative Example 1 7.1 3B B Comparative Example 2 7.9 3B 2B Comparative Example 3 7.5 2B 4B Comparative Example 4 7.6 4B 1B Comparative Example 5 7.5 4B 1B Comparative Example 6 7.6 4B 1B Example 1 6.6 5B H Example 2 6.7 5B H Example 3 6.6 5B H Example 4 6.7 5B H Example 5 6.7 5B H Example 6 6.8 5B 2H Example 7 6.6 5B 2H Example 8 6.7 5B 2H Example 9 6.6 5B 2H Example 10 6.7 5B 2H

As shown in Table 2, in the case of Comparative Examples 1 and 2 using only one binder, the adhesion force was measured to be significantly low due to poor wetting with the coated substrate, and the hardness was also measured to be low. In the case of Comparative Example 3 using a binder containing a polyolefin resin with a glass transition temperature (Tg) of 20°C or less and a binder containing a polyolefin resin not containing maleic anhydride, adhesion to polypropylene sheets and polyethylene films, which are crystalline polymers, was observed. Since it does not come out easily, rather than using a polyolefin-based binder alone, in the case of Example 1, which mixed a binder of a polyolefin resin containing maleic anhydride and a polyolefin resin with a glass transition temperature (Tg) of 20 ℃ or less, the sheet resistance and hardness were lower. You can see that it is getting better.

In addition, in Comparative Examples 4 to 6, in which a polyolefin-based binder with a glass transition temperature (Tg) of 25 ℃ or higher is used instead of a polyolefin-based binder with a glass transition temperature (Tg) of 20 ℃ or lower, the glass transition temperature (Tg) is 20. Compared to Examples 1 to 5 using a polyolefin-based binder with a temperature of ℃ or less, it was confirmed that not only the hardness and adhesion were low, but also the sheet resistance was high. Furthermore, when the alkoxy silane as a crosslinking agent was added in Examples 6 to 10, It was confirmed that hardness was improved.

[Experimental Example 2] Evaluation of properties according to change in content of conductive solution composition

In order to measure the properties (sheet resistance, adhesion, and coating film hardness) by content of the first binder and the second binder in the conductive solution composition prepared in Example 1, the conductivity of Examples 11 to 19 was measured in the ratios shown in Table 3 below. A solution composition was prepared, and the results of its properties are shown in Table 3 below. Here, the properties were measured in the same manner as in Experimental Example 1, and the first binder was denoted as A and the second binder was denoted as B.

A:B ratio Sheet resistance (Log R Ω/sq) Adhesion Coating film hardness Example 11 90:10 6.9 4B HB Example 12 80:20 6.7 5B H Example 13 70:30 6.7 5B H Example 14 60:40 6.8 5B H Example 15 50:50 6.8 5B H Example 16 40:60 6.7 5B H Example 17 30:70 6.7 5B H Example 18 20:80 6.9 5B H Example 19 10:90 6.8 4B HB

As shown in Table 3, when using a mixture of a polyolefin-based binder containing maleic anhydride and a polyolefin-based binder with a glass transition temperature (Tg) of 20 ℃ or less, sheet resistance, adhesion, and coating film hardness are improved, as shown in Examples 11 to 11. This could be confirmed in 19.

Specifically, the best properties were achieved when the content of the polyolefin-based binder containing maleic anhydride and the polyolefin-based binder with a glass transition temperature (Tg) of 20° C. or lower was 8:2 to 2:8 (Examples 12 to 18). You can check what it represents.

[Experimental Example 3] Evaluation of properties according to the type of polyolefin resin with a glass transition temperature (Tg) of 20 ℃ or less

Since the type of polyolefin resin is determined depending on the molecular weight, in order to measure the properties (sheet resistance, adhesion, and coating film hardness) according to the type of polyolefin resin with a glass transition temperature (Tg) of 20 ℃ or less, in Preparation Example 3 In addition to the prepared Example 1 (polyolefin resin with a molecular weight of 40,000 at a glass transition temperature (Tg) of 20°C or lower), properties were tested using polyethylene resins with molecular weights of 120,000, 80,000, and 20,000. The experimental method was a conductive solution composition prepared in the same manner as Example 1, except that polyethylene resins with molecular weights of 120,000, 80,000, and 20,000 were used instead of polyolefin resins with a molecular weight of 40,000 and a glass transition temperature of 20 ℃ or less (Example 20 To 22) were used to measure the properties, and the results are shown in Table 4 below.

Binder composition and addition amount Sheet resistance Adhesion Hardness Example 1 (Tg 20℃) Molecular weight 40000 Polyethylene resin 5% 6.6 5B H Example 20 (Tg 20℃) Molecular weight 120000 Polyethylene resin 5% 6.8 5B H Example 21 (Tg 20℃) Molecular weight 80000 Polyethylene resin 5% 6.7 5B H Example 22 (Tg 20℃) Molecular weight 20000 Polyethylene resin 5% 6.6 5B H

As shown in Table 4, even if the weight average molecular weight of the second binder used in the present invention is different, if the weight average molecular weight of the present invention is satisfied, sheet resistance, adhesion, and hardness are measured similarly, and the glass transition temperature is 20. It can be seen that sheet resistance, adhesion, and hardness are improved when polyolefin resin with a temperature of ℃ or lower is used.

Claims (13)

A first binder containing a first polyolefin resin containing maleic anhydride;
A second binder containing a second polyolefin resin having a glass transition temperature of -15°C or more and 20°C or less;
conductive filler; and
A conductive solution composition comprising a dispersion medium. The method of claim 1, wherein the content of the first binder is 0.01 to 30% by weight, the content of the second binder is 0.01 to 10% by weight, the content of the conductive filler is 0.001 to 40% by weight, and the dispersion medium A conductive solution composition having a content of 20 to 99% by weight. The conductive solution composition of claim 1, wherein the first binder is represented by the following formula (1).
[Formula 1]

In Formula 1, m and n are wt% of each repeating unit relative to the total repeating units constituting the first polyolefin containing maleic anhydride, m is 90 to 99.9 wt%, and n is 0.1 to 10 wt%. am. The conductive solution composition of claim 1, wherein the second binder has a weight average molecular weight of 10,000 to 400,000 g/mol. The conductive solution composition according to claim 1, wherein the first binder and the second binder are used in an amount ratio of 1:9 to 9:1, respectively. The conductive solution composition of claim 1, further comprising a cross-linking agent. The conductive solution composition according to claim 6, wherein the crosslinking agent is represented by the following formula (2).
[Formula 2]

In Formula 2, R ₁ is an alkene group having 1 to 10 carbon atoms or an aryl group having 4 to 10 carbon atoms containing 0 to 2 oxygen atoms, and R is an alkyl group having 1 to 10 carbon atoms. The conductive solution composition of claim 1, wherein the conductive filler is selected from the group consisting of graphene, graphene oxide, graphite, carbon black, carbon nanotubes, polyethylenedioxythiophene, and mixtures thereof. Board; and
A conductive structure comprising a first binder containing a first polyolefin resin containing maleic anhydride, a second binder containing a second polyolefin resin having a glass transition temperature of -15°C or more and 20°C or less, and a coating film containing a conductive filler. The conductive structure of claim 9, wherein the coating film has a thickness of 0.3 to 60 ㎛. The conductive structure of claim 9, wherein the coating film is in direct contact with one surface of the substrate. The conductive structure according to claim 9, wherein the substrate and the coating film have a two-layer structure. The conductive structure of claim 9, wherein the substrate is a crystalline polymer resin.