JP2018027869A - Glass component for water-area - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glass component for water-area, capable of retaining antifogging properties for a long period immediately after use start, and usable in an indoor water-area circumstance.SOLUTION: A glass component for water-area is used in an indoor water-area circumstance. The glass component for water-area includes a glass substrate, and an amorphous carbon layer provided on the surface of the glass substrate, and containing a hydrogen atom and a carbon atom. The amorphous carbon layer has a density of less than 2.0 g/cm. The amorphous carbon layer further contains an oxygen atom, and in the amorphous carbon layer, an O/C ratio on the surface is larger than 0.3.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a glass member for water supply in which an amorphous carbon layer is formed on the surface of the glass for water supply.

Glass used around indoor water (hereinafter also referred to as water-use glass, glass substrate, or glass) is used indoors in an environment where water exists. Water-use glass is used in an environment where water exists indoors, for example, as a mirror, a door of a shower booth, a water splash preventing member of a kitchen sink, or the like. Therefore, water tends to adhere to the surface of the water glass. There is a known problem that water adhering to the surface of the water supply glass dries, and scales containing silica and calcium, which are components contained in tap water, are formed on the surface of the water supply glass. Yes. There is also a known problem that dirt such as protein, sebum, mold, microorganisms and soap adheres to the surface of the water glass.
When these water-use glasses are used in a high humidity environment such as a bathroom or a washroom, it is also required to suppress fogging of the surface.

  Japanese Patent Laid-Open No. 2000-72488 (Patent Document 1) discloses that a silicon-based layer and an amorphous carbon layer are sequentially formed on a glass substrate, so that inorganic stains are difficult to adhere or stains are easily removed. It is described that it becomes. Further, it is described that the contact angle can be increased to 100 ° or more by further increasing the water repellency by doping the amorphous carbon layer with fluorine.

  A method of hydrophilizing an amorphous carbon layer that is originally hydrophobic has also been studied.

In JP 2003-534223 A (Patent Document 2), in order to lower the contact angle of the diamond-like carbon (DLC) layer, boron (B), nitrogen (N) or the like may be doped into the DLC layer. Have been described. The density of the DLC layer is described to be preferable is 2.4 g / cm ³ or 2.5~3.0g / cm ^3.

JP 2005-509584 (Patent Document 3) discloses diamond-like carbon (DLC) on glass in order to improve the visibility by reducing the possibility of water droplets taking a spherical form and being deposited on a substrate. And a coated glass article in which a contact angle with water droplets is not larger than about 20 degrees by forming a containing layer and irradiating the DLC-containing layer with ultraviolet rays using an ultraviolet ray source. It is described that the formation of bead-like condensate is suppressed by making the surface of the glass article hydrophilic. Density of DLC layer is described to be preferable is 2.4 g / cm ³ or 2.5~3.0g / cm ^3.

  JP 2010-5428 A (Patent Document 4) discloses that a DLC film is irradiated with, for example, oxygen plasma to cleave part of diamond (carbon-carbon) bonds on the surface of the DLC film, thereby forming a hydroxyl group in the DLC film. It is described that the surface of the DLC film is made hydrophilic by introduction.

  JP 2012-46278 A (Patent Document 5) discloses that an oxygen-containing functional group is chemically bonded to the surface of a carbon material by irradiating the carbon material with ultraviolet light in the presence of hydrogen peroxide water. Have been described.

JP 2000-72488 A Special table 2003-534223 gazette JP 2005-509584 A JP 2010-5428 A JP 2012-46378 A

When a DLC film is provided on the glass surface to suppress dirt adhesion as in Patent Document 1, it is difficult to effectively suppress fogging because the DLC film is originally hydrophobic.
On the other hand, Patent Documents 2 to 5 disclose methods for making the surface of the DLC film hydrophilic. In Patent Documents 2 and 3, since the density of the DLC film is as high as 2.4 g / cm ³ or more, the contact angle may decrease over time in an environment where sunlight is directly irradiated for a long period of time. However, it has been found that in an environment where only a small amount of ultraviolet light is irradiated, such as an indoor environment around water, it is difficult to be hydrophilized over time. Since all of Patent Documents 3 to 5 are made hydrophilic by treating the surface of the DLC film, the surface of the DLC film is worn over time, so that the internal DLC film is exposed and gradually becomes hydrophobic. It is difficult to develop cloudiness over a long period of time.

  The inventors of the present invention have made an amorphous carbon layer that is initially hydrophobic to be hydrophilized over time by providing a relatively low-density amorphous carbon layer on the surface of glass for water used in indoor water environment. I found out that I can. When the density of the amorphous carbon layer is lower than a predetermined value, it is considered that the amorphous carbon layer is gradually decomposed by a small amount of ultraviolet rays when used in an indoor water environment, and the surface becomes hydrophilic. However, in this case, the antifogging property cannot be enjoyed until the amorphous carbon layer is worn out.

Therefore, in the present invention, by further devising the O / C ratio of the surface of the amorphous carbon layer to be larger than a predetermined value, the antifogging property can be enjoyed over a long period while enjoying the antifogging property immediately after the start of use. The knowledge that it can be maintained was obtained.
Moreover, since the amorphous carbon layer is provided, excellent antifouling properties can be enjoyed.

  An object of the present invention is to obtain a glass member for water use that is used in an indoor water environment capable of maintaining anti-fogging properties immediately after the start of use and over a long period of time.

In order to achieve the above object, the present invention provides a water-use glass member used in an indoor water-use environment. The glass member for water is provided with a glass substrate and an amorphous carbon layer provided on the surface of the glass substrate and containing hydrogen atoms and carbon atoms. In the amorphous carbon layer, the density is less than 2.0 g / cm ³ . The amorphous carbon layer further contains oxygen atoms. In the amorphous carbon layer, the surface O / C ratio is larger than 0.3.

  By increasing the O / C ratio on the surface of the amorphous carbon layer and lowering the density of the glass member for water, the antifogging property can be quickly developed immediately after the start of use. It becomes possible to maintain the cloudiness for a long time.

Moreover, in the glass member for water supply concerning this invention, it is preferable that the hydrogen amount of an amorphous carbon layer is 0.3-0.8.
In the water-use glass member, it is possible to make the surface of the amorphous carbon layer more hydrophilic after being worn by reducing the density of the amorphous carbon layer while keeping the amount of hydrogen within a predetermined range.

Moreover, in the glass member for water supply concerning this invention, it is preferable that the density of an amorphous carbon layer is 1.1 g / cm < ³ > or more.
In the glass member for water, excessive wear of the amorphous carbon layer can be suppressed by increasing the density of the amorphous carbon layer to a predetermined value or more. Therefore, it becomes possible to express antifogging properties over a long period of time.

In the glass member for water according to the present invention, the value (X) obtained by dividing the color difference (ΔE) before and after the amorphous carbon layer is formed by the film thickness of the amorphous carbon layer may be less than 4.0. It is preferably 1.0 or less.
By making the color difference X per unit film thickness smaller than a predetermined value, the antifogging property can be expressed while maintaining the appearance.

Moreover, in the glass member for water supply concerning this invention, it is preferable that an amorphous carbon layer further contains silicon (Si).
In the glass member for water, when the amorphous carbon layer further contains silicon, the durability of the amorphous carbon layer can be further increased, and the antifogging property can be maintained over a long period of time.

Moreover, in the glass member for water supply concerning this invention, it is preferable to further provide an intermediate | middle layer between a base material and an amorphous carbon layer.
By providing the intermediate layer in the glass member for water, the adhesion between the amorphous carbon layer and the base material can be increased, and the antifogging property can be maintained over a long period of time.

  Moreover, this invention provides the manufacturing method of the member for water circumferences. This manufacturing method includes a step of placing glass for water on a substrate support provided in a container, a step of depressurizing the inside of the container, introducing a raw material into the container, and adjusting the inside of the container to a predetermined pressure. A high-density plasma generation step for generating a high-density plasma by converting the raw material into a plasma; a step for applying a voltage to the substrate support; a high-density plasma is deposited on the surface of the water-use glass; A step of forming an amorphous carbon layer on the surface of the glass, and a step of introducing a hydrophilic binding species to the surface of the amorphous carbon layer.

  In the method for manufacturing a water-use member according to the present invention, the high-density plasma is any one of inductively coupled plasma, surface wave plasma, helicon wave plasma, electron cyclotron resonance plasma, Penning ion gauge discharge plasma, and hollow cathode discharge plasma. The above is preferable, and inductively coupled plasma is more preferable.

Moreover, in the manufacturing method of the member for water circumferences of this invention, it is preferable that the voltage applied to a base-material support part is larger than -1 kV.
In the method for producing a water-use member according to the present invention, it is preferable that the high-density plasma is generated by supplying power to the antenna disposed in the container and converting the raw material into plasma.
In the method for manufacturing a water-use member according to the present invention, it is preferable that the step of introducing the hydrophilic bonding species includes a step of irradiating the amorphous carbon layer with oxygen plasma.

  ADVANTAGE OF THE INVENTION According to this invention, the glass member for water circumferences used in the indoor water circumference environment which can maintain anti-fogging property immediately after a use start and for a long term can be obtained.

Schematic showing the structure which provided the amorphous carbon layer on the base material. Schematic showing the structure which provided the intermediate | middle layer and the amorphous carbon layer on the base material. Schematic which shows an example of a structure of the plasma CVD apparatus which can be utilized in this invention.

  As shown in FIG. 1, the glass member for water use used in the indoor water environment of the present invention includes a base material 1 and an amorphous carbon layer 2 provided on the surface thereof. As shown in FIG. 2, the water-use glass member may include an intermediate layer 3 provided between the base material 1 and the amorphous carbon layer 2.

  The water circumference in which the glass member for water circumference of the present invention is used may be any place where water is used, and examples thereof include houses, public facilities such as parks and department stores. For example, it is used in bathrooms, washrooms, kitchens, toilets, and the like. Specifically, the water-use glass member of the present invention is preferably used as a mirror, wall, floor, window, bathroom door, bathroom wall, shower booth panel, kitchen sink water splash prevention member, and the like. . It is more preferable that the glass member for water around the present invention is used in a bathroom. Specifically, it is more preferably used as a mirror, bathroom door, shower booth panel, window or the like. It is further preferable that the water-use glass member of the present invention is used as a mirror used in a bathroom. Thereby, it is possible to maintain the image clarity that is a function of the mirror.

(Base material)
In the present invention, the substrate is a glass for water. That is, it is glass used in the place using water mentioned above. The surface property of the glass for water is not particularly limited, and a glossy mirror surface, satin, hairline, or the like can be applied.

(Amorphous carbon layer)
In the present invention, the amorphous carbon layer contains an amorphous compound containing carbon atoms and hydrogen atoms. The amorphous carbon layer further contains oxygen atoms. The amount of carbon atoms in the amorphous carbon layer is greater than, for example, 30 atm%.

(Amorphous carbon layer thickness)
In the present invention, the film thickness of the amorphous carbon layer is, for example, 100 nm or less. More preferably, it is 30 nm or less. Thereby, it becomes possible to obtain the glass member for water circumferences with high transparency.

  In the present invention, “anti-fogging” means that an appropriate amount of water or hot water is applied to form and maintain a water film on the surface of the water-use glass member, and the water film can be used even in a saturated steam environment or an environment where steam is generated. It shows the property that the surface of the surrounding glass member is not fogged. In addition, hydrophilicity can be used as a substitute characteristic for anti-fogging, and a static water contact angle of 20 ° or less is one standard.

  In the present invention, “high transparency” means a property that does not impair the original visibility of glass. For example, when the amorphous carbon layer is provided on the glass and the appearance thereof is not changed, the “transparency” is high. On the other hand, a state in which the appearance is changed by providing the amorphous carbon layer is assumed to have low “transparency”.

  In the present invention, “antifouling” refers to the property that the scale can be removed by light load cleaning (scale removal).

(density)
In the present invention, the density of the amorphous carbon layer is preferably less than 2.0 g / cm ³ , more preferably 1.9 g / cm ³ or less.
In general, it is known that an amorphous carbon layer is hydrophobic and has a high contact angle with water. On the other hand, when a minute amount of ultraviolet rays is irradiated for a long period of time, a part of the carbon-carbon bond of the amorphous carbon layer is cut, and a new carbon-oxygen bond or carbon-hydrogen bond is formed with oxygen and water. The The present inventors have found that when the density of the amorphous carbon layer is as small as less than 2.0 g / cm ³ , the contact angle of the amorphous carbon layer can be reduced over time in an indoor use environment. For example, when the contact angle of the amorphous carbon layer is lowered, the surface changes from hydrophobic to hydrophilic. And if a contact angle becomes small, the wettability of the water droplet adhering to the surface will improve. As a result, a water film can be formed and maintained on the surface of the glass member for water supply by applying an appropriate amount of water or hot water. In other words, the present inventors have newly found that by reducing the density of the amorphous carbon layer below a predetermined value, antifogging properties can be obtained in which the surface of the member does not become cloudy even in a saturated water vapor environment or an environment where steam is generated. I found it. Since the density of the amorphous carbon layer is lower than a predetermined value in the water glass member used in the indoor water environment according to the present invention, it can have antifogging properties over time.

The density of the amorphous carbon layer is preferably greater than 1.1 g / cm ³ . More preferably, it is 1.4 g / cm ³ or more. Thereby, even under a very small amount of ultraviolet irradiation, it is possible to suppress the disappearance of the amorphous carbon layer due to long-term use, and it is possible to maintain antifogging properties for a long period of time.

(Density measurement)
In the present invention, the density of the amorphous carbon layer is measured by XRR using the following method. As a measuring device, for example, an X-ray diffractometer X′PertPROMPD (manufactured by PANaltical) can be used. As measurement conditions, CuKα rays and measurement angles (0.2 to 4 °) are used. Measurement data of X-ray scattering intensity is obtained under these conditions. The density is obtained for the obtained measurement data using data analysis software. As the data analysis software, for example, X'Pert Reflectivity (manufactured by PANaltical) can be used. The data analysis software performs simulation using the film thickness, density, and interface roughness as parameters to obtain simulation data. The optimum values of each parameter are obtained by fitting by the least square method so that the X-ray scattering intensity measurement data and the simulation data X-ray scattering intensity values are close to each other, and the film thickness, density, and interface roughness values are determined. Ask. Each optimum value is determined so that the FitValue value indicating the degree of fitting is 10 or less.

(Anti-fogging evaluation)
Static water contact angle measurement is performed as an index of hydrophilicity, which is a substitute characteristic of antifogging properties. As a measurement assumption, for example, a contact angle meter CA-X150 type (manufactured by Kyowa Interface Science Co., Ltd.) can be used. For the measurement, distilled water is used as a dropping liquid. Evaluation of rapid hydrophilization and evaluation of hydrophilization after surface wear as an evaluation of anti-fogging properties appearing immediately after the start of use, and continuing antifogging properties even after long-term use over the years. To implement. Immediate evaluation of hydrophilization is performed by performing an operation of bringing tap water into contact with the sample surface in flowing water once a day for 1 minute, and measuring a static water contact angle. The evaluation of hydrophilization after surface wear assuming long-term use is performed by using an ultraviolet irradiator to wear the surface of the amorphous carbon layer and evaluating the hydrophilization of the sample.

  It has been found that when the density of the amorphous carbon layer is low, it becomes hydrophilic when used around aged water. Specifically, the amorphous carbon layer is indirectly irradiated with a small amount of ultraviolet rays through a window or the like, water or hot water is applied to the amorphous carbon layer during use, or the amorphous carbon layer is acidic or alkaline such as a detergent during cleaning. When the density is low due to contact with the liquid, the amorphous carbon layer can be hydrophilized over time. Therefore, it can have anti-fogging properties after many years of use.

The reason why the density of the amorphous carbon layer affects the antifogging property is considered as follows, but the present invention is not limited to this mechanism of action.
When the density is lowered in the amorphous carbon layer, it is considered that the surface of the amorphous carbon layer is oxidized by the use over time, and oxygen is introduced into the amorphous carbon layer to show hydrophilicity. In order for oxygen to be introduced into the amorphous carbon layer, carbon atoms in the vicinity of the surface of the amorphous carbon layer must be bonded to oxygen atoms contained in air or water to form a carbon-oxygen bond. For this purpose, it is desirable that the carbon-carbon bond in the amorphous carbon layer is likely to react with oxygen atoms contained in air or water. For this reason, in the present invention, the density of the amorphous carbon layer is set to a specific value or less. Thereby, the carbon-carbon bond distance in an amorphous carbon layer can be made into a long state, ie, the bond energy of a carbon-carbon bond can be made low. Therefore, it is considered that the surface of the amorphous carbon layer is easily oxidized, and hydrophilicity is easily exhibited.

  Furthermore, the present inventors have found that the antifogging property can be expressed promptly after the start of use by subjecting the amorphous carbon layer to surface hydrophilic treatment with oxygen plasma.

(Surface oxygen / carbon ratio (O / C ratio))
In the present invention, the oxygen / carbon ratio of the surface of the amorphous carbon layer is preferably greater than 0.3. More preferably, it is 0.8 or more. Thereby, the bond type containing carbon-oxygen on the surface of the amorphous carbon layer, for example, hydroxyl group (C—OH), carbonyl group (—CO—), aldehyde group (—CHO), carboxyl group (C—COOH), A hydrophilic bond species such as an ether bond (—O—) and an ester bond (—COO—) can be added in an amount sufficient to quickly develop antifogging properties.

(Calculation method of surface oxygen / carbon ratio (O / C ratio))
In the present invention, the oxygen / carbon ratio (hereinafter referred to as O / C ratio) of the surface of the amorphous carbon layer is the ratio of the peak height of oxygen (O1s) and carbon (C1s) obtained by an X-ray electron spectrometer (XPS). It can be calculated from As a measuring device, for example, PHI5000 VersaProbe (manufactured by ULVAC-PHI) can be used. The measurement conditions are an X-ray condition (100 μm, 25 W, 15 kv), a neutralization gun condition (emission: 20 μA), and an ion gun condition (beam: 1.000 kV, TargetEmission: 7.00 mA). As the measurement element, elements such as carbon in the amorphous carbon layer, oxygen, and optionally provided intermediate layer, silicon derived from a substrate such as glass, mirror, and the like can be measured as necessary.
Here, the surface means an angle resolution method (tilt angle) when the X-ray penetration depth irradiated from the X-ray source (Mgkα, Alkα) of the apparatus at a normal tilt angle (45 °) is about 10 nm. This means the measurement result of the surface of about 1.2 nm obtained at 5 °. In the present invention, charge correction is performed with the tilt angle of 5 ° and the C1s peak at 284.8 eV under the conditions of a step (20 ms), and then oxygen atoms (O1s) and carbon atoms (C1s) are respectively 532 to 552 eV and 285 to 305 eV. The O / C ratio calculated from the ratio of the peak height obtained by narrow scanning in the range of was used as the oxygen / carbon ratio of the surface of the amorphous carbon layer.

  In the XPS measurement performed for calculating the O / C ratio, it is preferable to sufficiently remove the surface contamination. Specifically, ultrasonic cleaning in acetone is performed twice or more.

The reason why the O / C ratio of the present invention affects the quick antifogging property is considered as follows, but the present invention is not limited to this mechanism of action.
Amorphous carbon layers that are inherently hydrophobic are thought to show hydrophilicity by being gradually oxidized by reducing the density and using oxygen over time in indoor environments by introducing oxygen into the amorphous carbon layer. . Therefore, the antifogging property is not exhibited immediately after the start of use. Thus, by forcibly introducing oxygen into the amorphous carbon layer by surface hydrophilization treatment using O ₂ plasma or the like, antifogging properties can be quickly developed without waiting for long-term use. Since the numerical value indicating the degree of the hydrophilic treatment is the O / C ratio of the surface, setting the numerical value of the O / C ratio of the surface of the amorphous carbon layer to a predetermined value or more expresses quick antifogging properties. I think it's important above.

The reason why the density and O / C ratio of the present invention affect the rapid antifogging property and long-term maintenance of the antifogging property is considered as follows, but the present invention is limited to this action mechanism. Is not to be done.
As described above, the surface O / C ratio affects the rapid development of antifogging properties. However, the amorphous carbon layer is worn by ultraviolet rays. In addition to the surface of the amorphous carbon layer, it is necessary to make the interior hydrophilic. An important factor in the hydrophilization inside is the density. When the density is low, the carbon-carbon bond of the amorphous carbon layer chemically bonds with oxygen and water supplied from the water environment, even in an environment where only a small amount of ultraviolet light is irradiated, such as a water environment. Since the hydrophilic binding species can be gradually formed, the antifogging property can be secured over time and in the long term. Here, even if it takes a certain amount of time to develop antifogging properties inside the amorphous carbon layer, if the surface O / C ratio satisfies a predetermined condition, the antifogging properties are developed immediately after the start of use. Since the internal anti-fogging property can be expressed during the period when the surface of the amorphous carbon layer is worn out, the anti-fogging property is expressed continuously from the beginning, which is preferable in practical use.
Therefore, by setting the two values of the density and the O / C ratio to predetermined values, it is possible to continuously enjoy the antifogging property from the beginning of use to the long term.

(Hydrogen content)
In the present invention, the amount of hydrogen in the amorphous carbon layer is preferably 0.3 or more, more preferably 0.4 or more. Thereby, in the bond type containing carbon-oxygen on the surface of the amorphous carbon layer, the bond type containing oxygen-hydrogen bond, for example, hydroxyl group (C—OH), aldehyde group (—CHO), carboxyl group (C— Since the ratio of hydrophilic functional groups such as (COOH) can be increased, the antifogging property of the amorphous carbon layer can be further improved. The amount of hydrogen in the amorphous carbon layer is preferably less than 0.8. Thereby, it becomes possible to improve the weather resistance of the amorphous carbon layer.

(Measurement of hydrogen content)
The amount of hydrogen contained in the amorphous carbon layer of the present invention is measured by Raman spectroscopy. For example, RAMANImage (manufactured by Nanophoton) can be used as the measuring device. The measurement conditions are a laser power of 0.2 mW, a center wave number of 1400 cm ⁻¹ , and a diffraction grating of 600 gr / mm. Measurement data is obtained under these conditions. For the obtained measurement data, the ratio of the G band peak intensity and the baseline intensity is determined using data analysis software. This is based on the fact that the value of the ratio between the G band peak intensity and the baseline intensity is correlated with the emission intensity of hydrogen evaluated by a glow discharge emission spectrometer (GDS). For example, OriginPro (manufactured by Lightstone) can be used as the data analysis software. Plot about 4 baseline points in the measurement data, calculate the subtraction value (S) from the measurement data, and subtract the value data (S) from the peak value (S + N) near 1530 cm ^{−1 of the} G band peak. To calculate the baseline value (N). Thereby, the ratio N / (S + N) of the G band peak intensity and the baseline intensity can be obtained. This intensity ratio corresponds to the amount of hydrogen.

  Since dirt adhering to the surface of the measurement sample for measuring the amount of hydrogen affects the amount of hydrogen, the surface of the measurement sample is thoroughly cleaned before measurement. Specifically, it is preferable to perform ultrasonic cleaning in acetone twice or more.

The reason why the amount of hydrogen contained in the amorphous carbon layer of the present invention affects the antifogging property is considered as follows, but the present invention is not limited to this mechanism of action.
By setting the amount of hydrogen contained in the amorphous carbon layer to a specific amount or more, when the surface is hydrophilized by oxygen plasma, or when the surface is gradually oxidized over time, the surface of the amorphous carbon layer It becomes easy to form a bond type having hydrophilicity (for example, a hydroxyl group, a carboxyl group, etc.). From the above, it is considered that hydrophilicity can be easily imparted to the surface of the amorphous carbon layer, and higher antifogging properties can be obtained.

(Transparency)
In the present invention, as a parameter representing the transparency of the amorphous carbon layer, a value obtained by dividing the color difference (ΔE) before and after the amorphous carbon layer is formed on the surface of the water-use glass by the film thickness of the amorphous carbon layer (hereinafter also referred to as X) Say). The transparency X is expressed by the following formula.
X (nm ⁻¹ ) = ΔE / Amorphous carbon layer thickness (nm)
The transparency X is a color difference per unit film thickness of the amorphous carbon layer. That is, the transparency is an index of film quality. The present inventors have found that the amorphous carbon layer may have different film quality even with the same color difference, the same film thickness, or the same density. By setting the transparency X, density, and film thickness within the predetermined ranges, it is possible to provide an amorphous carbon layer with good film quality while maintaining the original transparency of the glass, and to exhibit antifouling properties over a long period of time. .

In order to improve the film quality of the amorphous carbon layer, it is preferable to increase the value of the transparency X. Specifically, in the present invention, the transparency X is 0.2 or more.
On the other hand, in order to increase transparency in the amorphous carbon layer, that is, to suppress a change in appearance due to the provision of the amorphous carbon layer, X is preferably a small value. When X is a large value, the amorphous carbon layer can be provided only by an extremely thin film in order to suppress the change in appearance, and it becomes difficult to develop functions such as antifouling properties and antifogging properties over the long term. In the present invention, the transparency X is, for example, less than 4.0. Preferably, the transparency X is 1.0 or less. This makes it possible to obtain transparency.

(Measurement of film thickness)
The film thickness of the amorphous carbon layer can be determined, for example, by X-ray reflectometry (hereinafter referred to as XRR) reflection spectroscopy, X-ray photoelectron spectroscopy, glow discharge emission spectrometry, or the like. In addition, the film thickness of the amorphous carbon layer can be measured using a scanning electron microscope (SEM), a transmission electron microscope (TEM), a step meter, or the like.
In the water-use glass member used in the indoor water-use environment according to the present invention, when the thickness of the amorphous carbon layer is as thin as 30 nm or less, for example, the film thickness is preferably measured using XRR. When XRR is used, the interface between the amorphous carbon layer having an amorphous structure and the substrate can be distinguished. When XRR is used, it can be obtained by the same method as the method for obtaining the density described above.

(Measurement of color difference)
ΔE can be measured using a spectrocolorimeter or the like. ΔE can be obtained by the following method. First, L ^* ₀ , a ^* ₀ , b ^* ₀ of the glass for water circumference which is a base material is measured, respectively. Next, L ^* , a ^* , b ^* of the glass member for water use in which an amorphous carbon layer is formed on the surface of the glass for water use is measured. Thereafter, ΔE is obtained using the following equation.
ΔL ^* = L ^* −L ^* ₀
Δa ^* = a ^* −a ^* ₀
Δb ^* = b ^* −b ^* ₀
ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2

When ΔE is obtained from a water-use glass member in which an amorphous carbon layer is formed on the surface of the water-use glass, it can be obtained by the following method. L ^* , a ^* , b ^* of the glass member for water is measured. Thereafter, the amorphous carbon layer is removed, and L ^* ₀ , a ^* ₀ , and b ^* ₀ of this base material are measured. Using the obtained value, ΔE can be obtained by the same method as described above.

When an amorphous carbon layer is formed on both sides of the water-use glass, ΔE is calculated for each side. First, L ^* , a ^* , and b ^* of one surface of the water glass are measured with the amorphous carbon layers formed on both surfaces of the water glass. Next, the amorphous carbon layer is removed from only one surface, and L ^* ₀ , a ^* ₀ , and b ^* ₀ are measured on the surface of the water-use glass. Using the obtained value, ΔE of one surface is calculated by the same method as described above. L ^* , a ^* , b ^* in a state where an amorphous carbon layer is formed is measured on the other surface of the glass for water. Next, the amorphous carbon layer on the other surface of the water-use glass is removed, and L ^* ₀ , a ^* ₀ , b ^* ₀ on the surface of the water-use glass are measured. Using the obtained value, ΔE of the other surface of the water-use glass is calculated in the same manner as described above.

  As a method of removing the amorphous carbon layer, a method of physically removing by mechanical polishing or shot blasting, or a method of removing by etching using argon plasma or oxygen plasma can be used.

(Doping of other elements)
In the present invention, the physical properties of the surface of the amorphous carbon layer can be modified by doping the amorphous carbon layer with other elements.
The element to be doped is preferably selected from elements other than titanium, chromium, aluminum, iron, nickel, copper, silver, gold, niobium, molybdenum, and tungsten. Preferred elements include silicon, oxygen, sulfur, nitrogen and the like. In particular, it is known that when the amorphous carbon layer is doped with silicon and / or oxygen, the hydrophilicity of the amorphous carbon layer is improved. When the amorphous carbon layer further contains silicon and / or oxygen, the dirt attached to the surface can be made less noticeable.

(Middle layer)
In the present invention, an intermediate layer may exist between the amorphous carbon layer and the substrate. The intermediate layer preferably contains carbon, hydrogen, and silicon. The amount of silicon contained in the intermediate layer is preferably larger than the amount of silicon contained in the amorphous carbon layer. By providing such an intermediate layer, it becomes possible to improve the adhesion between the amorphous carbon layer and the substrate. By including a bond of silicon and carbon in the intermediate layer, it becomes possible to improve the adhesion between the amorphous carbon layer and the intermediate layer. Moreover, the intermediate layer material may be mixed in the amorphous carbon layer.

(Production method)
Examples of the method for forming the amorphous carbon layer include a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD method). Examples of the PVD method include a sputtering method and an ion plating method. Examples of the CVD method include a thermal CVD method, a plasma CVD method, and an ionized vapor deposition method.

(Plasma CVD method)
In the present invention, the amorphous carbon layer is preferably formed using a plasma CVD method.

  Although the manufacturing method of the glass member for water circumferences of this invention is not limited to a specific thing, For example, the following methods are mentioned. A step of disposing a glass member for water supply on a substrate support provided in the container, a step of depressurizing the inside of the container, a step of introducing a raw material into the container and adjusting the inside of the container to a predetermined pressure, and a raw material A high-density plasma generating step for generating high-density plasma by converting the plasma into a plasma, a step for applying a voltage to the substrate support, and a plasma-generated raw material is deposited on the surface of the water-use glass. And a step of forming an amorphous carbon layer on the surface.

  In the plasma CVD method, an amorphous carbon layer is generally formed in a decompressed container. Therefore, the inside of the container is decompressed using the decompression means. The inside of the container is preferably decompressed to 100 Pa or less.

  The raw material is introduced into the container as a gas through the raw material introduction part. Therefore, the concentration of the raw material in the container can be made uniform, and the plasma existing in the vicinity of the substrate surface can be made uniform. Thereby, the variation in the film thickness of the amorphous carbon layer can be reduced, and an amorphous carbon layer having a uniform film thickness can be formed. As the raw material, a raw material containing a hydrocarbon can be used. As the hydrocarbon, it is preferable to use at least one of methane, ethane, propane, ethylene, acetylene, toluene, and benzene. Of these, acetylene is more preferably used. Thereby, an amorphous carbon layer having a uniform film thickness and density can be formed. Moreover, it becomes possible to maintain antifouling property uniformly for a long period of time at any position of the glass member for water. As a raw material, not only hydrocarbons but also oxygen, nitrogen, sulfur and the like can be used.

  The inside of the container after introducing the raw material is adjusted to a predetermined pressure using a decompression means. This pressure is preferably adjusted to 100 Pa or less.

  In the present invention, it is preferable to use at least one of inductively coupled plasma, electron cyclotron resonance plasma, helicon wave plasma, surface wave plasma, Penning ion gauge discharge plasma, and hollow cathode discharge plasma as the high density plasma. Of these, inductively coupled plasma is more preferably used. As a result, high-density plasma can be generated with a simple apparatus, and an amorphous carbon layer can be formed on a large-area substrate.

  When the intermediate layer is formed between the amorphous carbon layer and the base material, it can be formed by the same method as the amorphous carbon layer by changing the raw material.

  As a raw material for the intermediate layer, one or more raw materials selected from the group consisting of hexamethyldisiloxane (HMDSO), tetramethylsilane (TMS), and tetraethoxysilane (TEOS) can be used as the first component. One or more raw materials selected from the group consisting of hydrogen, oxygen, and hydrocarbons can be used as a second component by mixing with the first component.

(Preprocessing)
In this invention, when forming an amorphous carbon layer or an intermediate | middle layer in the base-material surface, the pre-processing of a base material can be performed. The pretreatment includes (1) removing organic and inorganic adsorbates adhering to the substrate surface, (2) improving adhesion by removing the oxide layer, (3) adjusting the substrate surface roughness, (4) It is carried out for the purpose of activation by plasma on the substrate surface. The pretreatment may be performed in the same process for forming the intermediate layer or the amorphous carbon layer, or may be performed as a separate process.

In the present invention, as a pretreatment, it is preferable to perform sputtering using Ar gas or O ₂ gas on the base material before forming the amorphous carbon layer or the intermediate layer.

(Plasma CVD equipment)
In the plasma CVD method, an amorphous carbon layer is formed using a plasma CVD apparatus. An example of a plasma CVD apparatus usable in the present invention is shown in FIG. The plasma CVD apparatus generally includes a container 11 for forming an amorphous carbon layer, a decompression means 12 for decompressing the inside of the container 11, a raw material introduction unit 13 for introducing a raw material into the container, The base material support part 14 which supports the base material 1, the voltage application means 15 which applies a voltage to the base material support part 14, and the high density plasma generation means for making a raw material into plasma and producing | generating a high density plasma 16. It is considered that the raw materials plasmified in the container 11 repeat chemical reactions with each other on the surface of the base material 1, thereby depositing on the base material 1 and forming an amorphous carbon layer on the base material 1. Since the raw material is turned into plasma, the temperature in the container 11 can be kept at a low temperature of 200 ° C. or lower. This makes it possible to use a glass substrate that is combined with a resin such as a mirror.

  The decompression unit 12 includes a vacuum pump 19, an exhaust port 17, and a pressure adjustment unit 18. The gas in the container 11 can be exhausted and reduced in pressure by the vacuum pump 19, and the inside of the container 11 can be adjusted to a target pressure by the pressure adjusting means 18. As the pressure adjusting means 18, the pressure in the container 11 can be adjusted, and examples thereof include a pressure adjusting valve.

  The voltage applying means 15 is an electrode 20 that is a part of the base material support portion 14 and a power source 21 connected to the electrode 20. As the power source 21, any one or more of an AC power source, a DC power source, and a pulse power source can be used. The AC power source includes a high frequency power source. By applying a bias voltage to the electrode 20, an action of drawing ions contained in the plasma into the base material 1 supported by the base material support portion occurs. Thereby, the energy of ions colliding with the substrate 1 can be increased. Thereby, the density of the amorphous carbon layer can be increased.

  In the present invention, it is preferable to use a pulse power source as the power source 21 in the voltage applying means 15 described above. More preferably, a high voltage pulse power supply is used. By using a high voltage pulse power supply, a high voltage pulse voltage of −1 kV or higher is applied to the electrode 20. Thereby, the energy of the ion which collides with a base material can be made high. Therefore, the adhesion of the amorphous carbon layer to the base material can be improved, and the antifouling property can be maintained for a long time.

  The amorphous carbon layer of the present invention is preferably formed using an apparatus provided with high density plasma generation means 16 for generating high density plasma by converting the raw material into plasma. By making the plasma generated in the container high-density plasma, radicals in the plasma can be increased. Since the radicals are not affected by the pull-in caused by the bias voltage applied to the base material support portion 14, it is possible to deposit the radicals on the base material with low energy. Therefore, the density of the amorphous carbon layer can be lowered by increasing the number of radicals in the plasma.

  In the present invention, by using the high-density plasma generating means 16 and the voltage applying means 15, it becomes possible to independently control the radical abundance and ion energy in the plasma. Thereby, it becomes easy to control the density of the amorphous carbon layer within a preferable range.

  The high density plasma generating means 16 generates at least one of inductively coupled plasma, electron cyclotron resonance plasma, helicon wave plasma, surface wave plasma, Penning ion gauge discharge plasma, and hollow cathode discharge plasma as high density plasma. It is preferable.

  The high-density plasma generating means 16 is preferably an antenna or electrode 22 and a power source 23 connected to the antenna or electrode 22. For example, the inductively coupled plasma can be generated by using an antenna and a high frequency power source. Helicon wave plasma can be generated by using an antenna, a high-frequency power source, and a magnetic field generating means. The surface wave plasma can be generated by using an antenna, a microwave power source, and a dielectric. The hollow cathode discharge plasma can be generated by using a cathode electrode and an AC power source that are opposed to each other with a gap between the anode electrode and the anode.

  In the present invention, it is more preferable to use inductively coupled plasma as the high density plasma. As a result, high-density plasma can be generated with a simple apparatus, and an amorphous carbon layer can be formed on a large-area substrate.

  When generating inductively coupled plasma, it is preferable to use an antenna and a high frequency power source as the high density plasma generating means 16. A dielectric may be provided between the antenna and the raw material, and an electric field may be applied to the raw material via the dielectric. A high frequency current is passed through the antenna, and the raw material is excited by an electric field induced by a magnetic field generated around the antenna, so that inductively coupled plasma is generated. The antenna can be placed either inside or outside the container. In the present invention, the antenna is preferably disposed inside the container. As a result, plasma can be generated by efficiently supplying the output of the high-frequency power source to the raw material, so that high-density plasma can be generated even when a low-power high-frequency power source is used.

(Surface hydrophilization treatment)
In the present invention, a treatment for forcibly introducing oxygen into the surface of the formed amorphous carbon layer is performed as the surface hydrophilization treatment. As an implementation means, it is preferable to perform oxygen plasma treatment using oxygen gas.

Example 1
(Deposition system)
A container for forming an amorphous carbon layer, a decompression means for decompressing the container, a raw material introduction part for introducing a raw material into the container, a base material support part for supporting the base material, and a base material support part The plasma CVD apparatus provided with the obtained electrode plate, the voltage application means which applies a voltage to an electrode plate, and the high density plasma production | generation means which produces | generates high density plasma was used. An antenna and a high frequency power source were used as high density plasma generation means.

(Base material)
As a substrate, a soda lime glass plate used as a glass for water circumference was used. In order to remove dirt on the substrate surface, washing with ion-exchanged water and ethanol was sequentially performed.

(Pretreatment process 1)
The base material was arrange | positioned at the base-material support part, and it pressure-reduced to the high vacuum state (1 Pa or less) by the pressure reduction means. Next, oxygen gas was introduced and the pressure in the container was adjusted to be 0.01 to 2.0 Pa. The substrate surface was pretreated at a high frequency output of 100 to 500 W and a substrate temperature of 100 ° C. or lower.

(Pretreatment process 2)
After performing the pretreatment step 1, argon gas was introduced and the pressure in the container was adjusted to 0.01 to 2.0 Pa. The substrate surface was pretreated for a predetermined time by adjusting the high frequency output to 100 to 500 W and adjusting the voltage applied to the electrode plate to −10 kV to −0.1 kV.

(Amorphous carbon layer deposition process)
Acetylene was used as a raw material for the amorphous carbon layer. Film formation for a predetermined processing time by adjusting the pressure in the container to 0.001 to 2 Pa, the output of the high frequency power source to 100 to 500 W, and the voltage applied to the electrode plate to -12 to -0.1 kV As a result, an amorphous carbon layer was formed on the substrate.

(Surface hydrophilization process)
After forming the amorphous carbon layer, oxygen gas was introduced and the pressure in the container was adjusted to 0.01 to 2.0 Pa. A surface hydrophilization treatment was performed at a high frequency output of 100 to 500 W and a treatment time of 1 to 600 Sec to obtain a sample of Example 1. Each evaluation was performed about this sample.

Examples 2-3
In Examples 2 to 3, samples were obtained by the same method as in Example 1 except that the pressure in the container, the output of the high-frequency power source, and the voltage applied to the substrate were changed within the described range of Example 1. It was. Each evaluation was performed about this sample.

Evaluation (measurement of density and film thickness)
The density and film thickness of the amorphous carbon layer of each sample were measured by XRR. As a measuring device, an X-ray diffractometer X'PertPROMPD (manufactured by PANaltical) was used. CuKα rays and measurement angles (0.2 to 4 °) were used as measurement conditions. Under this condition, measurement data of the X-ray scattering intensity of each sample was obtained. The density was calculated for the obtained measurement data using data analysis software. As the data analysis software, X'Pert Reflectivity (manufactured by PANaltical) was used. Simulation data was obtained with data analysis software using film thickness, density, and interface roughness as parameters. The optimum values of each parameter are obtained by fitting by the least square method so that the X-ray scattering intensity measurement data and the simulation data X-ray scattering intensity values are close to each other, and the film thickness, density, and interface roughness values are determined. Asked. Each optimum value was determined so that the FitValue value indicating the degree of fitting was 10 or less. The obtained film thickness and density are shown in Table 1.

(Measurement of surface O / C ratio)
The oxygen / carbon ratio (hereinafter referred to as O / C ratio) of the surface of the amorphous carbon layer of each sample is determined from the ratio of the peak heights of oxygen (O1s) and carbon (C1s) obtained by an X-ray electron spectrometer (XPS). Calculated. As a measuring device, PHI5000 VersaProbe (manufactured by ULVAC-PHI) was used. Measurement conditions are X-ray conditions (100 μm, 25 W, 15 kv), neutralization gun conditions (emission: 20 μA), ion gun conditions (beam: 1.000 kV, TargetEmission: 7.00 mA), and surface measurement is performed. All elements were surveyed in the range of 15.5 to 1100 eV under the conditions of an inclination angle of the X-ray source (Mgkα, Alkα) of 5 ° and a step (20 ms). Narrow scan measurement was performed on oxygen atoms (O1s) and carbon atoms (C1s) in the ranges of 532 to 552 eV and 285 to 305 eV, respectively.
The obtained spectrum is obtained by performing charge correction using data analysis software (MultiPuk) with a C1s peak of 284.8 eV, and then the peak heights of oxygen atoms (O1s) and carbon atoms (C1s) obtained by narrow scan measurement. And the O / C ratio was calculated as the oxygen / carbon ratio of the surface of the amorphous carbon layer from these ratios.

(Measurement of hydrogen content)
The amount of hydrogen in the amorphous carbon layer of each sample was measured by Raman spectroscopy. As a measuring apparatus, RAMANImage (manufactured by Nanophoton) was used. As measurement conditions, a laser power of 0.2 mW, a center wave number of 1400 cm ⁻¹ , and a diffraction grating of 600 gr / mm were used. Measurement data was obtained under these conditions. For the obtained measurement data, the ratio of the G band peak intensity and the baseline intensity was determined using data analysis software. This is based on the fact that the value of the ratio between the G band peak intensity and the baseline intensity has a correlation with the emission intensity of hydrogen evaluated by a glow discharge emission spectrometer (GDS). OriginPro (manufactured by Lightstone) was used as data analysis software. Of the four baseline points in the measurement data, calculate the subtraction value (S) from the measurement data, and subtract the subtraction value data (S) from the peak value (S + N) near 1530 cm ^{-1 of the} G band peak. The baseline value (N) was calculated. As a result, the ratio N / (S + N) between the G band peak intensity and the baseline intensity was determined and used as the hydrogen amount.

(Measurement of color difference and evaluation of transparency and transparency)
A spectrocolorimeter (model number: CM-2600d, manufactured by Konica Minolta) was used to measure the color difference of each sample. F2 was used as the observation light source. The measuring instrument was calibrated with a white calibration plate. First, before forming an amorphous carbon layer, L ^* ₀ , a ^* ₀ , and b ^* ₀ of the substrate were measured. Next, L ^* , a ^* , and b ^* of the prepared sample were measured. Thereafter, ΔE was determined using the following equation.
ΔL ^* = L ^* −L ^* ₀
Δa ^* = a ^* −a ^* ₀
Δb ^* = b ^* −b ^* ₀
ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
The obtained ΔE is shown in Table 1. Moreover, transparency X was calculated | required from the following formula using obtained (DELTA) E and the obtained film thickness. The obtained transparency X is shown in Table 1.
X (nm ⁻¹ ) = ΔE / Amorphous carbon layer thickness (nm)
Furthermore, the transparency was evaluated as follows. Those having a transparency X of 1.0 or less were judged as ◎ (very good) less than 4.0, ◯ (good), and those having X greater than 4.0 were judged as x (bad).

(Anti-fogging evaluation)
Static water contact angle measurement was carried out as an index of hydrophilicity, which is a substitute characteristic of antifogging properties. When the water contact angle is 20 ° or less, antifogging properties are exhibited by applying water such as tap water or hot water to the surface. A contact angle meter CA-X150 type manufactured by Kyowa Interface Science Co., Ltd. was used as the measuring device, and distilled water was used as the dropping liquid. Immediate hydrophilization as an evaluation of anti-fogging properties appearing immediately after the start of use of a mirror in a bathroom, etc., and that the anti-fogging properties will continue to be maintained even after long-term use over a year in such an indoor environment. And the evaluation of hydrophilization after surface wear were evaluated as antifogging properties.

Evaluation Method for Rapid Hydrophilization of Amorphous Carbon Layer The water contact angle on the surface of the amorphous carbon layer was measured for the mirror sample on which the amorphous carbon layer was formed, and was confirmed to be 30 ° or more. When the angle was less than 30 °, the state was adjusted to 30 ° or more by standing still in a dry state in a dark room for an initial contact angle. If the correct contact angle value cannot be obtained due to the surface contamination of the sample, remove the surface contamination thoroughly by washing the surface with a neutral detergent and water or ethanol beforehand. It is desirable to perform contact angle measurements.

  For samples with an initial contact angle of 30 ° or more, the operation of bringing tap water into contact with the surface of the sample in a flowing state once a day for 1 minute in an indoor condition where it was not exposed to direct sunlight was continued. . After contact with running water every day, tap water remaining on the surface is removed with a jet gas from a commercial dust blower, and after confirming that there is no water wetting on the surface part where the contact angle is measured, 5 The water contact angle was measured within minutes. Thereafter, the sample was left in the indoor air until the next day, when it was running.

  As the evaluation index for rapid hydrophilization, the number of days when the water contact angle value after running water contact is 20 ° or less is set, and the evaluation value of the sample with the number of days within 2 days is A, within 8 days. The evaluation value of the sample was B, the evaluation value of the sample that was within 30 days was C, and the evaluation value of the sample that did not become 20 ° or less by 30 days was D.

Evaluation method of hydrophilization after surface wear of amorphous carbon layer When a mirror with an amorphous carbon layer is used for a long time, the amorphous carbon layer is subject to mechanical sliding load such as light irradiation and cleaning in indoor environment. Assuming that the surface is consumed, the hydrophilicity of the amorphous carbon layer after consumption was evaluated by the following method. With respect to the amorphous carbon layer of the mirror sample formed with the amorphous carbon layer described above, ultraviolet rays (typical irradiation wavelength: 365 nm, irradiation intensity: 5 mW) using an ultraviolet irradiator in an environment of room temperature and humidity: 50% RH or higher. / Cm ² or more) was irradiated for 20 hours or more, so that the surface of the amorphous carbon layer was consumed and the film remained. In addition to the ultraviolet irradiation by the ultraviolet irradiator, it can be considered that the amorphous carbon layer is worn by direct solar radiation for a long time or excessive sliding wear. For example, oxygen bonding species on the surface disappear. It is preferable to remove the amorphous carbon layer having a thickness of about 1 nm or more, and evaluate the hydrophilization after wear on the surface where the amorphous carbon layer remains. The use of ultraviolet rays in the wavelength region of sunlight that is indirectly incident indoors is a way of causing actual wear.

  Subsequently, after the irradiation, a treatment for standing for 20 hours or more at room temperature in an indoor environment is performed to confirm that the water contact angle is a value exceeding 20 °, and thereafter, once a day for 1 minute. The operation of bringing tap water into contact with the surface under running water was continued. After contact with running water every day, tap water remaining on the surface is removed with a jet gas from a commercial dust blower, and after confirming that there is no water wetting on the surface area where the contact angle is measured, 5 minutes after contact with running water The water contact angle was measured within. After that, the sample was left in the indoor environment until the next day.

  As an evaluation index for hydrophilization after surface wear, the number of days when the water contact angle after running water contact was 20 ° or less was counted from the day after the start of running water, and the evaluation value of the sample that was within 5 days A, the evaluation value of the sample that was within 10 days was b, the evaluation value of the sample that was within 30 days was c, and the evaluation value of the sample that was not less than 20 ° by 30 days was d.

  Table 1 shows the evaluation results of hydrophilization in Examples 1 to 3 and Comparative Examples 1 to 3. “Anti-fogging property (rapid)” in Table 1 is a value based on an evaluation method for rapid hydrophilization of an amorphous carbon layer, and “anti-fogging property (long term)” is an evaluation of hydrophilization after surface wear of the amorphous carbon layer. It shows as a value based on a method, respectively.

(Evaluation of antifouling properties)
20 μl of tap water was dropped on the surface of the amorphous carbon layer and left for 24 hours to form scale on the sample surface. The sample in which scale was formed was evaluated under the following conditions. An appropriate amount of detergent was applied to the surface of the amorphous carbon layer, and was slid back and forth 5 times with respect to the surface of the amorphous carbon layer using a urethane foam surface of a sponge. A neutral detergent for bathroom cleaning was used as the detergent. Thereafter, the detergent on the sample surface was washed away with running water, and water was removed with an air duster. It was judged visually whether water scale remained on the sample surface. The case where the scale did not remain was judged as ◯ (good), and the case where the scale remained was judged as x (poor). The results are shown in Table 1.

Comparative Example 1
In Comparative Example 1, a sample was obtained in the same manner as in Example 3, except that the surface hydrophilization treatment step was not performed on Example 3.

Comparative Example 2
Comparative Example 2 is a commercial product in which DLC is formed on glass.

Comparative Example 3
In Comparative Example 3, a surface hydrophilization treatment step is performed on Comparative Example 2.

  About the sample of Comparative Examples 1-3, evaluation similar to an Example was performed. The results are shown in Table 1.

In Examples 1, 2, and 3, since the density is less than 2.0 g / cm ³ and the O / C ratio is greater than 0.3, the antifogging property (rapid) is B or more and the antifogging property ( (Long term) is also equal to or greater than c, quickly exhibiting antifogging properties, and maintaining antifogging properties even after the amorphous carbon layer is worn out. Here, the antifogging property (long-term) is c, but in actual use, it takes time to wear the surface of the amorphous carbon layer. The anti-fogging property will be exhibited continuously from the beginning, and the anti-fogging property which is good in practical use can be enjoyed.

On the other hand, since Comparative Example 2 has a density of 2.0 g / cm ³ or more and an O / C ratio of 0.3 or less, the antifogging property (rapid) and the antifogging property (long term) are D. , D and has no anti-fogging property. Further, in Comparative Example 1, the density is less than 2.0 g / cm ³ , but since the O / C ratio is 0.3 or less, the antifogging property (rapid) is C, and the antifogging is promptly performed after the start of use. Sex cannot be expressed, which is not preferable in practical use.
In Comparative Example 3, although the O / C ratio is larger than 0.3, the density is 2.0 g / cm ³ or more, so that the antifogging property (rapid) is A, but the antifogging property (long term) is d. Thus, when the amorphous carbon layer is worn out by long-term use, the antifogging property is lost. Therefore, in order to quickly have antifogging properties and maintain antifogging properties even after long-term use, the density is less than 2.0 g / cm ³ and the O / C ratio is more than 0.3. There is a need.

Example 1 and Example 2 have almost the same values of density and O / C ratio, but Example 2 has higher results in both antifogging property (rapid) and antifogging property (long term). This is presumably because the amount of hydrogen in Example 1 is 0.43, whereas the amount of hydrogen in Example 2 is as high as 0.68. On the other hand, Comparative Example 2 has a high hydrogen content of 0.83, but neither has antifogging properties (rapid) or antifogging properties (long term). This is thought to be because hydrogen atoms do not exist as hydrophilic bonding species (for example, hydroxyl groups and carboxyl groups) because the O / C ratio is as low as 0.25 and the amorphous carbon layer has less oxygen. . Further, since the density is 2.0 g / cm ³ or more, antifogging properties are not exhibited even when used for a long time in an indoor environment. In Comparative Example 3, the O / C ratio is as high as 0.73. Therefore, the antifogging property (rapid) is very good as A. However, since the density is 2.0 g / cm ³ or more, hydrophilic bonding species (for example, a hydroxyl group and a carboxyl group) are not formed even inside the amorphous carbon layer when the film is worn out. Long-term use in which the amorphous carbon layer is worn out loses antifogging properties. Therefore, when the density and O / C ratio satisfy the predetermined conditions, the antifogging property can be enjoyed immediately after the start of use over a long period of time, and when the hydrogen amount also satisfies the predetermined condition, the antifogging property can be further improved. Can be increased.

DESCRIPTION OF SYMBOLS 1 Base material 2 Amorphous carbon layer 3 Intermediate | middle layer 11 Container 12 Depressurization means 13 Raw material introduction part 14 Base material support part 15 Voltage application means 16 High-density plasma generation means 17 Exhaust port 18 Pressure adjustment means 19 Vacuum pump 20 Electrode plate 21 Power supply 22 Antenna or electrode 23 Power supply

Claims (13)

A glass member for water used in an indoor water environment,
A glass substrate;
Provided on the surface of the glass substrate, an amorphous carbon layer containing hydrogen atoms and carbon atoms,
With
In the amorphous carbon layer, the density is less than 2.0 g / cm ³ ,
The amorphous carbon layer further includes oxygen atoms,
In the amorphous carbon layer, the surface O / C ratio is greater than 0.3,
Glass member for water.   The glass member for water circumference | surroundings of Claim 1 whose hydrogen amount computed from N / (S + N) measured by the Raman spectroscopy in the said amorphous carbon layer is 0.3-0.8. The glass member for water supply according to claim 1 or 2, wherein the amorphous carbon layer has the density of 1.1 g / cm ³ or more.   4. The value (X) obtained by dividing the color difference (ΔE) before and after the formation of the amorphous carbon layer by the film thickness of the amorphous carbon layer is less than 4.0. 5. Glass parts for water.   The value (X) obtained by dividing the color difference (ΔE) before and after the amorphous carbon layer is formed by the film thickness is 1.0 or less, according to any one of claims 1 to 3. The glass member for water circumferences of description.   The said amorphous carbon layer is a glass member for water circumferences as described in any one of Claims 1-5 which further contains a silicon | silicone.   The glass member for water supply of any one of Claims 1-6 further provided with the intermediate | middle layer provided between the said base material and the said amorphous carbon layer. In the manufacturing method of the glass member for water circumferences as described in any one of Claims 1-7,
Arranging a glass for water around the substrate support provided in the container;
Reducing the pressure in the container;
Introducing the raw material into the container and adjusting the inside of the container to a predetermined pressure;
A high-density plasma generation step of generating high-density plasma by converting the raw material into plasma;
Applying a voltage to the substrate support,
Depositing the high-density plasma on the surface of the water glass, and forming an amorphous carbon layer on the surface of the water glass;
Introducing a hydrophilic binding species to the amorphous carbon layer surface;
The manufacturing method of the glass for water circumferences containing.   The water according to claim 8, wherein the high-density plasma is one or more of inductively coupled plasma, surface wave plasma, helicon wave plasma, electron cyclotron resonance plasma, Penning ion gauge discharge plasma, and hollow cathode discharge plasma. Manufacturing method of glass member for surroundings.   The method for producing a glass member for water supply according to claim 8 or 9, wherein the high-density plasma is inductively coupled plasma.   The manufacturing method of the glass member for water supply as described in any one of Claims 8-10 whose voltage applied to the said base material instruction | indication part is larger than -1 kV.   The glass member for water supply according to any one of claims 8 to 11, wherein the high-density plasma is generated by supplying electric power to an antenna disposed in the container and converting the raw material into plasma. Manufacturing method.   The method for producing a water-use glass member according to any one of claims 8 to 12, wherein the step of introducing the hydrophilic binding species includes a step of irradiating the amorphous carbon layer with oxygen plasma.

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