JPH1149965A - Resin composition and conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition whose conductivity (surface conductivity) is optionally controllable by blending a conductive metal oxide and a hygroscopic compound into the composition. SOLUTION: As a conductive metal oxide, a zinc antimonate, a tin oxide doped with antimony, an indium oxide or the like can be used and a zinc antimonate anhydride sol whose primary particle diameter is usually not more than 0.5 μm is preferable. The content is preferably 30-70 wt.% as a solid component in the nonvolatile component of the resin composition. A hygroscopic compound has a characteristics to absorb (adsorb) water in the air and preferably is soluble to water and monatomic alcoholes such as methanol, isopropanol and the like. A water soluble alkali metal salt, a water soluble alkaline earth metal salt, a water soluble alcohol having 3 or more hydroxide groups in the molecule and a water soluble amine derivative having 2 or more amino groups in the molecule can be used as the hygroscopic compound. As a resin, an ultraviolet curing resin which is a polymerizing resin is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for imparting an antistatic property to a plastic surface, and more particularly to a resin composition suitable for applying to a plastic surface such as polyester, acrylic, and polycarbonate. Resin composition which is transparent and excellent in abrasion resistance, chemical resistance and antistatic property, and antistatic property (conductive) obtained by coating and curing it
About the film.

[0002]

2. Description of the Related Art At present, plastics are used in large quantities in various industries including the automobile industry and the home appliance industry.
The reason why a large amount of plastic is used is not only its workability and transparency, but also its light weight and low cost. However, it has drawbacks such as being softer than glass or the like and easily scratching the surface. In addition, plastic has a high volume resistivity, so that static electricity is easily applied to the contact surface due to friction or the like, and the static electricity does not leak. Therefore, a decrease in transparency due to the adsorption of dust and a malfunction of the computer are problematic. 2. Description of the Related Art In recent years, there has been a growing need to provide antistatic protection for semiconductor wafer storage containers and other electronic and electrical components, architectural components such as flooring materials, carpets, and wall materials. Electric resistance of the member surface is 1E10 ohm / cm
^It is said that the charge can be prevented by setting the value to ² or less (Surfactant Handbook, P506-516, Sangyo Tosho Co., Ltd., 196).
0). For this purpose, it is common practice to increase the surface hardness by coating a hard coat agent on the surface and to impart an antistatic function with a surfactant having an antistatic property. In order to provide antistatic properties, organic materials with ion conductivity such as alkylamine halides have been kneaded and applied to plastics, but their performance depends on humidity, especially under dry conditions. Is reduced. In addition, although inorganic fillers such as carbon and metal powders have been used, their performance does not depend on humidity but is inferior in terms of spoiling the appearance. As a solution to this, Japanese Patent Laid-Open No. 60-1616
No. 6 discloses a paint comprising a conductive powder mainly composed of tin oxide and a photocurable paint binder mainly composed of a (meth) acrylic oligomer having a (meth) acryloyl group. Japanese Patent Application Laid-Open No. Sho 62-170330 discloses a conductive plate in which a coating film containing a conductive fine powder containing tin oxide as a main component is laminated.

[0003]

As described above, conductive paints using metal oxide fine particles as a conductive agent have been used to provide antistatic properties.
There is no known method for adjusting the value as needed.

[0004]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides (1) a resin composition containing a conductive metal oxide and a hygroscopic compound, and (2) the conductive metal oxide is zinc antimonate, antimony-doped tin oxide, or indium oxide. (3) The resin composition according to (1) or (2), wherein the content of the conductive metal oxide is 5 to 80% by weight, and (4) the water-absorbing compound is water-soluble. (1) An alkali metal salt, a water-soluble alkaline earth metal salt, a water-soluble polyhydric alcohol having three or more hydroxyl groups in a molecule or a water-soluble amine derivative having two or more amino groups in a molecule. (5) The resin composition according to (1), wherein the content of the hygroscopic compound is in the range of 0.005 to 3% by weight, and (6) the resin is a polymerizable resin. (7) The resin composition according to any one of (1) to (5), Resin is an ultraviolet curable resin (6)
(8) A conductive film having a cured film layer of the resin composition according to (1) to (7), (9) a conductive film according to (8), wherein the cured film layer is transparent. ,

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the conductive metal oxide used in the present invention include zinc antimonate, antimony-doped tin oxide, indium oxide, and the like. Particularly, an anhydrous zinc antimonate sol having a primary particle diameter of usually 0.5 μm or less is preferable. is there. The content of the conductive metal oxide in the nonvolatile component of the resin composition is 5 to 80% by weight as solid content, preferably 30 to 7% by weight.
It is about 0% by weight.

A method for producing anhydrous zinc antimonate is described in, for example, JP-A-6-219743, and includes methanol (Celnax CX-Z400, manufactured by Nissan Chemical Industries, Ltd.) or methanol / isopropanol. (Celnax CX-Z300IM, Nissan Chemical Co., Ltd.
) Can be obtained as an organosol. The sol primary particles of these anhydrous zinc antimonates are usually 0.5 μm or less, but in order to obtain a transparent coating, it is necessary to remove the coarse particles mixed therein through a filter of 0.6 μm or less.

[0007] The anhydrous zinc antimonate sol is stable and does not agglomerate in methanol to increase the particle size. The particles are unstable and agglomerate in the particle, causing the particle diameter to increase, or the dispersion being destroyed, resulting in separation and sedimentation. In order to stably disperse these resins and solvents, it is necessary to use a dispersant to disperse them.
As a dispersant in this case, a cationic, weak cationic, nonionic or amphoteric surfactant is effective, and particularly, an alkylamine EO / PO adduct (for example, Solsperse 2)
0000, manufactured by Zeneca Corporation), alkylamine EO adducts (for example, TAMNO-15, TAMNS-10 and TAMNS-10)
AMNO-5, manufactured by Nikko Chemical Co., Ltd.) and ethylenediamine PO-EO condensate (for example, Pluronic TR-7)
01, TR-702 and TR-704, manufactured by Asahi Denka Kogyo KK) and the like. The addition amount is 0.05 to 40% by weight with respect to zinc antimonate. Outside this range, the dispersion stability is not sufficient, and the haze increases even if the dispersion stability is good, and the coating becomes transparent. In some cases, the property may be lost, or the surface conductivity may be reduced, thereby impairing practicality. In addition, examples of the alkyl group of the alkylamine include a methyl group, an ethyl group, a lauryl group, and a stearyl group. The number of moles of EO (ethylene oxide) or PO (propylene oxide) to be added is suitably from several moles to about 100 moles per mole of amine, but is not limited thereto.

The hygroscopic compound has a property of absorbing (adsorbing) water in the atmosphere, and is preferably a compound which is soluble in water, a monohydric alcohol such as methanol or isopropanol, and is preferably, for example, a water-soluble alkali metal salt. And water-soluble alkaline earth metal salts, water-soluble alcohols having three or more hydroxyl groups in the molecule, and water-soluble amine derivatives having two or more amino groups in the molecule. Preferred water-soluble alkali metal salts include, for example, sodium salts, potassium salts, lithium salts and the like, and preferable water-soluble alkaline earth metal salts include, for example, magnesium salts, calcium salts, strontium salts, barium salts, and the like. Examples of the water-soluble alcohols having three or more hydroxyl groups include glycerin, pentaerythritol and triethanolamine. Preferred examples of the water-soluble amine derivatives having two or more amino groups in the molecule include urea and thiol. Urea, melamine and the like can be mentioned. Particularly preferred are potassium acetate, sodium acetate, potassium chloride,
Sodium chloride, lithium chloride, calcium chloride, lithium perchlorate, glycerin, pentaerythritol and urea. These hygroscopic compounds can be used alone or as a mixture. If necessary, it may be added after dissolving in a small amount of water or alcohol. By adjusting the type and amount of the hygroscopic compound, it is not affected by the environment at the time of application,
Conductivity (surface resistance) after curing is 1 × 10 ⁶ ohm / c
It can be arbitrarily adjusted between m ^{2 and} 1 × 10 ¹⁰ ohm / cm ² . The content of the hygroscopic compound is 0.005 to 3% by weight as a solid content in the nonvolatile component of the resin composition,
Considering transparency, preferably 0.01 to 0.5% by weight
It is about.

The resin used in the resin composition of the present invention includes, for example, a polymerizable resin. Examples of the polymerizable resin include an ultraviolet-curable resin, a thermosetting resin, and an oxidative-polymerizable resin. An ultraviolet-curable resin is simple and preferable. As the ultraviolet curable resin, for example, an acrylate resin can be used. The acrylate resin is an ultraviolet-curable acrylate having one or more acryloyl groups in a molecule, for example, pentaerythritol monoacrylate.
, Neopentyl glycol diacrylate, 1,6 hexanediol diacrylate, trimethylolpropane triacrylate, ditrimethylol propane tetraacrylate, pentaerythritol tetraacrylate
Polyacrylate such as dipentaerythritol hexaacrylate, diacrylate of bisphenol A diglycidyl ether, neopentyl glyco-
Epoxy acrylates such as diacrylate of rudiglycidyl ether and diacrylate of 1,6 hexanediol-diglycidyl ether; polyhydric alcohols and polycarboxylic acids and / or anhydrides thereof and acrylics Polyurethane acrylates and polysiloxanes obtained by reacting polyester acrylates, polyhydric alcohols, polyvalent isocyanates and hydroxyl-containing acrylates obtainable by esterifying an acid. Polyacrylate and the like can be raised. The above polymerizable acrylates may be used alone or as a mixture of two or more kinds. The content thereof is 10% in the nonvolatile component of the resin composition.
It is -90% by weight, preferably 30-70% by weight.

In order to improve the adhesion to various substrates,
Further polymers can be added. Examples of such a polymer include an acrylic resin, a polyester resin, and a butyral resin. Particularly, acrylic resin and polyester resin are preferable. The content is usually 0-50% by weight in the nonvolatile components of the hard coat resin composition.

For the same purpose, an oligomer having an unsaturated double bond copolymerizable at the terminal can be added. Such oligomers include terminal methacrylic acid.
Polymethyl methacrylate, terminal styryl polymethacrylate, terminal methacrylate polystyrene, terminal methacrylate polyethylene glycol, terminal methacrylate
Macromonomers such as triacrylonitrile-styrene copolymer and terminal methacrylate-styrene-methyl methacrylate copolymer can be described, and the content is usually 0 to 50% by weight in the nonvolatile component of the resin composition. It is.

In order to make the resin composition of the present invention an ultraviolet-curable resin composition, a photopolymerization initiator is used. The photopolymerization initiator is not particularly limited, and various known ones can be used. Specific examples of the photopolymerization initiator include photoinitiators such as Irgacure-184, Irgacure-651 (manufactured by Ciba Geigy), Darocure-1173 (manufactured by Merck), benzophenone, methyl benzoylbenzoate, and P-dimethyl. Benzoic acid esters, thioxanthone and the like can be used.

In addition, in addition to the above components, a leveling agent and an antifoaming agent can be added if necessary. In order to produce the resin composition of the present invention, for example, the above components may be uniformly mixed in the presence or absence of a solvent. The mixing order of each component can be obtained by adding the other components to the metal oxide sol and then gradually adding the ultraviolet-curable resin composition with stirring to obtain the desired resin composition. It is also possible to add an ultraviolet curable resin composition containing other components to a metal oxide sol with a dispersant added thereto. Examples of the solvent include lower alcohols such as methanol, and aromatic hydrocarbons such as benzene and toluene.

[0014] The conductive film of the present invention is characterized by having a cured film layer of the above resin composition. The thickness of the cured film layer is usually 1 to 10 microns, preferably 2 μm.
About 5 microns. As the film, a transparent film is preferable, and examples thereof include a polyester film, a polycarbonate film, a triacetyl cellulose film, and a vinyl chloride film.

To produce the conductive film of the present invention,
For example, the above resin composition may be applied to a film in a liquid state using an applicator, and the coating may be cured by a method such as ultraviolet irradiation, heating, and air drying in the atmosphere. The thus obtained conductive film of the present invention is provided with a pressure-sensitive adhesive layer on the back surface and used by being attached to various articles. In particular, it is used by attaching it to the front of the display device to prevent the image quality of the display device from deteriorating.

[0016]

The present invention will be described more specifically with reference to the following examples. Unless otherwise noted, parts are parts by weight. In the examples, the surface resistivity was measured by Megar manufactured by Shisido Electrostatic Co., Ltd.
The measurement was performed using esta (trade name).

Example 1 Dipentaerythritol hexaacrylate (KAYA)
RAD DPHA (Nippon Kayaku Co., Ltd.) 70 parts, photoinitiator Irgacure-184 (Ciba-Geigy) 6.5
Part, silicone slip agent SF-8 as slip agent
421 (manufactured by Toray Dow Corning) and 20 parts of toluene are mixed to obtain an ultraviolet curable resin composition (A). To 43 parts of this ultraviolet-curable resin composition (A), 2 parts of Solsperse 20000 (manufactured by Zeneca Corporation) was blended as a dispersant, and methanol / isopropanol sol of zinc antimonate (Celnax CX- Z300
IM) and 0.02 part of potassium acetate (reagent: manufactured by Junsei Chemical Co., Ltd.) as a hygroscopic compound were obtained to obtain a resin composition (1) of the present invention. 18 in an environment with a temperature of 15 ° C
An 8 micron polyester film (trade name: Toyobo ester film, manufactured by Toyobo Co., Ltd.) was coated with a microgravure coater so that the thickness of the conductive layer at the time of curing was 4 microns, and then cured with ultraviolet light. Its surface resistance was 68 × 10 ⁷ ohm / cm ² .

Example 2 A resin composition (2) was obtained in the same manner as in Example 1 except that the amount of the hygroscopic compound (potassium acetate, reagent, manufactured by Junsei Chemical Co., Ltd.) was changed to 0.04 part. Coating was performed in the same manner as in Example 1. The surface resistance of this is 32 × 1
0 ⁷ ohm / cm ^2, the surface resistance by the hygroscopic compound twice became about 1/2.

Example 3 Resin composition (3) was prepared in the same manner as in Example 1 except that glycerin (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the hygroscopic compound and the amount was 0.1 part. Was obtained and coated in the same manner as in Example 1. Its surface resistance was 21 × 10 ⁷ ohm / cm ² .

Example 4 A resin composition (4) was obtained in the same manner as in Example 1 except that the amount of the hygroscopic compound (glycerin, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.2 part. The coating was performed in the same manner as in Example 1. The surface resistance of this is 11 × 1
0 ⁷ ohm / cm ^2, the surface resistance by the hygroscopic compound twice became about 1/2.

Example 5 A resin composition was prepared in the same manner as in Example 1 except that the hygroscopic compound was changed to lithium perchlorate (reagent, manufactured by Wako Pure Chemical Industries, Ltd.), and the amount was 0.05 parts. (5) was obtained and coated in the same manner as in Example 1. Its surface resistance was 19 × 10 ⁷ ohm / cm ² .

Example 6 A resin composition (6) was prepared in the same manner as in Example 5, except that the amount of the hygroscopic compound (lithium perchlorate, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.15 part. Was obtained and coated in the same manner as in Example 1. The surface resistance was 6.8 × 10 ⁷ ohm / cm ² , and the surface resistance was reduced to about 約 by doubling the amount of the hygroscopic compound.

Example 7 Urea (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a hygroscopic compound.
Example 1 except that the amount was 0.02 parts.
In the same manner as in Example 1, a resin composition (7) was obtained, and coating was performed in the same manner as in Example 1. Its surface resistance is 2
It was 5 × 10 ⁷ ohm / cm ² .

Example 8 Hygroscopic compound (urea, reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
A resin composition (8) was obtained in the same manner as in Example 1 except that the compounding amount of 0.1 was changed to 0.1 part, and coating was performed in the same manner as in Example 1. The surface resistance of this is 5.6 × 10 ⁷
Ohm / cm ² , and the surface resistance was reduced to about 1/5 by increasing the hygroscopic compound by 5 times.

Comparative Example 1 A resin composition (9) was obtained in the same manner as in Example 1 except that no hygroscopic compound was added, and coating was performed in the same manner as in Example 1. Its surface resistance was 89 × 10 ⁷ ohm / cm ² .

[0026]

By using the resin composition of the present invention, it is possible to obtain a conductive film whose surface resistance can be reliably controlled. Further, it is excellent in transparency, and can be attached to, for example, a front surface of a display as an antistatic film to prevent dust from adsorbing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/24 C08K 3/24 5/053 5/053 5/17 5/17 // C09D 5/00 C09D 5/00 P 5 / 24 5/24

Claims (9)

[Claims] 1. A resin composition comprising a conductive metal oxide and a hygroscopic compound. 2. The resin composition according to claim 1, wherein the conductive metal oxide is zinc antimonate, antimony-doped tin oxide, or indium oxide. 3. The resin composition according to claim 1, wherein the content of the conductive metal oxide is 5 to 80% by weight. 4. The hygroscopic compound has a water-soluble alkali metal salt, a water-soluble alkaline earth metal salt, a water-soluble polyhydric alcohol having three or more hydroxyl groups in a molecule or two or more amino groups in a molecule. The resin composition according to claim 1, which is a water-soluble amine derivative. 5. The resin composition according to claim 1, wherein the content of the hygroscopic compound is in the range of 0.005 to 3% by weight. 6. The resin according to claim 1, wherein the resin is a polymerizable resin.
The resin composition according to any one of the above. 7. The resin composition according to claim 6, wherein the polymerizable resin is an ultraviolet curable resin. 8. A conductive film comprising a cured film layer of the resin composition according to claim 1. 9. The conductive film according to claim 8, wherein the cured film layer is transparent.