KR100254012B1 - Process for preparing polycarbonate transparent plate enhanced abrasion resistance and scratch resistance - Google Patents

Abstract

PURPOSE: A method for preparing a polycarbonate transparent plate is provided, to improve the adhesion between a polycarbonate layer and a glass layer, thereby to improve the abrasion resistance and the scratch resistance. CONSTITUTION: The method comprises the steps of sputtering and etching a polycarbonate resin by using an argon beam of 700-1,400 eV at the pressure of 10-4 Torr to remove the impurities on the surface; forming a middle layer by using the mixture of an organic material and argon gas by ion beam evaporation, on the polycarbonate resin; forming a glass layer by using an electron beam and an oxygen gas by evaporation at the pressure of 10-5 Torr, on the middle layer; and increasing the pressure to the atmospheric pressure to obtain a polycarbonate transparent plate comprising a polycarbonate layer, a middle layer and a glass layer. Preferably the thickness of the middle layer is 100-1,000 Angstrom and the thickness of the glass layer is 0.1-3 micrometers.

Description

Manufacturing method of polycarbonate transparent plate with improved wear resistance and scratch resistance

The present invention relates to a method for producing a polycarbonate transparent plate with improved wear resistance and scratch resistance, and more particularly, to solve the adhesion between glass and plastic in a glass coated transparent plate of a polycarbonate plate through glass film deposition. It is a method for producing a glass-coated polycarbonate plate that forms an intermediate layer of an organic material by the method and is excellent in wear resistance, and does not peel off the glass film due to temperature change.

Polycarbonate resins have excellent mechanical and chemical properties and are widely used in various fields. In particular, the resin has a low weight, high transparency, and a strong impact strength compared to glass, and thus is widely used in automobile headlights, transparent soundproof walls, etc. in place of glass materials. However, the application is limited due to the relatively low wear and scratch resistance compared to the glass. Various methods are used to overcome such disadvantages, and techniques for increasing wear resistance by coating organic or inorganic materials on polycarbonate resins have been actively studied.

Coating with these organic materials improves the wear resistance of the polycarbonate resin, but it is difficult to obtain high wear resistance such as glass because the material to be coated is an organic material. Therefore, in applications where high wear resistance is required, the glass replacement wear resistant polycarbonate product is preferably produced by an inorganic coating method.

As a form of inorganic coating, a method of improving the wear resistance by depositing a glass thin film on a plastic resin has been studied. Examples of this are French Patent No. 1,520,125 and British Patent No. 1,144,099, which report that the scratch and abrasion resistance of polycarbonate plates is improved when the glass (SiO ₂ ) is deposited on the polycarbonate resin at a thickness of 1 μm. have. The deposition of glass was made using oxygen gas and electron beam under high vacuum, and the plastic resin was designed to move constantly in the glass vapor during processing. However, the glass-coated wear-resistant polycarbonate resin produced by this technology has a disadvantage in that the glass film and the resin are easily cracked due to a strong impact or a large temperature change due to the large thermal expansion difference between the resin and the glass.

Many methods have been proposed to solve the cracking or peeling of the glass film. U. S. Patent No. 3,645, 779 introduces a method for producing a transparent, scratch-resistant plastic transparent plate by depositing B ₂ O ₃ -SiO ₂ glass containing 5 wt% or less of Na ₂ O on a polycarbonate resin. have.

In addition, US Pat. No. 3,713,869 describes a technique for forming an intermediate layer between two layers to improve the adhesion between the plastic and the glass plate. In the glow discharge state, the vapor of the low molecular weight organic material is polymerized to form an intermediate layer on the surface of the polymer resin. The increase in organic matter was made with organics containing acetylene, xylene and silicon (Si).

In addition, US Pat. No. 4,200,681 describes a technique for producing glass-coated polycarbonate consisting of an intermediate layer prepared by photopolymerizing a polycarbonate resin, a glass film, and an acrylic monomer by ultraviolet light. The glass-coated polycarbonate resin produced by this technique has improved cracking and glass peeling problems compared to the polycarbonate prepared by the prior art, but has a problem of weak adhesive strength or crack resistance.

In order to solve the problem of adhesion between glass and plastic, which is a problem in the glass coating technology of the polycarbonate plate through conventional glass film deposition, the present invention provides an excellent wear resistance and temperature change by manufacturing an intermediate adhesive layer using an ion beam deposition method. It is a technical subject to provide the manufacturing method of the glass-coated polycarbonate board which does not peel a glass film by this.

1 is a schematic view showing an ion beam deposition apparatus used in the present invention.

According to the present invention, a polycarbonate resin is put in a vacuum apparatus, and the vacuum degree of the vacuum apparatus is lowered to 10 ^-4 Torr, followed by removing impurities on the surface of the resin by sputter-etching using an argon ion beam having an energy of 700 to 1400 eV, followed by an organic material. Preparing an intermediate layer by ion beam deposition using an argon mixed gas, and preparing an intermediate layer having the desired thickness, and depositing the intermediate layer glass using an electron beam and oxygen gas at a vacuum degree of about 10 ⁻⁵ Torr, and then A method of manufacturing a glass-coated polycarbonate transparent plate having improved wear resistance and scratch resistance composed of a polycarbonate, an intermediate layer, and a glass film, comprising the steps of: depositing a glass to a desired thickness and then raising the vacuum apparatus to atmospheric pressure. .

Hereinafter, the present invention will be described in more detail.

The present invention is a technique for depositing glass on the surface of the resin in order to improve the wear resistance and scratch resistance of the polycarbonate resin, characterized in that for producing an intermediate layer using an ion beam device and an organic material to improve the adhesion between the glass and the resin.

The method for producing a wear resistant scratch resistant polycarbonate resin plate according to the present invention proceeds in the following order.

First, the surface of the polycarbonate resin sample is removed using a chemical solvent such as ethanol or isopropyl alcohol to remove contaminants, and then dried well using nitrogen gas. The sample is put into the apparatus shown in FIG. 1 used in the present invention, and the air inside the apparatus is discharged using a vacuum pump. When a vacuum degree of 10 ⁻⁴ Torr is obtained, argon ions (Ar ⁺ ) are irradiated to the polycarbonate sample with an energy of 700 eV to 1400 eV using an ion beam apparatus. The irradiation of argon ions is intended to remove contaminants that may be present on the resin surface (sputter etching) and to activate the resin surface to improve adhesion with the intermediate layer.

Subsequently, an intermediate layer is prepared on the surface of the resin using an organic material selected by ion beam deposition. In the ion beam deposition, the ratio of the organic material and the argon mixed gas is 1:10 to 1: 0 (only pure organic materials are used). The degree of vacuum at this time is 1 × 10 ^-3 to 1 × 10 ^-4 Torr.

The strength, thickness, etc. of the intermediate layer thus obtained vary depending on the amount of organic matter flowing into the ion beam apparatus, the energy of the ion beam deposition time, and the organic materials used include methane, ethane gas, silicon, oxygen, carbon, nitrogen, and the like. Use organic materials to Examples of such organic materials include hydrocarbons such as methane and ethane gas, or cyclohexane, tetramethylcyclosiloxane, hexamethyl disiloxane, hexamethyldisilazne, tetraethoxy Organic materials including silane (Tetraethoxylsilane), octamethylcyclotetrasiloxane (Octamethylcyclo tetra siloxane) and the like.

The color of the intermediate layer is thus different depending on the organic material and ion beam energy used, but care should be taken not to affect the transparency of the polycarbonate resin by minimizing the thickness of the intermediate layer. The thickness of the intermediate worm produced by ion beam deposition is about several hundreds of micrometers to several thousand micrometers, and can be obtained by adjusting the deposition time and the ion beam intensity. After the preparation of the intermediate layer having a desired thickness by ion beam deposition, the vacuum degree of the apparatus was again obtained by using a vacuum pump. During the glass deposition process, the vacuum degree was removed to about 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, and then the prepared intermediate layer An electron beam is deposited on the glass (SiO ₂ ) while flowing oxygen gas into it. The thickness of the deposited glass may be prepared in the range of 0.1 μm to several μm, and the thickness of the glass film is most suitable in the range of 0.5 μm to 1.5 μm in consideration of wear resistance and work characteristics. In order to improve adhesion between the intermediate layer and the glass film, an oxygen ion beam having an energy of 50 to 600 eV may be irradiated before or during the deposition.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Example 1

Polycarbonate samples of 10 cm × 10 cm size were placed in isopropyl alcohol, washed with an ultrasonic cleaner for about 1 hour, and dried using nitrogen gas. The well-dried polycarbonate resin was placed in a vacuum apparatus, and a vacuum degree of about 10 ⁻⁴ Torr was obtained by using a vacuum pump, and impurities were removed by sputter-etching the surface of the resin using an argon ion beam of 1 KeV. A mixed gas having a mixing ratio of methane gas and argon gas of 1: 1 was placed in an ion beam apparatus, and an intermediate layer was formed on the resin surface through ion beam deposition. At this time, the ion beam energy used is weak yellow in the intermediate layer made of 100 eV. When the thickness of the intermediate layer was 500Å, the ion beam deposition was stopped, and the vacuum degree was lowered to 10 ⁻⁵ Torr, and the glass film was deposited to a thickness of 1 μm using an electron beam and oxygen gas.

Example 2

Polycarbonate samples of 10 cm × 10 cm size were placed in isopropyl alcohol, washed with an ultrasonic cleaner for about 1 hour, and dried using nitrogen gas. The well-dried polycarbonate resin was placed in a vacuum apparatus, and a vacuum degree of about 10 ⁻⁴ Torr was obtained by using a vacuum pump, and impurities were removed by sputter-etching the surface of the resin using an argon ion beam of 1 KeV. A mixed ratio of octamethylcyclo tetra siloxane and argon gas with a 4: 1 mixed gas was placed in an ion beam apparatus to form an intermediate layer on the resin surface through ion beam deposition. At this time, the ion beam energy used was a very good transparency of the intermediate layer made of 100eV. When the thickness of the intermediate layer was 500Å, the ion beam deposition was stopped, the vacuum degree was lowered to 10 ⁻⁵ Torr, and the glass film was deposited by using the electron beam and oxygen gas.

Comparative Example 1

A polycarbonate resin (aromatic polycarbonate transparent plate) plate was prepared without depositing an intermediate layer and a glass layer.

Comparative Example 2

After washing as in Example 1, the well-dried polycarbonate resin was put in a vacuum apparatus, and a vacuum degree of about 10 ^-5 Torr was obtained using a vacuum pump without forming an intermediate layer, and then glass was deposited using oxygen gas and an electron beam. It was.

[Test Example]

The specimens obtained in Examples and Comparative Examples were subjected to the glass film peeling test using abrasion resistance and hot water.

The abrasion resistance test was performed using a taper type abrasion resistance measuring instrument, and the conditions used were wear lubrication CS-10, wear cycle 100 cycles, and load 500g. The Δ% haze value was measured using the Gardner hazemeter before the abrasion test and measured the haze value of four samples and the four haze values after abrasion. Got it. Glass film peeling experiment by hot water was soaked in 100 ℃ water for 10 minutes with the prepared sample was confirmed whether the surface of the glass film peeling.

TABLE 1

As shown in Table 1, it was confirmed that the specimens coated with the glass film had a high wear resistance as compared to the polycarbonate resin plate as in Comparative Example 1, and in the embodiment conditions according to the present invention, the thermal expansion rate between the glass and the polycarbonate resin The introduction of a uniform intermediate layer that buffers the difference well yielded a stable wear resistant polycarbonate resin even in hot water of high temperature.

The present invention is characterized in that the ion beam deposition method is used to prepare the intermediate layer introduced to improve the adhesion between the glass film and the plastic and to reduce the peeling of the glass film. The intermediate layer made of ion beam has excellent adhesion with plastics, and the properties of the prepared intermediate layer have very uniform and high hardness to the entire surface of the plastic, so that the plastic resin and glass film have excellent adhesion, peeling and cracking due to temperature change. Improved.

Claims (5)

Putting polycarbonate resin in the vacuum apparatus, lowering the vacuum degree of the vacuum apparatus to 10 ⁻⁴ Torr, and then removing impurities on the surface of the resin by sputter-etching using an argon ion beam having an energy of 700 to 1400 eV; Then preparing an intermediate layer by ion beam deposition using an organic material and argon mixed gas; Preparing an intermediate layer having the desired thickness, and depositing the intermediate layer glass using an electron beam and oxygen gas at a vacuum degree of about 10 ⁻⁵ Torr; Subsequently, the method of manufacturing a glass-coated polycarbonate transparent plate having improved abrasion resistance and scratch resistance composed of a polycarbonate, an intermediate layer and a glass film, comprising the steps of depositing a glass to a desired thickness and then raising the vacuum apparatus to atmospheric pressure. . The method of claim 1, wherein the ratio of the organic material and the argon mixed gas during ion beam deposition is 1:10 to 1: 0, the vacuum degree is 1 × 10 ^-3 to 1 × 10 ^-4 Torr, the vacuum degree during the glass deposition process Is 1 × 10 ^-4 to 10 × ^-5 Torr. The method of claim 1, wherein the intermediate layer has a thickness of 100 kPa to 1,000 kPa and the thickness of the deposited glass film is 0.1 µm to 3 µm. The method according to claim 1, wherein an oxygen ion beam having an energy of 50 to 600 eV is irradiated before or during glass deposition in order to improve adhesion between the intermediate layer and the glass film. The method of claim 1, wherein the organic material is hydrocarbons such as methane, ethane gas or cyclohexane, tetramethylcyclosiloxane, hexamethyldisiloxane, hexamethyldisilase, tetraethoxysilane, octamethylcyclotetrasiloxane, and the like. And an organic material comprising silicon, oxygen, carbon, nitrogen, and the like.

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