JPS58132029A - Surface treatment of substrate - Google Patents

Abstract

PURPOSE:To impart improved adhesiveness to the surface of a substrate comprising an organic polymer material without causing its coloration or loss of transparency, by subjecting the surface to gas discharge and chemical treatments. CONSTITUTION:The surface of a substrate comprising an organic polymer material is subjected to gas discharge and chemical treatments. The gas discharge treatment which can be applied includes a vauum glow discharge treatment, corona discharge treatment and plasma discharge treatment, among which the former two are preferred. The chemical treatment includes an acid treatment, alkali treatment, and coupling agent treatment, and especially, a treatment is preferred in which a substrate is immersed in an alkaline solution containing alkali metal or alkaline earth metal ions. This surface treatment process is most suitable when a polymethyl methacrylate resin or its derivative is used as an organic polymer material desirable for use in an information recording system in which recording is performed through a transparent substrate excellent in smoothness, such as an optical information recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface treatment method for a substrate made of an organic polymer material, and a method for surface treatment of a substrate, which is characterized in that the surface of the substrate is subjected to gas discharge treatment and chemical treatment. Regarding.

Conventionally, plastic films, plastic plates, etc. have been subjected to vacuum dull discharge treatment, plasma discharge treatment, and corona discharge treatment for the purpose of improving adhesion to the polymer layer, metal layer, or ship's shunt provided on the surface. The surface treatment mentioned earlier, including gas discharge treatment, has been carried out.

However, in order to improve the surface adhesion of a substrate made of an organic polymer material to a desired level using these methods, it is necessary to increase the time of the gas discharge treatment or to increase the time of the gas discharge treatment. Since the strength must be made thicker, the substrate itself becomes yellowish. Such coloring is unfavorable in terms of material properties and product image. Particularly when the substrate is used as an optical member, coloring the substrate during surface treatment is a fatal defect. If the substrate is made of an organic polymer material, the substrate is used under conditions where light can pass through it, and in particular, when the substrate is used for an optical information woven material, the coloring of the substrate is This phenomenon is caused by a substantial decrease in optical energy during writing and reading of information recorded on the substrate, or by scattering of light such as laser light, resulting in a decrease in information recording sensitivity and an increase in the reproduction signal. This caused extremely serious defects in practice, such as a decrease in the N ratio. If the degree of treatment is reduced by shortening the treatment time or weakening the discharge stiffness, the above-mentioned disadvantages can be prevented, but the desired adhesion of the recording layer provided on the substrate can be improved. Until now, it was considered that gas discharge treatment could not be practically used because of the characteristics listed in the table, such as the properties of the metal.

In addition to the above-mentioned coloring problem, the phenomenon of devitrification and clouding caused by strong discharge treatment can also be caused by the use of gas discharge treatment.
was limited.

The purpose of the present invention is to improve the OiI adhesion between a substrate made of an organic polymer material and a brass layer provided thereon by applying an optical surface treatment method while suppressing such coloration or devitrification. It's about doing.

This object is achieved by a method for surface treatment of a substrate, which comprises subjecting both surfaces of a substrate made of an organic polymeric material to gas discharge treatment and chemical treatment.

According to a preferred embodiment of the present invention, the gas discharge treatment is a plasma discharge treatment or an expanding corona discharge@layer, and the chemical treatment is performed in an alkali 111 solution containing alkali metal or alkaline earth metal ions. According to another preferred embodiment, the surface treatment method is characterized in that the organic polymer material is polymethyl methacrylic acid or its 11-4 form. That's true.

The present invention will be explained in detail below.

The gas discharge treatment according to the present invention refers to III: empty Darrow discharge treatment, CO2 discharge treatment, plasma discharge treatment, and the like. Here, the Makabe Gou discharge treatment ffi performs surface treatment on a substrate made of an organic polymer material by exposing it to glow discharge light emitted near the cathode of a high voltage applied electric field in a high vacuum. It is something. In the corona discharge treatment, a DC high voltage or an AC high voltage is applied across one edge in the atmosphere or vacuum to cause a corona discharge, ionize the atmospheric gas, and apply a substrate made of a 411 polymer material to this ion flow. The surface treatment of the substrate is performed by exposing the substrate. Also,
In plasma discharge treatment, aJ#M wave oscillation is performed in the atmosphere or in a specific gas at low and intermediate pressures to ionize the gas in the plasma discharge f: irradiation atmosphere, and this ion IK organic polymer material substrate is By doing this, the surface of the substrate is processed. In the present invention, plasma discharge treatment and corona discharge treatment are most preferred in terms of preventing contamination of the surface of the substrate with organic moieties.

The chemical treatment of the present invention includes acid treatment, alkali treatment, coupling agent treatment, for example, treatment using silane thread or titanium coupling agent, etc. The combination of the expression [blind.

The advantage of the surface treatment method of the present invention is that chemical treatment is performed after gas discharge treatment, thereby substantially preventing devitrification during coloring of the substrate made of an organic polymer material, and improving light intensity such as attachability. surface properties can be obtained. Since it is not necessary to use an Fi adhesive or a different type of subbing layer on the organic polymer material substrate treated with the surface treatment method of the present invention, it is possible to avoid problems of deterioration over time such as chemical changes. Among the advantages of the -B- treatment method of the present invention.

The surface treatment method of the present invention is particularly effective for organic polymeric materials that become colored or devitrify in conventional gas discharge treatment. Examples of the organic polymer material of the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, polystyrenes such as poly-α-methylstyrene, polymethyl methacrylate, polyethyl methacrylate, and polyhydrox-7-ethyl The surface treatment method of the present invention can be applied to any of 111% cellulose such as tecrylic esters such as methacrylate, polycarbonates, cellulose triacetate, and cellulose acetate butyrate.

The thickness of the substrate made of the above-mentioned organic polymer material is not limited, and can be used, for example, from 79 mm thick in the form of a film to a plate-like substrate with a thickness of 30 mm thick.

Optical information recording: Recording, reading, etc. of information is generally performed using a laser beam narrowed to a beam diameter of around 1 μm through a transparent and flat substrate, such as an optical information recorder. In the case of polymethyl methacrylate resin and its rust conductor, the surface treatment method of the present invention is most preferable as an organic polymer material preferably used in such an information recording method.

Ll in the gas discharge treatment performed in the surface treatment method of the present invention.
) Particularly preferred treatment methods are plasma discharge treatment and corona discharge treatment.

The corona discharge treatment can be carried out in the atmosphere under normal pressure using a DC high voltage or AC high voltage generator, preferably a gold-containing generator with a voltage of 1 to 100 KV and an output of 1 to 20 KW. This treatment involves transporting a substrate made of an organic or molecular material on a leopard electric support roller at a speed of 1 to 500 nm per minute through an atmosphere in which gas is ionized under corona discharge at a discharge position. It is preferable to carry out a direct treatment. The discharge electrode is preferably a thin 1ml tungsten wire, gold metal key, etc., and is placed at a position of 0.1 to 50 mm from the organic polymer material substrate to generate a uniform discharge.
I can smell it.

The plasma discharge treatment of the present invention is the most preferred treatment method. [o, o It is carried out in an atmosphere of low to medium pressure of 1 to 20 Torr, preferably 0.1 to 2 Torr. If the pressure is too low, the plasma treatment effect will not be sufficient,
If the voltage is too high, excessive current will flow, which is dangerous.

The voltage Fi applied to the aIbfi111tIL oscillation power supply that causes one lasma discharge is preferably 0.5 to 5 KV, and the oscillation output is preferably 1 to 10 GW. If it is too low, the ionization of the dregs will be reduced, and plasma will not be generated stably, and if it is too high, it is dangerous.

As the plasma discharge gas, an inert gas containing Fikrs N2% is suitable, but gases such as CF4 and CF14 can also be used. 14 depending on the oscillation conditions of the 1lId wave used by Kasu flow company, but in the case of Ar it is 10 to 50 times per minute.
m is preferred.

1. The distance between the electrodes for lasma discharge is set between 1 and 10 cm, although it varies depending on the aI class of the gas, the flow rate, and the oscillation conditions of the planar wave.

The organic polymeric material is placed or transported in a gas atmosphere under plasma discharge.

By setting the conditions as described above, it is possible to generate a powerful plasma toward the substrate made of an organic polymer material, and a preferable in-plane treatment can be performed.

In the above treatment method, the surface FkJ of the substrate is activated to a suitable state and imparts optical surface characteristics to the subsequent chemical treatment of the substrate.

The chemical treatment carried out in the surface 6-salt method of the present invention includes all treatment methods that can improve the hydrophilicity of the surface of a substrate made of an organic polymer material, including the 1alii11 composition, degree of polymerization, and average molecular weight of the organic polymer. It varies depending on the S type and properties of the layer provided by vapor deposition, etc., and is not uniformly determined, but acid treatment, alkali treatment,
Coupling agent treatment is included.

For acid treatment, a 1 to 50% by weight aqueous solution of an inorganic acid such as nitric acid or bolic acid is used, and for alkali treatment, an alkali metal such as sodium hydroxide or potassium hydroxide or an alkaline earth metal such as magnesium hydroxide is used. An aqueous solution containing ions of 1 to 50 weight percent, an alcohol solution such as methanol or ethanol, or a mixed solution of the alcohol and water in any ratio is used. Both acid treatment and alkali treatment have a treatment time of 1 to 30 minutes and a treatment time of 10 to 30 minutes.
Although the treatment lml1j at 90°C causes hyzing, in order to prevent the polymeric material itself from dissolving in the processing liquid, discoloring, and devitrification, the preferable processing conditions are 50°C and about 10 minutes.

Light and water rinsing after the chemical treatment is required to maintain the cleanliness of the substrate surface.

Further, in the coupling agent treatment, an aqueous or alcoholic solution of 0.1 to 100 weight percent of a silane coupling agent or a titanium coupling agent is used.

The treatment time is 1 to 30 minutes, and the treatment temperature is 10 to 70°C.

As a silane coupling agent, for example, SH6020, SH6026, 5) 1603 manufactured by Toray Silicone ■
2. SH6040, SH6050, SH6075, KBM-403, KBM-503, Kfl manufactured by Shin-Etsu Chemical ■
M-602 etc. can be used, but 8H-6040
provides favorable adhesion, especially when using polymethyl methacrylate resins.

As a titanium-based coupling agent, for example, Kenri Co., Ltd.
ch Petroch@m1cals Blen Act TT8.38S, 4611, 55, 1388° 134
8% can be used, but when used in dilute solution,
For polymethyl methacrylate resin.

46B provides favorable ItC'iM properties.

The am formula of various coupling agents or their main components used in the present invention is jlI9 below.

Below margin 5H6020: H2N-(CH2)2-N[(-(
CI(2), -8i(QC)15)3SH6026:
Aminosilane (CH2) 3-81 (OCH5) 5SH6040
; CHz-CI-CH20-(CH2)3-8i(
OCH5)s\8) (6050: Mixture of primary, secondary and tertiary aminosilane S■ 6075: CH2=CH81
(OCOC[(3).

KIM 602: H2N-(C12)2-NH
-(CH2)5-81(OCH3)3H5 TTg: CH3-CH-0-Ti-(OCOC
17H35)5H 461a; (CslH170)1-'rt-
(P-(OC15H27), OR14[P+0c15H
z7) 20H) 2 - In addition to using both the silane thread coupling agent and the titanium coupling agent in the St state as a surface treatment agent for substrates, it is also used as a solid content of 0.01 to 10% by weight in the fabric solution. It is added to provide adhesion that can withstand optical Kf even when used during installation.

An 1114 layer provided on a substrate made of a polymeric material subjected to the surface treatment of the present invention, for example, a layer made of a polymer in which gold Is image particles are dispersed, as a recording layer for an optical information recording medium. When using pipes, the effect of the surface treatment method of the present invention is extremely large. For example, adhesion is significantly improved in a gelatin layer containing silver particles, a polyvinyl alcohol layer containing copper particles, and a polystyrene layer containing iron particles.

By using a substrate made of an organic polymer material treated by the surface treatment method of the present invention, it has become possible to stably supply high quality optical information recording media. Media using such organic polymer materials are easier to handle than those using glass as the substrate material. It is a benefit,
It has the advantage that the high-speed rotation operation for writing information, reading out information, and playing back the history record can be performed safely without being easily damaged. be.

1. To examine the strength, adhesion, etc. of a cloth thin film when it is provided on a substrate treated with the surface treatment method of the present invention as a recording layer etc., a cloth sample is provided on the substrate. The dry adhesion property of refers to the adhesion force of one cloth @O to a substrate made of an organic polymer material, and the measurement method in the examples described later is to apply a self-adhesive tape [3M: Scotch tape] on top of the thin layer. ] was pasted on the film, and the tape was rapidly peeled off from the film, and evaluation was made based on whether or not the thin film peeled off.

Preferred embodiments of the present invention will be described in detail and specifically based on the following examples. However, embodiments of the present invention are not limited thereto.

Example 1 A clean 8-inch square O1 polymethacrylate methacrylate substrate (manufactured by Mitsubishi Rayon ■, Acrylite) was subjected to plasma discharge treatment using a plasma CVO apparatus manufactured by Nichiden ANELVA@. Plasma discharge treatment is performed using argon gas.
Applying a voltage of I KV under a vacuum of 4 Torr,
Plasma is generated with WO high # wave output, processing time is 10
Nine minutes.

Treated polymethyl methacrylate substrate at 50℃olo7
It was chemically treated by immersing it in an 11% potassium water solution for 10 minutes, washing with water, and drying.

On the treated substrate, 0.5% by weight of silane coupling M()-Reken Silicone ■No. 81(-604) was applied.
0) Wire a gelatin solution containing colloidal silver to a dry film thickness of 0.5 m.

Comparison Example 9, in which the chemical treatment in Example 1 was omitted and only plasma treatment was performed.

The plasma discharge treatment fi1- in the real jli+flll was omitted and only the chemical treatment was performed.

Implementation fI12 After performing 1C plasma treatment in the same manner as in Example 1, it was immersed for 10 minutes at room temperature in a 1:111 solution of methanol and water (8H6040C)IOIIE volume percent, washed with water, and dried.

Colloidal silver gelatin solution i on the treated j18If substrate
Wire bar cloth was made so that the thickness was 5 m.

The dry adhesion properties of the samples obtained in Examples 1-2 and Comparative 9141-2 were evaluated, and the results are shown in Table 1.

From Table 1, Examples 1 and 2 using Gfllr combined with gas discharge treatment and chemical treatment based on the present invention.
It is clear that the surface treatment method shown in Figure 1 shows very favorable adhesion properties.

All of the samples evaluated here made of 9-polymethyl methacrylate substrates had excellent transparency, and no devitrification such as discoloration or cloudiness was observed in the surface area.

Margin below Chapter 1 Table ◎ mark: No peeling was observed.

Marked in parentheses: Partial peeling is observed.

X mark: Almost peeled off.

Example f13 In Example 1, even when a polyvinyl alcohol solution of colloidal gold was used as the -4 liquid, excellent dry adhesive properties were exhibited.

Even when a polycarbonate substrate was used in place of the polymethyl methacrylate substrate in Example 1i14 and m9@i, similarly excellent adhesive properties were exhibited, and transparency was not impaired.

Example 5 In Example f11, 12N sulfur was added to the potassium hydroxide aqueous solution as the chemical treatment liquid. Soak for 5 minutes using lI. The following fabric samples were prepared in the same manner and exhibited excellent adhesive properties.

Example 6 A clean 8-inch square polymethyl methacrylate substrate (Vat-aphon)
e) Under normal pressure using a 3 KW corona discharge treatment machine,
The substrate film FIa is subjected to a corona discharge treatment. The distance between the electrode and the substrate film was 1.5 cm, the output was 2 KW, and the third chemical treatment and subsequent treatments were carried out in the same manner as in Example 1 to obtain a ms sample, which showed excellent adhesion properties.

Claims (1)

[Claims] 6. A method for manufacturing a substrate, which comprises subjecting the surface of the substrate made of an organic polymer material to gas discharge treatment and chemical treatment.