JPWO2012060338A1 - Laminated body - Google Patents

Abstract

A laminate having a base and an organic layer made of a fluorine-containing resin provided on the base, the organic layer having a C—C bond in the depth direction of the organic layer measured by X-ray photoelectron spectroscopy and C—H bonds are most abundant at the interface between the substrate and the organic layer, and the C—C bonds and C—H bonds are present at 2 atomic% or less in the center in the depth direction of the organic layer. The C—F bond measured by X-ray photoelectron spectroscopy is 55 atomic% or more in the depth direction of the organic layer at least in the depth range of 0.2 to 0.8 normalized by the depth of the organic layer.

Description

The present invention relates to a laminate.

  At present, in various terminals such as portable terminals, a touch panel in which a human body operates by directly contacting the panel surface is used. The surface of the touch panel is provided with an antifouling layer (organic layer) because the human body is in direct contact with the panel surface and is easily damaged and dirty.

  An example of the antifouling layer is that a fluorine-based resin is used. As such a fluororesin, for example, one having a silicon atom at the end of a polymer main chain is known (for example, Patent Document 1).

Japanese Patent Laid-Open No. 2004-268311

The antifouling layer is required to have high sliding durability since the human body contacts itself as described above. In this case, high sliding durability means that, for example, the antifouling layer surface is slid with steel wool applied with a load (1000 g / cm ² ), and after being worn, water drops are dropped on the antifouling layer surface. When the number of sliding times is measured when the contact angle of the water droplet is 105 degrees or less, the number of slidable times is about 5000 times. However, the above-described fluororesin film has a problem that the number of slidable times is about 3000, that is, the sliding durability is low.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a laminate having an antifouling layer having high sliding durability.

  The laminate of the present invention is a laminate having a substrate and an organic layer made of a fluorine-containing resin provided on the substrate, and the organic layer has a depth of the organic layer measured by X-ray photoelectron spectroscopy. The C—C bond and C—H bond in the direction are most abundant at the interface between the substrate and the organic layer, and the C—C bond and C—H bond are present at the center in the depth direction of the organic layer. In a range of 0.2 to 0.8 at which the C—F bond, which is present at 2 atomic% or less and is measured by X-ray photoelectron spectroscopy, is at least normalized by the depth of the organic layer in the depth direction of the organic layer It is characterized by the presence of 55 atomic% or more. When the organic layer of the laminate has such a film composition, the sliding durability is improved.

  The abundance ratio in the depth direction of the organic layer of C—C bond and C—H bond measured by the X-ray photoelectron spectroscopy is the abundance ratio in the depth direction of the organic layer of Si—O bond measured by X-ray photoelectron spectroscopy. And at least simultaneously increase. When the organic layer of the laminate has such a film configuration, the sliding durability is further improved.

  The substrate preferably has an adhesion layer formed on the surface on which the organic layer is formed. By improving the adhesion, the sliding durability is further improved.

As a preferred embodiment of the present invention, the adhesion layer is an oxide of at least one metal selected from Si, Al, Ta, Nb, Ti, Zr, Sn, Zn, Mg, and In, an oxynitride, It is a film made of nitride, and more preferably, at least the surface of the adhesion layer is a SiO ₂ film.

3 is a schematic cross-sectional view of a laminate according to Embodiment 1. FIG. 4 is a graph showing the XPS analysis result of the antifouling layer according to Embodiment 1. It is a graph which shows the XPS analysis result of the pollution protection layer concerning a reference example. 1 is a schematic diagram illustrating a schematic configuration of a film forming apparatus that forms a stacked body according to Embodiment 1. FIG. It is a graph which shows the XPS analysis result which concerns on an Example and a comparative example. It is a graph which shows the XPS analysis result which concerns on an Example and a comparative example. It is a graph which shows the XPS analysis result which concerns on an Example and a comparative example.

(Embodiment 1)
The present invention will be described below with reference to FIG. FIG. 1 is a schematic cross-sectional view of the laminate 1. The laminate 1 includes a transparent substrate 2, an adhesion layer 3 formed on the transparent substrate 2, and an antifouling layer 4 laminated on the adhesion layer 3. The substrate of the present invention comprises a transparent substrate 2 and an adhesion layer 3.

  The transparent substrate 2 constitutes a touch panel by protecting elements housed on one side (the side opposite to the adhesion layer 3). Examples of the material of the transparent substrate 2 include a transparent resin film or glass. In this embodiment, it consists of glass. In addition, the transparent substrate 2 in this embodiment is not limited to a thing with 100% of transmittance | permeability, What is called translucent is also included.

  The adhesion layer 3 is for improving the adhesion between the antifouling layer 4 and the transparent substrate 2. As will be described in detail later, the surface of the adhesion layer 3 is cleaned and slightly etched by the plasma treatment process. For this reason, adhesiveness with the antifouling layer 4 can be improved more than before.

The adhesion layer 3 is formed from an inorganic material. Examples of the inorganic material include oxides, oxynitrides, and nitrides of at least one metal selected from Si, Al, Ta, Nb, Ti, Zr, Sn, Zn, Mg, and In. Of these, silicon oxide, silicon nitride, silicon nitride oxide, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium oxide, magnesium oxide, indium oxide, tin oxide, zinc oxide, tantalum oxide, niobium oxide, zirconium oxide and the like are preferable. These can be used alone or in any combination. In the present embodiment, the adhesion layer 3 is made of a SiO ₂ film having a particularly preferable transmittance.

  The thickness of the adhesion layer 3 can be appropriately set in the range of 1 to 1000 nm, preferably 5 to 150 nm. If the thickness of the adhesion layer 3 is less than the above range, adhesion cannot be expressed, and if the thickness of the adhesion layer 3 exceeds the above range, conversely, cracks due to stress or the like are likely to occur. The time required for film formation is undesirably long.

The antifouling layer 4 is an organic layer containing fluorine. By forming the antifouling layer 4, for example, the surface of the touch panel is protected from scratches, fingerprints, and the like that can be caused by contact with the human body. Examples of the fluororesin constituting the antifouling layer 4 include those in which the polymer main chain has a repeating unit such as CF ₂ =, —CF ₂ —, —CFH—, etc. Those having a perfluoropolyether group having a chain structure are used. The fluororesin constituting the antifouling layer 4 in this embodiment has a silicon atom at the end of the polymer main chain, and the silicon atom located at the end of the polymer main chain has an alkoxy group. It is added by an oxygen-silicon bond.

  Moreover, it is preferable that the average molecular weight of this fluorine-type resin is 1000-500000, Furthermore, 5000-100000 are more preferable. Further, the fluorine content is preferably 0.5 to 60% by mass, more preferably 1 to 40% by mass with respect to the entire fluororesin. Within this range, the coverage is high and film formation is easy.

  Although it does not restrict | limit especially as a film thickness of the pollution protection layer 4, It can set suitably in the range of 0.0005-5 micrometers. This is because if it is less than 0.0005 μm, it will be difficult to exhibit a sufficient dirt adhesion preventing function, and if it exceeds 5 μm, the light transmittance will be lowered. In this embodiment, the antifouling layer 4 is formed to have a thickness of 2 nm.

  In this embodiment, the antifouling layer 4 has anti-fouling at the interface with the adhesion layer 3 in the depth direction of the organic layer measured by X-ray photoelectron spectroscopy (XPS). Most present at the interface between the layer 4 and the adhesion layer 3, and this C—C bond and C—H bond are in the center of the antifouling layer 4 in the depth direction (near 0.9 nm to 1.1 nm). In 2 atomic% or less. Further, the C—F bond measured by X-ray photoelectron spectroscopy is 55 atomic% in the depth direction of the antifouling layer 4 at least in the depth range of 0.2 to 0.8 normalized by the depth of the antifouling layer. It exists above.

  This will be specifically described with reference to FIG. FIG. 2 is a plot of the abundance ratio in the depth direction based on the measurement result of the antifouling layer 4 according to the present embodiment by X-ray photoelectron spectroscopy (XPS). The measurement was performed by Thermo Fisher Scientific, trade name VG Thera Probe, irradiated X-ray: single crystal spectroscopic AlKα, X-ray spot diameter: 800 × 400 μm (elliptical shape), detection angle in angle-resolved lens mode: 81 The measurement was carried out under the following measurement conditions: .13 ° to 24.88 ° divided into 16 at 3.75 ° pitch, detection angle in standard lens mode: 53 °, neutralizing electron gun: used. The following measurement results by X-ray photoelectron spectroscopy (XPS) were also performed with the same measurement apparatus and measurement conditions.

  As shown in FIG. 2, in the XPS measurement result, the C1s orbit of the C—C bond and the C—H bond increases rapidly from the vicinity of the depth 1.5 nm of the antifouling layer 4. The C1s orbitals of the C—C bond and C—H bond have the highest abundance at the interface with the adhesion layer 3 (thickness of about 2.0 nm), and are about 27 atomic%. Further, the C—C bond and C—H bond are present at 2 atomic% or less in the range of the depth of the antifouling layer 4 from about 0.2 nm to about 1.7 nm. A portion where the depth is 0.2 nm, that is, the depth of the antifouling layer is about 10% of the total thickness of the antifouling layer is an impurity region containing a large amount of impurities. Further, in the antifouling layer 4, the F1s orbit of C—F bond measured by X-ray photoelectron spectroscopy is present at 55 atomic% or more up to the depth of 0 to 1.7 nm of the antifouling layer 4.

  The laminate 1 in the present embodiment has the antifouling layer 4 of the present embodiment, which is the XPS analysis result, and thus has higher sliding durability than the conventional antifouling layer. The inventors of the present invention have such an antifouling layer as a result of XPS analysis, that is, the C—C bond and the C—H bond are hardly present in the film, and are concentrated on the interface with the adhesion layer 3. In addition, the antifouling layer 4 in which a predetermined amount of C—F bond, which is a fluorine-containing bond, is included in the entire layer has higher sliding durability than a conventional antifouling layer (for example, slidable) The number of times is 5000 times or more).

  Further, as shown in FIG. 2, the antifouling layer 4 of the laminate 1 in the present embodiment has a C1s orbital existence probability of C—C bonds and C—H bonds from a depth of about 1.5 nm to Si— It increases simultaneously with the abundance ratio of O-bond O1s orbitals in the thickness direction. The antifouling layer 4 thus increasing has particularly high sliding durability (for example, the slidable number of times is 7000 times or more).

  As a reference example, FIG. 3 shows a measurement result by X-ray photoelectron spectroscopy (XPS) of a conventional antifouling layer.

  FIG. 3 shows the measurement results of a conventional antifouling layer (thickness 0.9 nm) by X-ray photoelectron spectroscopy (XPS). As shown in FIG. 3, in the XPS measurement results, C1s orbitals of C—C bonds and C—H bonds are always present in the entire antifouling layer at about 3 to 8% up to a depth of about 0.5 nm. The abundance ratio gradually increases as the depth increases from around 0.5 nm. The C1s orbitals of the C—C bond and C—H bond have the highest abundance at the interface with the adhesion layer (thickness of about 0.9 nm), and are about 20 atomic%. In this conventional antifouling layer, the F1s orbit of the C—F bond measured by X-ray photoelectron spectroscopy rises to a depth of 0.11 nm of the antifouling layer, and from this depth of 0.11 nm to about 0.8 nm. Although it is not constant, 55 atomic% or more exists. Such a conventional antifouling layer has, for example, about 3000 slidable cycles.

  On the other hand, the antifouling layer of this embodiment described above has a slidable number of times of 10,000, and the antifouling layer of this embodiment has a very high sliding durability compared to the conventional antifouling layer. .

  Such a laminate 1 is formed as follows.

First, the adhesion layer 3 is formed on the transparent substrate 2 that is a glass substrate. Examples of the method for forming the adhesion layer 3 include a CVD method, a plasma CVD method, a sputtering method, and an ion plating method. When the SiO ₂ film as the adhesion layer 3 is formed by sputtering, the formation conditions are, for example, sputtering target: Si target, sputtering gas: Ar + O ₂ , Ar gas flow rate: 50 sccm, O ₂ gas flow rate: 15 sccm, Input power: 2500 W.

  Next, plasma processing is performed on the transparent substrate 2 on which the adhesion layer 3 is formed (plasma processing step). In the present embodiment, this plasma treatment causes the surface of the adhesion layer 3 to be etched, thereby improving the adhesion with the antifouling layer 4 and removing impurities present on the surface of the adhesion layer 3. It is possible to form the antifouling layer 4 having the desired composition of the embodiment.

The plasma generation gas in the plasma treatment is a gas containing oxygen atoms (O). Examples of such a gas containing oxygen atoms include a gas containing oxygen atoms such as O ₂ and a gas containing O hydrogen atoms (H) such as an OH group-containing gas such as H ₂ O. One or two or more of these may be mixed and used, or an inert gas such as Ar or He may be mixed with these gases. Furthermore, O and H may be contained in separate gases and supplied to mix in the film formation chamber.

  In this plasma processing step, when a gas having oxygen atoms (oxygen gas in the present embodiment) is introduced as a plasma generation gas, the gas flow rate is 5 to 50 sccm, and the input power is 100 to 3000 W. In this embodiment, plasma treatment was performed using oxygen gas at a gas flow rate of 20 sccm and an input power of 1000 W for 60 seconds.

  Thereafter, the antifouling layer 4 is formed on the adhesion layer 3. Examples of the method for forming the antifouling layer 4 include a coating method and a vapor deposition method. In this embodiment, the vapor deposition method is used.

Examples of the vapor deposition method include a vacuum vapor deposition method, an ion beam vapor deposition method, and a resistance heating vapor deposition method. In this embodiment, a resistance heating vapor deposition method in which vapor deposition is performed by heating a vapor deposition source in a predetermined pressure state is used. The predetermined pressure state is 1 × 10 ⁻⁴ to 1 × 10 ⁻² Pa. In this embodiment, the product name OPTOOL DSX (manufactured by Daikin Industries, Ltd.) as a vapor deposition source is heated up to 220 ° C. by heating means while being held at 2 × 10 ⁻³ to 4 × 10 ⁻⁴ Pa. A vapor deposition film having a thickness of 2 nm is formed.

  The film forming apparatus according to this embodiment will be described below with reference to FIG. The film forming apparatus 10 is a so-called in-line film forming apparatus, in which processing chambers for performing predetermined processing on a substrate are connected in series. The film forming apparatus 10 includes a load lock chamber 11, an adhesion layer forming chamber 12, a plasma processing chamber 13, and an antifouling layer forming chamber 14 in this order. In addition, in the film-forming apparatus 10, the transparent substrate 2 is supported and conveyed by the conveyance tray as a conveyance means. In the present embodiment, the transport means includes a transport tray on which the transparent substrate 2 is placed and a moving means for moving the transport tray.

  The transparent substrate 2 is carried into the load lock chamber 11 from the atmosphere. The load lock chamber 11 is provided with a vacuum pump (not shown) so that the inside of the load lock chamber 11 is evacuated to a predetermined vacuum level and the vacuum level can be maintained. Although not shown, each processing chamber is provided with a vacuum pump so that each processing chamber can have a desired degree of vacuum.

  The adhesion layer forming chamber 12 is for forming the adhesion layer 3 (see FIG. 1) on the transparent substrate 2 by a sputtering method. The transparent substrate 2 transferred to the adhesion layer forming chamber 12 is set at the substrate setting position 121 by a transfer means (not shown). In the adhesion layer forming chamber 12, a sputtering target 122 is supported and installed by the target support portion 123 so as to face the transparent substrate 2 installed at the substrate installation position 121. A high frequency power supply 124 is connected to the target support portion 123 so that a voltage can be applied to the sputtering target 122.

The material of the sputtering target 122 is appropriately set according to the adhesion layer. In the present embodiment, a metal silicon target is installed as the sputtering target 122 in order to form the SiO ₂ film as the adhesion layer.

Further, in the adhesion layer forming chamber 12, two first gas sealing portions 125 in which a sputtering gas is sealed are respectively installed via first valves 126. By adjusting the opening degree of each first valve 126, a desired amount of sputtering gas can be introduced from the first gas sealing portion 125 into the adhesion layer forming chamber 12. In the present embodiment, Ar gas is sealed in one first gas sealing portion 125, and O ₂ gas is sealed in the other first gas sealing portion 125.

  The plasma processing chamber 13 is for performing plasma processing in the present invention. The plasma processing chamber 13 is provided with a voltage introduction part 131 for applying a high frequency voltage to the transparent substrate 2 placed on the transfer tray. A voltage applying unit 132 is connected to the voltage introducing unit 131 so that a voltage can be applied to the transparent substrate 2 placed on the transport tray. The voltage introducing unit 131 and the voltage applying unit 132 are not limited as long as they can form plasma.

The plasma processing chamber 13 is connected to a second gas sealing portion 133 in which a plasma generation gas (H ₂ O in this embodiment) is sealed through a second valve 134. By adjusting the opening degree of the second valve 134, a desired amount of plasma generation gas can be introduced into the plasma processing chamber 13 from the second gas enclosure 133.

  The antifouling layer forming chamber 14 is for forming the antifouling layer 4 (see FIG. 1) on the adhesion layer of the transparent substrate 2 by vapor deposition. The transparent substrate 2 transferred to the antifouling layer forming chamber 14 is set at the substrate setting position 141 by a transfer means (not shown). In the antifouling layer forming chamber 14, vapor deposition means 142 is installed so as to face the installed transparent substrate 2. Although the vapor deposition means 142 is based on a vapor deposition method, in this embodiment, the vapor deposition source which is not illustrated is installed in the crucible provided with the heating means.

The film formation in the film forming apparatus 10 will be described. When the transparent substrate 2 is transported to the load lock chamber 11, the load lock chamber 11 is evacuated and is in a vacuum state. After the desired vacuum state is reached, the transparent substrate 2 is transferred to the adhesion layer forming chamber 12. In the adhesion layer forming chamber 12, an adhesion layer is formed on the transparent substrate 2. Specifically, the opening of each first valve 126 is adjusted to introduce a sputtering gas (for example, O ₂ gas and Ar gas) from each first gas sealing portion 125, and a voltage is applied from the high frequency power supply 124 to the sputtering target 122. Is applied to start sputtering, and the adhesion layer 3 is formed.

  Next, the transparent substrate 2 is transferred from the adhesion layer forming chamber 12 to the plasma processing chamber 13. In the plasma processing chamber 13, plasma processing is performed on the adhesion layer 3 on the transparent substrate 2. Specifically, in the plasma processing chamber 13, the opening of the second valve 134 is adjusted to introduce the plasma generation gas from the second gas sealing part 133 and to apply a voltage from the voltage application unit 132 to the voltage introduction part 131. Then, the surface of the adhesion layer 3 is slightly etched, and the surface of the adhesion layer 3 is cleaned.

  Next, the transparent substrate 2 is transferred from the plasma processing chamber 13 to the antifouling layer forming chamber 14. In the antifouling layer forming chamber 14, the antifouling layer 4 is formed on the plasma-treated adhesion layer 3. Specifically, the crucible is heated by a heating means, and a heated vapor deposition source is attached to the adhesion layer 3 of the conveyed transparent substrate 2 to form the antifouling layer 4.

  After the antifouling layer 4 is formed, the transparent substrate 2 is transferred to the load lock chamber 11, released from the atmosphere in the load lock chamber 11, and then unloaded from the film forming apparatus 10.

  Thus, in the film forming apparatus 10 of the present embodiment, a desired plasma treatment can be performed by providing the plasma treatment chamber 13 between the adhesion layer forming chamber 12 and the antifouling layer forming chamber 14. As a result, the adhesion between the adhesion layer 3 and the antifouling layer 4 can be improved, and the desired antifouling layer 4, that is, the C—C bond and C measured by X-ray photoelectron spectroscopy at a desired abundance ratio. An antifouling layer in which —H bonds and C—F bonds exist in the film can be formed.

  Hereinafter, embodiments of the present invention will be described in more detail by way of examples.

(Examples 1 and 2)
The laminated body 1 was formed on each condition shown in Table 1 by the film forming apparatus according to the first embodiment. The conditions not described are the same as those described in the first embodiment.

(Comparative Example 1)
The laminated structure was formed under the same conditions as in Example 1 except that no O-containing gas was used in the plasma treatment step.

(Comparative Example 2)
The laminated structure was formed under the same conditions as in Example 2 except that the plasma treatment process was not used.

  The XPS measurement results of these examples and comparative examples are shown in FIGS.

  FIG. 5 shows the abundance ratio in the depth direction of the film after normalization of C1s orbitals of C—C bonds and C—H bonds. The normalization is standardized by the film thickness of the antifouling layer 4 of each film, and the post-standardization depth 1 corresponds to the interface between the antifouling layer 4 and the adhesion layer 3.

  As shown in FIG. 5, in Examples 1 and 2, both the C1s orbits of the C—C bond and the C—H bond have a normalized film depth of about 0.2 to 0.6 as well as the central portion. The abundance ratio is almost 0 (2 atomic% or less), and both of the abundance ratios suddenly increased when the normalized film depth exceeded 0.6, and both normalized film depths. 1, that is, the abundance ratio was highest at the interface between the antifouling layer 4 and the adhesion layer 3 (27 atomic% in Example 1 and 29 atomic% in Example 2).

  In Comparative Examples 1 and 2, the existence ratio of C1s orbitals of C—C bonds and C—H bonds is not less than 2 atomic% in the entire film, not only in the central part, and the interface between the antifouling layer 4 and the adhesion layer 3 The abundance increased relatively slowly in the vicinity.

  FIG. 6 shows the abundance ratio in the depth direction of the film after normalization of the F1s orbitals of C—F bonds measured by X-ray photoelectron spectroscopy.

  In Examples 1 and 2 and Comparative Example 1, the existence probability of the F1s orbit of the C—F bond exceeded 55 atomic% when the depth after normalization was 0.2 to 0.85. In Comparative Example 2, the existence probability of the F1s orbit of the C—F bond exceeded 55 atomic% when the depth after normalization was near 0.1 to 0.3, but decreased thereafter.

  FIG. 7 shows the existence ratio of C1s orbitals (thick lines) of C—C bonds and C—H bonds in the depth direction of the film measured by X-ray photoelectron spectroscopy, and the O1s orbitals (thin lines) of Si—O bonds. The abundance ratio in the depth direction is shown.

  Only in Example 1, the abundance ratio of C1s orbitals (thick lines) of C—C bonds and C—H bonds in the depth direction of the film and the abundance ratio of O1s orbitals (thin lines) of Si—O bonds in the depth direction of the film. The abundance ratio increased from the same depth (around 1.5 nm).

  On the other hand, in Example 2, the abundance ratio of C1s orbitals of C—C bonds and C—H bonds in the depth direction of the film is the presence of O1s orbitals (thin lines) of Si—O bonds in the depth direction of the film. It began to rise faster than the ratio.

  In Comparative Examples 1 and 2, the existence ratio of the C1s orbitals of the C—C bond and the C—H bond in the depth direction of the film is moderate, but the film of the O1s orbital (thin line) of the Si—O bond is thin. It began to rise faster than the existence ratio in the depth direction.

  As described above, in Examples 1 and 2, the antifouling layer 4 has a C—C bond and C— in the depth direction of the organic layer measured by X-ray photoelectron spectroscopy (XPS) at the interface with the adhesion layer 3. The H bond is most present at the interface between the antifouling layer 4 and the adhesion layer 3, and the CC bond and the C—H bond are in the center of the antifouling layer 4 in the depth direction (standardized). It was present at 2 atomic% or less at a depth of about 0.45 to 0.55. Further, the C—F bond measured by X-ray photoelectron spectroscopy is 55 atomic% in the depth direction of the antifouling layer 4 at least in the depth range of 0.2 to 0.8 normalized by the depth of the antifouling layer. There existed more. On the other hand, in Comparative Examples 1 and 2, the antifouling layer has the C—C bond and the C—H bond at the center in the depth direction of the antifouling layer 4 (standardized depth of 0.45 to 0). In Comparative Example 1, the C—F bond measured by X-ray photoelectron spectroscopy is at least the depth of the antifouling layer in the depth direction of the antifouling layer 4. No more than 55 atomic% was present in the depth range of 0.2 to 0.8 normalized by.

A sliding durability test was performed on each of the stacked structures of Examples 1 and 2 and Comparative Examples 1 and 2. In the sliding durability test, the surface of the antifouling layer of each laminated structure was slid with steel wool applied with a load (1000 g / cm ² ), and after wearing, water droplets were dropped on the surface of the antifouling layer, and the contact of the water droplets The number of times of sliding when the angle is 105 degrees or less is measured. That is, the greater the number of sliding times, the higher the sliding durability of the antifouling layer. The results are shown in Table 1.

  As shown in Table 1, it was found that the sliding durability was improved because all the examples had a larger number of sliding operations than the comparative example and could slide 7000 times or more.

  Therefore, the antifouling layer 4 of this embodiment has anti-fouling at the interface with the adhesion layer 3 in the depth direction of the organic layer measured by X-ray photoelectron spectroscopy (XPS). Most present at the interface between the layer 4 and the adhesion layer 3, and this C—C bond and C—H bond are in the center of the antifouling layer 4 in the depth direction (near 0.9 nm to 1.1 nm). In which the C—F bond measured by X-ray photoelectron spectroscopy is at least a depth of 0.2 to 0 normalized by the depth of the antifouling layer in the depth direction of the antifouling layer 4. In the range of .8, the presence of 55 atomic% or more improved the sliding durability. In addition, the existence probability of C1s orbitals of C—C bonds and C—H bonds increases simultaneously with the existence ratio of Si—O bonds in the thickness direction of O1s orbitals, thereby further improving sliding durability. It was.

(Other embodiments)
The present invention is not limited to the embodiment described above. For example, the film forming apparatus is not limited to the one described in the first embodiment, and may be any apparatus that can perform the film forming method according to each embodiment. For example, the plasma processing means and the vapor deposition means provided in the plasma processing chamber in the present embodiment may be provided in one film forming apparatus, and the substrate may be installed so as to face these. Good.

  In the present embodiment, a film having a desired high sliding durability is formed by plasma treatment with a gas containing oxygen. However, the present invention is not limited to this. The formation method is not limited as long as the desired film having high sliding durability can be formed.

  In the present embodiment, the high-frequency sputtering method is used as the sputtering method, but is not limited thereto, for example, a magnetron sputtering method using a magnetron discharge in which a magnetic field and an electric field are orthogonally set by placing a magnet behind the sputtering target, An ECR sputtering method in which sputtering is performed in a vacuum using ECR plasma may be used. Moreover, in this embodiment, although the high frequency voltage was applied between two sputtering targets, it is not restricted to such a so-called dual type sputtering method. For example, a high frequency power source may be connected to a single sputtering target, and a high frequency voltage may be applied between the grounded substrate and the sputtering target.

DESCRIPTION OF SYMBOLS 1 Laminated body 2 Transparent substrate 3 Adhesion layer 4 Antifouling layer 10 Film-forming apparatus 11 Load lock chamber 12 Adhesion layer formation chamber 13 Plasma processing chamber 14 Antifouling layer formation chamber

Claims (5)

A laminate having a base and an organic layer made of a fluorine-containing resin provided on the base,
The organic layer has the most C—C bonds and C—H bonds in the depth direction of the organic layer measured by X-ray photoelectron spectroscopy at the interface between the substrate and the organic layer, and this C—C bond. And C—H bonds are present at 2 atomic% or less in the center in the depth direction of the organic layer,
The C—F bond measured by X-ray photoelectron spectroscopy is present at 55 atomic% or more in the depth direction of the organic layer at least in the depth range of 0.2 to 0.8 normalized by the depth of the organic layer. A featured laminate.   The abundance ratio in the depth direction of the organic layer of C—C bond and C—H bond measured by the X-ray photoelectron spectroscopy is the abundance ratio in the depth direction of the organic layer of Si—O bond measured by X-ray photoelectron spectroscopy. The laminate according to claim 1, which increases at least simultaneously.   The laminate according to claim 1, wherein the base has an adhesion layer formed on the surface on which the organic layer is formed.   The adhesion layer is a film made of an oxide, oxynitride, or nitride of at least one metal selected from Si, Al, Ta, Nb, Ti, Zr, Sn, Zn, Mg, and In. The layered product according to any one of claims 1 to 3 characterized by things. The laminate according to claim 4, wherein at least a surface of the adhesion layer is a SiO ₂ film.

Images