JP5188782B2 - Plasma CVD apparatus and method for forming plastic surface protective film - Google Patents

Description

  The present invention relates to a plasma CVD apparatus and a plastic surface protective film forming method for forming a hard coat layer on the surface of a substrate to be processed.

  The surface of a plastic material is generally inferior in scratch resistance to glass due to its physical properties. A highly transparent plastic material is generally lightweight, has high impact resistance, and has various advantages such as easy processing. Widely used in place of glass as a cover glass. However, transparent plastic materials obtained from polycarbonate resin, acrylic resin, and CR-39 resin (diethylene glycol bisallyl carbonate polymer, the same shall apply hereinafter) and the like have high transparency when used, particularly in optical use. Since it is emphasized, it is naturally required that the surface is not easily scratched, and there are various surface curing methods for this purpose.

  As another conventional surface hardening method for plastic materials, there is a plasma polymerization method (CVD method). In the plasma polymerization method, if an organic compound has a vapor pressure that exists as a gas in a vacuum reaction vessel, almost all of these organic compounds are polymerized by plasma excitation in the vacuum reaction vessel. It utilizes the formation of a film free from defects such as holes. Further, the reaction in the plasma polymerization method in vacuum is a reaction at room temperature, and there is an advantage that a film can be formed at a temperature lower than the durable temperature of the plastic. Moreover, the reaction in this plasma polymerization method is performed at a relatively low temperature, but the electron temperature is high, so that a reaction that occurs only at a high temperature can be performed in a chemical reaction, so the degree of crosslinking is high and the hardness is high. There is an advantage that a film having the above can be formed.

  As a plasma processing method, there are disclosures in Patent Document 1, Patent Document 2, and the like. In Patent Document 1, the anode electrode and the reactive gas blowing means are integrated. The substrate to be processed is provided on the surface of the cathode electrode. Further, only the cathode electrode is cooled, and the anode electrode is not cooled.

In Patent Document 2, the substrate to be processed is provided on the surface of the anode electrode. Further, the anode electrode is cooled and the cathode electrode is not cooled.
Therefore, both the cathode electrode and the anode electrode are not cooled.

As in Patent Document 1, providing the substrate to be processed on the surface of the cathode electrode and cooling the cathode electrode is an effective means for preventing thermal deformation of the substrate to be processed by heat transfer of the cold heat.
However, when a large amount of power is applied for a certain period of time to secure a desired film thickness, the heat generated in the electrodes is large, and it is difficult to avoid thermal deformation of the plastic substrate. In particular, thermal deformation becomes more significant as the thickness of the plastic substrate increases. In the case of a thin plastic substrate, it becomes possible to prevent thermal deformation of the plastic substrate by the heat transfer of the cold heat accompanying cooling the facing electrode, but in the case of a thick plastic substrate, the heat transfer amount is reduced. This is thought to be due to a limit.
Japanese Patent Laid-Open No. 2003-1000072 JP-A-6-228346

  Therefore, the main problem to be solved by the present invention is to prevent thermal deformation of the substrate to be processed. Another object of the present invention is to prevent thermal deformation even when the film thickness is increased with respect to a thick substrate.

The present invention that has solved this problem is as follows.
[Invention of Claim 1]
Oppositely disposed in the vacuum vessel, and having a pair of electrodes connected to a power source and grounded, and introducing the reaction gas into the vacuum vessel in a reduced pressure state, the plasma of the reaction gas is A plasma CVD apparatus formed between electrodes,
A plastic substrate is disposed on one electrode surface, and includes cooling means for forcibly cooling the electrodes,
Cold heat by the cooling means for said one electrode is, Ri relationship near cooling the substrate to be processed by heat transfer,
The one electrode is a cathode electrode and the other electrode is an anode electrode;
The substrate to be processed and the other electrode spaced apart from the substrate to be processed are provided, the reaction gas introduction head is provided therebetween, the other electrode is cooled by another cooling means, and the reaction gas Is configured to be blown out toward the substrate to be processed through the introduction head,
The inlet head has an epoxy resin, glass-epoxy laminates, fluorine resin, polycarbonate resin, selected from the group consisting of phenolic resins plasma CVD apparatus according to claim Rukoto.

(Function and effect)
In the present invention, cooling means for forcibly cooling both electrodes is provided. As described above, when a desired film thickness is to be ensured by applying a large amount of power for a certain period of time, the heat generated in the electrodes is large, and it is difficult to avoid thermal deformation of the plastic substrate.
As a result of diligent research and investigations, the present inventors have found that heat is generated not only in the amount of heat accompanying power loss in the electrode, but also in heat generated at the interface between the plasma space and the electrode. However, according to the present invention, not only the electrode on which the plastic substrate is placed but also the other electrode is cooled, so that the heat generated at the interface between the other electrode and the plasma space can be suppressed. Thermal deformation of the processing substrate can be prevented.

  One electrode is a first electrode surface (cathode electrode), and a substrate to be processed is provided thereon. As a result, a hard film can be obtained and the adhesion of the film to the substrate to be processed is higher than when a substrate to be processed is provided on the second electrode surface (anode electrode) as the other electrode. Become. The reason is considered to be that the potential difference between the plasma and the electrode surface is larger in the cathode electrode than in the anode electrode, and ions having higher energy exist.

As in Patent Document 1, the reaction gas is not blown out from the second electrode surface (anode electrode) itself, but from the reaction gas introduction head between the substrate to be processed and the second electrode surface (anode electrode). To blow out. When the reactive gas is blown out from the second electrode surface (anode electrode) itself as in Patent Document 1, plasma is turned on at the blowout port, causing abnormal discharge, or the reaction product powder is blown out from the blowout portion. It has been found that there is a case where it accumulates on the surface. Then, when the reaction gas passes through the plasma-lit outlet, the above-mentioned powder causes a coating film that should be transparent to be slightly white turbid, or a film with nonuniform film thickness or partial hardness. There is a risk of generating.
Here, as another cooling means, the same cooling method as that of one electrode (first electrode), that is, the same cooling source (for example, cooling medium) can be circulated to the other electrode (second electrode).
Further, the introduction head is heated by the generation of plasma, and may be about 100 ° C., for example. Therefore, the material of the introduction head is required to have a heat resistance of, for example, 150 ° C. or higher, but the listed materials satisfy the heat resistance. Materials such as glass and alumina are also excellent in heat resistance and can be used as the introduction head, but they are difficult to process. If the relative permittivity of the introduction head is larger than that of the vacuum, the electric field distribution can be changed. From the viewpoint of electric field distribution necessary for good film formation, it is known that the relative dielectric constant is preferably about 2.5 to 12.0. However, the listed materials are within the range of the relative dielectric constant. Exists. In conclusion, the listed materials are suitable materials from the viewpoint of heat resistance, workability, and electric field distribution necessary for good film formation.

[Invention of Claim 2 ]
The other cold heat by the cooling means, the plasma CVD apparatus according to claim 1, wherein configured to cool the reaction gas through the inlet head.

(Function and effect)
By configuring so that the reaction gas passing through the introduction head is cooled by cooling by another cooling means, not only can the generated heat at the interface between the other electrode (second electrode) and the plasma space be suppressed, Since the temperature of the reaction gas itself blown toward the processing substrate can be lowered, the effect of preventing thermal deformation of the plastic substrate to be processed becomes high.

[Invention of Claim 3 ]
The surface of the substrate has a curved surface, this and the opposed facing surfaces of the inlet head, claim 1 or 2 so as to have a curved surface so as to have a target substrate substantially uniformly spaced The plasma processing apparatus as described.

(Function and effect)
When the surface of the substrate to be processed has a curved surface, the opposing surface of the introduction head opposite to the surface to be processed has a curved surface so as to have a substantially uniform distance from the substrate to be processed, thereby making plasma uniform and stable. Therefore, a film having uniform film characteristics and a uniform film thickness can be formed on the substrate to be processed.

[Invention of Claim 4 ]
The introduction head has a large number of outlets on a wall on the substrate to be processed, and the outlets are formed in a matrix or a staggered pattern with substantially equal intervals, the shape is circular, and the diameter is 2 The plasma processing apparatus according to claim 1 , which is ˜7 mm.

(Function and effect)
The outlets are formed in a matrix or zigzag pattern with substantially uniform intervals, and if the shape is circular, the flow rate of the blowing gas from each outlet becomes uniform, and the effect of generating plasma uniformly and stably is obtained. It will be expensive. Further, when the diameter is 2 to 7 mm, the plasma reaction is stabilized and the film thickness is highly uniform. This point will be clarified by examples and comparative examples described later.

[Invention of Claim 5 ]
The plasma processing apparatus according to claim 4 , wherein a pitch of the outlets is 4 to 20 mm.

(Function and effect)
When the pitch is 4 to 20 mm, the distributed supply of the reaction gas is made uniform, so that the plasma polymerization reaction on the surface of the substrate to be processed is stabilized and the film thickness is made uniform.

[Invention of Claim 6 ]
The plasma processing apparatus according to any one of claims 1 to 5, wherein the substrate to be processed is made of a plastic material, and organosiloxane or a mixed gas of organosilane and oxygen gas is used as a reaction gas, the substrate to be processed. A method of forming a plastic surface protective film by plasma treatment, comprising forming a hard coat layer on a surface by a polymer produced by bringing the reaction gas into a plasma state.

(Function and effect)
In the present invention, the reaction gas is not limited, but when an organosiloxane or a mixed gas of organosilane and oxygen gas is used as the reaction gas, a uniform and hard film can be formed.

  According to the present invention, if necessary, thermal deformation of the substrate to be processed can be prevented. In addition, even when the film thickness is increased with respect to a thick substrate, thermal deformation can be prevented.

Next, an embodiment of the present invention will be described.
(First embodiment)
1 and 2 are illustrations of the basic form of the present invention. In the illustrated example, the first electrode 10, the second electrode 20, the processing substrate 30, and the introduction head 40 are arranged in the vertical direction, but the effect of the present invention is substantially the same even if they are arranged in the horizontal direction. I refuse to appear in advance.

  In the plasma processing apparatus of the present invention, a first electrode (cathode electrode) 10 and a second electrode (anode electrode) 20 are arranged facing the inside of the vacuum vessel 1. A substrate to be processed 30 is disposed on the surface of the first electrode 10 and supported by the holder 12. The inside of the vacuum vessel 1 is decompressed by the vacuum pump 5 from the exhaust port 4, and the reaction gas 7 is introduced into the vacuum vessel 1 from the outside through the introduction head 40, and the plasma of the reaction gas is supplied to the first electrode (cathode). An electrode) 10 and a second electrode (anode electrode) 20 are formed.

  The first electrode (cathode electrode) 10 is connected to the power source 2 via the matching box 3. The vacuum vessel 1 is insulated by an insulating seal 6. Further, although not shown in detail, a cooling medium 6A is circulated in the first electrode (cathode electrode) 10, and the substrate 30 to be processed is cooled by cooling heat transfer through the interface. Further, a shield member 14 is provided on the outer peripheral surface of the first electrode (cathode electrode) 10 excluding the surface facing the second electrode (anode electrode) 20 with a slight gap. The second electrode (anode electrode) 20 is grounded.

In the present invention, an introduction head 40 for the reaction gas 7 is provided between the substrate 30 to be processed and the second electrode (anode electrode) 20.
On the other hand, in the illustrated example, the introduction head 40 is in contact with the second electrode (anode electrode) 20, and the introduction head 40 is cooled to deform the object to be processed (substrate to be processed and / or film) by heat. In order to prevent alteration, the cooling medium 6A is circulated in the second electrode (anode electrode) 20 similarly to the first electrode (cathode electrode) 10, and cooling of the introduction head 40 is performed by cooling heat transfer through the interface. Is planned. Accordingly, the reaction gas passing through the introduction head 40 is also cooled as the second electrode (anode electrode) 20 is cooled.

  The introduction head 40 has a box shape and has a large number of outlets 40A, 40A,... On the wall on the substrate 30 side, and the reaction gas 7 is introduced into the introduction head 40 through the inflow holes 40B, 40B,. It has become. The reaction gas 7 is configured to be blown out from the blowout ports 40A, 40A,.

The introduction head 40 may be a flat box shape, and its outer shape is determined by the shape and dimensions of the substrate 30 to be processed. In the illustrated example, the shape is a flat quadrangular box, and the reaction walls 7 have inflow holes 40B, 40B,. The reason why the inflow holes 40B, 40B,... Are formed in the peripheral wall with substantially equal intervals is that if they are not uniform, a vortex is generated as a flow of the reaction gas 7 in the introduction head 40, and white powder is generated in the introduction head 40. This is for the purpose of avoiding that it is difficult to achieve uniform blowout from the blowout ports 40A, 40A.
The introduction head 40 may be a box-like structure that is uniformly dispersed from the outlets 40A, 40A..., And thus the wall 40C that is in close contact with the second electrode (anode electrode) 20 may be omitted.

The outlets 40A, 40A,... Can be formed in a matrix or zigzag as shown in FIG. The shape is preferably circular in order to ensure the uniformity of the blowing flow. It is particularly desirable that the diameter is 2 to 7 mm.
It is preferable that the pitch of the outlets 40A and 40A is 10 to 20 mm.

The introduction head 40 is preferably selected from the group of epoxy resin, glass / epoxy laminate, fluororesin, polycarbonate resin, and phenol resin for the reasons described above.
The substrate to be processed 30 is not limited to a metal plate, an inorganic material plate, or a plastic plate. Suitable plastic plates include acrylic resin and polycarbonate resin, diethylene glycol bisallyl carbonate polymer, sulfur-containing urethane resin, urethane resin, fumaric acid ester allyl resin, triazine ring acrylic resin, bromine compound resin A plate such as a sulfur-containing urethane-radical resin or a thioether ester resin can be selected.
As the reaction gas, a silicon compound is suitable, and as described in Japanese Patent No. 3446150 and Japanese Patent Laid-Open No. 5-194770, a silicon compound containing a carbon atom or a carbon atom and an oxygen atom are preferable. Alternatively, it is desirable to use a silicon compound containing a nitrogen atom.
Specific compounds include, for example, tetramethoxysilane, vinyltrimethoxysilane, octamethylcyclotetrasiloxane, tetraethoxysilane, hexamethylcyclotrisiloxane, octamethyltrisiloxane, hexamethyldisiloxane, hexamethyldisiloxane, hexaethyldisiloxane. Siloxane, hexaethylcyclotrisiloxane, tetramethylsilane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetramethyldisilazane, pentamethyldisiloxane, hexamethyldisilazane, heptamethyl Disilazane, 1,3-dimethoxytetramethyldisiloxane, 1,3-diethoxytetramethyldisiloxane, hexamethylcyclotrisilazane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1, 1, , 3,5,5,5-heptamethyltrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,3,5,5,7,7-octamethylcyclotetrasilazane, tris (trimethylsiloxy) silane, decamethyltetrasiloxane, and the like.
As a power source, a high frequency power source, a DC pulse power source, an MF power source, or the like can be used. Particularly desirable are a high frequency power source and a DC pulse power source.

(Other embodiments)
As shown in FIG. 3, in the case where the substrate to be processed 31 has a curved surface, if the wall on the side of the substrate to be processed 31 has a curved surface that is substantially the same as the curved surface of the substrate to be processed 31, The film can be stably generated, and a film having a uniform film characteristic and a uniform film thickness can be obtained on the substrate 31 to be processed. If necessary, it is desirable that the opposing surfaces of the first electrode (cathode electrode) 10 and / or the second electrode (anode electrode) 20 have the same curved surface. The first electrode (cathode electrode) 10 has the same curved surface, and the substrate 31 to be processed is cooled, and the second electrode (anode electrode) 20 has the same curved surface, so that the introduction head 41 is cooled well by heat transfer. it can. FIG. 3 shows an example in which the wall in close contact with the second electrode (anode electrode) 20 is eliminated as described above. 41B is an inflow hole for the reaction gas 7, and 41B is an inflow hole.

  As an electrode cooling means, it is simple and practical to form, for example, a bellows-like flow path in the electrode, and to circulate a cooling medium such as cooling water. It will be apparent to those skilled in the art that other cooling means can be employed.

Next, the effects of the present invention will be clarified while showing examples and comparative examples.
[Comparative example]
Based on the apparatus configuration shown in FIG. 1, the reaction gas was uniformly supplied and dispersed. The film forming conditions are as follows. In this example, the anode electrode 20 was not cooled, but only the cathode electrode was cooled. The film forming conditions are as follows. As a film formation method for ensuring the adhesion and hardness of the generated film to the substrate, the oxygen flow rate and the input power are continuously changed with the passage of the film formation time, as in the method described in Japanese Patent No. 3446150. Changed.
Deposition conditions Substrate: Polycarbonate (Thickness: 3mm)
Monomer: Octamethylcyclotetrasiloxane monomer flow rate: 20 sccm
Oxygen flow rate: 30 → 500sccm
Pressure: 1 → 4Pa
High frequency power: 50 → 800W
Deposition time: 7 minutes Cooling water temperature: 23 ° C
From the photographs shown as FIGS. 4 and 5, the substrate was thermally deformed. In order to increase the wear resistance and form a film with good adhesion, it is desirable to increase the input power of the high-frequency power supply, but one electrode (first electrode: cathode electrode) on which the substrate to be processed is installed It has been found that the thermal deformation of the substrate cannot be prevented only by cooling only the substrate.
A supplementary explanation will be given regarding the form appearing in each of the photographs. That is, when the plastic material is exposed to a temperature equal to or higher than its heat-resistant temperature, gas is generated from the inside of the resin, and a hollow can be formed inside. The size and amount of the humps differ depending on the temperature and time of exposure, and the impression received is different, but when the thermal effect is small, the humps are independent and transparent. The diameter is about 3 mm at the maximum, and most of the bumps below this diameter can be disordered. When the influence of heat increases, the number of humps increases and overlaps with each other. Also, a plurality of humps are combined, and the substrate itself is curved. In this state, the transparent material appears white

[Example]
Experiments were performed using the apparatus configuration shown in FIG. While the anode electrode 20 was also cooled, the reaction gas was cooled and supplied and dispersed uniformly from the introduction head. The film forming conditions are as follows. As a film formation method for ensuring the adhesion and hardness of the generated film to the substrate, the oxygen flow rate and the input power are continuously changed with the passage of the film formation time, as in the method described in Japanese Patent No. 3446150. Changed.
Deposition conditions Substrate: Polycarbonate (Thickness: 3mm)
Monomer: Octamethylcyclotetrasiloxane monomer flow rate: 20 sccm
Oxygen flow rate: 30 → 640sccm
Pressure: 1 → 4.5Pa
High frequency power: 50 → 800W
Deposition time: 7 minutes Cooling water temperature: 20 ° C
From the photographs shown as FIGS. 6 and 7, the substrate was not thermally deformed and was in a good surface state. This is because the substrate is cooled by cooling the cathode electrode, the anode electrode is cooled, and the temperature of the reaction gas blown out from the anode electrode is lowered to face the surface of the substrate to be processed installed on the cathode electrode. This is a result of reducing the amount of heat reaching the interface with the plasma space. When surface treatment is performed on a thick substrate, if the temperature of the electrode is increased to such a degree that the plastic material of the substrate is thermally deformed, thermal deformation of the substrate cannot be prevented only by cooling the cathode electrode provided with the substrate.

  According to the present invention, it is possible to form a uniform film on various substrates to be processed, which is hard and excellent in adhesion to the substrate to be processed. Therefore, glass substitutes such as eyeglass lenses and watch cover glasses can be obtained.

It is a schematic diagram showing an embodiment of the present invention. An example of an electrode is shown, (a) is a horizontal sectional view, and (b) shows an example of the arrangement of a large number of outlets on the substrate-side wall. It is a schematic diagram which shows another embodiment of this invention. It is a front photograph of the board | substrate obtained by the comparative example. It is a perspective photograph of the board | substrate obtained by the comparative example. It is a front photograph of the board | substrate obtained by the Example. It is a perspective photograph of the board | substrate obtained by the Example.

  DESCRIPTION OF SYMBOLS 1 ... Vacuum container, 2 ... Power supply, 5 ... Vacuum pump, 10 ... Cathode electrode, 20 ... Anode electrode, 30 ... Substrate to be processed.

Claims (6)

Oppositely disposed in the vacuum vessel, and having a pair of electrodes connected to a power source and grounded, and introducing the reaction gas into the vacuum vessel in a reduced pressure state, the plasma of the reaction gas is A plasma CVD apparatus formed between electrodes,
A plastic substrate is disposed on one electrode surface, and includes cooling means for forcibly cooling the electrodes,
Cold heat by the cooling means for said one electrode is, Ri relationship near cooling the substrate to be processed by heat transfer,
The one electrode is a cathode electrode and the other electrode is an anode electrode;
The substrate to be processed and the other electrode spaced apart from the substrate to be processed are provided, the reaction gas introduction head is provided therebetween, the other electrode is cooled by another cooling means, and the reaction gas Is configured to be blown out toward the substrate to be processed through the introduction head,
The inlet head has an epoxy resin, glass-epoxy laminates, fluorine resin, polycarbonate resin, selected from the group consisting of phenolic resins plasma CVD apparatus according to claim Rukoto. The other by cold by the cooling means, construction claims 1 plasma CVD apparatus according to cool the reaction gas through the inlet head. The surface of the substrate has a curved surface, this and the opposed facing surfaces of the inlet head, claim 1 or 2 so as to have a curved surface so as to have a target substrate substantially uniformly spaced The plasma processing apparatus as described. The introduction head has a large number of outlets on a wall on the substrate to be processed, and the outlets are formed in a matrix or a staggered pattern with substantially equal intervals, the shape is circular, and the diameter is 2 The plasma processing apparatus according to claim 1 , which is ˜7 mm. The plasma processing apparatus according to claim 4 , wherein a pitch of the outlets is 4 to 20 mm. The plasma processing apparatus according to any one of claims 1 to 5, wherein the substrate to be processed is made of a plastic material, and organosiloxane or a mixed gas of organosilane and oxygen gas is used as a reaction gas, the substrate to be processed. A method of forming a plastic surface protective film by plasma treatment, comprising forming a hard coat layer on a surface by a polymer produced by bringing the reaction gas into a plasma state.

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