JP2006309139A - Manufacturing method of stain-proof optical article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make performance of respective stain-proof films formed on respective surfaces of an optical article equivalent. <P>SOLUTION: An object A and an object B denote two members among a support device 80, a cover 82 and a substrate 40. When clearance (a distance) L between the object A and the object B is not more than twice an ion sheath Id, a cation Ic is defeated by suction force with which the object A and the object B are charged negative and is attracted to the object A or the object B and the cation Ic cannot pass between the object A and the object B. Accordingly when the clearance (the distance) L between the object A and the object B is 0.1 times or more the ion sheath Id and not more than twice, the cation cannot reach at rear surfaces of the object A and the object B. Thereby the rear surfaces of the object A and the object B are not sputtered by the cation and thus the stain-proof films or other processing films located at the rear surfaces of the object A and the object B can maintain states before performing the processing. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a high-performance water-repellent / anti-fouling treatment for plastic and glass optical articles (plastic eyeglass lenses, lenses for optical devices, display panel windows such as substrates of liquid crystal display devices).

  For film deposition equipment and vapor deposition equipment used to form an antireflection film and other vapor deposition films on a conventional lens, keep the lens holding posture constant with respect to the vapor deposition source in a vacuum vessel, and invert multiple lenses There is a disclosure of forming an antireflection film on the front and back of the lens (for example, Patent Document 1).

JP 2000-303167 A

  However, in order to provide an optical article with antifouling properties (performance that can be removed relatively easily when the surface becomes dirty due to dust, finger fingerprints, etc.), the antifouling film and the optical are simply deposited in a vacuum container. Adhesion with the article cannot be obtained. Further, in an optical article such as a spectacle lens, it is necessary to provide an antifouling film on the front and back of the spectacle lens.

  After the treatment for improving the adhesion between the antifouling film and the optical article, an antifouling film is formed on one surface of the spectacle lens, and the antifouling film and the optical article are further formed on the other surface of the spectacle lens. A treatment for improving adhesion is performed. When performing this treatment, the antifouling film formed earlier is partially removed by the positive ions generated in the treatment for improving the adhesion, and the antifouling performance is impaired. was there.

  The present invention has been made in view of the above problems, and an object thereof is to equalize the performance of an antifouling film formed on each film formation surface of an optical component.

  In order to solve the above problems, in the present invention, in the film forming chamber, the first antifouling film adhesion improvement is performed by applying the antifouling film adhesion improving process to one surface of the film forming body having a plurality of film forming surfaces. A first step of forming a first antifouling film after the treatment; and a surface of the film-deposited body on which the first antifouling film is formed in the film forming chamber after the first step. On the other hand, the second antifouling film is formed after the second antifouling film adhesion improving process for applying the antifouling film adhesion improving process to the other film forming surface of the film forming object. A process for producing an antifouling optical article comprising the steps of: when performing the second antifouling film adhesion improving treatment, the film-formed body formed in the first step; Cover with a film-forming body cover member and a film-forming body holding member, and a gap between the film-forming body cover member and the film-forming body holding member, and hold the film-forming body and the film-forming body. The gap between the wood, both ion sheath of 0.1 times or more, and the subject matter to be doubled within.

According to this, the first antifouling film provided on one surface of the film formation body in the first step and the second antifouling film provided on the other film formation surface of the film formation body in the second step. The antifouling property of the antifouling film can be made equivalent. Here, if the gap between the film formation body cover member and the film formation body holding member and the gap between the film formation body and the film formation body holding member is set to less than 0.1 times the ion sheath, each member A high level of smoothing is required on the contact surfaces between the member and the film-forming body, or a flexible sealing material is required, which increases the processing cost. .
On the other hand, if the gap between the film-forming body cover member and the film-forming body holding member, and the film-forming body and the film-forming body holding member exceeds twice that of the ion sheath, the positive ions enter. Since 1 antifouling layer is eroded, it is not preferable. This erosion mechanism will be described later.

The gist of the present invention is a method for producing an antifouling optical article, wherein the first and second antifouling film adhesion improving treatments are plasma treatment or ion gun treatment.
According to this, since the antifouling film adhesion improving process is a plasma process or an ion gun process, the first antifouling film provided on one surface of the film formation target in the first step, and the second antifouling film adhesion improving process The antifouling property of the second antifouling film provided on the other film forming surface of the film forming object can be made equal in the process.

  The gist of the present invention is a method for producing an antifouling optical article, wherein the first antifouling film and / or the second antifouling film is formed by a vacuum deposition method. .

  According to this, since the first antifouling film and / or the second antifouling film is formed by a vacuum deposition method, the performance of the antifouling film formed on each film formation surface of the optical component is improved. Can be equivalent.

  The present invention is a method for producing an antifouling optical article, wherein the first antifouling film and / or the second antifouling film is formed by forming a fluorine-containing silane compound. To do.

  According to this, by forming a first antifouling film and / or a second antifouling film using a fluorine-containing silane compound having water repellency, dirt due to water droplets, tears, sweat, etc. can be easily obtained. Can be wiped off.

The present invention is a method for producing an antifouling optical article, wherein the fluorine-containing silane compound as the first antifouling film and / or the second antifouling film is represented by the general formula (1). This is the gist. However, in the general formula (1), Rf ² includes a unit represented by — (C _k F _2k ) O—, in which _k is an integer of 1 to 6, and is a straight-chain par having no branch. Represents a divalent group having a fluoropolyalkylene ether structure. R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and J represents a hydrolyzable group or a halogen atom. p represents an integer of 0 or more and 2 or less. n represents an integer of 1 to 5. m and r each represents an integer of 2 or 3.

  According to this, by forming a first antifouling film or a second antifouling film using a fluorine-containing silane compound having water repellency, dirt due to water drops, tears, sweat, etc. can be easily wiped off. be able to.

The present invention is a method for producing an antifouling optical article, wherein the fluorine-containing silane compound as the first antifouling film and / or the second antifouling film is represented by the general formula (2). This is the gist. In general formula (2), Rf ¹ is a perfluoroalkyl group, X is hydrogen, bromine, or iodine, Y is hydrogen or a lower alkyl group, Z is fluorine or a trifluoromethyl group, R ¹ is a hydroxyl group or hydrolyzable. R ² represents hydrogen or a monovalent hydrocarbon group. a, b, c, d and e are integers of 0 or more, a + b + c + d + e is at least 1 or more, and the order of existence of each repeating unit delimited by a, b, c, d and e is not limited in the formula . f represents an integer of 0 or more and 2 or less. g represents an integer of 1 to 3. h represents an integer of 1 or more.

  According to this, by forming a first antifouling film and / or a second antifouling film using a fluorine-containing silane compound having water repellency, dirt due to water drops, tears, sweat, etc. can be easily obtained. Can be wiped off.

  Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic view of a film forming apparatus used in the present invention.
In FIG. 1, a film forming apparatus 50 has a film formation body and a substrate 40 as an optical article placed on a dome 81 as a film formation body holding member and substantially covered with a cover 82 as a film formation body cover member. The support device 80 is provided with three chambers CH1, CH2 and CH3 that can pass through the inside. These chambers CH1 to CH3 are sequentially connected, and the support device 80 is transported by a transport device (not shown). Further, the chambers CH1 to CH3 can be sealed from each other. Each chamber CH1 to CH3 is provided with each vacuum generation device 52, 53, and 54, and the pressure in each chamber CH1 to CH3 is controlled by the vacuum generation devices 52, 53, and 54, respectively.

  The chamber CH1 is an entrance or gate chamber, and after the support device 80 on which the substrate 40 is placed is introduced into the chamber CH1 by the carry-in device, the inside of the chamber CH1 is held at a predetermined pressure or lower for a predetermined time. As a result, the substrate 40 is degassed. Note that the inside of the chamber CH1 is controlled to a predetermined pressure by a vacuum generation device 52 including a rotary pump 52a, a roots pump 52b, and a cryopump 52c.

  The chamber CH2 is a so-called electron beam evaporation apparatus with an ion irradiation apparatus. Therefore, inside the chamber CH2, vapor deposition sources 55a and 55b for vapor depositing two kinds of substances, electron guns 56a and 56b for evaporating the respective vapor deposition sources 55a and 55b, and an openable / closable shutter for adjusting the vapor deposition amount. 57a and 57b are provided. Note that the inside of the chamber CH2 is maintained at a predetermined pressure by a vacuum generation device 53 including a rotary pump 53a, a roots pump 53b, and a cryopump 53c.

  The chamber CH2 is provided with a high-frequency plasma generator 51 for performing plasma processing. The high-frequency plasma generator 51 includes an RF coil 60 in the chamber CH2, and includes a matching box 61 connected to the RF coil 60 outside the chamber CH2 and a high-frequency transmitter 62 connected to the matching box 61. Further, the chamber CH2 includes an oxygen gas supply source 63 or an argon gas supply source 64 introduced at the time of plasma processing. These oxygen gas supply source 63 or argon gas supply source 64 is predetermined by an auto pressure controller 65. The flow rate is controlled by the mass flow controller 66a so as to be the pressure.

  Further, an ion irradiation apparatus 90 is disposed in the chamber CH2 in order to perform the antifouling film adhesion improving process. The ion irradiation apparatus 90 includes an ion gun 91, a DC power source 92 and an RF power source 93 that control the amount and irradiation time of ions from the ion gun 91, and a mass flow controller 66b. The mass flow controller 66b is connected to the oxygen gas supply source 63 or the argon gas supply source 64, and controls the flow rate of each gas (oxygen, argon gas) introduced during ion irradiation.

  The chamber CH3 is a chamber for forming an antifouling film by depositing a fluorine-containing silane compound (details will be described later) on the outermost surface film of the substrate 40. In the chamber CH3, an antifouling film deposition source 59 impregnated with a fluorine-containing silane compound, a heater 68 made of, for example, a halogen lamp, and a correction plate 67 are disposed. The correction plate 67 is a fixed type and adjusts the degree of vapor deposition emitted toward the support device 80 by adjusting the opening degree. Note that the inside of the chamber CH3 is maintained at a predetermined pressure by a vacuum generation device 54 including a rotary pump 54a, a roots pump 54b, and a turbo molecular pump 54c.

FIG. 2 is a flowchart of the first process and the second process for explaining the process of the antifouling film on the substrate 40.
The first step is a step of providing an antifouling film on one surface of the substrate 40, and the second step is a step of providing an antifouling film on the other surface of the substrate 40. In step S1 of the first process, one surface of the substrate 40 as a film formation body having a plurality of film formation surfaces is aligned, and one or more are set side by side on the dome 81 as a film formation body holding member. The method of arranging will be described later.

  In step S2, the dome 81 on which the substrate 40 is set is placed on a vapor deposition apparatus as a film forming chamber. The dome 81 is substantially semicircular and has a curvature such that the distance from the vapor deposition source of the vapor deposition apparatus is substantially uniform.

  In step S3, plasma processing is performed to clean the substrate surface. The positive ions in the plasma sputter the substrate surface to remove surface contaminants and improve the adhesion with the antireflection film in the next step.

  In step S4, an antireflection film is deposited.

  In step S5, plasma processing is performed. The plasma treatment as the first antifouling film adhesion improving treatment activates the surface of the substrate 40, and the generated positive ions sputter the surface of the substrate 40. In this process, the surface of the substrate 40 is activated, and the adhesion with the substance to be deposited in the subsequent process can be improved. During the plasma processing, the dome 81 is rotated to equalize the quality among the plurality of substrates 40.

  In step S6, an antifouling substance is deposited. The first antifouling film formed by depositing and depositing an antifouling substance is a fluorine-containing silane compound. Details of the fluorine-containing silane compound will be described later. When the antifouling substance is deposited, the dome 81 is rotated to equalize the quality among the plurality of substrates 40.

  In step S7, the dome 81 is taken out from the vapor deposition apparatus. Through the steps so far, the first antifouling film made of the fluorine-containing silane compound is formed and formed on one surface as the film formation surface of the substrate 40 as the film formation body.

  Next, in step S8 of the second process, the substrate 40 in the state of step S7 of the first process is turned over and set again on the dome 81. As a result, the first antifouling film formed by the film formation in the first step is positioned on the back side with respect to the ion gun or the evaporation source.

  In step S9, the cover 82 is set on the dome 81 on which the substrate 40 is set. The cover 82 as the film formation body cover member is formed by using the first antifouling film formed by the film formation in the first step, the dome 81 as the film formation body holding member, and the film formation body cover member. And a cover 82 as a cover. The gap between the members is in the range of 0.1 to 2 times that of the ion sheath. However, it is quite difficult to cover the dome 81 as the film formation body holding member and the cover 82 as the film formation body cover member without any gap. Similarly, when the substrate 40 is set on the dome 81, it is difficult to eliminate the gap between the substrate 40 and the dome 81 or between the substrate 40 and a ring (details will be described later). .

  Although the step of setting the cover 82 is not shown in the flowchart of the first step of providing the antifouling film on one surface of the substrate 40, there is no problem even if the cover is set on the dome in the first step. In that case, the process of setting the cover on the dome is set between step S1 and step S2.

  In step S10, the dome 81 on which the substrate 40 and the cover 82 are set is placed on the vapor deposition apparatus.

  In step S11, plasma processing is performed to clean the substrate surface. The positive ions in the plasma sputter the substrate surface to remove surface contaminants and improve the adhesion with the antireflection film in the next step.

  In step S12, an antireflection film is deposited.

  In step S13, plasma processing is performed. By rotating the dome 81, it is possible to equalize the quality among the plurality of substrates 40. During the plasma treatment as the second antifouling film adhesion improving treatment, the dome 81 as the film formation body holding member, the cover 82 as the film formation body cover member, and the substrate 40 as the film formation body. And a dome 81 serving as a deposition target holding member, a positive ion passes through the gap and forms a film in the first step. The first antifouling film formed in this way is sputtered, and a portion where the first antifouling film is partially lost is generated.

  If the first antifouling film is partially lost, the antifouling is caused by the surface of the substrate 40 on which the first antifouling film is formed and the antifouling film (second antifouling film) formed on the other surface. A difference occurs in gender. Specifically, when wiping off dirt such as fingerprints attached to the first antifouling film, the wiping property of the second antifouling film is inferior.

  In step S14, an antifouling substance is deposited. The second antifouling film formed by depositing and depositing an antifouling substance is a fluorine-containing silane compound. Details of the fluorine-containing silane compound will be described later. When the antifouling substance is deposited, the dome 81 is rotated to equalize the quality among the plurality of substrates 40.

  In step S15, the dome 81 is taken out from the vapor deposition apparatus. Through each of the steps so far, an antifouling film having antifouling properties is formed on each film formation surface of the substrate 40.

  FIG. 3A is a schematic diagram for explaining the potential of the surface of the floating electrode in the plasma, and FIG. 3B shows the relationship between the dome 81, the cover 82, the plurality of substrates 40 and the ions as the floating electrode. (C), (d) is a schematic diagram explaining the behavior of positive ions in the relationship between the ion sheath and the gap (distance) between the objects of the floating electrode.

  In FIG. 3A, all the members and the cover 82 attached to the support device 80 are floating electrodes in an electrically floating state in the chamber CH <b> 2 of the film forming device 50. The floating electrode placed in the plasma is negatively charged by excessive inflow of electrons, and an ion sheath is formed near the surface. Positive ions in the sheath are accelerated at right angles toward the floating electrode by an electric field in the ion sheath and injected into the floating electrode. Therefore, the positive ions in the sheath are accelerated toward the floating electrode from all directions.

  In FIG. 3A schematically showing this state, an ion sheath is formed on all the members mounted on the support device 80 and all the surfaces of the cover 82 or adjacent spaces. The negative potential is maximized on the surface of the floating electrode, and as the distance from the surface increases, the space charge weakens and reaches the distance d, and the space charge becomes substantially zero.

This state is expressed as follows.
As a phenomenon on the surface of the object placed in the plasma, when an object having a floating electrode voltage Vf is placed in the plasma having the potential Vp, the ion particle flux density Im incident on the object is expressed by the ion particle density Ni ( Pcs / cm ³ ) and the average velocity Vi of the ion particles are expressed as follows.
Im = 1/4 × Ni × Vi (pieces / cm ² ) (Equation 1)
The electron particle bundle density Dm is expressed as follows by the electron particle density Ne (number / cm ³ ) and the average velocity Ve of the electron particles.
Dm = 1/4 × Ne × Ve (pieces / cm ² ) (Equation 2)
Average speed Vi of the ion particles, by mass Mi temperature Ti and ions of the particles of the Boltzmann constant K _B and the ion of the particles, expressed as the following (Formula 3).

また、電子粒子の平均速度Ｖｅは、ボルツマン定数Ｋ_Bと電子の粒子の温度Ｔｅと電子の粒子の質量Ｍｅとによって、以下の（数式４）のように表せる。

The average speed Ve of the electronic particles by a mass Me of the temperature Te and electron particle Boltzmann constant K _B and electron particle, expressed as the following (Formula 4).

Physically, Me << Mi, and in the case of non-thermal equilibrium plasma, Te >> Ti, so Ve >> Vi. Further, since Ne = Ni, Im <Dm.
Further, the surface of the floating electrode is negatively charged due to excessive inflow of the electron particle bundle. Positive ions collide with the negatively charged floating electrode, and the surface of the floating electrode is sputtered.

  FIG. 3B shows a place where positive ions are accelerated toward the support device 80, the cover 82, and the substrate 40. In this case, when there are gaps between the support device 80, the cover 82, and the substrate 40, the relationship between the gaps (distances) L1 to L6 and the ion sheath described above will be described with reference to FIG. . Here, in the present invention, the distance d shown in FIG. 3A is defined as an ion sheath Id.

  In FIG. 3C, when any member of the support device 80, the cover 82, and the substrate 40 is the object A and the object B, the gap (distance) L between the object A and the object B is the ion sheath Id. When it is larger than twice, the positive ion Ia passes between the object A and the object B by overcoming the attractive force in which the object A and the object B are negatively charged. The positive ions Ia that have passed reach the back surfaces of the object A and the object B. The reached positive ions Ia are accelerated and collide with the back surfaces of the object A and the object B, and the back surfaces of the object A and the object B are sputtered by the positive ions.

  When the gap (distance) L between the object A and the object B remains unchanged and follows the same path as the positive ion Ia, the next positive ion Ib reaches the back surfaces of the object A and the object B. Will continue to sputter. In this way, the positive ions reach the back surfaces of the object A and the object B from one to the next and are continuously sputtered.

In FIG. 3D, when any member of the support device 80, the cover 82, and the substrate 40 is the object A and the object B, the gap (distance) L between the object A and the object B is the ion sheath Id. In the case of less than 2 times, the positive ion Ic is attracted to the object A or the object B by being attracted to the object A or the object B, and is attracted to the object A or the object B, and is attracted between the object A and the object B. Can't pass.
Therefore, when the gap (distance) L between the object A and the object B is within twice the ion sheath Id, positive ions cannot reach the back surfaces of the object A and the object B. This means that the back surfaces of the object A and the object B are not sputtered by positive ions, and the antifouling film or other treatment film on the back surface of the object A and the object B maintains the state before this treatment is performed. be able to.

ここで、電子の粒子密度Ｎｅと電極電位Ｖｓに対するイオンシースＩｄの量を具体的に計算して表したものが表１である。この表１の中で二点鎖線で示した内部が実際に本実施例での使用範囲である。このことから、物体Ａ及び物体Ｂとの隙間（距離）Ｌを２ｍｍ以内にすることによって、例え隙間があっても正イオンに物体Ａ及び物体Ｂの裏面をスパッタされることはなく、物体Ａ及び物体Ｂの裏面にある防汚膜或いは他の処理膜はこの処理を施す以前の状態を維持することができる。

Here, Table 1 shows the specific calculation of the amount of the ion sheath Id with respect to the electron particle density Ne and the electrode potential Vs. The inside indicated by the two-dot chain line in Table 1 is actually the range of use in this embodiment. Therefore, by setting the gap (distance) L between the object A and the object B within 2 mm, the back surface of the object A and the object B is not sputtered by positive ions even if there is a gap. In addition, the antifouling film or other treatment film on the back surface of the object B can maintain the state before the treatment.

Next, details of the antifouling film formation will be described.
FIG. 4 is a partial cross-sectional view in which the substrate 40 is set on the dome 81 and the cover 82 is set. FIG. 4 shows a set state in the second step in which the substrate 40 is inverted and the convex surface is faced down.

  The dome 81 serving as the film-forming member holding member is provided with a number of holes 81 a and 81 b corresponding to the substrate 40 so that a plurality of substrates 40 can be set. The holes 81a and 81b are substantially opened in the direction of the electron guns 56a and 56b, and the uniformity of the film deposited on the substrate 40 is achieved. In the holes 81a and 81b, frames 83a and 83b are provided as film-forming member holding members, respectively. Further, the substrate 40, the periphery of which is held by the ring 84, is inserted into the frames 83a and 83b with the convex surface facing downward. In this way, the dome 81 on which the plurality of substrates 40 are set is inserted into the rotating portion 85 for rotating the dome 81.

  Further, a cover 82 as a film-forming body cover member is mounted above the dome 81 on which the plurality of substrates 40 are set, and is screwed to the dome 81. At the center is a circular opening 82a with a diameter of 180 mm. This is for the light-receiving part for monitoring the deposited film thickness, and is also used as a hand hook for handling. There is a gap of about 20 mm between the opening 82 a and the upper surface of the dome 81. A sealing material 86 is attached to the gap. By closing the gap with the sealing material 86, it is possible to prevent positive ions from entering the upper portion of the dome 81 during plasma processing and ion gun processing.

  As a substrate 40, a plastic lens for spectacles (manufactured by Seiko Epson Corporation: Seiko Super Sovereign) having a hard coat film 42 formed on a plastic substrate 41 is set on the dome 81 of the support device 80 with the concave surface down. A cover 82 was placed thereon.

Next, after degassing in the chamber CH1, 100% argon gas was introduced into the chamber CH2, and plasma was generated by the high-frequency plasma generator 51 while controlling the pressure to 4.0 × 10 ⁻² Pa. Plasma generation conditions were 13.56 MHz and 400 W, and the treatment was performed for 1 minute. This is intended to clean the substrate surface in order to improve the adhesion between the substrate 40 and the antireflection film 43.

Subsequently, SiO ₂ and ZrO ₂ films were alternately deposited to form an antireflection film 43 composed of these films. The uppermost film of the antireflection film 43 is a SiO ₂ film. Subsequently, 100% oxygen gas was introduced into the chamber, and plasma was generated by a high-frequency plasma generator while controlling the pressure to 4.0 × 10 ⁻² Pa. Plasma generation conditions were 13.56 MHz and 400 W, and the treatment was performed for 2 minutes. This is intended to activate the surface of the antireflection film 43 and promote chemical bonding with the antifouling film 44 (see FIG. 6 described later).

  Subsequently, the antifouling film 44 was formed by moving the support device 80 to the chamber CH3. As the antifouling film deposition source 59, a fluorine-containing organosilicon compound (product name KY-130) manufactured by Shin-Etsu Chemical Co., Ltd. was used. It is represented by the following general formula (1).

ただし、一般式（１）中、Ｒｆ²は、ｋが１以上６以下の整数である、−（Ｃ_kＦ_2k）Ｏ−で表される単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する２価の基を表す。Ｒ³は炭素原子数が１以上８以下の一価炭化水素基であり、Ｊは加水分解性基又はハロゲン原子を表す。ｐは０以上２以下の整数を表す。ｎは１以上５以下の整数を表す。ｍ及びｒは２又は３の整数を表す。

However, in the general formula (1), Rf ² includes a unit represented by — (C _k F _2k ) O—, in which _k is an integer of 1 to 6, and is a straight-chain par having no branch. Represents a divalent group having a fluoropolyalkylene ether structure. R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and J represents a hydrolyzable group or a halogen atom. p represents an integer of 0 or more and 2 or less. n represents an integer of 1 to 5. m and r each represents an integer of 2 or 3.

  Here, KY-130 is diluted with a fluorine-based solvent (Sumitomo 3M Co., Ltd .: Novec HFE-7200) to prepare a 3% solid content solution, and 1 g of this is impregnated into a porous ceramic pellet and dried. This was set as an antifouling film deposition source 59 in the chamber CH3.

  During film formation, a halogen lamp was used as the heater 68 and the pellet of the antifouling film deposition source 59 was heated to 600 ° C. to evaporate the fluorine-containing organosilicon compound. The deposition time is 3 minutes. After the antifouling film 44 was formed, the support device 80 was taken out from the chamber CH3, the substrate 40 was inverted and set on the dome 81 of the support device 80 with the convex surface down, and the cover 82 was covered. A sealing material 86 (see FIG. 4) is attached to the opening 82a at the center of the cover 82. Thereafter, the same process as described above was performed again to form the antifouling film 44 on both surfaces of the substrate 40.

FIG. 5 is a perspective view showing the relationship among the substrate 40, the ring 84 and the frame 83.
The substrate 40 is urged and attached to the ring 84 and is inserted into the frame 83. The ring 84 is formed such that a part of a plate having elasticity is wound twice. The inner diameter of the formed ring 84 is smaller than the outer shape of the substrate 40. When the substrate 40 is mounted on the ring 84, the substrate 40 is inserted by energizing in the direction described in the ring 84 to increase the inner diameter of the ring 84.

  By inserting the upper end 40a of the substrate 40 in accordance with the upper end 84a of the ring 84, the distance between the vapor deposition sources 55a, 55b and the plurality of substrates 40 can be made uniform. Further, since the ring 84 is a single plate having a thickness of 1 mm or less and having elasticity, the gap between the substrate 40 and the ring 84 is 1 mm or less. That is, the gap is smaller than twice the ion sheath Id. Further, since the gap between the ring 84 and the frame 83 is set to be 1 mm or less, the gap is smaller than twice the ion sheath Id.

  Further, the vertical positions of the ring 84 and the substrate 40 on the paper surface are determined in a state in which the lower surfaces of the four projecting portions 84b to 84e provided to project from the ring 84 are in contact with the upper surface 83c of the frame 83. It has become. In addition, an edge 83d having an inclination is provided on the outer periphery of the frame 83, and the inclination of the edge 83d of each frame 83 is adjusted according to the curvature of the dome 81, so that the substrate 40 faces in the direction of the vapor deposition sources 55a and 55b. It is like that.

  In this example, a fluorine-containing organosilicon compound different from that in Example 1 was deposited as the antifouling film 44 in the chamber CH3.

  As the antifouling film deposition source 59, a fluorine-containing organosilicon compound (OPTOOL DSX) manufactured by Daikin Industries, Ltd. was used. It is represented by the following general formula (2).

ただし、一般式（２）中Ｒｆ¹はパーフルオロアルキル基、Ｘは水素、臭素、又はヨウ素、Ｙは水素又は低級アルキル基、Ｚはフッ素又はトリフルオロメチル基、Ｒ¹は水酸基又は加水分解可能な基、Ｒ²は水素又は１価の炭化水素基を表す。ａ、ｂ、ｃ、ｄ、ｅは０以上の整数で、ａ＋ｂ＋ｃ＋ｄ＋ｅは少なくとも１以上であり、ａ、ｂ、ｃ、ｄ、ｅでくくられた各繰り返し単位の存在順序は、式中において限定されない。ｆは０以上２以下の整数を表す。ｇは１以上３以下の整数を表す。ｈは１以上の整数を表す。

In general formula (2), Rf ¹ is a perfluoroalkyl group, X is hydrogen, bromine, or iodine, Y is hydrogen or a lower alkyl group, Z is fluorine or a trifluoromethyl group, R ¹ is a hydroxyl group or hydrolyzable. R ² represents hydrogen or a monovalent hydrocarbon group. a, b, c, d and e are integers of 0 or more, a + b + c + d + e is at least 1 or more, and the order of existence of each repeating unit delimited by a, b, c, d and e is not limited in the formula . f represents an integer of 0 or more and 2 or less. g represents an integer of 1 to 3. h represents an integer of 1 or more.

  Optool DSX is diluted with a fluorine-based solvent (Daikin Kogyo Co., Ltd .: demnum solvent) to prepare a 3% solid content solution, and 1 g of this is impregnated into a porous ceramic pellet and dried. It was set in the chamber CH3 as the dirty film deposition source 59. Others are the same as in the first embodiment.

In this embodiment, a hard coat film 42 is formed on a plastic substrate 41, an antireflection film 43 is further formed thereon, and an antifouling film 44 is formed on the outermost surface.
FIG. 6 is a partial cross-sectional view of the substrate 40.
As a substrate 40, a plastic lens for spectacles (manufactured by Seiko Epson Corporation: Seiko Super Sovereign) having a hard coat film 42 formed on a plastic substrate 41 is set on the dome 81 of the support device 80 with the concave surface down. A cover 82 was placed thereon. A sealing material 86 (see FIG. 4) is attached to the opening 82a at the center of the cover 82.

Next, after degassing in the chamber CH1, in the chamber CH2, a 100% oxygen gas was introduced into the ion gun 91 in a controlled manner to 35 SCCM, and ions were irradiated. As ion irradiation conditions, treatment was performed for 90 seconds at a frequency of 13.56 MHz, RF 450 W, acceleration voltage 500 V, and suppressor voltage 300 V. The pressure during the treatment was 4 × 10 ⁻³ Pa. The purpose of this is to clean the surface of the substrate 40 in order to improve the adhesion between the substrate 40 and the antireflection film 43.

Subsequently, SiO ₂ and TiO ₂ films were alternately deposited, and an antireflection film 43 made of these films was formed. The uppermost film of the antireflection film 43 is a SiO ₂ film. Further, TiO ₂ deposition, by ion-assisted deposition was performed. The ion irradiation conditions at this time are the same as described above.

  After the deposition of the antireflection film 43 was completed, 100% oxygen gas was introduced into the ion gun 91 while controlling it at 35 SCCM, and ions were irradiated. The conditions are the same as above except that the irradiation time is 2 minutes. The purpose of this is to activate the surface of the antireflection film 43 and promote chemical bonding with the antifouling film 44.

  Subsequently, the antifouling film 44 was formed by moving the support device 80 to the chamber CH3. As the antifouling film deposition source 59, a fluorine-containing organosilicon compound (product name KY-130, general formula (2)) manufactured by Shin-Etsu Chemical Co., Ltd. was used. Here, KY-130 is diluted with a fluorine-based solvent (Sumitomo 3M Co., Ltd .: Novec HFE-7200) to prepare a 3% solid content solution, and 1 g of this is impregnated into a porous ceramic pellet and dried. This was set as an antifouling film deposition source 59 in the chamber CH3.

  During film formation, a halogen lamp was used as the heater 68 and the pellet of the antifouling film deposition source 59 was heated to 600 ° C. to evaporate the fluorine-containing organosilicon compound. The deposition time is 3 minutes.

  After the antifouling film 44 is formed, the support device 80 is taken out from the chamber CH3, and the substrate 40 is inverted and set on the dome 81 of the support device 80 with the convex surface down, covered with the cover 82, and the same processing as above is performed again. By performing, the antifouling film | membrane 44 was formed on both surfaces of the board | substrate 40. FIG.

In this embodiment, a fluorine-containing organosilicon compound different from that in Embodiment 3 is deposited as the antifouling film 44 in the chamber CH3.
As the antifouling film deposition source 59, a fluorine-containing organosilicon compound (OPTOOL DSX, general formula (1)) manufactured by Daikin Industries, Ltd. was used. Optool DSX is diluted with a fluorine-based solvent (Daikin Kogyo Co., Ltd .: demnum solvent) to prepare a 3% solid content solution, and 1 g of this is impregnated into a porous ceramic pellet and dried. It was set in the chamber CH3 as the dirty film deposition source 59. Others are the same as in the third embodiment.

(Comparative Example 1)
In the second step, a comparative example is used in which the seal member 86 is not attached to the opening 82a at the center of the cover 82. Others are the same as Example 1.

(Comparative Example 2)
In the second step, a comparative example is used in which the seal member 86 is not attached to the opening 82a at the center of the cover 82. Others are the same as in the second embodiment.

(Comparative Example 3)
This is a comparative example in which the cover 82 is not used in the second step. Others are the same as Example 1.

(Comparative Example 4)
This is a comparative example in which the cover 82 is not used in the second step. Others are the same as in the second embodiment.

(Comparative Example 5)
The second step is a comparative example using the cover 82, and the gaps between the cover 82, the dome 81, and the substrate 40 are set to about 2.5 mm to 3 mm. Others are the same as Example 1.

(Comparative Example 6)
In the second step, a cover 82 is used as a comparative example, and the gaps between the cover 82, the dome 81 and the substrate 40 are formed by using a vacuum flexible material (for example, DuPont, trade name: Viton ( (Registered trademark)) and sealed to be less than 0.1 mm. Others are the same as Example 1.

The antifouling performance on the surface of the substrate 40 manufactured in Examples 1 to 4 and Comparative Examples 1 to 6 was compared. As a method of comparing the antifouling performance, a straight line of about 4 cm is drawn on the surface of the substrate 40 with a black oil marker (“Himackey Care” manufactured by Zebra Co., Ltd.), and the antifouling performance is prevented according to the following criteria depending on the ink repelling state. Dirty performance was determined.
◯: The ink becomes one line or dot.
Δ: The ink is partially repelled.
X: A line can be drawn clearly.

  The evaluation results are shown in Table 2 below.

  The ink repellency of the concave surface (first antifouling film) in the case of using the cover 82 with the sealing material 86 maintains good performance in the same manner as the convex surface (second antifouling film).

  On the other hand, when the cover 82 without the sealing material 86 is used and when the cover 82 is not used, the repellency of the concave surface (first antifouling film) with respect to the convex surface (second antifouling film). Decrease is observed.

  In the case where the cover 82 was not used (Comparative Examples 3 and 4), the decrease in the repellency of the concave surface was further remarkable.

  Even when the cover 82 is used, if the gap between the cover 82, the dome 81, and the substrate 40 exceeds 2 mm (Comparative Example 5), the repellency of the concave surface (first antifouling film) is reduced. Became remarkable.

  When the cover 82 is used and all the gaps between the cover 82, the dome 81, and the substrate 40 are less than 0.1 mm (Comparative Example 6), the ink on the concave surface (first antifouling film) is repelled. As with the convex surface (second antifouling film), the property keeps good performance. However, in order to make all the gaps less than 0.1 mm, it is necessary to use a large amount of vacuum flexible material (for example, DuPont, trade name: Viton (registered trademark)). However, it was not worth the cost.

  From this result, by using the cover 82 with the sealing material 86, the ink repellency of the concave surface as the first antifouling film and the convex surface as the second antifouling film of the substrate 40, that is, the antifouling property is equal. It was confirmed that it could be kept well.

The schematic diagram of the film-forming apparatus used for this invention. The flowchart figure of the 1st process and 2nd process explaining the process of the antifouling film | membrane of the board | substrate 40. FIG. (A) is a schematic diagram explaining the electric potential of the floating electrode surface when ion is irradiated from the ion irradiation apparatus 90, (b) is the dome 81 as a floating electrode, the cover 82, the some board | substrate 40, and It is a schematic diagram explaining the relationship with ion, (c), (d) is a schematic diagram explaining the behavior of the positive ion in the relationship with the clearance gap (distance) between the objects of an ion sheath and a floating electrode. FIG. 4 is a partial cross-sectional view in which a substrate 40 is set on a dome 81 and a cover 82 is set. The perspective view which shows the relationship between the board | substrate 40, the ring 84, and the frame 83. FIG. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 40 ... Substrate as a film-forming body, 40a, 84a ... Upper end, 41 ... Plastic substrate, 42 ... Hard coat film, 43 ... Antireflection film, 44 ... Antifouling film, 50 ... Film-forming device, 51 ... High frequency plasma generation Apparatus, 52, 53, 54 ... Vacuum generator, 52a, 53a, 54a ... Rotary pump, 52b, 53b, 54b ... Roots pump, 52c, 53c ... Cryo pump, 54c ... Turbo molecular pump, 55a, 55b ... Deposition source, 56a, 56b ... electron gun, 57a, 57b ... shutter, 59 ... antifouling film deposition source, 60 ... RF coil, 61 ... matching box, 62 ... high frequency transmitter, 63 ... elementary gas supply source, 64 ... argon gas supply source 65 ... Auto pressure controller, 66a, 66b ... Mass flow controller, 67 ... Correction plate, 68 ... Heating heater, 80 ... Support Device: 81: Dome as film-forming body holding member, 81a, 81b ... Hole, 82: Cover as film-forming body cover member, 82a ... Opening, 83, 83a, 83b ... As film-forming body holding member Frame, 83c ... upper surface, 83d ... edge, 84 ... ring, 84b, 84c, 84e, 84h ... projection, 85 ... rotating part, 86 ... sealing material, 90 ... ion irradiation device, 91 ... ion gun, 92 ... DC Power source, 93 ... RF power source, A, B ... Object, CH1, CH2, CH3 ... Chamber, Id ... Ion sheath, d ... Distance, Dm ... Electron particle flux density, Ia, Ib, Ic ... Positive ion, Im ... Ion particle Bundle density, K _B ... Boltzmann constant, L, L1 to L6 ... gap (distance), Me ... mass of electron particles, Mi ... mass of ion particles, Ne ... density of electron particles, Ni ... particle density of ions, Te ... Electronic Temperature of the child, Ti ... temperature of ion particles, Ve ... average velocity of the electron particles, Vf ... floating electrode voltage, the average rate of Vi ... ion particles.

Claims (6)

In the film formation chamber, the first antifouling film is formed after the first antifouling film adhesion improving process for performing the antifouling film adhesion improving process on one surface of the film forming body having a plurality of film forming surfaces. A first step;
After the first step, in the film formation chamber, the surface of the film formation target on which the first antifouling film has been formed is protected against the other film formation surface of the film formation target. A method for producing an antifouling optical article comprising a second step of forming a second antifouling film after the second antifouling film adhesion improving process for performing the fouling film adhesion improving process,
When performing the second antifouling film adhesion improving process, the film-formed body formed in the first step is covered with a film-formed body cover member and a film-formed body holding member, The gap between the film formation body cover member and the film formation body holding member and the gap between the film formation body and the film formation body holding member are each 0.1 times or more of the ion sheath, and A method for producing an antifouling optical article, characterized in that it is within 2 times.   The method for producing an antifouling optical article, wherein the first and second antifouling film adhesion improving treatments according to claim 1 are plasma treatment or ion gun treatment.   An antifouling optical article, wherein the first antifouling film according to claim 1 or 2 and / or the second antifouling film is formed by a vacuum deposition method. Production method.   The first antifouling film according to any one of claims 1 to 3 and / or the second antifouling film is formed by forming a fluorine-containing silane compound. A method for producing an antifouling optical article. The antifouling property, wherein the fluorine-containing silane compound as the first antifouling film according to claim 4 and / or the second antifouling film is represented by the general formula (1). A method for manufacturing an optical article.
However, in the general formula (1), Rf ² includes a unit represented by — (C _k F _2k ) O—, in which _k is an integer of 1 to 6, and is a straight-chain par having no branch. Represents a divalent group having a fluoropolyalkylene ether structure. R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and J represents a hydrolyzable group or a halogen atom. p represents an integer of 0 or more and 2 or less. n represents an integer of 1 to 5. m and r each represents an integer of 2 or 3.

The antifouling property, wherein the first antifouling film according to claim 4 and / or the fluorine-containing silane compound as the second antifouling film is represented by the general formula (2). A method for manufacturing an optical article.
In general formula (2), Rf ¹ is a perfluoroalkyl group, X is hydrogen, bromine, or iodine, Y is hydrogen or a lower alkyl group, Z is fluorine or a trifluoromethyl group, R ¹ is a hydroxyl group or hydrolyzable. R ² represents hydrogen or a monovalent hydrocarbon group. a, b, c, d and e are integers of 0 or more, a + b + c + d + e is at least 1 or more, and the order of existence of each repeating unit delimited by a, b, c, d and e is not limited in the formula . f represents an integer of 0 or more and 2 or less. g represents an integer of 1 to 3. h represents an integer of 1 or more.

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