JPH02206624A - Synthetic resin molded article coated with silicon dioxide and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject molded article having excellent adhesivity, abrasion resistance, weather resistance, chemical resistance, etc., by successively forming a coating layer composed mainly of a specified copolymer and a silicon dioxide coating layer on a molded article of a synthetic resin composed of a polymer containing carbonyl bond. CONSTITUTION:The objective molded article is produced by (1) contacting a molded article of a synthetic resin composed mainly of a polymer having carbonyl bond in the recurring unit with an organic solvent solution containing (A) an aminostyrene derivative having primary amino group or secondary amino group and (B) a comonomer selected from an alpha,beta-unsaturated acid anhydride monomer, a silylated butadiene monomer and a monomer having alkoxysilane group on the side chain and containing double bond, (2) copolymerizing the above components attached to the surface of the molded article to form a primary coating layer composed of a copolymer of the components A and B and finally (3) forming a silicon dioxide coating layer on the primary coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a coated synthetic resin molded article on which a silicon dioxide coating is formed, and more specifically, the silicon dioxide coating has excellent adhesion, wear resistance, and weather resistance. , relates to a coated synthetic resin molded article with improved surface conditions such as chemical resistance, and a method for producing the same.

[Conventional technology]

Techniques for coating synthetic resin molded bodies with metal oxides such as silicon dioxide, metal nitrides, etc. in order to modify the surface thereof are well known.

Conventionally, various methods such as vacuum evaporation, sputtering, ion blating, and plasma CVD have been known as methods for coating metal oxides, etc., but these film forming methods require special equipment or However, it is difficult to form a coating on the surface of a large molded product or a molded product with a complicated shape. Another problem is that the adhesion between the synthetic resin molded body and the coating is insufficient.

Recently, it is no longer necessary to directly coat the surface of a synthetic resin molded body with a silicon dioxide film. A method of creating a silicon dioxide film with good adhesion to the primary film has been proposed (Japanese Patent Application Laid-Open No. 12734/1983), that is, this method:
A primary coating is formed by coating and curing a synthetic resin molded article with at least one silicon compound selected from the group consisting of silicon compounds represented by the following general formula (1), their hydrolysates, and colloidal silica. After that, the synthetic resin molded article with the primary coating is brought into contact with a supersaturated hydrofluorosilicic acid solution of silicon dioxide to form a silicon dioxide coating on the primary coating. This is a method for manufacturing a resin molded body.

R'nS i (R"L-0CI) (wherein R1 is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, an epoxy group, an amino group, a mercapto group, an organic group having fluorine or chlorine, , R2 is one or more bonds/groups selected from an alkoxy group, an alkoxyalkoxy group, an acetoxy group, and a chlorine element, and n is O to 4.) According to this method, compared to the conventional method described above, Since a coating with good durability can be obtained by applying the coating method and a dipping method can be used, it can also be applied to synthetic resin moldings of large or complex shapes.However, this method Although the adhesion between the silicon coating and the brimer is good, the adhesion between the synthetic resin molded body and the brimer is still insufficient.The reason is that there is a strong bond between the silicon compound used as the brimer and the synthetic resin molded body. This is presumed to be due to the fact that almost no chemical bonds are formed.For this reason, in the method described above, the adhesion of the silicon dioxide coating to the synthetic resin molded article is still insufficient.

By the way, among synthetic resin moldings, polycarbonate resin moldings are transparent, have excellent impact resistance, and have good heat resistance, but they have the drawbacks of being easily scratched and worn on the surface, and easily attacked by alkali. There is. Conventionally, various surface hardening coating methods have been proposed, but a coated polycarbonate resin molded article with strong adhesion to a silicon dioxide coating has not been obtained.

Furthermore, as engineering plastics that have carbonyl bonds in their repeating units like polycarbonate, many polymers have been developed and put into practical use, such as polyethylene terephthalate, polyamide, polyether ketone, and polyimide. No improved method for surface modification of synthetic resin molded bodies by coating them with silicon dioxide has been proposed.

[Problems to be Solved by the Invention] An object of the present invention is to provide a synthetic resin molded article having a silicon dioxide film with excellent adhesion.

In addition, it is particularly an object of the present invention to provide a silicon dioxide-coated synthetic resin molded article using a brimer having excellent adhesion to both a synthetic resin molded article mainly composed of a polymer having a carbonyl bond in its repeating unit and a silicon dioxide coating. Our goal is to provide the following.

A further object of the present invention is to provide a silicon dioxide-coated synthetic resin molded article with improved surface conditions such as abrasion resistance, weather resistance, and chemical resistance.

As a result of intensive research in order to overcome the problems of the prior art, the present inventors have developed a synthetic resin molded body mainly composed of a polymer having a carbonyl bond in its repeating unit, such as polycarbonate, with primary amine, non-groups. or an aminostyrene derivative monomer having the 21st amino group and α, β
- contacted with an organic solvent solution containing at least one comonomer selected from unsaturated acid anhydride monomers, silylated putadiene monomers, and monomers having an alkoxysilane in the side chain and having double bonds; Thereafter, the monomer components adhering to the surface of the synthetic resin molded body are copolymerized to form a first coating layer containing a copolymer of the monomer components as a main component, and then on the first coating layer. By forming a silicon dioxide film on the material, the primary coating layer (brimer) is firmly bonded to both the synthetic resin molding and the silicon dioxide film, resulting in a coating with a silicon dioxide film with excellent adhesion. It was discovered that a synthetic resin molded article can be obtained, and the present invention was completed based on this knowledge.

[Means to solve the problem]

That is, the gist of the present invention is as follows.

(1) (A) A synthetic resin molded body mainly composed of a polymer having a carbonyl bond in its repeating unit, (B) an aminostyrene derivative monomer having a primary amino group or a secondary amino group, and α, β-unsaturated A primary component mainly comprising a copolymer with at least one comonomer selected from an acid anhydride monomer, a silylated putadiene monomer, and a monomer having an alkoxysilane in a side chain and a double bond. A silicon dioxide-coated synthetic resin molded article comprising: a coating layer; and (C) a silicon dioxide coating layer formed on the first coating layer.

(2) A synthetic resin molded body mainly composed of a polymer having a carbonyl bond in the repeating unit, an aminostyrene derivative monomer having a primary amino group or a secondary amino group, and an acid anhydride of an α,β-unsaturated acid. After contacting with an organic solvent solution containing a monomer, a silylated butadiene monomer, and at least one type of monomer selected from a monomer having an alkoxysilane in a side chain and having a double bond, the synthetic resin is The monomer components adhered to the surface of the molded article are copolymerized to form a first coating layer mainly composed of a copolymer of the monomer components, and then a silicon dioxide coating is formed on the first coating layer. 1. A method for producing a silicon dioxide-coated synthetic resin molded article, characterized in that it forms a silicon dioxide-coated synthetic resin molded article.

Each component of the present invention will be explained below.

(Synthetic resin molded article) The synthetic resin molded article used in the present invention is mainly composed of a polymer having carbonyl bonds in repeating units. By using a polymer having a carbonyl bond, the primary coating layer containing the above-mentioned specific copolymer as a main component and the surface of the synthetic resin molded article are firmly bonded.

Examples of polymers having a carbonyl bond in the repeating unit include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, wholly aromatic polyester, polyurethane, polyetherketone, polyetheretherketone, polyarylene sulfide ketone, polyamide, polyimide, etc. be able to.

Polymers with carbonyl bonds include not only ketone groups but also acid amide bonds, ester bonds, etc. in the molecular structure (
>C=O) means a polymer having a bond.

These polymers may be used alone or in a blend with each other, or may be used in combination with other polymers, such as various thermoplastic resins such as ABS resin, polystyrene, polyacrylonitrile, polyethylene, polypropylene, and polymethyl methacrylate, to the extent that the object of the present invention is not impaired. may be used in a blend as a minor component.

Further, the shape of the synthetic resin molded product is not particularly limited, and molded products of any shape can be used, from large products to those with complicated shapes.

(Aminostyrene derivative monomer) The aminostyrene derivative monomer having a primary amino group or a secondary amino group used in the present invention includes O-aminostyrene, m-aminostyrene, p-aminostyrene,
p-N-laurylaminostyrene, p-N-stearylaminostyrene, p-N-methylaminostyrene, p-
These include aminostyrene derivatives such as N-ethylaminostyrene; benzylamino derivatives such as p-vinylbenzylamino, p-vinylbenzylethylamino, and m-vinylbenzylamino.

These aminostyrene derivatives can be used alone or in combination of two or more.

(Comonomer) In the present invention, as a comonomer forming a copolymer with the aminostyrene derivative monomer, an acid anhydride monomer of an α,β-unsaturated acid, a silylated putadiene monomer, and an alkoxysilane having an alkoxysilane in the side chain, At least one comonomer selected from monomers having double bonds is used.

α-monomer Examples of α,β-unsaturated acid anhydride monomers used in the present invention include acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride, dimethyl maleic anhydride, etc. can be mentioned.

Silyl butadiene monomer Examples of the silylated butadiene monomer used in the present invention include 1-(trimethoxysilyl)1,3-butadiene, 1-(triethoxysilyl)1,3-butadiene, and the like. .

Examples of monomers having an alkoxysilane in the side chain and a double bond used in the present invention include γ-methacryloxypropyltrimethoxysilane, γ-acroyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyl Trimethoxysilane and the like can be mentioned.

In addition, these comonomers may be used alone or in combination of two or more of the same or different types of monomers (method for forming the first coating layer). First, the first
From an aminostyrene derivative monomer having an amino group or a secondary amino group, an acid anhydride monomer of an α,β-unsaturated acid, a silylated putadiene monomer, and a monomer having an alkoxysilane in the side chain and a double bond. A first coating layer (brimer) mainly composed of a copolymer with one selected comonomer is formed, and then a silicon dioxide coating layer is formed on the first coating layer. By forming the first coating layer, the synthetic resin molded article and the first coating layer are firmly bonded, and the first coating layer and the silicon dioxide coating layer are also firmly bonded.

Brimer 9-5 An aminostyrene derivative monomer having a primary or secondary amino group, an acid anhydride monomer of an α,β-unsaturated acid, a silylated putadiene monomer, and an alkoxysilane having an alkoxysilane in the side chain. and at least one comonomer selected from monomers having a double bond in an organic solvent to prepare a brimer solution.

The organic solvent is not particularly limited, and any organic solvent that can dissolve the monomer component, such as n-hexane, cyclohexane, dioxane, isopropyl alcohol, and methyl ethyl ketone, can be used.

In addition, when the surface of the molded body is slightly dissolved or swollen using a solvent (good solvent) that can dissolve or swell the synthetic resin molded body as an organic solvent, or a mixed solvent of a good solvent and a non-(poor) solvent, The adhesion between the molded body and the brimer layer becomes even stronger.

The ratio of the amitunostyrene derivative monomer and the above-mentioned comonomer depends on the type of each monomer component, but usually,
Molar ratio: 30:70 to 70:30, preferably 4
Use at a ratio of 0:60 to 60:40. In addition to the above monomer components, other copolymerizable monomers may be used as minor components.

As a polymerization catalyst, a radical polymerization initiator such as a peroxide compound or an azo compound may be added if desired.
Furthermore, when copolymerizing by ultraviolet irradiation, a photosensitizer may be added.

Add 1 ml of this brimer solution to a synthetic resin molded body at room temperature (23°C).
before and after) or at a temperature (up to about 40° C.) that does not cause polymerization of the monomer components. Any method can be used to make the contact, such as immersing the synthetic resin molded body in a brimer solution, letting the brimer solution flow down onto the surface of the synthetic resin molded body, or applying with a spin coater or roll coater. . In the case of large-sized or complex-shaped synthetic resin molded articles, the dipping method is preferred.

After bringing the synthetic resin molded body into contact with the brimer solution, the monomer components adhering to the surface of the synthetic resin molded body are heated.
The carbonyl bond of the synthetic resin molding and the primary amino group or secondary amino group in the aminostyrene derivative monomer are bonded by a chemical reaction, and the monomer components are copolymerized simultaneously or subsequently, or the synthetic resin is molded by heating. The carbonyl bond of the body and the aminostyrene derivative monomer are chemically bonded, and then copolymerized by irradiation with an electron beam or ultraviolet rays. Electron beam or ultraviolet irradiation methods are heat resistant (
It is suitable for molded articles using synthetic resins with low heat distortion temperatures. In copolymerization by electron beam or ultraviolet irradiation, it is not necessary to add a polymerization catalyst to the brimer solution. When using the ultraviolet irradiation method, it is preferable to add a photosensitizer.

When using the above polymerization catalyst, for example, 80°C to 150°C
It may be heated at a high temperature of about ℃ for several minutes to about 1 hour.

Of course, these temperatures and heating times can be changed as appropriate depending on the type of synthetic resin, the shape of the molded product, the monomer components, the type of polymerization catalyst, etc. Examples of heating means include a hot air oven. In the case of electron beam irradiation,
The surface of the immersed synthetic resin molded body may be irradiated with energy of about several Mrad to tens of Mrad for several minutes to several tens of minutes. In addition, in the case of ultraviolet irradiation, for example.

It is sufficient to irradiate continuous ultraviolet rays in the wavelength range of 250 to 450 nm using a high-pressure mercury lamp.Of course, in the present invention, the heating means, electron beam irradiation method, and ultraviolet irradiation method are not limited to specific means. do not have.

The average thickness (film thickness) of the brimer can be appropriately determined from about a monomolecular film to about several micrometers, but is usually preferably in the range of about 0.01 micrometers to several micrometers.

Methods for forming a silicon dioxide film on the primary coating layer mainly composed of the above-mentioned copolymer of NiK include a CVD method using silane gas, a sputtering method using a quartz plate as a target, and a method using an organosilicon compound. Examples include a dipping method using an organic solvent, and a precipitation method in which silicon dioxide is immersed in a supersaturated hydrofluorosilicic acid solution to deposit a silicon dioxide film. Among these, the precipitation method is preferred because it is easy to work with and can form a uniform film.

As for this precipitation method, a known method disclosed in detail in JP-A-61-12734 can be applied. A supersaturated hydrofluorosilicic acid solution of silicon dioxide is made by dissolving silicon dioxide (silica gel, aerosil, silica glass, other silicon dioxide-containing materials, etc.) in a hydrosilicic acid solution, and then using water or a reagent (boric acid, Aluminum chloride, etc.) is added to create a supersaturated state of silicon dioxide. The synthetic resin molded body subjected to the brimer treatment may be brought into contact with this treatment liquid. The contact may be carried out by immersing the synthetic resin molded body in the treatment liquid or by allowing the treatment liquid to flow down onto the surface of the molded body, but the immersion method is preferable in order to form a uniform coating.

The concentration of hydrofluorosilicic acid in the treatment solution is preferably 1 to 2 mol/I2, and in particular, after saturating silicon dioxide in an aqueous solution of hydrofluorosilicic acid with a concentration higher than 2 mol/I2, the concentration is diluted with water to give a concentration of 1 to 2 mol/I2. A concentration of 2 mol/i is desirable because the film formation rate is fast and coating can be carried out efficiently. While the synthetic resin molded article is immersed in the treatment solution, it is preferable to continuously add and mix the boric acid aqueous solution, circulate the treatment solution, and filter it through a filter in order to efficiently obtain a homogeneous coating.

The thickness of the silicon dioxide film can be adjusted appropriately depending on the purpose of use, but the purpose of surface modification can usually be achieved with a thickness of several lOO to several i,000.

(2) In conventional primer treatment using a silicon compound such as a silane coupling agent, no strong chemical bond is formed between the primer (primary coating) and the surface of the synthetic resin molded article.

On the other hand, a synthetic resin molded body mainly composed of a polymer having a carbonyl bond in a repeating unit is brought into contact with an organic solvent solution containing an aminostyrene derivative monomer having a primary amino group or a secondary amino group and the comonomer. After that, in the method of the present invention, the monomer components adhering to the surface of the synthetic resin molded article are copolymerized to form a primary coating layer mainly composed of a copolymer of the monomer components. On the surface of the molded article, the carbonyl bond (>C=O>) in the synthetic resin and the primary amino group or secondary amino group in the aminostyrene derivative monomer chemically react to form a chemical bond, and simultaneously or subsequently It is presumed that by copolymerizing the monomer components, the resulting copolymer forms a film firmly bonded to the surface of the molded article.

When the synthetic resin molded article on which the first coating layer has been formed is immersed, for example, in a supersaturated hydrofluorosilicic acid solution of silicon dioxide, the comonomer is α,β-unsaturated because the aqueous solution is acidic. When an acid anhydride monomer is used, the acid anhydride bond in the copolymer is hydrolyzed to form a dicarboxylic acid. In addition, when a silylated putadiene monomer or a monomer having an alkoxysilane in the side chain and a double bond is used as a comonomer, the alkoxysilane residue in the copolymer, for example, -
3L (OCH-) is hydrolyzed to -Si (OH
) - yell. The OH group of this dicarboxylic acid or -5i (
OH), the OH group of Si is deposited on the surface of the primary coating layer.
In the process of polycondensation to Sing, (OH)4 participates in the polycondensation reaction, so it can be assumed that the primary coating and the silicon dioxide film are firmly adhered to each other by chemical bonding.

As described above, since the primary coating layer of the present invention is strongly bonded to both the synthetic resin molded article and the silicon dioxide coating layer, it is possible to obtain a silicon dioxide-coated synthetic resin molded article with excellent adhesion. .

(Margins below) [Examples] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples. The methods for measuring physical properties such as adhesion tests in Examples and Comparative Examples are as follows.

Method for Measuring Physical Properties> On L1 Unis; Attach adhesive tape to the surface of the silicon dioxide-coated synthetic resin flat plate and rapidly peel it off in a 90 degree direction.

When the silicon dioxide film peeled off, it was marked as "X", and when it did not peel off, it was marked as "○". In addition, when a part of the film peeled off, it was marked as △.

The surface of the silicon dioxide-coated synthetic resin flat plate was exposed for 200 hours in a carbon arc type Weatherometer (WE-Sun-DC; manufactured by Toyo Rika Co., Ltd.), and then an adhesion test was conducted. The evaluation method is the same as the adhesion test.

On the nose: After boiling the silicon dioxide-coated synthetic resin flat plate in hot water for 1 hour, an adhesion test was conducted. The evaluation method is the same as the adhesion test.

After leaving the silicon dioxide-coated synthetic resin flat plate in an oven at 80° C. for 50 hours, an adhesion test was conducted. The evaluation method is the same as the adhesion test.

On the stomach: Heat the silicon dioxide-coated synthetic resin flat plate in a constant temperature machine for 65 minutes.
After being left at 95% RH for 3 weeks, an adhesion test was conducted. The evaluation method is the same as the adhesion test.

[Example 1] A primer was prepared by dissolving 1 part of p-aminostyrene, 70 parts by weight of maleic anhydride, and 10 parts by weight of benzyl peroxide in 50 parts by weight of n-hexane.

Add a polycarbonate plate (vertical 10 mm) to this brimer solution.
0mm, width 100mm, thickness 2mm) was immersed for 1 minute, then pulled out and heated at 80°C for 30 minutes in a hot air dryer to separate the carbonyl groups in the polycarbonate and the amino groups of p-aminostyrene. reaction and copolymerization reaction were carried out. The thickness of the obtained primary coating layer was 1 μm.

A silicon dioxide film was deposited on the polycarbonate flat plate subjected to the above treatment using a silicon dioxide film manufacturing apparatus similar to that shown in JP-A-61-12734.

That is, the silicon dioxide coating manufacturing apparatus has a dipping tank consisting of an outer tank and an inner tank, and the space between the inner tank and the outer tank is filled with water. This water is heated with a heater to a temperature of 35° C., and is stirred with a stirrer to make the temperature distribution uniform. The inner tank consists of a front part, a middle part, and a rear part, and each part is filled with an aqueous solution of hydrofluorosilicic acid at a concentration of 2.0 mol/min, which is saturated with silicon dioxide, using industrial silica gel powder as a source of silicon dioxide. It is filled with a 3°C reaction solution diluted to 20% using . At this point, the circulation pump was activated to discharge a certain amount of the reaction liquid from the rear of the inner tank, filter it with a filter, and start circulating the treated liquid back to the front of the inner tank.

Thereafter, a 0.5 mol/β boric acid aqueous solution was continuously poured into the rear part of the inner tank and maintained for 10 hours. In this state, the reaction solution became a treatment solution having an appropriate degree of silicon dioxide supersaturation.

Here, the absolute removal rate of the filter is set to 1.5 μm, and the treatment liquid circulation [ffi is set to 240 mff/min (the total amount of treatment liquid is approximately 3μm).
Therefore, the circulation rate was adjusted to 8%/min).

Then, the polycarbonate plate subjected to the above treatment was immersed vertically in the middle of the inner tank, and the above conditions (0.5 mol/β boric acid aqueous solution was added at 0.2 mj 27 minutes, circulation was performed at 8%/min, 1. Filter with a 1.5 μm filter)
It was held for 6 hours.

The thickness of the silicon dioxide coating layer on the resulting coated polycarbonate plate was approximately 5,000 mm.

Table 1 shows the results of measuring the properties of the silicon dioxide-coated synthetic resin molded article.

[Example 2] A polyurethane flat plate (length 1.00
A polyurethane plate coated with silicon dioxide was obtained in the same manner as in Example 1, except that a polyurethane plate having a width of 100 mm, a width of 100 mm, and a thickness of 1.6 mm was used.

[Example 3] A brimer solution was prepared by dissolving 100 parts by weight of p-N-methylanostyrene, 70 parts by weight of maleic anhydride, and 2 parts by weight of 2,2'-azobisisobutyronitrile in 50 mm parts of isopropyl alcohol. did.

A polyether ether ketone flat plate (length 100 mm, width 100 mm, thickness 2 mm) was immersed in this brimer solution for 1 minute, then taken out and heated in a hot air dryer at 80°C for 10 minutes to remove the polyether Carbonyl bond of ether ketone and NH of p-N-methylaminostyrene
After that, the temperature was raised to 150''C and held for an additional 10 minutes to carry out a copolymerization reaction.The thickness of the obtained primary coating layer was 0.8 μm.

The above-treated polyetheretherketone flat plate was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polyetheretherketone flat plate.

[Example 4] 100 parts by weight of p-aminostyrene, 70 parts by weight of maleic anhydride
A brimer was prepared by dissolving 1 part by weight of benzoin and 1 part by weight of Michler's ketone in 50 parts by weight of methyl ethyl ketone.

A polyethylene terephthalate flat plate (length: 100 mm, width: 100 mm, thickness: 1.6 mm) was immersed in this brimer solution for 1 minute, then taken out, heated at 80°C for 10 minutes in a hot air dryer, and then heated at 2 kW. 2 minutes with a high-pressure mercury lamp (manufactured by Ushio Inc.), wavelength range 250-450
nm (365 nm is the main wavelength, 254.303.4
Continuous ultraviolet rays were irradiated at 05.436 nrn (efficiently emitting radiation). The thickness of the obtained primary coating layer was 1 μm.

The above-treated flat plate was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polyethylene terephthalate flat plate.

[Example 5J A polycarbonate plate coated with silicon dioxide was obtained in the same manner as in Example 1 except that itaconic anhydride was used as the α,β-unsaturated acid anhydride monomer.

[Example 6] 100 parts by weight of p-aminostyrene, 70 parts by weight of maleic anhydride
parts by weight and 10 parts by weight of benzyl peroxide in n-
Brimer was prepared by dissolving it in 50 parts by weight of hexane.

This brimer solution was applied to a polycarbonate disk (outer diameter 130 mm, inner diameter 25 mm, thickness 1
．． 2 mm). Number of spin code swings,
The coating amount was adjusted so that the desired film thickness could be obtained by overcoating. Next, the coated disk was heated at 80° C. for 30 minutes in a hot air dryer to cause a reaction and a copolymerization reaction between the carbonyl groups in the polycarbonate and the amino groups of p-aminostyrene. The thickness of the obtained primary coating layer was 0.5 μm.

The disk subjected to the above treatment was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polycarbonate disk.

[Comparative Example 1] For comparison, a silicon dioxide film was formed in the same manner as in Example 1 on a polycarbonate resin molded body that had not been subjected to the brimer treatment.

Table 1 summarizes the results of measuring the characteristics of the silicon dioxide-coated synthetic resin molded bodies obtained in Examples 1 to 6 and Comparative Example 1.

As is clear from Table 1, the silicon dioxide-coated synthetic resin molded article of the present invention has excellent adhesion and is excellent in weather resistance, heat resistance, moisture resistance, and the like.

On the other hand, in the silicon dioxide-coated synthetic resin molded article of Comparative Example which does not have a primary coating layer, the coating layer easily peels off and
Adhesion was poor.

(Left below) [Example 7J 100 parts by weight of p-aminostyrene, 100 parts by weight of l-(trimethoxysilyl)-1,3-butadiene and 10 parts by weight of benzyl peroxide were dissolved in 50 parts by weight of n-hexane. A brimer solution was prepared.

Add a polycarbonate plate (vertical 10 mm) to this brimer solution.
0mm, width 100mm, thickness 2mm) was immersed for 1 minute, then pulled out and heated at 80°C for 30 minutes in a hot air dryer to separate the carbonyl groups in the polycarbonate and the amino groups of p-aminostyrene. reaction and copolymerization reaction were carried out. The thickness of the obtained primary coating layer was 1 μm.

The flat plate subjected to the above treatment was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polycarbonate flat plate.

Table 2 shows the results of measuring the properties of the silicon dioxide-coated synthetic resin molded article.

[Example 8] A polyurethane flat plate (100 m long) was used as a synthetic resin molded body.
m, width 100 mm, thickness 1. ．． A polyurethane plate coated with silicon dioxide was obtained in the same manner as in Example 7 except that a polyurethane plate having a thickness of 6 mm was used.

[Example 9] 100 parts by weight of p-N-methylaminostyrene, 100 parts by weight of 1-(trimethoxysilyl)-1,,3-butadiene, and 2 parts by weight of 2,2'-azobisisobutyronitrile were added to isopropyl A brimer solution was prepared by dissolving it in 50 parts by weight of alcohol.

A polyether ether ketone flat plate (length 100 mm, width 100 mm, thickness 2 mm) was immersed in this brimer solution for 1 minute, then taken out and heated in a hot air dryer at 80°C for 10 minutes to remove the polyether Carbonyl bond of ether ketone and NH of p-N-methylaminostyrene
, groups, and then the temperature was raised to 150° C. and held for an additional 10 minutes to carry out a copolymerization reaction. The thickness of the obtained primary coating layer was 0.8 μm.

The above-treated polyetheretherketone flat plate was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polyetheretherketone flat plate.

[Example 10] 100 parts by weight of p-aminostyrene, 100 parts by weight of 1-(trimethoxysilyl)-1,3-butadiene, 1 part by weight of benzoin and 1 part by weight of Michler's ketone were dissolved in 50 parts by weight of methyl ethyl ketone to prepare a primer. Prepared.

A polyethylene terephthalate flat plate (length: 100 mm, width: 100 mm, thickness: 1.6 mm) was immersed in this brimer solution for 1 minute, then pulled out and heated in a hot air dryer at 80°C for 10 minutes. Similar to example 4, 2k
Wavelength range 250-450 for 2 minutes with W high-pressure mercury lamp.
Continuous ultraviolet rays were irradiated at nm. The thickness of the obtained primary coating layer was 1 um.

The above-treated flat plate was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polyethylene tere-17 phthalate flat plate.

[Example 11] 100 parts by weight of p-aminostyrene, 100 parts by weight of 1-(trimethoxysilyl)-1,3-butadiene, and 10 parts by weight of benzyl peroxide were dissolved in 50 parts by weight of n-hexane to prepare a brimer solution. Prepared.

This brimer solution was applied to a polycarbonate disk (outer diameter 130 mm, inner diameter 25 mm, thickness 1
．． 2 mm). Number of spin code swings,
The coating amount was adjusted so that the desired film thickness could be obtained by overcoating. Next, the coated disk was heated at 80° C. for 30 minutes in a hot air dryer to cause a reaction and a copolymerization reaction between the carbonyl groups in the polycarbonate and the amino groups of p-aminostyrene. The thickness of the obtained primary coating layer was 0.5 μm.

The disk subjected to the above treatment was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polycarbonate disk.

The results of measuring the properties of the silicon dioxide-coated synthetic resin molded bodies obtained in Examples 7 to 11 are summarized in Table 2.

As is clear from Table 2, the silicon dioxide-coated synthetic resin molded article of the present invention has excellent adhesion and is excellent in weather resistance, heat resistance, moisture resistance, etc.

(The following is a blank space) [Example 12] A brimer solution was prepared by dissolving 100 parts by weight of p-aminostyrene, 130 parts by weight of γ-methacryloxytrimethoxysilane, and 10 parts by weight of benzyl peroxide in 50 parts by weight of n-hexane. .

Add a polycarbonate plate (vertical 10 mm) to this brimer solution.
0 mm, width 100 mm, thickness 2 mm) was immersed for 1 minute, then pulled out and heated at 80°C for 30 minutes in a hot air dryer to separate the carbonyl groups and p-
Reactions and copolymerization reactions with amino groups of aminostyrene were carried out. The thickness of the obtained primary coating layer was 1 μm.

The flat plate subjected to the above treatment was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polycarbonate flat plate.

Table 3 shows the results of measuring the properties of the silicon dioxide-coated synthetic resin molded article.

[Example 13] A polyurethane flat plate (100 m long) was used as a synthetic resin molded body.
A polyurethane plate coated with silicon dioxide was obtained in the same manner as in Example 12, except that a polyurethane plate having a width of 100 mm and a thickness of 1.6 mrn was used.

[Example 14] 100 parts by weight of p-N-methylaminostyrene, 130 parts by weight of γ-methacryloxytrimethoxysilane, and 2.
A brimer solution was prepared by dissolving 2 parts by weight of 2'-azobisisobutyronitrile in 50 parts by weight of isopropyl alcohol.

A polyether ether ketone flat plate (length 100 mm, width 100 mm, thickness 2 mm) was immersed in this brimer solution for 1 minute, then taken out and heated in a hot air dryer at 80°C for 10 minutes to remove the polyether Carbonyl bond of ether ketone and NH of p-N-methylaminostyrene
A chemical reaction was carried out with the I group, and then the temperature was raised to 150° C. and maintained for an additional 10 minutes to carry out a copolymerization reaction. The thickness of the obtained primary coating layer was 0.8 gm.

The above-treated polyetheretherketone flat plate was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polyetheretherketone flat plate.

[Example 15] 100 parts by weight of p-aminostyrene, 130 parts by weight of γ-methacnoloxytrimethoxysilane, 1 part by weight of benzoin and 1 part by weight of Michler's ketone were mixed with 25 parts by weight of methyl ethyl ketone.
Brimer was prepared by dissolving 0 parts by weight.

A polyethylene terephthalate flat plate (length: 100 mm, width: 100 mm, thickness: 1.6 mm) was immersed in this brimer solution for 1 minute, then pulled out, heated at 80°C for 10 minutes in a hot air dryer, and then , similar to Example 4, 2k
Wavelength range 250-450 for 2 minutes with W high-pressure mercury lamp.
Continuous ultraviolet light was irradiated at nm. The thickness of the obtained primary coating layer was 1 μm.

The above-treated flat plate was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polyethylene terephthalate flat plate.

[Example 16] A polycarbonate plate coated with silicon dioxide was obtained in the same manner as in Example 12, except that 130 parts by weight of vinyl acetoxysilane was used instead of γ-methacryloxytrimethoxysilane.

[Example 17] A brimer solution was prepared by dissolving 100 parts by weight of p-aminostyrene, 130 parts by weight of γ-methacryloxytrimethoxysilane, and 10 parts by weight of benzyl peroxide in 50 parts by weight of n-hexane.

This brimer solution was applied to a polycarbonate disk (outer diameter 130 mm, inner diameter 25 mm, thickness 1
．． 2 mm). Number of spin code swings,
The coating amount was adjusted so that the desired film thickness could be obtained by overcoating. Next, the coated disk was heated at 80° C. for 30 minutes in a hot air dryer to cause a reaction and a copolymerization reaction between the carbonyl groups in the polycarbonate and the amino groups of p-aminostyrene. The thickness of the obtained primary coating layer was O,FzLm.

The disk subjected to the above treatment was treated in the same manner as in Example 1 to obtain a silicon dioxide-coated polycarbonate disk.

The results of measuring the properties of the silicon dioxide-coated synthetic resin molded bodies obtained in Examples 12 to 17 are summarized in Table 3.

As is clear from Table 3, the silicon dioxide-coated synthetic resin molded article of the present invention has excellent adhesion, and is excellent in weather resistance, heat resistance, moisture resistance, etc.

(The following is a blank space) [Effects of the Invention] According to the present invention, an aminostyrene derivative monomer having a primary amino group or a secondary amino group, an acid anhydride monomer of an α,β-unsaturated acid, and a silylated putadiene monomer Carbonyl It is possible to obtain a silicon dioxide-coated synthetic resin molded article having a brimer layer with excellent adhesion on both the bonded synthetic resin molded surface and the silicon dioxide coating.

The silicon dioxide-coated synthetic resin molded article of the present invention is
It is a molded product with greatly improved adhesion to silicon dioxide coating, surface hardness, weather resistance, chemical resistance, moisture permeability, moisture absorption, etc., so it can be used, for example, as a substrate for magneto-optical disks, substrates for magnetic disks, and automobiles. It can be used in a wide range of fields, including as a synthetic resin substrate as a substitute for train window glass.

Claims (3)

[Claims] (1) (A) A synthetic resin molded body mainly composed of a polymer having a carbonyl bond in its repeating unit, (B) an aminostyrene derivative monomer having a primary amino group or a secondary amino group, and α, β-unsaturated acid anhydride monomers,
a first coating layer mainly comprising a copolymer of a silylated putadiene monomer and at least one comonomer selected from monomers having an alkoxysilane in a side chain and a double bond, and (C) A silicon dioxide-coated synthetic resin molded article comprising a silicon dioxide coating layer formed on the first coating layer. (2) A synthetic resin molded body mainly composed of a polymer having a carbonyl bond in the repeating unit, an aminostyrene derivative monomer having a primary amino group or a secondary amino group, and an acid anhydride of an α,β-unsaturated acid. After contacting with an organic solvent solution containing at least one comonomer selected from a monomer, a silylated butadiene monomer, and a monomer having an alkoxysilane in a side chain and having a double bond, the surface of the synthetic resin molded body is The monomer components deposited thereon are copolymerized to form a first coating layer mainly composed of a copolymer of the monomer components, and then a silicon dioxide film is formed on the first coating layer. A method for producing a silicon dioxide-coated synthetic resin molded article, characterized in that: (3) A film of silicon dioxide is formed on the first coating layer by contacting the synthetic resin molded article on which the first coating layer has been formed with a supersaturated hydrofluorosilicic acid solution of silicon dioxide. Item 2. A method for producing a silicon dioxide-coated synthetic resin molded article.