JP3347973B2 - Method for producing plasma polymerized film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a plasma-polymerized film using discharge plasma under a pressure near atmospheric pressure.

[0002]

2. Description of the Related Art Conventionally, a method of modifying a surface by plasma polymerization using plasma generated by glow discharge under low pressure conditions has been put to practical use. In particular,
Methods for forming hydrophilic plasma polymerized films are described in Hozumi et al., Polymers, Vol. 42, No. 12, pp. 881-890 and Vol. 52, No. 2, p.
It is disclosed on pages 76-82. However, in this method, the film formation rate of the polymer film is as low as about 8 ° / sec. As a method for forming a hydrophilic plasma polymerized film, Japanese Patent Application Laid-Open No. 4-74525 discloses a method in which a treatment is carried out by a plasma generated in an atmosphere of argon, helium and / or acetone under a pressure near atmospheric pressure. It has been disclosed.

[0003]

However, in each of the above proposed methods, an expensive helium gas is used as a gas atmosphere, which is disadvantageous for industrial use.

The present invention has been made in view of the above problems, and uses argon or nitrogen, which is less expensive than helium, as a gas atmosphere, generates discharge plasma under a pressure near atmospheric pressure, and performs plasma polymerization of unsaturated alcohol. It is an object of the present invention to provide a method for performing the processing at higher speed than before.

[0005]

In order to achieve the above object, the present invention provides a method for producing a plasma-polymerized film, in which a plasma is applied by applying a voltage between a pair of electrodes facing each other under a pressure near atmospheric pressure. Generating a plasma-polymerized film on the substrate surface, wherein the current density is 5 to 40 mA in an atmosphere composed of argon and unsaturated alcohol.
/ Cm ² and a ratio of the current density to the unsaturated alcohol concentration (vol%) of 2.5 to 80.

In addition, nitrogen may be used in place of argon, and in an atmosphere composed of nitrogen and unsaturated alcohol, the current density is set to 10 to 120 mA / cm ² and the unsaturated alcohol concentration ( vo
1%) is preferably 5.0 to 240.

[0007] In the above-mentioned argon gas or nitrogen gas, a discharge plasma having a high current density can be generated at a pressure close to the atmospheric pressure, and stable processing can be performed. Further, since these gases are inexpensive compared to helium, they have great industrial advantages.

[0008] Here, the current density means a current per unit area flowing between the opposed electrodes. The plasma polymerization in an atmosphere consisting of argon and unsaturated alcohols of the present invention, the current density is preferably 5 to 40 mA / cm ^2, more preferably 10~30mA / cm ^2. When the current density is less than 5 mA / cm ² , the polymerization reaction of the monomer hardly proceeds, and a solid film is not formed, and an oily substance is generated. On the other hand, if the current density exceeds 40 mA / cm ² , the reaction of generating particulate matter in the gas phase proceeds, and powder is deposited on the processing substrate.

In the plasma polymerization of the present invention in an atmosphere comprising nitrogen and an unsaturated alcohol, the current density is 1
It is preferable that the 0~120mA / cm ^2, but more preferably 50~110mA / cm ^2. When the current density is less than 10 mA / cm ² , the polymerization reaction of the monomer hardly proceeds, and a solid film is not formed, and an oily substance is generated. On the other hand, if the current density exceeds 120 mA / cm ² , the reaction of generating particulate matter in the gas phase proceeds, and powder is deposited on the processing substrate.

In the plasma polymerization in an atmosphere of argon and unsaturated alcohol according to the present invention, the ratio of the current density to the unsaturated alcohol concentration (vol%) is preferably 2.5 to 80. If this ratio is less than 2.5, the energy required to form a solid film is not decomposed into alcohol monomers, and an oily substance is generated without forming a solid film. On the other hand, when this ratio exceeds 80, excessive energy is applied to the alcohol monomer, and the reaction of generating particulate matter in the gas phase proceeds, and powder is deposited on the processing substrate.

In the plasma polymerization of the present invention in an atmosphere composed of nitrogen and unsaturated alcohol, the ratio of the current density to the unsaturated alcohol concentration (vol%) is set to 5.
It is preferable to set it to 0 to 240. If this ratio is less than 5, the energy required for forming a solid film is not decomposed into alcohol monomers, and an oily substance is generated without forming a solid film. On the other hand, if this ratio exceeds 240, excessive energy is applied to the alcohol monomer, and the reaction of generating particulate matter proceeds in the gas phase, whereby powder is deposited on the processing substrate.

The unsaturated alcohol used in the method of the present invention includes unsaturated alcohols having a double bond or triple bond in the main chain, and the primary alcohol is 2-propyn-1-ol (propanol). Gil alcohol), 2-propen-1-ol (allyl alcohol), 3-
Butyn-1-ol, 2-butyn-1-ol, 2-butyn-1,4
-Diol, 3-buten-1-ol, 2-buten-1,4-diol, 4-pentyn-1-ol, 4-penten-1-ol,
5-hexyn-1-ol, 5-hexen-1-ol, 4-hexen-1-ol, 3-hexen-1-ol, 2-hexen-1
-Oars and the like. As a secondary alcohol, 3-
Buten-2-ol, 1-pentene-3-ol, 3-pentene
2-ol, 4-penten-2-ol, 1-hexen-3-ol, 1-octin-3-ol and the like. Examples of the tertiary alcohol include 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, and the like. But,
For reasons described below, 2-propyn-1-ol (propargyl alcohol) and 2-propen-1-ol (allyl alcohol) are preferred. Since these alcohols are liquid at normal temperature and normal pressure, they are used after being vaporized by means such as heating and decompression.

In general, when plasma polymerization of a monomer having a hydroxyl group is performed, the hydroxyl group in the monomer or oligomer is easily desorbed in high-energy plasma, and it is difficult to form a hydrophilic film. In consideration of this elimination, it is desirable to select a monomer from those having a high oxygen content in one monomer molecule. It is also desirable to select a monomer having a high ratio of unsaturated bonds among carbon-carbon bonds in the molecule. This has the effect of increasing the polymerization rate and the degree of cross-linking, and the effect of reducing the level of plasma electron energy required for the polymerization reaction and reducing the desorption of oxygen. For the above reasons, among the unsaturated alcohols, it is the simplest chain alcohol having a double bond or triple bond
Desirably, 2-propyn-1-ol (propargyl alcohol) and 2-propen-1-ol (allyl alcohol) are selected.

The above-mentioned pressure near the atmospheric pressure is defined as 10
A pressure range of 0 to 800 Torr is preferable, and a pressure range of 700 to 780 Torr is particularly preferable, in which pressure adjustment is easy and the apparatus is simple.

In the method of the present invention, it is preferable that a solid dielectric is provided on a surface facing at least one of the pair of electrodes. In this case, when a solid dielectric is provided on one of the opposing surfaces of the pair of electrodes, between the solid dielectric provided on the opposing surface of the one electrode and the other electrode, and on the opposing surface of both electrodes. In the case where a solid dielectric is provided, the substrate is disposed between the solid dielectrics to perform the processing.

When the solid dielectric is placed on one or both of the opposing surfaces of the electrodes, the solid dielectric and the electrode on the side on which the solid dielectric is placed are in close contact and completely cover the opposing surface of the contacting electrode. To This is because if there is a portion where the electrodes directly face each other without being covered by the solid dielectric, an arc discharge occurs therefrom.

Examples of the solid dielectric include plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, metal oxides such as silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide, and double oxides such as barium titanate. No.

The solid dielectric may be in the form of a sheet or a film, but preferably has a thickness of 0.05 to 4 mm. If the thickness is too large, a high voltage is required to generate discharge plasma. If the thickness is too small, dielectric breakdown occurs when a voltage is applied, and arc discharge occurs.

In the discharge plasma processing method of the present invention, a pulse electric field may be applied between the pair of electrodes.
It is preferable because the degree of freedom of the atmosphere gas to be used can be increased. Therefore, in the method of the present invention, a pulse electric field is formed by applying a pulse voltage between the pair of electrodes. In this case, the rise time and / or the fall time of the pulse electric field are both in the range of 40 ns to 100 μs, and the intensity of the pulse electric field is 1 to 100 kV / cm.
Is preferably within the range. Further, the rise and / or fall time of the pulse electric field is more preferably 50 ns to 5 μs. If the rise and / or fall time is less than 40 ns, it is not realistic, and if it exceeds 100 μs, the discharge state easily shifts to an arc and becomes unstable.

Here, the rise time refers to the time during which the direction of the voltage change is continuously positive, and the fall time refers to the time during which the direction of the voltage change is continuously negative. I do.

On the other hand, if the intensity of the pulse electric field is less than 1 kV / cm, the time required for the surface treatment becomes long, and if it exceeds 100 kV / cm, an arc discharge is generated, which is not preferable.

Further, when the formation time of one pulse waveform in the pulse electric field is in the range of 1 μs to 1000 μs,
The frequency is preferably in the range of 1 kHz to 100 kHz, and more preferably 3 μs to 200 μm.
s. Here, the formation time of one pulse waveform refers to the duration of one pulse waveform in a pulse electric field in which ON / OFF is repeated as shown in FIG. 1, in other words, the pulse duty time.

On the other hand, if the frequency is less than 1 kHz, the processing takes too much time, and if it exceeds 100 kHz, arc discharge is likely to occur. If the formation time of one pulse waveform is less than 1 μs, the discharge becomes unstable, and if it exceeds 1000 μs, the transition to arc discharge becomes easy.

Further, it is preferable that the pulse electric field is formed by applying a high-voltage pulse obtained by converting a high-voltage direct current with a semiconductor element having a turn-on time and a turn-off time of 500 ns or less.

The counter electrode preferably has a structure in which the distance between the counter electrodes is substantially constant in order to avoid occurrence of arc discharge due to electric field concentration. Examples of an electrode structure that satisfies this condition include a parallel plate type, a cylindrical opposed plate type, a spherical opposed plate type, a hyperboloid opposed plate type, and a coaxial cylindrical structure.

The distance between the electrodes depends on the thickness of the solid dielectric,
It is determined in consideration of the magnitude of the applied voltage, the purpose of utilizing the plasma, and the like, and is preferably 1 to 50 mm.
If it is less than 1 mm, it is not enough to install the electrodes at intervals. If it exceeds 50 mm, it is difficult to generate uniform discharge plasma.

Hereinafter, a technique for generating plasma by a pulse voltage according to the present invention will be described. In the present invention,
Although the pulse waveform of the reference pulse voltage applied between the electrodes is not particularly limited, an impulse type as illustrated in FIGS. 2A and 2B and a square wave type as illustrated in FIG. , (D) can be used. Although FIG. 2 illustrates an example in which the applied voltage is a repetition of positive and negative, a pulse voltage having only positive or negative polarity, that is, a so-called one-wave pulse voltage may be applied.

In the present invention, as for the pulse voltage applied between the electrodes, the shorter the rise time and the fall time of the pulse, the more efficiently the gas is ionized during the generation of plasma.

Further, different modulation may be performed on the pulse waveform, the rise time and the fall time, and the frequency. FIG. 3 is a block diagram showing a configuration example of a power supply circuit for forming a pulse electric field that satisfies the above conditions. FIG. 4 shows the principle of the operation by an equivalent circuit diagram. Referring to FIG.
Reference numeral 4 denotes a semiconductor element that functions as a switch in the switching inverter circuit in FIG. 3. By using a semiconductor element having a turn-on time and a turn-off time of 500 ns or less as these elements, an electric field intensity of 1 to 100 kV / cm and A high-voltage and high-speed pulse electric field having a pulse rise time and a fall time of 40 ns to 100 μs can be realized.

Next, the principle of operation will be briefly described with reference to FIG. + E is a DC voltage supply of positive polarity,-
E is a negative DC voltage supply unit. SW1 to SW4 are switch elements composed of the high-speed semiconductor elements described above. D1~4 is a diode, I ₁ ~I ₄ indicates the direction of movement of the charge.

First, when SW1 is turned on, the electric charge is I ₁
Then, one side (positive load) of a pair of electrodes placed at both ends of the discharge space is charged. Next, S
By turning off W1 and then turning on SW2 instantaneously, the charge charged to the positive load becomes SW2 and D
4 through movement in the direction of I _3.

Next, after SW2 is turned off, SW3
The If instant is turned ON to charge the other side of the electrode (negative loading) moves in the direction of charge I _2. Furthermore, after the SW3 to OFF, by turning ON the SW4 instantaneously, the charge stored in the load polarity through SW4 and D2 moves in the direction of I _4.

By repeating the above operation, an output pulse having the waveform shown in FIG. 5 can be obtained. [Table 1]
The operation table is shown in FIG. The numerical values shown in Table 1 correspond to the numerical values given to the waveforms in FIG.

[0034]

[Table 1]

The advantage of the above circuit is that even if the load impedance is high, the charged electric charge is transferred to SW
2 and D4 or SW4 and D2 can be reliably discharged, and high-speed charging can be performed using SW1 and SW3 which are high-speed turn-on switching elements. Pulse-like voltage with extremely short time and fall time,
It is possible to apply the voltage to a load, that is, between a pair of electrodes.

The pulse electric field used in the discharge plasma generating method of the present invention does not prevent a DC electric field from being superimposed on the pulse electric field thus obtained.

[0037]

EXAMPLES Examples in which discharge plasma is actually generated by applying the method of the present invention or surface treatment is performed using the discharge plasma will be described together with comparative examples. In addition, the contact angle of the obtained surface-treated product immediately after the treatment was measured. At this time, a contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. (trade name: CA-
X150) was used to measure the static contact angle. <Example 1> The apparatus used in Example 1 is schematically shown in FIG. In this apparatus, an upper electrode 12 and a lower electrode 13 are arranged in a chamber 11 having a capacity of 8 liters made of glass so as to face each other, and a pulse voltage is applied between the electrodes 12 and 13 from a pulse power supply 15. The lower electrode 13 is in a so-called electrically floating state by being supported on the chamber 11 via the insulator 16. Further, on the upper surface of the lower electrode 13, that is, the surface facing the upper electrode 13, the fixed dielectric 14 was placed in close contact. Further, an oil rotary pump (not shown) was connected to the container 11 so that the inside thereof could be evacuated. The upper electrode 12 used in this embodiment is a sprayed film of zirconium partially stabilized with 8 wt% of yttrium oxide (dielectric constant 16, film thickness 5).
Electrode (stainless steel (SUS30
4) Made, size: φ80, thickness of 80mm, φ1mm holes are arranged at 5mm intervals) as the upper electrode, this upper electrode and lower electrode (made of stainless steel (SUS304), size: φ80, thickness 80mm) 12m between electrodes
A film made of 13% titanium oxide and 87% aluminum oxide by plasma spraying on one surface of a carbon steel plate (SS41, size: φ140 mm, thickness 10 mm) as a solid dielectric on the lower electrode in a space of m 14. Thickness:
(500 μm) is placed on the lower electrode so as to cover the lower electrode, and a polyethylene base material (polybag: NP-70, manufactured by Sekisui Chemical Co., Ltd., size: 100 × 100 m) is placed on the lower electrode.
m, thickness 40 μm). The inside of the apparatus was evacuated with an oil rotary pump until the pressure reached 1 Torr.

Next, an argon gas flow rate of 990 sccm was mixed with a propargyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 10 sccm by a vaporizer in the liquid source supply apparatus by a liquid source supply apparatus (not shown). Gas (monomer concentration 1.0%) gas inlet tube (not shown)
And introduced into the container until the pressure reached 760 Torr. Thereafter, 8 kHz between electrodes and a rising speed of 500 ns
c, A pulse voltage of 2.5 kV peak-to-peak voltage was applied for 5 seconds to generate discharge plasma, which was brought into contact with a polyethylene substrate to obtain a treated product. The discharge plasma generated with the application of the voltage was in a uniform light emitting state.

For an electrode voltage of 2.5 kV, 587.5
mA current flowed and a current density of 11.7 mA / cm ² was obtained. FIG. 7 shows the waveform of the applied pulse electric field. Using the obtained surface-treated product, the contact angle immediately after the treatment and the contact angle after washing with running water for 1 minute with ion-exchanged water after the treatment were evaluated based on the above-mentioned measurement methods.

The contact angle of the substrate used in the method of the present invention was 9
6.2 degrees. <Example 2> An electrode (stainless steel) coated with a sprayed zirconium film (dielectric constant 16, film thickness 500 µm) partially stabilized with 8 wt% yttrium oxide was the same as the upper electrode used in Example 1. SUS304), size:
φ80, thickness 80 mm, φ1 mm holes are arranged at 5 mm intervals) as the upper electrode, and an Ar gas flow rate of 985 sc
15g of propagyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) vaporized by the vaporizer in the liquid raw material supply device
The same procedure as in Example 1 was performed, except that the treatment was performed with an applied voltage of 5.5 kV peak-peak voltage using a gas (monomer concentration 1.5%) mixed with ccm.

For an electrode voltage of 5.5 kV, 1360 m
A current flowed, and a current density of 27.2 mA / cm ² was obtained. <Example 3> Nitrogen gas was used instead of argon gas at a flow rate of 99.
0 sccm and a gas mixture of propargyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 10 sccm vaporized by a vaporizer in the liquid source supply device (monomer concentration 1.0
%) And the process was performed in the same manner as in Example 1 except that the treatment was performed at an applied voltage of 9.1 kV peak-peak voltage.

For a voltage between electrodes of 9.1 kV, 2516 m
A current flowed, and a current density of 50.3 mA / cm ² was obtained. <Example 4> A gas (monomer concentration 1.5%) obtained by mixing a nitrogen gas flow rate of 985 sccm with a propagyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 15 sccm vaporized by a vaporizer in a liquid material supply device was used. Example 3 was the same as Example 3 except that the treatment was performed with an applied voltage of 12.8 kV peak-peak voltage.

For an interelectrode voltage of 12.8 kV, 5282
mA current flowed and a current density of 105.6 mA / cm ² was obtained. <Example 5> The same procedure as in Example 1 was performed, except that the treatment was performed at an applied voltage of 3.3 kV peak-peak voltage using allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) instead of propargyl alcohol.

For an electrode voltage of 3.3 kV, 793.7
mA current flowed and a current density of 15.8 mA / cm ² was obtained. <Example 6> Same as Example 2 except that the treatment was performed at an applied voltage of 6.7 kV peak-peak voltage using allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) instead of propargyl alcohol.

For an interelectrode voltage of 6.7 kV, 1678 m
A current flowed, and a current density of 33.4 mA / cm ² was obtained. <Example 7> The procedure of Example 3 was repeated except that the treatment was performed at an applied voltage of 10.3 kV peak-peak voltage using allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) instead of propargyl alcohol.

For a voltage between electrodes of 10.3 kV, 2883
mA current flowed and a current density of 57.4 mA / cm ² was obtained. <Example 8> The same procedure as in Example 4 was performed except that the treatment was performed at an applied voltage of peak-peak voltage of 10.3 kV using allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) instead of propargyl alcohol.

For the inter-electrode voltage of 13.7 kV, 5687
mA current flowed, and a current density of 113.2 mA / cm ² was obtained. <Comparative Example 1> Glass (size: 140) as a solid dielectric
× 140 mm, thickness 2 mm, permittivity 5), and the same as Example 1 except that processing was performed with an applied voltage of 1.5 kV peak-peak voltage.

For an electrode voltage of 1.5 kV, 175.8
mA current flowed and a current density of 3.5 mA / cm ² was obtained. Comparative Example 2 Example 2 was the same as Example 2 except that the processing was performed with an applied voltage of 10.9 kV peak-peak voltage.

For an interelectrode voltage of 10.9 kV, 2723
mA current flowed and a current density of 54.2 mA / cm ² was obtained. <Comparative Example 3> Glass (size: 140) as a solid dielectric
× 140 mm, thickness 2 mm, permittivity 5), and the same as Example 3 except that processing was performed with an applied voltage of 4.3 kV peak-peak voltage.

For an electrode voltage of 4.3 kV, 416.9
mA current flowed and a current density of 8.3 mA / cm ² was obtained. Comparative Example 4 A sprayed zirconium film partially stabilized with 8 wt% yttrium oxide (dielectric constant 16, film thickness 50)
0μm) coated electrode (stainless steel (SUS304)
Made, size: φ80, thickness 80mm, 5 holes of φ1mm
(provided at mm intervals) as the upper electrode, and the process was carried out except that the treatment was performed with an applied voltage of peak-peak voltage 13.7 kV using allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) instead of propargyl alcohol. Same as Example 4.

For the inter-electrode voltage of 13.7 kV, 6506
mA current flowed and a current density of 129.5 mA / cm ² was obtained. <Comparative Example 5> A gas (monomer concentration: 7.0%) obtained by mixing an Ar gas flow rate of 930 sccm and a propagyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 70 sccm vaporized by a vaporizer in a liquid material supply apparatus was used. Example 1 was the same as Example 1 except that the treatment was performed with an applied voltage of a peak-peak voltage of 2.3 kV.

527.5 for an electrode voltage of 2.3 kV
mA current flowed and a current density of 10.5 mA / cm ² was obtained. <Comparative Example 6> A gas (monomer concentration: 0.4%) obtained by mixing an Ar gas flow rate of 996 sccm and a propagyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 4 sccm vaporized by a vaporizer in a liquid source supply apparatus was used. Example 2 was the same as Example 2 except that the treatment was performed with an applied voltage of 7.6 kV peak-peak voltage.

When the voltage between electrodes is 7.6 kV, 1934 m
A current flowed, and a current density of 38.5 mA / cm ² was obtained. Comparative Example 7 A peak was obtained using a gas (monomer concentration: 7.0%) obtained by mixing a nitrogen gas flow rate of 930 sccm and an allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 70 sccm vaporized by a vaporizer in a liquid raw material supply device. Example 3 except that processing was performed with an applied voltage of 7.7 kV peak voltage
And the same.

For a voltage between electrodes of 7.7 kV, 1577 m
A current flowed, and a current density of 31.4 mA / cm ² was obtained. Comparative Example 8 A peak was obtained using a gas (monomer concentration: 0.4%) obtained by mixing a nitrogen gas flow rate of 996 sccm and an allyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 4 sccm vaporized by a vaporizer in a liquid material supply device. Example 4 except that processing was performed with an applied voltage of 12.8 kV peak voltage
And the same.

For the inter-electrode voltage of 12.8 kV, 5682
A current of mA flowed and a current density of 113.1 mA / cm ² was obtained. <Example 9> Using a gas (monomer concentration 1.5%) obtained by mixing a nitrogen gas flow rate of 985 sccm and a propagyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 15 sccm vaporized by a vaporizer in a liquid material supply device, At an applied voltage of 13.2 kV peak-peak voltage, a slide glass (manufactured by Matsunami Glass Co., Ltd., micro cover glass, size: 40 × 50 mm, thickness: 120 to 170 μ) was applied to the treated substrate.
m) and the same as Example 2 except that the processing time was 3 seconds.

For the inter-electrode voltage of 13.2 kV, 3985
mA current flows and a current density of 79.7 mA / cm ² (current density / monomer concentration = 79.7 / 1.5 = 53.
1) was obtained.

When the obtained surface-treated product was subjected to XPS analysis (using apparatus: JPS-90SX manufactured by JEOL Ltd.), no Si atom peak was observed in the analysis chart. Since detection in the depth direction of XPS is about 100 °, it is considered that a polymer film of 100 ° or more is formed on the glass substrate. From this, it is considered that the film forming rate according to the present invention is 30 ° / sec or more. <Comparative Example 9> A method of forming a hydrophilic plasma polymerized film by generating glow discharge plasma under a low temperature condition as described in the prior art (Polymer Papers, Vol. 42, No. 12, pp. 881) -89
0 and Vol. 52, No. 2, pp. 76-82), and plasma polymerization of propargyl alcohol was carried out.

The apparatus shown in FIG. 6 (chamber: glass, capacity: 8)
Liter), the upper electrode (stainless steel (SUS3
04), size: φ80, thickness 80 mm, holes of φ1 mm are arranged at 5 mm intervals) 12 and lower electrode (made of stainless steel (SUS304), size: φ80, thickness 80 mm)
The lower electrode 1 in a space of 350 mm between the electrodes 13 and 13
3 on a polyethylene substrate (poly-bag made by Sekisui Chemical Co., Ltd .: NP-70, size: 100 × 100 mm, thickness 4)
0 μm). The oil rotary pump
Evacuation was performed until the pressure reached 4 Torr.

Next, a propargyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) gas flow rate of 10 sccm vaporized by a vaporizer in the liquid material supply device was introduced into the vessel from the gas supply tube by the liquid material supply device, and the pressure was set to 0.1 Torr. Pressure equilibrium state. Thereafter, an AC voltage of 13.56 kHz and a peak-to-peak voltage of 1.64 kV was applied between the electrodes for 5 seconds to generate discharge plasma, which was brought into contact with a polyethylene substrate to obtain a processed product. Similarly, the processing time is 10 seconds, 15
In seconds, a processed product was obtained. The discharge plasma generated by each voltage application in each treatment was in a uniform light emitting state.

When the XPS analysis of the obtained surface-treated product was performed in the same manner as in Example 9, peaks of Si atoms were recognized in the analysis charts of the 5-second treated product and the 10-second treated product,
No peak of Si atoms was observed in the 15-second processed product. Since detection in the depth direction of XPS is about 100 °, it is considered that a polymer film of 100 ° or more is formed on the glass substrate. From this, it is considered that the film forming rate according to the present invention is between 6.7 ° / sec and 10 ° / sec, and this value is equivalent to the film forming rate (about 8 ° / s) described in the literature.
ec). From this, the film formation rate (30 ° / sec or more) according to the method of the present invention obtained in Example 9 is:
It can be said that this is an improvement over the prior art.

The processing results of Examples 1 to 8 and Comparative Examples 1 to 8 are shown in [Table 2] and [Table 3].

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

As described above, according to the method for producing a plasma-polymerized film of the present invention, argon or nitrogen, which is cheaper than helium, is used as a gas atmosphere, and discharge plasma is generated under a pressure near atmospheric pressure. In addition, plasma polymerization of unsaturated alcohol can be performed at a higher speed than before. Further, as is clear from Tables 2 and 3, the hydrophilicity of the substrate surface can be improved by the plasma polymerized film formed by the method of the present invention.

[Brief description of the drawings]

FIG. 1 is a diagram showing one pulse electric field of a pulse electric field applied to the present invention.

FIG. 2 shows a waveform of a pulse electric field applied to the present invention.

FIG. 3 is a block diagram of a power supply for generating a pulse electric field.

FIG. 4 is an equivalent circuit diagram of a power supply that generates a pulse electric field.

FIG. 5 is a diagram of an output pulse signal corresponding to an operation table of a pulse electric field.

FIG. 6 is a schematic diagram showing a configuration of a discharge plasma generator used in each embodiment of the present invention.

FIG. 7 is a diagram showing a waveform of a pulse electric field applied in the first embodiment of the present invention.

[Explanation of symbols]

 Reference Signs List 11 chamber 12 upper electrode 13 lower electrode 14 solid dielectric 15 pulse power supply

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-10-154598 (JP, A) JP-A-9-59777 (JP, A) JP-A-9-49083 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08J ^7/ 00-7/18 C23C 14/12

Claims (6)

(57) [Claims] 1. A method for generating a plasma by applying a voltage between a pair of electrodes facing each other under a pressure close to the atmospheric pressure to form a plasma polymerized film on a surface of a substrate, comprising: In an atmosphere consisting of, while the current density is 5 to 40 mA / cm ² ,
The unsaturated alcohol concentration of the current density (vol%)
A method for producing a plasma-polymerized film, wherein the ratio to the ratio is 2.5 to 80. 2. A method for generating a plasma by applying a voltage between a pair of electrodes facing each other under a pressure close to the atmospheric pressure to form a plasma polymerized film on the surface of a base material, comprising the steps of: Wherein the current density is 10 to 120 mA / cm ² and the ratio of the current density to the unsaturated alcohol concentration (vol%) is 5 to 240 in an atmosphere consisting of Method. 3. A pulse electric field is formed by applying a pulse voltage between the pair of electrodes, and the rise and / or fall time of the pulse electric field is
3. The method according to claim 1, wherein the pulse electric field is in a range of 40 ns to 100 [mu] s and the intensity of the pulse electric field is in a range of 1 to 100 kV / cm. 4. The plasma polymerized film according to claim 3, wherein the time for forming one pulse waveform in the pulse electric field is in the range of 1 μs to 1000 μs, and the frequency is in the range of 1 kHz to 100 kHz. Production method. 5. The pulse electric field according to claim 3, wherein the pulse electric field is formed by applying a high-voltage pulse obtained by converting a high-voltage direct current by using a semiconductor device having a turn-on time and a turn-off time of 500 ns or less. Production method of plasma polymerized film. 6. A solid dielectric is provided on at least one of the opposing surfaces of the pair of electrodes, and between the solid dielectric provided on the opposing surface of the one electrode and the other electrode, or a pair of electrodes. The process according to claim 1, 2, 3, 4, or 5, wherein a treatment is performed by disposing a base material between the solid dielectrics provided on both of the opposed surfaces. Method.