JP2008062561A - Method of manufacturing article equipped with hydrophilic laminated film, and article equipped with hydrophilic laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an article equipped with a hydrophilic laminated structure formable by a low temperature vapor phase growing method. <P>SOLUTION: The article has base materials 1 and 2, on their surfaces of which a micro irregular shape is formed, and a hydrophilic material film 3; and the surface shape of the hydrophilic material film 3 is an irregular shape following the surface shape of the base materials 1 and 2. An intermediate layer 6 for protecting the micro irregular shape of the base material 2 when the hydrophilic material film 3 is arranged between the base material 2 and the hydrophilic material film 3. By this structure, since the intermediate layer 6 acts to protect the micro irregular shape of the base materials when the hydrophilic material film 3 is formed, the hydrophilic material film 3 is made possible to be formed by the low temperature vapor phase growing method using a high density plasma. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing an article provided with a hydrophilic film exhibiting an antifogging effect, and more particularly to a laminated structure of a hydrophilic film that can be formed at a low temperature.

  As a method of imparting antifogging performance to an article, a method of imparting hydrophilicity to the surface of the article is known. For example, a method of bonding a hydrophilic group to the base resin constituting the article itself or a method of forming a hydrophilic coating layer on the surface of the article is used.

  Patent Document 1 discloses a structure in which a hydrophilic substance is fixed to an antireflection film or the like on the surface of an optical article. In Patent Document 1, in order to fix a hydrophilic substance on the surface without deteriorating the optical properties of an inorganic substance film such as an antireflection film, pores and fine irregularities are generated on the surface of the antireflection film, A hydrophilic substance is fixed inside the pores and recesses. As a technique for generating pores and irregularities on the surface of an antireflection film or the like, Patent Document 1 uses a method of performing vacuum deposition at a low vacuum while introducing an active gas. Thereby, the filling rate of the formed anti-reflective film etc. can be reduced, and a pore and an unevenness | corrugation can be produced. As a method of fixing the hydrophilic substance inside the pores and irregularities of the antireflection film, etc., the article with the inorganic substance film is immersed in a reaction liquid having a predetermined composition, and then the reaction is caused by pulling up, ultraviolet irradiation and heat treatment. The hydrophilic substance is generated on the inorganic substance film surface.

  On the other hand, Non-Patent Document 1 discloses a structure in which hydrophilicity is further increased by increasing the surface area by forming fine irregularities on the hydrophilic coating layer formed on the mirror surface for anti-fogging. Yes. In Non-Patent Document 1, in order to form fine irregularities in the hydrophilic coating layer, fine particle silica is added to the hydrophilic coating layer. Further, a coating method is used as a method for forming the hydrophilic coating layer.

  In Patent Document 1 and Non-Patent Document 1 described above, a dipping method or a coating method is used as a method for forming a hydrophilic layer, but a hydrophilic material layer having fine irregularities on the surface using a vapor phase growth method. If it can form, mass-productivity will improve. In addition, since the vapor deposition method can control the film thickness with higher accuracy than the coating method, the optical characteristics of the article including the hydrophilic material layer can be easily controlled.

As a method for producing an antifogging glass using a vapor phase growth method, Patent Document 2 discloses that a SiO ₂ layer or a TiO ₂ layer is formed on a glass substrate by sputtering, and then the surface of the film is chemically etched. A method of forming a film having fine irregularities on the surface and exhibiting high water wettability is disclosed. In Patent Document 2, it is described that it is preferable to heat the glass substrate to 150 ° C. to 300 ° C. or more during film formation in order to exhibit high water wettability.

  On the other hand, Patent Document 3 discloses a method of forming a water-repellent film having unevenness on the surface by a low-temperature plasma CVD method, although it is not a hydrophilic material layer. In this method, irregularities are formed on the film surface by using an organosilicon compound as a source gas and appropriately setting the conditions of the low temperature plasma CVD method.

Further, in Patent Document 4, as a method of manufacturing a light scattering plate having minute irregularities, a base layer on a substrate is exposed to plasma in advance, and metal contained in the base layer is released on the surface to form micro protrusions. By forming a protective layer thereon, a protective layer having irregularities following the fine protrusions of the underlayer is formed. In this method as well, it is described that the substrate is preferably maintained at 200 to 300 ° C.
Japanese Patent No. 3694881 JP 61-91042 A JP-A-11-263860 JP-A-8-334747 Matsushita Electric Engineering Aug. p.80-85 (2001)

As described in Patent Document 2, the method of forming a hydrophilic SiO ₂ layer with a concavo-convex surface by sputtering requires application of the substrate to a heat-resistant plastic substrate. Can not do it. In addition, by applying the method of Patent Document 4 to form microprotrusions on the underlying layer and laminating a SiO ₂ layer exhibiting hydrophilicity thereon, hydrophilic SiO2 having irregularities following microprotrusions on the surface It is conceivable to form _two layers. However, the base film forming method disclosed in Patent Document 4 cannot be applied to a plastic substrate because the substrate needs to be heated.

  On the other hand, a method of forming a water-repellent silicon oxide film having unevenness as disclosed in Patent Document 3 by low-temperature plasma CVD can be formed at a low temperature, and can also be formed on a plastic substrate. However, a film formed by the technique described in Patent Document 4 is a water-repellent silicon oxide film, which is a film having a property opposite to that of hydrophilicity. For this reason, in order to form a layer having irregularities on the surface and showing hydrophilicity, the irregularities are formed on the water-repellent silicon oxide film having irregularities formed by the low temperature plasma CVD method described in Patent Document 3. It is conceivable to form a hydrophilic silicon oxide film by a low temperature plasma CVD method. However, the hydrophilicity of the silicon oxide film varies depending on the composition ratio of oxygen in the film. To form a hydrophilic silicon oxide film, the oxygen partial pressure in the plasma is increased and the oxygen composition in the film is increased. There is a need. In general, plasma CVD with an increased oxygen partial pressure significantly reduces the film formation rate and increases the etching effect of the plasma. Therefore, damage to the water-repellent silicon oxide film having unevenness as an underlayer is caused. A problem arises in that the uneven shape of the underlayer is impaired.

  An object of the present invention is to provide a method for forming a hydrophilic laminated film structure having irregularities on its surface on the surface of an article by a low-temperature vapor phase growth method.

  In order to achieve the above object, the following method for manufacturing an article is provided in the first aspect of the present invention. That is, a method for producing an article comprising a hydrophilic laminated film including a step of forming the hydrophilic material layer on a substrate having irregularities on a surface by a vapor phase growth method using plasma, Before forming the hydrophilic material layer, an intermediate layer made of a material resistant to plasma at the time of forming the hydrophilic material layer is formed on the substrate.

  The intermediate layer can be formed at a deposition rate higher than the deposition rate of the hydrophilic material layer by a vapor phase growth method using plasma. By increasing the deposition rate, the intermediate layer can be deposited while suppressing damage to the substrate surface.

  An organic silicon compound layer can be formed as the intermediate layer. In this case, when forming the organic silicon compound layer which is an intermediate layer, it is preferable to generate a silicon oxide phase in the layer. Thereby, since the hardness of an intermediate | middle layer can be enlarged, the intermediate | middle layer of material whose hardness is larger than the material which comprises a base-material surface can be formed into a film.

  As the hydrophilic material layer, a layer containing silicon oxide as a main component can be formed. Thereby, both the intermediate layer and the hydrophilic material layer can be continuously formed by a vapor phase growth method using plasma using an organic silicon compound gas as a source gas.

  According to the present invention, an article provided with a hydrophilic laminated film can be produced by the production method of the first aspect.

  The material of the intermediate layer of the article has a concentration ratio of the number of Si, C, and O atoms of O / Si = 1.49, C / Si = 0.66 to O / Si = 1.55, C / Si = 0. It can be a silicon compound in the range of .59.

  The surface of the hydrophilic material film of the article can have an irregular shape having an arithmetic average roughness Ra of 0.05 μm or more and 0.2 μm or less.

  The base material of the article can be configured to include a base and a concavo-convex layer provided on the surface and having a concavo-convex surface. In this case, the uneven layer can be formed of an organic silicon compound. The uneven layer can also be formed of an inorganic metal oxide.

An article provided with a hydrophilic laminated structure according to an embodiment of the present invention will be described with reference to the drawings.
As shown in FIG. 1, an article having a hydrophilic laminated structure of the present embodiment has a configuration in which a fine uneven layer 2, an intermediate layer 6, and a hydrophilic material layer 3 are laminated on a substrate 1. is there. The substrate 1 is made of a transparent resin. The substrate 1 may be a film.

The minute uneven layer 2 has an uneven shape on the surface in order to form an uneven shape with a predetermined roughness on the surface of the hydrophilic material layer 3. If the micro uneven | corrugated layer 2 is a method which does not give the damage by the heat | fever to the base material 1, it can be formed by a desired method. As a material of the fine uneven layer 2, for example, an organic silicon compound, an inorganic metal oxide such as In ₂ O ₃ , ZnO, or SnO can be used. In addition, it is also possible to form the micro uneven layer 2 integrally with the base material 1 by processing the surface of the base material 1 by etching or the like.

  The intermediate layer 6 and the hydrophilic material layer 3 are formed by a method that does not damage the resin base material 1 during the film formation, for example, a low temperature plasma chemical vapor deposition (CVD) method. In particular, in this embodiment, film formation is performed by a CVD method using high-density and low-temperature plasma generated by arc discharge. High density / low temperature plasma refers to plasma having a discharge current of 10 A or more and a discharge voltage of 150 V or less. It is possible to form not only the intermediate layer 6 and the hydrophilic material layer 3 but also the minute uneven layer 2 by a low temperature plasma CVD method. In that case, the minute uneven layer 2, the intermediate layer 6, the hydrophilic material layer 3 can be continuously formed by the same CVD apparatus.

The intermediate layer 6 acts to prevent the unevenness on the surface of the fine uneven layer 2 from being damaged by being exposed to the plasma during the film formation of the hydrophilic material layer 3. maintain. The surface shape of the intermediate layer 6 is a shape that is similar to the uneven shape of the fine uneven layer 2. As the material of the intermediate layer 6, for example, an organic silicon compound composed of elements of Si, C, H, and O, and a transparent inorganic metal oxide such as ZnO and SnO ₂ can be used. When the material of the intermediate layer 6 is an organic silicon compound, the concentration ratio of the number of atoms of Si, C, and O is changed from O / Si = 1.49, C / Si = 0.66 to O / Si = 1.55. C / Si = 0.59 is preferable. For example, the composition ratio can be Si: C: O = 1: 1.55: 0.6.

  Further, when the organic silicon compound film contains a SiOx phase, it is preferable as the intermediate layer 6. This is because the organic silicon compound containing the SiOx phase in the film has a high film hardness, so that the intermediate layer 6 has a greater effect of protecting the minute uneven layer 2 from the plasma during the formation of the hydrophilic material layer 3.

When the intermediate layer 6 is formed of an organic silicon compound, a low temperature plasma chemical vapor deposition (CVD) method using an organic silicon compound monomer gas (for example, hexamethyldisiloxane: HMDSO) as a raw material gas can be used. . When the intermediate layer 6 is formed of a transparent inorganic metal oxide such as ZnO or SnO ₂ , ion plating or plasma chemical vapor deposition (CVD) using high-density plasma as used in this embodiment is used. ) Can be used.

The hydrophilic material layer 3 is formed of a material that exhibits hydrophilicity. For example, it can be composed of silicon oxide having a hydrophilic composition. The oxygen composition of silicon oxide is desirably in the range of SiO _{1.6 to} SiO ₂ . For example, the hydrophilic material layer can be formed of silicon oxide having a composition ratio of Si and O of Si: O = 1.00: 1.71. The surface of the hydrophilic material layer 3 is provided with an uneven shape similar to the uneven shape of the intermediate layer 6. The hydrophilic material layer 3 not only exhibits hydrophilicity due to its material (silicon oxide having a hydrophilic composition), but also exhibits greater hydrophilicity by increasing the surface area due to surface irregularities, and has an antifogging effect. Demonstrate.

  The irregularities on the surface of the hydrophilic material layer 3 are desirably arithmetic average roughness Ra = 0.05 μm or more and 0.2 μm or less. The unevenness of the fine unevenness film 2 is set to a roughness in which unevenness with the roughness in the above range appears on the surface of the hydrophilic material layer 3 in consideration of the film thickness of the intermediate layer 6 and the hydrophilic material layer 3 and the film forming method. Has been.

  When the hydrophilic material layer 3 is formed of silicon oxide, a low temperature plasma chemical vapor deposition (CVD) method using an organic silicon compound monomer gas (for example, hexamethyldisiloxane: HMDSO) as a source gas is used. it can.

  A method for manufacturing an article provided with the hydrophilic film of the present embodiment will be described. Here, as an example, the micro uneven layer 2 is an organic silicon compound layer, the intermediate layer is an organic silicon compound layer containing a SiOx phase, and the hydrophilic material layer 3 is a silicon oxide layer. A case where a film is formed by a CVD method using the above will be described.

  For film formation, a film formation apparatus having the high-density plasma source shown in FIG. 2 is used. This apparatus includes a film forming vacuum container 15 that forms a film forming space, and a plasma gun 8 connected to a plasma inlet 15 a of the film forming vacuum container 15. The plasma gun 8 includes a composite cathode 9 disposed in a plasma generation chamber (not shown), an intermediate electrode 10 having an orifice, and an anode (between the intermediate electrode 10 and the film forming vacuum vessel 15). A) 23a, an anode (B) 23b arranged in the film-forming vacuum vessel 15, and an electromagnetic coil 13 for converging plasma and allowing the intermediate electrode 10 to pass therethrough. A plasma generation power source 14 is connected between the composite cathode 9 and the anode (A) 23a and between the composite cathode 9 and the anode (B) 23b via switches 24 and 25, respectively. The composite cathode 9 and the intermediate electrode 10 are insulated by an insulating insulator 11. A discharge gas 12 is supplied into the plasma gun 8.

  The structure of the composite cathode 9 uses a known composite cathode structure capable of generating a high-density plasma by shifting from glow discharge to arc discharge. For example, an auxiliary cathode that generates glow discharge and is heated by collision of countercurrent ions and a main cathode that is heated by radiant heat of the auxiliary cathode and generates arc discharge can be used.

  In the film forming space between the anode 23b and the plasma inlet 15a, a substrate holder 16 for holding the transparent base material 1 and source gas introduction pipes 19 and 21 for supplying source gases (material gases) 18 and 20 are arranged. Has been. An organic silicon compound monomer gas (for example, hexamethyldisiloxane: HMDSO) is used as the source gas 18. Further, oxygen is introduced as necessary as the source gas 20. The film formation vacuum vessel 15 is connected to a vacuum pump by an exhaust pipe 17.

When film formation is performed in the film formation apparatus having such a structure, the film formation vacuum vessel 15 is evacuated and then a discharge gas such as Ar, He, Kr, Xe, H _{2 is applied} to the composite cathode 9 of the plasma gun 8. 12 is introduced, and a direct current voltage is applied between the composite cathode 9 and the anode 23 (A) 23 a or the anode 23 (B) 23 b by the power source 14 to be discharged. Although it is glow discharge immediately after ignition, when the back-flow ions of the ionized discharge gas collide with the composite cathode 1 and the composite cathode is heated, thermal electrons are emitted, thereby increasing the ionization degree of the glow discharge. And transition to arc discharge. The arc discharge is a high-density discharge having a current amount of about 10 to 100A. The high-density plasma 22 generated by this discharge is converged in a beam shape by the magnetic field of the electromagnetic coil 13, passes through the central hole (orifice) of the intermediate electrode 10, and is drawn out to the vicinity of the substrate holder 16 of the film-forming vacuum vessel 15. It is. The extracted plasma is mixed with the source gases 18 and 20, whereby when the reaction plasma 22 a of the source gases 18 and 20 is generated, the source gas 1 decomposes and reacts, and then the base material 1 on the substrate holder 16. The micro uneven film 2, the intermediate layer 6, and the hydrophilic material layer 3 are laminated. When the anode (A) 23a is used, the switch 24 is closed and the switch 25 is opened, and the plasma 22 once drawn to the vicinity of the substrate holder 16 is drawn back and flows into the anode (A) 23a. On the other hand, when the anode (B) 23b is used, the switch 24 is opened, the switch 25 is closed, and the plasma 22 flows into the anode (B) 23b arranged oppositely. The anode (A) 23 a is used when forming the fine uneven film 2, and the anode (B) 23 b is used when forming the intermediate layer 6 and the hydrophilic material layer 3.

  When forming the fine concavo-convex film 2 of the organic silicon compound layer, an organic silicon compound monomer gas (for example, hexamethyldisiloxane: HMDSO) is introduced as the source gas 18, and the oxygen gas 20 is not introduced. By appropriately setting the film forming conditions such as the film forming pressure and the partial pressure ratio between the discharge gas and the organic silicon compound monomer gas, the organic silicon compound which is a decomposition / polymerized product of the organic silicon compound monomer gas 18 is deposited. Do the membrane. At this time, by appropriately setting the film forming conditions, it is possible to form a fine uneven film having unevenness on the surface while forming the film.

  Thereafter, the intermediate layer 6 is continuously formed without opening the film formation vacuum vessel 15. An organosilicon compound monomer gas 18 and an oxygen gas 20 are introduced as source gases to deposit an organosilicon compound containing SiOx. At this time, by appropriately setting the film formation pressure, the mixing ratio of the organic silicon compound monomer gas 18 and the oxygen gas 20, etc., a film formation process by decomposing and polymerizing the organic silicon compound monomer gas 18 is performed. It is more advantageous than the etching process using oxygen plasma. Thereby, the intermediate layer 6 can be formed with almost no damage given to the uneven shape of the minute uneven film 2. In CVD using an organic silicon compound gas containing oxygen and carbon, Si—O bonding force is stronger than Si—C, and thus Si—O in the deposit is difficult to be etched. As a result, the intermediate layer 6 made of an organic silicon compound containing a SiOx phase can be deposited. Since the SiOx phase is contained, the intermediate layer 6 has a higher hardness than the organic silicon compound-only layer, and is less susceptible to etching by oxygen plasma when the hydrophilic material layer 3 is formed. Thereby, the organic silicon compound layer containing the deposited SiOx phase can act as an intermediate layer 6 that protects the micro uneven layer 2.

  When forming the hydrophilic material layer 3, an organic silicon compound monomer gas (for example, hexamethyldisiloxane: HMDSO) and an oxygen gas 20 are introduced as the source gas 18. The hydrophilic silicon oxide film 3 is formed by depositing silicon oxide by appropriately setting the film forming pressure, the mixing ratio of the organic silicon compound monomer gas 18 and the oxygen gas 20, and the like.

  When the hydrophilic material layer 3 is formed, the oxygen gas 20 is introduced in addition to the organic silicon compound monomer gas 18, so that oxygen plasma excited by the oxygen gas is generated and the surface of the base film is etched. An effect occurs. For this reason, when the intermediate layer 6 is not disposed, oxygen plasma etches the surface of the micro uneven film 2, thereby causing a problem that the uneven surface of the micro uneven film 2 is flattened. In the present embodiment, since the intermediate layer 6 that is not easily etched by oxygen plasma is laminated on the micro concavo-convex film 2, it is possible to prevent the concavo-convex of the micro concavo-convex film 2 from being flattened. The shape can be maintained.

  In the above-described example, the oxygen gas 20 is introduced when the intermediate layer 6 is formed. However, it is possible to set a condition in which the oxygen gas 20 is not introduced.

  In these high-density and low-temperature plasma CVD methods, it is not necessary to heat the substrate 1 when forming the micro uneven film 2, the intermediate layer 6 and the hydrophilic material layer 3, so that film formation is performed while maintaining the temperature low. Can do. Specifically, film formation can be performed while maintaining the temperature of the substrate 1 at about 120 ° C. or less.

  As described above, in the present embodiment, the concave / convex shape of the micro concave / convex film 2 is almost lost by disposing the intermediate layer 6 exhibiting excellent resistance to the plasma etching action generated when the hydrophilic material layer 3 is formed. Without any problem, the hydrophilic material layer 3 can be formed by a vapor phase growth method using high-density plasma. The concave / convex shape of the concave / convex film 2 can be maintained when the intermediate layer 6 is formed by damaging the concave / convex film 2 by forming the intermediate layer 6 at a high film formation rate using a low voltage-low temperature plasma of 150 V or less. This is considered to be due to the fact that is relaxed compared with the case where high temperature plasma is used. Further, the vapor phase growth method using high-density plasma can produce the hydrophilic material layer 3 and the like at a low temperature, so that the substrate 1 is hardly damaged by heat. This film forming method is suitable for mass production since the film forming speed is high. Furthermore, since the hydrophilic material layer 3 can be formed by a vapor phase growth method, the film thickness can be easily controlled and can be easily set to a film thickness that does not affect the optical characteristics of the substrate 1.

  The article provided with the superhydrophilic film manufactured according to the present embodiment exhibits excellent antifogging properties since the hydrophilic film having irregularities on the surface is disposed on the outermost surface.

  In the film forming method of the present embodiment, not only the hydrophilic material layer 3 but also the micro concavo-convex film 2 and the intermediate layer 6 can be formed by a vapor phase growth method using high-density plasma. Therefore, it is not necessary to take out the substrate 1 from the film formation apparatus in the middle and perform heat treatment or the like, and the film formation can be continuously performed in the same film formation apparatus, so that mass productivity can be improved. it can.

  In addition, as the micro uneven | corrugated layer 2, an anti-reflective film and a hard-coat layer can be combined. That is, it can be used as the fine uneven layer 2 having fine unevenness on the surface of the antireflection film or the hard coat layer of the substrate 1.

  In addition to the method of forming irregularities on the surface while forming a film as described above, the method of forming irregularities on the minute irregularity layer 2 can be achieved by forming a flat film and then etching or plasma-treating the surface. It is also possible to use a forming method. It is also possible to form the unevenness while forming the minute uneven layer 2 by vacuum deposition with a low degree of vacuum and by reducing the filling rate. Furthermore, it is also possible to form micro unevenness on the surface by adding fine particles to the material constituting the micro uneven layer 2.

Examples of the present invention and comparative examples will be described below.
(Example)
In this example, an article provided with the hydrophilic laminated film of FIG. 1 of the above embodiment was manufactured. As the substrate 1, a polycarbonate plate having a thickness of 3 mm was used. On the base material 1, the micro uneven | corrugated film | membrane 2, the intermediate | middle layer 6, and the hydrophilic material layer 3 were continuously formed into a film by CVD method using the film-forming apparatus of FIG.

First, an organic silicon film (composition Si: C: O = 1: 1.36: 0.19) was formed as the fine uneven film 2. Table 1 shows the conditions for forming the fine uneven film 2. As shown in Table 1, hexamethyldisiloxane (HMDSO) and oxygen gas 20 were introduced as the raw material gas 18. Ar was used as the discharge gas. As shown in Table 1, the deposition pressure, the discharge gas, the HMDSO gas, and the oxygen gas mixing ratio were set. By forming a film under these conditions, an organic silicon film having minute irregularities on the surface could be formed. The surface roughness was Ra = ˜0.1 μm, and the film thickness was 6000 Ř1 μm. The base material holder 16 holding the base material 1 was not heated, and the temperature of the base material 1 was maintained at 120 ° C. or lower. Although the oxygen gas 20 is introduced here, the minute uneven film 2 can be formed by appropriately setting the conditions without introducing the oxygen gas 20.

Subsequently, an organic silicon film was formed as the intermediate layer 6. Table 2 shows the conditions for forming the intermediate layer 6. As shown in Table 2, HMDSO gas and oxygen gas 20 were introduced as the source gas 18. Ar was used as the discharge gas. As shown in Table 2, the deposition pressure, the discharge gas, the HMDSO gas, and the oxygen gas mixing ratio were set. By forming a film under these conditions, an organic silicon film having minute irregularities on the surface could be formed. When the mixing ratio of HMDSO gas and oxygen gas was set to 10: 4, an organic silicon film having a composition Si: C: O = 1: 1.55: 0.6 was obtained. The deposition rate was 70 angstrom / s. The substrate holder 16 holding the substrate 1 was not heated, and the temperature was maintained at 120 ° C. or lower.

  In addition, in order to optimize the film forming conditions before forming the intermediate layer 6, the following experiment was performed in advance. First, the HMDSO partial pressure was changed, the oxygen partial pressure and the discharge gas partial pressure were fixed, and the deposition rate of the organic silicon film was measured. The result is shown in FIG. In the region 30 where the partial pressure is about 0.1 Pa, the film formation rate is extremely low, but in the region 31 where the partial pressure is 1.0 Pa or more, the film formation rate rises. Therefore, in this region 31, it is considered that the decomposition / polymerization film formation process of the organic silicon compound monomer gas 18 is superior to the etching process using oxygen plasma. It was judged that there was little action to damage.

Next, the obtained organic silicon film was subjected to composition analysis by XPS (X-ray photoelectron spectroscopy analyzer). Table 3 shows the atomic concentrations of Si, C, and O of the film obtained for each HMDSO partial pressure during film formation. The constituent atoms of the film obtained at a HMDSO partial pressure of around 0.086 Pa were mainly Si and O, but it was found that the organic silicon layer contained a certain amount of oxygen at 0.76 Pa or higher. Further, when XPS binding peaks of the films obtained at 0.76 Pa and 2.14 Pa were examined, a peak of 103 eV indicating SiO ₂ binding was confirmed in both cases. From this, it was found that the SiO ₂ phase was formed in the film by forming the film at a HMDSO partial pressure of 0.76 Pa or more.

  From these facts, by forming the intermediate layer 6 in the region 31 where the HMDSO partial pressure is 1.0 Pa or more, damage to the fine uneven layer 2 during the process can be reduced, and the SiOx phase is not present in the film. Since the contained hard organic silicon film can be formed, it is suitable as a film forming condition for the intermediate layer 6.

  After the formation of the intermediate layer 6, a silicon oxide film containing carbon (composition Si: C: O = 1: 1.7: 0.03) was formed as the hydrophilic material layer 3. Table 4 shows the conditions for forming the hydrophilic material layer 3. As shown in Table 4, HMDSO gas 18 and oxygen gas 20 were introduced as source gas 18, and the mixing ratio of HMDSO gas and oxygen gas was set to 1: 4. In addition, as shown in Table 4, the film forming pressure and the discharge gas partial pressure were set. The deposition rate of the hydrophilic material layer 3 was about 1.0 angstrom / s. The substrate holder 16 holding the substrate 1 was not heated, and the temperature was maintained at 120 ° C. or lower.

The intermediate layer 6 and the hydrophilic material layer 3 are continuously formed. The thickness of the two layers is 2000 to 2300 angstroms in total, and the surface roughness of the outermost surface of the hydrophilic material phase 3 is Ra = ˜0. It was 1 μm.

(Comparative example)
As a comparative example, an article provided with only the micro uneven film 2 and the hydrophilic material layer 3 without forming the intermediate layer 6 was manufactured. The film forming conditions are the same as those shown in Tables 1 and 4.

(Evaluation)
FIG. 4 shows an AFM image (atomic force microscope image) of the surface of the hydrophilic material layer 3 having a laminated structure obtained in the above example. As is apparent from FIG. 4, the surface of the hydrophilic material layer 3 of the example was clearly uneven, and the average surface roughness Ra obtained by the measurement was about 0.1 μm.

  Moreover, when the contact with respect to the water of the base material 1 provided with the laminated structure (three layers 2, 6, 3) manufactured by the present Example was measured, it was 1 degrees or less, and favorable hydrophilicity was shown. Moreover, the transmittance | permeability was 94.5% and the haze rate was 8.7%, and the transparency of the base material 1 was maintained.

  On the other hand, FIG. 5 shows an AFM image of the surface of the laminated structure without the intermediate layer 6 manufactured in the comparative example. As can be seen from FIG. 5, the surface has minute unevenness, but the AFM image of the comparative example has a low unevenness compared to the AFM image of FIG. It was about 2.

Thus, it is estimated that the roughness of the surface of the laminated structure without the intermediate layer 6 manufactured in the comparative example is reduced because of the mechanism as shown in FIG. That is, when the hydrophilic material layer 3 is formed directly on the micro uneven film 2, the film forming speed is extremely slow (about 1 angstrom / s), so that it takes time to form the film. The time for which the unevenness 2 is exposed to the plasma 4 of the source gas becomes longer. For this reason, it is presumed that the fine uneven layer 2 is damaged by the oxygen gas plasma 5 contained in the plasma 4 and the surface unevenness of the hydrophilic material layer 3 is also reduced. On the other hand, in the laminated structure of the present embodiment, the intermediate layer 6 is arranged on the fine concavo-convex layer 2 so as to have the surface shape. Since the intermediate layer 6 is an organic silicon layer containing a SiO ₂ phase and has a hardness greater than that of the micro uneven layer 2, the intermediate layer 6 is not easily damaged even when exposed to oxygen plasma for a long time during the formation of the hydrophilic material layer 3. Since the uneven shape of the surface can be maintained, it is presumed that the uneven surface of the hydrophilic material layer 3 has increased.

  Next, in order to measure the hydrophilic durability of the article provided with the hydrophilic laminated structure obtained in the example and the article provided with the laminated structure obtained in the comparative example, the article of this example is used. The articles of Comparative Examples were stored in a constant temperature and humidity chamber at a temperature of 50 ° C. and a humidity of 98%, and the change in contact angle was measured. The result is shown in FIG. The article of this example maintained a highly hydrophilic contact angle of 15 ° or less until about 150 hours, but the article of the comparative example deviated from 20 ° in about 50 hours, and the contact angle increased speed. Increased at an acceleration of more than double that of the article of this example. From this result, it was confirmed that the superhydrophilic property can be maintained for a long time by the laminated structure including the intermediate layer 6 of this example as compared with the laminated structure of the comparative example not including the intermediate layer 6.

  Next, the haze test of the article provided with the laminated structure obtained in the example was performed using the experimental apparatus of FIG. A water tank 124 having an opening in the upper lid contains hot water 128 maintained at 40 ° C. In the opening of the lid, the article of the example is arranged as the test object 125 with the hydrophilic material layer 3 facing the hot water 128. The distance 127 from the liquid level of the hot water 128 to the test object 125 is 5 cm. The water vapor 126 evaporates from the liquid surface of the hot water 128 toward the opening, and condensation occurs on the surface of the test object 125. In the article of this example, even after 10 minutes, the dew condensation spreads on the surface of the hydrophilic material layer 3 to form a water film and did not cause fogging.

  As described above, in this example, it was possible to form a superhydrophilic laminated structure excellent in durability by a vapor phase growth method using high-density and low-temperature plasma. Thereby, compared with the apply | coating method, the anti-fogging process which forms a super hydrophilic film | membrane could be performed efficiently, and mass productivity could be improved. In addition, since low temperature processing is possible, even when a resin is used as the base material 1, heat during film formation does not adversely affect the optical characteristics of the base material 1. In addition, since the vapor deposition method can control the film thickness with high accuracy, a film configuration for making the optical characteristics of the substrate 1 including the hydrophilic laminated structure predetermined optical characteristics can be easily achieved. be able to.

Sectional drawing which shows the structure of the articles | goods provided with the hydrophilic laminated film of this Embodiment. 1 is a block diagram illustrating a structure of a film formation apparatus that performs a vapor deposition method using high-density plasma in this embodiment mode. The graph which shows the relationship between the HMDSO partial pressure at the time of film-forming, and the film-forming speed | velocity | rate in order to optimize the film-forming conditions of the intermediate | middle layer 6 in a present Example. The AFM image about the surface of the articles | goods provided with the hydrophilic laminated film of a present Example. The AFM image about the surface of the articles | goods provided with the hydrophilic laminated film of the comparative example. Explanatory drawing which shows that a micro unevenness | corrugation is planarized at the time of film-forming of the hydrophilic laminated film of a comparative example. The graph which shows a time-dependent change of a contact angle about the articles | goods provided with the hydrophilic laminated film of the Example and the comparative example. Explanatory drawing which shows the apparatus structure used for the fog test of the articles | goods provided with the hydrophilic laminated film of the Example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Base material, 2 ... Micro uneven | corrugated film, 3 ... Hydrophilic material layer, 6 ... Intermediate layer, 8 ... Plasma generation source, 9 ... Cathode, 10 ... Intermediate Electrode, 11 ... Insulating insulator, 12 ... Discharge gas, 13 ... Electromagnetic coil, 14 ... Power supply, 15 ... Deposition vacuum vessel, 16 ... Substrate holder, 17 ... Vacuum Exhaust pipe, 18, 20 ... source gas, 19, 20 ... source gas introduction pipe, 23 ... anode, 24 ... switch connecting plasma power source and anode A, 25 ... plasma power source A switch for connecting the anode B, 124 ... water tank, 125 ... test object, 126 ... water vapor, 128 ... hot water.

Claims (12)

A method for producing an article comprising a hydrophilic laminated film including a step of forming the hydrophilic material layer on a substrate having irregularities on a surface by a vapor phase growth method using plasma,
Before forming the hydrophilic material layer, an intermediate layer is formed on the substrate by a material resistant to the plasma at the time of forming the hydrophilic material layer. A method for producing an article provided with a membrane.   The method for manufacturing an article provided with the hydrophilic laminated film according to claim 1, wherein the intermediate layer is formed at a deposition rate larger than the deposition rate of the hydrophilic material layer by a vapor phase growth method using plasma. A method for producing an article provided with a hydrophilic laminated film, characterized by forming a film.   The manufacturing method of the article | item provided with the hydrophilic laminated film of Claim 1 or 2 WHEREIN: An organic silicon compound layer is formed into a film as said intermediate | middle layer, The manufacturing method of the article | item provided with the hydrophilic laminated film characterized by the above-mentioned. .   In the manufacturing method of the article | item provided with the hydrophilic laminated film of Claim 3, when forming the organic silicon compound layer which is the said intermediate | middle layer, the phase of a silicon oxide is produced in a layer, It is characterized by the above-mentioned. A method for producing an article provided with a hydrophilic laminated film.   5. The method for manufacturing an article provided with the hydrophilic laminated film according to claim 1, wherein a layer of a material having a hardness higher than that of a material constituting the substrate surface is formed as the intermediate layer. A method for producing an article provided with a hydrophilic laminated film.   6. The method for manufacturing an article provided with the hydrophilic laminated film according to claim 1, wherein a layer mainly composed of silicon oxide is formed as the hydrophilic material layer. A method for producing an article provided with a hydrophilic laminated film.   The method for manufacturing an article provided with the hydrophilic laminated film according to any one of claims 1 to 6, wherein the intermediate layer and the hydrophilic material layer both use plasma using an organic silicon compound gas as a source gas. A method for producing an article provided with a hydrophilic laminated film, characterized in that the film is continuously formed by a conventional vapor deposition method.   An article comprising a hydrophilic laminated film produced by the method for producing an article comprising the hydrophilic laminated film according to any one of claims 1 to 7.   The article provided with the hydrophilic laminated film according to claim 8, wherein the intermediate layer is an organic silicon compound, and the concentration ratio of the number of atoms of Si, C, and O is O / Si = 1.49, C / Si. = 0.66 to O / Si = 1.55 and C / Si = 0.59, an article provided with a hydrophilic laminated film.   The article provided with the hydrophilic laminated film according to claim 8 or 9, wherein the surface of the hydrophilic material film has an uneven shape having an arithmetic average roughness Ra of 0.05 μm or more and 0.2 μm or less. Article having a hydrophilic laminated film.   The article provided with the hydrophilic laminated film according to any one of claims 8 to 10, wherein the base material provided with irregularities on the surface comprises a substrate and irregularities on the surface disposed on the substrate. An article provided with a hydrophilic laminated film characterized by comprising an uneven layer.   The article provided with the hydrophilic laminated film according to claim 11, wherein the concavo-convex layer is composed of an organic silicon compound or an inorganic metal oxide.