JPH0890745A - Production of laminate and production of protective material for pen input panel - Google Patents

Abstract

PURPOSE: To obtain a laminate wherein a porous film excellent in scratch resistance, high in reflection preventing effect and free from a change with elapse of time is provided on a base material by mixing specific tetraalkoxysilane, a basic aq. soln. and an org. solvent and performing the partial hydrolysis and polycondensation of tetraalkoxysilane. CONSTITUTION: A condensation compsn. (A) obtained by mixing 1mol of tetraalkoxysilane represented by general formula Si(OR)4 , 2-8mol of a basic aq. soln. with pH10.0-12 and 10-30mol of an org. solvent and a condensation compsn. (B) obtained by mixing 1mol of alkoxysilane represented by general formula (R<2> )n Si(OR<1> )4-n , 3-8mol of an acidic aq. soln. with pH0-2.6 and 10-30mol of an org. solvent are mixed in a ratio of A/B-0.4-2.4 (wt.ratio) to prepare an inorg. compsn. which is, in turn, applied to a base material to be cured. Glow discharge plasma obtained by exciting an inert gas under a pressure of 1×10<-4> -100Torr is brought into contact with the film surface of the base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminate in which a porous coating film having excellent scratch resistance, antireflection effect and time-dependent change is formed on a substrate, and a protective material for a pen input panel. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Glass is widely used in cathode ray tubes for color televisions, windshields for automobiles, solar cells, etc. However, when external light rays are reflected on the glass surface, images and internal objects can be seen due to glare. It becomes difficult and the energy conversion efficiency of the solar cell becomes low. In order to solve this problem, there is a method in which a low refractive index antireflection porous thin film is laminated on glass to form a laminated body, and the reflection of external light rays is reduced. As a method for producing this laminate, for example, a composition comprising a sol solution obtained by mixing an alkoxysilane with colloidal silica dispersed in water or an organic solvent, and hydrolyzing and partially polycondensing a mixed solution dissolved in alcohol. A method of forming a porous thin film by utilizing the difference in thermal contraction between silica sol and colloidal silica at the time of coating and heat treatment on glass (JP-A-62-1704).
No. 4), but this method has a problem that a step of uniformly dispersing colloidal silica in an alkoxysilane is required, and a high-performance device is required to improve the dispersion. There is.

In recent years, transparent plastic materials have been widely used for optical lenses, spectacle lenses, windows of buildings, etc. in place of glass, taking advantage of their characteristics of light weight, easy workability and impact resistance. , Has poor scratch resistance and requires hard coating treatment. Further, it is necessary to reduce the reflection of external light rays by laminating an antireflection thin film like glass to form a laminated body. As a method for producing this laminated body, for example, a method of applying a fluororesin-based material to a transparent plastic material and heat-treating it to form a thin film (Japanese Patent Laid-Open No. Hei 2)
However, this fluororesin-based material has a problem in strength and is difficult to use in applications such as eyeglass lenses that require scratch resistance.

The reason why glass and transparent plastics materials reflect external light rays is that when light enters a different substance from the medium, it is reflected at the interface due to the difference in its refractive index. In the above case, since the refractive index of air as a medium and the refractive index of the glass or transparent plastics material as the base material are different, reflection and loss of light occur at the interface.

In order to reduce the above-mentioned reflection and loss of light, there has been a method of laminating multiple thin films having different refractive indexes by using a vacuum vapor deposition method, an ion plating method, a sputtering method or the like. Although this method has advantages such as film thickness control and antireflection effect in a wide wavelength range, it is not suitable for a large-area substrate because it produces a thin film in a limited space, and it is costly. There is a problem that it is not industrially suitable and cannot be applied to a base material having a complicated shape.

The laminating conditions of thin films for reducing the reflectance of a certain substrate to 0 are expressed by equations (1) and (2). n ₁ = (n _o n _s ) ^0.5 ... (1) n ₁ t ₁ = (λ / 4), (3λ / 4), (5λ / 4) ... (2) n _o : Refraction of air Index (n _o = 1), n _s : refractive index of base material, n ₁ : refractive index of thin film, t ₁ : thin film thickness,
λ: Incident light wavelength As described above, it is necessary to control the refractive index and the film thickness of the thin films to be laminated according to the refractive index of the base material.

The invention according to claim 4 provides a method for manufacturing a protective material for a pen input panel. The protective material for pen input panel is a material used for protecting the surface of the pen input panel. The pen input panel is a panel using a tablet that allows characters and figures to be input on the display surface with a pen, and is used in personal computers, portable electronic notebooks, word processors and the like.

There are an electromagnetic induction method, a resistance film method, an electrostatic coupling method, etc. as a position detection method for the tablet of the pen input panel. The electromagnetic induction method is used for a personal computer and the resistance film method is used for an electronic notebook. There is.

A pen input panel using an electromagnetic induction type tablet generally has a structure shown in FIG. 110 is a protective film or surface treatment layer, 120 is a protective material made of glass or an acrylic plate, 130 is an LCD (liquid crystal display element) unit, 140 is a sensor plate in which an antenna circuit is formed in a grid pattern, and 150 is a printed wiring board. Etc., 160 is a support plate.

The input is the electromagnetic wave generated by the electronic pen,
This is a method in which the antenna in the sensor plate 140 receives and detects the position on the screen where the pen tip exists. . By continuing such operations, it becomes possible to draw characters and figures and input information.

A pen input panel using a resistance film type tablet generally has a structure shown in FIG. 210 is a protective film, 220 is an upper transparent sheet such as a polyester film or polyethylene terephthalate film, 230 is a transparent conductive thin film obtained by applying a conductive material to the above transparent sheet by a sputtering method, a vacuum deposition method, or the like, 240 Is a dot spacer, 250 is a lower transparent sheet such as a polyester film or polyethylene terephthalate film, and 260 is a supporting substrate such as glass.

As an input method, first, a user draws a character or figure to be input on the upper transparent sheet 220 having the protective film 210 with a pen. A current flows when the upper transparent sheet 220 and the lower transparent sheet 250 come into contact with each other, and the computer instantly detects the horizontal direction and the vertical direction from the resistance value at that time, and displays the image on the screen. By continuing such operations, it becomes possible to draw characters and figures and input information.

Conventionally, these pen input panels do not have proper friction between the protective film 110 or the protective film 210 for preventing scratches due to input work and the input pen, so that they are slippery and have a feeling of writing. It was lacking.

Regarding the pen input panel using the resistance film type tablet, there is a pen input panel in which the dot diameter and the dot height of the dot spacer 240 are adjusted to improve the writing feeling in order to improve the writing feeling. (JP-A-4-62
3 gazette). Basically, the smaller the dot diameter and the dot height, the better the resolution for input. Therefore, a certain size is required to obtain a feeling of writing with the diameter and height of the dot spacers, which may impair resolution. Further, since the portion directly contacting the input pen is the protective film 210, it cannot be said that the sliding feeling between them is sufficiently improved, and the writing feeling like writing on a paper with a pencil cannot be obtained.

Further, conventionally, this type of protective film 110 or
The material of the protective film 210 is SiO ₂System and SiO₂And yes
A laminate of machine membranes was used (Japanese Patent Laid-Open No. 4-17).
No. 1521). The surface condition of these films is
Therefore, when writing, the pen is slippery and the writing feel is poor.
And because of the high refractive index (SiO₂Has a refractive index of 1.4
6), the screen is difficult to see due to external light rays
There was a problem such as.

At present, most of the members used for the protective material 120 and the upper transparent film 220 have a refractive index in the range of 1.5 to 1.6. Therefore, when calculated by the above equations (1) and (2), The refractive index of the thin films to be laminated is 1.22-1.
A range of 26 is required. At present, there is no stable material having such a low refractive index, and the refractive index of the thin film to be laminated is reduced as much as possible to reduce the reflectance. With these low refractive index materials
Although there is a fluororesin-based material proposed in Japanese Patent No. 123771, this material has a problem in strength, cannot be used as a protective film, and has a low friction property due to fluorine. No improvement can be obtained.

[0017]

SUMMARY OF THE INVENTION The present invention is intended to solve these problems, and an object thereof is to provide a porous film which has excellent scratch resistance and a high antireflection effect and does not change with time. It is an object of the present invention to provide a method for easily producing a laminated body having a sheet formed thereon, and a method for producing a protective material for a pen input panel which has excellent scratch resistance, has a good writing feeling, and is highly antireflection.

[0018]

The present invention 1 (the present invention 1
The condensation composition (A) used for the production of the inorganic composition used in the invention according to claim 1) has a general formula Si.
(OR) ₄ (wherein R is an alkyl group having 1 to 5 carbon atoms), a tetraalkoxysilane, a basic aqueous solution, and an organic solvent are mixed, and the tetraalkoxysilane is partially hydrolyzed and polycondensed. To be

In the tetraalkoxysilane represented by the above general formula Si (OR) ₄ , when the carbon number of R increases, the stability of the inorganic composition decreases and the long-term stability deteriorates. It is limited to 1 to 5 alkyl groups, for example, methyl group, ethyl group, n-propyl group, iso-
Propyl group, n-butyl group, sec-butyl group, ter
Examples thereof include t-butyl group.

Examples of the tetraalkoxysilane represented by Si (OR) ₄ include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane,
Tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane and the like can be mentioned. From the viewpoint of reactivity in hydrolysis and polycondensation, tetramethoxysilane and tetraethoxy Silanes are preferred and tetraethoxysilane is especially preferred.

The above-mentioned basic aqueous solution refers to one having a pH of 10.0 to 12.0 in which a base species is dissolved in water. The base species is not particularly limited as long as it can adjust the pH of the basic aqueous solution to 10.0 to 12.0, and examples thereof include ammonia, ammonium hydroxide, potassium hydroxide, etc. Ammonia is preferred because it is easy.

When the pH of the basic aqueous solution is low, the molecular weight of the colloidal silica obtained is low, making it difficult to form an antireflection coating, and when the pH is high, the stability of the condensation composition (A) obtained is low. Therefore, 10.0-12.
It is limited to 0, 10.3-11.5 are preferable, and 10.
Especially preferred is 8 to 11.4.

When the amount of the basic aqueous solution is small, the molecular weight of the obtained colloidal silica is low, and it becomes difficult to form an antireflection coating. When the basic aqueous solution is large, the stability of the condensation composition (A) is low. ) ₄ to 1 mole of tetraalkoxysilane represented by 2 to 8 moles added,
It is preferable to add 3 to 4 moles.

The organic solvent is not particularly limited as long as it is compatible with the tetraalkoxysilane represented by Si (OR) ₄ and the basic aqueous solution.
Methyl alcohol, ethyl alcohol, isopropyl alcohol, ethoxyethyl alcohol, allyl alcohol and the like can be mentioned, but isopropyl alcohol is particularly preferable.

When the amount of the organic solvent added is small, the stability of the condensation composition (A) is low, and when it is large, the molecular weight of the obtained colloidal silica is low, which makes it difficult to form an antireflection coating. It is limited to 10 to 30 mol per 1 mol of tetraalkoxysilane represented by Si (OR) ₄ , and from the viewpoint of stability of the inorganic composition, 13 to 18 mol is preferable relative to 1 mol of tetraalkoxysilane.

The method for preparing the condensation composition (A) is not particularly limited, and for example, a tetraalkoxysilane represented by Si (OR) ₄ , a basic aqueous solution, and an organic solvent are supplied to a stirrer and mixed to prepare. There is a method. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

The temperature for preparing the condensation composition (A) is
When it becomes lower, the polycondensation reaction becomes insufficient, and when it becomes higher,
Since the stability of the condensation composition (A) is reduced, 10 to 30
It is preferably carried out at a temperature of 20 ° C., particularly preferably 20 to 25 ° C.

The time for preparing the condensation composition (A) is
When the length is short, the hydrolysis and polycondensation reactions are insufficient, and when the length is long, the stability of the condensation composition (A) is lowered.
1 to 10 hours are preferable, and 2 to 4 hours are particularly preferable.
Therefore, the condensation composition (A) is prepared at 10 to 30 ° C.
It is preferable to carry out for 1 to 10 hours, at 20 to 25 ° C. for 2 to
It is particularly preferable to carry out for 4 hours.

The condensation composition (B) used for producing the inorganic composition used in the present invention 1 has the general formula (R ² ) _n S
i (OR ¹ ) _4-n (wherein R ¹ and R ² are each a carbon number of 1 to
It is obtained by mixing an alkoxysilane represented by an alkyl group of 5 and n is an integer of 0 to 3, an acidic aqueous solution and an organic solvent, and partially hydrolyzing and polycondensing the alkoxysilane.

The above general formula (R ² ) _n Si (OR ¹ )
_{In the} alkoxysilane represented by _4-n , when R ¹ and R ² have a large number of carbon atoms, the stability of the inorganic composition decreases and the long-term stability deteriorates. And a methyl group, an ethyl group, n
-Propyl group, iso-propyl group, n-butyl group, s
Examples thereof include an ec-butyl group and a tert-butyl group. In addition, n shows the integer of 0-3.

The alkoxysilane represented by (R ² ) _n Si (OR ¹ ) _4-n is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane and tetra-n-.
Propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-propoxysilane, monomethyl. Tri-iso-propoxysilane, monomethyltri-n-butoxysilane, monomethyltri-sec-butoxysilane, monomethyltri-tert-butoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-.
Propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-
sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane, trimethylmono-n-butoxysilane , Trimethylmono-sec-butoxysilane, trimethylmono-tert-butoxysilane, triethylethoxysilane, and the like, and from the viewpoint of reactivity, tetramethoxysilane, tetraethoxysilane, and monomethyltriethoxysilane are preferable, and tetraethoxysilane is particularly preferable. Is preferred.

The above-mentioned acidic aqueous solution has a pH of 0 to 2.6 in which an acidic species is dissolved in water. The acidic species is not particularly limited as long as it can adjust the pH of the acidic aqueous solution to 0 to 2.6, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid and the like, hydrochloric acid and nitric acid are preferable, and hydrochloric acid is particularly preferable. .

When the pH of the acidic aqueous solution is low, the stability of the condensation composition (B) may be lowered, and when it is high, the hydrolysis of the alkoxysilane is insufficient.
It is limited to 0 to 2.6, preferably 1.0 to 1.7,
1.1 to 1.2 are particularly preferable.

If the amount of the acidic aqueous solution added is small, the hydrolysis of the alkoxysilane will be insufficient, and furthermore, it will be difficult to apply the resulting inorganic composition to the substrate, and if it is large, the amount of the condensation composition (B) will be increased. Since the stability decreases, (R
² ) _n Si (OR ¹ ) _4-n is limited to 3 to 8 mol, preferably 4 to 7 mol, per 1 mol of the alkoxysilane represented by _n .

The above organic solvent is (R ² ) _n Si (O
There is no particular limitation as long as it is compatible with the alkoxysilane represented by R ¹ ) _4-n and the acidic aqueous solution, and for example, the same one as used in the production of the condensation composition (A) can be used. When the addition amount of the organic solvent is small, the stability of the condensation composition (B) is lowered, and when the addition amount is large, the alkoxysilane is not sufficiently hydrolyzed, so (R ² )
_It is limited to 10 to 30 mol, preferably 13 to 18 mol, per 1 mol of the alkoxysilane represented by _n Si (OR ¹ ) _4-n .

The method for preparing the condensation composition (B) is not particularly limited, and for example, an alkoxysilane represented by (R ² ) _n Si (OR ¹ ) _4-n , an acidic aqueous solution and an organic solvent may be added to a stirrer. The method of supplying, mixing and preparing is mentioned. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

The temperature for preparing the condensation composition (B) is
When it becomes lower, the polycondensation reaction becomes insufficient, and when it becomes higher,
Since the stability of the condensation composition (B) decreases, it is 10 to 30.
It is preferably carried out at a temperature of 20 ° C., particularly preferably 20 to 25 ° C.

The time for producing the condensation composition (B) is
When the length is short, a sufficient molecular weight cannot be obtained, and when the length is long, the stability of the condensation composition (B) is lowered. Therefore, 1 to 10 hours are preferable, and 2 to 4 hours are particularly preferable. Therefore, the production of the condensation composition (B) is preferably carried out at 10 to 30 ° C. for 1 to 10 hours, particularly preferably at 20 to 25 ° C. for 2 to 4 hours.

In the production of the inorganic composition used in the present invention 1, the condensation composition (A) and the condensation composition (B) are mixed in a weight ratio A / B = 0.4 to 2.4.

When the amount of the condensation composition (A) is small, the porosity of the obtained coating film is low and the antireflection effect of the obtained laminate is low, and when it is large, the adhesion between the obtained coating film and the substrate is low. Therefore, the weight ratio of the condensation composition (A) and the condensation composition (B) is limited to 0.4 to 2.4, which improves the stability of the inorganic composition and the adhesion between the coating and the substrate. For,
1.5 to 2.3 is preferable.

If the temperature at which the condensation composition (A) and the condensation composition (B) are mixed is lowered, the polycondensation of the colloidal silica and silica sol becomes difficult, and the antireflection effect of the resulting coating is lowered, and the temperature is high. If so, the stability of the obtained inorganic composition decreases, so that it is preferably carried out at -10 to 30 ° C, particularly preferably -8 to 25 ° C.

When the time for mixing the condensation composition (A) and the condensation composition (B) is short, polycondensation of the colloidal silica and silica sol becomes insufficient, and the antireflection effect of the obtained coating is lowered, and Since the stability of the inorganic composition decreases as the time increases, 0.5 to 4 hours are preferable, and especially 2
~ 3 hours are preferred. Therefore, the mixing of the condensation composition (A) and the condensation composition (B) should be 0.5 to 4 at -10 to 30 ° C.
It is preferably carried out for an hour, particularly preferably at -8 to 25 ° C for a few hours.

The method of mixing the condensation composition (A) and the condensation composition (B) is not particularly limited. For example, the condensation composition (A) and the condensation composition (B) are supplied to a stirrer and mixed by stirring. And a method of manufacturing the same. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

The method for producing a laminated body of the present invention 1 comprises the steps of applying the inorganic composition obtained by the above method onto a substrate and curing the same, and applying the obtained inorganic composition to the cured film surface.
It is a method comprising a step of bringing into contact glow discharge plasma in which an inert gas is excited under a pressure of × 10 ^{-4 to} 100 Torr.

The above-mentioned substrate is not particularly limited as long as it can be coated with the inorganic composition, and examples thereof include silicate glass, alkali silicate glass, soda lime glass, potassium lime glass and lead lime glass. Inorganic substrates made of silicate glass such as barium glass and borosilicate glass, and organic substrates made of polycarbonate, acrylic resin, polyvinyl chloride, polystyrene, polyester, polyurethane and the like.

Of the inorganic substrates, silicate glass, alkali silicate glass and soda lime glass are preferred. In the organic base material, polycarbonate and acrylic resin are preferable. Further, the shape of the base material is not particularly limited.

The method of applying the inorganic composition is not particularly limited, and examples thereof include brush, spray coat, dip coat,
Examples of the coating method include spin coating, roll coating, and flow coating. In addition, when the humidity in the atmosphere is high, the coating film becomes cloudy, so the relative humidity in the atmosphere is 5
It is preferably performed at 0% or less.

When the inorganic composition is applied onto the substrate, the film thickness is not particularly limited, but the inorganic composition is applied so that a film having the following relationship with the wavelength at which the antireflection effect is desired is obtained. That is, the antireflection effect can be improved, which is preferable.

D = (1/4 + m / 2) × λ / n

D: film thickness of coating λ: wavelength at which antireflection effect is desired n: refractive index of coating m: 0 or natural number

When the inorganic composition is applied, it is preferable to dilute it with a solvent to adjust the viscosity of the inorganic composition, if necessary, because the efficiency of applying the inorganic composition onto the substrate is improved. is there.

In this case, the solvent used is not particularly limited as long as it is compatible with the inorganic composition,
For example, isopropyl alcohol, ethoxy ethanol, allyl alcohol and the like can be mentioned, and from the viewpoint of improving the porosity of the obtained coating, isopropyl alcohol and ethoxy ethanol are preferable.

The above-mentioned curing method is not particularly limited, and may be naturally dried and cured at room temperature, or may be dried by heating and cured. For example, when the inorganic composition is laminated on the surface of silicate glass as a base material by the above method and naturally dried at room temperature and then cured at a temperature of 60 to 300 ° C., the silica sol in the inorganic composition becomes A laminate having an antireflective coating, which is made porous by the difference in shrinkage between the cured silicon matrix and colloidal silica, is obtained. Further, for example, after laminating on the surface of a plastic product as a base material and naturally drying at room temperature, it is 60 to 150 ° C., preferably 80 to 100.
Curing at a temperature of 0.degree. C. gives a similarly porous laminate with an antireflective coating.

However, in the curing step only, unreacted alkyl groups and solvents remain in the porous coating film, and the residual amount tends to increase as the curing temperature becomes relatively low. A non-curable substrate does not have sufficient antireflection durability. Therefore, in the present invention, the residual alkyl group and the solvent are removed by bringing the discharge plasma, which will be described in detail below, into contact with the plasma, and the curing is further advanced.

Noble gases such as helium, argon, neon and xenon, and nitrogen gas are used alone or in combination as the inert gas used in the method for producing a laminate of the present invention 1.

In the method for producing a laminate of the present invention 1,
Oxygen atom-containing gas is used with the active gas as needed.
May be used. Examples of the oxygen atom-containing gas include
For example, oxygen, ozone, water vapor, nitric oxide, nitrogen dioxide.
Elemental, carbon monoxide, carbon dioxide, etc.
Used alone or in combination. Contains inert gas and oxygen atoms
By using mixed gas with gas, residual alkyl
The groups and solvents are removed more effectively. Also, containing oxygen atoms
Carbon tetrafluoride in a volume ratio of 50% or less with respect to the gas
(CF _Four), Carbon hexafluoride (C₂F₆), Propyl fluoride
Ren (C₃F₆) And other fluorocarbon gases are mixed and used.
This is preferable because fluorine improves the oxidizability.

The inert gas and the oxygen atom-containing gas added as necessary are excited by plasma. As the excitation means, for example, a method of plasma decomposition by applying a direct current, a method of plasma decomposition by applying a high frequency, a method of plasma decomposition by microwave discharge,
Examples include a method of decomposing plasma by electron cyclotron resonance and a method of decomposing by heating with a hot filament.

If the processing pressure during plasma processing becomes low, an expensive vacuum chamber or vacuum exhaust device is required. Further, when processing a large-area substrate, the processing container must be made larger or the vacuum exhaust device must be installed. It is necessary to have a high output, and if it becomes higher, thermal plasma will be generated until finally arc discharge occurs unless a special method as disclosed in the present invention 2 is used, so that the heat resistance is low. Since it is unsuitable for a substrate, it is limited to 1 × 10 ^{−4 to} 100 Torr. This pressure varies depending on the excitation means,
It is preferably 1 × 10 ^{-2 to} 100 Torr, which is simple in equipment and capable of applying a direct current or high frequency capable of generating glow discharge plasma even when the processing pressure is relatively high. In addition, when the oxygen atom-containing gas is used, the pressure of the mixed gas of the inert gas and the oxygen atom-containing gas is 1 × 10 ^{−4 to} 100.
The pressure is in the range of Torr.

The input power required for the glow discharge plasma treatment varies depending on the electrode area, shape, etc., but if it is too low,
If the plasma density becomes low and the processing time is long, and the plasma density becomes too high, the damage to the base material will increase, so in general,
10 to 200 W is preferable.

Next, the plasma processing method will be described with reference to the drawings. FIG. 3 is an explanatory view showing a part of an example of the plasma processing apparatus used in the present invention in cross section.
This apparatus comprises a power supply unit 1, a processing container 2, and a plasma processing unit 3 between a metal upper electrode 4 and a metal lower electrode 5 facing each other.
It consists of The power supply unit 1 can apply a frequency of 10 to 30 kHz. Plasma is generated by applying a high voltage to the electrodes.
It is preferable to apply a voltage so that the voltage is about 40 kV / cm.

The processing container 2 can be exhausted from the exhaust port 10 by an exhaust device (not shown) consisting of an oil rotary vacuum pump. The processing container 2 is made of glass, but may be made of metal as long as it is insulated from the electrodes. The plasma processing unit 3 by glow discharge plasma is a space between a parallel plate type metal upper electrode 4 and a metal lower electrode 5 facing each other. The electrode arrangement structure may be a coaxial cylinder type, a cylinder facing flat plate type, a sphere facing flat plate type, a hyperboloid pair flat plate type, or a plurality of thin wires, other than the parallel plate type.
When the electrode arrangement structure is a parallel plate type, a coaxial cylinder type, or a face-to-face parallel type, a direct current or a high frequency is applied in a capacitive coupling type. Further, in the case of applying a high frequency, it is possible to apply in an induction type by using an external electrode.

In the apparatus of FIG. 3, the inert gas may be supplied from the upper electrode 4 having a porous structure via the gas introduction pipe 7, or from the gas introduction pipe 8 provided on the side surface of the processing container 2, It is supplied to the plasma processing unit 3.

When an oxygen atom-containing gas is used as necessary, the oxygen atom-containing gas is passed through the gas introduction pipe 7 from the upper electrode 4 having a porous structure, and the inert gas is passed through the gas introduction pipe 8. , And are supplied to the plasma processing unit 3, respectively. In FIG. 3, the upper electrode 4 is a porous electrode having a gas passage inside. In this way, when the upper electrode 4 also serves as a gas inlet and an electrode and has a porous structure, the oxygen atom-containing gas is treated with the plasma treatment unit 3.
It is preferable to uniformly supply the oxygen atom-containing gas to the plasma processing unit 3 by, for example, supplying the gas in a stirring state or blowing the gas at a high speed. If possible, the porous structure may not be used.

When the oxygen atom-containing gas is used, the inert gas may be mixed with the oxygen atom-containing gas and introduced from the upper electrode 4. In addition, it is preferable that the oxygen atom-containing gas is introduced through the gas introduction pipe 7 from the upper electrode 4 having a porous structure that also serves as an electrode and the gas and the inert gas is introduced from the gas introduction pipe 8. It should be noted that, as shown in FIG. 3, the tip of the gas introducing pipe 8 inside the processing container 2 has a ring shape with a large number of holes, and gas is supplied into the processing container 2 through the holes. It is preferable because the inert gas and the oxygen atom-containing gas are easily mixed uniformly.

Although not shown, the inert gas and the oxygen atom-containing gas are preferably supplied with their flow rates controlled by a mass flow controller.

The distance between the upper electrode 4 and the lower electrode 5 facing each other is appropriately determined depending on the treatment pressure, the thickness of the substrate to be treated, etc., but if it is too long, the plasma density will decrease and high power will be required. It is preferable to make the base material as short as possible within the range where it can be mounted between the electrodes.

The base material 6 coated with the inorganic composition and cured is
It is mounted on the electrode or in the space between both electrodes. Figure 3
In the above, it is mounted on the lower electrode 5.

Excessive inert gas and oxygen atom-containing gas are discharged from the gas outlet 9 of the processing container 2. Also,
When introducing the inert gas or the oxygen atom-containing gas into the processing container 2, it is preferable that the air remaining in the processing container 2 be exhausted from the exhaust port 10.

In order to actually perform plasma treatment with this apparatus, the base material 6 coated with the inorganic composition and cured is used as the lower electrode 5.
After the cured film surface is mounted on the upper side, the inside of the processing container 2 is evacuated from the exhaust port 10 to 1 × 10 ⁻³ Torr or less. Next, while adjusting the flow rate of the inert gas with the mass flow controller, the gas pressure is introduced from the gas introduction pipe 8 into the plasma processing unit 3 at a gas pressure of 1 × 10 ^{−4 to} 100 To.
Adjust to be rr. Then, when the gas pressure in the processing container 2 becomes stable, glow discharge plasma of an inert gas generated by applying a high voltage to the upper electrode 4 is brought into contact with the film surface of the base material 6 on which the inorganic composition is applied and cured. Plasma treatment is carried out.

When the oxygen atom-containing gas is used together with the inert gas, the base material 6 on which the inorganic composition is applied and cured is attached to the lower electrode 5 with the cured film surface facing upward, and then treated. The inside of the container 2 is evacuated to 1 × 10 ⁻³ Torr or less through the exhaust port 10. Next, while adjusting the flow rate of the oxygen atom-containing gas with the mass flow controller, the gas is introduced through the gas introduction pipe 7 from the porous upper electrode 4 into the plasma processing section 3, and at the same time the flow rate of the inert gas is adjusted with the mass flow controller. The gas pressure is 1 × 10 ^{−4 to} 100 To when introduced into the plasma processing unit 3 from the gas introduction pipe 8.
Adjust to be rr. Next, when the gas pressure in the processing container 2 becomes stable, the inorganic composition is applied and cured by glow discharge plasma of a mixed gas consisting of an inert gas and an oxygen atom-containing gas generated by applying a high voltage to the upper electrode 4. Plasma treatment is performed by bringing the film surface of the base material 6 into contact.

The curing treatment with plasma in the present invention 1 does not require heating or cooling of the substrate, and is sufficient at room temperature. Also, the plasma processing time is
Although the inorganic composition varies depending on the thickness and applied power of the coating film applied, it is necessary to lengthen the treatment time as the thickness of the coating becomes thicker, and if the applied power is high, the plasma treatment time tends to be short. Generally, when the treatment time becomes short, the scratch resistance and durability of the coating cannot be sufficiently obtained, and conversely, when the treatment time is too long, there is a limit to the improvement of the scratch resistance and durability of the coating. 10 seconds to 10 minutes is preferable.

The invention according to claim 2 (hereinafter referred to as "present invention 2")
The method for producing a laminate according to claim 1) comprises a step of applying the inorganic composition according to claim 1 on a substrate and curing the substrate, and a substrate on which the obtained inorganic composition is applied and cured, at least one of the facing surfaces. Placed between opposing metal electrodes on which a solid dielectric is disposed, a high voltage is applied between the metal electrodes under a pressure near the atmospheric pressure of an inert gas, and the discharge plasma of the generated gas is converted into the inorganic composition. It is a method comprising a step of bringing an object into contact with a cured film surface.

In the method for producing a laminate of the present invention 2, the same steps as those of the present invention 1 are performed up to the step of applying the inorganic composition according to claim 1 on a substrate and curing the same. The type of substrate used, the method of applying the inorganic composition, the film thickness when applying the inorganic composition onto the substrate, and the curing method are also the same as those of the first embodiment. However, as in the case of the first aspect of the present invention, unreacted alkyl groups and solvents remain in the porous coating film only when the step of applying the inorganic composition on the substrate and curing is performed, and the curing temperature is relatively low. The residual amount tends to increase, and the durability of the antireflection effect is not sufficient for a substrate such as plastic that cannot be cured at high temperature. Therefore, in the present invention 2, the residual alkyl groups and the solvent are removed by bringing the discharge plasma, which will be described in detail below, into contact with the plasma, and the curing is further advanced.

As the inert gas used in the method for producing a laminate of the present invention 2, rare gases such as helium, argon, neon, xenon and nitrogen gas are used alone or in combination, but are metastable. Helium is more preferable because discharge plasma is easily generated because it has a long life in the state. When a gas other than helium is used as the inert gas, it is preferable to mix a vapor gas such as acetone and methanol and a hydrocarbon gas such as methane and ethane at a ratio of 2% by volume or less.

In the method for producing a laminated body of the present invention 2,
Oxygen atom-containing gas is used with the active gas as needed.
May be used. Examples of the oxygen atom-containing gas include
For example, oxygen, ozone, water vapor, nitric oxide, nitrogen dioxide.
Elemental, carbon monoxide, carbon dioxide, etc.
Used alone or in combination. Contains inert gas and oxygen atoms
By using mixed gas with gas, residual alkyl
The groups and solvents are removed more effectively. Also, containing oxygen atoms
Carbon tetrafluoride in a volume ratio of 50% or less with respect to the gas
(CF _Four), Carbon hexafluoride (C₂F₆), Propyl fluoride
Ren (C₃F₆) And other fluorocarbon gases are mixed and used.
This is preferable because fluorine improves the oxidizability.

In the above mixed gas of the inert gas and the oxygen atom-containing gas, the proportion of the oxygen atom-containing gas varies depending on the kind of the gas, but when the proportion of the oxygen atom-containing gas increases, the arc discharge is caused by the application of a high voltage. 10% by volume or less is preferable, and more preferably,
It is 0.1 to 5% by volume.

The pressure of the inert gas used in the present invention 2 is near atmospheric pressure. Specifically, 100 to 800
Since it is set to Torr, the pressure adjustment is easy and the apparatus is simple, the range of 700 to 780 Torr is preferable. In addition,
When the oxygen atom-containing gas is used, the pressure of the mixed gas of the inert gas and the oxygen atom-containing gas is set to near atmospheric pressure.

At the time of plasma treatment, it is not necessary to heat or cool the substrate, and room temperature is sufficient. Although the treatment time varies depending on the gas composition and the applied electric power, a laminate having a small change in the refractive index with time can be obtained in about 5 seconds. When a mixed gas of an oxygen atom-containing gas and a fluorocarbon gas is used, if the treatment time is set to 1 minute or more, the porous inorganic film is easily etched.

The plasma treatment step of the method for producing a laminate of the second invention will be described below. FIG. 4 is an explanatory view showing a part of an example of the plasma processing apparatus used in the present invention 2 in section. This apparatus includes a power supply unit 1, a processing container 2,
It is composed of an upper electrode 4 and a lower electrode 5. Power supply 1
Although a frequency in the kHz range can be applied, the treatment of a base material having low heat resistance has a small influence on the base material 10 to 35.
A frequency of kHz is preferred. The discharge plasma is formed by applying a high voltage, but when the applied voltage becomes low, the plasma density and the self-bias become small, so that it takes a long processing time. It is preferable to apply a voltage so that the voltage is about 50 kV / cm.

Although the processing container 2 is made of glass, it may be made of plastic such as acrylic resin or polycarbonate, and may be made of metal such as stainless steel or aluminum as long as it is insulated from the electrodes.

A pair of opposed parallel plate type upper and lower electrodes 4 and 5 are arranged in the processing container 2. The electrode arrangement structure may be a coaxial cylinder type, a cylinder facing flat plate type, a sphere facing flat plate type, a dual-phase pair flat plate type, or a plurality of fine wires, in addition to the parallel plate type. The material of the electrode is not particularly limited as long as it is a metal, and may be, for example, a multi-component metal such as stainless steel or brass, or a pure metal such as copper or aluminum.

In the second aspect of the invention, the solid dielectric 11 is provided on at least one of the facing surfaces of the upper electrode 4 and the lower electrode 5. In the device of FIG. 4, the solid dielectric 11 is arranged on the lower electrode 5. The solid dielectric 11 needs to be disposed on the entire surface of the facing surface of the opposing electrodes. Even if a part of the facing surface is exposed, arc discharge occurs during plasma processing.

As the solid dielectric 11, for example, plastics such as polyfluoroethylene (PTFE) and polyethylene terephthalate (PET); glass and ceramics such as silica, Pyrex glass, alumina, titanium oxide, etc. are used, and even in sheet form. It may be a film. However, when the thickness is thin, dielectric breakdown occurs when a high voltage is applied and arc discharge easily occurs, and when the thickness is thick, it is difficult to discharge, so a thickness of 0.05 to 4 mm is preferable.

In the apparatus of FIG. 4, the inert gas may be supplied from the upper electrode 4 having a porous structure via the gas introduction pipe 7, or from the gas introduction pipe 8 provided on the side surface of the processing container 2, It is supplied to the plasma processing unit 3.

When an oxygen atom-containing gas is used as necessary, the oxygen atom-containing gas is passed through the gas introduction pipe 7 from the upper electrode 4 having a porous structure, and the inert gas is passed through the gas introduction pipe 8. , And are supplied to the plasma processing unit 3, respectively. In FIG. 4, the upper electrode 4 is a porous electrode having a gas passage inside. In this way, when the upper electrode 4 also serves as a gas inlet and an electrode and has a porous structure, the oxygen atom-containing gas is treated with the plasma treatment unit 3.
It is preferable to uniformly supply the oxygen atom-containing gas to the plasma processing unit 3 by, for example, supplying the gas in a stirring state or blowing the gas at a high speed. If possible, the porous structure may not be used.

When an oxygen atom-containing gas is used, the inert gas may be mixed with the oxygen atom-containing gas and introduced from the upper electrode 4. In addition, it is preferable that the oxygen atom-containing gas is introduced through the gas introduction pipe 7 from the upper electrode 4 having a porous structure that also serves as an electrode and the gas and the inert gas is introduced from the gas introduction pipe 8. It should be noted that, as shown in FIG. 4, the distal end portion of the gas introduction pipe 8 inside the processing container 2 has a ring shape with a large number of holes, and gas is supplied into the processing container 2 through the holes. It is preferable because the inert gas and the oxygen atom-containing gas are easily mixed uniformly.

Although not shown, the inert gas and the oxygen atom-containing gas are preferably supplied with their flow rates controlled by a mass flow controller.

In order to plasma-treat the substrate 6 on which the inorganic composition has been applied and cured by using the plasma treatment apparatus of FIG. 4, the above-mentioned substrate 6 is placed on the solid dielectric 11 and is made inert. Gas or a mixed gas of an inert gas and an oxygen atom-containing gas, if necessary, is brought to a pressure near atmospheric pressure, a voltage is applied between the metal electrodes to generate discharge plasma, and the plasma is converted to the above-mentioned base. Contact the material 6. In this way, the residual alkyl group and the solvent are removed and the curing proceeds.

In this example, the base material 6 is processed only on one side (upper surface in FIG. 1) on which the base material 6 is arranged. It is necessary to float between the upper electrode 4 and the lower electrode 5.

The distance between the upper electrode 4 and the lower electrode 5 is appropriately determined by the flow rate of the gas supplied, the magnitude of the applied voltage, the material and thickness of the solid dielectric material, the thickness of the base material, and the like. However, when the distance is small, the amount of unused gas is large, which is inefficient, and when the distance is large, the uniformity of the gas in the electrode space is likely to be impaired, so 1 to 20 mm is preferable.

Excessive inert gas and oxygen atom-containing gas are discharged from the gas outlet 9 of the processing container 2. Also,
When introducing the inert gas or the oxygen atom-containing gas into the processing container 2, it is preferable that the air remaining in the processing container 2 be exhausted from the exhaust port 10.

The invention according to claim 3 (hereinafter referred to as "present invention 3")
The method for producing a laminate according to claim 1) comprises a step of coating the inorganic composition according to claim 1 on a substrate and curing the same, and bringing the obtained inorganic composition into contact with corona discharge plasma. It is a method consisting of steps.

In the method for producing a laminated body of the present invention 3, the same steps as those of the present invention 1 are performed up to the step of coating the inorganic composition according to claim 1 on a substrate and curing it. The type of substrate used, the method of applying the inorganic composition, the film thickness when applying the inorganic composition onto the substrate, and the curing method are also the same as those of the first embodiment. However, as in the case of the first aspect of the present invention, unreacted alkyl groups and solvents remain in the porous coating film only when the step of applying the inorganic composition on the substrate and curing is performed, and the curing temperature is relatively low. The residual amount tends to increase, and the durability of the antireflection effect is not sufficient for a substrate such as plastic that cannot be cured at high temperature. Therefore, in the present invention 3, the residual alkyl groups and the solvent are removed by contacting with discharge plasma, which will be described in detail below, and curing is further advanced.

Air, argon and a mixed gas of these are used as the exciting gas used in the method for producing a laminate of the present invention 3, but air is preferable from the viewpoint of easy handling. When argon is used as the excitation gas, it is necessary to mix a vapor gas such as acetone and methanol and a hydrocarbon gas such as methane and ethane at a ratio of 2% by volume or less.

The corona discharge treatment device generally comprises a high frequency oscillator, electrodes, and a treatment table. The high frequency oscillator can apply frequencies on the order of kHz. The frequency of the high voltage applied to the electrodes is not particularly limited, but a frequency of 5 to 120 kHz is preferable. The discharge plasma is formed by applying a high voltage, but when the applied voltage becomes low, the plasma density becomes small, so that it takes time to perform the treatment, and when it becomes high, a behavior of transitioning to arc discharge is exhibited. Therefore, 20-60 kV is preferable.

The electrodes are for converting the output of the high frequency power supply into a discharge phenomenon. The material used for the electrode is not particularly limited, but, for example, stainless steel, aluminum, quartz or the like is selected according to the treated substrate.

In order to uniformly and stably perform the discharge phenomenon by the electrodes, the processing table is placed at a certain distance from the electrodes, and some of them are coated with a dielectric depending on the type of electrode and some of which are metallic. . Examples of the material of the dielectric include ceramics and silicon rubber, and the metal includes
Examples include iron, aluminum, stainless steel, and the like.

The distance between the processing table and the electrode is appropriately determined depending on the magnitude of the applied voltage and the thickness of the base material. However, if the distance is short, the processing operation becomes inconvenient, and if the distance is long, the arc discharge easily occurs. -20 mm is preferable.

The invention according to claim 4 (hereinafter referred to as "present invention 4")
The method for producing a protective material for a pen input panel according to claim 1) comprises a step of applying the inorganic composition according to claim 1 onto a transparent substrate and curing the same, and a step of applying the obtained inorganic composition to the substrate. , Is disposed between opposing metal electrodes having a solid dielectric disposed on at least one opposing surface, and a high voltage is applied between the metal electrodes under a pressure near the atmospheric pressure of an inert gas to generate a gas It is a method comprising the step of bringing discharge plasma into contact with the film surface on which the inorganic composition has been cured.

The transparent base material used in the method for producing the protective material for a pen input panel of the present invention 4 is not particularly limited as long as it is a transparent base material, and an inorganic base material or an organic base material can be used. Examples of the base material include a glass plate,
Examples of the organic base material include plastic films such as polyethylene terephthalate and plastic plates such as acrylic resin.

In the method for producing a protective material for a pen input panel of the present invention 4, when the inorganic composition is applied by a dip coating method, one side of the base material is masked so that both sides of the base material are not applied. Good to keep.

In the method for producing the protective material for a pen input panel of the present invention 4, the method of curing the applied inorganic composition is not particularly limited, and it may be naturally dried at room temperature to be cured. Alternatively, it may be dried by heating and cured. The method of plasma treatment is the same as the method of the second aspect of the invention. Further, as in the method of the second aspect of the present invention, as the gas used for the plasma treatment, an oxygen-containing gas may be used in combination with an inert gas, if necessary.

As a method for producing a protective material for a pen input panel, a step of applying the inorganic composition according to claim 1 on a transparent substrate and curing it, and a film obtained by curing the obtained inorganic composition. A method comprising contacting the surface with glow discharge plasma in which an inert gas or a mixed gas of an inert gas and an oxygen atom-containing gas is excited if necessary under a pressure of 1 × 10 ^{−4 to} 100 Torr is there.

The transparent base material used in the method for producing the above-mentioned protective material for pen input panel is not particularly limited as long as it is a transparent base material, and an inorganic base material or an organic base material can be used. Examples thereof include a glass plate, and examples of the organic substrate include a plastic film such as polyethylene terephthalate and a plastic plate such as an acrylic resin.

In the above-mentioned method for producing a protective material for a pen input panel, when the inorganic composition is applied by a dip coating method, one surface of the base material is masked so that both surfaces of the base material are not applied. Is good.

In the above-mentioned method for producing a protective material for a pen input panel, the method for curing the applied inorganic composition is not particularly limited, and may be naturally dried at room temperature for curing. You may heat-dry and harden. The method of plasma treatment is the same as the method of the first invention.

Further, as a method for producing a protective material for a pen input panel, a step of applying the inorganic composition according to claim 1 on a transparent substrate and curing it, and curing the obtained inorganic composition. There is also a method including a step of bringing corona discharge plasma into contact with the film surface.

The transparent base material used in the method for producing the above-mentioned protective material for pen input panel is not particularly limited as long as it is a transparent base material, and an inorganic base material or an organic base material can be used. Examples thereof include a glass plate, and examples of the organic substrate include a plastic film such as polyethylene terephthalate and a plastic plate such as an acrylic resin.

In the above-mentioned method for producing a protective material for a pen input panel, when the inorganic composition is applied by the dip coating method, one side of the base material is masked so that both sides of the base material are not applied. Is good.

In the above-mentioned method for producing a protective material for a pen input panel, the method of curing the applied inorganic composition is not particularly limited, and it may be naturally dried at room temperature to be cured. You may heat-dry and harden. Further, the method of corona discharge plasma treatment is the same as in the present invention 3
It is similar to the method of.

[0111]

In the method for producing a laminate of the present invention 1, in the condensation composition (A), polycondensation of tetraalkoxysilane is considerably advanced and colloidal silica is formed, and in the condensation composition (B), the alkoxysilane of Polycondensation does not progress relatively and is suppressed at the stage of silica sol, and the inorganic composition which is a mixture of the two is a mixture of colloidal silica and silica sol. After coating the inorganic composition on a substrate and curing it, the residual alkyl group and the solvent are removed by bringing the inorganic composition into contact with glow discharge plasma in which an inert gas is excited under a pressure of 1 × 10 ^{−4 to} 100 Torr, Further curing makes it possible to obtain a porous film due to the difference in shrinkage between silica sol and colloidal silica.

In the method for producing a laminate of the present invention 2, in the condensation composition (A), polycondensation of the tetraalkoxysilane is considerably advanced to form colloidal silica, and in the condensation composition (B), the alkoxysilane of the alkoxysilane is formed. Polycondensation does not progress relatively and is suppressed at the stage of silica sol, and the inorganic composition which is a mixture of the two is a mixture of colloidal silica and silica sol. The inorganic composition is applied on a substrate, cured, and then contacted with a discharge plasma in the vicinity of atmospheric pressure to remove residual alkyl groups and solvents, and further cured to cause polycondensation reaction of silica sol and colloidal silica. By advancing the above, a porous coating film can be obtained due to the difference in shrinkage ratio between silica sol and colloidal silica.

In the method for producing a laminate of the present invention 3, in the condensation composition (A), polycondensation of the tetraalkoxysilane is considerably advanced to form colloidal silica, and in the condensation composition (B), the alkoxysilane of the alkoxysilane is formed. Polycondensation does not progress relatively and is suppressed at the stage of silica sol, and the inorganic composition which is a mixture of the two is a mixture of colloidal silica and silica sol. The inorganic composition is applied on a substrate, cured, and then contacted with corona discharge plasma to remove residual alkyl groups and solvents, and further cured to give a porous structure due to the difference in shrinkage between silica sol and colloidal silica. A cured coating can be obtained.

The protective material for a pen input panel obtained by the manufacturing method of the present invention 4 is less likely to be scratched even when the surface coating is rubbed by a hard material such as steel wool, and is unlikely to cause deterioration in appearance due to scratches. In addition, since the surface has fine irregularities, it has a friction coefficient suitable for an input pen such as acetal resin, so that it has a feeling of writing like writing on a paper with a pencil. Further, since the coating film is porous and has a low refractive index, reflection of external light rays can be prevented.

[0115]

Embodiments of the present invention will be described below. In addition, the evaluation method of each physical property regarding the laminated body shown in the result was as follows.

(1) Reflectance Using a spectrophotometer (manufactured by Shimadzu Corp., specular reflection measuring device “incident angle 5 °”), the light transmittance of the laminate having the antireflection coating laminated is in the range of 300 to 800 nm. Then, the minimum reflectance Rmin is calculated, and the one-sided minimum reflectance (R) is measured by the following equation. R = Rmin / 2

(2) Pencil Hardness The antireflection coating of the obtained laminate was conformed to JIS K540
It was measured according to 0 and evaluated.

(3) Scratch resistance test The surface of the antireflection coating of the obtained laminate was coated with a flannel cloth.
A load of 1000 g / cm ² was applied, and the sample was rubbed 100 times back and forth to visually inspect the surface for scratches. (Judgment Criteria) O: No scratch was confirmed. X: Scratches could be confirmed, or the film was peeled off.

(4) Aging Change The obtained laminate was left in a thermo-hygrostat set at 60 ° C. and a relative humidity of 95% for 1 week, and the reflectance and pencil hardness were measured and a scratch resistance test was conducted. The change over time was observed.

The evaluation method of each physical property of the protective material for pen input panel was as follows. That is, in addition to the above-described measurement of reflectance and pencil hardness, the following surface shape measurement was performed. Further, after being left for 1 week in a thermo-hygrostat set at 60 ° C. and a relative humidity of 95%, the reflectance and pencil hardness were measured and the surface shape was measured to observe the change with time. (5) Surface shape measurement The surface of the obtained coating film of the protective material for a pen input panel was measured with a surface shape measuring instrument (manufactured by Nippon Vacuum Technology Co., Ltd., trade name "DEKTA").
C-303 "). The surface unevenness is represented by the uneven width a and the uneven height b shown in FIG.

(Examples 1 to 6 and Comparative Examples 1 to 13) A predetermined amount of tetraethoxysilane, a basic aqueous solution whose pH was adjusted with ammonia, and isopropyl alcohol shown in Tables 1 and 2 were applied to a magnetic stirrer. Supplying and mixing at 800 rpm for 2 hours at 20 ° C., a condensation composition (A) was obtained.

A predetermined amount of tetraethoxysilane, dimethyldiethoxysilane, an acidic aqueous solution whose pH was adjusted by hydrochloric acid, and isopropyl alcohol shown in Tables 1 and 2 were supplied to a magnetic stirrer at 800 rp.
m and mixed at 20 ° C. for 2 hours to obtain a condensation composition (B).

The obtained condensation composition (A) and condensation composition (B) were magnetic stirrer at a weight ratio (condensation composition (A) / condensation composition (B)) shown in Tables 1 and 2. And mixed at 20 ° C. for 2 hours at 800 rpm to obtain an inorganic composition.

Manufacture of Laminated Body: To the prepared inorganic composition,
Substrates shown in Table 1 and Table 2 [Slide glass (NAKA
RAI, S-2111, 76mm x 26mm x 1m
m) or a polycarbonate plate (manufactured by Teijin Ltd., trade name “Teijin Panlite”, 100 mm × 40 mm × 1 m)
m)] was dipped and pulled up at a speed of 100 to 300 mm / min, and then dried and cured at room temperature for 10 minutes to obtain a base material in which the inorganic composition was applied to both surfaces of the base material.

In Table 2, S1 in the tetraalkoxysilane and alkoxysilane columns represents tetraethoxysilane, IPA in the IPA column represents isopropyl alcohol, P in the base material column represents a polycarbonate plate,
G represents a slide glass.

Next, the film surface coated and cured with the above-mentioned inorganic composition was subjected to a plasma treatment under the conditions shown in Table 3 by using a high frequency sputtering device (manufactured by Nippon Vacuum Technology Co., Ltd., model SH-100). Got Using the obtained laminate, each physical property was evaluated based on the above measurement method, and the results are shown in Table 3.
It was shown to.

In Comparative Example 2, the amount of the acidic aqueous solution added at the time of preparing the condensation composition (B) was too small. In Comparative Example 6, the condensation composition (A) and the condensation composition (B) were mixed. The coating was not possible because the mixing ratio was too large. Further, Comparative Example 4 shows the pH of the basic aqueous solution at the time of preparing the condensation composition (A).
Is too high, and Comparative Example 8 is a condensation composition (A)
Since the amount of the organic solvent at the time of preparation was too small, the condensation composition (A) was gelated and the inorganic composition could not be produced.

Comparative Example 9 is the same as Example 1 except that the plasma treatment is not performed. In addition, Comparative Example 10
No coating was possible because the inorganic composition became cloudy. In Comparative Example 11, the inorganic composition became unstable, the coating film became non-uniform, and it became cloudy. In Comparative Examples 12 and 13, since the amount of the organic solvent was too large, the hydrolysis and polycondensation reaction rates were extremely slow, and the reaction was insufficient, so that the base material could not be coated.

(Comparative Example 14) A slide glass (manufactured by Asahi Glass Co., Ltd., trade name "CYTOP CTL-102A"), S-211 manufactured by NAKARAI Co., Ltd.
1, 76 mm x 26 mm x 1 mm), and
After pulling up at a speed of 300 mm / min, it was dried at 80 ° C. to obtain a laminate coated on both sides of the base material. Using the obtained laminate, based on the measurement method, to evaluate each physical property,
The results are shown in Table 3.

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

[Table 3]

(Examples 7 to 12, Comparative Examples 15 to 18) Predetermined amounts of tetraethoxysilane, basic aqueous solution whose pH was adjusted by ammonia, and isopropyl alcohol shown in Table 4 were supplied to a magnetic stirrer at 800 rpm. The mixture was mixed for 2 hours at 20 ° C. to obtain a condensation composition (A).

The pH was adjusted with tetraethoxysilane, methyltriethoxysilane and hydrochloric acid in the respective prescribed amounts shown in Table 4.
Adjusted acidic aqueous solution, isopropyl alcohol,
The condensation composition (B) was obtained by supplying to a magnetic stirrer and mixing at 800 rpm for 2 hours at 20 ° C.

The condensation composition (A) and the condensation composition (B) thus obtained were supplied to a magnetic stirrer in a weight ratio (condensation composition (A) / condensation composition (B)) shown in Table 4.
The mixture was mixed at 800 rpm for 2 hours at 20 ° C. to obtain an inorganic composition.

Manufacture of Laminated Body: To the prepared inorganic composition,
Immerse the base material shown in Table 4 [Slide glass (NAKARAI, S-2111, 76 mm x 26 mm x 1 mm) or polycarbonate plate (Teijin, trade name "Taijin Panlite", 100 mm x 40 mm x 1 mm)] Then, after pulling up at a speed of 100 to 300 mm / min,
It was dried and cured at room temperature for 10 minutes to obtain a base material having both surfaces of the base material coated with the inorganic composition.

Next, the device shown in FIG. 4 (metal electrode 80 m
mφ), in the electrode space having the distance between the electrodes shown in Table 5, as the solid dielectric body 11, 120 × 12 with a thickness of 1 mm
The base material on which the above-mentioned inorganic composition film was formed was placed on the lower electrode on which a 0 mm square polytetrafluoroethylene was mounted, and the oil was evacuated by an oil rotary pump to 1 Torr.

Next, the oxygen atom-containing gas shown in Table 5 was introduced into the container from the upper electrode 4 having a porous structure at a predetermined gas flow rate and the inert gas from the gas introduction pipe 8 to the atmospheric pressure. After that, a voltage was applied to the electrodes at the frequencies shown in Table 5 and left for 10 seconds. The emission of discharge plasma was observed with the application of high voltage. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement method, and the results are shown in Table 5.

[0139]

[Table 4]

[0140]

[Table 5]

(Examples 13 to 18, Comparative Examples 19 to 22)
A predetermined amount of tetraethoxysilane, a basic aqueous solution of which pH was adjusted with ammonia, and isopropyl alcohol shown in Table 6 were supplied to a magnetic stirrer and mixed at 800 rpm for 2 hours at 20 ° C. to form a condensation composition (A). Got

The pH was adjusted with tetraethoxysilane, dimethyldiethoxysilane and hydrochloric acid in the respective prescribed amounts shown in Table 6.
Adjusted acidic aqueous solution, isopropyl alcohol,
The condensation composition (B) was obtained by supplying to a magnetic stirrer and mixing at 800 rpm for 2 hours at 20 ° C.

The condensation composition (A) and the condensation composition (B) thus obtained were supplied to a magnetic stirrer in a weight ratio (condensation composition (A) / condensation composition (B)) shown in Table 6.
The mixture was mixed at 800 rpm for 2 hours at 20 ° C. to obtain an inorganic composition.

Manufacture of Laminated Body: To the prepared inorganic composition,
Dip the substrate shown in Table 6 [Slide glass (NAKARAI, S-2111, 76 mm x 26 mm x 1 mm) or polycarbonate plate (Teijin Corp., trade name "Teijin Panlite", 100 mm x 40 mm x 1 mm)] Then, after pulling up at a speed of 100 to 300 mm / min,
It was dried and cured at room temperature for 10 minutes to obtain a base material having both surfaces of the base material coated with the inorganic composition.

Next, a corona discharge treatment device (Model HF, manufactured by Kasuga Denki Co., Ltd.) was applied to the film surface coated with the above-mentioned inorganic composition and cured.
Using SS-103), plasma treatment was performed under the conditions shown in Table 7 to obtain a laminate. Using the obtained laminate, each physical property was evaluated based on the above measurement method, and the results are shown in Table 7.

[0146]

[Table 6]

[0147]

[Table 7]

(Examples 19 to 24, Comparative examples 23 to 27)
A predetermined amount of tetraethoxysilane, a basic aqueous solution whose pH was adjusted with ammonia, and isopropyl alcohol shown in Tables 8 and 9 were supplied to a magnetic stirrer and mixed at 800 rpm for 2 hours at 20 ° C. to form a condensation composition. (A) was obtained.

A predetermined amount of tetraethoxysilane, methyltriethoxysilane, an acidic aqueous solution whose pH was adjusted by hydrochloric acid, and isopropyl alcohol shown in Tables 8 and 9 were supplied to a magnetic stirrer at 800 rp.
m and mixed at 20 ° C. for 2 hours to obtain a condensation composition (B).

The obtained condensation composition (A) and condensation composition (B) were magnetic stirrer at the weight ratios (condensation composition (A) / condensation composition (B)) shown in Tables 8 and 9. And mixed at 20 ° C. for 2 hours at 800 rpm to obtain an inorganic composition.

A polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name “Luminar”, 100 mm × 40 mm × 0.25 mm) was dipped in the above inorganic composition, pulled up at a speed of 100 mm / min, and then at room temperature for 10 minutes.
After being dried and cured for a minute, a protective material for pen input panel was obtained.

Next, the device shown in FIG. 4 (metal electrode 80 m
mφ), 120 × 120 with a thickness of 2 mm as the solid dielectric 11 in the electrode space having the distance between electrodes shown in Table 10.
A polyethylene terephthalate film having the above-mentioned inorganic composition coating formed thereon was placed on a lower electrode equipped with a square quartz glass of mm, and the oil was evacuated by an oil rotary pump to 1 Torr.

Next, the oxygen atom-containing gas shown in Table 10 was introduced into the container at a predetermined gas flow rate from the upper electrode 4 having a porous structure, and the inert gas was introduced into the container from the gas introduction pipe 8 to bring the pressure to the atmospheric pressure. After that, a voltage was applied to the electrodes at the frequencies shown in Table 10 and left for 10 seconds. The emission of discharge plasma was observed with the application of high voltage. Using the obtained protective material for pen input panel, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 11.

Comparative Example 27 is the same as Example 19 except that the plasma treatment is not performed and the base material is a polyethylene terephthalate film.

(Comparative Example 28) A polyethylene terephthalate film (manufactured by Toray Industries, Inc., manufactured by Asahi Glass Co., Ltd., trade name "CYTOP CTL-102A") coating liquid was used.
Product name "LUMINAR", 100mm x 40mm x 0.25
mm) was dipped, pulled up at a rate of 100 to 300 mm / min, and then dried at 80 ° C. to obtain a pen input panel protective material applied to both surfaces of the base material. Using the obtained protective material for pen input panel, each physical property was evaluated based on the above-mentioned measuring methods, and the results are shown in Table 11.

(Comparative Example 29) Polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "LUMINAR", 100 m
m x 40 mm x 0.25 mm), using a vacuum deposition method (vacuum degree, 1.3 x 10 ^-4 Torr), a SiO ₂ thin film was laminated to a thickness of 1 μm to obtain a protective material for a pen input panel. It was Using the obtained protective material for pen input panel, each physical property was evaluated based on the above-mentioned measuring methods, and the results are shown in Table 11.

[0157]

[Table 8]

[0158]

[Table 9]

[0159]

[Table 10]

[0160]

[Table 11]

[0161]

The constitution of the method for producing a laminate of the present invention 1 is as described above, and a simple mixing device such as a magnetic stirrer is used for preparing the condensation compositions (A) and (B). A simple stirrer such as a magnetic stirrer is sufficient as a mixing device because it is easy to uniformly disperse the colloidal silica in the alkoxysilane in the production of the inorganic composition. And does not require high performance equipment. Therefore, this inorganic composition is easy to manufacture, and the obtained inorganic composition is applied onto a substrate and, after curing, 1 × 10 ^{−4 to} 100 To.
When contacted with glow discharge plasma in which an inert gas is excited under a pressure of rr, a porous coating film excellent in scratch resistance and which does not change with time is provided. Therefore, for example, a laminate used as an antireflection body or the like. Can be easily manufactured. Moreover, in the method for producing a laminate of the present invention 1, when an oxygen atom-containing gas is used together with an inert gas and a glow discharge plasma in which the oxygen atom-containing gas is excited together with the inert gas is used, residual alkyl groups and a solvent are Since it is more effectively removed, a laminate suitable for use as an antireflection body or the like can be easily manufactured.

The structure of the method for producing a laminate of the present invention 2 is as described above, and a simple stirrer such as a magnetic stirrer as a mixing device is used for preparing the condensation compositions (A) and (B). Is sufficient, and similarly in the production of the inorganic composition, since it is easy to uniformly disperse the colloidal silica in the alkoxysilane, a simple stirrer such as a magnetic stirrer as a mixing device is sufficient. You don't need high performance equipment. Therefore, this inorganic composition is easy to produce, the resulting inorganic composition is applied on a substrate, after curing, when contacted with a discharge plasma in the vicinity of atmospheric pressure of an inert gas, excellent scratch resistance Since it provides a porous film that does not change over time, for example, a laminate used as an antireflection body or the like can be easily manufactured. Further, in the method for producing a laminate of the present invention 2, when the oxygen atom-containing gas is used together with the inert gas and the discharge plasma in which the oxygen atom-containing gas is excited together with the inert gas is used, the residual alkyl group and the solvent are more Since it is effectively removed, a laminate suitable for use as an antireflection body or the like can be easily manufactured.

The structure of the method for producing a laminate of the present invention 3 is as described above, and a simple stirrer such as a magnetic stirrer as a mixing device is used for preparing the condensation compositions (A) and (B). Is sufficient, and similarly in the production of the inorganic composition, since it is easy to uniformly disperse the colloidal silica in the alkoxysilane, a simple stirrer such as a magnetic stirrer as a mixing device is sufficient. You don't need high performance equipment. Therefore, this inorganic composition is easy to produce, the resulting inorganic composition is applied on a substrate, after curing, when contacted with corona discharge plasma, porous with excellent scratch resistance and without change over time. Since the coating film of 1) is provided, for example, a laminate used as an antireflection body or the like can be easily manufactured.

Further, from the alkoxysilane polycondensation composition in which colloidal silica is uniformly dispersed on the surface of the laminate obtained by the method for producing a laminate of the present invention 1, the invention 2, or the invention 3. It is difficult to get scratches even when rubbed with a hard material such as steel wool, does not easily deteriorate the appearance due to scratches, has excellent scratch resistance, has a high antireflection effect, and forms a porous film that does not change over time .

Therefore, the present invention 1, the invention 2, or the invention 3
The laminated body obtained by using the method for producing a laminated body is, for example, in the field of spectacles such as eyeglass lenses, goggles and contact lenses; in the field of automobiles such as car windows, instrument panel and navigation systems; Building field; Energy fields such as solar cells, photovoltaic cells and lasers;
Fields of electronic information equipment such as notebook computers, electronic organizers, LCD TVs, in-vehicle TVs, LCD video, projection TVs, optical fibers, optical disks; lighting gloves,
Household items such as fluorescent lamps, mirrors and watches; showcases
It can be used as a material in the fields such as forehead, semiconductor lithography, copy machines, and other commercial fields; liquid crystal game machines, pachinko machine glasses, game machines, and other entertainment fields. Of these, especially eyeglass lenses, car windows, instrument panels,
It can be suitably used as a material for navigation systems, solar cells, photocells, lasers, notebook computers, electronic organizers, liquid crystal televisions, in-vehicle televisions, liquid crystal videos, projection televisions, optical disks, fluorescent lamps, liquid crystal game machines, and the like.

The construction of the method for producing a protective material for a pen input panel of the present invention 4 is as described above, and the obtained protective material for a pen input panel has its surface coating rubbed with a hard material such as steel wool. Also, it is hard to be scratched, and it is difficult to cause deterioration of appearance due to scratches. In addition, since the surface has fine irregularities, it has a friction coefficient suitable for an input pen such as acetal resin, so that it has a feeling of writing like writing on a paper with a pencil. Further, since the coating film is porous and has a low refractive index, reflection of external light rays can be prevented. Therefore,
It is suitable as a protective material for a pen input panel.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a configuration of a pen input panel using an electromagnetic induction type tablet.

FIG. 2 is a cross-sectional view showing a configuration of a pen input panel using a resistance film type tablet.

FIG. 3 is an explanatory view showing a part of an example of a plasma processing apparatus in section.

FIG. 4 is an explanatory view showing a part of an example of a plasma processing apparatus in section.

FIG. 5 is a view showing surface irregularities measured by a surface profilometer.

[Explanation of symbols]

 1 Power Supply Section 2 Processing Container 3 Plasma Processing Section 4 Upper Electrode 5 Lower Electrode 6 Base Material 7 Gas Introducing Tube 8 Gas Introducing Tube 9 Gas Outlet 10 Exhaust Outlet 11 Solid Dielectric

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical indication location C09D 183/04 PMM C23C 16/50 (72) Inventor Kazuaki Miyamoto Kami Tobaue tone, Minami-ku, Kyoto 2-2, Sekisui Kagaku Kogyo Co., Ltd. (72) Inventor, Motowa Yuasa 2-1 Hyakuyama, Shimamoto-cho, Mishima-gun, Osaka Prefecture 2-1 Sekisui Chemical Co., Ltd.

Claims (4)

[Claims] 1. A tetraalkoxysilane represented by the general formula Si (OR) ₄ (wherein R is an alkyl group having 1 to 5 carbon atoms), 1 mol, and a basic aqueous solution having a pH of 10.0 to 12.0. 2 to 8 mol and 10 to 30 mol of an organic solvent are mixed to obtain a condensation composition (A), and a compound represented by the general formula (R ² ) _n Si (OR
¹ ) _4-n (wherein, R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms, n is an integer of 0 to 3), 1 mol of alkoxysilane, acidic pH of 0 to 2.6 An inorganic composition obtained by mixing the condensation composition (B) obtained by mixing 3 to 8 mol of an aqueous solution and 10 to 30 mol of an organic solvent at A / B = 0.4 to 2.4 (weight ratio). A step of coating and curing on a substrate,
And 1 × 1 on the surface of the cured film of the obtained inorganic composition.
A method for producing a laminate, comprising the step of bringing into contact glow discharge plasma in which an inert gas is excited under a pressure of 0 ^{-4 to} 100 Torr. 2. A step of applying the inorganic composition according to claim 1 on a substrate and curing the same, and a substrate on which the obtained inorganic composition is applied and cured, wherein a solid dielectric is provided on at least one of opposing surfaces. A film in which a high voltage is applied between metal electrodes under a pressure near the atmospheric pressure of an inert gas, which is disposed between opposing metal electrodes, and discharge plasma of the generated gas cures the inorganic composition. A method for producing a laminated body, which comprises a step of contacting a surface. 3. A step of applying the inorganic composition according to claim 1 on a substrate and curing it, and a step of bringing corona discharge plasma into contact with the film surface on which the obtained inorganic composition is cured. A method for producing a laminated body characterized by the above. 4. A step of applying the inorganic composition according to claim 1 on a transparent base material and curing the same, and a base material on which the obtained inorganic composition is applied and cured on at least one opposing surface of a solid dielectric. The inorganic composition is placed between opposing metal electrodes on which the body is placed, and a high voltage is applied between the metal electrodes under a pressure near the atmospheric pressure of an inert gas to cure the discharge plasma of the generated gas with the inorganic composition. A method for producing a protective material for a pen input panel, which comprises the step of bringing the protective material into contact with the film surface.