JP2015199802A - Conductive resin composition and planar heating element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive resin composition and a planar heating element using the same, capable of efficiently enhancing uniformity (leveling property) of film thickness on an obtained coated film, conductivity and adhesiveness to a substrate.SOLUTION: There is provided a conductive resin composition containing following (A) to (C) components: (A) a polythiophene conductive polymer of 100 pts.wt.; (B) an aqueous polyester resin having a sulfonate base of 200 to 530 pts.wt.; and (C) a vinylpyrrolidone-vinyl acetate copolymer of 7 to 230 pts.wt.

Description

The present invention relates to a conductive resin composition and a planar heating element.
In particular, the present invention relates to a conductive resin composition capable of effectively improving film thickness uniformity, conductivity, and adhesion to a substrate in the resulting coating film, and a planar heating element using the same.

Conventionally, in order to prevent defrosting of passenger car headlights and fogging of a windshield or rear glass, a transparent planar heating element is laminated on the glass.
In addition, as a method for producing such a transparent planar heating element, a method of applying and drying a conductive resin composition on a substrate on which an electrode pattern is printed is widely practiced (for example, Patent Documents). 1).

That is, Patent Document 1 includes (A) a π-conjugated conductive polymer and (B) a binder, and (A) the conductivity of the π-conjugated conductive polymer is 0.15 (S / cm) or more. (B) The binder contains a polyester resin or a polyurethane resin, and the blending amount of (B) binder is 0.1 to 500 parts by mass with respect to 100 parts by mass of (A) π-conjugated conductive polymer. A conductive coating agent for forming a transparent surface heating element and a transparent surface heating element obtained by using the same are disclosed.
In the specification of Patent Document 1, it is described that a polythiophene conductive polymer is used as the π-conjugated conductive polymer, and polyvinyl acetate or the like is used as a binder other than the polyester resin or the polyurethane resin.

Further, although it is an invention of a paste for screen printing mainly for forming an electrode, Patent Document 2 includes a solution or dispersion of a conductive polymer and optionally a binder, a thickening agent and a filler. A screen printing paste having a viscosity of 1 to 200 dPas is disclosed.
Patent Document 2 describes that a polythiophene conductive polymer is used as the conductive polymer, and polyvinyl pyrrolidone, polyester, polyvinyl alcohol, or the like is used to adjust the viscosity.

WO2012 / 073474 (Claims) JP-T-2002-500408 (Claims)

However, the conductive coating agent described in Patent Document 1 has insufficient compatibility between the polyester resin or polyurethane resin as the binder and the polythiophene-based conductive polymer, and the uniformity of the film thickness in the resulting coating film, There was a problem that conductivity and adhesion to the substrate were low.
Moreover, even when it used together with polyvinyl acetate which is binders other than a polyester resin or a polyurethane resin, the problem that the problems, such as the uniformity of the film thickness in the obtained coating film, could not be solved was seen.

In addition, the screen printing paste described in Patent Document 2 also has insufficient compatibility between the polyester resin functioning as a binder and the polythiophene-based conductive polymer. And the problem that the adhesiveness with respect to a base material is low was seen.
Moreover, even when polyvinyl pyrrolidone or polyvinyl alcohol was used in combination to adjust the viscosity, there was a problem that problems such as film thickness uniformity in the obtained coating film could not be solved.

Therefore, the present inventors diligently studied the conventional problems, and as a result, an aqueous polyester resin having a sulfonate group with respect to the polythiophene-based conductive polymer and a vinylpyrrolidone-vinyl acetate copolymer, respectively, with a predetermined blending ratio. It has been found that the above-mentioned problems can be solved by blending in an amount, and the present invention has been completed.
More specifically, by adding a vinylpyrrolidone-vinyl acetate copolymer, the compatibility between the aqueous polyester resin having a sulfonate group as the main binder resin and the polythiophene-based conductive polymer is effectively improved. As a result, it was found that the uniformity of film thickness, conductivity, and adhesion to the substrate can be effectively improved in the resulting coating film.
That is, an object of the present invention is to provide a conductive resin composition that can effectively improve film thickness uniformity, conductivity, and adhesion to a substrate in the resulting coating film, and a planar heating element using the same. Is to provide.

According to this invention, the conductive resin composition characterized by including the following (A)-(C) component is provided, and the problem mentioned above can be solved.
(A) Polythiophene-based conductive polymer 100 parts by weight (B) Aqueous polyester resin having a sulfonate group 200 to 530 parts by weight (C) Vinylpyrrolidone-vinyl acetate copolymer 7 to 230 parts by weight That is, the conductivity of the present invention If it is a resin composition, an aqueous polyester resin having a sulfonate group, a vinylpyrrolidone-vinyl acetate copolymer, and a solvent are blended in predetermined blending amounts with respect to the polythiophene-based conductive polymer. Therefore, the compatibility between the aqueous polyester resin having a sulfonate group as a main binder resin and the polythiophene conductive polymer can be effectively improved.
As a result, it is possible to effectively improve film thickness uniformity (hereinafter sometimes referred to as “leveling property”), conductivity, and adhesion to the substrate in the obtained coating film.
Moreover, if it is the conductive resin composition of this invention, various characteristics requested | required of conductive resin compositions, such as transparency, storage stability, and drying property, can be exhibited with sufficient balance.

In constituting the conductive resin composition of the present invention, the polythiophene-based conductive polymer as the component (A) is poly (3,4-ethylenedioxythiophene) and the poly (3,4-ethylenediethylene). Oxythiophene) and a polystyrene sulfonic acid as a dopant forming an ion pair are preferable.
By comprising in this way, compatibility with the aqueous polyester which has a sulfonate group can be improved more, exhibiting the electroconductivity in the coating film obtained effectively.

Further, in constituting the conductive resin composition of the present invention, the weight average molecular weight of the aqueous polyester resin having a sulfonate group as the component (B) is set to a value within the range of 5,000 to 30,000. preferable.
By comprising in this way, the adhesiveness with respect to a base material can be improved more, and abrasion resistance can also be improved, hold | maintaining the electroconductivity in the coating film obtained effectively.

In constituting the conductive resin composition of the present invention, the weight average molecular weight of the vinylpyrrolidone-vinyl acetate copolymer as the component (C) may be set to a value within the range of 10,000 to 500,000. preferable.
By configuring in this way, the compatibility between the aqueous polyester resin having a sulfonate group and the polythiophene-based conductive polymer can be more effectively improved while effectively maintaining the conductivity in the resulting coating film. Can do.

In composing the conductive resin composition of the present invention, the copolymerization ratio (in terms of mole) of vinylpyrrolidone: vinyl acetate in the vinylpyrrolidone-vinyl acetate copolymer as component (C) is 90:10 to 55. : A value within the range of 45 is preferable.
By comprising in this way, compatibility with the aqueous | water-based polyester resin which has a sulfonate group, and a polythiophene type conductive polymer can be improved further.

Moreover, in composing the conductive resin composition of the present invention, the component (D) includes an acetoacetyl group-modified polyvinyl alcohol resin as component (D), and the blending amount of the acetoacetyl group-modified polyvinyl alcohol resin as component (A). It is preferable to set it as the value within the range of 0.7-15 weight part with respect to 100 weight part of polythiophene type conductive polymer.
By comprising in this way, the compatibility of the water-based polyester resin which has a sulfonate group, and a polythiophene-type conductive polymer can be improved further, and it also improves the abrasion resistance in the coating film obtained. be able to.

Further, in constituting the conductive resin composition of the present invention, as the component (E), an aqueous polyether urethane resin is included, and the blending amount of the aqueous polyether urethane resin is changed to a polythiophene-based conductive material as the component (A). The value is preferably in the range of 25 to 170 parts by weight with respect to 100 parts by weight of the conductive polymer.
By comprising in this way, adjusting the viscosity of the conductive resin composition to a suitable range while effectively maintaining the conductivity and adhesion in the resulting coating film, the film thickness of the resulting coating film Uniformity can be further improved.

Further, in constituting the conductive resin composition of the present invention, the surfactant is included as the component (F), and the blending amount of the surfactant is 100 weight of the polythiophene-based conductive polymer as the component (A). It is preferable to set it as the value within the range of 50-370 weight part with respect to a part.
By comprising in this way, it is possible to effectively improve the compatibility between the aqueous polyester resin having a sulfonate group and the polythiophene-based conductive polymer while effectively maintaining the conductivity in the resulting coating film. it can.

Further, in constituting the conductive resin composition of the present invention, the (G) component contains the solvents (A) to (C), and the blending amount of the solvent is changed to the polythiophene type (A) component. The value is preferably in the range of 8,000 to 12,000 parts by weight with respect to 100 parts by weight of the conductive polymer.
By comprising in this way, the viscosity and drying property of a conductive resin composition can be adjusted to a suitable range, and the electroconductivity in the coating film obtained can be stabilized.

Moreover, when comprising the conductive resin composition of this invention, it is preferable that the solvent as (G) component contains water and ethylene glycol.
By comprising in this way, the viscosity and drying property of a conductive resin composition can be adjusted to a more suitable range, and the electroconductivity in the coating film obtained can be stabilized more.

Another embodiment of the present invention is a planar heating element including a base material and a heat generating layer formed on the surface of the base material, wherein the heat generating layer contains the following components (A) to (C): A planar heating element obtained by applying and drying a conductive resin composition.
(A) Polythiophene-based conductive polymer 100 parts by weight (B) Aqueous polyester resin having a sulfonate group 200 to 530 parts by weight (C) Vinylpyrrolidone-vinyl acetate copolymer 7 to 230 parts by weight In the case of a heating element, since the heating layer is formed using a predetermined conductive resin composition, the uniformity of the film thickness in the heating layer, the conductivity, and the adhesion to the substrate can be effectively improved. In addition, the transparency of the heat generating layer can be effectively improved.
Therefore, it is possible to obtain a high-quality planar heating element excellent in various characteristics.

FIG. 1 is a diagram provided for explaining the relationship between the blending amount of an aqueous polyester resin having a sulfonate group as the component (B) and the leveling properties and adhesion in the resulting coating film. FIG. 2 is a diagram for explaining the relationship between the copolymerization ratio in the vinylpyrrolidone-vinyl acetate copolymer as the component (C) and the leveling property in the obtained coating film. FIG. 3 is a diagram provided for explaining the relationship between the blending amount of the vinylpyrrolidone-vinyl acetate copolymer as the component (C) and the leveling property and conductivity in the obtained coating film. FIG. 4 is a diagram provided for explaining the planar heating element.

[First Embodiment]
1st Embodiment of this invention is a conductive resin composition characterized by including the following (A)-(C) component.
(A) Polythiophene-based conductive polymer 100 parts by weight (B) Aqueous polyester resin having a sulfonate group 200 to 530 parts by weight (C) Vinylpyrrolidone-vinyl acetate copolymer 7 to 230 parts by weight Hereinafter, a first embodiment (A)-(C) component etc. which are each component requirements of are concretely demonstrated.

1. Component (A): Polythiophene Conductive Polymer The conductive resin composition of the present invention is characterized by including a polythiophene conductive polymer as the component (A).
The reason for this is that by including a polythiophene-based conductive polymer, conductivity can be imparted to the resulting coating film.

(1) Kind In addition, the kind of the polythiophene-based conductive polymer is not particularly limited, and conventionally known ones can be used. In particular, poly (3,4-ethylenedioxythiophene) and It is preferable to use a complex composed of the poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid as a dopant forming an ion pair.
This is because, in such a composite, the sulfonate group as the component (B) is obtained by the action of the vinylpyrrolidone-vinyl acetate copolymer as the component (C) described later while effectively exhibiting conductivity. This is because it is possible to effectively improve the compatibility of the aqueous polyester having a solvent and the solvent as the component (D).
Examples of the above-described poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid complex include “CLEVIOS P HCV4” and “CLEVIOS PH 500” manufactured by Heraeus Co., Ltd.

(2) Compounding quantity Moreover, it is preferable to make the compounding quantity of a polythiophene type conductive polymer into the value within the range of 0.1 to 2 weight% with respect to the whole quantity (100%) of a conductive resin composition. .
The reason for this is that if the blending amount is less than 0.1% by weight, the conductivity of the resulting coating film may be excessively lowered. On the other hand, when the blending amount exceeds 2% by weight, the obtained coating film becomes excessively brittle, and the adhesiveness to the substrate may be easily lowered.
Therefore, the blending amount of the polythiophene-based conductive polymer is more preferably set to a value within the range of 0.5 to 1.8% by weight with respect to the total amount (100% by weight) of the conductive resin composition. More preferably, the value is in the range of 1 to 1.5% by weight.

2. (B) Component: Aqueous Polyester Resin Having Sulfonate Group The conductive resin composition of the present invention is characterized by containing an aqueous polyester resin having a sulfonate group as the component (B).
The reason for this is that if it is a water-based polyester resin having a sulfonate group, it exhibits the function as the main binder resin, and effectively maintains the conductivity in the resulting coating film, while leveling and adhesion to the substrate. This is because the predetermined wear resistance can be obtained.
Moreover, it is because compatibility with the polythiophene-based conductive polymer as the component (A) can be effectively improved by the action of the vinylpyrrolidone-vinyl acetate copolymer as the component (C) described later.

(1) Kind In addition, the aqueous polyester resin having a sulfonate group is, for example, a 5-sodiosulfoisophthalic acid having a polyol such as ethylene glycol, a polyvalent carboxylic acid such as isophthalic acid or terephthalic acid, and a sodium sulfonate base. It is a polyester resin obtained by a polycondensation esterification reaction with a polyvalent carboxylic acid having a sulfonate group such as.
In addition to sulfonic acid Na base, sulfonic acid K base, sulfonic acid Li base, sulfonic acid Ca base, sulfonic acid Mg base, sulfonic acid Al base, sulfonic acid Sb base, sulfonic acid Sn base, as well as sulfonic acid Na base. Etc.

(2) Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of the water-based polyester resin which has a sulfonate group into the value within the range of 5,000-30,000.
The reason for this is that by setting the weight-average molecular weight of the aqueous polyester resin having a sulfonate group to a value within this range, the conductivity in the resulting coating film is effectively maintained, and the leveling property and adhesion to the base material are maintained. This is because the wear resistance can be improved.
That is, when the weight average molecular weight is less than 5,000, the coating film strength is remarkably lowered and the wear resistance may be lowered. On the other hand, when the weight average molecular weight exceeds 30,000, the coating film becomes extremely fragile and may easily cause poor adhesion to the substrate.
Therefore, the weight average molecular weight of the aqueous polyester resin having a sulfonate group is more preferably set to a value in the range of 8,000 to 25,000, and is set to a value in the range of 10,000 to 20,000. Further preferred.
In addition, the weight average molecular weight of the water-based polyester resin which has a sulfonate group can be measured as a molecular weight of polystyrene conversion by gel permeation chromatography (GPC).

(3) Blending amount The blending amount of the aqueous polyester resin having a sulfonate group is set to a value within the range of 200 to 530 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). It is characterized by that.
The reason for this is that when the blending amount is less than 200 parts by weight, the leveling property and adhesion to the substrate in the resulting coating film are significantly lowered, and it may be difficult to obtain sufficient wear resistance. Because there is. On the other hand, when the blending amount exceeds 530 parts by weight, the leveling property and conductivity in the resulting coating film are remarkably lowered, and it may be difficult to obtain a predetermined surface resistance value.
Therefore, the blending amount of the aqueous polyester resin having a sulfonate group is more preferably set to a value within the range of 170 to 500 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). More preferably, the value is in the range of 180 to 480 parts by weight.

Next, the relationship between the blending amount of the aqueous polyester resin having a sulfonate group as the component (B) and the leveling property and adhesion in the obtained coating film will be described with reference to FIG.
That is, in FIG. 1, the horizontal axis represents the blending amount (parts by weight) of the aqueous polyester resin having a sulfonate group as the component (B) with respect to 100 parts by weight of the polythiophene-based conductive polymer as the component (A). A characteristic curve A that takes leveling property (evaluation point) is shown on the vertical axis, and a characteristic curve B that takes adhesion (evaluation point) on the right vertical axis.
Moreover, the evaluation score of leveling property and adhesiveness evaluates the leveling property and adhesiveness as described in an Example, and the obtained result is digitized according to the following reference | standard.
In addition, details, such as a composition of a conductive resin composition, apply to Example 1.

(Leveling)
4: Repelling and pinholes are not confirmed and the coating is smooth 3: Repelling and pinholes are not confirmed, but wavy parts are confirmed on the coating 2: Repelling and pinholes are slightly confirmed In addition, a wavy portion is confirmed in the coating film 1: Many repellencies and pinholes are confirmed, and the coating film is entirely wavy.

(Adhesion)
4: The ratio of the grid not peeled is a value of 99% or more 3: The ratio of the grid not peeled is a value less than 95 to 99% 2: The ratio of the grid not peeled is 75 to 95% The value is less than 1: The ratio of the grid not peeled off is less than 75%

First, from the characteristic curve A, it is understood that there is an optimum range for the blending amount of the component (B) when leveling properties are improved.
That is, it is understood that the leveling property once increases and then decreases as the blending amount of the component (B) increases.
More specifically, if the blending amount of component (B) is a value within the range of 200 to 530 parts by weight, the leveling evaluation point can be stably set to a value of 3 or more, otherwise In this numerical range, it is understood that it becomes difficult to stably maintain the leveling evaluation point at a value of 3 or more, and it becomes difficult to maintain excellent leveling properties.

Also, the characteristic curve B is the same as the characteristic curve A. If the blending amount of the component (B) is a value within the range of 200 to 530 parts by weight, the adhesion evaluation score is stably 3 or more. Even if the value is less than 3, it can be a value in the vicinity of 3, but in other numerical ranges, the adhesion evaluation point is stably maintained at a value of 3 or more, or a value in the vicinity of 3. It is understood that it will be difficult to do.
Therefore, the leveling property in the obtained coating film and the adhesiveness with respect to a base material are made by making the compounding quantity of (B) component into the value within the range of 200-530 weight part with respect to 100 weight part of (A) component. It is understood that it can be effectively improved.

3. Component (C): Vinylpyrrolidone-vinyl acetate copolymer The conductive resin composition of the present invention includes a vinylpyrrolidone-vinyl acetate copolymer as the component (C).
The reason for this is that if it is a vinylpyrrolidone-vinyl acetate copolymer, the compatibility between the aqueous polyester resin having a sulfonate group as the component (B) and the polythiophene-based conductive polymer as the component (A) is effective. This is because it can be improved.
As a result, the leveling property, conductivity, and adhesion to the substrate in the obtained coating film can be effectively improved.

(1) Copolymerization ratio The vinylpyrrolidone: vinyl acetate copolymerization ratio (in terms of mole) in the vinylpyrrolidone-vinyl acetate copolymer is preferably set to a value within the range of 90:10 to 55:45.
The reason for this is that by setting the copolymerization ratio of vinyl pyrrolidone and vinyl acetate to a value within this range, the polyester resin having a sulfonate group as the component (B) and the polythiophene-based conductive polymer as the component (A) This is because the compatibility with can be further improved.
That is, when the copolymerization ratio of vinyl pyrrolidone exceeds 90:10, the cohesive strength of the vinyl pyrrolidone-vinyl acetate copolymer decreases, and compatibility with the polythiophene-based conductive polymer as component (A) This is because the leveling property and adhesion in the resulting coating film may be excessively decreased due to a decrease in the viscosity of the conductive resin composition or an excessive increase in the viscosity of the conductive resin composition. On the other hand, when the copolymerization ratio of vinyl pyrrolidone is less than 55:45, the water solubility of the vinyl pyrrolidone-vinyl acetate copolymer is remarkably lowered and the storage stability becomes unstable. This is because the leveling property and adhesion in the case may be excessively lowered.
Therefore, the vinylpyrrolidone: vinyl acetate copolymer ratio (molar conversion) in the vinylpyrrolidone-vinyl acetate copolymer is more preferably set to a value in the range of 85:15 to 58:42, and 83:17 to 60 : More preferably, the value is within the range of 40.

Next, the relationship between the copolymerization ratio (in terms of mole) in the vinylpyrrolidone-vinyl acetate copolymer as the component (C) and the leveling property in the resulting coating film will be described with reference to FIG.
That is, in FIG. 2, the horizontal axis represents the copolymerization ratio (in terms of mole) of vinylpyrrolidone when the total of vinylpyrrolidone and vinyl acetate in the vinylpyrrolidone-vinyl acetate copolymer as component (C) is 100. ), And the vertical axis shows a characteristic curve taking leveling properties (evaluation points).
In addition, the reference | standard of the evaluation score of leveling property, etc. is the same as that of the case of the characteristic curve shown in FIG.

From this characteristic curve, it is understood that there is an optimum range for the copolymerization ratio of vinylpyrrolidone in improving the leveling property.
That is, it is understood that the leveling property once increases and then decreases as the copolymerization ratio of vinylpyrrolidone increases.
More specifically, if the copolymerization ratio of vinyl pyrrolidone is a value within the range of 55 to 90, even if the evaluation score of leveling property is a value of 3 or more stably or less than 3, it is around 3. On the other hand, in other numerical ranges, it is understood that it is difficult to stably maintain the leveling evaluation score at a value of 3 or more or a value in the vicinity of 3.
Therefore, the vinylpyrrolidone copolymerization ratio (in terms of mole) (-) is within the range of 55 to 90 when the total of vinylpyrrolidone and vinyl acetate in the vinylpyrrolidone-vinyl acetate copolymer as component (C) is 100. It is understood that the leveling property in the obtained coating film can be effectively improved by setting the value of.
In addition, although graphing was abbreviate | omitted, from Example 1, 5-6, and Comparative Examples 6-7, also about the adhesiveness, the copolymerization ratio of vinylpyrrolidone is the range of 55-90 similarly to the leveling property mentioned above. It is understood that

(2) Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of a vinylpyrrolidone-vinyl acetate copolymer into the value within the range of 10,000-500,000.
The reason for this is that by setting the weight average molecular weight of the vinylpyrrolidone-vinyl acetate copolymer to a value within this range, the aqueous polyester resin having a sulfonate group as the component (B) and the polythiophene as the component (A) This is because the compatibility with the conductive polymer can be more effectively improved.
In other words, when the weight average molecular weight is less than 10,000, it becomes extremely hygroscopic and it may be difficult to control the conductivity in the resulting coating film. On the other hand, when the weight average molecular weight exceeds 500,000, the compatibility with the components (A) and (B) may be significantly reduced.
Accordingly, the weight average molecular weight of the vinylpyrrolidone-vinyl acetate copolymer is more preferably set to a value within the range of 30,000 to 300,000, and is preferably set to a value within the range of 50,000 to 200,000. Further preferred.
The weight average molecular weight of the vinylpyrrolidone-vinyl acetate copolymer can be measured as a molecular weight in terms of polystyrene by gel permeation chromatography (GPC).

(3) Blending amount The blending amount of the vinylpyrrolidone-vinyl acetate copolymer is set to a value within the range of 7 to 230 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). It is characterized by that.
The reason for this is that when the blending amount is less than 7 parts by weight, the compatibility between the aqueous polyester resin having a sulfonate group as the component (B) and the polythiophene conductive polymer as the component (A) is incompatible. This is because the leveling property and conductivity in the resulting coating film may be excessively lowered. On the other hand, when the blending amount exceeds 230 parts by weight, the compatibility of the conductive resin composition is decreased, and the leveling property and conductivity in the obtained coating film may be excessively decreased. It is.
Therefore, the blending amount of the vinylpyrrolidone-vinyl acetate copolymer is more preferably set to a value in the range of 13 to 220 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). More preferably, the value is within the range of 20 to 215.

Next, the relationship between the blending amount of the vinylpyrrolidone-vinyl acetate copolymer as the component (C) and the leveling property and conductivity in the obtained coating film will be described with reference to FIG.
That is, in FIG. 3, the blending amount (parts by weight) of the vinylpyrrolidone-vinyl acetate copolymer as the component (C) with respect to 100 parts by weight of the polythiophene-based conductive polymer as the component (A) is plotted on the horizontal axis. A characteristic curve A that takes leveling properties (evaluation points) is shown on the vertical axis, and a characteristic curve B that takes electrical conductivity (evaluation points) is shown on the right vertical axis.
In addition, the evaluation point of conductivity is obtained by conducting the evaluation of conductivity described in the examples and quantifying the obtained result according to the following criteria.
In addition, the reference | standard of the evaluation score of leveling property, etc. is the same as that of the case of the characteristic curve shown in FIG.

(Conductivity)
4: The obtained surface resistance value is less than 600 Ω / □ 3: The obtained surface resistance value is less than 600 to 800 Ω / □ 2: The obtained surface resistance value is 800 to 1,000 Ω The value is less than 1 / □, and the obtained surface resistance value is 1,000Ω / □ or more.

First, it is understood from the characteristic curve A that there is an optimum range for the blending amount of the component (C) when leveling properties are improved.
That is, as the blending amount of the component (C) increases, it is understood that the leveling property once increases rapidly and then decreases.
More specifically, if the blending amount of the component (C) is a value within the range of 7 to 230 parts by weight, the leveling evaluation score can be stably set to 3 or more, otherwise In this numerical range, it is understood that it becomes difficult to stably maintain the leveling evaluation point at a value of 3 or more, and it becomes difficult to maintain excellent leveling properties.

Further, the characteristic curve B is the same as the characteristic curve A, and if the blending amount of the component (C) is a value within the range of 7 to 230 parts by weight, the conductivity evaluation point is stably 3 or more. Even if the value is less than 3, it can be a value in the vicinity of 3, but in other numerical ranges, the conductivity evaluation point is stably maintained at a value of 3 or more, or a value in the vicinity of 3. It is understood that it will be difficult to do.
Therefore, the leveling property and electroconductivity in the obtained coating film are effectively obtained by setting the blending amount of the component (C) to a value within the range of 7 to 230 parts by weight with respect to 100 parts by weight of the component (A). It is understood that it can be improved.

4). (D) component: acetoacetyl group-modified polyvinyl alcohol resin In constituting the conductive resin composition of the present invention, it is preferable to include an acetoacetyl group-modified polyvinyl alcohol resin as the component (D).
The reason for this is that if it is an acetoacetyl group-modified polyvinyl alcohol resin, the compatibility between the aqueous polyester resin having a sulfonate group as the component (B) and the polythiophene conductive polymer as the component (A) is further improved. This is because the wear resistance of the resulting coating film can be improved.
The acetoacetyl group-modified polyvinyl alcohol resin can be easily produced by reacting a polyvinyl alcohol resin and diketene by a known method.

(1) Degree of acetylation Moreover, it is preferable to make the degree of acetylation (in molar conversion) in the acetoacetyl group-modified polyvinyl alcohol resin within a range of 1 to 15%.
This is because when the degree of acetylation is less than 1%, the cohesive strength of the acetoacetyl group-modified polyvinyl alcohol resin is lowered, and the viscosity of the conductive resin composition may be excessively increased. On the other hand, when the degree of acetylation exceeds 15%, the water-solubility of the acetoacetyl group-modified polyvinyl alcohol resin is remarkably lowered or the compatibility with the polythiophene-based conductive polymer as the component (A) is lowered. This is because there is a case of doing.
Therefore, it is more preferable to set the acetylation degree (molar conversion) in the acetoacetyl group-modified polyvinyl alcohol resin to a value in the range of 1.2 to 12%, and to a value in the range of 1.5 to 10%. Is more preferable.

(2) Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of an acetoacetyl group modified polyvinyl alcohol resin into the value within the range of 10,000-100,000.
The reason for this is that when the weight average molecular weight is less than 10,000, the wear resistance of the resulting coating film may be significantly reduced. On the other hand, when the weight average molecular weight exceeds 100,000, an aqueous polyester resin having a sulfonate group as the component (B), a polythiophene conductive polymer as the component (A), and a component (D) This is because it may be difficult to sufficiently obtain the effect of improving the compatibility with the solvent.
Therefore, the weight average molecular weight of the acetoacetyl group-modified polyvinyl alcohol resin is more preferably set to a value within the range of 20,000 to 95,000, and further preferably set to a value within the range of 25,000 to 90,000. preferable.
The weight average molecular weight of the acetoacetyl group-modified polyvinyl alcohol resin can be measured as a molecular weight in terms of polystyrene by gel permeation chromatography (GPC).

(2) Blending amount The blending amount of the acetoacetyl group-modified polyvinyl alcohol resin is a value within the range of 0.7 to 15 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). It is preferable to do.
The reason for this is that when the blending amount is less than 0.7 parts by weight, the obtained aqueous polyester resin having a sulfonate group as the component (B) and the polythiophene-based conductive polymer as the component (A) This is because not only the effect of improving the compatibility is insufficient, but also the effect of improving the wear resistance in the obtained coating film may be insufficient. On the other hand, if the blending amount exceeds 15 parts by weight, the compatibility with the polythiophene conductive polymer as the component (A) may decrease.
Therefore, the blending amount of the acetoacetyl group-modified polyvinyl alcohol resin is more preferably 1 to 12 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). More preferably, the value is within the range of 10 parts by weight.

5. (E) Component: Aqueous Polyether Urethane Resin Further, in constituting the conductive resin composition of the present invention, it is preferable to include an aqueous polyether urethane resin as the (E) component.
The reason for this is that an aqueous polyether urethane resin can be obtained by adjusting the viscosity of the conductive resin composition to a suitable range while effectively maintaining the conductivity and adhesion in the resulting coating film. This is because the leveling property in the film can be further improved.

(1) Type It is also preferable that the aqueous polyether urethane resin is an associative polyether urethane resin.
The reason for this is that the associative polyether urethane resin can be obtained by adjusting the viscosity of the conductive resin composition to a suitable range while more effectively maintaining the conductivity and adhesion in the resulting coating film. It is because the leveling property in the coating film obtained can be further improved.
Here, the associative polyether urethane resin is a reaction product of a polyether polyol, an organic isocyanate, and a polyol as a reactant for bonding a terminal constituent group, for example, polyethylene as a polyether polyol. 3-nonylphenoxy-1,2-propanediol, or 1,2-hexadecanediol as a polyol that is a reactant for bonding a glycol, isophorone diisocyanate as an organic isocyanate, or hexamethylene diisocyanate, and a terminal constituent group And a polyether urethane resin obtained by the reaction.

(2) Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of aqueous polyether polyurethane resin into the value within the range of 10,000-500,000.
This is because when the weight average molecular weight is less than 10,000, the thickening effect is remarkably lowered, and the leveling property in the obtained coating film may be excessively lowered. On the other hand, when the weight average molecular weight exceeds 500,000, the thickening effect is remarkably increased, and on the contrary, the leveling property in the obtained coating film may be excessively lowered.
Therefore, the weight average molecular weight of the aqueous polyether urethane resin is more preferably set to a value within the range of 15,000 to 400,000, and further preferably set to a value within the range of 20,000 to 300,000.
In addition, the weight average weight average molecular weight of aqueous polyether urethane resin can be measured as a molecular weight of polystyrene conversion by gel permeation chromatography (GPC).

(3) Compounding quantity Moreover, it is preferable to make the compounding quantity of water-based polyether urethane resin into the value within the range of 25-170 weight part with respect to 100 weight part of polythiophene type conductive polymers as (A) component. .
The reason for this is that when the blending amount is less than 25 parts by weight, the thickening effect is remarkably lowered, and the leveling property in the obtained coating film may be excessively lowered. On the other hand, when the blending amount exceeds 170 parts by weight, the thickening effect is remarkably increased, and on the contrary, the leveling property in the obtained coating film may be excessively lowered.
Accordingly, the blending amount of the aqueous polyether urethane resin is more preferably set to a value in the range of 30 to 130 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). More preferably, the value is within the range of parts by weight.

6). (F) Component: Surfactant In constituting the conductive resin composition of the present invention, it is preferable that a surfactant is included as the (F) component.
The reason for this is that an aqueous polyester resin having a sulfonate group as the component (B) and a polythiophene as the component (A) while effectively maintaining the conductivity in the resulting coating film by containing a surfactant. This is because the compatibility with the conductive polymer can be effectively improved.

(1) Kind Moreover, as a kind of surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, a fluorine-type surfactant, etc. are mentioned.
More specifically, alkylsulfonic acid, alkylbenzenesulfonic acid, alkylcarboxylic acid, alkylnaphthalenesulfonic acid, α-olefinsulfonic acid, dialkylsulfosuccinic acid, α-sulfonated fatty acid, N-methyl-N-oleyl taurine, petroleum sulfone Acid, alkyl sulfuric acid, sulfated oil, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, naphthalene sulfonic acid formaldehyde Condensates and anionic surfactants such as salts thereof, primary to tertiary aliphatic amines, quaternary ammonium, tetraalkylammonium, alkylbenzylammoniumalkylpyridinium , 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium, N, N-dialkylmorpholinium, polyethylene polyamine fatty acid amide, polyethylene polyamine fatty acid amide urea condensate, polyethylene polyamine fatty acid amide urea condensate Cationic surfactants such as quaternary ammonium and salts thereof, N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, N , N-dialkyl-N, N-bispolyoxyethyleneammonium sulfate betaine, betaines such as 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, N, N-dialkylaminoalkylenecarboxylic acid Amphoteric surfactants such as aminocarboxylic acids such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-propylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxy Ethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, alcohol alkoxylate, fatty acid diethanolamide, polyoxyethylene alkylamine, triethanolamine fatty acid partial ester, trialkylamine Nonionic surfactants such as oxide and acetylene glycol, fluoroalkylcarboxylic acid, perfluoroalkylcarboxylic acid Perfluoro alkyl benzene sulfonic acid, one or two or more combinations of such fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol.
Among these, it is preferable to use acetylene glycol and alcohol alkoxylate because excellent leveling properties can be obtained while effectively maintaining the conductivity in the resulting coating film.
In addition, acetylene glycol exerts an excellent defoaming effect when a conductive resin composition is applied, so it effectively suppresses the occurrence of repellency and pinholes in the coating film, resulting in better leveling properties. Can be obtained.

Moreover, when using alcohol alkoxylate, it is preferable to make carbon number in alcohol alkoxylate into the value within the range of 10-30.
The reason for this is that when the number of carbon atoms is less than 10, the leveling property of the obtained coating film may be easily lowered. On the other hand, when the number of carbon atoms exceeds 30, the storage stability of the conductive resin composition may be excessively lowered.
Therefore, the number of carbon atoms in the alcohol alkoxylate is more preferably set to a value within the range of 12 to 25, and further preferably set to a value within the range of 15 to 20.

(2) Compounding quantity Moreover, it is preferable to make the compounding quantity of surfactant into the value within the range of 50-370 weight part with respect to 100 weight part of polythiophene type conductive polymers as (A) component.
The reason for this is that when the blending amount is less than 50 parts by weight, it may be difficult to sufficiently exhibit the effect of improving the leveling property in the obtained coating film. On the other hand, when the blending amount exceeds 370 parts by weight, the storage stability of the conductive resin composition may be decreased, or the conductivity in the obtained coating film may be easily decreased. .
Therefore, it is more preferable to set the blending amount of the surfactant to a value within the range of 60 to 230 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A), and 100 to 200 parts by weight. It is more preferable to set the value within the range.
In particular, it is preferable to use a mixture of acetylene glycol and alcohol alkoxylate as a surfactant. In that case, the blending ratio (weight ratio) of acetylene glycol and alcohol alkoxylate is from 9:99 to 28:72. A value within the range is preferable, and a value within the range of 15:85 to 33:67 is more preferable.

7). (G) component: solvent It is preferable that the conductive resin composition of this invention contains the solvent of (A)-(C) component as (G) component.
The reason for this is that by including a solvent, not only can the viscosity and drying property of the conductive resin composition be adjusted to an appropriate range, but also the conductivity in the resulting coating film can be stabilized.

(1) Types The types of solvents include water, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, and glycerin, ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone, and ethylene. Ethylene glycols such as glycol, ethylene glycol methyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol, diethylene glycol mono-n-butyl ether, propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol propyl ether, N- Pyrrolidones such as methyl pyrrolidone and N-ethyl pyrrolidone, dimethylformamide, dimethylacetamide and the like One kind alone or a combination of two or more kinds such as amides, hydroxyethyls such as methyl lactate and ethyl lactate may be mentioned.
Among these, it is preferable to contain water and ethylene glycol.
This is because, by using water and ethylene glycol in combination, not only can the viscosity and drying property of the conductive resin composition be adjusted to a suitable range, but also the conductivity in the resulting coating film can be further stabilized. This is because it can.

(2) Compounding quantity Moreover, it is preferable to make the compounding quantity of a solvent into the value within the range of 8,000-12,000 weight part with respect to 100 weight part of polythiophene type conductive polymers as (A) component. .
This is because the viscosity of the conductive resin composition may become excessively high when the amount is less than 8,000 parts by weight. On the other hand, when the blending amount exceeds 12,000 parts by weight, the drying property when forming the coating film may be excessively lowered.
Therefore, it is more preferable that the blending amount of the solvent is set to a value within the range of 8,500 to 11,600 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). More preferably, the value is in the range of ˜11,300 parts by weight.
In particular, when water and ethylene glycol are used in combination as the solvent, the blending ratio (weight ratio) of water and ethylene glycol is preferably set to a value within the range of 90:10 to 75:25. More preferably, the value is within the range of 15 to 80:20.

8). Crosslinking agent Moreover, from the viewpoint of improving the water resistance of the resulting coating film, the conductive resin composition of the present invention may contain a crosslinking agent such as a silane coupling agent or an isocyanate compound.

[Second Embodiment]
2nd Embodiment of this invention is a planar heating element containing the base material and the heat generating layer formed in the said base material surface, Comprising: A heat generating layer has the following (A)-(C) component. A planar heating element obtained by applying and drying a conductive resin composition.
(A) Polythiophene-based conductive polymer 100 parts by weight (B) Aqueous polyester resin having a sulfonate group 200 to 530 parts by weight (C) Vinylpyrrolidone-vinyl acetate copolymer 7 to 230 parts by weight The planar heating element of the embodiment will be specifically described.

1. Heat generation layer The heat generation layer in the planar heating element of the present invention can be obtained by applying and drying the conductive resin composition described above on a substrate.
From the viewpoint of maintaining transparency, the thickness of the heat generating layer is preferably set to a value in the range of 0.01 to 20 μm, more preferably set to a value in the range of 0.1 to 10 μm. More preferably, the value is in the range of ˜5 μm.
Note that the details of the conductive resin composition have been described as the first embodiment, and thus will be omitted.

2. Base Material The base material is not particularly limited, and examples thereof include plastic base materials such as polyester, polycarbonate, polyimide, acrylic, ABS, polystyrene, nylon, and polypropylene, glass, and metal materials.

3. Manufacturing Method The planar heating element of the present invention can be manufactured by applying a conductive resin composition to a substrate having an electrode pattern or the like printed on the surface and drying it to form a heating layer.
Examples of the method for applying the conductive resin composition include screen printing, offset printing, gravure printing, ink jet printing, dip coating, spray coating, bar coating, etc., from the viewpoint of obtaining a more uniform coating film. Printing is particularly preferred.

4). Applications Further, the sheet heating element of the present invention can be used for, for example, defrosting automobile headlights, transparent sheet heating elements for preventing windshield or rear glass from fogging, and fogging of window glass such as bathrooms in buildings. It can be suitably used as a transparent sheet heating element for preventing, and can also be used as a transparent sheet heating element for keeping the surface temperature of the liquid crystal display constant.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples without a particular reason.

[Example 1]
1. Preparation of conductive resin composition After containing the following composition in a container equipped with a stirrer, the mixture was mixed using a stirrer until uniform to obtain a conductive resin composition.
In addition, the compounding quantity in the following is the value converted into solid substance.
(A) Poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid complex
100 parts by weight (manufactured by Heraeus Co., Ltd., CLEVIOS P HC V4)
(B) Aqueous polyester resin having a sulfonate group 333 parts by weight (C) Vinylpyrrolidone-vinyl acetate copolymer 20 parts by weight (D) Acetoacetyl group-modified polyvinyl alcohol resin 2 parts by weight (E) Aqueous polyether urethane resin 60 Part by weight (F1) Acetylene glycol 33 parts by weight (manufactured by Nissin Chemical Co., Ltd., Olphine AF-104)
(F2) Alcohol alkoxylate 67 parts by weight (BYK D-800, manufactured by BYK Chemie)
(G1) Ethylene glycol 1,000 parts by weight (G2) Water 8,267 parts by weight

Moreover, the sulfonate group in the aqueous polyester resin having the sulfonate group as the component (B) described above was a sulfonate Na base, and the weight average molecular weight was 16,000.
Further, the vinylpyrrolidone-vinyl acetate copolymer as the component (C) described above had a weight average molecular weight of 50,000, and the vinylpyrrolidone: vinyl acetate copolymerization ratio (in terms of mole) was 60:40.
Moreover, the weight average molecular weight of the acetoacetyl group-modified polyvinyl alcohol resin as the component (D) described above was 45,000, and the degree of acetylation (in terms of mole) was 10%.
Further, the weight average molecular weight of the aqueous polyether urethane resin as the component (E) described above was 60,000.
Furthermore, the carbon number of the alcohol alkoxylate as the component (F2) described above was 16.

2. Evaluation of conductive resin composition (1) Evaluation of leveling property The leveling property in the obtained conductive resin composition, that is, the uniformity of the obtained coating film was evaluated.
That is, after the obtained conductive resin composition was screen-printed (polyester screen 300 mesh, emulsion film thickness 10 μm) on an untreated polyester film (Toray Co., Ltd., Lumirror T-125 μm), 120 ° C. And dried for 20 minutes to form a coating film having a thickness of 1 μm.
Subsequently, the obtained coating film was visually confirmed and evaluated according to the following criteria. The obtained results are shown in Table 1.
◎: No repelling or pinholes are observed, and the coating is smooth. ○: No repelling or pinholes are observed, but wavy portions are confirmed on the coating. △: Slight repelling or pinholes are confirmed. In addition, a wavy portion is confirmed in the coating film. X: Many repellings and pinholes are confirmed, and the coating film is generally wavy.

(2) Evaluation of adhesiveness The adhesiveness in the coating film formed with the obtained conductive resin composition was evaluated.
That is, a coating film was formed under the same conditions as the evaluation of leveling property, and the adhesion was evaluated by a cross-cut cello tape (registered trademark) peel test in accordance with JIS-K-5600 5.6.
More specifically, the 100th grid is made on the coating film using a cutter guide with a gap interval of 1 mm, and after applying the cello tape, it is peeled off and the percentage of the grid that has not been peeled off (%) Evaluated along. The obtained results are shown in Table 1.
A: Ratio of grids not peeled off is 99% or more ○: Ratio of grids not stripped is a value less than 95-99% Δ: Ratio of grids not stripped is 75-95% Less than x: The ratio of the grids that did not peel off is less than 75%

(3) Evaluation of electroconductivity Moreover, the electroconductivity in the coating film formed with the obtained electroconductive resin composition was evaluated by surface resistance value (ohm / square).
That is, a coating film was formed under the same conditions as the evaluation of leveling properties, and using an resistance measuring instrument (Loresta MP MCP-350, manufactured by Mitsubishi Chemical Corporation) in an environment of a temperature of 24 ° C. and a relative humidity of 55%. The surface resistance value (Ω / □) was measured by the four-probe method while conforming to JIS-K-6911, and evaluated according to the following criteria. The obtained results are shown in Table 1.
A: The obtained surface resistance value is less than 600 Ω / □. O: The obtained surface resistance value is less than 600 to 800 Ω / □. Δ: The obtained surface resistance value is 800 to 1,000 Ω. / A value less than □: The obtained surface resistance value is a value of 1,000 Ω / □ or more.

(4) Evaluation of transparency The transparency in the coating film formed with the obtained conductive resin composition was evaluated by the total light transmittance (%).
That is, a coating film was formed under the same conditions as the evaluation of leveling properties, and using a haze meter (NDH2000 (D65 light source) manufactured by Nippon Denshoku Industries Co., Ltd.) in an environment of a temperature of 24 ° C. and a relative humidity of 55%. The total light transmittance (%) was measured in accordance with JIS-K-7150, and evaluated according to the following criteria.
A: The obtained total light transmittance is a value of 84% or more. B: The obtained total light transmittance is a value of less than 77 to 84%. Δ: The obtained total light transmittance is 70 to 77%. Less than x: The obtained total light transmittance is less than 70%

(5) Evaluation of exothermicity Moreover, the exothermicity in the planar heating element formed by connecting a power source to the coating film formed from the obtained conductive resin composition was evaluated.
That is, as shown in FIG. 4, the coating film 12 is formed as a heat generating layer so that the printing area is 60 mm × 60 mm under the same conditions as the leveling evaluation, and the environment is at a temperature of 24 ° C. and a relative humidity of 55%. , A constant pressure power source (DIAMOND ANTENNA Co., Ltd., POWER SUPPLY MODEL GS-400V) (not shown) is connected to the coating film 12 via the copper foil 11 and the silver paste 13 to form a sheet heating element 10. A voltage of 13.5 V is applied to the coating film 12 as the heat generation layer, and the temperature rise is measured using a thermometer (Shinwa Co., Ltd., IR THERMOMETER) and evaluated according to the following criteria: did. The obtained results are shown in Table 1.
A: Temperature rise temperature is a value of 10 ° C. or higher. O: Temperature rise temperature is a value less than 5-10 ° C. Δ: Temperature rise temperature is a value less than 1-5 ° C. x: Temperature rise temperature is 1 It is less than ℃

[Example 2 and Comparative Examples 1 to 3]
In Example 2 and Comparative Examples 1 to 3, when preparing the conductive resin composition, the blending ratio of the poly (3,4-ethylenedioxythiophene) polystyrene sulfonic acid complex as the component (A) is shown in Table 1. A coating film was formed and evaluated in the same manner as in Example 1 except that the change was made as shown in FIG. The obtained results are shown in Table 1.

[Examples 3 to 4 and Comparative Examples 4 to 5]
In Examples 3 to 4 and Comparative Examples 4 to 5, when the conductive resin composition was prepared, the compounding amount of the vinyl pyrrolidone-vinyl acetate copolymer as the component (C) was changed as shown in Table 2. Otherwise, a coating film was formed and evaluated in the same manner as in Example 1. The obtained results are shown in Table 2.

[Examples 5-6 and Comparative Examples 6-7]
In Examples 5 to 6 and Comparative Examples 6 to 7, when the conductive resin composition was prepared, the vinylpyrrolidone: vinyl acetate copolymer ratio (mole) in the vinylpyrrolidone-vinyl acetate copolymer (C) component A coating film was formed and evaluated in the same manner as in Example 1 except that a copolymer or a polymer having a weight average molecular weight of 50,000 was changed as shown in Table 3. The obtained results are shown in Table 3.
In Comparative Example 6, since the copolymerization ratio of vinyl pyrrolidone: vinyl acetate was 100: 0, exactly “vinyl pyrrolidone” was used instead of “vinyl pyrrolidone-vinyl acetate copolymer”. become.
Further, in Comparative Example 7, since the copolymerization ratio of vinylpyrrolidone: vinyl acetate was 0: 100, exactly “polyvinyl acetate” was used instead of “vinylpyrrolidone-vinyl acetate copolymer”. It will be.

[Examples 7 to 8 and Comparative Example 8]
In Examples 7-8, when preparing a conductive resin composition, the compounding quantity of the acetoacetyl group modified polyvinyl alcohol resin which is (D) component was changed as shown in Table 4, and in Comparative Example 8, (C ) A coating film was formed and evaluated in the same manner as in Example 1 except that the amount of the vinylpyrrolidone-vinyl acetate copolymer as a component was changed. Table 4 shows the obtained results.

[Examples 9 to 10 and Comparative Examples 9 to 10]
In Examples 9 to 10 and Comparative Examples 9 to 10, when preparing the conductive resin composition, the blending amount of the aqueous polyester resin having a sulfonate group as the component (B) was changed as shown in Table 5. Otherwise, a coating film was formed and evaluated in the same manner as in Example 1. The results obtained are shown in Table 5.

[Examples 11 to 12 and Comparative Example 11]
In Examples 11-12, when preparing a conductive resin composition, the compounding quantity of the water-based polyether urethane resin as (E) component was changed as shown in Table 6, and in Comparative Example 11, (C) component was further changed. A coating film was formed and evaluated in the same manner as in Example 1 except that the amount of the vinylpyrrolidone-vinyl acetate copolymer was changed. The results obtained are shown in Table 6.

[Examples 13 to 15 and Comparative Example 12]
In Examples 13 to 15, when preparing the conductive resin composition, the amount of acetylene glycol as the component (F1) was changed as shown in Table 7, and in Comparative Example 12, vinyl as the component (C) was further changed. A coating film was formed and evaluated in the same manner as in Example 1 except that the blending amount of the pyrrolidone-vinyl acetate copolymer was changed. The results obtained are shown in Table 7.

[Examples 16 to 18 and Comparative Example 13]
In Examples 16-18, when preparing a conductive resin composition, the compounding quantity of the alcohol alkoxylate as (F2) component was changed as shown in Table 8, and in Comparative Example 13, it further added as (C) component. A coating film was formed and evaluated in the same manner as in Example 1 except that the amount of the vinylpyrrolidone-vinyl acetate copolymer was changed. Table 8 shows the obtained results.

[Examples 19 to 20 and Comparative Example 14]
In Examples 19 to 20, when preparing the conductive resin composition, the blending amount of ethylene glycol as the component (G1) was changed as shown in Table 9, and in Comparative Example 14, vinyl as the component (C) was further changed. A coating film was formed and evaluated in the same manner as in Example 1 except that the blending amount of the pyrrolidone-vinyl acetate copolymer was changed. Table 9 shows the obtained results.

According to the conductive resin composition or the like of the present invention, an aqueous polyester resin having a sulfonate group and a vinylpyrrolidone-vinyl acetate copolymer are blended in predetermined blending amounts with respect to the polythiophene-based conductive polymer, respectively. As a result, the compatibility between the polythiophene-based conductive polymer and the aqueous polyester resin having a sulfonate group as the main binder resin can be effectively improved.
As a result, it became possible to effectively improve the uniformity of film thickness, conductivity, and adhesion to the substrate in the resulting coating film.
Therefore, the conductive resin composition of the present invention and the planar heating element using the same are expected to significantly contribute to improving the quality of the planar heating element.

10: planar heating element, 11: copper foil, 12: coating film (heating layer), 13: silver paste

Claims (11)

A conductive resin composition comprising the following components (A) to (C):
(A) Polythiophene-based conductive polymer 100 parts by weight (B) Aqueous polyester resin having a sulfonate group 200 to 530 parts by weight (C) Vinylpyrrolidone-vinyl acetate copolymer 7 to 230 parts by weight   The polythiophene-based conductive polymer as the component (A) is poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid as a dopant that forms an ion pair with the poly (3,4-ethylenedioxythiophene). The conductive resin composition according to claim 1, wherein the conductive resin composition is a composite comprising:   The conductive resin according to claim 1 or 2, wherein the weight average molecular weight of the aqueous polyester resin having a sulfonate group as the component (B) is set to a value in the range of 5,000 to 30,000. Composition.   The weight average molecular weight of the vinylpyrrolidone-vinyl acetate copolymer as the component (C) is set to a value within the range of 10,000 to 500,000. The conductive resin composition as described.   The vinylpyrrolidone: vinyl acetate copolymer ratio (molar conversion) in the vinylpyrrolidone-vinyl acetate copolymer as the component (C) is set to a value within the range of 90:10 to 55:45. The conductive resin composition according to any one of claims 1 to 4.   The component (D) contains an acetoacetyl group-modified polyvinyl alcohol resin, and the blending amount of the acetoacetyl group-modified polyvinyl alcohol resin is 0 with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). It is set as the value within the range of 0.7-15 weight part, The conductive resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.   The component (E) contains an aqueous polyether urethane resin, and the amount of the aqueous polyether urethane resin is 25 to 170 parts by weight with respect to 100 parts by weight of the polythiophene conductive polymer as the component (A). The conductive resin composition according to any one of claims 1 to 6, wherein the conductive resin composition has a value within a range of.   (F) While containing surfactant as a component, the compounding quantity of the said surfactant exists in the range of 50-370 weight part with respect to 100 weight part of polythiophene type conductive polymers as said (A) component. It is set as a value, The conductive resin composition as described in any one of Claims 1-7 characterized by the above-mentioned.   (G) As a component, while containing the solvent of (A)-(C) component, the compounding quantity of the said solvent is 8,000- with respect to 100 weight part of polythiophene type conductive polymers as said (A) component. It is set as the value within the range of 12,000 weight part, The conductive resin composition as described in any one of Claims 1-8 characterized by the above-mentioned.   The solvent as said (G) component contains water and ethylene glycol, The conductive resin composition as described in any one of Claim 9 characterized by the above-mentioned. A planar heating element including a base material and a heat generation layer formed on the surface of the base material,
A sheet heating element, wherein the heating layer is formed by applying and drying a conductive resin composition containing the following components (A) to (C).
(A) Polythiophene-based conductive polymer 100 parts by weight (B) Aqueous polyester resin having a sulfonate group 200 to 530 parts by weight (C) Vinylpyrrolidone-vinyl acetate copolymer 7 to 230 parts by weight

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