JPH05202211A - Abrasion-resistant plastic molding and its production - Google Patents

Abstract

PURPOSE: To provide a plastic molded article excellent in physical properties such as hardness, anti-wear properties and the like.

CONSTITUTION: An anti-wear plastic molded article is characterized by forming a hard film composed of a non-columnar structure of an Si compd. on the surface of the molded article through an intermediate layer or directly. In a Taber abrasion test, the haze change of this molded article after rotation of 5,000 times is 5% or less and, in a micro-abrasion test, this molded article has hardness of 100 kg/mm² or more.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wear-resistant plastic molding provided with a hard film, which is particularly suitable as a vehicle window, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, glass has been mainly used for vehicle windows, but the weight reduction thereof has been a serious problem for the purpose of energy saving and reduction of fuel consumption. As part of this, it is being considered to replace glass with transparent plastic. As an example, the surface of a plastic molded product is coated with organosilicon and cured, or PVD (Physical) such as ion plating is used.
Vapor Deposition) method and plasma CVD (Chemical Vapor Depos)
It is a method of forming a SiO ₂ film by an ionization method.

[0003]

However, a method of coating organosilicon (Japanese Patent Laid-Open No. 57-17702).
Since the film formed by Japanese Patent Laid-Open No. 8 and Japanese Patent Laid-Open No. 61-143445 is an organic substance, it is apt to be scratched in practical use such as a vehicle window, which is a practical problem.
Further, the PVD method (JP-A-58-29835, JP-A-63-114957) has the drawback that it is difficult to form a film uniformly over a wide area and the film formation rate is low.

Plasma CVD method (Japanese Patent Laid-Open No. 64-4343)
In Japanese Patent Laid-Open No. 2-66172), a SiO ₂ film is deposited after coating with organosilicon to enhance the hardness, adhesion and weather resistance of the film, but this is not sufficient, and SiO ₂ film is not sufficient. Wet process of coating organosilicon to deposit film and SiO ₂
Therefore, there is a problem that productivity is poor because two steps, a dry step of depositing hydrogen, are required. Japanese Patent Laid-Open No. 64-4343
The publication describes that the reaction gas may be supplied in a laminar flow with a Reynolds number of 2.5, but there is no mention of the film structure obtained thereby. In addition, the film obtained by this prior art shows a small change in haze of 1% in the Taber abrasion test after 1000 times of abrasion, but a film thickness of at least 5 μ is required to obtain characteristics comparable to Pyrex. In addition, at the number of wear of 5000 times,
The durability of the film deteriorates and haze increases.

The inventors of the present invention have made various studies on the conditions of the plasma CVD method for the purpose of solving the above-mentioned problems, and have made diligent studies on the relationship between the film structure and the film characteristics. Membranes obtained by reacting under certain specific conditions, which are not disclosed in Japanese Patent Laid-Open No. 64-4343,
It has been found that the cross-sectional structure is non-columnar, and the film properties are high in hardness and excellent in wear resistance. Further, it has been found that a film having a columnar cross-sectional structure has poor wear resistance, but has sufficient durability against thermal stress, and that further heat stress resistance can be imparted by using it in combination with a hard film. In addition, ZnO is used as an intermediate layer.
By using as a UV resistant layer, it is possible to efficiently absorb UV rays without impairing the transparency of the plastic molded article, and to find that the plastic molded article does not deteriorate even under a long-term UV irradiation environment. Was completed.

[0006]

That is, the present invention is characterized in that a hard film having a non-columnar structure of a Si compound is formed on the surface of a plastic molded product with or without an intermediate layer. A wear-resistant plastic molded article having a haze change of 5% or less after rotation of 5000 times in a Taber wear test and a hardness of 100 kg / mm ² or more in a micro hardness test. On the surface of molded products and plastic molded products,
Plasma CVD by parallel plate type CVD is performed under the following conditions (1) to (4) with or without an intermediate layer interposed therebetween to form a hard film having a non-columnar structure of a Si compound. Method for producing abrasion-resistant plastic molded article, (1) Reaction temperature is 130 ° C. or less, and pressure is 1.0 torr or less. (2) Velocity gradient of reactive gas 8000 cm / sec · c
m or more and a power density of 0.3 w / cm ³ or less. (3) The reactive gas must contain at least silane. (4) The gas in the reaction chamber is laminar and has a Reynolds number greater than 10.

It is characterized in that a soft film having a columnar structure of Si compound is formed on the surface of a plastic molded product, and a hard film having a non-columnar structure of Si compound is formed with or without an intermediate layer. A soft film having a columnar structure of a Si compound is formed on the surfaces of the wear-resistant plastic molded product and the plastic molded product, and a hard film having a non-columnar structure of the Si compound is formed with or without an intermediate layer. Parallel plate CVD under the following conditions (1) to (3) when producing a wear-resistant plastic molded product
Is used to form a soft film having a columnar structure of a Si compound, thereby producing a wear-resistant plastic molded product. (1) The reaction temperature is 130 ° C. or lower and the pressure is 3.0 torr or lower. (2) Velocity gradient of reactive gas 7000 cm / sec · c
m or less and power density of 0.3 w / cm ³ or less. (3) The reactive gas must contain at least silane.

Further, the above-mentioned abrasion resistant plastic molded article is characterized in that the intermediate layer is an ultraviolet resistant layer.

The present invention will be described in more detail below.

When a SiO ₂ film or the like is formed on the surface of a plastic, its hardness increases, but even if the film has the same composition, the hardness and wear resistance of the film differ if the microstructure is different. If the formed film has a columnar structure, when tensile force is applied to the film, cracks run along the grain boundaries and the film breaks. Therefore, if the substrate has a large coefficient of thermal expansion, such as plastic, 100
Even if the film is heated at a temperature of ℃ or less, the film immediately cracks. On the other hand, since the non-columnar hard film formed by the present invention is a homogeneous film, it has sufficiently high durability against tensile force. Whether the film is non-columnar or columnar depends on the film forming conditions.

In the present invention, the judgment as to whether the structure of the hard film is columnar or non-columnar is made by cleaving the substrate and separating the film by SE.
It can be performed by observing M (electron microscope). FIG. 1 shows an SEM photograph of a non-columnar structure, and FIG. 2 shows an SEM photograph of a columnar crystal structure. The non-columnar hard film in the present invention is fine particles having an average particle size of less than 1000Å, and the film is homogeneous.
On the other hand, in the columnar structure, the ratio of the columnar particle diameter to the length (measured in the thickness direction of the film) is 1:10 or more, and the particle diameter is 1000Å or more.

As described above, the hard film formed by the present invention is a non-columnar structure composed of fine particles having an average particle size of less than 1000Å. The constituent component is a Si compound, specifically, a Si oxide, a nitride, a carbide, or a mixture thereof, and among them, an amorphous is desirable. Amorphous means X
In line diffraction, it means that the diffraction intensity is broad.

The thickness of the hard film is preferably 1 to 5 μm, and if it is less than 1 μm, sufficient hardness and abrasion resistance cannot be obtained. On the other hand, if it is more than 5 μm, when the plastic molded product is deformed. Moreover, the film is likely to be cracked.

In the present invention, the hard film is formed on one side or both sides of the plastic molded product. Further, the hard film may be formed on the outermost surface of the plastic molded product as the final molded product, and an intermediate layer may be interposed between the plastic molded product and the hard film. The intermediate layer has the functions of enhancing the adhesion between the plastic molded product and the hard film, relaxing the difference in the coefficient of thermal expansion between the plastic molded product and the hard film, and preventing the plastic molded product from being deteriorated by ultraviolet rays.

When the intermediate layer is provided, it is desirable that the total thickness of the intermediate layer and the hard film does not exceed 10 μm. Specifically, when the intermediate layer is a ZnO layer, its film thickness is preferably 0.1 to 1 μm.
If the total film thickness exceeds 10 μm, the film is likely to be cracked or peeled. The intermediate layer is preferably provided by a film formation method involving plasma in the chamber at the same time as the formation of the hard film or in a continuous chamber from the viewpoint of improving productivity and reducing apparatus cost. Specifically, when the intermediate layer is a ZnO layer, a vapor deposition method,
It is formed by a sputtering method, an ion plating method, a plasma CVD method, or the like.

Taking an example of the intermediate layer, in order to improve the adhesiveness, a layer obtained by etching the surface of the polycarbonate plate with Ar plasma to activate it, a layer oxidized with oxygen plasma, and the like. In order to alleviate the coefficient of thermal expansion, a layer on which an a-Si or SiN film having a large coefficient of thermal expansion is deposited. In order to prevent ultraviolet ray deterioration, a layer in which a metal oxide such as ZnO or a band gap such as SiN having a band gap of about 3 eV is deposited. Is mentioned.

Further, in the present invention, a hard film and a soft film having a columnar structure can be used together. A soft film is prone to cracking, but once cracked, it becomes very strong against subsequent thermal stress and does not progress, so combining a soft film and a hard film also resists thermal stress and is resistant to thermal stress. A film having good abrasion resistance can be obtained.

FIG. 5 shows an SEM photograph of a film in which a columnar structure was formed in the same chamber and subsequently a non-columnar structure was formed. The average particle size of the columnar structure, which is a soft film formed by the present invention, is 1000Å to 5000Å according to SEM observation, and the film has a columnar structure. Further, the ratio of the columnar particle diameter to its length (measured in the thickness direction of the film) is 1:10 or more,
The particle size is also 1000Å or more.

As described above, the soft film formed by the present invention has a columnar shape with an average particle size of 1000 to 5000Å, and its constituent components are Si compounds, specifically Si oxides and nitrides, It is a carbide or a mixture thereof, and among them, amorphous is desirable. Amorphous means that the diffraction intensity is broad in X-ray diffraction.

The thickness of the soft film is preferably from 2 to 5 μm. When it is less than 2 μm, sufficient stress relaxation is not achieved, and when it is more than 5 μm, sufficient abrasion resistance cannot be obtained.

The thickness of the hard film is preferably 1 to 5 μm for the same reason as described above.

The soft film and the hard film are formed on one side or both sides of the plastic molded product. Further, the soft film may be formed on the surface of the plastic, and the hard film may be formed on the outermost surface of the plastic molded product as the final molded product, and the intermediate layer is further interposed between the soft film and the hard film. It may be one. The intermediate layer enhances the adhesion between the soft film and the hard film,
It fulfills functions such as preventing plastic molded products from being deteriorated by ultraviolet rays.

When the intermediate layer is provided, it is desirable that the total thickness of the intermediate layer, the soft film and the hard film does not exceed 10 μm. Specifically, the intermediate layer is ZnO.
In the case of a layer, the film thickness is preferably 0.1 to 1 μm. If the total film thickness exceeds 10 μm, the film is likely to be cracked or peeled. When the intermediate layer is a ZnO layer, it is formed by a vapor deposition method, a sputtering method, an ion plating method, a plasma CVD method or the like.

Taking an example of the intermediate layer, in order to enhance the adhesion between the hard film and the soft film, a layer which continuously changes from a columnar structure of the soft film to a non-columnar structure of the hard film, and to prevent ultraviolet deterioration, Examples of the layer include a metal oxide such as ZnO and a layer having a bandgap of about 3 eV such as SiN.

As the plastic molded product used in the present invention, a plastic molded product made of any resin such as acrylic resin, polycarbonate resin, polyester resin or the like can be used. Polycarbonate resin is the best choice for vehicle windows. The shape of the plastic molded product may be either a plate shape or a shape having a curved surface, and the size thereof is completely free, and a size of about 1 m can be used without any problem.

Hard films are evaluated by a thermal shock tester (Yashima Seisakusho TSER-2252-A), AS.
Taber abrasion test and dynamic hardness tester defined by TM-D1044 (DUH-20 manufactured by Shimadzu Corporation)
0). Thermal shock test condition is +8
Holding at 0 ° C. for 1 hr and −40 ° C. for 1 hr are repeated as one cycle, and the number of times the film peels from the substrate is examined. The specific conditions for the Taber abrasion test are the abrasion wheel CS-
10 F, load 500 g, wear count 5000 times, and haze before and after wear was measured by a haze meter (Nippon Denshoku Industries Co., Ltd.).
It can be evaluated by measuring with Z-Sigma 80) manufactured by K.K.
The dynamic hardness tester is basically the same as the Vickers hardness test, except that the dynamic hardness test measures the indentation depth when the indenter is pressed against the membrane. This tester can measure the hardness of thin films on the order of microns. As the measurement conditions, a load of 0.5 g and an indenter having a ridge angle of 115 degrees are used.

The weather resistance test of the sunshine weather meter was conducted at a substrate temperature of 63 ° C. in a dry atmosphere without water spraying.
After irradiating the sample with the ultraviolet ray by the carbon arc for 1000 hours, the spectrophotometer (HITACHI automatic spectrophotometer 340 type) measures the spectroscopic spectrum.

When sputtering is carried out at a low temperature and a low vacuum, it is a common phenomenon that the film grows in a columnar shape. It is believed that this is because the active species that contribute to the film grow in the gas phase and reach the surface of the plastic molded product, and then are deposited without lateral diffusion. From this, it is possible to obtain a hard film having a non-columnar structure and a soft film having a columnar structure as in the present invention by controlling the growth of active species until reaching a plastic molded article and the energy of diffusion after reaching the plastic molded article, respectively. You can The method will be described below.

The method of the present invention forms a hard film having a non-columnar structure of a Si compound and a soft film having a columnar structure on the surface of a plastic molded product by selecting specific plasma CVD conditions. Briefly, the present invention provides a gas containing a compound and / or a simple substance gas containing one or more kinds of elements constituting a hard film and a soft film to be formed into a plasma state, and a gas phase reaction or a plastic molded article. This is a method of forming a desired hard film or soft film by a chemical reaction on the surface.

The present invention is characterized in that a film can be formed at a lower temperature than the PVD method, and that the film formation rate is high. In the present invention, the plasma CVD method is r
The method using the parallel plate type of f. In addition, in the present invention, the size of the plastic molded product on which the hard film is formed is 1 m or more in consideration of the substitution of glass.
As the plasma CVD method, a capacitively coupled CV capable of efficiently confining plasma in parallel plate electrodes
D or magnetron type CVD is preferred.

First, the conditions for forming the hard film will be described.

The first condition is that the plasma CVD conditions are such that the reaction temperature is 130 ° C. or less and the pressure is 1.0 torr or less. Since a hard film is formed on a plastic molded product, the reaction temperature must be 130 ° C. at the maximum. The pressure is 1 torr or less, preferably 0. It is 1 to 1 torr. When it exceeds 1 torr, diffusion of active species on the surface of the plastic molded product is inhibited and the film has a columnar structure. On the other hand, when it is less than 0.1 torr, rf is obtained.
It becomes difficult to stabilize the discharge.

The second condition is a velocity gradient 800 of the reactive gas.
0 cm / sec · cm or more, power density 0.3 w / cm
It is to be ³ or less.

The film forming conditions for forming a hard film having a non-columnar structure are important factors such as the flow rate and composition of gas, the pressure during film formation, the distance between electrodes, etc., but these vary greatly depending on the apparatus. The present inventors defined the velocity gradient by dividing the gas velocity by the distance between the gas outlet and the plastic molded article that is the substrate, and this velocity gradient and the plasma state, specifically the density of electrons and ions. It was found that the conditions for forming a non-columnar hard film are determined by the energy of electrons and ions.

However, since it is difficult to measure the above-mentioned plasma state, in the present invention, the value obtained by dividing the power applied to the plasma by the inter-electrode volume is defined as the power density to define the plasma state. Velocity gradient is 8000 cm / se
If it is smaller than c · cm, the film will have a columnar structure regardless of how low the power density is, and the power density will be 0.3 w / cm.
^If it exceeds ³ , even if the velocity gradient is increased, the reaction becomes violent and particles are easily formed to form a columnar structure.

The third condition is that the reaction gas contains at least silane. The gas used is a gas containing oxygen as an element (N
₂ O, CO ₂ , O ₂ etc. and silane gas (SiH ₄ , Si
₂ H ₆ etc.) are mixed and introduced into the reaction chamber. N for nitride film
H ₃ , N ₂ and the like are used, and CH ₄ , C ₂ H _{6 and the} like are used for the carbonized film. In the present invention, the above-mentioned gas containing no silane is defined as a reactant gas, and the gas composition is preferably reactant gas: silane = 50 to 5: 1 in terms of molar ratio. When the proportion of silane is high, unreacted silane is taken into the film and the hardness of the film decreases.

The fourth condition is that the gas in the reaction chamber is laminar and the Reynolds number is larger than 10. When the Reynolds number is 10 or less, the film has a columnar structure. The upper limit is not particularly limited, but if it exceeds 30, the flow of gas is disturbed and the uniformity of the film thickness deteriorates, and even if it exceeds 30, the deposition rate of the film does not change so much. Considering efficiency, the Reynolds number is preferably 10 to 30.

Further, electrodes and substrates (plastic molded products)
From the viewpoint of productivity, the distance between them is preferably 1.5 to 3.0 cm.

Next, the conditions for forming the soft film will be described.

The first condition is that the plasma CVD conditions are a reaction temperature of 130 ° C. or lower and a pressure of 3.0 torr or lower. Since it forms a soft film on a plastic molded product, the reaction temperature must be at most 130 ° C. The pressure is 3 torr or less, preferably 0. 1 to 3 torr. Above 3 torr, active species grow violently in the gas phase to become fine powder, while 0.
If it is less than 1 torr, it becomes difficult to stabilize the rf discharge.

The second condition is the velocity gradient 700 of the reactive gas.
0 cm / sec · cm or less, power density 0.3 w / cm
It is to be ³ or less. Power density is 0.3W / cm
^{When it is} larger than ³ , the film structure becomes columnar, but stress remains in the film and the film is easily peeled off from the substrate due to thermal shock. If the velocity gradient is greater than 7000 cm / sec · cm, the film structure becomes a non-columnar structure or a mixed structure of columnar and non-columnar structures, and sufficient stress relaxation cannot be achieved.

The third condition is that the reaction gas contains at least silane. The gas used is a gas containing oxygen as an element (N
₂ O, CO ₂ , O ₂ etc. and silane gas (SiH ₄ , Si
₂ H ₆ etc.) are mixed and introduced into the reaction chamber. N for nitride film
H ₃ , N ₂ and the like are used, and CH ₄ , C ₂ H _{6 and the} like are used for the carbonized film. In the present invention, the above-mentioned gas not containing silane is defined as a reactant gas, and the gas composition is preferably a reactant gas: silane = 10 to 5: 1 in a molar ratio. If the proportion of silane is high, unreacted silane is taken into the film, and a large amount of SiH bonds are present in the film. This SiH bond becomes S over time.
The stability of the film deteriorates because the bond is changed to iO and SiOH.

Also, electrodes and substrates (plastic molded products)
From the viewpoint of productivity, the distance between them is preferably 1.5 to 3.0 cm.

[0044]

Embodiments of the present invention will now be described with reference to the drawings.

Examples 1 to 5 and Comparative Examples 1 to 9 As plastic molded products, annealing treatment was performed 10
used cm × 10 cm of the polycarbonate resin, by a plasma CVD apparatus shown in FIG. 3, SiO ₂ according to the following
A film was formed.

The plastic molded article 1 was placed on the tray 2, the shutter 3 was opened, the article was conveyed into the chamber 7, and the article was placed at a position facing the gas hole electrode 4. After that, close the shutter and operate the exhaust device to 1.0 ×
A vacuum state of 10 ^-5 torr is applied, and the heater 5 is used
While heating and holding at 0 ° C, the reaction gas 6 is fed with the gas hole electrode 4
It was supplied from the fine holes of.

Under the conditions shown below and the conditions shown in Table 1, a SiO ₂ film having a film thickness of 3 μm was formed.

Reaction temperature: 80 ° C. Pressure: 0.4 torr Reactant gas and its flow rate: N ₂ O 300 SCCM Discharge frequency: 13.56 MHz The evaluation results are shown in Table 2 along with the gas velocity gradient and power density and film structure. The relationship is shown in FIG. It can be seen from FIG. 4 that when the pressure is 0.4 torr, the film structure changes from columnar to non-columnar due to the velocity gradient and the power density. Although not shown in the figure, when the pressure is lowered, the region of the columnar structure is narrowed. On the contrary, when the pressure exceeds 1.0 torr, the columnar structure is formed even within the velocity gradient range of the present invention. Further, when the power density exceeded 0.3 w / cm ³ , the material became columnar.

FIG. 1 shows a SEM photograph of a crystal structure of a typical hard film having a non-columnar structure (Example 1), and FIG. 2 shows a SEM photograph of a crystal structure of a film having a columnar structure (Comparative Example 8). Show. From this, the average particle diameter of the hard film formed by the present invention is fine particles of less than 1000Å, and the film has a uniform structure. On the other hand, in the columnar structure, the ratio of the columnar particle diameter to the length (measured in the thickness direction of the film) is 1:10 or more,
It can be seen that the particle size is 1000 Å or more.

As is clear from Table 2, the films having non-columnar structures (Examples 1 to 5) had a thickness of 3 μm, but 50
It is extremely excellent against abrasion up to 00 times and is almost equivalent to Pyrex glass (Comparative Example 9). On the other hand, if the structure is a mixture of columnar and non-columnar (Comparative Examples 1 to 4), 1
Up to 000 times, the haze is on the order of 1%, which is not much different from that of a non-columnar film, but wear up to 5,000 times led to deterioration and increased haze.

On the other hand, the columnar structure films (Comparative Examples 5 to 8) are
The haze exceeds 2% after 1000 times of wear and the wear resistance is poor.

The film having a non-columnar structure having the same film quality had a dynamic hardness more than double that of the columnar structure.

Examples 6 to 8 and Comparative Examples 10 to 13 Under the conditions shown below and the conditions shown in Table 3, a SiO ₂ film having a thickness of 3 μm was formed in the same manner as in Example 1.

Reaction temperature: 80 ° C. Power: 50 W Power density: 0.07 W / cm³  Discharge frequency: 13.56MH Table 4 shows the z evaluation results.

From Example 6 and Comparative Examples 10 and 11, even if the velocity gradient is greater than 8000 cm / sec.cm and the power density is 0.3 w / cm ³ or less, the degree of vacuum is 1.0 to.
When it exceeds rr, the film has a columnar structure and is inferior to the film of the present invention in hardness and Taber abrasion test. From Examples 7 and 8 and Comparative Examples 12 and 13, when the Reynolds number is 10 or less, the film becomes columnar, and the film hardness and Taber abrasion test are inferior to the film of the present invention.

Examples 9 to 11 and Comparative Examples 14 to 19 Plastic moldings (Comparative Examples 14 to 19) described in JP-A-64-4343 and Comparative Example 14 were changed in film forming time to obtain film thicknesses. Modified plastic moldings (Example 9-
Table 5 shows a comparison of 11). In 1000 abrasion tests, the molded product of the present invention shows a haze equivalent to that of Pyrex with a film thickness of about 3 μm, whereas the conventional molded product shows
It can be seen that a film thickness of at least 5μ is necessary. In addition, the molded article of the present invention is excellent in durability as well.
Obvious from 0 wear test.

Examples 12 to 15 Annealing treatment was performed as a plastic molded product 10
A polycarbonate resin having a size of 10 cm × 10 cm was used to form a soft film and a hard film in this order by the plasma CVD apparatus shown in FIG.

After depositing a soft film having a film thickness of 2 μm under the conditions shown below and the conditions shown in Table 6, subsequently, in the same tank,
A hard film having a film thickness of 4 μm was deposited under the conditions shown below, and a thermal shock test, a Taber abrasion test, and a hardness test were performed.

Conditions for forming a soft film Reaction temperature: 80 ° C. Reactant gas and its flow rate: N ₂ O 300 SCCM Discharge frequency: 13.56 MHz Electrode distance: 2.0 cm

Hard film forming conditions Reaction temperature: 80 ° C. Pressure: 0.4 torr Reactant gas and its flow rate: N ₂ O 300SCCM, S
iH ₄ 30 SCCM Discharge frequency: 13.56 MHz Power density: 0.1 W / cm ³ Electrode distance: 2.0 cm Velocity gradient: 9676 cm / sec · cm Reynolds number: 19 Evaluation results are shown in Table 7.

In Examples 12 to 14, the soft film was formed under pressure 3
Since a good columnar structure was formed because the power density was 0.3 W / cm ³ or less at a speed gradient of 7,000 cm / cm · sec or less at a torr or less, film peeling did not occur even in the thermal shock test.

From the results of the Taber abrasion test and the micro hardness test of these samples, the change in haze after 5000 times was in the order of 3%, which was about the same as in Example 15 in which no soft film was added, and the abrasion resistance was good. ..

Examples 16 to 20 Under the conditions shown below, a soft film and a hard film were formed using the same substrate as in Example 12. When the film thickness of the soft film was changed to 2 to 5 μm and the film thickness of the hard film was changed to 1 to 5 μm, thermal shock test, Taber abrasion test and hardness test were conducted.

Conditions for forming a soft film Reaction temperature: 80 ° C. Pressure: 0.6 torr Reactant gas and its flow rate: N ₂ O 300SCCM, S
iH ₄ 10SCCM Discharge frequency: 13.56 MHz Electrode distance: 2.0 cm Velocity gradient: 6060 cm / sec · cm

Hard film forming conditions Reaction temperature: 80 ° C. Pressure: 0.4 torr Reactant gas and its flow rate: N ₂ O 300SCCM, S
iH ₄ 30 SCCM Discharge frequency: 13.56 MHz Power density: 0.1 W / cm ³ Distance between electrodes: 2.0 cm Velocity gradient: 9676 cm / sec · cm Reynolds number: 19 Table 8 shows the evaluation results.

It can be seen that all of the examples are excellent in wear resistance, hardness, and thermal stress resistance (thermal shock).

Example 21 Using the same substrate as in Example 12, a surface activation treatment was performed with Ar plasma using a magnetron sputtering apparatus, and then a ZnO film having a thickness of 0.3 μm was formed under the following conditions.

Reaction temperature: 80 ° C. Pressure: 0.007 torr Reactant gas and its flow rate: Ar 40 SCCM, O ₂
3.6 SCCM Discharge frequency: 13.56 MHz Power: 100 W Next, a hard film having a film thickness of 4 μm was formed by the plasma CVD apparatus of FIG. 3 under the same conditions as in Example 15.

Example 22 Z was formed in the same manner as in Example 21 between the soft film and the hard film.
A soft film and a hard film were formed under the same conditions as in Example 12 except that the nO film was formed.

Example 23 A soft film and a hard film were formed under the same conditions as in Example 22 except that ZnO was formed under the following conditions with the CVD apparatus shown in FIG.

Reaction temperature: 70 ° C. Pressure: 0.3 torr Diethyl zinc: 70 SCCM Reactant gas and its flow rate: He 70 SCCM, O ₂
150SCCM Distance between electrode and substrate: 2.0 cm Discharge frequency: 13.56 MHz Power: 150 W Examples 21 to 23 and 12 were subjected to Taber abrasion test, hardness test, thermal shock test and weather resistance test. The results are shown in Table 9.

[0072]

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Table 8]

[0081]

[Table 9]

[0082]

As in the present invention, by forming a hard film having a non-columnar structure of a Si compound on the surface of a plastic molded product by a plasma CVD method under specific conditions, the physical properties such as hardness and abrasion resistance can be improved. An excellent plastic molded product can be obtained.

Furthermore, a soft film having a columnar shape of a Si compound is formed on the surface of the plastic molded product by a plasma CVD method under a specific condition, and a hard film having a non-columnar structure of the Si compound is formed thereon. It is possible to obtain a plastic molded product having excellent physical properties such as thermal shock, hardness, and abrasion resistance.

By forming an ultraviolet absorbing layer made of ZnO as an intermediate layer, a plastic molded product having excellent physical properties such as thermal shock, abrasion resistance, hardness and weather resistance can be obtained.

[Brief description of drawings]

FIG. 1 is an electron micrograph showing a crystal structure of a hard film portion of a plastic molded article provided with a hard film having a non-columnar structure of the present invention.

FIG. 2 is an electron micrograph showing a crystal structure of a film having a columnar structure of a comparative example.

FIG. 3 is a schematic explanatory diagram of a plasma CVD apparatus.

FIG. 4 is a diagram showing the relationship between the velocity gradient, the power density, and the film structure.

FIG. 5 is an electron micrograph showing a crystal structure of a hard film portion of a plastic molded product having a hard film having a non-columnar structure on a soft film having a columnar structure of the present invention.

[Explanation of symbols]

 l Plastic molded product 2 Tray 3 Shutter 4 Gas hole electrode 5 Heater 6 Reaction gas 7 Chamber

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Mukawa 3-5-1, Asahi-cho, Machida-shi, Tokyo Denka Kagaku Kogyo Co., Ltd. (72) Inventor Tetsuya Wada 3 Asahi-cho, Machida-shi, Tokyo Chome 5-1 Denka Kagaku Kogyo Co., Ltd. Research Institute (72) Inventor Suzuya Yamada 3-5-1 Asahimachi, Tokyo Machida-shi Denka Kagaku Kogyo Co., Ltd. Research Institute (72) Inventor Satoshi Tanaka 3-5-1, Asahimachi, Machida-shi, Tokyo Inside the Research Institute of Electrochemical Research (72) Inventor Naosuke Okamoto 3-5-1, Asahimachi, Machida-shi, Tokyo Inside Research Center for Electrochemical Research ( 72) Inventor Masahiro Kikuni 3-5-1, Asahimachi, Machida-shi, Tokyo Inside Denka Kagaku Kogyo Co., Ltd. (72) Inventor Shinji Nakai 3-5, Asahimachi, Machida-shi, Tokyo Number 1 Denka Kagaku Kogyo Co., Ltd. Research Institute (72) Inventor Gene Christophe Rostain France. 78000 Versailles. Le Ardi. 23 (72) Inventor Henri Schvell 2-5-7 Tokodai, Tsukuba City, Ibaraki Prefecture (72) Inventor François Coule France. 78280 · Guiancourt. Reciprocity Les Symphonies. Beady Beethoven. 63 (72) Inventor Eiichi Ozawa 4-5-24 Ozugaoka, Numanan-cho, Higashi-Katsushika-gun, Chiba Prefecture

Claims (6)

[Claims] 1. A wear-resistant plastic molded article, characterized in that a hard film having a non-columnar structure of a Si compound is formed on the surface of the plastic molded article with or without an intermediate layer interposed therebetween. , 5 in Taber abrasion test
A wear-resistant plastic molded product having a haze change of 5% or less after 000 rotations and having a hardness of 100 kg / mm ² or more in a micro hardness test. 2. The surface of a plastic molded article, with or without an intermediate layer, under the following conditions (1) to (4):
A method for producing a wear-resistant plastic molded product, which comprises performing plasma CVD by parallel plate type CVD to form a hard film having a non-columnar structure of a Si compound. (1) The reaction temperature is 130 ° C. or less and the pressure is 1.0 torr or less. (2) Velocity gradient of reactive gas 8000 cm / sec · c
m or more and a power density of 0.3 w / cm ³ or less. (3) The reactive gas must contain at least silane. (4) The gas in the reaction chamber is laminar and has a Reynolds number greater than 10. 3. A plastic molded article having a soft film having a columnar structure of a Si compound formed on the surface thereof, and a hard film having a non-columnar structure of a Si compound formed with or without an intermediate layer. A wear-resistant plastic molding characterized by: 4. A plastic molded article having a soft film having a columnar structure of a Si compound formed on the surface thereof and a hard film having a non-columnar structure of a Si compound formed with or without an intermediate layer. When manufacturing an abradable plastic molded product, the parallel plate type C is used under the following conditions (1) to (3).
A method for producing a wear-resistant plastic molded article, which comprises performing a plasma CVD by VD to form a soft film having a columnar structure of a Si compound. (1) The reaction temperature is 130 ° C. or lower and the pressure is 3.0 torr or lower. (2) Velocity gradient of reactive gas 7000 cm / sec · c
m or less and a power density of 0.3 w / cm ³ or less. (3) The reactive gas must contain at least silane. 5. The abrasion-resistant plastic molded product according to claim 1, wherein the intermediate layer is an ultraviolet resistant layer. 6. The wear-resistant plastic molded product according to claim 5, wherein the ultraviolet resistant layer is ZnO.