JPH07166325A - Method for manufacturing laminated body - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a laminate having excellent water repellency and scratch resistance (hard coat). [Structure] Targets 2a and 2b made of a metal oxide and a fluorine-based resin are arranged around a base material 4, and while the base material 4 is being rotated, electric power is applied to the target to carry out sputtering, whereby A coating film made of a metal oxide and a fluororesin is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminate which forms a coating film having excellent water repellency and scratch resistance (hard coat) on a substrate.

[0002]

2. Description of the Related Art As a method for forming a highly water-repellent coating on a substrate such as plastic or glass, for example, a fluorine-containing resin such as polytetrafluoroethylene resin (hereinafter referred to as PTFE) is used as a target material. For example, a vacuum deposition method and a sputtering method are disclosed (JP-A-56-98475 and JP-A-56-98469). However, although a fluorine-based resin such as a polytetrafluoroethylene resin has excellent water repellency, it has a problem in scratch resistance, so that it is difficult to use it as a hard coat film.

In order to solve this problem, a method of providing a composite film of a fluororesin and a metal oxide on a plastic substrate has been disclosed (JP-A-3-153859). In this method, the SiO ₂ target is mixed with P
Using a composite target partially coated with TFE resin,
By performing high-frequency sputtering for 10 minutes at a high-frequency output of 50 W, a SiO ₂ -PTFE-based composite film having a film thickness of 500 Å is formed on a plastic substrate.
This is a method of providing water repellency and scratch resistance.

However, in the above-mentioned SiO ₂ -PTFE type composite film, if the proportion of the metal oxide in the composite film is increased in order to improve the scratch resistance, the water repellency is remarkably lowered and the water repellency is improved. Therefore, when the proportion of the fluororesin in the composite film is increased, the scratch resistance is significantly reduced, and it is impossible to impart excellent water repellency and scratch resistance at the same time.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above drawbacks, and an object thereof is to provide a method for producing a laminate having excellent water repellency and scratch resistance. .

[0006]

The method for producing a laminate of the present invention is a method for forming a coating film composed of a metal oxide and a fluororesin on a substrate by a co-sputtering method of a metal oxide and a fluororesin. Is.

Examples of the metal oxide include Mg
O, Al ₂ O ₃ , SiO ₂ , CaO, TiO ₂ , Ni
O, ZnO, Ga ₂ O ₃ , GeO ₂ , Y ₂ O ₃ , ZrO
₂ , CdO, In ₂ O ₃ , SnO ₂ , BaO, Hf
O ₂ , PbO, Bi ₂ O _{3 and the} like are mentioned, and these may be used alone or in combination of two or more kinds.

Examples of the fluorine-based resin include polytetrafluoroethylene (hereinafter referred to as PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP), polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer. Examples thereof include polymers, polyvinyl fluoride, polyvinylidene fluoride, and the like, with PTFE and FEP being particularly preferable. These may be used alone or in combination of two or more.

Both the above metal oxides and fluororesins are used as target materials in the sputtering method.

Examples of the substrate include glass, plastic, metal, ceramics and the like.

In the present invention, a sputtering method is used as a method for forming a coating film composed of a metal oxide and a fluororesin on a substrate.

As the method of the above-mentioned sputtering method, a direct method is used.
Flow sputtering and high frequency sputtering
It ZnO, Sn as a target of metal oxide
O₂, In ₂O₃When a conductive material such as
DC sputtering or high frequency sputtering is used
It can be used. Also, as a target of metal oxide,
If an insulating material is used, high frequency sputtering
used.

FIG. 1 shows a high frequency spattering device used in the present invention. In the figure, 1 indicates a vacuum chamber, and the vacuum chamber 1
Is a specified pressure (preferably 1 ×
10 ⁻⁴ Pa or less). Further, two targets 2a and 2b are provided on the side surface in the vacuum chamber 1, one of which is a metal oxide (eg, SiO ₂ ) and the other is a fluororesin (eg, PTFE). is there.

A shutter 3 is provided on the front surface of each of the above targets. Two targets 2a and 2
b is connected to a separate matching device (not shown) and an RF power source (not shown), and targets 2a and 2
b can be sputtered with a separate high frequency (13.56 MHz) power supply.

The target 2b can also be sputtered with direct current by switching to a direct current power source (not shown). Further, the composition of the coating film formed on the substrate 4 can be controlled by controlling the power applied to the two targets 2a and 2b separately.

A substrate holder 5 for mounting a substrate 4 (for example, a glass plate) on which a coating film is formed is arranged at the center of the vacuum chamber 1 and is rotatable by a rotary shaft 7. .

When the rotation speed of the substrate holder 5 becomes slow, the obtained coating becomes a laminated film of metal oxide and fluororesin, and when the outermost layer is a metal oxide layer, scratch resistance is satisfactory. However, it is not preferable because sufficient water repellency cannot be obtained. Also, when the outermost layer is a fluororesin layer, sufficient scratch resistance cannot be obtained even if the water repellency is satisfied, which is not preferable. On the other hand, if the rotation speed of the base material holder 5 is high, there is no particular problem, but if it is too high, the base material 4 may scatter due to centrifugal force, which is not preferable.

Therefore, the rotation speed of the base material holder 5 is preferably 5 to 200 rotations / minute, more preferably 1 rotation.
It is 0-80 rpm. Further, the base material 4 itself may be rotated in order to make the thickness of the coating uniform.

The targets 2a and 2b are arranged around the base material holder 5, and the target 2a is made of metal oxide (or fluorine resin) and the target 2b is made of fluorine resin (or metal oxide). Is used.

If the distance between the targets 2a and 2b is too short, the sputtered plasmas interfere with each other to prevent uniform sputtering, or depending on the combination of the metal oxide and the fluorine-based resin, the sputtering may occur. Since the particles react with each other and are discharged, the formation of the coating film is significantly hindered. Therefore, it is preferable to provide the particles at a certain distance. Further, it is preferable to provide the targets 2a and 2b and the base material 4 at positions facing each other.

By rotating the substrate 4 mounted on the substrate holder 5, the targets 2a and 2b are alternately exposed to particles sputtered to form a film on the substrate 4.

Hereinafter, a method for forming a coating film made of a metal oxide and a fluororesin on the base material 4 using the high frequency sputtering apparatus shown in FIG. 1 will be described. First, after the base material 4 (for example, slide glass) is attached to the base material holder 5 using a fluorine resin (for example, PTFE) for the target 2a and the metal oxide (for example, SiO ₂ ) for the target 2b, the base material 4 is rotated at a constant rotation speed.

Next, the inside of the vacuum chamber 1 is evacuated to 1 × 10 ⁻³ Pa or less by an exhaust device (not shown), and then the gas introduction valve 6 is opened to remove an inert gas such as argon gas. It is introduced into the vacuum chamber 1. The pressure in the vacuum chamber 1 is controlled by adjusting the amount of inert gas introduced by a mass controller, and the pressure in the chamber during film formation is 0.1 to 10
Control within the range of Pa. This is because if the pressure in the tank exceeds this range, the discharge becomes unstable and continuous film formation becomes difficult.

Subsequently, high-frequency (13.56 MHz) power (high-frequency power and direct-current power when a conductive material is used for 2b) is applied to the targets 2a and 2b by independent power sources to form discharges. Sputter the target. The electric power supplied to the targets 2a and 2b is set to a predetermined electric power value, and after the discharge is stabilized, the shutter 3 is opened and formation of a film on the base material 4 is started.

The mixing ratio of the metal oxide and the fluorine-based resin in the coating film can be changed by individually controlling the ratio of electric power supplied to both targets. That is, in order to obtain high water repellency, it is sufficient to increase the input power to the fluororesin target, and to obtain high scratch resistance, the input power to the metal oxide target can be increased. .

Further, after the film formation is started, the mixing ratio in the thickness direction of the film can be changed by changing the power supplied to the fluorine-based resin target and the power supplied to the metal oxide target. For example, by increasing the proportion of the metal oxide immediately after the start of film formation and gradually increasing the proportion of the fluororesin, it is possible to form a film having excellent adhesion to the substrate and excellent water repellency.

The thickness of the coating is preferably thick in order to obtain high scratch resistance, but if it becomes too thick, the substrate warps or peels off due to the stress of the coating itself.
It is preferably 100 μm or less, more preferably 20 μm or less.

When the thickness of the film is small, the scratch resistance is easily affected by the base material. For example, in the case where the base material is a material having a hard surface such as glass, in order to obtain sufficient scratch resistance,
The thickness of the coating is preferably 0.005 μm or more, more preferably 0.05 μm or more, and further preferably 0.1.
It is 1 μm or more. When the substrate has a soft surface such as polycarbonate, the thickness is preferably 0.1 μm or more, more preferably 0.3 μm or more.

Next, the present invention 2 will be described. The method for producing a laminate of the present invention 2 is a method of forming a coating film made of a metal oxide and a fluororesin on a base material by a simultaneous sputtering method of a metal oxide and a fluororesin.

The same metal oxide and fluorine resin as those used in the present invention can be used for forming the coating film.

As the base material used for forming the above-mentioned coating, the same base material as used in the present invention can be used.

A sputtering method is used as a method for forming a coating film composed of the metal oxide and the fluororesin on the substrate.

The method of the above-mentioned sputtering method is the same as that of the present invention.

FIG. 4 shows the high frequency sputtering used in the present invention.
It is a schematic diagram which shows an example of a ring device. In the figure, 11 is true
An empty tank is shown, and the vacuum tank 11 is an oil rotary pump and an oil diffusion pump.
With an exhaust device (not shown) combining
Pressure (specifically 1 x 10 ^-FiveMaintained below Torr)
It In addition, the lower part of the vacuum chamber 11 has two targets.
2A and 2B are provided.

The targets 2A and 2B are respectively connected to the matching box 12 and the RF power source 13 which are different from each other, and the targets 2A and 2B can be spattered with different high frequency powers. Further, the target 2B can be switched to the DC power supply 14, and the DC power supply 14 can also perform sputtering. Further, the sputtering apparatus can individually control the power applied to the targets 2A and 2B, and the composition of the coating film formed on the base material 41 can be changed by changing the power applied to the targets 2A and 2B. Can be controlled.

The target 2 in the upper part of the vacuum chamber 11
Substrate 41 for forming a film at a position facing A and 2B
A sputter table 15 for mounting (for example, a glass plate) is arranged. This spatter table 1
5 is rotated by a motor 16 to form a film while rotating the base material 41 at a constant rotation speed. Further, the base material 41 can be attached to any position on the sputter table 15.

To actually perform sputtering, first,
After the target 2A is made of a fluororesin (eg PTFE), the target 2B is fitted with a metal oxide (eg ZrO ₂ ), and the sputter table 15 is fitted with the base material 41 (eg a glass plate), and then the motor 16 is rotated at a constant speed Rotate at (10 to 1000 rpm).
At this point, the shutter 17 remains closed.

Next, after the inside of the vacuum chamber 11 is evacuated to 1 × 10 ^-5 Torr or less) by an exhaust device (not shown),
By opening the gas introduction valve 18, an inert gas such as argon gas is introduced into the vacuum chamber 11. Vacuum tank 11
The internal pressure is controlled by adjusting the amount of inert gas introduced by a mass controller (not shown), and the internal pressure of the bath during film formation is in the range of 1 × 10 ⁻³ to 1 × 10 ⁻¹ . The reason is that if the pressure in the vacuum chamber 11 exceeds this range, the discharge becomes unstable and continuous film formation becomes difficult.

Subsequently, high-frequency power (high-frequency power and direct-current power when a conductive material is used for 2B) is applied to the targets 2A and 2B by independent power sources to discharge the targets 2A and 2B. To do. After setting the input power to the targets 2A and 2B to predetermined power values, respectively, the shutter 17 is opened,
The film formation on the base material 41 is started.

After the film formation is started, if the electric power supplied to each of the targets 2A and 2B is kept constant, a film in which the ratio of the metal oxide and the fluororesin is constant in the film thickness direction is laminated on the base material 41. By controlling the input power to each target,
It is possible to control the film formation rates of the fluororesin and the metal oxide, and to control the contents of the fluororesin and the metal oxide in the coating film. Therefore, the electric power applied to each of the targets 2A and 2B may be appropriately determined depending on which of water repellency and scratch resistance is to be emphasized, depending on the application. That is,
When importance is attached to water repellency, the electric power supplied to the target 2A (fluorine-based resin) may be higher than that of the target 2B (metal oxide).

As shown in FIG. 5, the targets 2A and 2B are arranged so as to be substantially equidistant from each other in the direction orthogonal to the rotary shaft 20 of the sputter table 15, and the shortest distance between the rotary shaft 20 and the base material 41 is set. When the distance is X and the shortest distance between the rotary shaft 20 and both targets is Y, the base material 41 and the targets 2A and 2B are arranged so as to satisfy the relationship of X> Y.

As shown in FIGS. 7 and 8, the mounting position of the base material 41 is divided into three regions I, II and III in a concentric manner from the center of the sputter table 15 in the radial direction. In the region (2), the base material 41 is placed inside both targets 2A and 2B due to the rotation of the sputter table 15, and the relation X> Y is not satisfied. Since it is carried out actively, the resulting coating has many composition defects, and water repellency and scratch resistance are impaired.

On the other hand, in the regions II and III, the substrate 41 is arranged at the center of the targets 2A and 2B or outside the center by rotation of the sputter table 15, and X> Y. Since the relationship is satisfied, the obtained coating film has excellent water repellency and scratch resistance.

The rotation speed of the base material 41 is 1
It is preferable that the film thicknesses formed by sputtering the targets 2A and 2B during rotation are each set to 10 Å or less. For example, under certain conditions (constant substrate distance, input power, gas pressure), the larger film formation rate of the targets 2A and 2B is V (A / min).
Then, the rotation speed R (revolution / min) is V / R ≦ 10.
It is preferable that the range satisfies the following relationship.

If the rotation speed of the base material 41 exceeds the range of the above formula (V / R> 10), the possibility that the coating film becomes a laminated film increases, so that water repellency and scratch resistance should be imparted at the same time. Is difficult and not preferable. In addition, in the case of film formation by sputtering, the film formation speed rarely exceeds 10,000 A / min, so the rotation speed is 100 rotations / m.
By setting to in, the above formula can be satisfied in most cases.

If the film thickness of the above coating is 100 Å or more, sufficient water repellency is exhibited, and as for the scratch resistance, if the base material is a relatively hard material such as glass, 100 Å or more provides sufficient performance. . However, when the base material is a material having a relatively low hardness, the scratch resistance is easily affected by the base material, and a film thickness of 1000 Å or more is preferable in order not to be affected by the effect.

[0047]

In the manufacturing method of the present invention, the target of the metal oxide and the fluororesin is arranged around the base material, and sputtering is performed while rotating the base material, so that the ratio of the metal oxide and the fluororesin is constant. Since it forms a film
A laminate having constant water repellency and scratch resistance can be obtained.

In the manufacturing method of the present invention 2, the targets of the metal oxide and the fluorine-based resin are arranged so as to be substantially equidistant in the horizontal direction from the perpendicular from the center of the rotation axis of the sputter table, and the metal oxide and the fluorine-based target are respectively arranged. When the shortest distance in the horizontal direction between the perpendicular and the base material is X and the shortest distance in the horizontal direction between the perpendicular and both targets is Y, the target of the resin-based resin is the base material and both targets.
By arranging so that the relation of> Y is satisfied, the base material can be attached while avoiding the region where the chemical reaction between the sputtered particles is occurring, so that the composition defect in the coating film can be reduced. Furthermore, by applying different powers to both targets, a laminate having uniform water repellency and scratch resistance can be obtained.

[0049]

EXAMPLES Examples of the present invention will be described below. Example 1
~ 8 and Comparative Examples 1 to 4 correspond to the present invention, and Examples 9 to 1
4 and Comparative Examples 5 to 11 correspond to the present invention 2.

(Examples 1 to 3) A slide glass ("S1111" manufactured by Matsunami Co., size 80 mm x 30 mm) was placed on the substrate holder of the high frequency sputtering apparatus shown in FIG.
X 1 mm) was attached, and PTFE (manufactured by Nippon Bulker Co., Ltd.) was used for the fluororesin target 2a and SiO ₂ was used for the metal oxide target 2b. Next, after evacuating the inside of the vacuum chamber 1 to 1 × 10 ⁻³ Pa or less, argon gas was introduced to adjust the pressure inside the vacuum chamber 1 to 0.67 Pa, and then high frequency power (13.56 MHz) was applied to both targets. Throw in,
Sputtering with argon plasma was started. 5
After three minutes, the shutter 3 placed in front of each target was opened, and the SiO ₂ and PTFE were applied onto the slide glass substrate 4 at the substrate holder rotation speed, the power input to the target and the sputtering time shown in Table 1. A laminated body having a coating film was obtained.

(Example 4) Si was formed on a slide glass substrate in the same manner as in Example 3 except that an FEP (Yodogawa Kasei Co.) target was used in place of the PTFE target.
A laminate having a coating film of O ₂ and PTFE was obtained.

(Embodiment 5) A laminate having a coating film made of SiO ₂ and PTFE formed on a slide glass substrate was prepared in the same manner as in Embodiment 1 except that a TiO ₂ target was used instead of the SiO ₂ target. Obtained.

(Example 6) Lamination in which a coating film made of SiO ₂ and PTFE was formed on a slide glass substrate in the same manner as in Example 1 except that a ZrO ₂ target was used instead of the SiO ₂ target. Got the body

Example 7 Except that the rotation speed of the substrate holder and the sputtering time were changed as shown in Table 1,
In the same manner as in Example 1, SiO ₂ was formed on the slide glass substrate.
A laminated body having a film made of a PTFE film was obtained.

Example 8 The procedure of Example 1 was repeated except that a polycarbonate plate (made by Asahi Glass Co., Ltd.) was used instead of the slide glass as the substrate, and SiO ₂ and P were formed on the substrate.
A laminate having a film made of TFE was obtained.

Comparative Example 1 A slide glass substrate was prepared in the same manner as in Example 1 except that the power supplied to the target and the sputtering time were changed as shown in Table 1 without rotating the substrate holder. A laminated body having a coating film made of SiO ₂ and PTFE formed on the material was obtained.

(Comparative Example 2) A film made of only PTFE was prepared on a slide glass substrate in the same manner as in Comparative Example 1 except that only PTFE was used as a target and the PTFE target was fixed at a position facing the substrate. A laminated body having the above was obtained.

(Comparative Example 3) As shown in FIGS. 2 and 3, a composite target 8 in which the surface of the SiO ₂ target 8a was partially covered with a PTFE sheet 8b (coverage ratio 1 in area ratio 1
0%) was used in the same manner as in Comparative Example 1 to obtain a laminate in which a coating film made of only PTFE was formed on the slide glass substrate.

(Comparative Example 4) The same procedure as in Comparative Example 1 was repeated except that the composite target 8 (70% in area ratio) in which the surface of the SiO ₂ target 8a was partially covered with the PTFE sheet 8b was used. PT on the slide glass substrate
A laminated body having a film formed of only FE was obtained.

[0060]

[Table 1]

Performance Evaluation of Coatings The coatings obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were subjected to the following performance evaluations and the results are shown in Table 2. (A) Film thickness measurement A film is formed by masking a part of the base material, and the step between the masking part and the film forming part is measured by a surface shape measuring instrument (“Dektak3030” manufactured by Sloan Co., Ltd.) to obtain the film thickness. I asked.

(B) Water repellency test The contact angle to water was measured by a contact angle meter (Kyowa Interface Science Co., Ltd.
AA type ") was measured by a droplet method.

(C) Scratch resistance test: # 0000 steel wool was pressed against the surface of the coating at a constant pressure, and after 20 reciprocations on the coating, the surface state of the coating was visually observed to scratch the coating surface. The maximum pressure when there was no scratch was used as an index of scratch resistance (hard coat).

[0064]

[Table 2]

(Examples 9 to 14, Comparative Examples 9 to 11) FIG.
Slide glass (“S1111” manufactured by Matsunami Co., Ltd., size 80 mm × 30 mm ×) as the base material 41 on the sputter table 15 using the high frequency sputtering apparatus shown in FIG.
1 mm) was attached to the position shown in Table 3 among the three regions I, II, and III shown in FIGS. Then
After using the predetermined targets shown in Table 3 and then evacuating the inside of the vacuum chamber 11 to 1 × 10 ⁻⁵ Torr or less,
The gas introduction valve 18 was opened, and Ar gas was used as a sputtering gas by using the mass flow controller 19 in the vacuum chamber 11
45 sccm is introduced into the chamber, and the pressure in the vacuum chamber 11 is set to 6 × 10
^-3 Torr.

Subsequently, while rotating the sputter table 15 by the motor 16 at a rotation speed of 20 rpm,
After the discharge was formed by applying the predetermined high frequency power (frequency 13.56 MHz) shown in Table 3 to the targets 2A and 2B, the shutter 17 was opened and the film formation was started. After the predetermined film formation time shown in Table 3 from the start of film formation, the shutter 17 was closed, power supply to the targets 2A and 2B was stopped, and the film formation was completed.

(Comparative Examples 5 to 8) As a target, as shown in FIG.
10 and 10, the composite target 28 in which SiO ₂ was coated with PTFE was used, and the film was formed under the film forming conditions shown in Table 3 without rotating the sputter table 15. still,
As the composite target 28, the one having the coverage shown in Table 3 was used.

[0068]

[Table 3]

Performance Evaluation of Coating Films The coating films obtained in Examples 9 to 14 and Comparative Examples 5 to 11 were subjected to the following performance evaluations and the results are shown in Table 4. (A) Film thickness measurement, (b) Water repellency test, and (c) Scratch resistance test Measurement and evaluation were carried out by the same method as in Example 1.

(D) Evaluation of coating defect The Si / O ratio was obtained by composition analysis by ES41A.
The coating defects were evaluated according to the following evaluation criteria. <Evaluation Criteria> ◯: A Si / O ratio of 0.4 or more and a film without defects was obtained. (Triangle | delta): Si / O ratio was 0.3-0.4 and the coating film with few defects was obtained. X: A Si / O ratio of less than 0.3 and a film with many defects were obtained.

[0071]

[Table 4]

[0072]

The method for producing a laminate of the present invention is as described above, and it is possible to form a coating film having both water repellency and scratch resistance on a substrate by a sputtering method, depending on the purpose. The water repellency and scratch resistance can be controlled by changing the ratio of the metal oxide and the fluororesin in the coating. The production method of the present invention can be used as a protective film for lenses, mirrors, automobiles, window glass for construction and other transparent molded articles, and since it has flexibility by containing a fluorine resin, it is an agricultural film. It can also be used as a stain-proof film.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a high frequency sputtering apparatus used in the present invention.

FIG. 2 is a side view showing a composite target used in the present invention.

FIG. 3 is a plan view showing a composite target used in the present invention.

FIG. 4 is a schematic view showing an example of a high frequency sputtering apparatus used in the present invention 2.

FIG. 5 is a schematic diagram showing a positional relationship between a target and a base material in FIG.

FIG. 6 is a schematic diagram showing a positional relationship between a sputter table and a target.

FIG. 7 is a schematic diagram showing a positional relationship between a sputter table and a target.

FIG. 8 is a schematic diagram showing a positional relationship between a sputter table and a target.

FIG. 9 is a side view showing a composite target used in the present invention.

FIG. 10 is a plan view showing a composite target used in the present invention.

[Explanation of symbols]

 1, 11 Vacuum tank 2a, 2b, 2A, 2B Target 3 Shutter 4,41 Substrate 5 Substrate holder 6 Gas introduction valve 7 Rotating shaft 8, 28 Complex target 12 Matching box 13 High frequency power supply 14 DC power supply 15 Sputter table 16 Motor 17 Shutter 18 Gas introduction valve 19 Mass flow controller 20 Rotating shaft

Claims (2)

[Claims] 1. A metal oxide and a fluororesin target are arranged on the outside of a base material, and electric power is applied to the target while the base material is rotated to perform sputtering, whereby the metal oxide is deposited on the base material. And a water-repellent hard coat layer made of a fluororesin, which is laminated. 2. By rotating a sputter table equipped with a base material and applying electric power to both the metal oxide target and the fluororesin target to perform sputtering,
A method for forming a composite film of a metal oxide and a fluororesin on a base material, wherein the both targets are arranged so as to be substantially equidistant in a direction orthogonal to the rotation axis of the sputter table, and the rotation axis The shortest distance between
When the shortest distance between the rotary shaft and both targets is Y, the base material and the target are arranged so as to satisfy the relationship of X> Y, and a coating film made of a metal oxide and a fluororesin is formed on the base material. A method for producing a laminated body, which comprises forming the laminated body.