JP6991707B2 - Conductive coating liquid and conductive rough surface - Google Patents

Description

The present invention relates to a conductive coating liquid and a conductive rough surface.

Conventionally, a conductive coating liquid containing a conductive resin has been used for the purpose of applying a conductive coating liquid on a substrate having no irregularities to form a conductive coating layer without irregularities and imparting conductivity. For example, Patent Document 1 describes that a laminated film having no unevenness is formed on at least one surface of a thermoplastic resin film having no unevenness by using a composition containing a conductive resin to form a laminated film for protecting a polarizing plate. Has been done. Further, Patent Document 2 describes that an intermediate layer or the like having no unevenness is formed on a base material having no unevenness with a material containing a polythiophene-based conductive polymer to form a release film for producing a green sheet. There is.

However, in recent years, higher productivity has been required, and formation of a conductive coating layer having irregularities such as a light diffusing film and a reflective film has been required. For example, in Patent Document 3, an antistatic agent such as polythiophene and an antistatic back surface protective layer containing fine particles and having irregularities are formed on one surface of a base film having no irregularities to form an optical light diffusion film. It is stated that. However, the optical light diffusing film described in Patent Document 3 has a problem that it cannot sufficiently meet the recent demand for high antistatic properties. In this method, it is considered that many fine particles blended in order to obtain desired unevenness block the conductive path, and therefore sufficient antistatic property cannot be exhibited.

On the other hand, when the conventional conductive coating liquid is applied on a base material having unevenness, if it is applied thinly in order to leave the unevenness of the base material, the conductive coating layer becomes too thin in the convex portion and the desired conductivity is obtained. If the coating is thickly applied to obtain the desired conductivity, the concave portion is buried by the conductive coating layer, and there is a problem that the unevenness cannot be maintained.

Japanese Unexamined Patent Publication No. 2006-243216 JP-A-2015-66908 Japanese Unexamined Patent Publication No. 2007-206375

According to the present invention, the conductive coating layer can be formed with a uniform film thickness even when applied on a substrate having irregularities, so that the irregularities of the substrate can be maintained and there is no unevenness. It is an object of the present invention to provide a conductive coating liquid capable of exhibiting the same degree of conductivity as when coated on a substrate.

As a result of diligent studies, the present inventor has conducted a uniform application even when a conductive coating liquid containing a conductive resin, a non-conductive resin, and a specific amount of a leveling agent is applied onto a substrate having irregularities. We have found that the conductive coating layer can be formed with a uniform film thickness, so that the unevenness of the base material can be maintained, and that the same degree of conductivity as when applied to a base material without unevenness can be exhibited. Completed the invention.

That is, the conductive coating liquid of the present invention is
Conductive resin (a) in an amount of 1 to 20% by weight based on the total solid content,
20 to 98.9% by weight of the non-conductive resin (b) in the total solid content, and
A conductive coating liquid containing 0.1 to 60% by weight of the leveling agent (c) in the total solid content.
The solid content ratio of the leveling agent (c) to the conductive resin (a) is 0.1 to 3.
The surface resistivity when coated on a substrate having Ra of 0.2 μm at a film thickness of 0.05 μm is 5 of the surface resistivity when coated on a substrate having Ra of 0.02 μm at a film thickness of 0.05 μm. Less than double,
It is characterized in that it is used for coating on the surface of a rough surface.

In the conductive coating liquid of the present invention, the conductive resin (a) is a composite of polyethylene dioxythiophene (a1) and polystyrene sulfonic acid (a2), and the weight average molecular weight of polystyrene sulfonic acid (a2) is 20. It is preferably 1,000 to 1,000,000.

In the conductive coating liquid of the present invention, the leveling agent (c) is preferably a polymer having a siloxane skeleton or an alkylene oxide skeleton, and the pH of the conductive coating liquid is preferably 4 to 10.

The conductive rough surface of the present invention is
A thermoplastic resin layer (I), a filler-containing layer (II), and a conductive coating layer (III) formed by using the conductive coating liquid of the present invention are provided in this order.
Ra on the surface of the conductive coating layer (III) is 0.1 μm or more, and Rz is 0.5 μm or more.

In the conductive rough surface of the present invention, the filler-containing layer (II) contains a filler having an average particle diameter of 0.2 μm or more and a thermoplastic resin.
It is preferable that Ra on the surface of the filler-containing layer (II) is 0.1 μm or more and Rz is 0.5 μm or more.

In the conductive rough surface of the present invention, it is preferable that the thermoplastic resin layer (I) contains at least one selected from the group consisting of polyester, polyurethane, polyethylene, polypropylene, rayon, nylon and polystyrene.

The conductive light diffusing film of the present invention is characterized by having the conductive rough surface of the present invention.

The conductive reflective film of the present invention is characterized by comprising the conductive rough surface of the present invention.

Since the conductive coating liquid of the present invention contains a conductive resin, a non-conductive resin, and a specific amount of a leveling agent, it is conductive with a uniform film thickness even when coated on a substrate having irregularities. Since the property-coated layer can be formed, the unevenness of the base material can be maintained, and the same degree of conductivity as when coated on a base material having no unevenness can be exhibited.

<< Conductive coating liquid >>
The conductive coating liquid of the present invention is used.
Conductive resin (a) in an amount of 1 to 20% by weight based on the total solid content,
20 to 98.9% by weight of the non-conductive resin (b) in the total solid content, and
A conductive coating liquid containing 0.1 to 60% by weight of the leveling agent (c) in the total solid content.
The solid content ratio of the leveling agent (c) to the conductive resin (a) is 0.1 to 3.
The surface resistivity when coated on a substrate having Ra of 0.2 μm at a film thickness of 0.05 μm is 5 of the surface resistivity when coated on a substrate having Ra of 0.02 μm at a film thickness of 0.05 μm. Less than double,
It is characterized in that it is used for coating on the surface of a rough surface.

<Conductive resin (a)>
The conductive resin (a) is a compound for imparting conductivity to the conductive coating liquid. The conductive resin (a) is not particularly limited, and conventionally known conductive resins can be used. Specific examples thereof include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, and derivatives thereof. Can be mentioned. These may be used alone or in combination of two or more. Among them, a conductive resin containing at least one thiophene ring in the molecule is preferable because a molecule having high conductivity is easily formed by containing the thiophene ring in the molecule. The conductive resin (a) may form a composite with a dopant such as a poly anion.

Among the conductive resins containing at least one thiophene ring in the molecule, poly (3,4-disubstituted thiophene) is more preferable in that it is extremely excellent in conductivity and chemical stability. When the conductive resin is poly (3,4-disubstituted thiophene) or a composite of poly (3,4-disubstituted thiophene) and a poly anion (lactone), the temperature is low and the time is short. The conductive coating layer (III) can be formed, and the productivity is also excellent. The polyanion is a dopant of a conductive resin, and its contents will be described later.

As the poly (3,4-disubstituted thiophene), poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferable. The poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) has the following formula (I):

A cationic form of polythiophene consisting of the repeating structural units indicated by is preferred.
Here, R ¹ and R ² independently represent a hydrogen atom or an alkyl group of C _1-4 , or if R ¹ and R ² are bonded, an alkylene group of C _1-4 . Represents. The alkyl group of C _1-4 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. ..
When R ¹ and R ² are bonded, the alkylene group of C _1-4 is not particularly limited, but for example, a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1, 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. Can be mentioned. Among these, a methylene group, a 1,2-ethylene group and a 1,3-propylene group are preferable, and a 1,2-ethylene group is more preferable. The alkyl group of C _1-4 and the alkylene group of C _1-4 may be partially substituted with hydrogen. As the polythiophene having an alkylene group of C _1-4 , polyethylene dioxythiophene (a1) is particularly preferable.

The weight average molecular weight of the conductive resin (a) is not particularly limited, but is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 1500 to 20,000. If the weight average molecular weight is less than 500, the required viscosity cannot be secured when the conductive coating liquid is used, and the conductivity when the conductive coating layer (III) is used may be lowered. ..

The dopant is not particularly limited, but a poly anion is preferable. The polyanion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water. The polyanion is not particularly limited, and is, for example, carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (for example, polystyrene sulfonic acid, polyvinylsulfonic acid, polyisoprene, etc.). Sulfonic acid, etc.) and the like. These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers, such as acrylates, styrene, vinyl naphthalene and other aromatic vinyl compounds. It may be. Of these, polystyrene sulfonic acid (a2) is particularly preferable.

The weight average molecular weight of the polystyrene sulfonic acid (a2) is not particularly limited, but is preferably 20,000 to 1,000,000, more preferably 50,000 to 500,000. If polystyrene sulfonic acid (a2) having a molecular weight outside this range is used, the dispersion stability of the polythiophene-based conductive resin in water may decrease. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

The composite of the conductive resin (a) and the polyanion is preferably a composite of polyethylene dioxythiophene (a1) and polystyrene sulfonic acid (a2) because it is particularly excellent in conductivity.

The conductivity of the conductive resin (a) is not particularly limited, but is preferably 0.01 S / cm or more, preferably 1 S / cm, from the viewpoint of imparting sufficient conductivity to the conductive coating layer (III). The above is more preferable.

In the conductive coating liquid of the present invention, the content of the conductive resin (a) is not particularly limited as long as it is 1 to 20% by weight in the total solid content, but is preferably 2 to 10% by weight. If the content of the conductive resin (a) is less than 1% by weight in the total solid content, the expression of conductivity may become unstable, and if it exceeds 20% by weight, the conductivity becomes the surface roughness of the base material. It may be easy to depend on it.

<Non-conductive resin (b)>
The non-conductive resin (b) is not particularly limited, and examples thereof include polyester, polyurethane, melamine, acrylic, polyolefin, and polyether. These non-conductive resins (b) may be used alone or in combination of two or more.

The non-conductive resin (b) preferably contains a thermoplastic resin. The thermoplastic resin is not particularly limited, and examples thereof include polyester, polyurethane, and acrylic. These thermoplastic resins may be used alone or in combination of two or more.

The glass transition temperature (Tg) of the thermoplastic resin is not particularly limited, but is preferably 70 ° C. or lower, and more preferably 30 ° C. or lower. If the glass transition temperature of the thermoplastic resin exceeds 70 ° C, it may be difficult to form a uniform film on a rough surface having low heat resistance because the flattening of the thermoplastic resin is delayed during low-temperature drying. be.

The average particle size of the thermoplastic resin is not particularly limited, but is preferably 100 nm or less, and more preferably 50 nm or less. If the average particle size of the thermoplastic resin exceeds 100 nm, it may be difficult to exhibit sufficient antistatic properties because the conductive path is easily blocked. The lower limit of the average particle size of the thermoplastic resin is not particularly limited and may be dissolved in a solvent.

When the non-conductive resin (b) contains a thermoplastic resin, its content (solid content) is not particularly limited, but is preferably 20% by weight or more, preferably 50% by weight, based on the solid content of the component (b). The above is more preferable. When the content of the thermoplastic resin is less than 20% by weight in the solid content of the component (b), the proportion of the curable resin is relatively large, and curing shrinkage is likely to occur. It may be difficult to form a uniform film.

In the conductive coating liquid of the present invention, the content of the non-conductive resin (b) is not particularly limited as long as it is 20 to 98.9% by weight in the total solid content, but is preferably 50 to 85% by weight. .. If the content of the non-conductive resin (b) is less than 20% by weight in the total solid content, the adhesion to the substrate and the film strength of the conductive coating layer may be insufficient, and 98.9% by weight. If it exceeds, the content of the conductive resin (a) is relatively reduced, so that the development of conductivity may become unstable.

<Leveling agent (c)>
The leveling agent (c) is not particularly limited, and examples thereof include polysiloxane, polyalkylene oxide, and fluorine compounds. Further, the surfactant can also be used as the leveling agent (c). These leveling agents (c) may be used alone or in combination of two or more.

The leveling agent (c) is preferably a polymer having a siloxane skeleton or an alkylene oxide skeleton from the viewpoint of the followability of the conductive coating layer to the unevenness of the base material.

The leveling agent (c) preferably has a hydroxyl group from the viewpoint of the followability of the conductive coating layer to the unevenness of the base material. The number of hydroxyl groups per molecule is not particularly limited, but is preferably 2 or more, and more preferably 4 or more.

In the conductive coating liquid of the present invention, the content of the leveling agent (c) is not particularly limited as long as it is 0.1 to 60% by weight in the total solid content, but is preferably 4 to 20% by weight. If the content of the leveling agent (c) is less than 0.1% by weight of the total solid content, the conductivity may easily depend on the surface roughness of the base material, and if it exceeds 60% by weight, the base material Adhesion to the surface and the film strength of the conductive coating layer may be insufficient.

In the conductive coating liquid of the present invention, the solid content ratio of the leveling agent (c) to the conductive resin (a) is not particularly limited as long as it is 0.1 to 3, but is preferably 1 to 3. If the solid content ratio of the leveling agent (c) to the conductive resin (a) is less than 0.1, the conductivity may easily depend on the surface roughness of the base material, and if it exceeds 3, the conductivity is conductive. The mechanical strength and water resistance of the coating layer may be insufficient.

The conductive coating liquid of the present invention may optionally contain other components in addition to the above-mentioned components (a) to (c). Examples of other components include, but are not limited to, antioxidants, preservatives, solvents, slip agents, release agents, antifoaming agents and the like. These may be used alone or in combination of two or more.

The conductive coating liquid of the present invention has a surface resistivity (hereinafter, also referred to as surface resistivity A) when coated on a substrate having a Ra of 0.2 μm with a film thickness of 0.05 μm, and has a Ra of 0.02 μm. It is 5 times or less of the surface resistivity (hereinafter, also referred to as surface resistivity B) when coated on a substrate with a film thickness of 0.05 μm. The magnification of the surface resistivity A with respect to the surface resistivity B is not particularly limited as long as it is 5 times or less, but is preferably 3 times or less, and more preferably 2 times or less. If the magnification of the surface resistivity A with respect to the surface resistivity B exceeds 5 times, sufficient conductivity may not be obtained when applied onto the rough surface body.

The pH of the conductive coating liquid of the present invention is not particularly limited, but is preferably 4 to 10, and more preferably 5 to 9. If the pH of the conductive coating liquid of the present invention is less than 4, the stability of the non-conductive resin (b) or the leveling agent (c) in the conductive coating liquid may be insufficient. If it exceeds, the storage stability of the conductive resin (a) in the conductive coating liquid may be insufficient.

The conductive coating liquid of the present invention is used to form the conductive coating layer (III) in the conductive rough surface of the present invention described later.

<< Conductive rough surface >>
The conductive rough surface of the present invention is
A thermoplastic resin layer (I), a filler-containing layer (II), and a conductive coating layer (III) formed by using the conductive coating liquid of the present invention are provided in this order.
Ra on the surface of the conductive coating layer (III) is 0.1 μm or more, and Rz is 0.5 μm or more.

<Thermoplastic resin layer (I)>
The material of the thermoplastic resin layer (I) is not particularly limited, and examples thereof include polyester, polyurethane, polyethylene, polypropylene, rayon, nylon, polystyrene, polyolefin, and acrylic resin. These may be used alone or in combination of two or more. Among these, from the viewpoint of easy moldability, at least one selected from the group consisting of polyester, polyurethane, polyethylene, polypropylene, rayon, nylon and polystyrene is preferable.

The thickness of the thermoplastic resin layer (I) is not particularly limited, but is preferably 10 to 1000 μm, more preferably 20 to 800 μm. If the thickness of the thermoplastic resin layer (I) is less than 10 μm, the mechanical strength of the rough surface body may be insufficient, and if it exceeds 1000 μm, the rough surface body is stretched to adjust to a predetermined thickness and width. It may be difficult to wind it up into a roll or cut it into a predetermined size.

<Filler-containing layer (II)>
By forming the filler-containing layer (II) on the thermoplastic resin layer (I), the surface of the thermoplastic resin layer (I) can be easily roughened, and in addition, the light scattering property is further improved. Can be granted. The filler-containing layer (II) is not particularly limited as long as it contains the filler, but contains the filler and the thermoplastic resin from the viewpoint of adhesion to the thermoplastic resin layer (I), mechanical strength, and easy moldability. Is preferable.

The filler is not particularly limited, and examples thereof include metal oxide particles such as silica, titania, and zirconia, and organic resin particles such as acrylic beads and urethane rubber. Among these, metal oxide particles are preferable from the viewpoint of light scattering property. These may be used alone or in combination of two or more.

The average particle size of the filler is not particularly limited, but is preferably 0.2 μm or more, and more preferably 1 μm or more. If the average particle size of the filler is less than 0.2 μm, it may be difficult to form a rough surface having a predetermined surface roughness.

The thermoplastic resin is not particularly limited, and examples thereof include polyester, polyurethane, polyethylene, polypropylene, rayon, nylon, polystyrene, polyolefin, acrylic resin and the like. These may be used alone or in combination of two or more.

The Ra on the surface of the filler-containing layer (II) is not particularly limited, but is preferably 0.1 μm or more, and more preferably 0.2 μm or more. If the Ra on the surface of the filler-containing layer (II) is less than 0.1 μm, properties due to surface roughness such as light scattering resistance and blocking resistance may be insufficient. The Rz on the surface of the filler-containing layer (II) is not particularly limited, but is preferably 0.5 μm or more, and more preferably 1.0 μm or more. If the Rz of the surface of the filler-containing layer (II) is less than 0.5 μm, the properties due to the surface roughness such as light scattering resistance and blocking resistance may be insufficient.

Ra and Rz on the surface of the filler-containing layer (II) can be finely adjusted by treating with a mold processed into a fine uneven structure by sandblasting or chemical etching.

In the present invention, Ra refers to the arithmetic mean roughness, and Rz refers to the ten-point average roughness. These are standardized in JIS B0601 and the like.

The thickness of the filler-containing layer (II) is not particularly limited, but is preferably 1 to 500 μm, more preferably 2 to 200 μm. If the thickness of the filler-containing layer (II) is less than 1 μm, some of the filler may be detached due to friction or the like, and if it exceeds 500 μm, the filler may become difficult to line up on the surface. It can be difficult to get the rust.

<Conductive coating layer (III)>
The conductive coating layer (III) is formed on the filler-containing layer (II) using the conductive coating liquid of the present invention. The method for forming the conductive coating layer (III) using the conductive coating liquid of the present invention is not particularly limited, but the conductive coating liquid of the present invention is applied onto the filler-containing layer (II) and then dried. There is a method of making it.

The method for applying the conductive coating liquid of the present invention onto the filler-containing layer (II) is not particularly limited, and is, for example, a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, or a die coating method. , Blade coat method, gravure coat method, curtain coat method, spray coat method, doctor coat method, slit coat method and the like. The method for drying the conductive coating liquid of the present invention coated on the filler-containing layer (II) is not particularly limited, but 20 Examples thereof include a method of drying at ~ 200 ° C. for 0.1 to 30 minutes.

Ra on the surface of the conductive coating layer (III) is not particularly limited as long as it is 0.1 μm or more, but it is preferably 0.2 μm or more. If the Ra of the surface of the conductive coating layer (III) is less than 0.1 μm, the properties due to the surface roughness such as light scattering property and blocking resistance may be insufficient. The Rz on the surface of the conductive coating layer (III) is not particularly limited as long as it is 0.5 μm or more, but it is preferably 1.0 μm or more. If the Rz of the surface of the conductive coating layer (III) is less than 0.5 μm, the properties due to the surface roughness such as light scattering property and blocking resistance may be insufficient.

The thickness of the conductive coating layer (III) is not particularly limited, but is preferably 0.01 to 1 μm, and more preferably 0.02 to 0.5 μm. If the thickness of the conductive coating layer (III) is less than 0.01 μm, the conductivity may be insufficient, and if it exceeds 1 μm, the optical characteristics may be insufficient.

<< Conductive light diffusion film >>
The conductive light diffusing film of the present invention is characterized by having the conductive rough surface of the present invention.

<< Conductive reflective film >>
The conductive reflective film of the present invention is characterized by comprising the conductive rough surface of the present invention.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Hereinafter, "part" or "%" means "part by weight" or "% by weight", respectively, unless otherwise specified.

1. 1. Materials used In the following examples and comparative examples, the following materials were used.
1-1. Conductive resin (a)
-PEDOT: PSS (produced in Production Example 1, solid content 1.3% by weight)
Highly conductive PEDOT: PSS (produced in Production Example 2, solid content 1.2% by weight)
1-2. Non-conductive resin (b)
-Polyester (manufactured by Toagosei Co., Ltd., Aronmelt PES-2405A30, glass transition temperature 40 ° C., average particle diameter 80 nm, solid content 30% by weight)
-Polyurethane (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex 210, glass transition temperature 41 ° C, average particle size 40 nm, solid content 35%)
・ Melamine (manufactured by DIC Corporation, Beccamin M-3, solid content 77%)
-Acrylic (manufactured by DIC Corporation, Bon Coat 5400EF, glass transition temperature 6 ° C., average particle size 200 nm, solid content 55%)
1-3. Leveling agent (c)
-Polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-4952, number of hydroxyl groups per molecule: 2)
-Polyalkylene oxide (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Evan U-103, number of hydroxyl groups per molecule: 2)
1-4. Thermoplastic resin layer (I) and filler-containing layer (II)
-Polyester-based rough surface (manufactured in Production Example 3)
-Polyurethane-based rough surface (manufactured in Production Example 4)
-Polystyrene-based rough surface (manufactured in Production Example 5)

(Production Example 1) Preparation of PEDOT: Using a 2000 ml three-necked glass flask equipped with a cooling tube, 92.3 parts of an aqueous polystyrene sulfonic acid solution (VERSA-TL72, manufactured by Axonobel) and 3,4-ethylenedioxythiophene. 7.1 parts of (EDOT) was added to 1000 parts of ion-exchanged water to obtain a mixed solution. While stirring this mixture, a solution prepared by dissolving 4.0 parts of ferric sulfate and 14.8 parts of ammonium peroxodisulfate in 100 parts of ion-exchanged water is added, and the mixture is stirred at 20 ° C. for 24 hours for oxidative polymerization. Was done. Next, 15% by weight of each of a cation exchange resin (Amberlite IR120B, manufactured by Organo Corporation) and an anion exchange resin (Amberlite IRA67, manufactured by Organo Corporation) were added, and the mixture was further stirred for 18 hours. The obtained reaction mixture was filtered through a glass filter, homogenized 10 times at 100 MPa with a high-pressure homogenizer, and then 5% by weight of dimethyl sulfoxide was added to obtain a PEDOT: PSS aqueous dispersion. ..

(Production Example 2) Preparation of Highly Conductive PEDOT: PSS After ultrafiltration of a polystyrene sulfonic acid aqueous solution (Axonobel, VERSA-TL72) using an ultrafiltration module (Millipore, Biomax-50), By performing cation exchange and diluting with ion-exchanged water, an aqueous solution of 1,887 parts containing 22.2 parts of polystyrene sulfonic acid was obtained. Transfer this aqueous solution to a 2000 ml three-necked glass flask equipped with a cooling tube and a nitrogen introduction tube, and while stirring with a magnetic stirrer, repeat suction of the aspirator and introduction of nitrogen 5 times to degas the inside of the system, and then 1% of 49 parts. A ferric sulfate aqueous solution, 60 parts of concentrated nitric acid, 8.8 parts of 3,4-ethylenedioxythiophene, and 121 parts of a 10.9% peroxodisulfate aqueous solution were added. The reaction mixture was stirred at 18 ° C. for 19 hours. Next, 154 parts of a cation exchange resin (Amberlite IR120B, manufactured by Organo Co., Ltd.) and 273 parts of an anion exchange resin (Amberlite IRA67, manufactured by Organo Co., Ltd.) were added to this reaction mixture, and the mixture was stirred for 2 hours. After that, the obtained reaction mixture was filtered with a glass filter, homogenized 10 times at 100 MPa with a high-pressure homogenizer, and then 5% by weight of ethylene glycol was added to disperse the highly conductive PEDOT / PSS water. I got a body.

(Production Example 3) Preparation of polyester-based rough surface Acrylic polyol (manufactured by Dainippon Ink and Chemicals Co., Ltd., A-807) 162 parts by weight, isocyanate (manufactured by Takeda Yakuhin Kogyo Co., Ltd., D110N) 32 parts by weight, polystyrene particles (average) (Particle size 8.9 μm) 220 parts by weight, 215 parts by weight of methyl isobutyl ketone, and 215 parts by weight of butyl acetate were stirred and mixed to obtain a composition for forming the filler-containing layer (II). This composition is applied onto a polyethylene terephthalate film (manufactured by Toray Industries, Inc., T-60) as a thermoplastic resin layer (I) by a bar coating method, and dried to obtain the thermoplastic resin layer (I). A polyester-based rough surface body (thickness 100 μm) and a filler-containing layer (II) (thickness 12 μm) was obtained. The surface Ra and Rz of the formed filler-containing layer (II) were evaluated by the following method. The results are shown in Table 1.

(Production Example 4) Preparation of polyurethane-based rough surface body 100 parts by weight of urethane resin (made by ADEKA Co., Ltd., HUX-210), 1 part by weight of epoxy resin (manufactured by ADEKA Co., Ltd., EM-0427WC), silica particle dispersion (average particles) A composition for forming the filler-containing layer (II) was obtained by stirring and mixing 100 parts by weight (diameter 0.45 μm, solid content 40%) and 600 parts by weight of ethanol. This composition is applied onto a polyurethane film (manufactured by Bemis Associates, 3914CLR) as a thermoplastic resin layer (I) by a bar coating method, and dried to obtain a thermoplastic resin layer (I) (thickness 120 μm). ) And the filler-containing layer (II) (thickness 3 μm) to obtain a polyurethane-based rough surface. The surface Ra and Rz of the formed filler-containing layer (II) were evaluated by the following method. The results are shown in Table 1.

(Production Example 5) Fabrication of Polystyrene-based Rough Surface A polystyrene resin (HT516, manufactured by PS Japan Co., Ltd.) is used as a composition for forming a thermoplastic resin layer (I) to form a filler-containing layer (II). As the composition of the above, a melt-kneaded product of 60 parts by weight of polystyrene resin (HT516 manufactured by PS Japan Co., Ltd.) and 40 parts by weight of rutile-type titanium oxide particles (average particle diameter 0.28 μm) was used, and a multilayer by a multi-manifold die was used. By the coextrusion method, a polystyrene-based rough surface composed of the thermoplastic resin layer (I) (thickness 100 μm) and the filler-containing layer (II) (thickness 20 μm) was obtained. The surface Ra and Rz of the formed filler-containing layer (II) were evaluated by the following method. The results are shown in Table 1.

2. 2. Examples (Examples 1 to 4, Comparative Examples 1 to 3)
The conductive resin (a), the non-conductive resin (b), the leveling agent (c), and the hydrous alcohol (50 parts by weight of pure water, 50 parts by weight of isopropyl alcohol) are mixed so as to have the solid content ratio shown in Table 1. , A conductive coating liquid was obtained. Here, the amount of the hydrous alcohol was adjusted so that the solid content of the conductive coating liquid was 1%. The pH was adjusted by adding aqueous ammonia manufactured by Tokyo Chemical Industry Co., Ltd. Ra with respect to the surface resistivity (hereinafter, also referred to as surface resistivity B) when the obtained conductive coating liquid is coated on a substrate having Ra of 0.02 μm with a film thickness of 0.05 μm by the following method. The magnification and pH of the surface resistivity (hereinafter, also referred to as surface resistivity A) when coated on a substrate having a film resistivity of 0.2 μm with a film thickness of 0.05 μm were determined.
Then, the obtained conductive coating liquid is applied onto the filler-containing layer (II) of the rough surface obtained in Production Examples 3 to 5 by a bar coating method so that the dry film thickness is 0.04 μm. The conductive coating layer (III) was formed by drying at 100 ° C. for 2 minutes using a blower dryer to obtain a conductive rough surface. The surface Ra and Rz of the formed conductive coating layer (III) were evaluated by the following method. Further, the surface resistivity, water resistance, and adhesion of the obtained conductive rough surface were evaluated by the following methods. The above results are shown in Table 1.

3. 3. Evaluation method (magnification of surface resistivity A with respect to surface resistivity B)
On the polystyrene-based rough surface (Ra 0.2 μm) obtained in Production Example 5, No. The conductive coating liquid was applied using the wire bar of No. 6, and a coating film having a dry film thickness of 0.05 μm was obtained using a blower dryer at 70 ° C. The surface resistivity A of the obtained coating film was determined by Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation.
Further, on a polystyrene substrate (Ra 0.02 μm) obtained in the same manner as in Production Example 5 except that rutile-type titanium oxide particles were not used, No. The conductive coating liquid was applied using the wire bar of No. 6, and a coating film having a dry film thickness of 0.05 μm was obtained using a blower dryer at 70 ° C. The surface resistivity B of the obtained coating film was determined by Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation.
The ratio of the surface resistivity A to the surface resistivity B was calculated by the formula of surface resistivity B (Ω / □) ÷ surface resistivity A (Ω / □).

(PH)
It was measured using a pH meter (F-55, manufactured by HORIBA, Ltd.) under the condition of 25 ° C.

(Ra and Rz on the surface)
Measurements were made using an atomic force microscope (Nanocut, manufactured by SII Nanotechnology) in DFM mode and a scan speed of 0.5 Hz.

(Surface resistivity)
The following methods were selected and evaluated according to the surface resistivity of the conductive coating layer (III) and the measurable range of the apparatus.
When the surface resistivity is less than 1.0E + 06 (Ω / □): Measured at an applied voltage of 10V using an ESP probe of Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation.
When the surface resistivity is 1.0E + 06 (Ω / □) to 1.0E + 08 (Ω / □): Measured at an applied voltage of 10V using a UA probe of Mitsubishi Chemical Corporation High Resta UP (MCP-HT450 type). did.
When the surface resistivity is 1.0E + 08 (Ω / □) or more: Measured at an applied voltage of 250V using a UA probe of High Resta UP (MCP-HT450 type) manufactured by Mitsubishi Chemical Corporation.

(water resistant)
Using a non-woven fabric impregnated with pure water, a load of 500 g was applied and rubbed 15 times, and the appearance of the conductive coating layer (III) was visually evaluated in the following two stages.
○: No change ×: Clear scratches and peeling are seen

(Adhesion)
According to the grid peeling test of JIS K 5400, it was evaluated in the following two stages.
◯: 8 to 10 points ×: 0 to 7 points

Claims (8)

Conductive resin (a) in an amount of 1 to 20% by weight based on the total solid content,
20 to 98.9% by weight of the non-conductive resin (b) in the total solid content, and
A conductive coating liquid containing 4 to 60% by weight of the leveling agent (c) in the total solid content.
The solid content ratio of the leveling agent (c) to the conductive resin (a) is 1 to 3.
The surface resistivity when coated on a substrate having Ra of 0.2 μm at a film thickness of 0.05 μm is 5 of the surface resistivity when coated on a substrate having Ra of 0.02 μm at a film thickness of 0.05 μm. Less than double,
A conductive coating liquid, which is used for coating on the surface of a rough surface. The conductive resin (a) is a composite of polyethylene dioxythiophene (a1) and polystyrene sulfonic acid (a2), and the weight average molecular weight of polystyrene sulfonic acid (a2) is 20,000 to 1,000,000. The conductive coating liquid according to claim 1. The conductive coating liquid according to claim 1 or 2, wherein the leveling agent (c) is a polymer having a siloxane skeleton or an alkylene oxide skeleton, and the pH of the conductive coating liquid is 4 to 10. A thermoplastic resin layer (I), a filler-containing layer (II), and a conductive coating layer (III) formed by using the conductive coating liquid according to any one of claims 1 to 3 are provided in this order. ,
A conductive rough surface having a Ra of the surface of the conductive coating layer (III) of 0.1 μm or more and an Rz of 0.5 μm or more. The filler-containing layer (II) contains a filler having an average particle diameter of 0.2 μm or more and a thermoplastic resin.
The conductive rough surface body according to claim 4, wherein the Ra on the surface of the filler-containing layer (II) is 0.1 μm or more and the Rz is 0.5 μm or more. The conductive rough surface according to claim 4 or 5, wherein the thermoplastic resin layer (I) contains at least one selected from the group consisting of polyester, polyurethane, polyethylene, polypropylene, rayon, nylon and polystyrene. A conductive light diffusing film comprising the conductive rough surface according to any one of claims 4 to 6. A conductive reflective film comprising the conductive rough surface according to any one of claims 4 to 6.