JP5780154B2 - Method for producing substrate having thin film - Google Patents

Description

The present invention relates to a method for producing a substrate having a thin film having a gradient structure with a continuous film density.

  Thin film products such as anti-reflective coatings require high film density and high film hardness to improve durability and abrasion resistance. However, a thin film with high film density and film hardness is directly formed on a soft film. Then, adhesion failure and crack generation become a problem. It is known that adhesion and cracking are improved by forming a laminate having a graded structure with respect to film density (for example, Patent Document 1). However, when laminating a plurality of layers having stepped densities, for example, when forming a high film hardness and high density film on a low density film, the interface between the medium density film and the medium density film and the high density film. The interface of the film does not necessarily have sufficient adhesion, and cracks are likely to occur. As described above, in recent thin film products with advanced functions that require higher durability and abrasion resistance, further performance improvement is required.

International Publication No. 2006/033233 Pamphlet

  Accordingly, the object of the present invention is to provide high film density, high film hardness, good adhesion to the substrate and between the constituent layers, and hardly cause cracks on a flexible substrate. High durability and high abrasion resistance It is to obtain a substrate having a thin film.

  The above object of the present invention is achieved by the following means.

1. A method for producing a single layer film having a configuration in which both sides of a high film density region are sandwiched between regions where the film density continuously decreases in the thickness direction, or a substrate having these laminated films,
In a counter-roll type plasma CVD processing apparatus in which plasma discharge is performed by a pair of opposed roll electrodes, while transporting the base material to the discharge space of the plasma discharge, the maximum value of the film density per single-layer film and The single layer film is formed at a discharge intensity adjusted so that the ratio of the minimum values is 1.03 to 1.5 ,
The manufacturing method characterized by forming the said base material which has the said single layer film or these laminated films.

2. The single-layer film having a configuration in which both sides of the high-film density region are sandwiched between regions where the film density continuously decreases in the thickness direction, or a unit composed of these laminated films,
A base material formed by stacking a plurality of layers,
2. The manufacturing method according to 1 above, wherein the plurality of units form a substrate including at least units having different average film densities.

  According to the present invention, a thin film having a high film density and a high hardness with high abrasion resistance and durability in a thin film product can be obtained, and even when formed on a flexible substrate, a thin film that hardly causes poor adhesion or cracks. Is obtained.

It is the schematic which shows electrode arrangement | positioning of the plasma CVD processing apparatus of a parallel plate type and a counter roll system. It is a figure which shows typically an example of the plasma discharge processing apparatus which has two roll electrodes used for this invention. It is sectional drawing which shows typically the example which laminated | stacked the single layer film which has a gradient structure in film density. It is a figure which shows typically the example which laminated | stacked this unit as a unit by laminating | stacking a single layer film. It is a cross-sectional schematic diagram which shows an example of a structure of an antireflection film. It is a cross-sectional schematic diagram which shows the example which formed these laminated bodies using the single layer film of this invention. It is a figure which shows typically another example of the 2 frequency base plasma discharge processing apparatus using a roll electrode. It is a schematic diagram which shows an example of a gas supply means. It is a perspective view which shows an example of an applicable roll electrode. It is a figure which shows typically an example of the plasma CVD processing apparatus using a parallel plate type electrode structure. It is a figure which shows typically an example of the plasma discharge processing apparatus which used the counter electrode as the square rod-shaped electrode. It is a figure which shows typically another example of the plasma discharge processing apparatus which used the counter electrode as the square rod-shaped electrode.

  Hereinafter, modes for carrying out the present invention will be described. In addition, this invention is not limited by this.

  The present invention relates to a highly durable and highly abrasion-resistant thin film using a thin film such as a metal oxide, nitride, oxynitride or the like used for a thin film product such as an antireflection film and the production thereof.

  For example, a structure in which a low density film (low refractive index layer) of silicon oxide, a medium density film, and a high density film (high refractive index layer) such as titanium oxide are laminated on a soft resin film is well known. .

  As described above, the present invention is intended to obtain a thin film having high durability and high abrasion resistance as a thin film product on a base material in which a plurality of layers having different densities are laminated.

  The present invention is a substrate on which a thin film of metal oxide, nitride, oxynitride or the like used for thin film products is formed, and the film density is continuously increased in the thickness direction on both sides of the high film density region. Is a single-layer film having a configuration sandwiched between regions where the decrease occurs, or a substrate having a laminated film thereof, and the ratio of the maximum value of the film density and the minimum value of the single-layer film is 1.03 to It is a base material characterized by being 1.5. By having such a configuration, it is possible to improve adhesion and suppress cracks in the formed thin film product.

  In the present invention, a single layer film having a configuration in which a maximum film density region (referred to as a high film density region) in a layer having a predetermined density is sandwiched between regions where the film density continuously decreases in the thickness direction, or The substrate is characterized by using a single layer film having such a laminated film and having a gradient structure at such a film density.

  The so-called high film density region is usually a region exceeding 2.1 in the case of silicon oxide, for example, a high-density region close to the density of the bulk material in a thin film, and is a material such as alumina. If this is a region exceeding 3.5, for example, if it is titanium oxide, it is a region exceeding 4.0, and each region is formed with a film density close to the density of a dense bulk material.

  In the present invention, unlike this, the high film density region is a relative meaning of a high film density region and a low film density region in a single layer, and in an absolute sense, a high-density film of the material. It does not mean that.

  Therefore, if the film density in the high film density region of the formed single layer film is absolutely close to that of the bulk material and the average film density is increased in an absolute sense, a so-called “high density” film is obtained. When the film density of the region is formed at a relatively low film density and the average film density is set at a relatively low density, a so-called “low density” film is obtained. In short, the film density is characterized by an inclination.

  For example, when the density of the low density region is the same, when this ratio is large (for example, 1.5), a “high density” film as a whole with an inclined structure is used, and when the ratio is close to the minimum (for example, 1.03), “low density” Constitutes the membrane.

  In the single layer film according to the present invention, the ratio between the maximum value and the minimum value of the film density is in the range of 1.03 to 1.5.

  A single layer film having a film density ratio within the range of the present invention has good adhesion to the base material (also between the single layer films), film hardness, cracks, and the like. If the film density ratio is too small, as a result, in the case of a film having a high average film density, the adhesiveness is lowered and cracks and the like are easily generated. When the average film density is low, there is a problem with the film hardness. On the other hand, if the film density ratio is too large, the adhesion is good, but the cracks deteriorate and the film hardness of the surface also decreases.

  In the present invention, such a thin film having a continuously inclined structure in the film thickness direction is, for example, a coating method, a vapor deposition method, a sputtering method, a spray pyrolysis method, a low pressure plasma CVD method, an atmospheric pressure plasma CVD method. The method is not limited, but a method suitable for a continuous process is preferable in order to obtain a high productivity using a flexible substrate. Among them, atmospheric pressure plasma is preferable from the viewpoint of continuous productivity and film quality. The CVD method is preferred.

  In film formation using a plasma CVD discharge processing apparatus, a dense high film density thin film is formed in a plasma space where the discharge intensity is high, and a low film density film is formed where the discharge intensity is low. Accordingly, a film having a high film density is formed when the discharge output is large, and a film having a low film density is formed when the discharge output is small.

  For example, FIG. 1A shows an electrode arrangement of a plasma CVD processing apparatus having parallel plate electrodes. Since the gap between the electrodes between the parallel electrodes is uniform, the discharge intensity is also substantially uniform, and between the parallel plate electrodes. A monolayer film having a substantially uniform film density can be formed on a substrate conveyed (or placed) in the discharge space. When the discharge output is increased, the discharge intensity is increased and a film having a high film density is formed. When the discharge output is decreased, a film having a low film density is formed.

  In the case of a plasma CVD apparatus, the discharge intensity is approximately proportional to the light emission intensity in the discharge space, so that the light emission intensity and the film density are substantially correlated.

  FIG. 1B shows an outline of the electrode arrangement of the counter roll type plasma CVD processing apparatus. In this case, if the discharge output is increased between the counter roll electrodes, the discharge spreads in the roll circumferential direction. Because of the curvature of the roll electrode, the discharge intensity is distributed in the discharge space between the roll electrodes. That is, the discharge intensity is high in the central part where the discharge gap (interelectrode gap) is narrow, and the discharge intensity is low where the discharge gap is wide, away from the roll circumferential direction.

  When the parallel plate electrode is used in FIG. 1 (a), and when the counter roll type plasma CVD discharge treatment apparatus is used in FIG. 1 (b), the discharge intensity distribution between the respective electrodes and the substrate The density profile in the film thickness direction of each of the films formed above is schematically shown. In FIG. 1A, a single-layer film having a uniform film density profile is shown. In FIG. 1B, both sides of the maximum film density region are regions where the film density continuously decreases in the thickness direction. A single-layer film having an inclined structure in which the film density is sandwiched is obtained.

  Similarly, in the case of an electrode arrangement in which one side shown in FIG. 1 (c) is a roll electrode, a discharge intensity distribution is similarly generated, and a single layer film having a gradient film structure is obtained.

  In the opposed roll type plasma CVD processing apparatus, the substrate transported between the opposed roll electrodes is first formed into a film in a discharge space that is circumferentially separated from the center of the electrode where the discharge gap is the narrowest. While being transported, the film is gradually deposited at the portion of the discharge center where the discharge gap is the narrowest and the discharge intensity is large, and after this, the film is deposited again in the discharge space away from the center in the roll circumferential direction. Therefore, when looking at the film thickness profile, a single layer film having a gradient structure in which the film density sandwiched between the areas where the film density continuously decreases in the thickness direction on both sides of the maximum film density area can be obtained.

  The film thickness of such a single layer film having an inclined structure with a film density formed using a counter roll type plasma CVD discharge processing apparatus is determined by the transport speed, and the film thickness depends on the discharge conditions together with the transport speed. A density profile (maximum film density, minimum film density) is determined. By transporting the base material at a constant speed, a single-layer film having a gradient structure in which the film density is sandwiched between areas where the film density continuously decreases in the thickness direction on both sides of the maximum film density area as described above. Obtained above.

  In the obtained single-layer film, the region having the maximum film density is defined as one of the discharge gaps after the substrate is left in the discharge space and the film is formed under the same discharge conditions in the plasma CVD apparatus. Corresponds to the film density of the film formed at the narrowest electrode center, and the film density of the thin film formed in the discharge space separated in the circumferential direction of the roll electrode corresponds to the film density in the low film density region. .

  In this invention, although the density of the thin film formed on a resin base material can be calculated | required using a well-known analysis means, in this invention, the value calculated | required by the X-ray reflectivity method is used.

  The outline of the X-ray reflectivity method is described in page 151 of the X-ray diffraction handbook (Science Electric Co., Ltd., 2000, International Literature Printing Co., Ltd.) 22 can be performed.

  Specific examples of measurement methods useful in the present invention are shown below.

  The X-ray reflectivity method is a method in which X-rays are incident on a material having a flat surface at a very shallow angle, and measurement is performed using MXP21 manufactured by Mac Science. Copper is used as the target of the X-ray source and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator. The incident slit is 0.05 mm × 5 mm, and the light receiving slit is 0.03 mm × 20 mm. Measurement is performed by the FT method with a step width of 0.005 ° and a step of 10 seconds from 0 to 5 ° in the 2θ / θ scan method. With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. Curve fitting is performed using 1, and each parameter is obtained so that the residual sum of squares of the actual measurement value and the fitting curve is minimized. From each parameter, the thickness and density of the laminated film can be obtained. The film thickness evaluation of the laminated film in the present invention can also be obtained from the X-ray reflectivity measurement.

  Using this method, the density of a ceramic film such as silicon oxide, silicon nitride, or silicon oxynitride formed by another method such as an atmospheric pressure plasma method or a vapor deposition method can be measured.

  By changing the transport speed and film formation conditions by this method, it is possible to form a single layer film in which the ratio between the maximum value and the minimum value of the single layer film has various values. it can.

  In the present invention, the ratio between the maximum value of the film density and the minimum value of the single layer film having a structure in which both sides of the high film density region are sandwiched between regions where the film density continuously decreases in the thickness direction. Is in the range of 1.03-1.5. By using such a single layer film, it is possible to form a film on various substrates with good adhesion because of the stress relaxation action in the low density region, and the adhesion between the films is also good at the time of lamination.

  In the present invention, when a film is formed on a substrate, a low-density and therefore flexible film is formed at the initial stage of the film formation, so that the film is well attached and the substrate is also cracked by bending or the like. It becomes a difficult film. In addition, in the case of lamination of single-layer films having a gradient structure in film density, even if the average of the film density is a lamination of films that differ in stages, the interface is an interface between low-density films, Good adhesion and good film.

  In addition, since the low density region is flexible and has a stress relieving effect, when such a single layer film is used, cracks and the like are generated even when a plurality of layers are stacked as compared with the case where a single layer is formed with a high density film. Hateful.

  FIG. 3A is a cross-sectional view schematically showing an example in which such single-layer films having the same average film density are stacked.

  FIG. 3B is a cross-sectional view showing an example in which a plurality of single-layer films having different average film densities and inclined structures are laminated. Here, four single-layer films having different average film densities are laminated as one unit, and the average film density of each layer (unit) is, for example, base material F / layer 1 <layer 2 <layer 3> layer. 4 can be designed.

  FIG. 4 shows an example in which a single layer film having a gradient structure with the same average film density is laminated to form one unit, and this unit is laminated. A plurality of units having different average film densities are stacked using a unit in which a plurality of single-layer films having an inclined film density are stacked, and the average film density of each layer unit as described above is determined as layer unit 1 < It can also be designed as layer unit 2 <layer unit 3> layer unit 4. FIG. 4 schematically shows this example.

  In FIG. 4, two layers of single-layer films having a gradient structure are laminated to form one unit, but may be composed of three or more layers. Even if the number of single-layer films constituting one unit increases (even if the layer thickness increases), cracks and peeling occur as compared to a uniform single-layer film having the same film density and the same film thickness. A laminated film having flexibility that is difficult to crack and hardly cracks is formed.

  A film unit formed by laminating two single-layer films having an inclined film density structure is easily formed by using an atmospheric pressure plasma CVD processing apparatus having a counter roll electrode as shown in FIG. 7 described later. . In this apparatus, since the roll-shaped substrate is subjected to the plasma discharge treatment twice, the thin film having the continuous gradient structure as described above is laminated and formed twice. Therefore, when this is used as one unit and a plurality of thin films are further formed under different discharge conditions, the base material on which the units having different average film densities shown in FIG. 4 are stacked can be obtained.

  FIG. 5 shows an antireflection film in which a uniform low-density layer (low refractive index) L, medium-density layer (medium refractive index) M, and high-density layer (high refractive index) H are laminated on a substrate F. An example of the configuration is shown.

  The refractive index of the high-density layer (high refractive index) is, for example, 1.8 to 2.2 as the refractive index for a light beam with a wavelength of 450 nm, and the refractive index of the low-density layer (low refractive index) is 1.4. This is configured to be about 1.6 or less, and the intermediate density layer is selected to have an intermediate refractive index.

  Also in such a configuration, the stress relaxation action of the low density film is used, so that a certain amount of bending, thermal expansion, or the like is unlikely to cause cracks.

  However, there is a discontinuous density change at each layer interface of the high-density layer, medium-density layer, and low-density layer, and it cannot be said that the adhesiveness is sufficient. Cracks still occur when exposed. However, this problem can be solved by using a single-layer film unit having a gradient film density structure or a unit composed of a plurality of single-layer films according to the present invention shown in FIG. Even if the average film densities of the single-layer films having a gradient structure according to the present invention are different from each other, the film density on the film surface is lower than the film density at the center of the film thickness. There is no large density gap between the laminated films, and the adhesion is improved.

  FIG. 6 shows an example in which these laminated bodies are formed using the single layer film of the present invention having a gradient structure in film density.

  In FIG. 6A, the single layer film of the present invention having different average film densities is used as a low density layer (low refractive index) L, a medium density layer (medium refractive index) M, and a high density layer (high refractive index) H. In addition, in FIG. 6B, two single-layer films of the present invention having the same average film density are laminated to form a layer unit as a low-density layer (low refractive index) L and a medium-density layer (medium An example in which each layer unit is used as a refractive index (M) and a high-density layer (high refractive index) H is shown. When the above layers having different average film densities are laminated, the low-density regions are in close contact with each other between the constituent layers, so that there is a problem in adhesion even if the other layers have different average film densities. Hateful.

  Each single-layer film having a different path can be confirmed by a tomographic photograph.

  When such a film configuration is adopted, that is, each single layer film itself has a gradient structure with respect to the film density, and further, a laminated structure of films having different average densities as a whole has a further stress relaxation effect. Adhesion is improved, and there is a great effect in suppressing cracks.

  Next, a method for producing a single layer film according to the present invention having a configuration in which both sides of a high film density region are sandwiched by regions where the film density continuously decreases in the thickness direction will be described.

  As described above, the present invention can be carried out by utilizing the discharge intensity distribution using an opposed roll type atmospheric pressure plasma CVD processing apparatus. When the discharge output is increased by the opposed roll method, the discharge spreads in the circumferential direction, and the discharge space has a discharge intensity distribution due to its curvature. When the discharge gap is narrow, the discharge intensity is large, and at a wide portion, that is, at the discharge end, the discharge intensity is small. As a result, when the film is transported through the discharge space and deposited on the substrate, the film quality, particularly the film The density has an inclined structure in the thickness direction.

  Generally, the light emission intensity at the narrowest part of the discharge gap / the light emission intensity at the end of the discharge = 1.5 or more, and it can be considered that the light emission intensity distribution≈the discharge intensity distribution. The film density at the end is 1.5 or more.

  Therefore, in the present invention, by adjusting the light emission intensity, that is, the discharge intensity at the narrowest part of the discharge gap, the ratio of the maximum value and the minimum value of the film density of the formed single layer film is 1.03. Adjust to ~ 1.5. Those having a film density ratio in the range of the present invention have good adhesion to the substrate (and between the single-layer films), and also have good film hardness, cracks, and the like.

  Next, an atmospheric pressure plasma CVD processing apparatus will be described.

  FIG. 2 is an example of a plasma discharge treatment apparatus used in the present invention, and is a diagram schematically showing a plasma discharge treatment apparatus used for forming a thin film on a substrate using two roll electrodes. This plasma discharge processing apparatus has a pair of roll electrodes 10A and 10B having the same diameter, and a power supply 80 capable of applying a voltage for plasma discharge to these roll electrodes 10A and 10B is a voltage supply means 81. And 82 are connected. The roll electrodes 10 </ b> A and 10 </ b> B are rotating electrodes that can rotate while winding the base material F. The discharge unit (also referred to as discharge space) 100 is maintained at, for example, atmospheric pressure or a pressure in the vicinity thereof, the process gas G is supplied from the process gas supply unit 30, and plasma discharge is performed in the discharge unit 100 having the discharge space gap L. Is done.

  The base material F supplied from the pre-process or the original winding roll is brought into close contact with the roll electrode 10A by the guide roll 20 and is rotated and transferred in synchronization, and plasma discharge treatment is performed by the processing gas G in the discharge unit 100.

  The processing gas supply means 30 is preferably in the form of a slit that is the same as or slightly wider than the width of the base material, or pipe-shaped outlets are arranged side by side so as to be equivalent to the width of the base material. The processing gas G may be introduced into the discharge unit 100 at a uniform flow rate or flow rate throughout the width direction. The treated base material F passes through the roll 11 and is taken up or transferred to the next step (none is shown). The treated gas G ′ is exhausted from the exhaust port 40. The exhaust flow rate from the exhaust port 40 is preferably equal to or slightly higher than the flow rate from the processing gas supply means 30. The side surfaces of the roll electrodes 10A and 10B of the discharge unit 100 may be shielded, or the entire apparatus may be surrounded and filled with a rare gas or a processing gas.

  In the plasma discharge processing apparatus, the processing gas supply means supplies a processing gas having an atmospheric pressure or a pressure near it between the counter electrodes, or a discharge space is formed under an atmospheric pressure or a pressure near it. It is preferable.

  Plasma discharge treatment equipment performed at or near atmospheric pressure does not need to be reduced in pressure compared to plasma CVD under vacuum, and is not only highly productive, but also has a high plasma density. The film-forming speed is high, and further, under high pressure conditions such as under atmospheric pressure compared with the conditions of normal CVD method, the mean free path of gas is very short, so that an extremely high quality film can be obtained. In the present invention, the vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa, but 93 kPa to 104 kPa is preferable for obtaining a good effect.

  FIG. 2 shows a plasma discharge processing apparatus having a power source 80 that can apply a voltage for a single plasma discharge to the roll electrodes, and a high-frequency power source in one frequency band. A power source having a different frequency is installed in each roll electrode. It is also a preferable aspect to use a plasma discharge treatment apparatus that superposes the first high-frequency electric field and the second high-frequency electric field to perform plasma discharge.

  FIG. 7 is a diagram schematically showing a plasma discharge processing apparatus for processing a substrate using a two-frequency roll electrode as another example of the plasma discharge processing apparatus used in the present invention. This apparatus has a pair of roll electrodes 10A (first electrode) and a roll electrode 10B (second electrode). A first power supply 801 capable of applying a high-frequency voltage V1 having a frequency ω1 for plasma discharge is connected to the roll electrode 10A via a voltage supply unit 811. A second power source 802 capable of applying a high-frequency voltage V2 having a frequency ω2 for plasma discharge is connected to the roll electrode 10B via a voltage supply unit 812. The first power source 801 preferably has the ability to apply a higher frequency voltage (V1> V2) than the second power source 802, and the first frequency ω1 of the first power source 801 and the second frequency of the second power source 802 are the same. The frequency ω2 is preferably ω1 <ω2. Between the roll electrode 10A and the first power source 801, a first filter is installed (omitted) so that a current from the first power source 801 flows toward the roll electrode 10A, and the first power source 801 is omitted. The current I1 from the second power source 802 is designed to be less likely to pass to the ground side, and the current I2 from the second power source 802 is easily passed to the ground side. A second filter is provided between the roll electrode 10B and the second power source 802 so that the current from the second power source 802 flows toward the roll electrode 10C (omitted). Current I2 is less likely to pass to the ground side, and current I1 from the first power source 801 is designed to easily pass to the ground side.

  As another discharge condition, a high frequency voltage is applied between the first electrode and the second electrode facing each other, and the high frequency voltage is superimposed on the first high frequency voltage V1 and the second high frequency voltage V2. When the discharge start voltage is IV, it is preferable that V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied, and more preferably, V1> IV> V2.

  Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a sine wave or a pulse. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more.

  The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The base material F supplied from the pre-process or the original winding roll is brought into close contact with the roll electrode 10A by the guide roll 20 and is rotated and transferred in synchronization, and plasma discharge treatment is performed by the processing gas G in the discharge unit 100.

  The processing gas supply means 30 is preferably in the form of a slit that is the same as or slightly wider than the width of the base material, or pipe-shaped outlets are arranged side by side so as to be equivalent to the width of the base material. The processing gas G may be introduced into the discharge unit 100 at a uniform flow rate or flow rate throughout the width direction. The treated base material F passes through the folding rolls 11A, 11B, 11C and 11D, is transferred in the reverse direction, is held by the roll electrode 10B, is again subjected to plasma discharge treatment in the discharge unit 100, and is wound up via the guide roll 21. Or transferred to the next step (both not shown). The treated gas G ′ is exhausted from the exhaust port 40. The exhaust flow rate from the exhaust port 40 is preferably equal to or slightly higher than the flow rate from the processing gas supply means 30. The side surfaces of the roll electrodes 10A and 10B of the discharge unit 100 may be shielded, or the entire apparatus may be surrounded and filled with a rare gas or a processing gas.

  In the plasma discharge processing apparatus, the processing gas supply means supplies a processing gas having an atmospheric pressure or a pressure near it between the counter electrodes, or a discharge space is formed under an atmospheric pressure or a pressure near it. It is preferable.

  FIG. 7 shows a configuration in which a two-frequency system is applied as an applied power source, and since the base material F is discharged twice under the same conditions, a single layer film having the same inclined structure in the film thickness direction. Two layers can be formed at a time, and the two-layered film unit shown in FIG. 4 can be formed at a time.

As the first power source 2 (high frequency power source),
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
B6 Pearl Industry 20-99.9MHz RP-2000-20 / 100M
And the like, and any of them can be used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high frequency power source that can apply only a continuous sine wave.

[Gas supply means]
In the plasma discharge treatment apparatus, from the viewpoint of stably forming a thin film having an inclined structure in the film quality, it is a more preferable aspect to have various gas supply means shown below in the discharge part.

  FIG. 8 is a schematic diagram showing an example of gas supply means applicable to the plasma discharge processing apparatus.

  In FIG. 7, the processing gas G blows out in the direction of the gap between the roll electrodes 10A and 10B, but if the gap between the roll electrodes is narrow at that time, the entire amount of the blown processing gas cannot necessarily pass through the gap. A part of the gas leaks from the gap between the processing gas supply means 30 and the roll electrode and blows out to the outside, so that an extra processing gas is required and the processing chamber is filled. Here, as shown in FIG. 8, as a means for shutting out the leaked processing gas, the processing gas supply means 30 is provided with a blowing outlet for blowing the auxiliary gas CG in the same direction as the blowing direction of the processing gas.

  Here, the processing gas G is composed of a discharge gas and a thin film forming gas, the discharge gas is an inert gas such as a rare gas or nitrogen, and the thin film forming gas is a raw material gas that is a raw material that is a raw material of a deposited film and a decomposition gas. It consists of reactive gas that promotes. The auxiliary gas CG is made of an inert gas such as a rare gas or nitrogen, and preferably has the same composition as the discharge gas in the processing gas G or the same composition as the discharge gas and the reactive gas.

  Furthermore, the flow rate at which the auxiliary gas is blown out is preferably equal to or higher than the flow rate at which the processing gas G is blown out at the supply port of the processing gas supply unit 30. If it is less than this, the effect of the auxiliary gas is small, and if it is 5 times or more, it becomes difficult to supply the processing gas G to the discharge space 100.

  The angle θ at which the auxiliary gas CG is blown to the roll electrodes 10A and 10B is set between 0 ≦ θ <90 °, and along with the effect as the auxiliary gas CG, the accompanying air flows from the side surface of the processing gas supply means 30 and the roll electrode 10A, It can prevent mixing from between 10C. And preferably 0 ≦ θ <60 °, more preferably 0 ≦ θ <30 °. This is because when the angle is 90 ° or more, the component of the auxiliary gas CG toward the discharge space 100 decreases, and the effect cannot be obtained. Here, θ is an angle formed by the direction in which the processing gas blows out and the direction in which the auxiliary gas blows out. The material of the gas supply unit 30 for supplying the processing gas G and the auxiliary gas CG is preferably an insulating material such as ceramic such as alumina or resin, and particularly preferably a heat resistant resin such as PEEK (polyether ether ketone).

  The plasma discharge treatment apparatus that can be used in the present invention is further exemplified.

  FIG. 11 is a diagram schematically showing a plasma discharge processing apparatus for processing a substrate using a two-frequency roll electrode, which is an example of a plasma discharge processing apparatus in which only one side is a roll electrode and a counter electrode is a square rod electrode. It is. This apparatus has a roll electrode 10A (first electrode) and a square bar electrode 10C (second electrode). A first power supply 801 capable of applying a high-frequency voltage V1 having a frequency ω1 for plasma discharge is connected to the roll electrode 10A via a voltage supply unit 811. A second power source 802 capable of applying a high-frequency voltage V2 having a frequency ω2 for plasma discharge is connected to the rectangular rod-shaped electrode 10C via a voltage supply means 812. The first power source 801 preferably has the ability to apply a higher frequency voltage (V1> V2) than the second power source 802, and the first frequency ω1 of the first power source 801 and the second frequency of the second power source 802 are the same. The frequency ω2 is preferably ω1 <ω2. Between the roll electrode 10A and the first power source 801, a first filter is installed (omitted) so that a current from the first power source 801 flows toward the roll electrode 10A, and the first power source 801 is omitted. The current I1 from the second power source 802 is designed to be less likely to pass to the ground side, and the current I2 from the second power source 802 is easily passed to the ground side. In addition, a second filter is provided between the rectangular rod-shaped electrode 10C and the second power source 802 so that a current from the second power source 802 flows toward the roll electrode 10C (omitted), and the second power source 802 is omitted. The current I2 from the first power source 801 is designed to be easily passed to the ground side.

  As another discharge condition, a high frequency voltage is applied between the first electrode and the second electrode facing each other, and the high frequency voltage is superimposed on the first high frequency voltage V1 and the second high frequency voltage V2. When the discharge start voltage is IV, it is preferable that V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied, and more preferably, V1> IV> V2.

  As the frequency of the first power source, 200 kHz or less can be preferably used. The electric field waveform may be a sine wave or a pulse. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more.

  The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The base material F supplied from the pre-process or the original winding roll is brought into close contact with the roll electrode 10A by the guide roll 20 and is rotated and transferred in synchronization, and plasma discharge treatment is performed by the processing gas G in the discharge unit 100.

  The processing gas supply means 30 is preferably in the form of a slit that is the same as or slightly wider than the width of the base material, or pipe-shaped outlets are arranged side by side so as to be equivalent to the width of the base material. The processing gas G may be introduced into the discharge unit 100 at a uniform flow rate or flow rate throughout the width direction. The treated base material F is wound up through the guide roll 22 or transferred to the next step (none is shown).

  On the other hand, the base material F ′ transported in the reverse direction on the rectangular rod-shaped electrode 10C (second electrode) is a substrate for cleaning the rectangular rod-shaped electrode 10C, and a PET film or the like is used. 21 is wound up. Moreover, you may circulate and use.

  The treated gas G ′ is exhausted from the exhaust port 40. The exhaust flow rate from the exhaust port 40 is preferably equal to or slightly higher than the flow rate from the processing gas supply means 30. The side surfaces of the roll electrodes 10A and 10B of the discharge unit 100 may be shielded, or the entire apparatus may be surrounded and filled with a rare gas or a processing gas.

  In the plasma discharge processing apparatus, the processing gas supply means supplies a processing gas having an atmospheric pressure or a pressure near it between the counter electrodes, or a discharge space is formed under an atmospheric pressure or a pressure near it. It is preferable.

  Also for the plasma discharge processing apparatus shown in FIG. 11, the first power source (high frequency power source) and the second power source (high frequency power source) can be the same as those in the apparatus of FIG. 7.

  The gas supply means is also shown in FIG.

  FIG. 12 further shows another example of a plasma discharge processing apparatus in which only one side is a roll electrode and the counter electrode is a square bar electrode. The one shown in FIG. 11 is a simpler plasma discharge treatment apparatus that does not use a cleaning base material for the square bar electrode 10C (second electrode), and is suitable for implementation on a small scale. The configuration of the apparatus shown in FIG. 11 is basically the same as that of the other parts, and the description thereof is omitted.

  Next, details of main components of the plasma discharge processing apparatus used in the present invention will be described.

[Roll electrode]
FIG. 9 is a perspective view showing an example of an applicable roll electrode.

  The configuration of the roll electrode 10 will be described. In FIG. 9A, the roll electrode 10 is inorganic after a ceramic is sprayed on a conductive base material 200a (hereinafter also referred to as “electrode base material”) such as metal. It is composed of a combination in which a ceramic-coated dielectric 200b (hereinafter also simply referred to as “dielectric”) coated with a material is covered. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferably used because it is easily processed.

  Further, as shown in FIG. 9B, the roll electrode 10 ′ may be constituted by a combination in which a conductive base material 200A such as metal is coated with a lining dielectric 200B provided with an inorganic material by lining. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass and the like are preferably used. Of these, borate glass is more preferred because it is easy to process.

  Examples of the conductive base materials 200a and 200A such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing.

  As for each roll electrode 10 concerning the present invention, it is desirable to adjust temperature, such as heating or cooling, as needed. For example, a liquid is supplied into the roll electrode to control the temperature of the electrode surface and the temperature of the substrate. As the liquid that gives temperature, an insulating material such as distilled water or oil is preferable. Although the temperature of a base material changes with process conditions, it is usually preferable to set it as room temperature-200 degreeC, More preferably, it is set as room temperature-120 degreeC.

  The surface of the roll electrode is required to have high smoothness because the substrate is in close contact and the substrate and the electrode are transferred and rotated in synchronization. The smoothness is expressed as the maximum surface roughness height (Rmax) and centerline average surface roughness (Ra) defined in JIS B 0601. Rmax of the surface roughness of the roll electrode according to the present invention is preferably 10 μm or less, more preferably 8 μm or less, and particularly preferably 7 μm or less. Further, Ra is preferably 0.5 μm or less, and more preferably 0.1 μm or less.

  In the present invention, the gap between the roll electrodes is determined in consideration of the thickness of the solid dielectric, the magnitude of the applied voltage, the purpose of using plasma, the shape of the electrode, and the like. The distance between the electrode surfaces is preferably 0.5 to 20 mm, more preferably 0.5 to 5 mm, and particularly preferably 1 mm ± 0.5 mm from the viewpoint of uniformly generating plasma discharge. In the present invention, the gap between the roll electrodes refers to a distance at which the opposing electrode surfaces are closest to each other. The diameter of the roll electrode is preferably 10 to 1000 mm, more preferably 20 to 500 mm. Moreover, the peripheral speed of a roll electrode is 1-100 m / mim, More preferably, it is 5-50 m / mim.

[Processing gas]
A processing gas used when forming a thin film of metal oxide, nitride, oxynitride, or the like according to the present invention using a plasma discharge processing apparatus will be described.

  As the processing gas, it is particularly preferable to use a mixed gas mainly of a discharge gas and a thin film forming gas (also called a reactive gas).

(Discharge gas)
Examples of useful discharge gas (also referred to as rare gas) elements include nitrogen and group 18 elements of the periodic table, specifically nitrogen, helium, neon, argon, krypton, xenon, radon, and the like. In the present invention, nitrogen, helium and argon are preferable, and nitrogen is particularly preferable. The concentration of the rare gas in the processing gas is preferably 90% by volume or more in order to generate stable plasma. 90-99.99 volume% is especially preferable. The rare gas is necessary for generating plasma discharge, and the reactive gas in the plasma discharge is ionized or radicalized and contributes to the surface treatment.

(Thin film forming gas)
In the present invention, as the thin film forming gas, various substances are used depending on the type of the functional thin film formed on the substrate. For example, a low refractive index layer useful for an antireflection layer or the like can be formed by using a silicon compound as a thin film forming gas. Further, by using an organometallic compound containing a metal such as Ti, Zr, Sn, Si, or Zn, a metal oxide layer or a metal nitride layer can be formed. A useful medium refractive index layer or high refractive index layer can be formed, and a conductive layer or an antistatic layer can also be formed.

  Thus, a metal compound etc. can be mentioned preferably as a reactive gas substance useful for this invention.

  Examples of reactive gas metal compounds that can be preferably used in the present invention include Al, As, Au, B, Bi, Ca, Cd, Cr, Co, Cu, Fe, Ga, Ge, Hg, In, Li, Mg, and Mn. , Mo, Na, Ni, Pb, Pt, Rh, Sb, Se, Si, Sn, V, W, Y, Zn, Zr, and other metal compounds or organometallic compounds can be mentioned, and Al, Ge, In, Sb, Si, Sn, Ti, W, Zn or Zr is preferably used as the organometallic compound.

  Among these, examples of the silicon compound include silicon such as alkyl silane such as dimethylsilane and tetramethylsilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, and ethyltriethoxysilane. Examples include organosilicon compounds such as alkoxides; silicon hydrogen compounds such as monosilane and disilane, halogenated silicon compounds such as dichlorosilane, trichlorosilane, and tetrachlorosilane, and other organosilanes. The present invention is not limited to these. Moreover, these can be used in combination as appropriate. The above-mentioned organosilicon compounds are preferably silicon alkoxides, alkylsilanes, and organosilicon hydrogen compounds from the viewpoint of handling, are not corrosive, do not generate harmful gases, and have little contamination in the process. Silicon alkoxide is preferred.

  Although it does not specifically limit as a metal compound other than silicon as a reactive gas useful for this invention, An organometallic compound, a halogenated metal compound, a metal hydrogen compound etc. can be mentioned. The organic component of the organometallic compound is preferably an alkyl group, an alkoxide group, or an amino group, and preferred examples include tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and tetradimethylamino titanium. Examples of the metal halide compound include titanium dichloride, titanium trichloride, and titanium tetrachloride. Further, examples of the metal hydrogen compound include monotitanium and dititanium. In the present invention, a titanium-based organometallic compound can be preferably used.

  In order to introduce the organometallic compound into the discharge part, any of gas, liquid or solid may be used at normal temperature and pressure, but if it is liquid or solid, heating It may be used after being vaporized by means of a vaporizer such as reduced pressure or ultrasonic irradiation. In the present invention, it is preferable to use it by vaporizing or evaporating it into a gaseous state. If the boiling point of the liquid organometallic compound at room temperature and normal pressure is 200 ° C. or less, vaporization can be facilitated, which is suitable for the production of the thin film of the present invention. Further, when the organometallic compound is a metal alkoxide such as tetraethoxysilane or tetraisopropoxytitanium, it is easily soluble in an organic solvent, so that it may be diluted with an organic solvent such as methanol, ethanol, or n-hexane. Good. An organic solvent may be used as a mixed solvent.

  In the present invention, when an organometallic compound is used as a reactive gas in a processing gas, the content in the processing gas is preferably 0.01 to 10% by volume, more preferably 0.1 to 5%. % By volume. The above metal compounds may be used by mixing several kinds of the same or different metal compounds.

  In addition, hydrogen, oxygen, nitrogen, nitric oxide, nitrogen dioxide, carbon dioxide, ozone, and hydrogen peroxide are mixed in a reactive gas of the organometallic compound as described above in an amount of 0.1 to 10% by volume with respect to a rare gas. The hardness of the thin film can be remarkably improved by the auxiliary use as described above.

  When the substrate applied to the present invention is a film having an antireflection layer, for example, an organosilicon compound is suitable for forming a low refractive index layer having a small average film density while having a gradient structure of the film density, and Titanium-based organometallic compounds are suitable for forming a high refractive index layer having a large average film density, and any of them is preferably used. Moreover, the density (refractive index) can be controlled by adjusting the mixing ratio by using a gas in which these are mixed, so that a medium refractive index layer can be obtained.

〔Base material〕
Next, the base material according to the present invention will be described.

  Examples of the substrate according to the present invention include a cellulose ester film, a polyester film, a polycarbonate film, a polystyrene film, a polyolefin film, a polyvinyl alcohol film, a cellulose film, and other resin films. For example, a cellulose ester film As cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film, cellulose acetate phthalate film, cellulose triacetate, cellulose nitrate; as polyester film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene phthalate film 1,4-dimethylene cyclohexylene terf Copolyester film of rate or these structural units; Polycarbonate film of bisphenol A as a polycarbonate film; Syndiotactic polystyrene film as a polystyrene film; Polyethylene film or polypropylene film as a polyolefin film; Polyvinyl alcohol as a polyvinyl alcohol film Film, ethylene vinyl alcohol film; cellophane as cellulose film; norbornene resin film, polymethylpentene film, polyetherketone film, polyimide film, polyethersulfone film, polysulfone film, poly Ether ketone imide film, polyamide film Fluororesin film, nylon film, polymethyl methacrylate film, acrylic film or polyarylate film, a polyvinylidene chloride film or the like.

  A film obtained by appropriately mixing these film materials can also be preferably used. For example, a film obtained by mixing a commercially available resin such as ZEONEX (manufactured by ZEON Corporation) or ARTON (manufactured by JSR Corporation) can also be used. In addition, even for materials having a high intrinsic birefringence such as polycarbonate, polyarylate, polysulfone or polyether sulfone, the conditions such as solution casting or melt extrusion, and further the conditions for stretching in the vertical and horizontal directions, etc. By appropriately setting, a base material suitable for the present invention can be obtained. In the present invention, the film is not limited to the above-described film.

  As the thickness of the substrate suitable for the plasma discharge processing apparatus of the present invention, a film of about 10 to 1000 μm can be preferably used, more preferably 10 to 200 μm, and particularly a thin substrate of 10 to 60 μm. It can be preferably used.

[Thin films, laminates and films]
In the present invention, the thin film is formed by subjecting the base material to plasma discharge treatment with the above treatment gas at atmospheric pressure or a pressure in the vicinity thereof at the discharge portion in the gap between the counter electrodes. In the present invention, the plasma discharge treatment under atmospheric pressure or a pressure in the vicinity thereof can be performed with a substrate having a very wide width of, for example, 2000 mm, and a treatment speed of 100 m / min. You can also. In the present invention, when plasma discharge is started, first, a processing gas or a rare gas is introduced into the processing chamber while drawing the air in the processing chamber with a vacuum pump, and the processing gas is supplied to the discharge section after replacing the air. The discharge part is preferably filled. Thereafter, the substrate is transferred to carry out processing.

  Regarding the film density profile of the film to be formed (the maximum value of the film density, the ratio of the maximum value to the minimum value of the film density, etc.), the film thickness (with the maximum film density) is discharged as described above. The discharge intensity of the portion, and accordingly, the applied high-frequency power, the treatment gas concentration, the conveyance speed of the substrate, and the like can be appropriately adjusted.

  In the present invention, the conditions for forming a thin film by the plasma discharge processing apparatus have been described in the above-described plasma discharge processing apparatus, but other conditions for processing are also described.

  When forming the thin film of the present invention, it is easy to form a uniform thin film by subjecting the substrate to heat treatment at 50 to 120 ° C. and then plasma discharge treatment in advance, and preheating is a preferred method. By performing the heat treatment, the substrate that has absorbed moisture can be dried, and it is preferable to perform a plasma discharge treatment while maintaining a low humidity. It is preferable to perform plasma discharge treatment without absorbing moisture on a substrate conditioned at less than 60% RH, more preferably 40% RH. The moisture content is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less.

  Moreover, the thin film can be stabilized by heat-treating the substrate after the plasma discharge treatment in a heat treatment zone at 50 to 130 ° C. for 1 to 30 minutes, which is an effective means.

Furthermore, when a laminate is produced by the multistage plasma discharge treatment of the present invention, the treatment surface may be irradiated with ultraviolet rays before and after each plasma discharge treatment, and the adhesion (adhesion) of the formed thin film to the substrate And stability can be improved. Preferably as the ultraviolet irradiation amount is 50~2000mJ / cm ^2, the effect is not sufficient at less than 50 mJ / cm ^2, there is a fear that deformation occurs in exceeds 2000 mJ / cm ² substrate.

  The film thickness of the single layer film formed in the present invention is preferably in the range of 1 to 1000 nm.

  A single layer film having a structure (gradient structure of film density) in which both sides of a high film density region of the present invention are sandwiched between regions where the film density continuously decreases in the thickness direction, or a substrate having these laminated films Can be applied to, but is not limited to, an antireflection film, an antiglare antireflection film, an electromagnetic wave shielding film, a conductive film, an antistatic film, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Examples 1-3, Reference Example 6, Comparative Examples 1-3
<< Preparation of thin layer laminate >>
[Production of thin-layer laminate]
[Film forming process]
As a base material F, on a roll-shaped polyethylene terephthalate film having a thickness of 100 μm, plasma is generated by superimposing the first high-frequency electric field and the second high-frequency electric field on the atmospheric pressure plasma discharge treatment apparatus shown in FIG. The SiO 2 thin film having a thickness of 100 nm was formed by passing the discharge space 100 once under the following discharge conditions.

  In addition, used electrodes 10A and 10B were coated with a high-density, high-adhesion alumina sprayed film by an atmospheric plasma method on a base material made of titanium alloy T64 having cooling means with cooling water. During plasma discharge, the temperature was adjusted and maintained so that the electrode was 80 ° C.

(Film forming conditions)
<Gas conditions>
Discharge gas: Nitrogen gas 95.8% by volume
Thin film forming gas: Tetramethoxysilane (TMOS)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 0.3% by volume
Addition gas: 4.0% by volume of hydrogen gas
<Power supply conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density Change as shown in Table 1 (W / cm ² )
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density Change as shown in Table 1 (W / cm ² )
The first electrode output density and the second electrode output density were changed, the power supply conditions were changed as shown in Table 1, the emission intensity (discharge intensity) was changed, and film formation was carried out to give Examples 1 to 3, and Comparative Example 2, Three samples were prepared.

In addition, a plasma is generated by superimposing the first high-frequency electric field and the second high-frequency electric field on the atmospheric pressure plasma discharge processing apparatus shown in FIG. 11, and the discharge space 100 is passed once under the following discharge conditions. Thus, a SiO ₂ thin film having a thickness of 100 nm was formed.

The film formation conditions are the same as described above, and the electrode conditions are the same except that the electrode 10B is replaced with the electrode 10C, and the first electrode output density and the second electrode output density are formed as shown in Table 1. Thus, a sample of Reference Example 6 was produced.

Further, as Comparative Example 1, a uniform film having a thickness of 100 nm was prepared by using the plasma CVD processing apparatus in which the apparatus shown in FIG. 7 was changed to a parallel plate type electrode configuration including the electrodes 10a and 10b shown in FIG. A SiO ₂ thin film sample having a density configuration was prepared.

Discharge condition 1st electrode side Power supply type
Frequency 80kHz
Output density 8W / cm ²
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density 6W / cm ²
Table 1 shows the results of performing the following adhesion and film hardness tests on each sample using the film density (maximum film density value and minimum film density value) and density ratio in the formed film, and the density ratio. .

(Evaluation method)
Adhesion:
In accordance with JISK5600-5-6, a tape peel test was performed by a cross-cut method to evaluate adhesion.

○ The edges of the cuts are smooth and there is no peeling on the eyes of any lattice. (Classification 0)
Δ: Peeling occurs along the edge of the cut and at the intersection. (Classification 1-2)
× Peeling occurs partially or entirely along the cut. (Category 3-5)
Film hardness:
Evaluate the number of scratches / cm width after rubbing with steel wool # 0000.

(9.8 × 10 ³ Pa × 50 round trip)
○ No scratches are seen.

  Δ The number of scratches is less than 10 / cm.

X The number of scratches is 11 / cm or more.
crack:
After bending 100 times with a curvature of 50 mm in diameter, observed with a differential interference microscope made by Nikon.

× Generated on the entire surface Δ Generated in about half of the area ○ Not generated Note that the film density was measured by an X-ray reflectivity measurement method using MXP21 manufactured by Mac Science. The emission intensity was measured with an Auger electron spectrometer manufactured by Ocean Optics.

  As can be seen from the table, those having a film density ratio within the range of the present invention have good substrate (also between single layer films) and adhesion, film hardness (steel wool test), cracks, and the like. If the film density ratio is too small, the adhesion is lowered, and if the film density ratio is too large, cracks are deteriorated and the film hardness is also lowered.

Examples 4 and 5 and Comparative Examples 4 and 5
A thin layer laminate was prepared as follows.

For the samples of Examples 4 and 5 and Comparative Example 5, plasma was generated by superimposing the first high-frequency electric field and the second high-frequency electric field on the atmospheric pressure plasma discharge processing apparatus shown in FIG. Except for the conditions, the discharge space 100 was passed the same number of times as the number of single layers described in Table 2 under the same conditions as in Example 1, and the single layer film having the gradient structure has a number of stacked layers described in Table 2. been a thickness of 100nm each total, lowermost unit less than the average film density 1.9g / cm ³ (L), the average film density 1.9 g / cm ³ or more, an intermediate layer of less than 2.1 g / cm ³ A unit (M) and an uppermost layer unit (H) having an average film density of 2.1 g / cm ³ or more were formed, and a laminate composed of layer units composed of a plurality of single-layer films was produced. Table 2 shows the structure of the prepared laminate.

  Further, the film formation conditions (outputs of the first electrode and the second electrode) of the lowermost layer unit (L), the intermediate layer unit (M), and the uppermost layer unit in each laminate of Examples 4 and 5 and Comparative Example 5 The density is shown in Table 3. In these samples, the average film density of each layer unit (and therefore of the single layer film) was the same, but the film density ratio of the single layer film constituting each unit was changed thereby (described in Table 2).

For Reference Example 7, the first high-frequency electric field and the second high-frequency electric field were superimposed on the atmospheric pressure plasma discharge treatment apparatus shown in FIG. 11 under the same conditions as in Example 1 except for the discharge conditions. The plasma is generated, and the discharge space 100 is passed through the discharge layer 100 as many times as the number of single layers described in Table 2, and the total thickness of the single layer films having the gradient structure is stacked as shown in Table 2. is of 100nm, respectively, the average film density 1.9 g / cm ³ less than the lowermost unit (L), the average film density 1.9 g / cm ³ or more, 2.1 g / cm ³ less than the intermediate layer unit (M), Moreover, the uppermost layer unit (H) having an average film density of 2.1 g / cm ³ or more was formed, and a laminate composed of layer units composed of a plurality of single layer films was formed. Table 2 shows the structure of the prepared laminate.

Table 3 shows the film formation conditions (power density of the first electrode and the second electrode) of the lowermost layer unit (L), the intermediate layer unit (M), and the uppermost layer unit in each laminate of Reference Example 7. Indicated. In these samples, the average film density of each layer unit (and therefore of the single layer film) was the same, but the film density ratio of the single layer film constituting each unit was changed thereby (described in Table 2).

  Moreover, about the comparative example 4, it created using the atmospheric pressure plasma discharge processing apparatus of FIG. Similarly, the conditions for the output density are shown in Table 3, but each single-layer film shows a uniform film thickness profile (film density ratio 1.00).

  Table 2 shows the results of evaluating the obtained samples in the same manner as the samples of Examples 1 to 3 and Comparative Examples 1 to 3, together with their structures.

  The sample of the present invention has good adhesion, good film hardness, and no cracks are observed in the laminated film.

10A, 10B Roll electrode 11 Roll 11A, 11B, 11C, 11D Folding roll 20, 21 Guide roll 30 Processing gas supply unit 40 Exhaust port 80 Power supply 81, 82 Voltage supply means 801 First power supply 811 Voltage supply means 802 Second power supply 812 Voltage supply means 100 Discharge section (discharge space)
F Substrate G Processing gas G 'Gas after processing

Claims (2)

A method for producing a single layer film having a configuration in which both sides of a high film density region are sandwiched between regions where the film density continuously decreases in the thickness direction, or a substrate having these laminated films,
In a counter-roll type plasma CVD processing apparatus in which plasma discharge is performed by a pair of opposed roll electrodes, while transporting the base material to the discharge space of the plasma discharge, the maximum value of the film density per single-layer film and The single layer film is formed at a discharge intensity adjusted so that the ratio of the minimum values is 1.03 to 1.5 ,
The manufacturing method characterized by forming the said base material which has the said single layer film or these laminated films. The single-layer film having a configuration in which both sides of the high-film density region are sandwiched between regions where the film density continuously decreases in the thickness direction, or a unit composed of these laminated films,
A base material formed by stacking a plurality of layers,
The manufacturing method according to claim 1, wherein the plurality of units form a substrate including at least units having different average film densities.