JPH0384043A - Polycarbonate molded body coated with silicon oxide and its production - Google Patents

Abstract

PURPOSE:To obtain the subject molded body, excellent in durability, homogeneity and denseness of films and capable of sufficiently coating disk substrates, etc., in an uneven form into a thin film by successively laminating cured layers of a silicon compound and silicon dioxide films on a polycarbonate molded body. CONSTITUTION:The objective molded body obtained by coating and curing the surface of a polycarbonate molded body with one or two or more silicon compounds, expressed by formula I (R<1> is group containing amino group; R<2> is 1-6C alkyl; R<3> is 1-6C alkyl or alkoxyalkyl; (m) is 1-3; (n) is 0 or 1-2; (m+n)<=3) and having amino group, further coating and curing the resultant surface with a partial hydrolyzate of one or two or more tri- or tetrasubstituted silicon compounds expressed by formula II (R<4> is group having 1-6C alkyl, vinyl, etc.; R<5> is 1-6C alkyl, alkoxyalkyl, etc.; (n) is 0 or 1), bringing a silicon dioxide film into contact with a hydrosilicofluoric acid solution in a supersaturated state of silicon dioxide and laminating the resultant silicon dioxide films.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a plastic molded article whose surface is coated with a highly durable silicon dioxide coating, and a method for producing the same.

[Prior Art] A method of reducing the gas permeability of plastic by coating a plastic molded body with silicon oxide such as SiO, SiO2, etc. has conventionally been applied to food packaging films (for example, Japanese Patent Laid-Open No. 53-12953) or discs. It is applied to substrates (for example, Japanese Patent Laid-Open No. 58-32238).

Vacuum methods such as vapor deposition and sputtering are usually employed as these film forming methods.

On the other hand, as a method for producing a silicon dioxide film, in addition to these methods such as vapor deposition and sputtering, a silicon dioxide film is formed on the surface of the base material by immersing the base material in an aqueous solution of hydrosilicofluoric acid that is supersaturated with silicon dioxide. A method for forming the oxide (hereinafter abbreviated as "precipitation method") is known (for example, JP-A No. 62-20876).
.

Furthermore, a method of forming a silicon dioxide film on a plastic molded body, particularly a polycarbonate molded body, by a precipitation method is disclosed in JP-A-61-12734, in which organic silicon compounds, their hydrolysates, colloidal silica, etc. A first coating composition comprising a silicon compound containing a silicon compound having an amino group is coated and cured.
A method is known in which a silicon dioxide film is formed on the first film by a precipitation method after forming a second film (for example, in Japanese Patent Application Laid-Open No.
132640).

[Problems to be solved by the invention] When forming a silicon dioxide film on the surface of a plastic molded body by conventional vacuum methods such as M deposition or sputtering, ■ gas is generated from the plastic molded body, so it takes a long time to vacuum. It takes.

■ Therefore, it is difficult to obtain a high-quality film.

(2) It is impossible to simultaneously form a film on both sides of a plastic substrate or film.

(2) The obtained film has poor adhesion to the resin substrate and is easily peeled off due to temperature and humidity loads.

There were problems such as. - On the other hand, according to the precipitation method, compared to the silicon dioxide film formation method using the vacuum method, (1) film formation is possible at a temperature below the deformation temperature of plastic.

■ Simultaneous film formation is possible on both the front and back sides.

■ The resulting silicon dioxide film is highly dense even without firing.

It is expected that the above-mentioned effects will be achieved and the problems of the above-mentioned sputtering or vapor deposition methods will be solved to some extent.

However, in order to obtain a silicon dioxide film that is uniform, transparent, and has strong adhesion to a plastic molded body using the precipitation method, it is necessary to coat and harden silicon compounds such as organosilicon compounds, their hydrolysates, and colloidal silica. The first to be
It is necessary to make the subsequent coating as thick as 0.5 to 30 μm. For this reason, ■ "Cracks" and '6 cracks' occur due to temperature and humidity loads.
occurs.

■ When applied to plastic films, there is no flexibility in bending or folding, resulting in film peeling.

(2) When applied to a disk substrate, the surface shape is damaged by the primary film formation.

There are problems such as.

If the plastic is limited to polycarbonate, silicon dioxide with excellent durability can be produced by precipitation method even if the thickness of the primary coating is reduced to less than 10 nm by containing a silicon compound having an amino group in the primary coating. It is possible to obtain a coating. This has made it possible to apply the method to film-like molded bodies, and it has also become possible to coat molded bodies with fine surfaces with silicon dioxide without damaging the surface shape.

However, (1) Even if a polycarbonate substrate and a glass substrate are simultaneously coated with silicon dioxide by a precipitation method, the silicon dioxide coating obtained on polycarbonate may be thinner than that obtained on glass.

(2) Depending on the conditions of the precipitation method, silicon dioxide particles may be incorporated into the silicon dioxide film, causing uneven cloudy areas to be observed or deterioration of the film quality of the silicon dioxide film.

There were some problems.

[Means and effects for solving the problems] The present invention solves the above conventional problems by covering a plastic molded product, especially a polycarbonate molded product, with a highly durable and uniformly thick silicon dioxide film. , provides a method for manufacturing a substrate that combines the advantages of plastic and glass.

The present invention comprises a) a polycarbonate molded article, b) a layer formed by coating and curing one or more silicon compounds having an amino group represented by the general formula (1), 211 R'@-3i-(OR ') a-m-Il (1) r
In the formula, R1 is an organic group containing an amino group, R2 is an alkyl group having 11 to 6 carbon atoms, R3 is an alkyl group or alkoxyalkyl group having 1 to 116 carbon atoms, m11 is an integer of 1 to 3, and n
is O or an integer from 1 to 2, 1'-th, and m+n≦3
"C) A layer formed by coating and curing one or more partial hydrolysates of trisubstituted or tetrasubstituted silicon compounds of the hydrolyzable substituent represented by general formula (n), and R'n-S i - (OR') a-n (II)
r In the formula, R4 is an alkyl group having 1 to 6 carbon atoms, a vinyl 11 group, an epoxy group, a mercapto group, an organic group having fluorine or chlorine, R8 is an alkyl group having 1 to 611 carbon atoms,
Acoxyalkyl group, acetyyl group, n is 0 or l
"d> Silicon dioxide formed by laminating in the order of a), b), C) and d> a silicon dioxide film formed by contacting the layer C) with a supersaturated aqueous solution of silicon dioxide in hydrosilicofluoric acid The gist is a coated polycarbonate molded article.

In general, when a silicon dioxide film is directly coated on the surface of a plastic molded body by the precipitation method, the adhesion is weak due to the poor reactivity and wettability of the hydrosilicofluoric acid aqueous solution and the plastic.
In addition, only an uneven film can be obtained, but if the plastic molded body is coated with an organic silicon compound and cured in advance, the silanol groups on the surface will become a place for bonding with the silicon component in the aqueous solution of hydrosilicofluoric acid. It is possible to improve the adhesion and unevenness of silicon dioxide films obtained by rolling and precipitation methods.

However, the first method obtained by coating and curing an organosilicon compound
When reducing the thickness of the next coating to several tens of nanometers or less, it is necessary to use an organic silicon compound depending on the type of plastic to obtain a silicon dioxide coating that is uniform and has strong adhesion using a precipitation method. need to be selected.

The present inventors have conducted extensive research on organosilicon compounds suitable for forming a primary coating on polycarbonate molded bodies, and have found that in order to obtain a silicon dioxide coating with strong adhesion, the following formula A silicon compound having an amino group represented by (1) is optimal, and a hydrolyzate of a silicon compound represented by formula (II) above is optimal in order to obtain an even and uniform silicon dioxide coating. The present invention was completed based on this discovery.

The present invention will be explained in detail below.

In the present invention, the general formula (1) used for forming layer b)
) As a silicon compound having an amino group represented by γ
-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,
Examples include N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

These silicon compounds may be used alone or in combination of two or more.

In addition, examples of the silicon compound represented by the general formula (II) used for forming layer C) include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, vinyl (β-methoxysilane), ethoxy)silane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. These hydrolysates are defined by the formula (
(2) Silicon compounds in which part or all of the alkoxy, alkoxyalkoxy, or acetoxy groups in the silicon compound are substituted with a hydroxyl group, as well as those in which some of the substituted hydroxyl groups are naturally condensed with each other. I'm here. These hydrolysates can be easily obtained, for example, by hydrolysis in a mixed solvent such as water and alcohol in the presence of an acid.

These hydrolysates may be used alone or in combination of two or more types, but when using two or more types in combination, -
It is preferable to use a co-hydrolyzed mixture of two or more silicon compounds represented by the formula (If).

In the present invention, the layer b) is formed by coating a polycarbonate molded body with a coating liquid containing one or more silicon compounds having an amino group represented by formula (1) above and drying it. The coating liquid has a silicon compound content having an amino group of 10-3 g+ol/, Q or more, 1
It is preferable to adjust it by dissolving it in various solvents so that it becomes 0-'mol/,Q or less.

It is not appropriate to use a coating liquid with a concentration of less than 10-3 mol/ρ, as the adhesion strength of the silicon dioxide coating obtained by the precipitation method tends to decrease. In this case, b) is not suitable because it tends to cause whitening of the layer.

Coating methods for forming layer b) include the commonly used dipping method, spin code method, blow coat method, bar coder method, doctor blade method, spray method, reverse roll coater method, and gravure roll coater. - Any method can be adopted, and 40% after coating.
By drying and curing at a temperature above .degree. C. and below the deformation temperature of the base material, layer b) having excellent durability and adhesion can be obtained.

b obtained in this way on a polycarbonate molded body
) layer, although it is difficult to measure the film thickness, it is difficult to measure the thickness of the glass substrate (
For example, when a film is created under similar conditions on ordinary plate glass, soda lime glass, etc.
It has a thickness of about nm.

b) Applying a coating liquid containing one or more partial hydrolysates of silicon compounds represented by formula (If) to the polycarbonate molded body in which Fl has been formed;
Drying forms c) Fl. Here, C〉
The reason for forming the layer is to improve the film formability of the silicon dioxide film by the precipitation method. c) without forming Fl b)
When a polycarbonate molded body formed with only N and a glass substrate are simultaneously coated with silicon dioxide by a precipitation method, the silicon dioxide coating obtained on the polycarbonate molded body will be thinner than that obtained on the glass substrate. There are cases.

In addition, if the deposition method is used to form a film with only the b) layer formed, the silicon dioxide particles present near the liquid surface of the aqueous silicofluoric acid solution, which is supersaturated with silicon dioxide, are likely to be picked up, and the resulting These particles are incorporated into the silicon film, causing non-uniform cloudy areas to be observed and deterioration of the quality of the silicon dioxide film.

C) Layer formation is a measure to solve such defects by bringing the outermost surface of the polycarbonate molded body before coating with silicon dioxide by the precipitation method to the glass surface, and is based on the above-mentioned formula (I
There is no effect unless the silicon compound represented by I) is hydrolyzed and used.

Further, the coating liquid used is a partial hydrolyzate of a silicon compound represented by the general formula (II).
If it is less than 10-3 of/, Q in terms of z, it is not suitable because the effect of solving the above-mentioned drawbacks will be reduced.

Coating methods for forming the above C) layer include the commonly used dipping method, spin code method, flow coat method, bar coder method, doctor blade method, spray method, reverse roll coater method, and gravure roll coater. - After coating on the above layer b) by a method etc.
By drying and curing at a temperature above .degree. C. and below the deformation temperature of the base material, a layer C) having excellent durability and adhesion can be obtained.

The minimum thickness of the C) layer obtained in this way is approximately 1 nm when the thickness of each layer is determined by laminating the C) layer multiple times on a glass substrate under similar conditions.

In addition, b) layer and C) as a brimer for the precipitation method
Instead of having a two-layer structure, if a mixture of a silicon compound having an amino group represented by formula (■) and a hydrolyzate of a silicon compound represented by formula (II) is used, a white precipitate will form. This is not desirable as it tends to occur easily.

In the present invention, the polycarbonate molded article on which the layers b) and C) have been formed is then brought into contact with a supersaturated aqueous solution of hydrosilicofluoric acid containing silicon dioxide to form a silicon dioxide film on the layer C). .

A supersaturated silicofluoric acid aqueous solution of silicon dioxide (hereinafter referred to as
It is abbreviated as "processing liquid". > After dissolving silicon dioxide (silica gel, Aerosil, silica glass, other silicon dioxide-containing materials, etc.) in an aqueous solution of hydrosilicofluoric acid, water or a reagent (boric acid, aluminum chloride, metallic aluminum, etc.) is added. Silicon dioxide is brought into a supersaturated state by adding or raising the temperature of the processing solution.

In the present invention, the concentration of the treatment liquid that is brought into contact with the polycarbonate molded body to form the b) layer and the C) layer is 1
〜3+wol/, Q is preferable, and in particular, silicon dioxide is saturated in a hydrosilicofluoric acid aqueous solution having a concentration higher than 3Ilol/, and then diluted with water to obtain a concentration of 1 to 3μ/jJ.K is the film formation rate. This method is desirable because it allows for fast and efficient film formation.

In addition, the treatment liquid (a) also has the following properties when in contact with the compact: (1) an aqueous solution of additives such as boric acid or aluminum chloride is continuously added and mixed; and (2) metals such as aluminum are dissolved and mixed. ■It is a processing liquid whose supersaturation level is maintained at all times by means such as temporarily cooling the temperature to saturate silicon dioxide, and then raising the temperature again. It is preferable that 3% or more of the treatment liquid is the treatment liquid that is filtered through a filter and returned.

At the time of contact, it is preferable to (1) continuously add and mix an aqueous solution such as boric acid or (2) dissolve and mix a metal such as aluminum in order to improve the rate of film formation. In the case of boric acid, The amount added is 5X 10-'sol/Hr to 1 vol of hydrosilicic acid in the treatment solution
The range of X 10-”mol/Hr is preferable, and
When metallic aluminum is dissolved, the amount dissolved is I x 10" per 1 mol of hydrosilicic acid in the processing solution.
The range of mol/Hr to 4X 10-3 mol/Hr is preferable.

Further, circulating the treatment liquid at a concentration of 3% or more is effective for continuously obtaining a homogeneous coating, and filtering the treatment liquid with a filter is preferable for obtaining a coating without unevenness.

When the treatment liquid is placed in a dipping tank and brought into contact with the molded body, it is necessary to allow the treatment liquid to flow in a laminar flow on the surface of the molded body during immersion in order to obtain an even and homogeneous coating. effective.

FIG. 1 shows a system diagram of the silicon dioxide-covered MfM manufacturing apparatus used in the present invention.

In FIG. 1, the immersion tank consists of an outer tank 1 and an inner tank 2, and the space between the inner tank 1 and the outer tank 2 is filled with water 3.

This water is heated with a heater 4 to maintain a constant temperature and is stirred with a stirrer 6 to make the temperature distribution uniform.

The inner tank 2 consists of a front part 6, a middle part 7, and a rear part 8, and each part includes:
It is filled with an aqueous solution of hydrosilicofluoric acid of a predetermined concentration of 6.5 liters, which is made by dissolving and saturating silicon dioxide using industrial silica gel powder as a source of silicon dioxide.

Here, the three-way cock 13aS 13a' 13b.

13b' and operate the circulation bong 112a to pump out a certain amount of the reaction liquid from the rear part 8 of the inner tank and pass it through the filter 11a.
Circulation of the treated liquid, which was filtered and returned to the inner tank 6, was started.

Here, the mesh of the filter 11a was 1.5 μm, and the reaction liquid circulation flow rate was set to 520 mJ7/min (since the total amount of the reaction liquid was 6.51, the circulation flow rate was about 8%/min).

Thereafter, three A1 plates 15 each having a length of 50 mm, a width of 50 mm, and a thickness of 3 mm were immersed in the rear part 8 of the inner tank, and the stirrer 16 was activated to promote dissolution of the AN plates.

By maintaining this state for 16 to 30 hours, the reaction solution became a processing solution having an appropriate degree of silicon dioxide saturation (capable of forming a silicon dioxide film).

When the reaction solution has the ability to form a silicon dioxide film, silicon dioxide is generated in the form of particles in the reaction solution and grows.
Eventually, it is filtered by the filter 11a, causing the filter to become clogged. This tendency was observed 30 to 50 hours after the addition of Ap, resulting in a decrease in the amount of circulation. Therefore, after returning the reaction liquid in the piping and filter 11a to the inner tank 2, the reaction liquid is circulated from the rear part of the inner tank 8 to the filter 11b.
When the three-way cocks 13a, 13a', 13b, and 13b' were set so that the circulation pump 12a → the front part 6 of the inner tank and the circulation of the reaction liquid was restarted, the circulation rate of the reaction liquid was again 520 m p /min. I have recovered. Here, the mesh of the filter 11b is 1.6μ like the filter 11a.
In this state, the circulation pump 12b is operated, and the 5% hydrofluoric acid aqueous solution 10 is circulated in the order of cleaning liquid tank 9 → filter 11a → circulation pump 12b → cleaning liquid tank 9, thereby preventing clogging of the filter 11a. was washed and regenerated.

According to the above procedure, each time the filter is found to have a clogging tendency, the three-way cocks 13a, 13a' 13b, 13b
A silicon dioxide coating could be continuously obtained by immersing a polycarbonate molded body coated with glass or various silicon compounds in the inner tank middle part 7 for a predetermined time while adjusting the temperature and switching the filter.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples, and Reference Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist thereof. Add 0.5 g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane to 250 g of isopropyl alcohol.
Solution dissolved in mρ (silicon compound concentration approximately 9X 10-'
a + ol/J ) bath, length and width 100 mm each, thickness 1 m
A polycarbonate flat plate of m was immersed vertically, pulled up at a speed of 15 cm/min, and then dried in a hot air drying oven at 50° C. for 30 minutes to form layer b). When 104 layers b) were laminated on a glass substrate under the same conditions as the above operation, the film thickness was approximately 50 nm.

While mixing 100 g of tetraethoxysilane and 100 g of distilled water, 0.5 m of 0.1N hydrochloric acid, Q, was added, followed by stirring for 30 minutes to obtain a homogeneous solution. This hydrolysis solution 2
A solution prepared by diluting g with 250 mu of isopropyl alcohol (S i 02 equivalent solid content concentration approximately 1.9 x 10"
After crushing the polycarbonate plate on which the above b) N was formed in mol/p) and pulling it up at a speed of 15 cm/min,
It was dried for 30 minutes in a warm air drying oven at 0.degree. C. to form layer C) on layer b). C on the glass substrate under exactly the same conditions as the above operation.
) layers are stacked, and the film thickness is approximately 50 nm.
Met.

A silicon dioxide film is formed by dipping the polycarbonate flat plate obtained by laminating layers b) and c) in this order together with a glass substrate in the inner tank middle part 7 of the silicon dioxide film manufacturing apparatus shown in FIG. 1 for 80 minutes. did.

In addition, the temperature of the hydrosilicofluoric acid aqueous solution circulating in the silicon dioxide coating production apparatus was 2.5*ol/j:, and the heater 4 was adjusted so that the temperature during film formation was 35 ° C. .

When the film thicknesses of the silicon dioxide films obtained on the polycarbonate flat plate and the glass substrate were examined as described above, both were found to be 1100 nm. This film-formed area was examined using X-ray photoelectron spectroscopy (
ESCA; Electr.

n5pectroscopy for Ana
As a result of analysis using lys is), it was confirmed that ° consists mostly of 5j02.

The silicon dioxide coating obtained on the polycarbonate flat plate is
In a test in which cellophane adhesive tape was applied and peeled off, it was found to have strong adhesion that did not come off at all. Also,
The polycarbonate plate coated with silicon dioxide was immersed in boiling water for 1 hour, but there was no change in adhesion.

Example 2 100 g of r-glycidoxyprobyltrimethoxysilane
and 0.1N hydrochloric acid while mixing 100gtt of distilled water.
After adding 5m and Q, the mixture was stirred for 30 minutes to obtain a homogeneous solution. Using a solution obtained by diluting 6 g of this hydrolyzed solution with 250 mN isopropyl alcohol (R'SiOl, s equivalent solid content concentration of about 4.2 x 10-2 sol/N), the same procedure as in Example 1 was carried out. Layered length and width 100mm
, layer C) was formed on a polycarbonate flat plate with a thickness of 1 mm. When layer C) was formed on a glass substrate under the same conditions as the above operation, the film thickness was approximately 20 nm.

The obtained layer b) and layer C) were laminated in this order on a polycarbonate flat plate, and the same procedure as in Example 1 was applied to a glass substrate.
A silicon dioxide film was created under conditions that allowed a 100n silicon dioxide film to be obtained.

The silicon dioxide film obtained on the polycarbonate flat plate had a thickness of 1100 nm and was transparent and uniform. In addition, in a test in which cellophane adhesive tape was applied and peeled off, it had a strong adhesion that did not come off at all.

Comparative Example 1 A silicon dioxide film was formed in the same manner as in Example 1 except that a polycarbonate flat plate on which only the b) layer was formed without forming the C) layer was used, under the conditions that a 1100n silicon dioxide film was obtained on the glass substrate. was formed. However, the thickness of the silicon dioxide film obtained on the polycarbonate flat plate was 85 nm, which was smaller than the film thickness of 1100 nm obtained in Example 1.

From the results of Example 1.2 and Comparative Example 1, it is clear that the formation of layer C) has a positive effect on the film formability of silicon dioxide by the precipitation method.

Comparative Example 2 B) No layer was formed and only layer C) was formed 1) Same as Example 1 except that a carbonate flat plate was used, under conditions that a silicon dioxide coating of 1100N was obtained on the glass substrate. Form a silicon dioxide film.k.

The silicon dioxide film obtained on the polycarbonate flat plate had a thickness of 1100 nm and was transparent and uniform. However, in a test in which cellophane adhesive tape was applied and peeled off, it peeled off easily, indicating that the adhesive strength of the film was weak.

Example 1. From the results of Comparative Example 2, it is clear that the formation of layer b) improves the adhesion of the silicon dioxide film formed by the precipitation method and makes it stronger.

Example 3 A solution of 1 g of r-aminopropyltriethoxysilane dissolved in 400 rrl of isopropyl alcohol and 100 mJ2 of 1-butyl alcohol (silicon compound purity approximately 9 x 1
0-”mol/J) length and width 100mm% thickness 1mm
A polycarbonate flat plate was immersed and pulled up at a speed of 15 cm/min, then dried for 30 minutes in a hot air drying oven at 50°C.
> layer was formed.

10 layers of b) were deposited on the glass substrate under exactly the same conditions as the above operation.
When the layers were laminated, the film thickness was approximately 30 nm.

Hydrolyzate solution containing tetraethoxysilane as l component (
Solid content temperature 8%, C3GL-0803 (manufactured by Chisso ■)
〉2g dissolved in 400mp of isopropyl alcohol and 100m4 of l-butyl alcohol (Si02
The polycarbonate plate on which the above b) layer was formed was immersed in a converted solid content concentration of approximately 2.7 x 10” mol, l),
It was pulled up at a speed of 15 cm/min and then dried in a hot air drying oven at 50°C for 30 minutes to form layer C) on layer b). When ten layers of C) were laminated on a glass substrate under exactly the same conditions as the above operation, the film thickness was approximately 50 nm.

The obtained Thb) layer C) layer was laminated in this order, and the polycarbonate flat plate was immersed and held for 80 minutes together with the glass substrate in the inner tank middle part 7 of the silicon dioxide coating production apparatus shown in FIG. 1 to form a silicon dioxide coating. did. The concentration of the hydrosilicofluoric acid aqueous solution used was 2.5 mol/J, and the temperature during film formation was set at 35°C.

As described above, the thickness of the silicon dioxide film obtained on the polycarbonate flat plate and the glass substrate was examined and found to be 1100 nm for both.

The silicon dioxide coating obtained on the polycarbonate flat plate is
In a test in which cellophane adhesive tape was applied and peeled off, it was found to have strong adhesion that did not come off at all. Also,
The polycarbonate plate coated with silicon dioxide was immersed in boiling water for 1 hour, but there was no change in adhesion.

Example 4 While mixing 50 g of tetraethoxysilane, 50 g of γ-methacryloxypropyltrimethoxysilane, and 100 g of distilled water, 0.5 ml of 0.1N hydrochloric acid was added and stirred for 30 minutes to obtain a homogeneous solution. 15g of this co-hydrolyzed mW is
The b> layer was prepared in the same manner as in Example 3 using a solution diluted with isopropyl alcohol of 50 m, Q (S i 02 + R'S iO +, s-equivalent solid content concentration of about 4.4X 10-2 mol/fI). Formed length and width 100mm,
Layer C) was formed on a polycarbonate flat plate with a thickness of 1 mm. When a layer C was formed on a glass substrate under exactly the same conditions as the above operation, the film thickness was approximately 20 nm.

The obtained layer B〉layer C〉 layer was laminated in this order on a polycarbonate flat plate, and the same procedure as in Example 3 was applied to a glass substrate.
A silicon dioxide film was created under conditions that allowed a 100n silicon dioxide film to be obtained.

The silicon dioxide film obtained on the polycarbonate flat plate had a thickness of 1100 nm and was transparent and uniform. In addition, in a test in which cellophane adhesive tape was applied and peeled off, it had a strong adhesive strength that did not peel off at all. The silicon dioxide-coated polycarbonate flat plate was immersed in boiling water for 1 hour, but there was no change in adhesion.

Example 5 1 g of N-(β-aminoethyl)-γ-7 minopropylmethyldimethoxysilane was dissolved in 250 g of isopropyl alcohol.
Dissolve in mp solution (silicon compound concentration 1.9X 10
A polycarbonate flat plate having a length and width of 100 mm and a thickness of 1 mm was immersed in -2sol/JD, pulled up at a speed of 15 cm/min, and then dried for 30 minutes in a hot air drying oven at 50°C to form layer b). When layer b) was formed on a glass substrate under exactly the same conditions as the above operation, the film thickness was approximately 20 nm.

100g methyltriethoxysilane and 100gt distilled water
After adding 0.5 mgm of 0.1N hydrochloric acid while mixing, the mixture was stirred for a minute to obtain a homogeneous solution. A solution obtained by diluting 5 g of this hydrolyzed solution with 250 m, Q isopropyl alcohol (R'S i O+, solid concentration in terms of s approximately 5.8
The polycarbonate plate on which the above b) layer was formed was immersed in 10-2 mol/f), pulled up at a speed of 15 cm/min, and then dried in a hot air drying oven at 50°C for 30 minutes to form the c) layer on the b) layer. Formed. When 5 layers of c) FJI were laminated on a glass substrate under exactly the same conditions as the above operation, the film thickness was approximately 4.
It was 0 nm.

The obtained layer b) and layer C) were laminated in this order on a polycarbonate flat plate, and the same procedure as in Example 3 was applied to a glass substrate.
A silicon dioxide film was created under conditions that allowed a 100n silicon dioxide film to be obtained.

The silicon dioxide coating obtained on the polycarbonate flat plate is
The film thickness was 1100 nm, and it was transparent and uniform. In addition, in a test in which cellophane adhesive tape was applied and peeled off, it had a strong adhesion that did not come off at all.

The polycarbonate plate coated with silicon dioxide was immersed in boiling water for 1 hour, but there was no change in adhesion.

Example 6 Example 3 except that the concentration of the hydrosilicofluoric acid aqueous solution used to form a silicon dioxide film by the precipitation method was 3 ol/11.
In the same manner as above, a silicon dioxide film was formed on a polycarbonate flat plate under conditions that resulted in a silicon dioxide film of 1100 nm thick on a glass substrate.

The silicon dioxide film obtained on the polycarbonate flat plate had a thickness of 1100 nm and was transparent and uniform. In addition, in a test in which cellophane adhesive tape was applied and peeled off, it had a strong adhesive strength that did not peel off at all. Further, the polycarbonate flat plate coated with silicon dioxide was immersed in boiling water for 1 hour, but there was no change in adhesive strength.

Comparative Example 3 A silicon dioxide film was formed in the same manner as in Example 6, except that a polycarbonate flat plate was used in which only the layer B was formed without forming the C) layer, and under the conditions that a 1100N silicon dioxide film was obtained on the glass substrate. was formed.

However, the obtained silicon dioxide film was cloudy and uneven, and some areas where the film was not formed were observed.

Reference Example I 0.5 g of N-(β-aminoethyl)-r-aminopropyltriethoxysilane and 1.2 g of vinyltris(β-methoxyethoxy)silane (mixture D was dissolved in 200 mJ7 of isopropyl alcohol and 50 ml of 1-butyl alcohol) vertically into the solution (silicon compound concentration: 0.9% by weight),
A polycarbonate flat plate with a width of 100 mm and a thickness of 1 mm was immersed, pulled up at a speed of 15 cm/min, and then dried in a hot air drying oven at 50° C. for 30 minutes. When a primary film was formed on a glass substrate under the same conditions as the above operation, the film thickness was approximately 10 nm.

The obtained polycarbonate flat plate was coated with silicon dioxide by a precipitation method under the same conditions as in Example 6.

However, the obtained silicon dioxide film was cloudy and uneven, and some areas where the film was not formed were observed.

Example 7 A 100% silicon dioxide film was deposited on a glass substrate in the same manner as in Example 2, except that the temperature for forming a silicon dioxide film by the precipitation method was set at 40°C.
A silicon dioxide film was formed on a polycarbonate flat plate under conditions that allowed a silicon dioxide film of 100 nm in size to be obtained.

The silicon dioxide film obtained on the polycarbonate flat plate had a thickness of 1100 nm and was transparent and uniform. In addition, in a test in which cellophane adhesive tape was applied and peeled off, it had a strong adhesive strength that did not peel off at all. Further, the polycarbonate flat plate coated with silicon dioxide was immersed in boiling water for 1 hour, but there was no change in adhesive strength.

Comparative Example 4 A silicon dioxide film was formed in the same manner as in Example 7, except that a polycarbonate flat plate on which only the b) layer was formed without forming the C> layer was used, under the conditions that a 1100N silicon dioxide film was obtained on the glass substrate. was formed.

However, the obtained silicon dioxide coating was cloudy and uneven. When this cloudy part was observed using an electron microscope, it was found that silicon dioxide particles were incorporated into the silicon dioxide coating.

From the results of Example 6, Comparative Example 3, and Reference Example 1, and the results of Example 7 and Comparative Example 4, it is clear that the formation of C) layer has a positive effect on the uniformity of the silicon dioxide film formed by the precipitation method. It is.

Example 8 Instead of a polycarbonate flat plate with a flat surface, a polycarbonate optical disk substrate (depth 0.07 μm width 0.8 μm) was used.
A silicon dioxide coating (approximately 90 nm grooves with a pitch of 1.6 μm) was used in the same manner as in Example 3, except that
)It was created. When the film was formed and the Th21 portion was observed using an electron microscope and a mirror, it was found that silicon dioxide was formed to a uniform thickness along the fine irregularities of the polycarbonate disk substrate.

Example 9. Comparative Example 5 The following two types of polycarbonate flat plates measuring 50 mm in length and width and 1 mm in thickness were prepared.

■ A silicon dioxide film (10
(Example 9).

■ Silicon dioxide coating (100n) on one side by sputtering method.
m) (Comparative Example 5).

These were left in a constant temperature and humidity chamber maintained at 60° C. and relative humidity of 90±5% for 3 weeks, and then their appearance and adhesion were examined.

The silicon dioxide coating produced by the sputtering method (Comparative Example 5) completely peeled off and disappeared, whereas the silicon dioxide coating produced by the precipitation method (Example 9) had no change in appearance and was a coating with strong adhesion. there were.

Example 10. Comparative Examples 6 and 7 The following two types of polycarbonate flat plates measuring 200 mm in length and width and 1 mm in thickness were prepared.

■ A silicon dioxide film (10
Example 10).

■ Untreated Comparative Example 6.

These were placed in a sealed container, and the relationship between the elapsed time and the degree of vacuum was investigated when the inside of the container was evacuated using a vacuum pump. For comparison, a case where nothing was placed in the container (Comparative Example 7) was also conducted.

Table 1 shows the degree of vacuum when the 2 hour evacuation was continued.

Example 10. From the results of Comparative Examples 6 and 7, it is clear that if a silicon dioxide film is formed on a polycarbonate molded body by a precipitation method, the time required to reach a high vacuum during evacuation can be shortened.

Example 11. Comparative Example 8 The following two types of polycarbonate flat plates measuring 100 mm in length and width and 1 mm in thickness were prepared.

■ A silicon dioxide film (10
(Example 11).

■ Untreated (Comparative Example 8).

Table 1 Table 2 After drying these at 50°C for 24 hours, they were crushed in distilled water and kept for 24 hours. Table 2 shows the results of examining the rate of weight change (water absorption) before and after immersion in distilled water.

[Effects of the Invention] As detailed above, the method for producing a silicon dioxide-coated polycarbonate molded body of the present invention includes coating the surface of a polycarbonate molded body with a coating liquid containing a silicon compound having an amino group represented by general formula (1). By drying and curing,
By coating a very thin silicon-containing film with good adhesion as a first layer, and applying a coating liquid containing a hydrolyzate of a silicon compound represented by general formula (II) thereon and drying and curing, After coating a very thin silicon-containing coating with good adhesion to the first layer as a second layer, the second layer is further coated on top of the second layer.
The method of the present invention creates a silicon dioxide film with good adhesion to the layer. A coating with excellent durability can be formed.

■ In the coating method for forming the first and second layers, a dilute solution of a silicon compound can be used as the coating liquid, so even disk substrates with minute irregularities can be coated with a thin film without damaging the shape. can do.

(2) After the second layer is formed, silicon dioxide is precipitated into a film by contacting with a solution, so it is possible to form a silicon dioxide film that follows the uneven shape of the surface of a polycarbonate disk substrate, etc.

(2) Since the first and second layers can be made very thin, it can also be applied to film-like molded products.

(2) The formation of the second layer improves the performance of silicon dioxide produced by the precipitation method, resulting in a transparent silicon dioxide coating with excellent uniformity.

(2) The resulting silicon dioxide coating has excellent density and can improve the disadvantages of plastics (eg, water absorption, gas permeability, gas release).

Excellent effects such as these can be achieved.

[Brief explanation of drawings]

FIG. 1 is a system explanatory diagram of a silicon dioxide film manufacturing apparatus used to carry out the present invention. l-outer tank, 2-inner tank, 3-water
4-Heater 5-Agitator 6-Front part of inner tank 7-Middle part of inner tank 8-Rear part of inner tank 9-Cleaning liquid tank 10-5% HF aqueous solution 11-Filter 12-Circulation bomb 13-Three-way concrete 14-Polycarbonate molded body

Claims (3)

[Claims] (1) a) Polycarbonate molded body, b) A layer formed by coating and curing one or more silicon compounds having amino groups represented by the general formula (I), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) "In the formula, R^I is an organic group containing an amino group, R^2 is an alkyl group having 1 to 6 carbon atoms, R^3 is an alkyl group or alkoxyalkyl group having 1 to 6 carbon atoms, and m is an alkyl group having 1 to 6 carbon atoms. integer from 1 to 3, n
is 0 or an integer of 1 to 2, provided that m+n≦3” c) Partial hydrolyzate of one or more trisubstituted or tetrasubstituted silicon compounds of the hydrolyzable substituent represented by general formula (II) A layer obtained by hardening the coating, and R^4_n-Si-(OR^5)_4_-_n(II)"
In the formula, R^4 is an alkyl group having 1 to 6 carbon atoms, a vinyl group, an epoxy group, a mercapto group, an organic group having fluorine or chlorine, and R^5 is an alkyl group having 1 to 6 carbon atoms, an axoxyalkyl group, acetyl group, n is 0 or 1" d) A silicon dioxide coating formed by contacting the layer c) with a supersaturated aqueous solution of hydrosilicofluoric acid of silicon dioxide, a), b), c) and d) A silicon dioxide-coated polycarbonate molded body formed by laminating layers in this order. (2) a) On the surface of the polycarbonate molded body b) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) “In the formula, R^1 is an organic group containing an amino group, and R^2 is an organic group containing an amino group. an alkyl group having 1 to 6 carbon atoms, R^3 is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, m is an integer of 1 to 3, n is an integer of 0 or 1 to 2, provided that m+n≦3 One or two silicon compounds having the amino group shown
A coating solution containing 10^-^3 to 10^-^1 mol/l of seeds or more is applied and dried to form a hardened coating layer, c) general formula (II) R^4_n-Si-(OR^5 )_4_-_n(II)
In the formula, R^4 is an alkyl group having 1 to 6 carbon atoms, a vinyl group, an epoxy group, a mercapto group, an organic group having fluorine or chlorine, and R^5 is an alkyl group having 1 to 6 carbon atoms, an axoxyalkyl group, acetyl group, n is 0 or 1'' and a layer of a partial hydrolyzate of one or more trisubstituted or tetrasubstituted silicon compounds having a hydrolyzable substituent group represented by "acetyl group, n is 0 or 1" is coated and cured on the layer b), d) A method for producing a silicon dioxide-coated polycarbonate molded article, which comprises bringing a supersaturated aqueous solution of silicon dioxide into hydrosilicofluoric acid into contact with the layer c) to form a silicon dioxide coating thereon. (3) The layer c) is a partial hydrolyzate of a silicon compound represented by the general formula (II).
The method for producing a silicon dioxide-coated polycarbonate molded article according to claim 2, which is formed by applying and drying a coating liquid containing 10^-^3 mol/l or more in terms of 2.