JP2004244564A - Conductive hard court coating material and molding using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a conductive hard court coating material which provides a coating film with good transparency, and excellent scratch resistance and conductivity upon forming the coating film without using an organic solvent. <P>SOLUTION: The conductive hard court coating material comprises a polyethylene glycol diacrylate and/or a polypropylene glycol diacrylate as a binder resin component, an antimony dope tin oxide finely divided particle as a conductive finely divided particle, and as a dispersant, a polymer dispersant comprising a polypropylene glycol as a constituent unit. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００７５】
表１から明らかなように、実施例の導電性ハードコート塗料は、バインダー樹脂成分としてポリアルキレングリコールジアクリレート、導電性微粒子としてＡＴＯ微粒子、及び分散剤としてポリアルキレングリコールを構成単位とする高分子系分散剤を含むため、分散性、保存性の優れたものであった。また、実施例の導電性ハードコート塗料を用いた成形体は、導電性、透明性、表面硬度の優れたものとなった。
【００７６】
特に、実施例１〜４のものは、バインダー樹脂成分の５０重量％以上をポリエチレングリコールジアクリレート及び／又はポリプロピレングリコールジアクリレート（式量が２５０〜９００）とし、分散剤としてポリプロピレングリコールを構成単位とする高分子の主鎖の片末端に第３級アミノ基、及び第４級アンモニウム（ＡＴＯ微粒子親和性基）を有する直鎖状の構造の高分子分散剤を用いたため、分散性、保存性の極めて優れた導電性ハードコート塗料となり、これを用いた成形体も、導電性、及び透明性の極めて優れたものとなった。
【００７７】
一方、比較例１はバインダー樹脂成分をポリエチレングリコールジアクリレートでないものとしたため、比較例２は導電性微粒子をアルミニウムドープ酸化亜鉛としたため、比較例３は分散剤をポリアルキレングリコールを構成単位とする高分子系分散剤でないものとしたため、及び比較例４は分散剤を添加していないため、導電性微粒子の分散性の悪い導電性ハードコート塗料となった。また、このように導電性微粒子の分散性の悪い導電性ハードコート塗料を用いた比較例１〜４の成形体は、実施例のものと比べて透明性、導電性、及び耐擦傷性の劣るものとなった。
【００７８】
【発明の効果】
本発明によれば、バインダー樹脂成分をポリアルキレングリコールジアクリレートとし、導電性微粒子としてＡＴＯ微粒子、及び分散剤としてポリアルキレングリコールを構成単位とする高分子系分散剤を含有させることにより、有機溶剤を使用することなく、塗膜化した際に透明性が良好で優れた耐擦傷性と導電性の性能を付与する導電性ハードコート塗料が得られる。
【００７９】
また、上記導電性ハードコート塗料を樹脂成形体の表面に塗布硬化させることにより、表面に導電性の性能を付与されたハードコート性の塗膜を有する成形体が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a conductive hard coat paint that provides a surface cured film having excellent scratch resistance and conductivity, and more particularly to a conductive hard coat paint that can be used as a paint without a solvent even at room temperature.
[0002]
[Prior art]
In recent years, structural materials such as walls and floors, window materials of machines installed in rooms, electronic components of machines, or storage, transportation, BACKGROUND ART A resin molded article used in a manufacturing process is required to have transparency and abrasion resistance in order to maintain aesthetics or its performance in addition to conductive properties.
[0003]
Conventionally, the application of the conductive property of such a resin molded body has been performed by kneading and molding a conductive material such as carbon powder and metal fiber into a resin, but in these methods, the resin molded body becomes opaque. However, it has a drawback that it cannot be seen through a resin molding.
[0004]
Therefore, a method has been proposed in which a conductive paint containing conductive fine particles containing tin oxide as a main component in a paint binder is applied to a resin molded product (see Patent Document 1), but such a paint is used. Although the method has good conductivity, it has disadvantages such as a high haze value and poor transparency, and also has insufficient scratch resistance.
[0005]
In order to solve such a problem, by using a specific organic solvent as a solvent for dispersing the conductive fine particles in the conductive coating, the surface of the resin molded article is provided with excellent transparency, excellent scratch resistance and conductivity. A conductive hard coat paint that can be used has been proposed (see Patent Document 2).
[0006]
Such a paint has a low haze, has good transparency, and provides excellent scratch resistance and conductivity. However, when applied to the surface of a resin molded product, an organic solvent contained in the paint is not used. Due to evaporation, the working environment is significantly deteriorated. In order to prevent such a deterioration in the working environment, equipment for drying the applied resin molded body is required, which leads to an increase in the cost of the product. In addition, evaporating such a large amount of organic solvent into the atmosphere destroys the global environment.To avoid this, equipment for recovering the evaporated organic solvent is required, further increasing costs. I will invite you. Further, when the resin molded body to which such a paint is applied is relatively non-solvent-resistant, the surface of the resin molded body is affected by the organic solvent, so that it can be applied. There is also a problem that there is not.
[0007]
[Patent Document 1]
JP-A-57-85866 (claims)
[Patent Document 2]
JP-A-9-143456 (Claims 1 to 6, Paragraph No. 0004)
[0008]
[Problems to be solved by the invention]
Therefore, the present invention provides a conductive hard coat paint which imparts excellent scratch resistance and conductivity to a coating film when formed into a coating film without using an organic solvent. Aim.
[0009]
[Means for Solving the Problems]
The conductive hard coat paint of the present invention that solves the above object is a polymer based on polyalkylene glycol diacrylate as a binder resin component, antimony-doped tin oxide fine particles as conductive fine particles, and polyalkylene glycol as a dispersant. It is characterized by containing a dispersant.
[0010]
The conductive hard coat paint of the present invention is characterized in that the polyalkylene glycol diacrylate as the binder resin component is polyethylene glycol diacrylate and / or polypropylene glycol diacrylate.
[0011]
Preferably, the formula weight of the polyethylene glycol diacrylate and / or the polypropylene glycol diacrylate is 250 to 900.
[0012]
The conductive hard coat paint of the present invention is characterized in that the polyalkylene glycol, which is a constituent unit of the dispersant, is polypropylene glycol.
[0013]
Further, the conductive hard coat paint of the present invention is characterized in that the dispersant is a polymer having an antimony-doped tin oxide fine particle affinity group at one end of a main chain.
[0014]
The conductive hard coat paint of the present invention is characterized in that the content of the polyalkylene glycol diacrylate in all binder resin components in the conductive hard coat paint is 50% by weight or more.
[0015]
Further, the molded article of the present invention is characterized in that the conductive hard coat paint of the present invention is applied and cured on the surface of a resin molded article.
[0016]
Here, the antimony-doped tin oxide fine particles refer to tin dioxide fine particles doped with antimony pentoxide. Hereinafter, such antimony-doped tin oxide fine particles are referred to as “ATO fine particles”.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, each component of the conductive hard coat paint of the present invention and a molded article using the same will be described in detail.
[0018]
The conductive hard coat paint of the present invention contains polyalkylene glycol diacrylate as a binder resin main component, ATO fine particles as conductive fine particles, and a polymer dispersant having polyalkylene glycol as a constituent unit as a dispersant.
[0019]
In the present invention, the binder resin component, the conductive fine particles, and the dispersant are specified, so that a solvent-free conductive hard coat paint can be obtained. A conductive hard coat paint having good properties and imparting excellent abrasion resistance and conductivity can be obtained.
[0020]
The binder resin main component of the conductive hard coat paint of the present invention is a polyalkylene glycol diacrylate. Here, the binder resin component refers to a monomer, oligomer or polymer excluding the dispersant. By using a polyalkylene glycol diacrylate as the binder resin component, it is possible to maintain the surface hardness for forming a hard coat film when forming the film, and to make the conductive hard coat paint solvent-free. be able to.
[0021]
In order to make the paint solvent-free, the ATO fine particles must be dispersed in the binder resin component. Therefore, the binder resin component has a good compatibility with the ATO fine particles and the binder resin component as a dispersion medium. It must be a polyalkylene glycol diacrylate. Specific examples of such a polyalkylene glycol diacrylate include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, and 1,3. -Butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, etc. Use polyethylene glycol diacrylate and / or polypropylene glycol diacrylate from the viewpoint of easy application and easy handling. Is preferred. More preferably, the formula weight of the polyethylene glycol diacrylate and / or the polypropylene glycol diacrylate is desirably 250 to 900.
[0022]
The conductive hard coat paint of the present invention may contain a binder resin component other than the polyalkylene glycol diacrylate. Such a binder resin component is not particularly limited, but has a viscosity at room temperature (about 25 ° C.) of 14,000 mPa · s or less in consideration of the fact that the paint is solvent-free and to make the paint easy to apply and easy to handle. Those having a degree of fluidity are preferred. In addition, from the viewpoint of a conductive hard coat paint, those having a high surface hardness when formed into a coating film are preferable. As such a binder resin component, specifically, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaglycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, dipenta Erythritol hexaacrylate and the like.
[0023]
The content of polyalkylene glycol diacrylate in the binder resin component is preferably at least 50% by weight, more preferably at least 70% by weight. By setting the content of the polyalkylene glycol diacrylate to 50% by weight or more, the dispersibility of the ATO fine particles is improved, and when the film is formed, excellent conductivity performance is imparted to the film. Surface hardness can be maintained.
[0024]
Next, the ATO fine particles are fine particles of tin dioxide doped with antimony pentoxide as described above. By using such ATO fine particles, when formed into a coating film, the coating film can be imparted with good transparency and excellent conductivity and scratch resistance performance.
[0025]
Here, generally, the conductive fine particles include metal fine particles such as tin-doped indium oxide, aluminum-doped zinc oxide, gold, silver, and palladium. When formed into a film, a coating film having good transparency can be obtained. In addition, when the ATO fine particles are contained in the binder resin component, the surface hardness of the coating film can be improved when the coating film is formed.
[0026]
The tin oxide before the doping of the ATO fine particles may be produced by any known method such as a vapor phase method, a CVD method, a carbonate (or oxalate) method, and the like. The shape is not particularly limited, and may be any of a spherical shape, a needle shape, a plate shape, a chain shape, and the like.
[0027]
The size of the ATO fine particles is preferably about 1 nm to 100 nm as a secondary particle diameter, more preferably about 5 nm to 75 nm, and further preferably about 10 nm to 50 nm. By setting the size of the ATO fine particles to a secondary particle diameter of 1 nm or more, high conductivity can be imparted when a coating is formed, and the viscosity is not excessively increased, so that poor dispersion can be suppressed. When the thickness is 100 nm or less, irregular reflection of light in the coating film when the coating film is formed can be prevented, and a decrease in transparency can be prevented.
[0028]
The content of the ATO fine particles is about 100 to 500 parts by weight based on 100 parts by weight of all the binder resin components. By setting the content of the ATO fine particles to 100 parts by weight or more, the surface resistivity of the coating film when forming the coating film is 1 × 10 ⁶ Ω ~ 1 × 10 ¹¹ A high conductivity of about Ω can be obtained, and the surface hardness of the coating film can be improved. Further, when the amount is 500 parts by weight or less, it is possible to control the fluidity of the paint and to make the paint easy to apply, and to improve the dispersibility of the ATO fine particles in the binder resin component described above.
[0029]
Next, the dispersant needs to be a polymer dispersant having a polyalkylene glycol as a structural unit. When the dispersant is a polymer having polyalkylene glycol as a constituent unit, the dispersant exhibits an affinity for a binder resin component: polyalkylene glycol diacrylate as a dispersion medium, and can disperse the ATO fine particles without agglomeration. it can. Specific examples of the polyalkylene glycol which is a constitutional unit of the dispersant include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like, and among them, polypropylene glycol is preferable.
[0030]
The number average molecular weight of such a polymeric dispersant is not particularly limited, but is preferably about 100 to 10,000, more preferably about 1,000 to 5,000. By setting the number average molecular weight in such a range, the dispersibility of the ATO fine particles and the storage stability can be made sufficient, and when formed into a coating film, the transparency is good and the excellent conductivity is obtained. It can be a coating film having.
[0031]
Such a dispersant is preferably a polymer having an ATO fine particle affinity group at one end of the main chain. Here, the term “ATO fine particle affinity group” refers to a functional group having a strong adsorption force on the surface of the ATO fine particles, such as a tertiary amino group, a quaternary ammonium, or a heterocyclic group having a basic nitrogen atom. , A hydroxyl group, a carboxyl group and the like. By adopting a structure having one or a plurality of ATO fine particle affinity groups at one end of the main chain as described above, it can be sufficiently adsorbed on the surface of the ATO fine particles, and dispersibility and storage stability can be improved.
[0032]
The number of ATO microparticle-affinity groups in the dispersant having a structure having an ATO microparticle-affinity group at one end of the main chain is not particularly limited, but is preferably about 2 to 3000 per molecule. More preferably, about 5 to 1500 pieces are present. By setting the affinity group for the ATO fine particles in such a range, the dispersibility and storage stability of the ATO fine particles can be made sufficient, and when formed into a coating film, the transparency is good, and the conductive property is excellent. A coating film having properties is obtained.
[0033]
The content of the polymer dispersant is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, per 100 parts by weight of the ATO fine particles. When the amount is 1 part by weight or more, the dispersibility of the ATO fine particles becomes sufficient, and when the amount is 20 parts by weight or less, a coating film having excellent performance such as scratch resistance when formed into a coating film can be obtained.
[0034]
The conductive hard coat paint of the present invention has a lubricant, a colorant, a pigment, an antistatic agent, a flame retardant, an antibacterial agent, a fungicide, and an ultraviolet ray, as long as the effect of the present invention is not impaired. Additives such as an absorber, a light stabilizer, a heat stabilizer, an antioxidant, a plasticizer, a leveling agent, a flow regulator, an antifoaming agent, and a storage stabilizer may be added. In addition, when the conductive hard coat paint of the present invention is formed into a coating film, it is preferable to use an additive such as a thermal polymerization initiator when performing thermal curing, and to use a photopolymerization when curing by ultraviolet irradiation. It is preferable to use additives such as an initiator and a photopolymerization accelerator.
[0035]
Examples of the thermal polymerization initiator include diacyl such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanol peroxide. Peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 1,3-bis Dialkyl peroxides such as-(t-butylperoxyisopropyl) -benzene, peroxyketals such as 1,1-di-t-butylperoxycyclohexane, alkyl peresters such as t-butylperoxybenzoate, diisopropylperoxy Parkabo such as dicarbonate Organic peroxides such as salts, and azonitriles such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 2,2'-azobiscyclohexylnitrile And the like, and one or more of these are used.
[0036]
Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzyl methyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthone, and the like.
[0037]
Further, the photopolymerization accelerator is capable of reducing the polymerization hindrance caused by air during curing and increasing the curing speed. Examples thereof include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. can give.
[0038]
Such a conductive hard coat paint of the present invention includes the above-mentioned polyalkylene glycol diacrylate, ATO fine particles, a polymer dispersant having a polyalkylene glycol as a constituent unit, and other binder resin components to be added as necessary. And additives are mixed and dispersed using a known dispersion method, for example, an ultrasonic disperser, a homogenizer, a sand mill, or the like, to obtain a conductive hard coat paint.
[0039]
Such a conductive hard coat paint of the present invention is applied to a member to be coated such as a resin molded product, and is cured by heat curing or irradiation with ionizing radiation, whereby a hard coat having conductivity on the surface of the resin molded product is obtained. Can be formed.
[0040]
Next, the molded article of the present invention is obtained by applying and curing the above-described conductive hard coat paint of the present invention on the surface of the resin molded article to form a hard coat film having a conductive property on the surface. Have
[0041]
The resin molded body may be of any thickness such as “film”, “sheet”, “plate”, etc., or may have irregularities on its surface, or may have a three-dimensional form, for example. good.
[0042]
The type of resin of the resin molded body is not particularly limited, but in the case of a film or sheet, for example, those made of a resin such as acrylic, polycarbonate, polyvinyl chloride, polyester, polypropylene, polyethylene, and acetylcellulose, In the case of the above, there may be mentioned those made of a resin such as acrylic, polycarbonate, polyvinyl chloride and the like. Among such resin molded articles, the conductive hard coat paint of the present invention described above is solvent-free, and therefore, even those having no solvent resistance can be used.
[0043]
The surface of the resin molded body may be subjected to an easy-adhesion treatment for the purpose of improving the adhesiveness with the conductive hard coat paint of the present invention, or a separate easy-adhesion layer may be provided.
[0044]
Since the molded article of the present invention is obtained by applying and curing the above-described conductive hard coat paint of the present invention on the surface of such a resin molded article, the molded article has excellent transparency, conductivity, and excellent scratch resistance. ing. Further, even after heat molding such as bending, the cured coating film has good conductivity, transparency, and scratch resistance. Therefore, the molded article of the present invention is preferably used as an optical member requiring conductivity, transparency, and scratch resistance, a transparent material for image display such as a display screen, and the like. It can be used for applications such as wall and floor structural materials, window materials of machines installed in the room, and electronic components of machines used in a room such as a dust room (clean room).
[0045]
The molded article of the present invention is obtained by applying the conductive hard coat paint of the present invention to such a resin molded article by a conventionally known coating method, for example, a bar coater, a die coater, a blade coater, a spin coater, a roll coater, and a gravure coater. It can be obtained by applying the composition onto the above-mentioned resin molded product by a flow coater, spraying, screen printing, or the like, and then irradiating it with thermosetting or ionizing radiation.
[0046]
As a method of irradiating with ionizing radiation (ultraviolet rays or electron beams), an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. may be used, or a Cockloft-Walton type, Van der graph A method of irradiating an electron beam using various electron accelerators such as a mold, a co-transformer, an insulating core transformer, a dynamitron, and a high-frequency type can be adopted.
[0047]
The thickness of such a cured coating film is not particularly limited, but is about 2 μm to 50 μm, preferably about 5 μm to 30 μm, and more preferably about 8 μm to 20 μm. When the thickness is 2 μm or more, the surface resistivity becomes 10 ⁶ -10 ¹¹ The conductive property as high as about Ω can be maintained and the scratch resistance can be excellent. When the thickness is 50 μm or less, excellent transparency is obtained, the strength of warpage of the resin molded article due to curing shrinkage is reduced, and a decrease in surface hardness due to uncured binder resin component can be prevented.
[0048]
As described above, according to the conductive hard coat paint of the present invention, the binder resin component is made of polyalkylene glycol diacrylate, ATO fine particles are used as conductive fine particles, and a polymer dispersion containing polyalkylene glycol as a dispersant is a polymer dispersion. By containing an agent, even without a solvent, the ATO fine particles can be dispersed in the binder resin component without aggregating, and when formed into a coating film, have excellent transparency and excellent conductivity. A coating film having scratch resistance performance can be obtained.
[0049]
Further, by applying and curing the conductive hard coat paint of the present invention on the surface of the resin molded article as described above, since the surface has a hard coat property imparted with conductive performance, the conductivity and The molded article of the present invention having excellent scratch resistance is obtained.
[0050]
Although the conductive hard coat paint of the present invention can be used without solvent, it can be used by incorporating an organic solvent if necessary. The organic solvent is not particularly limited as long as it can be uniformly mixed with polyalkylene glycol diacrylate and other binder resin components and does not inhibit the dispersibility of the ATO fine particles. Those having a boiling point of 50 to 200 ° C. and a viscosity at room temperature of 10 mPa · s or less are suitable. Examples of such organic solvents include alcohols such as ethanol, isopropyl alcohol, normal propyl alcohol and normal butyl alcohol, aromatic hydrocarbons such as benzene and toluene, ketones such as acetone and methyl ethyl ketone, and ethers such as dioxane. And esters such as ethyl acetate and butyl acetate, and N, N-dimethylformamide.
[0051]
【Example】
Hereinafter, the present invention will be described in more detail based on examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.
[0052]
[Example 1]
1. Preparation of conductive hard coat paint
A conductive hard coat paint having the following composition, except for the photopolymerization initiator, was mixed and dispersed using a sand mill disperser (Nanomill: Asada Tekko Co., Ltd.), and then the photopolymerization initiator was added. Was prepared. The polymer dispersant a is a polymer dispersant having a polyalkylene glycol as a constituent unit, and a tertiary amino group at one end of a main chain of a polymer having a polypropylene glycol as a constituent unit, and a quaternary amino group. A linear structure having a secondary ammonium was used (the number average molecular weight was 2000).
[0053]
<Conductive hard coat paint of Example 1>
・ 100 parts of polyethylene glycol diacrylate
(Formula quantity 508)
・ ATO fine particles (primary particle diameter 20nm) 200 parts
(Conductive powder T-1: Mitsubishi Materials Corporation)
・ Polymer dispersant a 10 parts
・ Photopolymerization initiator 3 parts
(Irgacure 184: Ciba Specialty Chemicals)
[0054]
2. Production of molded article using the above conductive hard coat paint
An acrylic plate having a thickness of 2 mm was used as a resin molded body, and the hard coat paint of Example 1 was applied to one surface of the acrylic plate by a roll coater method, and irradiated with ultraviolet light from a high-pressure mercury lamp to form a 10 μm thick conductive hard coat. A film was formed, and a molded article of Example 1 using the conductive hard coat paint was produced.
[0055]
[Example 2]
In the same manner as in Example 1 except that the binder resin component was replaced with polyethylene glycol diacrylate (formula 508) with polypropylene glycol diacrylate (formula 536) in the conductive hard coat paint of Example 1 Then, a conductive hard coat paint of Example 2 and a molded article using the same were produced.
[0056]
[Example 3]
The conductive hard coat paint of Example 3 and molding using the same in the same manner as in Example 1 except that the conductive hard coat paint of the following composition was used instead of the conductive hard coat paint of Example 1. The body was made.
[0057]
<Conductive hard coat paint of Example 3>
・ Polyethylene glycol diacrylate 50 parts
(Formula quantity 508)
・ 50 parts of polypropylene glycol diacrylate
(Formula 536)
・ ATO fine particles (primary particle diameter 20nm) 200 parts
(Conductive powder T-1: Mitsubishi Materials Corporation)
・ Polymer dispersant a 10 parts
・ Photopolymerization initiator 3 parts
(Irgacure 184: Ciba Specialty Chemicals)
[0058]
[Example 4]
The conductive hard coat paint of Example 4 and molding using the same as in Example 1 except that the conductive hard coat paint of the following composition was used instead of the conductive hard coat paint of Example 1. The body was made.
[0059]
<Conductive hard coat paint of Example 4>
・ 80 parts of polyethylene glycol diacrylate
(Formula quantity 508)
・ Trimethylolpropane triacrylate 20 parts
(Formula weight 296)
・ ATO fine particles (primary particle diameter 20nm) 200 parts
(Conductive powder T-1: Mitsubishi Materials Corporation)
・ Polymer dispersant a 10 parts
・ Photopolymerization initiator 3 parts
(Irgacure 184: Ciba Specialty Chemicals)
[0060]
[Example 5]
The conductive hard coat paint of Example 1 was used in the same manner as in Example 1 except that the binder resin component used was polyethylene glycol diacrylate (formula 198) instead of polyethylene glycol diacrylate (formula 508). The conductive hard coat paint of Example 5 and a molded article using the same were produced.
[0061]
[Example 6]
In the same manner as in Example 2 except that polypropylene glycol diacrylate (formula 1316) was used instead of polypropylene glycol diacrylate (formula 536) as the binder resin component in the conductive hard coat paint of Example 2 The conductive hard coat paint of Example 6 and a molded article using the same were produced.
[0062]
[Example 7]
The conductive hard coat paint of Example 1 was replaced with a polymer-based dispersant having polybutylene glycol as a structural unit instead of the polymer-based dispersant a in the same manner as in Example 1, except that the polymer-based dispersant was used. 7 and a molded article using the same were prepared.
[0063]
Example 8
The conductive hard coat paint of Example 1 has a plurality of tertiary amino groups and quaternary ammonium other than one end of a polymer having polypropylene glycol as a structural unit instead of the polymer dispersant a. A conductive hard coat paint of Example 8 and a molded article using the same were produced in the same manner as in Example 1 except that a polymer dispersant was used.
[0064]
[Comparative Example 1]
The conductive hard coat paint of Comparative Example 1 was prepared in the same manner as in Example 1 except that the conductive hard coat paint of Example 1 was replaced by polyethylene glycol dimethacrylate (formula 330) instead of polyethylene glycol diacrylate. A paint and a molded article using the same were produced.
[0065]
[Comparative Example 2]
In the same manner as in Example 1, except that the conductive hard coat paint of Example 1 was replaced with aluminum-doped zinc oxide fine particles having a primary particle diameter of 50 nm (conductive zinc oxide 23K: Hakusui Tech Co., Ltd.) instead of the ATO fine particles, A conductive hard coat paint of Comparative Example 2 and a molded article using the same were produced.
[0066]
[Comparative Example 3]
Example 1 was the same as Example 1 except that the conductive hard coat paint of Example 1 was replaced with a polymer dispersant having hydroxystearic acid as a structural unit (Solsperse 24000: Avicia) in place of the polymer dispersion a. Similarly, a conductive hard coat paint of Comparative Example 3 and a molded article using the same were produced.
[0067]
[Comparative Example 4]
The conductive hard coat paint of Comparative Example 4 and a molded article using the same were prepared in the same manner as in Example 1 except that the polymer dispersion a was not added in the conductive hard coat paint of Example 1. did.
[0068]
The conductive hard coat paints obtained in Examples and Comparative Examples were evaluated for the dispersibility of the liquid immediately after preparation and the storage stability of the liquid after 7 days. The molded products obtained in the examples and comparative examples were evaluated for transparency, conductivity, and surface hardness. Table 1 shows the evaluation results.
[0069]
(1) Evaluation of conductive hard coat paint
In order to evaluate the dispersibility and storage stability of the conductive hard coat paints of Examples and Comparative Examples, the secondary particle diameter of the ATO fine particles immediately after the preparation of each conductive hard coat paint and after 7 days was measured by a particle size analyzer. (Microtrac UPA150: Nikkiso Co., Ltd.). The evaluation was "◎" when the secondary particle diameter was 10 nm or more and less than 50 nm, "O" when the secondary particle diameter was 50 nm or more and less than 100 nm, and "X" when the secondary particle diameter was 100 nm or more.
[0070]
(2) Evaluation of molded products using each hard coat paint
(B) Evaluation of transparency
In order to evaluate the transparency of the molded articles of Examples and Comparative Examples, the haze of the molded articles of Examples and Comparative Examples was measured using a haze meter (NDH2000: Nippon Denshoku Co., Ltd.) based on JIS-K7136: 2000. did. The evaluation was evaluated as “A” when the measured value was less than 1.0%, “A” when the measured value was 1.0% or more and less than 2.0%, and “X” when 2.0% or more. The measurement surface was a coating film surface.
[0071]
(B) Conductivity evaluation
The molded body using the conductive hard coat paint of the example and the comparative example was cut into a size of 10 cm × 10 cm, and measured with a surface resistance meter (digital multimeter resistance meter: HEWLETT PACKARD). 1 × 10 ⁹ What was less than Ω was evaluated as “◎”, 1 × 10 ⁹ Ω or more 1 × 10 ¹¹ Ω or less is “○”, 1 × 10 ¹² Those that were Ω or more were rated “x”.
[0072]
(C) Evaluation of surface hardness
In order to evaluate the abrasion resistance of the molded products of the examples and the comparative examples, the molded products of the examples and the comparative examples were added to # 0000 steel wool at 1.5 N / cm. ² After the surface was rubbed back and forth by applying a load of 10 times, "o" indicates that the surface had 5 or less scratches, and "x" indicates that the surface had 6 or more scratches.
[0073]
In addition, in order to evaluate the pencil hardness of the molded articles of the examples and the comparative examples, scratches were measured based on a pencil scratch value testing machine method of JIS-K5400: 1990. The evaluation was evaluated as "O" when the measured value was 2H or more, and "X" when the measured value was H or less.
[0074]
[Table 1]

[0075]
As is clear from Table 1, the conductive hard coat paints of the examples are polymer-based having polyalkylene glycol diacrylate as a binder resin component, ATO fine particles as conductive fine particles, and polyalkylene glycol as a dispersant. Since it contained a dispersant, it was excellent in dispersibility and storage stability. Further, the molded article using the conductive hard coat paint of the example had excellent conductivity, transparency, and surface hardness.
[0076]
In particular, in Examples 1 to 4, 50% by weight or more of the binder resin component was polyethylene glycol diacrylate and / or polypropylene glycol diacrylate (formula weight: 250 to 900), and polypropylene glycol was used as a dispersant as a structural unit. Since a polymer dispersant having a linear structure having a tertiary amino group and a quaternary ammonium (ATO fine particle affinity group) at one end of the main chain of the polymer to be used is used, dispersibility and storage stability An extremely excellent conductive hard coat paint was obtained, and a molded article using the same was also extremely excellent in conductivity and transparency.
[0077]
On the other hand, in Comparative Example 1, the binder resin component was not polyethylene glycol diacrylate. In Comparative Example 2, the conductive fine particles were aluminum-doped zinc oxide. In Comparative Example 3, Comparative Example 3 had a polyalkylene glycol as a dispersant. Since it was not a molecular dispersant and Comparative Example 4 did not contain a dispersant, the conductive hard coat paint had poor dispersibility of the conductive fine particles. Further, the molded articles of Comparative Examples 1 to 4 using the conductive hard coat paint having poor dispersibility of the conductive fine particles as described above are inferior in transparency, conductivity, and scratch resistance as compared with those of Examples. It became something.
[0078]
【The invention's effect】
According to the present invention, the binder resin component is a polyalkylene glycol diacrylate, ATO fine particles as conductive fine particles, and a polymer dispersant having a polyalkylene glycol as a structural unit as a dispersant, to contain an organic solvent. Without using, a conductive hard coat paint having good transparency and excellent scratch resistance and conductivity performance when formed into a film can be obtained.
[0079]
Further, by applying and curing the conductive hard coat paint on the surface of the resin molded article, a molded article having a hard coat coating film having a conductive property on the surface can be obtained.

Claims (7)

A conductive hard coat paint comprising: a polyalkylene glycol diacrylate as a binder resin component; antimony-doped tin oxide fine particles as conductive fine particles; and a polymer dispersant having polyalkylene glycol as a constituent unit as a dispersant. 2. The conductive hard coat paint according to claim 1, wherein the polyalkylene glycol diacrylate as the binder resin component is polyethylene glycol diacrylate and / or polypropylene glycol diacrylate. The conductive hard coat paint according to claim 2, wherein the formula weight of the polyethylene glycol diacrylate and / or the polypropylene glycol diacrylate is 250 to 900. The conductive hard coat paint according to claim 1, wherein the polyalkylene glycol as a constituent unit of the dispersant is polypropylene glycol. The conductive hard coat paint according to any one of claims 1 to 4, wherein the dispersant is a polymer having an antimony-doped tin oxide fine particle affinity group at one end of a main chain. Conductive hard coat paint. The conductive hard coat paint according to any one of claims 1 to 5, wherein the content of the polyalkylene glycol diacrylate in all binder resin components in the conductive hard coat paint is 50% by weight or more. . A molded article obtained by applying and hardening the conductive hard coat paint according to any one of claims 1 to 6 on the surface of a resin molded article.