JPH02280101A - Transparent molding having low reflectivity and electrical conductivity - Google Patents

Abstract

PURPOSE:To obtain the transparent molding having antireflection and antistatic properties and scratching resistance by providing two layers; a specific conductive layer consisting of inorg. fine particles and a high-refractive index layer on an air side on the surface of the molding. CONSTITUTION:The two layers; the conductive layer consisting of the inorg. fine particles and having <=10<10>(OMEGA/square) surface resistance value and the high- refractive index layer having >=0.1 refractive index difference from the refractive index of the conductive layer are provided on the air side on the surface of the molding formed of a transparent base material. The interference effect of light is utilized by adjusting the refractive indices and film thickness of the two layers; the conductive layer and the high-refractive index layer in this case; in addition, the layer contg. a material having an electrical conductivity is provided. The low reflectiveness is obtd. in this way and the electrical conductivity is obtd. as well. Since the fine particles of the metal oxide are used as the conductive material, the surface scratching resistance and durability are obtd.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a transparent molded body having low reflectivity and conductivity, and more particularly, (is) a transparent molded body having low reflectivity and electrical conductivity. This relates to a transparent molded body that has the effect of preventing the accumulation of static electricity on its surface and the adsorption of dust due to its conductivity. It can be suitably used as various displays such as covers.

[Prior Art] Light reflected from the front of the display causes eye fatigue and discomfort for workers, leading to a decrease in work efficiency. There is a strong need to develop transparent molded bodies that can provide low reflectivity and suppress obstacles (
It is desired and attempts are being made to develop it. For example,
9-51920, JP-A-59-51923, JP-A-59-51952, JP-A-59-133268, JP-A-60-245610, JP-A-61-76328, JP-A-61- No. 108520, JP-A-63-1911
Various proposals have been made in various publications such as No. 01 and Japanese Patent Publication No. 61-54066. However, these require an ultraviolet irradiation device to form a low-reflection coating, and a molding method using a special mold must be used to directly make the surface non-glare. There wasn't. In particular, the formed low-reflection coating has poor long-term durability, and the non-glare treatment on the surface reduces the hardness of the surface, which also causes a reduction in resolution in cathode ray tubes and the like.

Furthermore, in addition to the method of imparting song glare to the surface, several proposals have been made to apply light interference to achieve low reflectivity, but these methods lack low reflectivity or have poor scratch resistance on the surface. and had poor durability.

On the other hand, proposals have also been made to impart electrical conductivity to the surface, and further to provide it with low reflectivity. However, these methods provide a low refractive index layer on a layer containing an electrically conductive material, which is extremely disadvantageous in achieving electrical conductivity. In addition, the current situation is that there is a major problem in terms of durability.

[Problems to be Solved by the Invention] The present invention has been made in view of the current situation, and its purpose is to solve the problems of the prior art and to improve antireflection and antistatic properties. An object of the present invention is to provide a transparent molded article having the following properties and also having scratch resistance.

[Means for Solving the Problems] That is, the present invention provides a molded body formed from a transparent base material, the molded body having a surface resistance value of 10" (Ω/) made of inorganic fine particles on the air side of the surface of the molded body. mouth) the following conductive layer (A),
The object of the present invention is to provide a transparent molded article having low reflectivity and conductivity, which is provided with two layers: the refractive index of the refractive index of the refractive index of the refractive index of the refractive index of the refractive index of the refractive index (A) and the high refractive index layer (B) having a refractive index difference of 0.1 or more.

The present invention comprises two layers: a conductive layer (A) and a high refractive index layer (B).
By adjusting the refractive index and film thickness of the layer and utilizing the interference effect of light, one of the objectives, low reflectivity, is achieved.
By providing a layer containing a conductive material, another objective is to be achieved, which is conductivity. The feature of the present invention is that the layer containing this conductive material is provided as the first layer on the air side. In this way, the presence of the layer containing the conductive material in the air-side first layer produces effects as described later.

As the conductive material for forming the conductive layer (A),
Conductive resins, inorganic fine particles, etc. may be used, and their selection is made arbitrarily depending on the desired level of conductivity, such as antistatic, antistatic, semiconductive, conductive, or high conductivity. When considering surface abrasion resistance and durability, conductive resins are generally unsuitable for transparent substrates because they have relatively poor surface abrasion resistance. Therefore, it is often preferable to use inorganic fine particles, and in particular, metal oxide fine particles are suitable as a conductive material when the surface resistance value of the conductive layer (A) is 10" (Ω/hole) or less. Examples of such conductive materials include tin oxide, zinc oxide, indium oxide, etc., and at least one of these is used, and these can be doped with various compounds for the purpose of increasing conductivity. Of course, there is no problem even if the conductive layer (A) has a surface resistance value of more than 1010 (Ω/hole), which causes a problem because sufficient antistatic performance cannot be exhibited.

Various compounds are known for the high refractive index material of the high refractive index layer CB), but the high refractive index material in the present invention is a material that provides a refractive index higher than that of the conductive layer (A). Choose from. In principle, this refractive index difference should be (the refractive index of the first layer on the air side) and (the refractive index of the second layer on the air side), but in order to achieve excellent low reflectivity, the refractive index of both layers must be The difference in rate is 0.1
It is necessary that it is above. The high refractive index material may be resin or inorganic fine particles (the material is selected depending on the purpose.There are many materials with higher refractive index values of inorganic fine particles than resins, - There is a wide selection within the shell.

Particularly, metal oxide fine particles can be most preferably used among inorganic fine particles, and examples of such metal oxide fine particles include titanium oxide, zirconium oxide, antimony oxide, tantalum oxide, tin oxide, indium oxide, aluminum oxide, etc. These are not limited to one type (two or more types can also be used in combination. Air-side conductive layer (A)
In any of the high refractive index layers (B), the size of the inorganic fine particles may be arbitrary depending on the purpose, but if it is too large, the obtained film will likely become HAZE, so the average particle size is 3001 or less. is preferable. In addition, a conductive layer (
In A), the inorganic fine particle size for developing conductivity is 1 n because if it is too small, the conductivity will deteriorate.
It is desirable that it is more than m.

Various methods can be employed to obtain the transparent molded article of the present invention. Examples include PVD methods such as vacuum evaporation, sputtering, and ion-blating methods, CVD methods, and methods for applying coating compositions.

Among these various methods, the method of applying a coating composition is advantageous in terms of workability, cost, and ability to be applied to transparent molded bodies of complex shapes. Therefore, in order to obtain the transparent molded article of the present invention which is inexpensive and has a complicated shape, a composition containing a conductive material or a high refractive index material is applied to the surface of the molded article formed from a transparent base material to form a coating. The method of forming layers is the most optimal.

In order to obtain the transparent molded article of the present invention by the method of applying a coating composition, it is sufficient to simply apply a coating composition in which a conductive material or a high refractive index material is dissolved or dispersed to a transparent substrate. When preparing a product, there is no problem even if the inorganic fine particles are colloidal. Further, in order to make the composition suitable for coating, it is made into a solution using a solvent, and various solvents can be used to dissolve and disperse the conductive material and the high refractive index material. Examples include alcohol-based, ester-based, ketone-based, ether-based, halogenated hydrocarbon-based, and aromatic solvents, but there is no problem whether they are used alone or in combination. In the composition, the concentration of the materials can be arbitrary (depending on the desired thickness of the coating layer).

Here, in the present invention, the desired thickness of the coating layer basically refers to the thickness at which optical interference occurs between the base material and the two layers.

In the present invention, film-forming properties are also one of the important factors in forming a conductive layer (A) and a high refractive index layer (B) having excellent performance. Therefore, in the method of applying the coating composition, other components may be added to the resin or inorganic fine particles, or to the composition containing them, in order to improve film-forming properties. A suitable example of such other components is a silicon compound, which is a good additive component in that the addition of the silicon compound does not impair the scratch resistance of the formed coating layer. Examples of silicon compounds include methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate,
Tetraalkoxysilanes such as 5ee-butylsilicate and t-butylsilicate, and their hydrolysates, as well as methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyl Methoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3.3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β-(aminoethyl)
-di-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, tetraromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxy Silane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxy Silane, α-glycidoxyprobyltriethoxysilane,
β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxybrobyl Tribroboxysilane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β
-Glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ - glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β
-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxyethoxysilane,
β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ
-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)
Trialkoxysilanes such as butyltriethoxysilane, triazyloxysilane or triphenoxysilanes or their hydrolysates, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, γ-chloropropyl Methyldimethoxysilane, γ-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl Billmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyljethoxysilane , α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, α-glycidoxyprobil Methyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropylmethyljethoxysilane, γ-glycidoxybrobylmethyldibroboxysilane, γ-glycidoxybrobylmethyldipoxysilane,
γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyl ethyldimethoxysilane, γ-glycidoxypropyl ethyljethoxysilane, γ-glycid xybrobylethyldibroboxysilane, γ-glycidoxypropylbylvinyldimethoxysilane,
γ-glycidoxypropylvinyljethoxysilane, γ
-glycidoxypropylphenyldimethoxysilane, γ
-Glycidoxyprobylphenyldiethoxysilane, etc. Dialkoxysilanes or diacyloxysilanes are exemplified.

The silicon compounds exemplified above may be used alone or in a mixture of several kinds, either as they are or after being hydrolyzed. During hydrolysis, pure water may be simply added, but water may also be added in the presence of an acid. As the acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, etc. are used. Furthermore, a conventionally known curing catalyst or the like may be added in order to improve the scratch resistance of the formed coating layer.

Further, depending on the purpose, the most suitable resin can be selected in consideration of solubility, compatibility, molecular weight (distribution, degree of polymerization), functional groups contained, higher-order structure, etc. Furthermore, a surfactant or the like may be added to improve the leveling property, or other additives, ultraviolet absorbers, lubricants, etc. that can modify the formed coating layer may be added.

In the method of forming the coating layer of the present invention from the coating composition, conventionally known coating methods such as spin cord, dip coating, flow coating, spray coating, and brush coating can be employed. In order to form a coating layer with excellent performance, it is desirable to bake it after application.
The optimum conditions for the firing time and firing temperature are determined in consideration of the heat resistance of the base material, the type of material, etc. Further, it is possible to fire one layer at a time or two layers at the same time.

The transparent molded body in the present invention is formed from a transparent base material, and the transparent base materials include glass and plastic, and examples of glass include not only ordinary plate glass but also various processed glasses, especially the panel part of a cathode ray tube as a display body, etc. is suitable.

Examples of the material of the ζ plastic include polymethyl methacrylate, polycarbonate, polydiethylene glycol allyl carbonate, polystyrene, polyvinyl chloride, polyurethane, and unsaturated polyester.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

The method for evaluating the transparent molded bodies obtained in the examples is as follows.

(1) Evaluation of low reflectivity The luminous reflectance of one side of the substrate surface was measured using a GAMMA spectroscopic reflectance spectrometer.

(2) Evaluation of conductivity The surface resistance value of the substrate surface was measured using a Hiresta resistance measuring device (manufactured by Mitsubishi Yuka).

(3) Evaluation of scratch resistance and durability After moving back and forth on the base material surface 100 times with an eraser under a load of 1 kg,
Investigate how the surface gets scratched.

The criteria for evaluating scratch resistance are as follows: A: There are no scratches.

B: A few scratches (.

C: Many scratches occur.

In addition, as for durability, after evaluating the scratch resistance mentioned above, low reflectivity and conductivity were evaluated.

Example 1 Preparation of Coating Composition for E High Refractive Index Layer (U Solution) 30 g of titanium tetrachloride was gradually dropped into 970 g of n-butanol to dissolve it. (Hereinafter, abbreviated as U-1 liquid) [Coating composition for conductive layer (preparation of T liquid) 50 g of tetraethoxysilane was dissolved in 200 g of ethanol. Next, 46 g of 1% aqueous hydrochloric acid solution was gradually added dropwise to this. A partially hydrolyzed product was obtained by aging for 3 days.
00 g of ethanol-dispersed antimony-doped tin oxide sol (concentration: 3%, average particle size: 1100 nm) was added to prepare the sample. (Hereinafter, abbreviated as T-1 liquid) A pre-cleaned glass plate (loam x 10cm (thickness 3mm)) was heated under U at a room temperature of 25℃ and humidity of 45%.
-Immersed in liquid 1. After dipping, it was pulled up at a speed of 10 cm/win and baked at 100° C. for 10 minutes. Next, this glass plate was immersed in T-1, pulled up at a speed of 4 cm/min, and fired at 500°C for 30 minutes. In this way, a glass plate on which two coating layers were formed was obtained. This glass plate was evaluated according to the evaluation method described above, and the results are shown in Table 1.

Comparative Example 1 As a comparative example, the glass plate used in Example 1 was evaluated without forming a coating tank, and the results are shown in Table 1.

Table 1 Example 2 The glass plate in Example 1 was evaluated on a television cathode ray tube panel, and the results are shown in Table 2.

Comparative Example 2 As a comparative example, the panel portion of the television cathode ray tube used in Example 2 was evaluated without forming a coating layer.
The results are shown in Table 2.

Table 2 The plates were evaluated and the results are shown in Table 3.

[Preparation of U-2 liquid] 10 g of tetraethoxysilane was dissolved in 40 g of ethanol. 9 g of 1% hydrochloric acid aqueous solution was gradually added dropwise to this, and 3
A partially hydrolyzed product was obtained by aging for 1 day.

Next, mix this and 1000g of TJ-1 liquid to make U-2.
A liquid was prepared.

Table 3 Example 3 A glass plate on which two coating layers were formed was obtained in the same manner as in Example 1 except that the liquid U-1 in Example 1 was replaced with the liquid U-2 below. Examples 4 to 5 of this glass were prepared in the same manner as in Example 3, except that liquid U (coating composition for high refractive index layer) shown in the table below was used in place of liquid U-2 used in example 3. A glass plate having a coating layer formed thereon was obtained.

This glass plate was evaluated and the results are shown in Table 4.

Table 4 This glass plate was evaluated and the results are shown in Table 5.

Table 5 Examples 6 to 8 In the same manner as in Example 1, except that Liquid U (coating composition for high refractive index layer) shown in the table below was used instead of Liquid U-1 used in Example 1. A glass plate was obtained with a coating layer formed thereon.

Examples 9 to 11 After immersion in T-1 liquid in Example 1 and pulling up 50
Baking was performed at 0°C for 30 minutes, Example 9 was fired at 100°C, Example 1
A glass plate on which two coating layers were formed was obtained in the same manner except that the temperature was changed to 200° C. for Example 1 and 400° C. for Example 11.

This glass plate was evaluated and the results are shown in Table 6.

Table 6 This glass plate was evaluated and the results are shown in Table 7.

Table 7 Examples 12 to 14 A two-layer coating was prepared in the same manner as in Example 1, except that the T-liquid (coating composition for conductive layer) shown in the table below was used in place of the T-1 liquid in Example 1. A layered glass plate was obtained.

Examples 15 to 16 Glass plates on which two coating layers were formed were obtained in the same manner as in Example 1, except that the T liquid shown in the table below was used instead of the T-1 liquid in Example 1.

Examples 17 to 19 The same procedure was carried out except that the glass plate as the transparent molded body in Example 1 was replaced with a plastic as shown in the table below, and the firing temperature after immersion in T-1 liquid and lifting was as shown in the table below. A glass plate on which two coating layers were formed was obtained in the same manner as in Example 1.

This glass plate was evaluated and the results are shown in Table 7.

Table 8 This plastic plate was evaluated and the results are shown in Table 9.

Table 9 [Effects of the Invention] ■Since it has excellent conductivity, it prevents dust from adhering to it due to electrostatic action.

■Since it has excellent low reflectivity, discomfort and glare caused by reflected light are reduced.

■It has excellent scratch resistance and is also durable.

■Many materials can be selected, allowing for a wide range of performance (configurable).

There is a characteristic that In particular, the low reflectivity is not due to the light scattering effect due to surface irregularities (because it utilizes the interference effect of light, low reflectivity can be achieved without impairing transmittance. Therefore, this transparent molded body Due to its high transmittance and low reflectivity, the range of applications of transparent substrates has been further expanded.In particular, by applying it to CRTs, computer displays, etc., images can be easily seen and clear without being affected by the surroundings. The effect is recognized as follows.

Furthermore, since the technique can be applied to various transparent base materials, it also has the effect that the application is not limited by the base material.

Claims (9)

[Claims] (1) A molded body formed from a transparent base material, on the air side of the surface of the molded body, a conductive layer (A ), said (A
) High refractive index layer (B) with a refractive index difference of 0.1 or more
A transparent molded body having low reflectivity and conductivity, which is formed by providing two layers. (2) The transparent molded article according to claim 1, wherein the transparent base material is glass. (3) The transparent molded article according to claim 1, wherein the transparent base material is plastic. (4) The transparent molded article according to claim 1, wherein the inorganic fine particles of the conductive layer (A) are at least one selected from zinc oxide, tin oxide, and indium oxide. (5) The inorganic fine particles of the conductive layer (A) have an average particle diameter of 1 to 30
The transparent molded article according to claim 1 or 4, which has a particle diameter of 0 nm. (6) The transparent molded article according to claim 1, wherein the high refractive index layer (B) contains inorganic oxide fine particles. (7) The transparent molded article according to claim 6, wherein the inorganic oxide fine particles of the high refractive index layer (B) have an average particle diameter of 1 to 300 nm. (8) The inorganic oxide fine particles of the high refractive index layer (B) are at least one selected from titanium oxide, zirconium oxide, antimony oxide, tantalum oxide, zinc oxide, tin oxide, indium oxide, and aluminum oxide. or 7. The transparent molded article according to 7. (9) The transparent molded body according to claim 1, wherein the molded body formed from the transparent base material is a display body formed from glass.