JPS6147010A - Coated transparent conductive panel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transparent and electrically conductive glass substrate panel useful for image recognition and input devices with excellent durability.

C. Prior Art] Inputting information on the screen of a display according to the instruction 2 figures is easier and less likely to cause malfunctions than inputting at a location away from the screen using other keyboards. Furthermore, it is conceivable to make the input board constant and to enable a variety of inputs by replacing the input instructions under it with a table or the like. In this case, an input device is required that is transparent so that input can be made on the screen while viewing the variable table, and the input position can be detected. Various methods have been proposed, including methods in which input is made by contacting electrodes. The present invention relates to a coated transparent conductive panel to be overlapped on a display surface in a method in which a dielectric is coated on a transparent conductive film serving as a transparent electrode, and the input position is detected from a change in capacitance by touching the dielectric with a finger or other object. It is something. Here, a dielectric material having a capacitance within a predetermined range may be used as the film required to cover the transparent conductive film, but from the viewpoint of durability, especially maintaining transparency and protecting the insulating film, a hard material is preferable. The coating is preferred. Formation of inorganic thin films by vapor deposition and sputtering has long been known as a general method for forming such hard films on substrates, and organic thin films formed from a liquid phase, which are used for plastic lenses, etc. Silicon-based high hardness coating (e.g. Japanese Patent Publication No. 51-23
43, Japanese Patent Publication No. 52-119618), hardening of the surface by polyfunctional unsaturated compounds (e.g. Japanese Patent Publication No. 49-22951)
).

[Problem that the invention seeks to solve]

Dielectric coatings on transparent conductive panels are generally easily scratched;
It lacked durability.

Although inorganic thin films as hard coatings are effective in terms of hardness and adhesion, they have low efficiency in forming thin films.

Difficulty in controlling film thickness, especially low heat resistance in films with a thickness of around 1 μm or more, becomes a problem. On the other hand, 2. With ordinary organic coatings, especially in the case of wet coating, it is relatively easy to control the film formation efficiency and film thickness, but the durability of the coating is low, especially its hardness, so defects such as scratches easily occur. I wasn't getting anything. In addition, in the case of thermosetting hard coatings, cracks occur when the film thickness becomes too large, making it difficult to select a wide range of capacitance characteristics.

[Means to solve the problem]

The present invention solves these problems at once, and it has been discovered that a transparent conductive panel having a film obtained from the polyfunctional unsaturated compound described in the claims is easy to manufacture and effective. .

The present invention relates to a panel having a transparent conductive layer in the middle, which is formed by disposing a transparent conductive layer on the entire surface or a part of the glass substrate and disposing a dielectric coating thereon, wherein the dielectric coating is It consists of a film obtained by crosslinking and curing a compound having at least two polymerizable carbon-carbon unsaturated bonds in one molecule by irradiation with active energy rays.

The glass substrate used in the present invention is not particularly limited as long as it is transparent. Here, the term "transparent" means that various displays behind the transparent conductive plate can be sufficiently identified to the extent necessary for the purpose of the present invention, and it does not necessarily have to be colorless or clear. In order to increase the contrast of the image or eliminate flickering, it is also possible to use a colored substrate and provide minute irregularities to the extent that it does not interfere with the recognition of the 91 image.

Further, the shape of the substrate used does not necessarily have to be a flat plate; for example, when the display device is mounted on a curved display device such as a CRT, it may be preferable to use a substrate with a curved surface that matches the display device.

The transparent conductive film applied on the glass substrate can be made of various materials known under these names, such as metal thin films such as gold, silver, and palladium, and conductive inorganic oxide thin films. However, an indium oxide/tin oxide thin film (abbreviated as To) is particularly useful. These thin films are formed on the entire surface of the relevant glass substrate or in a pattern in which the input position is blocked, although this varies depending on the required input mechanism. The thickness of the thin film is selected depending on the required conductivity and transparency, but is preferably 10 nm to 300 nm.

Such thin films can be formed by vacuum evaporation, sputtering, other physical vapor phase methods, chemical vapor phase methods using metal halides or organic derivatives, or, in some cases, thin film forming methods from liquid phase. is used as appropriate. Various chemical and physical treatments of the glass surface for forming such a thin film,
Surface modification of glass can be performed as necessary.

As a dielectric coating to be formed on a glass substrate with a transparent conductive film formed on its surface, at least two
A film obtained by cross-linking and curing a compound having a number of polymerizable carbon-carbon unsaturated bonds by irradiation with active energy rays is applied. , polymers are available. Examples of the polymerizable carbon-carbon unsaturated bond include a vinyl group, an alkenyl group, and a vinylidene group, but an acrylic group H3 is particularly effective for the active energy helix used in the present invention.

An example of a compound containing two or more of these in one molecule is (meth)acrylate of polyfunctional alcohol.

(Meth)acrylate of polyfunctional phenol, reaction product of polyfunctional epoxy and (meth)acrylic acid.

Reaction product of polyisocyanate and hydroxyalkyl (meth)acrylate, 2 of hydroxyalkyl phosphoric acid
-3 (Meth)acrylic acid ester Methylene di(meth)acrylamide, various amine resins, or (meth)acryloxy substituted products of organopolysiloxane can be mentioned.

More specific examples of these include pog having 1 to 8 carbon atoms.
-7-#-Kylene di(meth)acrylate, carbon number 1~
12 aliphatic or alicyclic polyoxyalkylene glycol di(meth)acrylates.

Poly(meth)acrylate of glycerol or diglycerol, poly(meth)acrylate of pentaerythritol or its oligomer, neopentyl glycol di(meth)acrylate.

Poly(meth)acrylate of polyester polyol,
polyurethane polyol poly(meth)acrylate,
poly(meth)acrylate of nrubitol, hydroxyethyl bisphenol-A di(meth)acrylate, dihydroxyethyl phthalate, di(meth)acrylate of isophthalate or terephthalate, bisphenol-A di(meth)acrylate, resol di(meth)acrylate, phenol Resin oligomer poly(meth)acrylate, polyadduct of aliphatic or aromatic epoxy resin and (meth)acrylic acid, polyadduct of epoxy group-containing acrylic resin and (meth)acrylic acid, trimethylolpropane or trimethylolethane and tolylene diisocyanate, hexamethylene diincyanate, isophorone, diisocyanate or lysine diincyanate, and a hydroxyethyl (meth)acrylate polyadduct, a hexamer of tolylene diisocyanate or hexamethylene diincyanate. and hydroxyethyl (meth)acrylate polyadducts, hydroxyethyl (meth)acrylate polyadducts of lysine triincyanate, hydroxyethyl (meth)acrylate polyadducts of polyester urethane or polyether urethane, and hydroxyethyl (meth)acrylate polyadducts of polyester urethane or polyether urethane. ) Polycondensation of acrylic oxyethyl phosphate, methoxymethyl melamine and hydroxyethyl (meth)acrylate 1. Polyadduct of hydroorganopolysiloxane and allyl (meth)acrylate,
Examples include hydrolyzed condensates of (meth)acryloxyglobyl trialkoxysilanes and hydrolyzed condensates of (meth)acryloxypropylmethyldialkoxysilanes. These compounds can be used alone or in combination. Further, among these compounds, a compound having at least one polymerizable carbon-carbon unsaturated bond per molecular weight of 500 gives particularly favorable results.

Although these compounds can be applied as is, various working properties are required for film formation.

Various other substances can be used in combination depending on the various physical properties required for the film.

In order to form a film from these compounds, a composition containing these compounds is applied, the solvent is evaporated off by heating as necessary, and then active energy rays are irradiated.

Here, active energy rays refer to active light rays and ionizing radiation. Actinic rays refer to infrared rays, visible rays, or ultraviolet rays, and in particular, in the present invention, rays with a wavelength of 500 μm are used.
The following light rays are preferred, and more effectively, light rays containing ultraviolet rays. Various types of light sources can be used to generate actinic rays.

Low-pressure, high-pressure, and ultra-high-pressure mercury lamps in terms of processing efficiency, etc.

Xenon discharge lamps, arc lamps, etc. are preferably used.

Also, ionizing radiation refers to gamma rays emitted from cobalt-60,
Alternatively, electron beams generated by an electron beam accelerator, X-rays generated by an X-ray device, neutron beams generated by a nuclear reactor, etc. can also be used.

Electron beams are particularly preferred because they are easy to handle and obtain.

Specifically, an electron beam has an acceleration energy of 0.3 to 3 MeV.
It refers to the radiation emitted from various electron beam accelerators such as Bumpgra 7 type, Kotsukucroft type, Kotskucroft-Walton type, iron core insulated core type, Dynamidron type, resonant transformer type, and linear type. The appropriate irradiation dose is in the range of 0.1 to 10 M rad.

Such irradiation can be carried out at room temperature in air, and if necessary, heating and/or reduced pressure, and a non-oxygen atmosphere such as nitrogen can be used in combination.

Irradiation conditions must be determined experimentally to achieve the objectives of the present invention.

Application methods include various known methods, such as dip coating.

Spray coating, spin cord, curtain flow coating, etc. can be applied.

In addition to the solvent described above, various substances can be mixed into the film-forming composition for the purpose of improving physical properties.

Among these, curing catalysts, diluent monomers, modifying resins, etc. are preferably used. As the curing catalyst, various compounds hitherto known as radical initiators, photoinitiators, and photointensifiers are used as appropriate, usually in an amount of 10% by weight or less of the coating film-forming components.

Examples of these include various peroxides such as benzoyl peroxide, cumyl peroxide, alkyl peroxybenzoates, and inglovir peroxy carbonate; various aso-based compounds such as azobisisoputilonitrile and azobiscyclohexanonitrile; Biacetyl, benzophenone, mihiraketone, benzyl, benzoin, benzoin butyl ether, benzyl dimethyl ketal, tetramethylthiuramthrefite, 1-hydroxycyclohexylphenylketone, α-hydroxyimptylphe
Photoinitiators such as non-silica 9 are effective when used in combination with the above radical initiators and photoinitiators; amines such as n-butylamine, diethylamine ethyl methacrylate, ureas, thioureas, and sodium diethyldithiophosphate. , sulfur compounds such as aromatic sulfinic acids, phosphorus compounds such as tri-11-butylphosphine and sodium diethylthiophosphate, chlorine compounds such as carbon tetrachloride and hexachloroethane, N-nitrone hydroxylamine derivatives, and oxazoline compounds. There is a compounding agent. These may be used alone or in combination.

Any diluent monomer may be used as long as it has an unsaturated group copolymerizable with the above-mentioned carbon-carbon unsaturated bond, but (meth)acrylic acid esters are particularly suitable.

Acrylic acid, rylonitrile, vinyl chloride, ethyl acetate, maleic anhydride, and the like are preferably used. In order to maintain the improvement in surface hardness, which is the objective of the present invention, it is preferable that the amount of these components is 20% by weight or less of the coating film forming components.

The modifying resin may be any resin as long as it has compatibility to the extent that it does not impair the transparency of the film formed, but acrylic resins, polyvinyl butyral resins, polyethers, and vinyl acetate resins are particularly suitable.

Cellulose resins, polyester resins, and the like are preferred.

By using these compounds, the coating has not only the desired hardness and durability but also has improved stain resistance and deep layer resistance, and can also be provided with antistatic properties, antifogging properties, printability, and the like.

These formulations may contain at most 50% by weight of the film-forming ingredients.
It is preferable to use the following amount. If the amount is more than this, it becomes difficult to achieve the surface hardness that is the objective of the present invention.

As other additives, various surfactants are effective in controlling the fluidity of the coating film at the coating stage, increasing surface smoothness, and reducing the coefficient of friction of the surface. Furthermore, ultraviolet absorbers, antioxidants, anti-foaming agents, viscosity modifiers, etc. can be used as needed.

The dielectric constant of the obtained film varies depending on the method used as an input device, detection sensitivity, accuracy, etc., and also depends on the required film thickness, but 2-Q50, preferably 2 to 15 is used. Ru.

〔Example〕

The present invention will be explained in more detail below with reference to Examples.

Example 1 (1) Preparation of coating composition 40 g of dipentaerythritol hexaacrylate (Nippon Kayaku @ product), 1.2 g of benzyl dimethyl ketal (Irgacure 651" Ciba Geigy product), and 60 g of butyl acetate were mixed to prepare a coating composition. I got something.

(2) Coating and UV irradiation The coating composition described above was applied to the transparent conductive glass substrate with the TO film by the dipping method (pulling speed 20 = n 7 minutes) and heated in a hot air dryer at 110°C for 3 minutes. The substrate was placed in a vacuum-resistant container and exposed under vacuum for 180 seconds from a distance of 0.5 m using a 3 kW ultra-high pressure mercury lamp (manufactured by Oak Seisakusho ■).

(3) Test Results The following tests were conducted to test the performance of the coated transparent conductive panels obtained.

(a) Steel wool The coated surface was rubbed with steel wool having a hardness of ≠0000, and the extent of scratches was visually judged and evaluated in three grades:

A: It won't hurt at all.

B: Slight scars are visible.

C: Leaves scratches on the entire surface to the same extent as ordinary organic plastics.

(b) Transparency The total light transmittance (%) of the TO vapor deposited area was measured. The test results are shown in Table 1.

Example 2 32 g of dipentaerythritol hexaacrylate, polyester urethane acrylate (oligomer with a molecular weight of 1.900 obtained from hexamethylene diisocyanate/adipic acid and ethylene glycol-based polyester polyol/α-hydroxyethyl methacrylate) 1
A coating composition was obtained by mixing 1.4 g of benzyl dimethyl ketal, 1.2 g of benzyl dimethyl ketal, and 56.6 g of butyl acetate.

Coating and UV irradiation were performed in the same manner as in Example 1.

The test results are shown in Table 1.

Table 1 [Effects of the Invention] Results of Example 2 It can be seen that the transparent conductive panel having the coating of the present invention has both sufficient scratch resistance and transparency. The transparent conductive panel obtained according to the present invention is easy to manufacture, has a uniform film thickness, that is, a uniform capacitance, and can easily detect the input position.

Claims (1)

[Claims] A transparent conductive layer is provided on the entire surface or a part of the glass substrate, and a compound having at least two polymerizable carbon-carbon unsaturated bonds in one molecule is cross-linked and cured by irradiation with active energy rays. A coated transparent conductive panel provided with a film obtained by applying a coating.