JPH08224537A - Production of laminate - Google Patents

Abstract

PURPOSE: To obtain a porous film high in reflection preventing effect and not changed with the elapse of time by using an inorg. compsn. obtained by mixing a condensed compsn. consisting of basic water and an org. solvent of tetraalkoxysilane and a condensed compsn. consisting of acidic water and an org. solvent of alkoxysilane. CONSTITUTION: An inorg. compsn. is prepared by mixing a condensed compsn. A prepared by mixing 2-8mol of basic water with pH of 10.0-12.0 and 10-30mol of an org. solvent with 1mol of tetraalkoxysilane represented by Si(OR)4 (wherein R is a 1-5C alkyl group) and a condensed compsn. B prepared by mixing acidic water with pH of 0-26 and an org. solvent with 1mol of alkoxysilane represented by (R<2> )n Si(OR<1> )4-n (wherein R<1> and R<2> are each a 1-5C alkyl group and (n) is an integer of 0-3). This inorg. compsn. is applied to a base material and placed under environment of relative humidity of 70% or more and subsequently placed under environment of temp. 60 deg.C or higher and humidity of below 70% to obtain a required laminated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the production of a laminate having a porous film formed on a substrate, which is excellent in scratch resistance and adhesion to the substrate, has a high antireflection effect and does not change with time. Regarding the method.

[0002]

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

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

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

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

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

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve these problems, and its purpose is to provide an excellent anti-reflection effect with excellent scratch resistance and adhesion to a substrate. It is an object of the present invention to provide a method capable of easily producing a laminate having a porous coating film that is highly stable with time.

[0008]

The condensation composition (A) used in the production of the inorganic composition used in the present invention has a general formula Si (OR) ₄ (wherein R is a group having 1 to 5 carbon atoms). It is obtained by mixing a tetraalkoxysilane represented by an alkyl group), 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.

The condensation composition (B) used for producing the inorganic composition used in the present invention has 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.
Alkyl group, n is an integer of 0 to 3), an alkoxysilane represented by formula (1) is mixed with acidic water and an organic solvent, and the 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 S
It is limited to 10 to 30 mol, and preferably 13 to 18 mol, based on 1 mol of the alkoxysilane represented by i (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 inorganic composition used in the present invention is mixed by mixing the above condensation composition (A) and 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.

The method for producing a laminate of the present invention comprises the steps of applying the inorganic composition obtained by the above method onto a substrate, and applying the obtained inorganic composition to the substrate at a relative humidity of 70%.
The method comprises a step of placing in the environment described above, and then a step of placing the substrate in an environment of a temperature of 60 ° C. or higher and a relative humidity of less than 70%.

The above-mentioned substrate is not particularly limited as long as it can be coated with the inorganic composition, and examples thereof include silicate glass, alkali silicate glass, soda lime glass, potassium lime glass, and lead lime glass. 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 onto the substrate, the film thickness is not particularly limited, but the inorganic composition is applied so that a film having the following relationship with the wavelength at which the antireflection effect is desired is obtained. That is, the antireflection effect can be improved, which is preferable.

D = (1/4 + m / 2) × λ / n

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

When the inorganic composition is applied, it is preferable to dilute it with a solvent to adjust the viscosity of the inorganic composition, if necessary, because the efficiency of applying the inorganic composition onto the substrate is improved. is there. Further, at that time, when the solid content concentration of the inorganic composition is adjusted to a range of 1.0 to 4.0% by weight, the storage stability of the inorganic composition is improved, and the laminated coating film has a film thickness distribution. There is less and it is excellent in aesthetics.

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

When the base material is resin when the inorganic composition is applied, pretreatment such as corona discharge treatment improves the wettability of the coating liquid, resulting in a laminate having an excellent appearance. It is easy to obtain.

In the method for producing a laminate of the present invention, after the step of applying the inorganic composition onto the substrate, first, the substrate on which the obtained inorganic composition is applied is placed in an environment with a relative humidity of 70% or more. Take the step of putting it down. By this step, hydrolysis of residual unreacted alkyl groups in the coating film and polycondensation of residual unreacted silanol groups are promoted. The substrate coated with the inorganic composition may be dried before being placed in the environment where the relative humidity is 70% or more. The drying method is not particularly limited and may be naturally dried at room temperature.

In the present invention, the environment having a relative humidity of 70% or more is preferably 80% or more, more preferably 95% or more. When the relative humidity is less than 70%, the above-mentioned reaction of the residual unreacted alkyl group and the residual unreacted silanol group becomes insufficient.

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.

Although the time for placing in the environment with the relative humidity of 70% or more depends on the relative humidity, if the time becomes short,
Subsequent reaction of the residual unreacted alkyl group or residual unreacted silanol group becomes insufficient, and even if the time is too long, the effect according to the time cannot be obtained. Therefore, usually 24 to 1200 hours are preferable, and 100 to 1000 hours are more preferable. preferable.

In this manner, a laminate having a porous coating film which is not changed with time and has excellent durability is obtained by the step of placing in an environment having a relative humidity of 70% or more.
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, 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.

[0050]

In the method for producing a laminate according to the present invention, the condensation composition (A) undergoes a considerable amount of polycondensation of tetraalkoxysilane to form colloidal silica, and the condensation composition (B) has a weight of alkoxysilane. The condensation does not proceed relatively and is suppressed at the stage of silica sol, and the inorganic composition which is a mixture of both is a mixture of colloidal silica and silica sol. By coating the inorganic composition on a substrate and then placing the substrate coated with the obtained inorganic composition in an environment with a relative humidity of 70% or more, residual unreacted alkyl groups and residual unreacted The silanol groups are removed, the curing of the film is promoted, and a porous film can be obtained due to the difference in the shrinkage rate between silica sol and colloidal silica. Then, by further placing the base material in an environment of a temperature of 60 ° C. or higher and a relative humidity of less than 70%, water in the fine pores of the porous coating film is removed and a condensation reaction at the interface between the base material and the coating film is performed. Can also be promoted, and the adhesion between the substrate and the coating can be further improved.

[0051]

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) Adhesiveness The antireflection coating of the obtained laminated body was formed according to JIS K540
According to 0, a cross-cut tape peeling test was performed and evaluated. (Criteria for Judgment) Good: No peeling occurred. Δ: Partially peeled. ×:
Completely peeled off.

(3) Scratch resistance test The surface of the antireflection coating of the obtained laminate was coated with a flannel cloth.
A load of 1000 g / cm ² was applied, and rubbing was repeated 100 times, and the presence or absence of scratches on the surface was visually observed. (Judgment Criteria) O: No scratch was confirmed. X: Scratches could be confirmed, or the film was peeled off.

(4) Aging Change Test The obtained laminate was kept in an atmosphere of −40 ° C. for 30 minutes, taken out, and immediately thereafter, 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 scratch resistance tests were performed, and changes over time were observed.

(Examples 1 to 6, Comparative Examples 1 to 15) Tables 1 to 1
A predetermined amount of each of tetraethoxysilane shown in a molar ratio in 3, a basic water whose pH was adjusted by ammonia and isopropyl alcohol were supplied to a magnetic stirrer and mixed at 800 rpm for 2 hours at 20 ° C. to form a condensation composition. (A) was obtained.

Predetermined amounts of tetraethoxysilane, dimethyldiethoxysilane, shown in molar ratios in Tables 1 to 3,
Supply acidic water and isopropyl alcohol whose pH was adjusted with hydrochloric acid to a magnetic stirrer, 800 rp
m and mixed at 20 ° C. for 2 hours to obtain a condensation composition (B).

The obtained condensation composition (A) and condensation composition (B) were mixed in the weight ratios shown in Tables 1 to 3 (condensation composition (A)).
/ Condensation composition (B)) was supplied to a magnetic stirrer and mixed at 800 rpm for 2 hours at 20 ° C. to obtain an inorganic composition.

Manufacture of laminate: The obtained inorganic composition was
Base materials shown in Tables 1 to 3 [polycarbonate plate (manufactured by Teijin Ltd.,
Product name "Taijin Pan Light", 100mm x 40mm
X 1 mm) or acrylic resin plate (Mitsubishi Rayon Co., Ltd., trade name "Acrylite L-001", 100 mm x
40 mm × 1 mm)], and 100 to 300 mm /
After pulling up at a speed of a minute, it was dried at room temperature for 10 minutes to obtain a base material in which the inorganic composition was applied to both surfaces of the base material.

Next, the substrate coated with the above-mentioned inorganic composition was placed under the environment shown as "curing temperature and humidity conditions" in Table 4, and then placed under the environment shown as "curing temperature and humidity conditions". A laminated body was obtained. Using the obtained laminate, each physical property was evaluated based on the above-mentioned measurement method, and the results are shown in Table 4.

In Comparative Example 2, the amount of basic water added during preparation of the condensation composition (A) was too large, and in Comparative Example 3, acidic water during preparation of the condensation composition (B). The amount added was too small to be applied to the substrate. Comparative Example 4
Since the amount of acidic water added during the preparation of the condensation composition (B) is too large, the substrate is immersed in the inorganic composition, pulled up, dried at room temperature, and then dried in an environment of 70 ° C. and a relative humidity of 95% for 120 hours. However, the physical properties of the film were not measured because the film became cloudy. In Comparative Example 6, since the pH of the basic water during preparation of the condensation composition (A) was too high, the condensation composition (A) gelled and an inorganic composition could not be obtained.

Comparative Example 8 could not be applied because the mixing ratio of the condensation composition (A) and the condensation composition (B) was too large. In Comparative Example 10, 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 could not be obtained. In Comparative Example 11, the amount of the organic solvent at the time of preparation of the condensation composition (A) was too large, the hydrolysis and polycondensation reaction rates were extremely slow, and the reaction was insufficient, so that it could not be applied to the substrate. .

In Comparative Example 12, the amount of the organic solvent used in the preparation of the condensation composition (B) was too large, so that the hydrolysis and polycondensation reaction rates were extremely slow, and the reaction was inadequate. could not. In Comparative Example 13, since the temperature under the curing temperature and humidity conditions was low, the adhesion between the base material and the coating film was low.
In Comparative Example 14, since the relative humidity under the curing temperature and humidity conditions was high, the adhesion between the base material and the coating was low. Comparative Example 15
Since the relative humidity under curing temperature and humidity conditions was low, sufficient reliability was not obtained.

Comparative Example 16 A polycarbonate resin (manufactured by Asahi Glass Co., Ltd., trade name “CYTOP CTL-102A”) coating solution, a polycarbonate plate (manufactured by Teijin Ltd., trade name “Teijin Panlite”, 100 mm × 40 mm ×) 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 method, and the results are shown in Table 4.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

The structure of the method for producing a laminated body of the present invention is as described above, and when mixing the condensation compositions (A) and (B), stirring is not particularly necessary, and a homogeneous product is obtained. To
It is preferable to stir, but even in such a case, a simple stirrer such as a magnetic stirrer is sufficient as a mixing device, and the mixing of the inorganic composition is similarly uniform colloidal silica. In order to obtain a homogeneous product, it is preferable to stir it when it is dispersed in the alkoxysilane, and it is preferable to stir it. However, even in such a case, as a mixing device such as a magnetic stirrer. A simple stirrer will suffice and can be obtained without the need for high performance equipment. Therefore, this inorganic composition is easily obtained, and according to the present production method, the obtained inorganic composition is applied onto a base material, subjected to a curing treatment under an environment of relative humidity of 70% or more, and then subjected to a temperature treatment. By placing in an environment of 60 ° C. or higher and a relative humidity of less than 70%, a polycondensation composition of alkoxysilane in which colloidal silica is uniformly dispersed on the substrate, scratch resistance and adhesion to the substrate Since it is possible to easily obtain a laminate having a porous coating that is excellent in antireflection effect and does not change with time, it is possible to easily produce a laminate used as an antireflection body, for example. You can

Therefore, the laminated body obtained by using the method for producing a laminated body of the present invention can be used in, for example, the field of spectacles such as spectacle lenses, goggles and contact lenses; the field of automobiles such as car windows, instrument panel and navigation systems. ;
Housing and construction fields such as window glass; energy fields such as solar cells, photovoltaic cells and lasers; notebook computers, electronic notebooks,
Electronic information devices such as LCD TVs, car-mounted TVs, LCD video, projection TVs, optical fibers and optical disks; household goods such as lighting gloves, fluorescent lamps, mirrors and watches; showcases, foreheads, semiconductor lithography, copy equipment, etc. Commercial field: It can be used as a material in fields such as liquid crystal game machines, pachinko table glasses, and entertainment fields such as game machines. Among these, especially eyeglass lenses, car windows, instrument panels, navigation systems, solar cells,
It can be suitably used as a material for photocells, lasers, notebook computers, electronic notebooks, liquid crystal televisions, in-vehicle televisions, liquid crystal videos, projection televisions, optical disks, fluorescent lamps, liquid crystal game machines, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 17/06 B32B 17/06 27/00 101 27/00 101 27/20 27/20 Z G02B 1 / 11 G02B 1/10 A

Claims (1)

[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
2.4 (weight ratio), the step of applying the inorganic composition mixed on the substrate, the step of placing the substrate coated with the obtained inorganic composition in an environment of relative humidity 70% or more, A method for producing a laminate, comprising a step of placing a substrate in an environment having a temperature of 60 ° C. or higher and a relative humidity of less than 70%.