JP2014215422A - Glass sheet for display and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass sheet which suppresses exfoliation of a pattern made of resin formed on a glass surface, and a method for producing the same.SOLUTION: A glass sheet is formed by drawing tabular fusion glass. A surface roughening process is applied to a main surface of the glass sheet in which a pattern made of resin is formed. The average of roughness height (Ra) of the main surface is 0.2 nm or more, and the maximum valley depth (Rv) is 2 nm or more.

Description

  The present invention relates to a glass sheet for display and a method for producing the same.

  In the liquid crystal display, a TFT (Thin Film Transistor) that controls the amount of transmitted light, a liquid crystal, and a color filter are used as components. A manufacturing method of a color filter panel used for a color filter type display represented by a liquid crystal display usually forms a black matrix on the surface of a glass sheet, followed by red, green, blue, yellow and white. In addition, a method of sequentially forming different hues with a color pattern such as a stripe shape or a mosaic shape is used.

  As the display becomes higher in definition, the line width and pitch of the black matrix arranged on the surface of the glass sheet are reduced. For example, in order to achieve a high contrast of the display, the aperture ratio is improved by increasing the fineness and definition of the black matrix (specifically, the line width of less than 20 μm) and the high dimensional accuracy of the black matrix. There is a need for improved light shielding. As the number of display pixels increases, the pattern size varies depending on the use of the color filter and each color. For example, red, green, and blue pixels are changed from 200 to 300 μm to 100 μm, and the black matrix is 10 μm. Fine wire technology has been developed from 5 μm to 5 μm.

  The color filter manufacturing method includes an electrodeposition method, a dyeing method, a printing method, and a pigment dispersion method. Recently, the pigment dispersion method has become the mainstream. The pigment dispersion method is a method in which a color resist in which a pigment is dispersed in a photosensitive resin applied to a sheet or a color paste in which a pigment is dispersed in a non-photosensitive resin is patterned using a photolithographic processing method. Therefore, the manufacturing process can be simplified, and the obtained colored pixel has an advantage that it is excellent in light resistance and heat resistance and can form a highly accurate pixel. Further, a black matrix material made of resin containing a pigment (hereinafter also referred to as BM material) is considered to have low adhesion, and a silane coupling agent or the like is added to improve adhesion.

JP 2011-053710 A Japanese Patent Laid-Open No. 2000-212485

  However, the adhesion between the surface of the glass sheet and the pattern varies depending on the surface state of the glass sheet. For example, a resin black matrix that has been thinned to a thickness of 10 μm or less, particularly 5 μm or less, is easily affected by the surface condition of the glass sheet, and even if the same BM material is used due to the difference in the surface condition. As a result, there is a problem that the black matrix is easily peeled off.

  Therefore, the present invention provides a glass sheet that suppresses the peeling of a resin pattern formed on the glass surface and a method for producing the same.

  The glass sheet of the present invention is a glass sheet formed by stretching a plate-shaped molten glass, and the main surface of the glass sheet on which a resin pattern is formed is subjected to a roughening treatment, and the main surface The average roughness (Ra) is 0.2 nm or more, and the maximum valley depth (Rv) is 2 nm or more.

  The surface of the glass sheet has a distance (height / depth) from the reference line of 15 nm or less and a cut-off value of 1.0 in a measurement condition with a cut-off value of 0.8 to 10.0 mm in the surface measurement by Surfcom. It is preferable that the distance (height / depth) from the reference line is 45 nm or less under the measurement condition of ˜25.0 mm.

  The maximum valley depth (Rv) on the surface of the glass sheet opposite to the main surface is preferably smaller than the maximum valley depth (Rv) of the main surface.

  It is preferable that the glass sheet surface has a scratch having a length of at least 5 μm formed by the roughening treatment.

  In addition, the method for producing a glass sheet of the present invention includes a molding step of stretching a plate-shaped molten glass to form a glass sheet, and a roughening treatment on the main surface of the glass sheet, whereby the surface of the glass sheet is formed. And a roughening step in which the average roughness (Ra) of the surface is 0.2 nm or more and the maximum valley depth (Rv) is 2 nm or more.

  In addition, the method for producing a glass sheet according to the present invention comprises a molding step of forming molten glass into a glass sheet by an overflow downdraw method, and the main surface of the glass sheet is roughened so that the adhesion of the resin pattern is improved. And a roughening step.

  In the roughening step, surface treatment is preferably performed so that scratches are formed.

  ADVANTAGE OF THE INVENTION According to this invention, the glass sheet which suppresses peeling of the resin-made patterns formed on the glass surface, and its manufacturing method are provided.

It is a flowchart of the manufacturing method of the sheet glass which concerns on this embodiment. It is a schematic diagram which shows the manufacturing apparatus 1 of the sheet glass used with the manufacturing method of the sheet glass which concerns on this embodiment. It is a figure which shows the flow of the evaluation process of this embodiment. It is a figure which shows typically the photomask of this embodiment. It is a figure which shows typically the mask pattern of this embodiment. It is a figure for demonstrating the evaluation method of the resist pattern of this embodiment. 3 is an AFM image of the main surface of the glass sheet of Example 1. 6 is an AFM image of the main surface of the glass sheet of Example 2. It is an AFM image of the main surface of the glass sheet of a comparative example.

  Hereinafter, with reference to drawings, the manufacturing method of the glass sheet of this embodiment is demonstrated. In the manufacturing method of the sheet glass which concerns on this embodiment, sheet glass is manufactured using the down draw method.

[Outline of manufacturing method of sheet glass]
First, with reference to FIG. 1 and FIG. 2, the manufacturing method 1 of the sheet glass used for the some process included in the manufacturing method of a sheet glass and a several process is demonstrated. As shown in FIG. 1, the sheet glass manufacturing method mainly includes a melting step S1, a refining step S2, a forming step S3, a cooling step S4, a cutting step S5, and a roughening step S6.

The melting step S1 is a step in which the glass raw material is melted. After the glass raw material is prepared so as to have a desired composition, as shown in FIG. 2, the glass raw material is put into a melting apparatus 2 arranged upstream. Glass raw materials, for _{example, SiO 2, Al 2 O 3} , B 2 O 3, CaO, SrO, a composition of BaO or the like. Specifically, a glass material having a strain point of 660 ° C. or higher is used. The glass raw material is melted by the melting device 2 to become molten glass. The melting temperature is adjusted according to the type of glass. In this embodiment, the glass raw material is melted at 1500 to 1650 ° C. The molten glass is sent to the refining device 4 through the upstream pipe 3.

  The clarification step S2 is a step of removing bubbles in the molten glass. The molten glass from which bubbles have been removed in the refining device 4 is then sent to the forming device 6 through the downstream pipe 5.

  The forming step S3 is a step of forming the molten glass into a sheet-like glass (sheet glass). In this embodiment, an overflow downdraw method is used.

  The cooling step S4 is a step of cooling (slow cooling) the sheet glass. The sheet glass is cooled to a temperature close to room temperature through the cooling step S4. Note that the thickness (plate thickness) of the sheet glass, the amount of warpage of the sheet glass, and the amount of distortion of the sheet glass are determined according to the cooling state from the forming step S3 to the cooling step S4. The surface of the sheet glass may have low adhesion of a resin pattern such as a black matrix material.

[Roughening process]
In the roughening step S5, in order to suppress peeling when the resin pattern is formed by the roughening device 8, the rough surface of the main surface of the glass sheet is improved so that the adhesion of the resin pattern is improved. Make the surface. Here, the main surface of the glass sheet refers to a surface (part) on which a resin pattern is formed among the surfaces of the glass sheet, and is a surface serving as a product region. Moreover, the adhesiveness of a resin pattern is performed with the below-mentioned evaluation method. The phrase “so that the adhesiveness of the resin pattern is improved” means that the adhesiveness of the resin pattern by the evaluation method after the roughening step is higher than that before the roughening step.

  Examples of the roughening means include a method using physical means such as a sand blasting method, a liquid forming method, and a method of rubbing with a pad, and a method using chemical means for chemically corroding the glass surface. In the roughening step of the present invention, it is preferable to provide an anchor effect by forming a valley having a certain depth rather than increasing the surface area by roughening the surface. For this reason, the roughening means is preferably carried out by physical means, for example, by rubbing the surface of the sheet glass with a resin such as hard urethane to which a filler is added.

  The resin pattern is formed by exposing and developing a desired wiring pattern, but the developer used for development enters the interface between the glass and the resin pattern, and the resin pattern is peeled off. It may be easy to make it. In the roughening by the roughening step in the present invention, in addition to the anchor effect, an effect of suppressing the wraparound of the developer is also obtained. That is, by suppressing the developer from entering the interface between the glass and the resin pattern, it is possible to suppress a decrease in the ground contact surface between the glass and the resin pattern, thereby suppressing peeling.

  Examples of the filler include zirconia, ceria, and diamond. Among these, ceria is preferable. Ceria can roughen the sheet glass surface suitably by acting chemically on glass components such as silica. The loose abrasive may or may not be used. In the present embodiment, a hard urethane pad with internal ceria is used to roughen the main surface of the glass sheet by rubbing without using loose abrasive grains.

  In the roughening step S5, the surface treatment is preferably performed so that scratches are formed. The scratches may be observed in the AFM measurement at an arbitrary position in the product region of the glass sheet. Scratches appear as lines in the AFM image and can be easily observed and discriminated. The scratches preferably have a length of at least 5 μm.

  In the roughening step S5, the main surface of the sheet glass is subjected to a roughening treatment so that the average roughness (Ra) of the main surface is 0.2 nm or more and the maximum valley depth (Rv) is 2 nm or more. To do. By roughening the main surface of the sheet glass so as to have such a roughness, a resin pattern (for example, 10 μm or less, particularly 5 μm or less, formed on the glass surface). For example, peeling of the black matrix) is suppressed. The average roughness (Ra) of the main surface is less than 0.1 μm, specifically 0.2 nm or more and 10 nm or less, and further 0.2 to 1.0 nm, particularly 0.25 to 0.25 nm. It can be 0.5 nm.

  The roughening step may be performed on the glass plate after cutting the sheet glass. The sheet glass that has reached a temperature close to room temperature may be cut into a predetermined size by a cutting device to produce a glass plate. When cutting the sheet glass, a scribe line is formed on the sheet glass, and tensile stress is concentrated on the scribe line to cleave the sheet glass. The scribe line is generally formed by a method of mechanically forming using a diamond cutter or a method of causing an initial crack to proceed by heating and rapid cooling using a laser. When the scribe line is formed mechanically, fine cracks inevitably exist around the scribe line. When a scribe line is formed using a laser, a very sharp edge is formed at the corner between the end surface and the front and back surfaces of the divided glass plate PG. These edges are ground in a chamfering machine by using a diamond wheel for grinding on the short side end face of the rectangular glass plate PG so that the cross-sectional shape of the end face is curved, convex, arcuate or R-shaped. Is done.

  The arithmetic average roughness Ra of the end face of the glass plate is ground to be, for example, about 0.1 μm to 0.2 μm. However, a layer containing microcracks called microcracks or hair cracks is formed on the end face of the ground glass plate. This layer is called a work-affected layer or a fragile fracture layer, and exists in a thickness of about 1 μm to 3 μm, for example. The presence of such a layer reduces the breaking strength at the end face of the glass plate. In order to remove such a layer and improve the breaking strength at the end face of the glass plate, the end face of the glass plate is polished. You may perform the said roughening process on the glass plate after end surface grinding | polishing.

Surface measurement with surfcom In surface measurement with surfcom, after measuring the shape of the glass plate surface with a stylus type surface roughness meter, for example, surfcom made by Tokyo Seimitsu, the cut-off value 0.8 to 10.0mm built in the device, and cut By passing through a high-pass filter with an off value of 1.0 to 25.0 mm, only the minute irregularities on the surface are extracted, and the amplitude value of the minute irregularities is used as an index of the flatness of the glass plate surface. At this time, a characteristic indicating the relationship between the wavelength of the high-pass filter and the amplitude transmissibility is defined in JIS B0651. The amplitude value is a distance (height or depth) from the reference line. For the reference line, the flatness was measured using a line connecting the measurement start point and the measurement end point as a reference line. The measurement distance can be 150 mm to 250 mm. The measurement distance may be changed depending on the length of the striae. In this embodiment, the measurement was performed at 200 mm (measurement length was 200 mm) from the measurement start point to the measurement end point.

  The surface of the glass sheet has a distance (height or depth) from a reference line of 15 nm or less in a measurement condition of a cut-off value of 0.8 to 10.0 mm and a cut-off value of 1. It is preferable that the distance (height or depth) from the reference line in the measurement condition of 0 to 25.0 mm is 45 nm or less. Since the short cycle striae (unevenness) and the long cycle striae (unevenness) are small, the variation in the adhesion of the resin pattern can be further reduced.

Evaluation Method of Resin Pattern The formation state of the resin pattern on the glass sheet can be evaluated by the method described in Japanese Patent Application No. 2013-32451. That is, as shown in FIG. 3, with respect to the glass sheet, a sample preparation step B1 for cutting the sample glass by cutting into a predetermined size for evaluation, and a coating step B2 for coating the evaluation resist agent on the sample glass And a pre-baking step B3 for heating the sample glass coated with the evaluation resist, a pattern preparation step B4 for exposure using an ultraviolet exposure device and development with an alkaline aqueous solution, and a pattern formed on the sample glass. An evaluation step B5 is performed.

  In the resist coating process B2 for evaluation, when the photosensitive resin composition is applied to the sample glass in a liquid composition state, in addition to a known solution dipping method and spray method, a roller coater machine, a land coater machine, Any method such as a method using a spinner machine can be adopted. After applying to a desired thickness by these methods, the solvent is removed by pre-baking step B3, and a resist material is formed on the sample glass. Pre-baking is performed by heating with an oven, a hot plate, a thermal vacuum dryer or the like, or by heating under reduced pressure. The heating temperature and heating time in the pre-baking step B3 are appropriately selected according to the solvent to be used, and are performed, for example, at a temperature of 50 to 120 ° C. for 1 to 10 minutes.

In the pattern manufacturing process, a photomask 31 on which a pattern as shown in FIG. 4 is formed is used. Specifically, the photomask 31 includes a first mask pattern 32 formed by a plurality of lines having different line widths, and a second mask pattern 33 formed by two lines orthogonal to each other.
The photomask 31 is placed on the sample glass, and the BM material as a resin pattern is exposed. In the exposure, radiation having a wavelength in the range of 250 to 450 nm is preferable, but visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like may be used. Examples of the developer include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, or the like.

  The mask pattern and evaluation method in this embodiment will be described with reference to FIGS. The first mask pattern 32 shown in FIG. 5A is composed of five line patterns having different line widths. The line pattern 321 is 1 μm wide, the line pattern 322 is 3 μm wide, and is 5 μm wide. The line pattern 323 is formed of a line pattern 324 having a width of 10 μm and a line pattern 325 having a width of 20 μm. Further, the second mask pattern shown in FIG. 5B is formed in a cross shape in which lines formed with a width of 30 μm are orthogonal to each other. As shown in FIG. 4, two second mask patterns having different line widths may be formed on the photomask 31. The plurality of lines forming the mask pattern 32 of the first photomask have a line width of 1 μm or more and 30 μm or less, and the bending point forming the second mask pattern is an intersection formed by at least two lines. preferable.

The resist film formed on the sample glass is exposed and developed, whereby a resist pattern is formed on the sample glass.
FIG. 6 shows a state in which a part of the developed resist is peeled off and remains. The resist pattern 521 corresponds to the line pattern 321. On the sample glass, a pattern having a width of 1 μm does not remain and a resist pattern having a width of 3 μm and a width of 5 μm remains without being chipped or thinned. The adhesiveness can be evaluated by observing the residualness of these resist lines.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Examples 1 and 2
The glass sheet of Example 1, 2 was manufactured using the said glass sheet manufacturing apparatus 1 and the manufacturing method of a glass sheet. In Examples 1 and 2, roughening was performed using POLYPAS FX7L and FX7M (Fujibo Ehime Co., Ltd.), respectively.

Comparative Example A glass sheet was produced in the same manner as in Example except that the surface was not roughened.

<AFM image>
3 to 5 show AFM images (5 μm square) of the surfaces of the glass sheets of Examples 1 and 2 and Comparative Example. In the glass sheets of Examples 1 and 2, scratches (scratches) having a length of 5 μm or more crossing the 5 μm square AFM image could be easily observed and distinguished. In the glass sheet of the comparative example, scratches (scratches) could not be observed.

<Surface roughness Ra (nm)>
The surface roughness Ra (nm) of the glass sheets of Examples 1 and 2 and the comparative example was measured. The results are shown in Table 1. The average roughness (Ra) of the surface of the glass sheets of Examples 1 and 2 was 0.2 nm or more.

<Scratch depth index (nm)>
The depth of the valley side when measured by Rpv of the glass sheets of Examples 1 and 2 and the comparative example was measured. The results are shown in Table 1 as a scratch depth index. The maximum valley depth (Rv) on the surface of the glass sheets of Examples 1 and 2 was 2 nm or more.

<Surface measurement by Surfcom>
In the surface measurement by Surfcom, the glass sheet surfaces of Examples 1 and 2 and Comparative Example have a height (depth) from the reference line of 15 nm or less from the measurement conditions with a cutoff value of 0.8 to 10.0 mm. And the height (depth) from the reference line in the measurement conditions with a cut-off value of 1.0 to 25.0 mm was 45 nm or less.

<Evaluation of adhesion of resin pattern>
When the adhesiveness of the resin pattern was evaluated by the above evaluation method, in the sheet glass of Examples 1 and 2, the resist pattern (resin pattern) having a width of 3 μm and a width of 5 μm on the sample glass causes chipping and thinning. It remained without any problems and good adhesion was obtained.

  According to the present invention, the main surface of the glass sheet on which the resin pattern is formed is roughened, the main surface has an average roughness (Ra) of 0.2 nm or more, and the maximum valley depth. Since (Rv) is 2 nm or more and has an anchor effect, adhesion is improved. Specifically, the adhesiveness is improved by the BM material entering the formed trough to produce an anchor effect. Further, by suppressing the intrusion of the developer into the interface between the glass and the resin pattern, the reduction of the ground contact surface between the glass and the resin pattern is suppressed, and the peeling of the developer is suppressed by suppressing the wraparound of the developer.

Claims (7)

  A glass sheet formed by stretching a plate-shaped molten glass, wherein the main surface of the glass sheet on which a resin pattern is formed is subjected to a roughening treatment, and the average roughness (Ra) of the main surface Is 0.2 nm or more, and the maximum valley depth (Rv) is 2 nm or more. In the surface measurement by the surfcom, the main surface,
The height (depth) from the reference line is 15 nm or less under the measurement conditions with a cutoff value of 0.8 to 10.0 mm, and
The height (depth) from the reference line is 45 nm or less under the measurement conditions of a cut-off value of 1.0 to 25.0 mm.
The glass sheet according to claim 1.   The glass sheet according to claim 1 or 2, wherein a maximum valley depth (Rv) on a surface of the glass sheet opposite to the main surface is smaller than a maximum valley depth (Rv) of the main surface.   4. The glass sheet according to claim 1, wherein the glass sheet has a scratch having a length of at least 5 μm or more formed by the roughening treatment in a surface of the glass sheet. 5. A molding step of stretching a plate-shaped molten glass to form a glass sheet;
By roughening the main surface of the glass sheet, the surface has an average roughness (Ra) of 0.2 nm or more and a maximum valley depth (Rv) of 2 nm or more. Surface treatment process;
A method for producing a glass sheet, comprising: A molding process for molding molten glass into a glass sheet by an overflow downdraw method;
The manufacturing method of the glass sheet characterized by having the roughening process of roughening the main surface of the said glass sheet so that the adhesiveness of resin-made patterns may improve. The said roughening process is a manufacturing method of the glass sheet of Claim 6 which surface-treats so that a scratch may be formed.