JPH08319109A - Inorganic composition and production of laminate - Google Patents

Abstract

PURPOSE: To improve shelf stability of an inorganic composition by blending a condensed composition containing a specific tetraalkoxysilane, basic water and an organic solvent with another inorganic composition containing an alkoxysilane, acidic water and an organic solvent. CONSTITUTION: (A) A condensed composition is obtained by mixing 1mol of a tetraalkoxysilane of the formula Si(OR)4 (R is a 1-5C alkyl) with 2-8mol of basic water having pH10.0 to pH12.0 and 10-30mol of an organic solvent at 10-30 deg.C for 1-10 hours. (B) Another condensed composition is obtained by mixing 1mol of an alkoxysilane of the formula (R<2> )n Si(OR<1> )4-n (R<1> and R<2> are each R; (n) is 0-3) with 3-8mol of acidic water having pH0 to pH2.6 and 10-30mol of an organic solvent at 10-30 deg.C for 1-10 hours. The component A is mixed with the component B in the weight ratio of the components A/B of 0.4-2.4 and optionally diluted with an organic solvent in an amount to make the concentration of the solid content 1.0-4.0wt.% to give the objective inorganic composition.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention relates to an inorganic composition which is suitable for forming a porous film having excellent scratch resistance on a substrate and has good storage stability, and scratch resistance on the substrate. The present invention relates to a method for producing a laminated body on which a porous coating film having an excellent antireflection effect is formed.

[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.

[0007]

The present invention solves these problems, and an object thereof is to form a porous coating film having excellent scratch resistance and high antireflection effect on a substrate. To provide an inorganic composition having good storage stability, which is suitable for easily producing a laminated body, and a porous coating film having excellent scratch resistance and high antireflection effect is formed on a substrate. Another object of the present invention is to provide a method capable of easily manufacturing the laminated body.

[0008]

The condensation composition (A) used for producing the inorganic composition of the present invention 1 (the invention of claim 1 is referred to as the present invention 1) is represented by the general formula Si (OR).
It is obtained by mixing a tetraalkoxysilane represented by ₄ (wherein R is an alkyl group having 1 to 5 carbon atoms), basic water and an organic solvent, and partially hydrolyzing and polycondensing the tetraalkoxysilane.

In the tetraalkoxysilane represented by the above general formula Si (OR) ₄ , when R has a large number of carbons, 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
t-butyl group, n-pentyl group, iso-pentyl group,
Examples include neopentyl 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, tetra-n-pentoxysilane, tetra-iso-pentoxysilane, tetraneopentoxysilane, etc. From the viewpoint of reactivity in hydrolysis and polycondensation, tetramethoxysilane and tetraethoxysilane are preferable, and tetraethoxysilane is particularly preferable.

The basic water has a pH of 1 depending on the base species.
It means water adjusted to 0.0 to 12.0. The base species is not particularly limited as long as it can adjust the pH of water to 10.0 to 12.0, and examples thereof include ammonia, ammonium hydroxide, potassium hydroxide and the like, and the pH adjustment is easy. , Ammonia is preferred.

When the pH of the basic water is low, the molecular weight of the colloidal silica obtained is low, which makes it difficult to form an antireflection coating, and when it is high, the stability of the condensation composition (A) obtained is low. Therefore, it is limited to 10.0 to 12.0, preferably 10.3 to 11.5, and 10.8 to
11.4 is particularly preferred.

When the amount of basic water is small, the molecular weight of the colloidal silica obtained is low, making it difficult to form an antireflection coating, and when it is high, the stability of the condensation composition (A) is low. 2 to 8 mol is added to 1 mol of the tetraalkoxysilane represented by ₄ , and 3 to
It is preferable to add 4 mol.

The organic solvent is not particularly limited as long as it is compatible with the tetraalkoxysilane represented by Si (OR) ₄ and basic water, and examples thereof include methyl alcohol, ethyl alcohol and isopropyl alcohol. , Ethoxyethyl alcohol, allyl alcohol and the like, but isopropyl alcohol is particularly preferable.

When the amount of the organic solvent added decreases, the stability of the condensation composition (A) decreases, and when the amount of the organic solvent increases, the molecular weight of the obtained colloidal silica decreases and it becomes 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 mixing method of the condensation composition (A) is not particularly limited, and for example, in order to obtain a homogeneous one of tetraalkoxysilane represented by Si (OR) ₄ , basic water and an organic solvent, Preferably, the method of supplying to a stirrer and mixing is mentioned. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

The temperature at which the condensation composition (A) is mixed 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 mixing 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 mixed 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.

Used in the production of the inorganic composition of the present invention 1
The condensation composition (B) having the general formula (R ²)_nSi (O
R¹)_4-n(In the formula, R¹And R²Is a C1-C5
Alkyl group, n is an integer of 0 to 3)
Orchid, acidic water and organic solvent are mixed, and alkoxysilane
Is partially hydrolyzed and polycondensed.

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, a tert-butyl group, an n-pentyl group, an iso-pentyl group and a neopentyl 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, tetra-n-pentoxysilane, tetra-iso-pentoxysilane, tetraneopen Toxysilane, monomethyltrimethoxysilane, monomethyltriethoxysilane,
Monomethyltri-n-propoxysilane, monomethyltri-iso-propoxysilane, monomethyltri-n-
Butoxysilane, monomethyltri-sec-butoxysilane, monomethyltri-tert-butoxysilane, monomethyltri-n-pentoxysilane, monomethyltri-iso-pentoxysilane, monomethyltrineopentoxysilane, ethyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-ter.
t-butoxysilane, dimethyldi-n-pentoxysilane, dimethyldi-iso-pentoxysilane, dimethyldineopentoxoxysilane, diethyldiethoxysilane,
Trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane, trimethylmono-n-butoxysilane, trimethylmono-sec-
Butoxysilane, trimethyl mono-tert-butoxy silane, trimethyl mono-n-pentoxy silane, trimethyl mono-iso-pentoxy silane, trimethyl mono neopentoxy silane, triethyl ethoxy silane, etc. are mentioned, and tetra- Methoxysilane,
Tetraethoxysilane and monomethyltriethoxysilane are preferable, and tetraethoxysilane is particularly preferable.

The above acidic water has a pH of 0 depending on the acidic species.
It means water adjusted to 2.6. Acidic species increase the pH of water
It is not particularly limited as long as it can be adjusted 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 water is low, the stability of the condensation composition (B) may be reduced, and when it is high, the hydrolysis of the alkoxysilane is insufficient, so that the pH of the acidic water is 0 to 0.
It is limited to 2.6, 1.0 to 1.7 is preferable, and 1.1
~ 1.2 is particularly preferred.

When the amount of the acidic water added is small, the hydrolysis of the alkoxysilane is insufficient, and furthermore, it becomes difficult to apply the resulting inorganic composition to the substrate, and when it is large, the amount of the condensation composition (B) is increased. Stability is reduced,
The amount of alkoxysilane represented by (R ² ) _n Si (OR ¹ ) _4-n is limited to 3 to 8 mol, and preferably 4 to 7 mol.

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 acidic water, 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 that (R ² ) _n Si
It is limited to 10 to 30 mol, and preferably 13 to 18 mol, per 1 mol of alkoxysilane represented by (OR ¹ ) _4-n .

The mixing method of the condensation composition (B) is not particularly limited, and for example, an alkoxysilane represented by (R ² ) _n Si (OR ¹ ) _4-n , acidic water and an organic solvent are homogeneously mixed. In order to obtain the product, a method of supplying the mixture to a stirrer and mixing is preferable. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

The temperature at which the condensation composition (B) is mixed 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 mixing 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 condensation composition (B) is preferably mixed at 10 to 30 ° C. for 1 to 10 hours, particularly preferably at 20 to 25 ° C. for 2 to 4 hours.

The mixing for obtaining the inorganic composition of the present invention 1 is carried out by mixing the condensation composition (A) and the condensation composition (B) in a weight ratio ((A) / (B)) = 0.4 to 2 Mix at 4

When the amount of the condensation composition (A) is small, the porosity of the resulting coating film is low, and the antireflection effect of the resulting laminate is low, and when it is large, the adhesion between the resulting coating film and the substrate is low. Therefore, the weight ratio ((A) / (B)) of the condensation composition (A) and the condensation composition (B) is 0.4 to 2.4.
However, 1.5 to 2.3 is preferable in order to improve the stability of the inorganic composition and the adhesion between the coating film and the substrate.

If the temperature at which the condensation composition (A) and the condensation composition (B) are mixed is lowered, polycondensation of the colloidal silica and silica sol becomes difficult, and the antireflection effect of the obtained 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.

If the time for mixing the condensation composition (A) and the condensation composition (B) is shortened, polycondensation of the colloidal silica and silica sol becomes insufficient, and the antireflection effect of the obtained coating decreases, 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, and for example, in order to obtain a homogeneous composition of the condensation composition (A) and the condensation composition (B). In addition, preferably, a method of supplying to a stirrer and stirring and mixing can be mentioned. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

In the inorganic composition of the present invention 1, when the solid content concentration is low, the coating efficiency is low and the productivity is poor, and when the solid content concentration is high, silanol groups come close to each other in the solvent, and Condensation reaction becomes faster, and this tendency becomes remarkable when the environmental temperature becomes higher.For example, when used as a coating agent in an environment where temperature control is not possible, the inorganic composition changes with time, which may cause a problem that long-term storage is not possible. Therefore, the solid content concentration is 1.0 to 4.0.
It is limited to wt%, preferably 1.3 to 2.5 wt%.
Note that the solid concentration in the present invention 1, the weight percentage of the SiO ₂ inorganic composition when Si atoms of the inorganic composition is considered that all become SiO _2.

To produce the inorganic composition of the present invention 1,
A mixture of the condensation composition (A) and the condensation composition (B) at a weight ratio ((A) / (B)) of 0.4 to 2.4 has a solid content concentration of 1.0 to. An organic solvent is added and diluted so that it may be 4.0% by weight.

The organic solvent is not particularly limited as long as it is compatible with the mixture of the condensation composition (A) and the condensation composition (B). For example, in the production of the condensation composition (A). The same as that used is used.

Invention 2 (The invention according to claim 2 is the invention 2
Say. ) Is a method for producing a laminate, which comprises applying the inorganic composition according to claim 1 on a substrate and curing the composition.

The above-mentioned substrate is not particularly limited as long as it can be coated with the inorganic composition, and for example, silicate glass, alkali silicate glass, soda lime glass, potassium lime glass, lead lime glass. Examples include inorganic base materials made of silicate glass such as barium glass and borosilicate glass, and organic base materials made of polycarbonate, acrylic resin, polyvinyl chloride, polystyrene, polyester, polyurethane, cellulose triacetate 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, particularly preferably at 30% or less.

When the inorganic composition is applied on 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 and the base material is an organic base material, pretreatment such as corona discharge treatment improves the wettability of the coating liquid and provides a laminate having an excellent appearance. It is easier to get a body.

The above curing method is not particularly limited,
It may be naturally dried at room temperature or may be dried by heating.
For example, after coating the surface of the silicate glass with the inorganic composition by the method described above and naturally drying at room temperature, 60 to 30
When it is cured at a temperature of 0 ° C., a laminate having a porous antireflection coating is obtained due to the difference in shrinkage between the silicon matrix and colloidal silica in the inorganic composition. Further, for example, when the surface of a plastic product is coated, naturally dried at room temperature and then cured at a temperature of 60 to 150 ° C., a laminate having an antireflection coating is obtained.

Invention 3 (The invention according to claim 3 is the invention 3
Say. ), The boiling point of the organic solvent is 60 ° C. or higher, the inorganic composition according to claim 1 is applied onto an inorganic substrate,
The method for producing a laminate is characterized in that the laminate is left at 60 ° C., supercritically dried with carbon dioxide in a supercritical state, and then heated to 80 to 600 ° C. to be cured.

In other words, the present invention 3 limits the inorganic composition in which the organic solvent has a boiling point of 60 ° C. or higher in the method for producing a laminate of the present invention 2, and the base material is an inorganic base material. Further, the curing method is limited to 10 times for the coated substrate.
The method for producing a laminated body is characterized in that after leaving it at -60 ° C, it is supercritically dried with carbon dioxide in a supercritical state, and then heated at 80 to 600 ° C to be cured.

The boiling point of the organic solvent used in the present invention 3 is 6
The inorganic composition having a temperature of 0 ° C. or higher is produced by using only all the organic solvents used in the inorganic composition of the present invention 1 having a boiling point of 60 ° C. or higher under 1 atm. Is.

When the boiling point of the above-mentioned organic solvent becomes low, vaporization of the organic solvent from the coating proceeds immediately after the inorganic composition is applied on the substrate, and the coating becomes dense before passing through the supercritical drying step with carbon dioxide. It tends to become porous, and it is difficult to make the obtained coating porous. Therefore, the boiling point of the organic solvent under 1 atm is limited to 60 ° C or higher, and the boiling point under 1 atm is preferably 90 to 200 ° C.

Examples of the organic solvent having a boiling point of 60 ° C. or higher under 1 atm include isopropyl alcohol, ethoxyethyl alcohol, allyl alcohol and the like. From the viewpoint of improving the porosity of the obtained coating, Isopropyl alcohol and ethoxyethyl alcohol are preferred.

The above-mentioned inorganic substrate is not particularly limited as long as it is an inorganic substrate to which the above-mentioned inorganic composition can be applied.
For example, those exemplified in the description of the present invention 2 may be mentioned.
Further, the shape of the base material is not particularly limited.

In the production method of the present invention 3, the above-mentioned inorganic composition is applied onto an inorganic base material, the applied base material is allowed to stand, and then supercritical drying is carried out with carbon dioxide in a supercritical state.

When the temperature at which the coated substrate is left as described above is lowered, polycondensation of colloidal silica and silica sol becomes insufficient, the strength of the obtained antireflection coating becomes low, and the temperature becomes high. Since the vaporization of the organic solvent proceeds too much, the film becomes dense and the effect of the treatment with carbon dioxide in the supercritical state becomes low, the temperature is limited to 10 to 60 ° C, preferably 20 to 30 ° C.

Further, when the time for leaving the coated substrate to stand is shortened, the polycondensation reaction of colloidal silica and silica sol does not proceed, the strength of the obtained coating is lowered, and if the time is prolonged, The evaporation of the organic solvent has progressed too much,
Since the antireflection effect of the coating film becomes low, 10 minutes to 2 hours are preferable, and 0.5 to 1 hour is particularly preferable.

The supercritical carbon dioxide used in the present invention 3 means carbon dioxide at a critical temperature or higher and a critical pressure or higher. The critical temperature of carbon dioxide is 31.0
The temperature is 5 ° C. and the critical pressure is 7.38 MPa.

The conditions for supercritical drying with carbon dioxide in the supercritical state are not particularly limited, as long as the conditions are such that the supercritical state of carbon dioxide can be realized, since the effect does not change.

The above-mentioned supercritical drying with carbon dioxide in the supercritical state means that the water and the organic solvent in the coating film formed on the coated substrate are diffused into the carbon dioxide in the supercritical state, and To reduce the pressure of carbon and dry it.

In the production method of the present invention 3, the coating material supercritically dried as described above is then heated to obtain a laminate having an antireflection coating film formed on the substrate. The above heating method is not particularly limited, and examples thereof include a method of heating in an oven.

When the heating temperature in the above curing step is low, the strength of the obtained coating film is low, and when the heating temperature is high, the coating film is densified and the antireflection effect of the obtained coating film is low. Limited to ~ 600 ° C, 100
-300 degreeC is especially preferable.

Invention 4 (The invention according to claim 4 is the invention 4)
Say. ), The boiling point of the organic solvent is 60 ° C. or higher, the inorganic composition according to claim 1 is applied onto an organic substrate,
After being left at 60 ° C., it is supercritically dried with carbon dioxide in a supercritical state, and then heated at 80 to 120 ° C. to be cured, which is a method for producing a laminate.

In other words, the present invention 4 uses an organic base material instead of the inorganic base material in the method for producing a laminate of the present invention 3, and further heats the curing step in the method for producing a laminate of the present invention 3. The method is the same as the method for producing a laminate of the present invention 3 except that the temperature is 80 to 120 ° C. instead of 80 to 600 ° C.

The above-mentioned organic substrate is not particularly limited as long as it is an organic substrate to which the above-mentioned inorganic composition can be applied.
For example, those exemplified in the description of the present invention 2 may be mentioned.
Further, the shape of the base material is not particularly limited.

When the heating temperature in the above curing step is low, the strength of the obtained coating film is low, and when the heating temperature is high, the organic base material is easily deformed.
And 90 to 100 ° C. is preferable.

Invention 5 (The invention according to claim 5 is the invention 5
Say. ) Is a curing method according to the present invention 2, wherein
1 × 10 on the surface coated with the described inorganic composition on the substrate
^-4 is a method for producing a laminate, which comprises contacting glow discharge plasma excited with an inert gas under a pressure of ^{-4 to} 100 Torr.

In the present invention 5, the steps up to the step of applying the inorganic composition of the present invention 1 on a substrate are the same as those of the present invention 2. The type of substrate used, the method of applying the inorganic composition, and the film thickness when applying the inorganic composition onto the substrate are also the same as those of the second invention. In the curing of the inorganic composition,
For example, in a usual curing method such as heating, unreacted alkoxy groups and organic solvents remain in the porous film, and the remaining amount tends to increase as the curing temperature becomes relatively low,
The durability of the antireflection effect is not sufficient for a base material such as plastic which cannot be cured at a high temperature. Therefore, in the present invention 5,
By contacting discharge plasma, which will be described in detail below, residual alkoxy groups and organic solvent are removed, and curing is further promoted.

Noble gases such as helium, argon, neon, and xenon, and nitrogen gas are used alone or as a mixture as the inert gas used in the method for producing a laminate of the present invention 5.

In the method for producing a laminate of the present invention 5,
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 a mixed gas with the gas, residual alcohol
Si groups and organic solvents are more effectively removed. Also oxygen
Tetrafluoride at a volume ratio of 50% or less with respect to the atom-containing gas
Carbon (CF _Four), Carbon hexafluoride (C₂F₆), Fluoride
Ropylene (C₃F₆) And other fluorocarbon gases are mixed and used.
When used, it is preferable because fluorine improves the oxidizability.
Yes.

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.

When the processing pressure during the plasma processing becomes low, an expensive vacuum chamber and a vacuum exhaust device are required. Further, when processing a large-area substrate, the processing container must be made large and the vacuum exhaust device must be installed. It is necessary to have a high output, and if it becomes high, thermal plasma will be generated until finally arc discharge occurs unless a special method as disclosed in the present invention 6 is used. Therefore, 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 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. 1 is an explanatory view showing a part of an example of a 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) composed 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. 1, 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. 1, 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. 1, the tip portion 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 is mounted on the electrodes or in the space between the electrodes. In FIG. 1, 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 is mounted on the lower electrode 5 with the coated film surface facing upward, and then the treatment container 2
The inside is evacuated to 1 × 10 ⁻³ Torr or less through the exhaust port 10. Next, while controlling the flow rate of the inert gas with a 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 Torr.
Adjust so that 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 substrate 6 coated with the inorganic composition. Plasma treatment is performed by doing so.

When the oxygen atom-containing gas is used together with the inert gas, the base material 6 coated with the inorganic composition is attached to the lower electrode 5 with the coated film surface facing upward, and then the treatment container is treated. Exhaust port 1 below 2 below 1 × 10 ^-3 Torr
Evacuate from 0. 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 Torr by introducing the gas from the gas introducing pipe 8 to the plasma processing unit 3.
Adjust so that Then, when the gas pressure in the processing container 2 becomes stable, the inorganic composition is applied with 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. Base material 6
Plasma treatment is performed by bringing the film surface into contact with.

The plasma curing treatment of the present invention 5 does not require heating or cooling of the base material, 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.

Invention 6 (Invention 6)
Say. ) Is a curing method according to the present invention 2, wherein
The substrate coated with the inorganic composition described above is disposed between opposing metal electrodes having a solid dielectric disposed on at least one opposing surface, and the metal electrode is provided under a pressure near the atmospheric pressure of an inert gas. A high voltage is applied between them, and discharge plasma of the generated gas is brought into contact with the surface coated with the inorganic composition.

In the present invention 6, the steps up to the step of applying the inorganic composition of the present invention 1 on a substrate are the same as those of the present invention 2. The type of substrate used, the method of applying the inorganic composition, and the film thickness when applying the inorganic composition onto the substrate are also the same as those of the second invention. In the curing of the inorganic composition,
For example, in a usual curing method such as heating, unreacted alkoxy groups and organic solvents remain in the porous film, and the remaining amount tends to increase as the curing temperature becomes relatively low,
The durability of the antireflection effect is not sufficient for a base material such as plastic which cannot be cured at a high temperature. Therefore, in Invention 6,
By contacting discharge plasma, which will be described in detail below, residual alkoxy groups and organic solvent are removed, and curing is further promoted.

As the inert gas used in the method for producing a laminate of the present invention 6, 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 laminate of the present invention 6,
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 a mixed gas with the gas, residual alcohol
Si groups and solvents are more effectively removed. Also, oxygen atom
Carbon tetrafluoride at a volume ratio of 50% or less with respect to the contained 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. When the proportion of the oxygen atom-containing gas increases, 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 6 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 sixth invention will be described below. FIG. 2 is an explanatory view showing a part of an example of the plasma processing apparatus used in the present invention 6 in cross 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 disposed 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 present invention 6, 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. 2, the solid dielectric 11 is provided 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 and titanium oxide are used. 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. 2, 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. 2, 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. As shown in FIG. 2, 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.

To plasma-treat the substrate 6 coated with the inorganic composition using the plasma treatment apparatus shown in FIG.
The above-mentioned base material 6 is placed on the solid dielectric 11, and an inert gas or a mixed gas of an inert gas and an oxygen atom-containing gas is supplied as necessary to bring the pressure to a pressure close to the atmospheric pressure, and between the metal electrodes. A voltage is applied to generate discharge plasma, and the plasma is brought into contact with the base material 6. In this way, the residual alkoxy group and the organic solvent are removed and curing is promoted.

In this example, the base material 6 is processed only on one surface (upper surface in FIG. 2) 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.

Invention 7 (The invention according to claim 7 is the invention 7
Say. ) Is a curing method according to the present invention 2, wherein
A method for producing a laminate, which comprises bringing corona discharge plasma into contact with the surface coated with the inorganic composition described above on a substrate.

In the present invention 7, the steps up to the step of applying the inorganic composition of the present invention 1 on a substrate are the same as those of the present invention 2. The type of substrate used, the method of applying the inorganic composition, and the film thickness when applying the inorganic composition onto the substrate are also the same as those of the second invention. In the curing of the inorganic composition,
For example, in a usual curing method such as heating, unreacted alkoxy groups and organic solvents remain in the porous film, and the remaining amount tends to increase as the curing temperature becomes relatively low,
The durability of the antireflection effect is not sufficient for a base material such as plastic which cannot be cured at a high temperature. Therefore, in the present invention 7,
By contacting corona discharge plasma, which will be described in detail below, residual alkoxy groups and organic solvent are removed, and curing is further promoted.

As the gas to be excited used in the method for producing a laminate of the present invention 7, air, argon and mixed gas thereof are used, 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 to 60 kV is preferable.

The electrodes are where the output of the high frequency power supply is converted 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 carry out 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 material and some of which are metal depending on the type of the electrode. . 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 substrate. 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.

Invention 8 (Invention 8 is the invention 8)
Say. ) Is a curing method according to the present invention 2, wherein
A substrate coated with the described inorganic composition is treated with a relative humidity of 70
% Of the environment, and is a method for manufacturing a laminate.

In the present invention 8, the steps up to the step of applying the inorganic composition of the present invention 1 on a substrate are the same as those of the present invention 2. The type of substrate used, the method of applying the inorganic composition, and the film thickness when applying the inorganic composition onto the substrate are also the same as those of the second invention. In the curing of the inorganic composition,
For example, in a usual curing method such as heating, unreacted alkoxy groups and silanol groups remain in the porous film,
The lower the curing temperature is, the larger the residual amount tends to be, and the durability of the antireflection effect is not sufficient for a substrate such as plastic which cannot be cured at a high temperature. Therefore, in the present invention 8, the curing is further promoted by placing it in an environment having a relative humidity of 70% or more, which will be described in detail below, to hydrolyze the residual alkoxy group and polycondensate the residual silanol group.

In the eighth aspect of the present invention, the relative humidity is 70%.
The above environment is preferably 80% or more relative humidity, more preferably 95% or more relative humidity. If this relative humidity is less than 70%, the subsequent reaction of the residual alkoxy groups and residual silanol groups will be insufficient and curing cannot proceed.

The temperature when placed in an environment having a relative humidity of 70% or more is not particularly limited, but when the temperature is low, the treatment takes time, and when the temperature is high, the organic base material is deformed. Since it easily occurs, 40 to 100 ° C
Is preferable, and 50-90 degreeC is especially preferable.

The time for placing in the environment with the relative humidity of 70% or more depends on the relative humidity, but when the time becomes short,
Subsequent reaction of the residual alkoxy group or residual silanol group becomes insufficient, and even if the time is too long, the effect according to the time cannot be obtained. Therefore, usually 50 to 1200 hours are preferable, and 100 to 1000 hours are more preferable.

Invention 9 (The invention according to claim 9 is the invention 9
Say. ) Is a curing method according to the present invention 2, wherein
A substrate coated with the described inorganic composition is treated with a relative humidity of 70
%, And then the substrate is placed in an environment having a temperature of 60 ° C. or higher and a relative humidity of less than 70%.

In the present invention 9, the steps up to the step of placing the substrate coated with the inorganic composition according to claim 1 in an environment having a relative humidity of 70% or more are the same as in the present invention 8. Invention 8
According to the method for producing a laminated body of (1), a laminated body on which a porous coating film having no change over time and excellent in durability is formed can be obtained. However, in this step alone, water is likely to remain in the fine pores of the porous coating, and in a resin substrate or the like, the adhesion between the substrate and the coating may not always be sufficient.

In order to improve this, in the method for producing a laminate of the present invention 9, the substrate is placed in an environment having a relative humidity of 70% or more, and then the substrate is kept at a temperature of 60 ° C. or more and a relative humidity of 70%. Take the step of placing in an environment of less than%. If the temperature of this step is lowered, the effect of improving the adhesiveness between the base material and the coating film is lost. Therefore, the temperature is 60 ° C. or higher and the melting temperature of the base material or lower, and preferably 80 ° C. or higher. If the relative humidity in this step becomes higher, the residual water cannot be vaporized and the effect of improving the adhesion between the base material and the coating film is lost, so it is less than 70%, preferably less than 50%, and particularly preferably 30.
It is less than%. The base material in which the effect of improving the adhesiveness by this step is particularly seen is a base material in which the adhesiveness between the base material and the coating film is not relatively strong, for example, a polycarbonate base material.

Invention 10 (Invention of the invention of claim 10
It is called Ming 10. ) Is the general formula Si (OR)_Four(In the formula, R
Is an alkyl group having 1 to 5 carbon atoms)
PH is 10.0 to 12.0 with respect to 1 mol of xysilane.
2 to 8 mol of basic water and 10 to 30 mol of organic solvent are mixed.
And the general formula (R²) _n
Si (OR¹)_4-n(In the formula, R¹And R²Has 1 carbon
An alkyl group of 5 to 5, n is an integer of 0 to 3)
Acidic pH of 0-2.6 per mol of coxisilane
Mix 3-8 mol of water and 10-30 mol of organic solvent
The resulting condensation composition (B) was treated with (A) / (B) = 0.
4 to 2.4 (weight ratio) obtained by mixing
The organic composition (C) is applied onto a substrate to obtain the inorganic composition.
It is characterized in that the surface coated with (C) is irradiated with light.
Is a method for manufacturing a laminated body.

The inorganic composition (C) used in the present invention 10 corresponds to the inorganic composition of the present invention 1 in which the solid content concentration is not limited.

In the present invention 10, the inorganic composition (C) is used in place of the inorganic composition of the present invention 1 up to the step of coating the substrate with the inorganic composition (C). Other than the above, the present invention is the same as the second invention. Further, the type of the substrate used, the method of applying the inorganic composition (C), and the film thickness when the inorganic composition (C) is applied on the substrate are also the same as those of the inorganic composition of the present invention 1. It is the same as the present invention 2 except that the above-mentioned inorganic composition (C) is used.
In the curing of the inorganic composition (C), for example, in a usual curing method such as heating, unreacted alkoxy groups and silanol groups remain in the porous coating, and the lower the curing temperature is, the more it remains. The 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 temperatures. Therefore, in the present invention 10, residual alkoxy groups and silanol groups are removed by light irradiation, which will be described in detail below, and curing is further advanced.

The energy of the light to be irradiated is not particularly limited as long as it is the energy absorbed by the unreacted group.
5eV, which is considered to be effective for polycondensation of silanol groups
The above light is preferable.

The present invention 11 (the invention according to claim 11 is referred to as invention 11) is obtained by coating the substrate with the inorganic composition (C) according to claim 10, and coating the coated substrate with a relative humidity. The method for producing a laminate is characterized in that it is placed in an environment of 70% or more, and then the surface coated with the inorganic composition (C) is irradiated with light.

In the present invention 11, the inorganic composition (C) according to claim 10 is applied onto a base material, and the applied base material is placed in an environment having a relative humidity of 70% or more to give a residual alkoxy. By hydrolyzing the groups and further polycondensing the silanol groups, the durability of the antireflection effect of the coating can be improved, but this step alone produces a coating that does not change its antireflection effect with time even in a harsh environment. It takes a long time to get it. Therefore, the above relative humidity 70
%, By irradiating with light after the step of placing in an environment of 70% or more, it is possible to obtain a film whose antireflection effect does not change with time even if the step of placing in an environment of 70% or more of the relative humidity is performed for a short period of time. it can.

In the present invention 11, the inorganic composition (C) is used in place of the inorganic composition of the present invention 1 up to the step of coating the substrate with the inorganic composition (C). Other than the above, the present invention is the same as the second invention. Further, the type of the substrate used, the method of applying the inorganic composition (C), and the film thickness when the inorganic composition (C) is applied on the substrate are also the same as those of the inorganic composition of the present invention 1. It is the same as the present invention 2 except that the above-mentioned inorganic composition (C) is used.

The temperature when placed in an environment having a relative humidity of 70% or more is not particularly limited, but when the temperature is low, the treatment takes time, and when the temperature is high, the substrate is deformed in the organic substrate. Since it easily occurs, 40 to 100 ° C
Is preferable, and 50-90 degreeC is especially preferable.

The time for placing in the environment of the relative humidity of 70% or more depends on the relative humidity, but if the time becomes short,
Subsequent reaction of the residual alkoxy groups and residual silanol groups becomes insufficient, and even if the time is too long, the effect corresponding to the time cannot be obtained.
40 to 250 hours is more preferable.

The energy of the irradiation light is not particularly limited as long as it is the energy absorbed by the unreacted group.
5eV, which is considered to be effective for polycondensation of silanol groups
The above light is preferable.

The present invention 12 (the invention of claim 12 is referred to as the invention 12), wherein the inorganic composition (C) has a solid content concentration of 1.0 to 4.0% by weight. Is a method for manufacturing a laminated body.

In the inorganic composition (C), when the solid content concentration is low, the coating efficiency is low and the productivity is poor, and when the solid content concentration is high, silanol groups come close to each other in the solvent to cause polycondensation. The reaction becomes faster, and this tendency becomes remarkable when the environmental temperature becomes high. For example, when it is used as a coating agent in an environment where temperature control is not possible, the inorganic composition (C) changes over time, and there is a problem that it cannot be stored for a long time. As the solid content concentration is 1.0 to 4.0, it may occur.
It is limited to wt%, preferably 1.5 to 2.5 wt%.
Note that the solid concentration in the present invention 12, the weight percentages of the SiO ₂ inorganic composition when Si atoms in the mineral composition (C) is considered all become SiO _2.

Solid content concentration used in the present invention 1.
The method for producing the inorganic composition (C) in an amount of 0 to 4.0% by weight is the same as the method for producing the inorganic composition of the present invention 1.

The laminates obtained by the present inventions 2 to 12 are excellent antireflection bodies because the inorganic porous film laminated on the substrate has a low refractive index. When this anti-reflective body is used in a place with relatively few external rays, such as indoors, there is no particular problem with performance, but in places with many external rays, such as outdoors,
Further, even when indoors, when high performance is required as an antireflection body, the reflected image cannot be completely eliminated, which may not be satisfactory. In such a case, the present invention 2
In the laminated body manufacturing method of 12, it is effective to use a non-glare treated substrate as the substrate.

The non-glare-treated base material is a base material having a concavo-convex shape on the surface of the base material that causes diffuse reflection light, and is a base material capable of preventing reflection of an image by diffuse reflection of incident light.

Examples of the non-glare-treated base material include a resin film or sheet that has been embossed; a resin base material or an inorganic base material whose surface has been polished by brushing, sand spraying, or the like; a resin base material or an inorganic base. A material obtained by spray-coating a metal alkoxide hydrolyzed composition on the material surface; a composition in which fine particles having a size that causes scattering in the visible light wavelength region are dispersed on the surface of a resin substrate or an inorganic substrate. The thing obtained by apply | coating etc. is mentioned. When a metal oxide such as tin oxide is used as the fine particles, antistatic property can be imparted.

Further, in the case of the antireflection bodies obtained in the inventions 2 to 12, when stains such as fingerprints are attached, since the laminated coatings have a low refractive index, they may be very conspicuous and may be unfavorable in appearance. In this case, it is possible to wipe off stains on the surface of the coating with alcohol or the like, but it is preferable that stains are not easily attached.

As a method for making it difficult for the stains to adhere, a method of laminating a layer having a small surface energy on the inorganic porous coating film obtained in the present inventions 2 to 12 is effective.
The layer having a small surface energy, for example, is obtained by applying a hydrolyzed composition of an alkoxysilane having an alkyl group; a layer obtained by applying a hydrolyzed composition of a fluorine atom-containing alkoxysilane. And those obtained by coating with a fluororesin. In this case, when the refractive index of the layer having a small surface energy formed on the surface of the inorganic porous coating is higher than the refractive index of the inorganic porous coating, the antireflection effect decreases, so that the surface energy is small. It is preferable that the layer thickness is 500 Å or less.

[0135]

The inorganic composition of the present invention 1 is the condensation composition (A)
In the polycondensation of tetraalkoxysilane, colloidal silica is formed considerably, and in the condensation composition (B), polycondensation of alkoxysilane does not proceed relatively and is suppressed at the stage of silica sol. The inorganic composition that is a mixture is a mixture of colloidal silica and silica sol. When this inorganic composition is applied onto a base material and cured, a porous coating film can be obtained due to the difference in shrinkage between silica sol and colloidal silica. Moreover, since the solid content concentration is limited to 1.0 to 4.0% by weight, the storage stability is excellent.

The method for producing a laminate of the present invention 2 is the same as that of the present invention 1
By coating the inorganic composition obtained in the above on a substrate and curing it, the polycondensation reaction of silica sol and colloidal silica proceeds, and it is possible to obtain a porous film due to the difference in the contraction rate of silica sol and colloidal silica. it can.

In the method for producing a laminate of the present invention 3 and the present invention 4, the polycondensation reaction of silica sol and colloidal silica proceeds by coating the inorganic composition obtained in the present invention 1 on a substrate and leaving it to stand. Then, a porous coating film can be obtained due to the difference in shrinkage between silica sol and colloidal silica. Then, after leaving the coated material, further, while leaving the organic solvent and water in the film, by supercritical drying with carbon dioxide in a supercritical state, while leaving pores in the film, It is possible to completely vaporize the organic solvent and water. Further, by heating the dried coating material, the bond between the base material and the coating becomes strong.

The method for producing a laminate of the present invention 5 is the same as that of the present invention 1
After coating the inorganic composition obtained in 1) on a substrate, 1 × 10
-By contacting with glow discharge plasma in which an inert gas is excited under a pressure of ^{-4 to} 100 Torr, residual alkoxy groups and organic solvents are removed and cured, resulting in porosity due to the difference in shrinkage ratio between silica sol and colloidal silica. A coated film can be obtained.

The method for producing a laminate of the present invention 6 is the same as that of the present invention 1
Inorganic composition obtained in, after coating on the substrate, by contact with discharge plasma near atmospheric pressure, to remove residual alkoxy groups and organic solvents, by curing, polycondensation reaction of silica sol and colloidal silica To
A porous coating film can be obtained due to the difference in shrinkage between silica sol and colloidal silica.

The method for producing a laminate of the present invention 7 is the same as that of the present invention 1
After coating the inorganic composition obtained in, on the substrate, by contacting with corona discharge plasma to remove residual alkoxy groups and solvent, and further cured, due to the difference in shrinkage of silica sol and colloidal silica A cured coating can be obtained.

The method for producing a laminate of the present invention 8 is the same as that of the present invention 1
The inorganic composition obtained in 1. is applied on a substrate and then placed in a high-humidity environment to remove residual alkoxy groups and silanol groups, accelerate curing of the film, and reduce the shrinkage ratio between silica sol and colloidal silica. A porous coating film can be obtained.

The method for producing a laminate of the present invention 9 is the same as that of the invention 1
The inorganic composition obtained in 1. is applied on a substrate and then placed in a high-humidity environment to remove residual alkoxy groups and silanol groups, accelerate curing of the film, and reduce the shrinkage ratio between silica sol and colloidal silica. A porous coating film can be obtained. Then, by placing in a high temperature and low humidity environment, the bonding between the substrate and the coating is promoted.

In the method for producing a laminate of the tenth aspect of the present invention, after the inorganic composition (C) is applied onto a substrate, the residual alkoxy groups and silanol groups are removed by irradiating with light,
The hardening of the film is promoted, and a porous film can be obtained due to the difference in shrinkage between silica sol and colloidal silica.

In the method for producing a laminate of the present invention 11, the inorganic composition (C) is applied on a substrate and then placed in a high humidity environment to remove residual alkoxy groups, and then to irradiate with light. By that, polycondensation reaction of silica sol and colloidal silica with polycondensation of silanol group is advanced, and it is made porous due to the difference in contraction rate between silica sol and colloidal silica, and further, in a harsh environment, it also has an antireflection effect. It is possible to obtain a coating that is less likely to change with time. Further, the light irradiation step can shorten the time required to be placed in a high humidity environment.

Since the concentration of the inorganic composition (C) used in the present invention 10 or 11 is limited to 1.0 to 4.0% by weight in the method for producing a laminate of the present invention 12, the inorganic material used is The stability of the composition is good.

The laminate obtained by the method for producing a laminate of the present inventions 2 to 12 has a coating film having a low refractive index and is therefore used as an antireflection body. Further, when a non-glare-treated product having an uneven surface is used as the base material, incident light is diffusely reflected, and reflection can be prevented even in a place where external light rays are strong such as outdoors. Further, by providing a layer having a small surface energy on the laminate obtained in the present inventions 2 to 12, an antireflection body excellent in antifouling property can be obtained. Since the concentration of the inorganic composition (C) used in the present invention 10 or 11 is limited to 1.0 to 4.0% by weight, the stability of the inorganic composition used is good.

[0147]

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 laminated with the antireflection coating 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 laminated body was measured according 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 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 Test 1 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 the scratch resistance test was conducted. Then, the change with time was observed. (5) Aging change test 2 The obtained laminated body is kept in an atmosphere of −40 ° C. for 30 minutes, then taken out, and immediately after that, kept in an atmosphere of 80 ° C. for 30 minutes. This is one cycle, then take out,
Immediately after that, it is placed again in an atmosphere of -40 ° C to start the second cycle. Such thermal shock test was performed for 210 cycles. After the above thermal shock test was completed, the reflectance and pencil hardness were measured and the scratch resistance test was performed to observe the change over time. (6) Aging Change Test 3 The obtained laminated body is kept in an atmosphere of −20 ° C. for 30 minutes, then taken out, and immediately after that, kept in an atmosphere of 80 ° C. for 30 minutes. This is one cycle, then take out,
Immediately after that, it is placed again in an atmosphere of -20 ° C to start the second cycle. Such thermal shock test was performed for 210 cycles. After the above thermal shock test was completed, the reflectance and pencil hardness were measured and the scratch resistance test was performed to observe the change over time.

(7) Adhesiveness The antireflection coating of the obtained laminated body was applied to JIS K540
According to 0, a cross-cut tape peeling test was performed and evaluated according to the following criteria. (Judgment Criteria) O: No peeling at all. Δ: Some peeling occurred. X: Completely peeled.

(8) Storage Stability The storage time of the inorganic composition which gives a laminate having reproducible physical properties as described above.

(Examples 1 to 7, Comparative Examples 1 to 14) Tetraethoxysilane in a predetermined amount shown in Table 1 and Table 2 in molar ratio,
Basic water and isopropyl alcohol whose pH was adjusted with ammonia were supplied to a magnetic stirrer and mixed at 800 rpm for 2 hours at 20 ° C. to obtain a condensation composition (A).

A predetermined amount of each of tetraethoxysilane, dimethyldiethoxysilane, acidic water whose pH was adjusted by hydrochloric acid, and isopropyl alcohol shown in molar ratios in Tables 1 and 2 were supplied to a magnetic stirrer.
Mixing at 0 ° C. for 2 hours at 20 ° C., condensation composition (B)
I got

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 (C). When the solid content concentration of the obtained inorganic composition (C) does not fall within the range of 1.0 to 4.0% by weight, isopropyl alcohol was added to give the composition shown in Table 1.
And the solid content concentration shown in Table 2 was adjusted, and the inorganic composition was obtained.

Manufacture of Laminate: To the prepared inorganic composition,
The slide glass shown in Table 1 and Table 2 (NAKARA
I, S-2111, 76 mm x 26 mm x 1 mm)
Alternatively, a polycarbonate plate (manufactured by Teijin Ltd., trade name “Teijin Panlite”, 100 mm × 40 mm × 1 mm. In order to improve the film-forming property, the substrate is previously subjected to corona discharge treatment and the distance between the electrode and the substrate is 5 mm. What was performed at 0.5 kV for 1 second was used) was dipped, pulled up at a speed of 300 to 400 mm / min, and then dried at room temperature for 10 minutes to obtain a laminate. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement method, and the results are shown in Table 3.

Tables 1 and 2 and later-described Tables 4, 6, 8, 10, 12, 14, 15, 18, 20, and 2.
1, 24, 25, 28, 29 and 32, tetraalkoxysilane and S1 in the type column of alkoxysilane indicate tetraethoxysilane and S2 indicates dimethyldiethoxysilane. IPA indicates isopropyl alcohol, P in the base material column indicates a polycarbonate plate, and G indicates a slide glass.

In Comparative Example 3, the amount of basic water added during the preparation of the condensation composition (A) was too large.
The amount of acidic water added during the preparation of the condensation composition (B) was too small, and in Comparative Example 9, the mixing ratio of the condensation composition (A) and the condensation composition (B) was too large, so that It could not be applied. In Comparative Example 5, since the amount of acidic water added during the preparation of the condensation composition (B) was too large, after the substrate was dipped in the inorganic composition and dried at room temperature, the film became cloudy. No measurements were taken. Further, in Comparative Example 7, since the pH of the basic aqueous solution at the time of preparing the condensation composition (A) is too high,
In Comparative Example 11, since the amount of the organic solvent at the time of preparing the condensation composition (A) was too small, the condensation composition (A) was gelated and the inorganic composition (C) could not be produced. Comparative Example 12
Because the amount of the organic solvent at the time of preparing the condensation composition (A) is too large, the rate of hydrolysis and polycondensation reaction becomes extremely slow,
The reaction could not be done enough to paint the substrate. Comparative Example 1
In the case of No. 3, the amount of the organic solvent at the time of preparing the condensation composition (B) was too large, and the hydrolysis and polycondensation reaction rates were extremely slow. In Comparative Example 14, since the solid content concentration was low, the film could not be formed successfully.

[0160]

[Table 1]

[0161]

[Table 2]

[0162]

[Table 3]

Examples 8 to 14 and Comparative Examples 15 to 18 Tables were obtained in the same manner as in Example 1 except that the organic solvent used in Comparative Example 18 was diethyl ether (boiling point: 1 atm, 35 ° C.). An inorganic composition was prepared under the conditions shown in 4. The boiling point of isopropyl alcohol was 1 atm.
4 ° C.

The obtained inorganic composition was applied to a substrate in the same manner as in Example 1, left at 23 ° C. for 10 minutes and then supplied to a carbon dioxide supercritical extraction autoclave at 40 ° C.
The laminate was treated with carbon dioxide of 9.0 MPa, then, the obtained dried coating material was supplied to an oven and heated for 30 minutes under the temperature conditions shown in Table 4 to obtain a laminate.

Using the obtained laminate, each physical property was evaluated based on the above-mentioned measuring methods, and the results are shown in Table 5.

[0166]

[Table 4]

[0167]

[Table 5]

(Examples 15 to 21, Comparative Examples 19 to 24)
In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Table 6. The obtained inorganic composition was applied to a substrate in the same manner as in Example 1 and dried at room temperature for 10 minutes. Then
The film surface coated with the above-mentioned inorganic composition was subjected to plasma treatment under the conditions shown in Table 7 using a high frequency sputtering device (manufactured by Nippon Vacuum Technology Co., Ltd., model SH-100) to obtain a laminate. Using the obtained laminate, based on the above measurement method,
Each physical property was evaluated and the results are shown in Table 7.

[0169]

[Table 6]

[0170]

[Table 7]

(Examples 22 to 28, Comparative Examples 25 to 29)
In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Table 8. The obtained inorganic composition was applied to a substrate in the same manner as in Example 1 and dried at room temperature for 10 minutes. Next, in the device (metal electrode 80 mmφ) shown in FIG.
In the electrode space having the distance between the electrodes shown in FIG. 1, a base material on which the inorganic composition coating film is formed on the lower electrode on which a 120 mm × 120 mm square polytetrafluoroethylene having a thickness of 1 mm is mounted as the solid dielectric material 11. Installed, 1 Tor
The oil was pumped down to r with an oil rotary pump.

Next, the oxygen atom-containing gas shown in Table 9 was introduced 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 atmospheric pressure. Then, a voltage was applied to the electrodes at the frequencies shown in Table 9 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 methods, and the results are shown in Table 9.

[0173]

[Table 8]

[0174]

[Table 9]

(Examples 29 to 35, Comparative Examples 30 to 34)
In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Table 10. The obtained inorganic composition was applied to a substrate in the same manner as in Example 1 and dried at room temperature for 10 minutes.

Next, a corona discharge treatment device (Model HFSS, manufactured by Kasuga Denki Co., Ltd.) was applied to the film surface coated with the above-mentioned inorganic composition.
-103) was used to perform a plasma treatment under the conditions shown in Table 11 to obtain a laminate. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 11.

[0177]

[Table 10]

[0178]

[Table 11]

(Examples 36 to 43, Comparative Examples 35 to 39)
In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Table 12. The obtained inorganic composition was applied to a substrate in the same manner as in Example 1 and dried at room temperature for 10 minutes.

Next, the substrate coated with the above-mentioned inorganic composition was placed in the environment shown in Table 13 as "curing temperature and humidity conditions" to obtain a laminate. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 13.

[0181]

[Table 12]

[0182]

[Table 13]

(Examples 44 to 50, Comparative Examples 40 to 46)
In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Tables 14 and 15. The obtained inorganic composition was applied to a substrate in the same manner as in Example 1 and dried at room temperature for 10 minutes. In addition, what is shown as M in the base material column of Tables 14 and 15 is an acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd., product name “Acrylite L-001”, 100 mm × 40 mm ×).
1 mm. Corona discharge treatment was applied to the base material in advance to improve film forming properties.
What was done for a second was used. ).

Next, the substrate coated with the above-mentioned inorganic composition was placed under the environment shown as "curing temperature and humidity conditions" in Tables 16 and 17, and then placed under the environment shown as "curing temperature and humidity conditions". A stack was obtained by placing. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Tables 16 and 17.

(Comparative Example 47) A fluorocarbon resin (manufactured by Asahi Glass Co., Ltd., trade name "CYTOP CTL-102A") was coated with a polycarbonate plate (manufactured by Teijin Ltd., trade name "Teijin Panlite", 100 mm x 40 mm x). 1 mm), and pulling up at a speed of 100 to 300 mm / min, and then 8
It was dried for 1 hour under the conditions of 0 ° C. and 10% relative humidity to obtain a laminate coated on both sides of the base material. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 17.

[0186]

[Table 14]

[0187]

[Table 15]

[0188]

[Table 16]

[0189]

[Table 17]

(Examples 51 to 57, Comparative Examples 48 to 53)
In the same manner as in Example 1, an inorganic composition (C) was prepared under the conditions shown in Table 18. The obtained inorganic composition (C) was applied to a base material (however, the pretreatment of the base material by corona discharge treatment in the case of an organic base material was not performed) in the same manner as in Example 1, and the temperature was kept at room temperature for 10 minutes. Dried in. Next, in Example 51 and Comparative Example 48, the film surface coated with the inorganic composition (C) was 172 nm (7.2 eV) in air.
Was irradiated under the conditions of an irradiation distance of 1 mm and an irradiation time of 120 seconds (using Ushio Denki Co., Ltd., using a via discharge excimer lamp) to obtain a laminate. In addition, in Examples 52 to 57 and Comparative Examples 49 to 52, the film surface coated with the above-mentioned inorganic composition (C) was 254 nm (4.9 eV) in air and 1
84 nm (6.7 eV) light was irradiated under an irradiation distance of 20 mm and an irradiation time of 120 seconds (manufactured by SEN ENGINEERING, using an ultraviolet surface modifier) to obtain a laminate. Using the obtained laminate, based on the measurement method, to evaluate each physical property,
The results are shown in Table 19.

[0191]

[Table 18]

[0192]

[Table 19]

(Examples 58 to 65, Comparative Examples 54 to 60)
In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Tables 20 and 21. The obtained inorganic composition was applied to a substrate in the same manner as in Example 1 and dried at room temperature for 10 minutes. Then, Examples 58 and 65 and Comparative Examples 54 and 60
For, the film surface coated with the above inorganic composition was irradiated with light of 172 nm (7.2 eV) in the atmosphere at an irradiation distance of 1 m.
m and an irradiation time of 120 seconds (using Ushio Electric Co., Ltd., using a via discharge excimer lamp) were irradiated to obtain a laminate. In addition, in Examples 59 to 64 and Comparative Examples 55 to 58, the film surface coated with the inorganic composition was exposed to 2
Conditions of irradiation distance of 20 mm and irradiation time of 120 seconds with 54 nm (4.9 eV) and 184 nm (6.7 eV) light (SE
A laminated body was obtained by irradiation with N ENGINEERING (using an ultraviolet surface modifier). Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Tables 22 and 23.

[0194]

[Table 20]

[0195]

[Table 21]

[0196]

[Table 22]

[0197]

[Table 23]

(Examples 66 to 73, Comparative Examples 61 to 67)
In the same manner as in Example 1, the inorganic composition (C) was prepared under the conditions shown in Tables 24 and 25. The obtained inorganic composition (C) was applied to a base material (however, the pretreatment of the base material by corona discharge treatment in the case of an organic base material was not performed) in the same manner as in Example 1, and the temperature was kept at room temperature for 10 minutes. Dried in. Then
It was placed under the environment shown as curing temperature and humidity conditions in Tables 26 and 27, and then, for Example 66 and Comparative Example 61, the film surface coated with the above-mentioned inorganic composition (C) was subjected to 172 nm (7 Irradiation distance of 1 mm,
Irradiation was carried out under the condition of irradiation time of 120 seconds (using USHIO INC., Using a via discharge excimer lamp) to obtain a laminate. Also,
For Examples 67-73 and Comparative Examples 62-66,
The surface of the film coated with the above-mentioned inorganic composition is 254 in air.
condition (SEN EN for the irradiation distance of 20 mm and the irradiation time of 120 seconds for light of nm (4.9 eV) and 184 nm (6.7 eV)
The laminate was obtained by irradiating with a UV surface modification device manufactured by GINEERING. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Tables 26 and 27.

[0199]

[Table 24]

[0200]

[Table 25]

[0201]

[Table 26]

[0202]

[Table 27]

(Examples 74 to 82, Comparative Examples 68 to 74)
In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Tables 28 and 29. The obtained inorganic composition was applied to a substrate in the same manner as in Example 1 and dried at room temperature for 10 minutes. Then, it was placed in the environment shown as curing temperature and humidity conditions in Tables 30 and 31, and then, for Examples 74, 82 and Comparative Example 68, the film surface coated with the above-mentioned inorganic composition was subjected to 172 nm ( Light of 7.2 eV) was irradiated under the conditions of an irradiation distance of 1 mm and an irradiation time of 120 seconds (using Ushio Electric Co., Ltd., using a via discharge excimer lamp) to obtain a laminate. In addition, Examples 75 to 81 and Comparative Examples 69 to 73
For the above, the film surface coated with the above inorganic composition was exposed to 254 nm (4.9 eV) and 184 nm (6.7 nm) in the air.
eV) light was irradiated under an irradiation distance of 20 mm and an irradiation time of 120 seconds (manufactured by SEN ENGINEERING, using an ultraviolet surface modifier) to obtain a laminate. Using the obtained laminate,
Each physical property was evaluated based on the above-mentioned measuring methods, and the results are shown in Tables 30 and 31.

[0204]

[Table 28]

[0205]

[Table 29]

[0206]

[Table 30]

[0207]

[Table 31]

The following Examples 83, 84 and Comparative Example 75
The evaluation methods of the respective physical properties of the laminates Nos. To 78 were as follows.

(1) Reflectance Using a spectrophotometer (manufactured by Shimadzu Corporation, 60φ integrating sphere accessory "incident angle 8 °"), the light transmittance of the laminated body laminated with the antireflection coating was 300 to 800 nm. The minimum reflectance Rmin is measured in the range, and the one-sided minimum reflectance (R) is measured by the following formula. R = Rmin / 2

(2) Haze value 400-700 using the same device as the above reflectance measurement
The haze value was calculated by measuring the average specular reflectance and the average diffuse reflectance in the wavelength range of nm.

(3) Scratch resistance test The same as the scratch resistance test. (4) Water contact angle 2 μl of water was dropped on the surface of the coating film of the obtained laminate, and a static contact angle was measured by a contact angle meter (Kyowa Interface Science Co., Ltd., contact angle meter CA).
-Measure in A). The contact angle value was an average value of three points in the plane.

(5) Aging Change Test 2 The same as the above Aging Change Test 2. After the thermal shock test was completed, the reflectance, haze value, scratch resistance test and contact angle with water were measured.

(Example 83) In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Table 32. An acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd.,
Acrylite L-001, 100mm x 40mm x 1m
m. In addition, in order to improve the film-forming property, the one which was previously subjected to corona discharge treatment at a distance between the electrode and the substrate of 5 mm and 4.5 kV for 1 second was used. ) Was soaked, pulled up at a speed of 500 mm / min, and then dried at room temperature for 10 minutes to obtain an inorganic composition-coated substrate. The obtained inorganic composition-coated substrate was left under the curing temperature and humidity conditions shown in Table 32 to obtain a laminate. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 33.

(Example 84) In the same manner as in Example 1, an inorganic composition was prepared under the conditions shown in Table 32. A non-glare acrylic base material (Sumitomo Chemical Co., Ltd., Technoloy, 100 mm × 40 mm × 1 mm) was added to the obtained inorganic composition, and a corona discharge treatment was performed in advance to improve the film-forming property. 5 mm at 4.5 kV for 1 second was used) was immersed, pulled up at a speed of 400 mm / min, and dried at room temperature for 10 minutes to obtain an inorganic composition-coated substrate. The obtained inorganic composition-coated substrate is shown in Table 3.
The laminate was left under the curing temperature and humidity conditions shown in 2 to obtain a laminate. An antifouling layer was laminated on the obtained laminate as follows.

Lamination of Antifouling Layer 15 mol of isopropyl alcohol and 4 mol of 1N hydrochloric acid were mixed with 1 mol of methyltrimethoxysilane, and the mixture was stirred at room temperature for 2 hours to obtain a condensation composition. The above-mentioned laminated body is dipped in the obtained condensation composition, and the pulling speed is 50 mm.
After pulling up at a rate of 1 / min, it was dried for 1 hour under the conditions of 80 ° C. and a relative humidity of 10% to obtain a laminate coated on both sides of the base material. Using the obtained laminate, based on the above measurement method,
Each physical property was evaluated, and the results are shown in Table 33.

(Comparative Example 75) A laminate was produced in the same manner as in Example 83 except that the method for producing the inorganic porous coating film was changed to that shown in Table 32. Using the obtained laminate,
Each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 33.

(Comparative Examples 76 and 77) Example 84 was repeated except that the method for producing the inorganic porous coating film was changed to that shown in Table 32.
A laminate was produced in the same manner as in. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 33.

(Comparative Example 78) A non-glare acrylic base material (Sumitomo Chemical Co., Ltd., Technoloy, 100 mm × 40 mm × 1 mm) was applied in a coating solution of a fluororesin (Asahi Glass Co., Ltd., trade name “CYTOP CTL-102A”). Soak, 250
After pulling up at a speed of mm / min, 70 ° C, relative humidity 10
% For 1 hour to obtain a laminate coated on both sides of the substrate. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement methods, and the results are shown in Table 33.

[0219]

[Table 32]

[0220]

[Table 33]

[0221]

The composition of the inorganic composition of the present invention 1 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, the method for producing this inorganic composition is easy to produce, and the obtained inorganic composition is applied onto a substrate and cured to give a porous film having excellent scratch resistance, so that, for example, It is preferably used for producing a laminate used as an antireflection body or the like.
Further, since the solid content concentration is limited to 1.0 to 4.0% by weight, the storage stability is good.

The constitution of the method for producing a laminate of the present invention 2 is as described above, and a laminate used as an antireflection body or the like can be easily produced. Further, on the surface of the obtained laminate, colloidal silica is uniformly dispersed, which is composed of a polycondensation composition of alkoxysilane, is hard to be scratched even when rubbed with a hard material such as steel wool, and is scratched. A porous coating film is formed that is resistant to deterioration of appearance, has excellent scratch resistance, and has a high antireflection effect.

The constitution of the method for producing a laminated body of the present invention 3 and the present invention 4 is as described above, and all the effects of the present invention 2 described above are exhibited. Furthermore, according to the production methods of the present invention 3 and the present invention 4, carbon dioxide in a supercritical state is obtained after the inorganic composition is applied onto a substrate and left to stand, and the organic solvent and water are left in the film. Since it is supercritically dried with, it is possible to completely vaporize the organic solvent and water in the film while leaving pores in the film, and then the dried film is heated, so that the substrate and the film The bond becomes strong.

The construction of the method for producing a laminated body of the present invention 5 is as described above, and all the effects of the present invention 2 described above are exhibited. Furthermore, according to the production method of the present invention 5, since the inorganic composition is applied onto a substrate and then contacted with glow discharge plasma in which an inert gas is excited under a pressure of 1 × 10 ^{−4 to} 100 Torr, Thus, it is possible to easily manufacture a laminated body in which porous coatings having excellent scratch resistance and which do not change with time are laminated. Further, in the method for producing a laminate of the present invention 5, 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 alkoxy groups and organic solvents are used. Is more effectively removed, so that a laminate more suitable for use as an antireflection body or the like can be easily manufactured.

The constitution of the method for producing a laminate of the present invention 6 is as described above, and all the effects of the present invention 2 are obtained. Further, according to the production method of the present invention 6, since the inorganic composition is applied onto the substrate and then brought into contact with the discharge plasma of an inert gas in the vicinity of the atmospheric pressure, it is particularly excellent in scratch resistance and does not change with time. It is possible to easily manufacture a laminated body in which high quality coatings are laminated. Further, in the method for producing a laminate of the present invention 6, 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 alkoxy groups 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 7 is as described above, and all the effects of the present invention 2 described above are exhibited. Furthermore, according to the production method of the present invention 7, since the inorganic composition is applied onto a substrate and then brought into contact with corona discharge plasma, a porous film which is excellent in scratch resistance and does not change with time is provided. For example, a laminate used as an antireflection body or the like can be easily manufactured.

The structure of the method for producing a laminated body of the present invention 8 is as described above, and all the effects of the present invention 2 are obtained. Further, according to the production method of the present invention 8, after the inorganic composition is applied onto the substrate, the inorganic composition is placed in an environment having a relative humidity of 70% or more to carry out a curing treatment, whereby the colloidal silica is uniformly dispersed on the substrate. It is possible to obtain a laminated body formed of a polycondensation composition of an alkoxysilane, which is excellent in scratch resistance and has a high antireflection effect and does not change with time. It is possible to easily manufacture a laminate used as the above.

The construction of the method for producing a laminate of the present invention 9 is as described above, and all the effects of the present invention 2 described above are exhibited. Furthermore, according to the production method of the present invention 9, after the inorganic composition is applied onto the substrate, the inorganic composition is placed in an environment having a relative humidity of 70% or more to perform a curing treatment, and then a temperature of 60 ° C. or more and a relative humidity of less than 70%. By placing in an environment, colloidal silica is uniformly dispersed on the substrate, consisting of a polycondensation composition of alkoxysilane, excellent in scratch resistance and adhesion to the substrate,
Since it is possible to easily obtain a laminate on which a porous coating film having a high antireflection effect and which does not change with time can be easily obtained, for example,
A laminate used as an antireflection body or the like can be easily manufactured.

The construction of the method for producing a laminate of the present invention 10 is as described above, and all the effects of the present invention 2 described above are exhibited.
Furthermore, according to the production method of the present invention 10, after coating an inorganic composition on a substrate, by irradiating with light, a polycondensation composition of an alkoxysilane in which colloidal silica is uniformly dispersed on the substrate, It is possible to easily obtain a laminated body having a porous coating film which has excellent scratch resistance and adhesion to a substrate, and which has a high antireflection effect and does not change with time. The laminate used as can be easily manufactured.

The structure of the method for producing a laminated body of the present invention 11 is as described above, and all the effects of the present invention 2 are obtained.
Further, according to the production method of the present invention 11, after the inorganic composition is applied onto the substrate, the inorganic composition is placed in an environment having a relative humidity of 70% or more to be subjected to a curing treatment, and then the substrate is irradiated with light. A porous polycondensation composition of alkoxysilane in which colloidal silica is uniformly dispersed, which has excellent scratch resistance and adhesion to a substrate, and has a high antireflection effect even in a harsh environment and does not change with time. Since the laminated body having the coating film formed thereon can be easily obtained, for example, a laminated body used as an antireflection body or the like can be easily produced. In addition, since it has a light irradiation step, it is possible to shorten the time required to be placed in a high humidity environment.

The structure of the method for producing a laminate of the invention 12 is as described above, and the concentration of the inorganic composition (C) used in the invention 10 or 11 is limited to 1.0 to 4.0% by weight. Therefore, the stability of the inorganic composition used is good.
Further, all the effects of the invention of the tenth aspect or the eleventh aspect of the invention are exhibited.

Therefore, the laminate obtained by using the method for producing a laminate of the present inventions 2 to 12 is, for example, a spectacle lens,
Glasses such as goggles and contact lenses; car windows,
Automotive fields such as instrument panels and navigation systems; housing and construction fields such as window glass; energy fields such as solar cells, photocells and lasers; laptop computers, electronic organizers, LCD TVs, vehicle TVs, LCD video, projection TVs, optical fibers , Electronic information devices such as optical disks; household products such as lighting gloves, fluorescent lamps, mirrors and watches; commercial fields such as showcases, foreheads, semiconductor lithography, copy machines; LCD game machines, pachinko glass, game machines Can be used for materials in fields such as entertainment fields. Among these, in particular, eyeglass lenses, car windows, instrument panel, navigation system, solar cells, photocells, lasers, laptops, electronic organizers, LCD TVs, vehicle-mounted TVs, LCD videos, projection TVs, optical disks, fluorescent lamps, It can be suitably used as a material for liquid crystal game machines and the like.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a part of an example of a plasma processing apparatus in section.

FIG. 2 is an explanatory view showing a part of an example of a plasma processing apparatus in section.

[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 front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G02B 1/10 G02B 1/10 Z 1/11 A

Claims (12)

[Claims] 1. A pH of 10.0 to 12.0 with respect to 1 mol of a tetraalkoxysilane represented by the general formula Si (OR) ₄ (wherein R is an alkyl group having 1 to 5 carbon atoms). A condensation composition (A) obtained by mixing 2 to 8 mol of basic water and 10 to 30 mol of an organic solvent, and a general formula (R ² ) _n Si
(OR ¹ ) _4-n (In the formula, R ¹ and R ² have 1 to 5 carbon atoms.
Acid group having a pH of 0 to 2.6 with respect to 1 mol of the alkoxysilane represented by the alkyl group of n, n is an integer of 0 to 3).
To 8 mol and 10 to 30 mol of an organic solvent are mixed with the condensation composition (B) to obtain (A) / (B) = 0.4 to
An inorganic composition having a solid content concentration of 1.0 to 4.0% by weight obtained by mixing at 2.4 (weight ratio). 2. A method for producing a laminate, which comprises applying the inorganic composition according to claim 1 on a base material and curing the composition. 3. The inorganic composition according to claim 1, wherein the boiling point of the organic solvent is 60.degree.
A method for producing a laminate, which comprises: leaving at 60 ° C., supercritically drying with carbon dioxide in a supercritical state, and then heating to 80 to 600 ° C. to cure. 4. The inorganic composition according to claim 1, wherein the organic solvent has a boiling point of 60 ° C. or higher, and the organic composition is applied to an organic substrate for 10 to 10 minutes.
A method for producing a laminate, which comprises: leaving at 60 ° C., supercritically drying with carbon dioxide in a supercritical state, and then heating to 80 to 120 ° C. to cure. 5. The curing method according to claim 2, wherein
1 × 10 on the surface coated with the described inorganic composition on the substrate
^-4 . A method for producing a laminate, which comprises contacting glow discharge plasma excited with an inert gas under a pressure of ^{-4 to} 100 Torr. 6. The curing method according to claim 2, wherein:
The substrate coated with the inorganic composition described above is disposed between opposing metal electrodes having a solid dielectric disposed on at least one opposing surface, and the metal electrode is provided under a pressure near the atmospheric pressure of an inert gas. A method for producing a laminate, characterized in that a high voltage is applied in between, and discharge plasma of the generated gas is brought into contact with the surface coated with the inorganic composition. 7. The curing method according to claim 2, wherein
A method for producing a laminate, which comprises bringing corona discharge plasma into contact with the surface coated with the inorganic composition as described above. 8. The curing method according to claim 2, wherein
A substrate coated with the described inorganic composition is treated with a relative humidity of 70
%, The method for producing a laminated body is characterized by placing in an environment of not less than%. 9. The curing method according to claim 2, wherein
A substrate coated with the described inorganic composition is treated with a relative humidity of 70
%, And then the substrate is placed in an environment having a temperature of 60 ° C. or higher and a relative humidity of less than 70%. 10. The general formula Si (OR)_Four(In the formula, R is charcoal
Tetraalkoxy represented by an alkyl group having a prime number of 1 to 5)
A salt having a pH of 10.0 to 12.0 with respect to 1 mol of silane.
Mix 2 to 8 mol of basic water and 10 to 30 mol of organic solvent,
And the general formula (R)²)_nSi
(OR¹)_4-n(In the formula, R¹And R ²Has 1 to 5 carbon atoms
Alkyl group, n is an integer of 0 to 3)
Acidic water having a pH of 0 to 2.6 with respect to 1 mol of silane.
~ 8 mol and 10 to 30 mol of an organic solvent are mixed to obtain
And (A) / (B) = 0.4-
Inorganic substance obtained by mixing at 2.4 (weight ratio)
The composition (C) is applied onto a substrate, and the inorganic composition
It is characterized in that the surface coated with (C) is irradiated with light.
A method for manufacturing a laminated body. 11. The inorganic composition (C) according to claim 10.
Is applied to the base material, and the applied base material has a relative humidity of 70%.
A method for producing a layered product, which comprises placing in the above environment and then irradiating the surface coated with the inorganic composition (C) with light. 12. The method for producing a laminate according to claim 10, wherein the inorganic composition (C) has a solid content concentration of 1.0 to 4.0% by weight.