KR102297566B1 - Glass substrate, method for producing glass substrate and black matrix substrate - Google Patents

Abstract

It is a glass substrate made of silicate glass containing aluminum, and from the value of the ratio of the atomic concentration of aluminum and the atomic concentration of silicon in the inside of the glass substrate, measured by X-ray photoelectron spectroscopy, to the surface of the glass substrate The value obtained by subtracting the value of ratio of the atomic concentration of aluminum and the atomic concentration of silicon in is 0.25 or less of the glass substrate.

Description

A glass substrate, the manufacturing method of a glass substrate, and a black-matrix board|substrate TECHNICAL FIELD

This invention relates to a glass substrate, the manufacturing method of a glass substrate, and a black-matrix board|substrate.

The glass substrate used for FPD (Flat Panel Display), such as a liquid crystal display device (LCD), is shape|molded into a glass ribbon from a molten glass by a float method or a fusion method, for example, cut out from a glass ribbon, and is manufactured. On the surface of such a glass substrate, the high hydrophilicity layer (henceforth OH-rich hydrophilic layer) containing an OH group excessively may be formed.

It is remarkable, especially when grind|polishing the glass shape|molded into plate shape from molten glass with the grinding|polishing tool which rotates and revolves. In a grinding|polishing process, it forms in the thin plate shape of predetermined thickness (for example, 0.1-1.1 mm) which satisfy|fills the flatness requested|required of the glass substrate for FPDs by removing the micro unevenness|corrugation and undulation of the surface.

For polishing of such a glass substrate, for example, an abrasive (slurry) containing cerium oxide particles as an abrasive is used. Moreover, after grinding|polishing, residues, such as an abrasive grain adhering to the surface of a glass substrate, are wash|cleaned and removed with a washing|cleaning liquid (for example, refer patent document 1).

And in order to remove residues, such as an abrasive|polishing agent containing the abrasive grain of such a cerium oxide particle, the acidic washing liquid containing organic acids, such as organic phosphonic acid, is effective.

However, when a glass substrate made of aluminoborosilicate glass, such as for LCD, is washed with an acidic cleaning solution, glass components such as aluminum ions are removed from the surface (surface layer) of the glass substrate by leaching action. Sometimes going out As a result, it becomes easy to form an OH-rich hydrophilic layer on the surface of a glass substrate.

In the glass substrate in which the OH-rich hydrophilic layer was formed on the surface as mentioned above, the black matrix film|membrane for color filters (henceforth a BM film|membrane) using the resin composition containing a black pigment like carbon black on the surface. In the forming step, there was a problem that the developer penetrated the interface between the OH-rich hydrophilic layer and the resin-based BM film, and the BM film was easily peeled off from the OH-rich hydrophilic layer.

Japanese Patent Laid-Open No. 2009-215093

The present invention has been made in order to solve the above problems, and the adhesiveness of a resin-based BM film (hereinafter also referred to as a resin BM film) formed on the surface is high, and peeling of the resin BM film does not easily occur. is doing

Moreover, this invention suppresses the adhesive fall of the resin BM film|membrane formed in the surface of the glass substrate after washing|cleaning in wash|cleaning the surface of the glass substrate after grinding|polishing, and manufacture of the glass substrate which can prevent peeling of a resin BM film|membrane It aims to provide a method.

The glass substrate of the present invention is a glass substrate made of silicate glass containing aluminum, and the atomic concentration of aluminum (hereinafter referred to as Al concentration) and silicon in the inside of the glass substrate, measured by X-ray photoelectron spectroscopy. A value obtained by subtracting the Al/Si value on the surface of the glass substrate from the ratio of the atomic concentration (hereinafter referred to as Si concentration) (hereinafter referred to as Al/Si value) (hereinafter referred to as ΔAl/Si value) It is characterized in that it is 0.25 or less.

The glass substrate of this invention WHEREIN: As for the said (DELTA)Al/Si value, 0.19 or less is preferable. Moreover, it is preferable that the arithmetic mean surface roughness of the said glass substrate surface is 0.2 nm or less.

Further, a silicate glass containing the _{Al, SiO 2, Al 2 O 3} , B 2 O 3, and preferably in the alkali alumino borosilicate glass having a composition containing an oxide of the earth metal, and silicate containing the aluminum glass It is preferable that silver is an alumino borosilicate glass which does not contain an alkali metal component substantially.

The manufacturing method of the glass substrate of this invention is the method of manufacturing the said glass substrate of this invention, It is characterized by washing|cleaning the glass substrate grind|polished with the abrasive|polishing agent containing an abrasive with the aqueous cleaning liquid whose pH is larger than 2.7. . In the manufacturing method of the glass substrate of this invention, it is preferable that the said abrasive grain is a cerium oxide particle.

The black-matrix board|substrate of this invention is formed by BM film|membrane on the glass substrate of this invention, It is characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to the glass substrate and black-matrix board|substrate of this invention, the adhesiveness of the resin BM film|membrane formed in the surface is favorable, and peeling of a resin BM film|membrane is prevented.

Moreover, according to the manufacturing method of the glass substrate of this invention, the adhesiveness of the resin BM film|membrane formed in the surface is favorable, and the glass substrate which peeling of a resin BM film|membrane does not generate|occur|produce easily can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows one Embodiment of the washing|cleaning method for obtaining the glass substrate of this invention.
It is a graph which shows the relationship between Al concentration and Si concentration in the glass substrate obtained in Example 1, and sputtering time at the time of a measurement.
3 : is a graph which shows the relationship between the pH value of the washing|cleaning liquid in Examples 1-3 and the comparative example 1, and (DELTA)Al/Si value of the glass substrate after washing|cleaning.
It is a graph which shows the relationship between the ΔAl/Si value of the glass substrate obtained in Examples 1-3 and Comparative Example 1, and the residual resolution of a resin BM film|membrane.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. The present invention is not limited to this embodiment, and other embodiments may also fall within the scope of the present invention as long as they are consistent with the spirit of the present invention.

<Glass substrate>

The glass substrate according to the embodiment of the present invention is a glass substrate made of silicate glass containing aluminum, and is similarly measured by X-ray photoelectron spectroscopy from the Al/Si value in the glass substrate measured by X-ray photoelectron spectroscopy. The ΔAl/Si value, which is a value obtained by subtracting the Al/Si value of the surface of the glass substrate, is 0.25 or less. The ΔAl/Si value is preferably closer to 0 (zero). Specifically, 0.19 or less is preferable and, as for ΔAl/Si value, 0.15 or less is more preferable.

The glass substrate of embodiment is a glass substrate for FPDs like LCD, for example. Glass constituting the glass substrate is aluminum having as long as made of a silicate glass containing an aluminum component, the composition includes, but not limited _{to, SiO 2, Al 2 O 3} , B 2 O 3, and a composition containing an oxide of an alkaline earth metal Noborosilicate glass is preferable, and so-called alkali-free aluminoborosilicate glass which does not contain an alkali metal component substantially in a glass composition is more preferable. In addition, not containing an alkali metal component substantially is 1 mass % or less in total in content of the alkali metal oxide in a glass composition, Preferably it is 0.1 mass % or less.

For example, the glass substrate according to the embodiment of the present invention has a strain point of 630 ° C. or higher, preferably 650 ° C. or higher, and the composition is expressed as an oxide-based mass percentage,

SiO ₂ : 54 to 73

Al ₂ O ₃ : 10 to 23

B ₂ O ₃ : 0 ∼ 12

MgO: 0 ~ 12

CaO: 0 ~ 15

SrO: 0 ~ 16

BaO: 0 ~ 15

MgO + CaO + SrO + BaO: 8 to 26

An alkali free glass containing

Al concentration and Si concentration in the inside and surface of a glass substrate shall be the values measured by X-ray photoelectron spectroscopy. Here, it is preferable to make the depth from the surface of the point which measures Al concentration and Si concentration in a glass substrate into the depth determined as shown below.

That is, _{while forming a concave hole (crater) in a glass substrate using C 60} ion sputtering, the Al concentration and Si concentration are measured at the bottom of the concave hole of various depths, and the distribution of each atomic concentration in the depth direction is obtained. . Then, the depth at which the distribution of the Al concentration and the Si concentration in the depth direction becomes constant is obtained, and the value of the ratio of the Al concentration and the Si concentration measured at the depth is the Al/Si value inside the glass substrate, and from this value, free The ΔAl/Si value, which is a value obtained by subtracting the Al/Si value of the substrate surface, is obtained.

Thus, in the glass substrate of embodiment of this invention, since the grade of the fall of the Al/Si value of the glass substrate surface with respect to the Al/Si value inside a glass substrate is suppressed to predetermined value (0.25) or less, The adhesiveness of the resin BM film|membrane formed in the surface of a glass substrate is favorable, and peeling of a resin BM film|membrane does not generate|occur|produce easily.

As mentioned above, washing|cleaning after grinding|polishing of a glass substrate WHEREIN: OH-rich hydrophilic layer is formed in the surface of a glass substrate, so that there is much extraction amount of Al component of the surface (surface layer) of a glass substrate. And the ΔAl/Si value indicating how low the Al/Si value on the surface of the glass substrate is compared to the Al/Si value inside the glass substrate without extraction of the Al component described above is the degree of formation of the OH-rich hydrophilic layer. indicates That is, it means that there is little deficiency of the Al component in the surface of a glass substrate, and it has shown that the hydrophilicity resulting from the OH group on the surface of a glass substrate is low, so that ΔAl/Si value is low.

Specifically, when the ΔAl/Si value, which is a value obtained by subtracting the Al/Si value on the surface of the glass substrate from the Al/Si value inside the glass substrate, is 0.25 or less, the hydrophilicity resulting from the OH group on the surface of the glass substrate is low. Therefore, when forming a resin BM film|membrane on a glass substrate, penetration of the developing solution with respect to the interface of a glass substrate and the resin composition film for BM formation is suppressed, the adhesiveness of a resin BM film|membrane improves, and film peeling is prevented.

Thus, the glass substrate of this invention whose (DELTA)Al/Si value is 0.25 or less can be obtained with the following method.

<The manufacturing method of a glass substrate>

The glass substrate which concerns on embodiment of this invention is shape|molded from a molten glass into a plate-shaped glass ribbon by the float method or a fusion method, and is cut out from a glass ribbon to a predetermined size, and is manufactured. Moreover, the glass shape|molded in plate shape is grind|polished as needed.

The manufacturing method of the glass substrate of embodiment of this invention is demonstrated below as what has a grinding|polishing process. The manufacturing method of the glass substrate of embodiment is equipped with the grinding|polishing process of grind|polishing a glass substrate with the abrasive|polishing agent containing an abrasive grain, and the washing|cleaning process of wash|cleaning the grind|polished glass substrate. And the glass substrate of above-mentioned this invention can be obtained by washing|cleaning the glass substrate grind|polished with the abrasive|polishing agent containing an abrasive with the aqueous washing liquid larger than pH 2.7. 3.0 or more are preferable and, as for pH of an aqueous washing liquid, 3.5 or more are more preferable.

The glass substrate which is a cleaning object is a glass substrate for FPD like LCD, and grind|polished with the abrasive containing an abrasive grain.

Glass constituting the glass _{substrate,, SiO 2, Al 2 O} 3, B 2 O 3, and the alumino-borosilicate glass having a composition containing oxides of alkaline earth metals are preferred, and alkali metal component in the glass composition as described above, An aluminoborosilicate glass which does not contain substantially is more preferable.

In the grinding|polishing before washing|cleaning, the surface of such a glass substrate is grind|polished with the abrasive|polishing agent (slurry) containing an abrasive grain using a polishing pad, for example. The abrasive grains contained in the abrasive are not particularly limited, and include particles such as silica particles, alumina particles, cerium oxide particles, titania particles, zirconia particles, and manganese oxide particles. In terms of polishing efficiency, particularly cerium oxide particles are preferable. do. The average particle diameter of the abrasive grains is, for example, preferably in the range of 0.8 to 1.0 µm. It is preferable that arithmetic mean surface roughness Ra (JIS B0601-2013) of the surface of a glass substrate becomes 0.2 nm or less by passing through such a grinding|polishing process.

Examples of the aqueous cleaning liquid having a pH greater than 2.7 used in the embodiment of the present invention include an acidic cleaning liquid and an alkaline cleaning liquid containing an organic acid, which are shown below. In order to ensure the flatness of the surface of a glass substrate, less than 11 is preferable and, as for pH of an aqueous washing|cleaning liquid, less than 9 is more preferable. From the above, the pH of the aqueous washing liquid is more preferably in the range of 3.5 or more and less than 9.

(acidic cleaning solution)

Examples of the organic acid contained in the acidic washing liquid include, but are not limited to, organic carboxylic acids such as ascorbic acid and citric acid, and organic phosphonic acids. An inorganic acid (for example, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, hydrochloric acid, etc.) can be added to a washing|cleaning liquid together with these organic acids, and it is also possible to use an inorganic acid independently. Moreover, when the said inorganic acid is used, in order to suppress the fluctuation|variation of pH, it is also possible to add the salt of these acids together with an inorganic acid.

You may contain compounds, such as organic carboxylic acid and organic phosphonic acid which have a chelating effect, in a washing|cleaning liquid from a washability viewpoint. On the other hand, since there is a possibility of promoting the extraction of the Al component from the glass, it is better not to contain these compounds in the cleaning liquid from the viewpoint of adhesion of the resin BM film.

Here, as the organic carboxylic acid having a chelating effect, a dicarboxylic acid-based chelating agent, a tricarboxylic acid-based chelating agent, a gluconic acid-based chelating agent, a nitrilotriacetic acid-based chelating agent, an iminosuccinic acid-based chelating agent, and the like are mentioned. can

The organic phosphonic acid refers to an organic compound having a structure in which a phosphonic acid group represented by the formula: -P(=O)(OH) _{2 is bonded to a carbon atom.} 2 or more are preferable, as for the number of the phosphonic acid groups represented by the said formula per molecule of organic phosphonic acid, 2-8 are more preferable, and 2-4 are especially preferable.

As the organic phosphonic acid, a compound having a structure in which a hydrogen atom bonded to a carbon atom of hydrocarbons which may have a substituent is substituted with a phosphonic acid group, and a hydrogen atom bonded to a nitrogen atom of ammonia or amines, - A compound having a structure substituted with a methylenephosphonic acid group represented by CH ₂ -P(=O)(OH) _{2 is preferred.}

Specifically, organic phosphonic acids are methyldiphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetra( Methylenephosphonic acid), propylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), tris(2-aminoethyl)amine hexa(methylenephosphonic acid) , trans-1,2-cyclohexanediaminetetra(methylenephosphonic acid), glycol etherdiaminetetra(methylenephosphonic acid), and tetraethylenepentaminehepta(methylenephosphonic acid).

(Alkaline cleaning solution)

The alkaline washing liquid contains a base and may contain a chelating agent and a surfactant in addition to the base. The chelating agent may be contained in the cleaning liquid from the viewpoint of cleaning properties. On the other hand, since there is a possibility of promoting the extraction of the Al component from the glass, it is better not to contain the chelating agent in the cleaning solution from the viewpoint of adhesion of the resin BM film.

Examples of the base contained in the alkaline washing solution include alkali metal compounds such as alkali metal hydroxides and alkali metal carbonates, amines, and quaternary ammonium hydroxide. As a base, alkali metal hydroxides, such as potassium hydroxide and sodium hydroxide, are preferable.

Examples of the chelating agent include an ethylenediaminetetraacetic acid chelating agent, a gluconic acid chelating agent, a nitrilotriacetic acid chelating agent, and an iminosuccinic acid chelating agent. In particular, an ethylenediaminetetraacetic acid chelating agent is preferable.

As surfactant, a nonionic surfactant is preferable.

(cleaning process)

In the washing step, a dilution solution obtained by diluting an acidic detergent stock solution with water and having a pH greater than 2.7 (acidic washing solution) or a dilution solution obtained by diluting an alkaline detergent stock solution with water (alkaline washing solution) Clean the surface of the substrate. It is preferable to wash by a single-wafer method. The cleaning method is not particularly limited as long as it is a method of cleaning by bringing the cleaning liquid into direct contact with the surface of the glass substrate. As a washing method, scrub washing, shower washing (spray washing), dip (immersion) washing, etc. can be used, for example. The temperature of the washing|cleaning liquid is not specifically limited, It is used at room temperature (15 degreeC) - 95 degreeC. When it exceeds 95 degreeC, there exists a possibility that the water in a washing|cleaning liquid may boil, and it is inconvenient on washing|cleaning operation, and it is unpreferable. You may dry after washing|cleaning. As a drying method, the method of blowing warm air, the method of blowing compressed air, etc. are mentioned.

In a washing|cleaning process, as shown, for example in FIG. 1, by mechanisms, such as a conveyance roll 1, it wash|cleans in the upper and lower surfaces of the glass substrate 3 continuously conveyed in the inside of the washing|cleaning chamber 2 in a horizontal direction. A method of scrubbing (rubbing) the upper and lower surfaces of the glass substrate 3 with rotating brushes 6 disposed on the upper and lower both sides of the glass substrate 3 while spraying the aqueous cleaning liquid 5 sprayed from the nozzle 4 can be adopted The cleaning unit composed of the cleaning nozzle 4 and the rotary brush 6 for spraying the aqueous cleaning liquid 5 may be provided in one stage, or may be formed in multiple stages. In addition, in the washing|cleaning method shown in FIG. 1, the washing|cleaning part has two stages. When washing is performed in multiple stages, that is, when multiple stages of the washing unit are formed, the aqueous washing liquid 5 sprayed from each stage has the same composition as either an acidic washing liquid or an alkaline washing liquid from the viewpoint of workability. It is preferable to use phosphorus, but as long as the pH of the washing liquid is in the above range, washing may be performed using different aqueous washing liquids 5 at each stage.

Here, as the rotating brush 6 for washing|cleaning, it is a PVA (polyvinyl alcohol) foaming system, etc., and uses a plurality of cylindrical ones with an outer diameter of 70-100 mm. And, these rotary brushes 6 are set so that the rotational axis of the rotary brush 6 is perpendicular to the surface to be cleaned of the glass substrate 3, here, the upper and lower surfaces, and the tip of the rotary brush 6 is the glass substrate 3 . It is placed in contact with the surface to be cleaned of or placed at a distance of less than 2 mm from the surface to be cleaned. It is preferable that the rotation speed of the rotating brush 6 shall be 100-500 rpm.

As the aqueous cleaning liquid 5, the acidic cleaning agent stock solution or the alkaline cleaning agent stock solution described above is diluted with water to a desired pH. It is preferable to set it as 40 L/min. Moreover, it is preferable to make scrub time into 1.5 second or more.

In the manufacturing method of the glass substrate of embodiment, the glass substrate grind|polished with the abrasive|polishing agent containing cerium oxide particle|grains is washed with the aqueous cleaning liquid whose pH is larger than 2.7 in the said cleaning process, and Al/Si value inside a glass substrate The ΔAl/Si value obtained by subtracting the Al/Si value of the glass substrate surface is adjusted to 0.25 or less. In this way, in the surface of the glass substrate, as a result of suppressing the formation of the OH-rich hydrophilic layer, in the process of forming the resin BM film, the penetration of the developer into the interface between the surface of the glass substrate and the resin composition film for BM formation is suppressed, and the resin The adhesion of the BM film|membrane improves. Therefore, the adhesiveness of a resin BM film|membrane is favorable and the glass substrate by which film|membrane peeling was prevented can be obtained.

Example

Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, "%" means mass %, and "part" means mass parts.

(Examples 1 to 3, Comparative Example 1)

The surface of the glass substrate was polished as shown below. As a glass substrate, the glass substrate for LCDs (the Asahi Glass Company make, brand name: AN100) which consists of alumino borosilicate glass was used. Then, the surface of this glass substrate was polished using a polishing pad using a slurry-like abrasive containing cerium oxide particles having an average particle diameter of 0.8 to 1.0 µm (manufactured by Showa Denko Co., Ltd., trade name: SHOROX A10). .

And the glass substrate by which the surface was grind|polished was wash|cleaned using the washing|cleaning method shown in FIG.

In Example 1, an alkaline detergent stock solution (manufactured by Parker Corporation, trade name: PK-LCG28) diluted with water to a pH of 8.9 was used as an aqueous washing liquid.

Moreover, in Example 2 and Example 3, what diluted the acidic detergent stock solution with water so that pH might become 5.3 (Example 2) and 3.9 (Example 3), respectively, was used as an aqueous washing liquid. In addition, the organic phosphonic acid density|concentration in a liquid is what made PK-LCG492A (the brand name of the acidic detergent undiluted|stock solution manufactured by Parker Corporation) into 1/4 of the acidic detergent undiluted|stock solution.

In Comparative Example 1, an acidic detergent stock solution (manufactured by Parker Corporation, trade name: PK-LCG492A) was diluted with water to a pH of 2.7, and used as an aqueous washing solution.

And in each of Examples 1 to 3 and Comparative Example 1, the water-based cleaning liquid is sprayed on the surface of the glass substrate after polishing at a flow rate of 25 L (hereinafter also referred to as cleaning liquid flow rate) for 1 minute, while rotating PVA products The glass substrate was scrub-cleaned with a rotating brush. In addition, the temperature of the aqueous washing|cleaning liquid was 25 degreeC. Moreover, the scrub time in a washing|cleaning process was 3 to 5 second, respectively.

In this way, about the surface of the wash|cleaned glass substrate, the method shown below measured and evaluated the adhesiveness of a resin BM film|membrane. Moreover, the Al/Si value of the surface of a glass substrate (it is also called surface Al/Si value), the Al/Si value inside a glass substrate (it is also called an internal Al/Si value), and (DELTA)Al/Si value were calculated|required.

<Evaluation of adhesion of resin BM film>

First, each component shown below was mix|blended with the following compositions, it mixed uniformly, and the resin composition for photosensitive BM formation of 15% of solid content concentration was prepared.

[Composition of resin composition for BM formation]

・Binder resin (manufactured by Nippon Kayaku Co., Ltd., trade name: ZCR1569H): 28.4 parts

・Photoactivator (photopolymerization initiator)

(manufactured by Chiba Specialty Chemicals, trade name: Irgacure OXE02): 6.1 copies

Colloidal silica fine particles (manufactured by Nissan Chemical, trade name: PMAST): 20.3 parts

・Carbon Black: 32.5 parts

・Surfactant (manufactured by Big Chemie Japan, trade name: BYK306): 0.3 parts

・Crosslinking agent (manufactured by Nippon Kayaku Co., Ltd., trade name: UX5002D): 6.1 parts

(manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000H): 3.0 copies

· Silane coupling agent (manufactured by Shin-Etsu Chemical, trade name: KBM403): 3.0 parts

- Phosphoric acid compound (2:1 (mass ratio) mixture of phosphoric acid, monomethacryloyloxyethyl phosphate, and dimethacryloyloxyethyl phosphate): 0.3 parts

Next, this resin composition for BM formation was applied to the surface of the glass substrate after washing using a spin coating apparatus (manufactured by Mikasa Corporation, apparatus name: MS-A100) at 200 rpm for 10 seconds (spin coating), and then hot Using a plate (manufactured by Asone Corporation, device name: HI-1000), it was heated and dried at 90° C. for 60 seconds to form a coating film. Thereafter, using an exposure apparatus (manufactured by Dainippon Scientific Research Institute, apparatus name: MA-1200), exposure (illuminance: 30 mW/cm 2 , exposure dose: 30 mJ/cm 2 , exposure GAP: 50 µm) was carried out through a photomask. Then, it developed for 15 second using the 0.045% KOH aqueous solution using the developing apparatus (The Arctes company make, apparatus name: ADE-3000S). Then, the pattern of the resin BM film|membrane was formed in the surface of a glass substrate by pure water washing|cleaning.

The photomask had four types of pattern shapes of L1-L4 shown below, and set it as 110 types of patterns in which the line|wire width was changed at a time of 1 micrometer for each type.

L1 … … … 25 linear patterns in one block (2835 µm × 2000 µm) with a pattern interval of 100 µm (line width is variable in the range of 1 to 25 µm)

L2 … … … 30 linear patterns in one block (2952.6 µm × 2000 µm) with a pattern interval of 50 µm (line width is variable in the range of 1 to 30 µm)

L3 … … … 25 linear patterns in one block (2682.5 µm × 2000 µm) with a pattern interval of 200 µm (line width is variable in the range of 1 to 25 µm)

L4 … … … 25 short linear patterns in one block (2682.5 µm × 2000 µm) with a pattern interval of 200 µm (line width is variable in the range of 1 to 25 µm)

The glass substrate after pure water cleaning is observed with a laser microscope (manufactured by Keyence Corporation, device name: VK-9510), and the line width of the mask (hereinafter referred to as residual resolution) in which the pattern of the resin BM film remains on the glass substrate is L1- Each of the four types of pattern shapes of L4 was investigated. Then, the average of the residual resolution for each of the four types of pattern shapes was obtained. A result is shown in Table 1. Moreover, it has shown that the adhesiveness of the resin BM film|membrane formed on the glass substrate after washing|cleaning is so high that the value of the residual resolution is small.

<Measurement of surface Al/Si values>

The Al concentration and Si concentration on the surface of the glass substrate after washing were measured using X-ray photoelectron spectroscopy (hereinafter referred to as XPS) to determine the Al/Si value (atomic concentration ratio).

For the measurement, PHI5500 manufactured by Albac Pai Co., Ltd. was used, and the peaks of Si (2p) and Al (2p) were used to measure a path energy of 117.4 eV, an energy step of 0.5 eV/step, and a detection angle (between the sample surface and the detector). Angle) measurement was performed under the condition of 15°. Analysis software MultiPak was used for the analysis of the spectrum. The Shirley method was applied to the method of subtracting the background of the spectrum. The obtained result is shown in Table 1.

<Measurement of internal Al/Si values>

With respect to a glass substrate used for the measurement of surface Al / Si values, the depth direction distribution of Al concentration and Si concentration was determined by XPS using C ₆₀ ion sputtering. As for the XPS measuring apparatus and analysis software, the same thing as the measurement of the surface Al/Si value was used. Measurement conditions were 117.4 eV for pass energy, 0.5 eV/step for energy step, Si (2p) and Al (2p) for monitor peaks, and 75 degrees for detection angle. Then, the sputtering interval was 5 minutes, and the Al concentration and the Si concentration of the formed crater bottom were measured every time sputtering was performed for 5 minutes. Such measurements were carried out until the Al concentration and the Si concentration became constant. The depth direction distribution of the Al concentration in the glass substrate of Example 1 and Si concentration obtained in this way is shown in FIG. From this graph, it was judged that the Al concentration and the Si concentration became constant when the sputtering time was 40 minutes.

_{Moreover, as a result of measuring the sputtering rate of C 60} ion sputtering in the thermal oxide film (SiO ₂ film) on the Si wafer, it was 1.4 nm/min, so it is estimated that it is a similar sputtering rate also for a glass substrate. Therefore, it is thought that the Al concentration and Si concentration inside a glass substrate become constant at 56 nm or more which is a depth corresponding to 40 minutes of sputtering time.

Moreover, since Examples 1-3 and Comparative Example 1 are glass substrates of the same composition, the internal Al/Si value of Example 2, Example 3, and Comparative Example 1 can also be considered as the same thing as Example 1.

For the glass substrates obtained in Examples 1 to 3 and Comparative Example 1, the thus-measured residual resolution, surface Al/Si value, internal Al/Si value, and ΔAl/Si value are shown in Table 1, respectively.

Next, based on the measurement results in Table 1, the relationship between the pH of the aqueous cleaning solution and the ΔAl/Si value, and the relation between the ΔAl/Si value and the residual resolution were respectively investigated. The relationship between the pH of the aqueous cleaning solution and the ΔAl/Si value is shown in FIG. 3, and the relationship between the ΔAl/Si value and the residual resolution is shown in FIG. 4, respectively.

It can be seen from FIG. 3 that there is a negative correlation between the pH of the aqueous cleaning liquid and the ΔAl/Si value, and as the pH of the aqueous cleaning liquid increases, the ΔAl/Si value tends to decrease.

Also, from Fig. 4 , there is a positive correlation between the ?Al/Si value and the residual resolution, and it is confirmed that the residual resolution also decreases with the decrease of the ?Al/Si value. And, as mentioned above, since the adhesiveness of the resin BM film|membrane formed on the glass substrate after washing|cleaning is so high that the residual resolution is small, it turns out that the adhesiveness of a resin BM film|membrane is so high that ΔAl/Si value is small.

From the above, it was found that in Examples 1 to 3 in which the aqueous cleaning solution having a higher pH than in Comparative Example 1 was used, the ΔAl/Si value could be lowered to 0.25 or less, thereby improving the adhesion of the resin BM film. .

Industrial Applicability

ADVANTAGE OF THE INVENTION According to the glass substrate of this invention, the adhesiveness of the resin BM film|membrane formed in the surface is favorable, and peeling of a resin BM film|membrane is prevented. Therefore, the glass substrate of this invention can be effectively applied to the glass substrate used for FPD like LCD.

Moreover, according to the manufacturing method of the glass substrate of this invention, a glass substrate suitable as a glass substrate for FPD can be obtained efficiently in this way.

1: convey roll
2: cleaning room
3: Glass substrate
4: cleaning nozzle
5: water-based cleaning solution
6: Rotating brush

Claims (8)

It is a glass substrate which consists of silicate glass containing aluminum obtained by the float method,
And a silicate glass containing the Al, SiO alumino borosilicate glass having _{2, Al 2 O 3, B} 2 O 3, and a composition containing an oxide of an alkaline earth metal, the content of alkali metal oxide in the glass composition in total 0% by mass to 1% by mass or less,
From the value of the ratio of the atomic concentration of aluminum and the atomic concentration of silicon in the inside of the glass substrate measured by X-ray photoelectron spectroscopy, the atomic concentration of aluminum and the atomic concentration of silicon on the surface of the glass substrate A value obtained by subtracting the value of the ratio (ΔAl/Si value) is 0.25 or less. The method of claim 1,
The ΔAl/Si value is 0.19 or less, a glass substrate. 3. The method according to claim 1 or 2,
The glass substrate whose arithmetic mean surface roughness of the surface of the said glass substrate is 0.2 nm or less. 3. The method according to claim 1 or 2,
The said glass substrate is a glass substrate whose content of the alkali metal oxide in a glass composition is 0 mass % - 0.1 mass % or less in total. It is the method of manufacturing the glass substrate of Claim 1 or 2,
A glass substrate polished with an abrasive containing an abrasive is washed with an aqueous cleaning liquid having a pH greater than 2.7. 6. The method of claim 5,
The manufacturing method of the glass substrate whose said abrasive grain is a cerium oxide particle. A black matrix film|membrane is formed on the glass substrate of Claim 1 or 2, The black-matrix board|substrate characterized by the above-mentioned. A black matrix film|membrane is formed on the glass substrate of Claim 4, The black-matrix board|substrate characterized by the above-mentioned.

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