JP6067531B2 - Manufacturing method of coated glass plate with mark - Google Patents

Description

  The present invention relates to a marked coated glass plate and a method for producing the same.

  For example, for glass plates such as glass for vehicles, marks such as vehicle / glass manufacturer names, product numbers, and JIS marks are formed on the glass surface in the manufacturing process as necessary. One method for forming marks on the glass surface is screen printing. For example, Patent Document 1 describes a method of forming a black ceramic layer as a shielding layer by screen printing on the periphery of an automobile window glass and simultaneously forming a ceramic layer to be a mark by screen printing in a predetermined region.

  Moreover, it is common that a glass plate is provided with various coating films on the surface according to the use. Examples of the coating film provided on the surface of the glass plate include a water-repellent film (Patent Document 2), an infrared cut film (Patent Document 3), an ultraviolet cut film (Patent Documents 4 and 5), an antifogging film (Patent Document 6), and the like. There is.

JP 2004-058301 A International Publication No. 99/63022 International Publication No. 2005/095298 JP 2012-168540 A International Publication No. 2012/107968 International Publication 2012/073685

  The present inventors have found that when a coating film is provided on a glass plate having a mark formed by printing (when a coating glass plate with a mark is provided), the perspective distortion is increased around the mark.

  Then, an object of this invention is to provide the coating glass plate with a mark by which the perspective distortion in the mark periphery was improved.

  As a result of intensive studies, the present inventors have found that when a coating film is provided on a glass plate having a mark formed by printing, the perspective distortion around the mark becomes strong due to the following causes. The mark formed by printing protrudes from the glass surface (swells from the glass surface). When a coating film having a thickness of a specific thickness or more is formed on the surface of such a marked glass plate, particularly by a flow coating method, the flow of the coating liquid becomes uneven due to the protruding marks. The resulting coating film has uneven thickness. Perspective distortion becomes strong due to such uneven thickness.

Therefore, the marked coated glass plate of the present invention is
A glass plate having a first main surface and a second main surface facing each other;
A first coating film provided on the first main surface of the glass plate;
A mark formed by a thin film made of an opaque material provided on the second main surface of the glass plate;
Including, and
As an optional configuration, further comprising a second coating film provided on a surface constituted by the second main surface of the glass plate and the surface of the mark,
The first coating film has an outer surface having a thickness of 1.5 μm or more and a surface roughness Ra of 1 μm or less,
The mark has a thickness of 5 to 50 μm,
The second coating film has a thickness of 0.3 μm or less.
However, the surface roughness Ra is an arithmetic average roughness obtained in accordance with JIS B 0601 (2001).

The manufacturing method of the marked coated glass plate of the present invention is a method of manufacturing the marked coated glass plate of the present invention,
(I) preparing the glass plate having the first main surface and the second main surface facing each other, and forming the mark on the second main surface of the glass plate;
(Ii) forming the first coating film on the first main surface;
including.

  In the coated glass plate with a mark of the present invention, the coating film (second coating film) is not provided on the second main surface side where the mark formed by the thin film is provided, or the thickness is provided even when it is provided. Is thinly limited. Further, the coating film necessary for improving the function is provided on the first main surface opposite to the second main surface on which the mark is provided. With such a configuration, the necessary coating film is applied to the glass plate without causing the problem of uneven thickness of the coating film, which is caused by the mark protruding from the glass surface (second main surface). it can. Therefore, according to the present invention, it is possible to provide a marked coated glass plate with improved perspective distortion around the mark.

It is sectional drawing which shows one Embodiment of the coating glass plate with a mark concerning this invention. It is sectional drawing which shows another embodiment of the coating glass plate with a mark concerning this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

(Embodiment 1)
In FIG. 1, sectional drawing of the coating glass plate 1 with a mark of Embodiment 1 is shown. The coating glass plate 1 includes a glass plate 11 and a coating film (first coating film) 12.

  The glass plate 11 has the 1st main surface 11a and the 2nd main surface 11b which mutually oppose. A coating film (first coating film) 12 is disposed on the first main surface 11a. A mark 13 is provided on the second main surface 11b. The mark 13 is formed of a thin film made of an opaque material. In addition, the mark is not provided in the 1st main surface 11a. The coating film is not provided on the surface (the second main surface 11b with the mark 13) configured by the second main surface 11b and the surface of the mark 13. That is, the second main surface 11b with the mark 13 is exposed.

  As described above, the coating glass plate 1 is not provided with the coating film on the second main surface 11 b with the mark 13. Therefore, since the coating film thickness unevenness does not occur around the mark 13, no perspective distortion occurs around the mark 13. Thereby, the coating glass plate 1 can implement | achieve the outstanding transparency with few distortions compared with the coating glass plate with the conventional mark.

  The glass plate 11 is not particularly limited, and is a plate glass usually used for automobiles, buildings, industrial glasses, and the like, a float plate glass by a so-called float method, a template glass by a roll-out method, and the like. Glass plate 11 includes clear glass, various colored glass such as green and bronze, various functional glass, tempered glass and similar glass, laminated glass such as laminated glass, and various flat glass products such as flat plate or bent plate glass. Can be used as Moreover, the thickness of the glass plate 11 is about 1 mm-12 mm, for example, and 3 mm-10 mm are preferable especially for construction, and 1.3 mm-5 mm are preferable for motor vehicles.

The composition of the glass plate 11 is not particularly limited. For example, a soda-lime silicate glass plate having a composition in which the concentration of Fe ₂ O ₃ is increased and other ultraviolet absorbing components such as TiO ₂ and CeO ₂ are added as necessary can be used as the glass plate 11.

The glass plate 11 has a glass composition containing Fe ₂ O ₃ of 0.2% by mass or more, preferably 0.5% by mass or more, and has a light transmittance at a wavelength of 380 nm of 70% or less, preferably 50%. A soda-lime silicate glass plate having a light transmittance at a wavelength of 550 nm of 75% or more or a visible light transmittance (YA) of 70% or more is preferable. However, Fe ₂ content of O ₃ is 0.1 wt% or less, preferably it is also possible to use a soda lime silicate glass plate is 0.02% to 0.06%. In the above, the Fe ₂ O ₃ concentration is a numerical value calculated by converting total iron oxide contained in the glass plate (iron oxide exists in the glass as FeO) into Fe ₂ O ₃ .

  However, the glass plate 11 is not limited to the above, and may have a low light transmittance in the visible region. Examples of such a glass plate include a glass plate having a light transmittance of 20 to 60% at a wavelength of 550 nm, which is manufactured for a vehicle window glass.

  As described above, the mark 13 is formed of a thin film made of an opaque material. The thickness of the mark 13, that is, the thickness of the thin film forming the mark 13 is 5 to 50 μm. When the thickness of the mark 13 is less than 5 μm, the mark 13 is faint and visibility is deteriorated. When the thickness of the mark 13 exceeds 50 μm, the mark 13 is blurred or the adjacent marks 13 are partially connected to each other, so that the mark 13 has a defect.

  The type of the coating film 12 is not particularly limited because it can be appropriately selected according to the function required for the coating glass plate 1. However, the coating film 12 is required to have a thickness of 1.5 μm or more and an outer surface having a surface roughness Ra of 1 μm or less. In addition, surface roughness Ra is arithmetic mean roughness calculated | required based on JISB0601 (2001).

  A sufficient function can be imparted to the coated glass plate 1 by setting the thickness of the coating film 12 to 1.5 μm or more, preferably 1.7 μm or more, and more preferably 2 μm or more. If the coating film 12 is too thick, the transmittance of the film may be lowered and the transparency of the coating glass plate 1 may be impaired. In addition, if the coating film 12 is too thick, cracks are generated along with the evaporation of the liquid component contained in the film forming solution (coating liquid) when the coating film 12 is formed. As a result, a time difference occurs in the thickness direction of the film with respect to the evaporation of the liquid component (the surface of the film is dried before the inside of the film), and as a result, the difference in the degree of drying in the film results in the film. Problems such as a decrease in strength of the film due to the generation of stress may occur. Further, when the coating film 12 is lower in hardness than the glass plate 11, there is a problem that the coating glass plate 1 is easily damaged when the coating film 12 becomes too thick. Therefore, the thickness of the coating film 12 is desirably 10 μm or less, and more desirably 5 μm or less.

  By making the outer surface of the coating film 12 a smooth surface with a surface roughness Ra of 1 μm or less, it is possible to maintain good transparency of the coated glass plate 1.

  Since the coating film 12 is provided on the surface of the glass plate 11 opposite to the surface on which the mark 13 is formed, the refractive index of the coating film 12 and the glass plate 11 are secured in order to ensure the visibility of the mark 13. There is no need to increase the difference from the refractive index of. That is, according to the configuration of the present embodiment, it is possible to reduce the difference (refractive index difference) between the refractive index of the coating film 12 and the refractive index of the glass plate 11, for example, with a wavelength of 589 nm (sodium D line). The refractive index difference of light can also be made 0.02 or less.

  The coating film 12 may contain silica and a functional material. By including silica, the coating film 12 can hold the functional material more firmly in the film, and can effectively exhibit the function of the functional material. Furthermore, by including silica, it is possible to realize the coating film 12 that is more firmly bonded to the glass plate 11 and has excellent mechanical strength. The coating film 12 may be a film containing silica as a main component. Note that “silica is the main component” means that the silica content in the coating film 12 is 50 mass% or more.

  Examples of the functional material included in the coating film 12 include an ultraviolet cut agent, an infrared cut agent, and / or an antifogging functional material. Thereby, since the coating film 12 cuts ultraviolet rays, cuts infrared rays, and / or suppresses cloudiness due to condensation on the coating surface, the coated glass plate 1 can be suitably used as a window glass for buildings and vehicles. .

  The form of the functional material contained in the coating film 12 is not particularly limited, but fine particles are suitable as an example. When the functional material is contained in the coating film 12 in the form of fine particles, the functional material is not eluted from the coating film 12 even when used under high temperature and high humidity conditions for a long time, and the function is maintained. be able to.

  On the other hand, the coating film 12 may be a film mainly composed of an organic polymer as a functional material. Furthermore, the coating film 12 preferably contains silica in the form of fine particles. This silica is uniformly distributed in the film, thereby increasing the hardness of the coating film 12 and making the coating film 12 more difficult to be damaged.

  The fine particles contained in the coating film 12 desirably have an average particle size of 10 to 200 nm. By setting the average particle size of the fine particles within this range, the haze ratio of the coating film 12 is not significantly increased by the fine particles.

  In order to ensure high transparency of the coated glass plate 1, the haze ratio of the coating film 12 is desirably 4% or less.

  As described above, the coating film 12 is not particularly limited, and can be appropriately selected from known coating films having a function corresponding to the application of the coated glass plate 1. For example, an infrared cut film described in International Publication No. 2005/095298, an ultraviolet cut film described in Japanese Patent Application Laid-Open No. 2012-168540 and International Publication No. 2012/107968, and an International Publication No. 2012/073685 An antifogging film or the like that has been used can be used.

  In the coating glass plate 1 of the present embodiment, the example in which one coating film 12 is provided on the first main surface 11a has been described, but a plurality of coating films may be provided. For example, the coating glass plate 1 may further include another coating film (third coating film) formed on the coating film 12.

  Moreover, although the glass plate 11 demonstrated the example which is a flat plate in this embodiment, the glass plate 11 is the shape which curved so that the 1st main surface 11a might be a concave surface side and the 2nd main surface 11b might be a convex surface side, for example. It may be. Such a coated glass plate 1 can be used for, for example, a vehicle windshield, door glass, rear glass, and the like.

  When the coating glass plate 1 is a vehicle glass plate, it is desirable that the first main surface 11a be a glass plate positioned on the vehicle interior side and the second main surface 11b on which the mark is formed be positioned on the vehicle outer side.

  Next, the manufacturing method of the coating glass plate 1 is demonstrated.

The coated glass plate 1 is
(I) preparing a glass plate 11 having a first main surface 11a and a second main surface 11b facing each other, and forming a mark 13 on the second main surface 11b of the glass plate 11,
(Ii) forming a coating film 12 on the first major surface 11a;
It can manufacture by the method containing.

  The formation of the mark 13 in the step (i) can be performed by forming a thin film having a shape corresponding to the mark 13 to be formed on the second main surface 11b of the glass plate 11. For forming the thin film, for example, a screen printing method can be used. Opaque materials used in the formation of thin films include, for example, colored ceramic colors used in shielding layers formed on the periphery of automobile window glass, and conductive materials used in heating wire prints to remove fog on automobile window glass. Various commercial products suitable for printing on glass, such as paste, can be used.

  Colored ceramic colors for glass printing include, for example, colored pigments, glass frit for heat-bonding with glass plates to develop mechanical strength, organic binders that can be removed by firing, and viscosity suitable for screen printing. And an organic solvent such as pine oil. As the coloring pigment, a known pigment can be used. For example, in the case of a black pigment, at least one kind of chromium oxide, cobalt oxide, copper oxide, or a combination thereof, which exhibits concealability after firing and makes the appearance appear black, is included as the pigment. As the glass frit, a suitable one can be appropriately selected and used in consideration of a balance such as a firing temperature and a heat shrinkage rate. The glass frit includes, for example, crystallized glass such as bismuth borosilicate and zinc borosilicate and amorphous glass as an essential component, and optionally includes a transition metal including at least one oxide of vanadium, manganese, iron, and cobalt. Additives such as oxides and alumina can be included. The organic binder is not particularly limited as long as it is a material that can be removed by firing. Examples of materials that can be easily removed by thermal decomposition by firing include resins such as acrylic, methylcellulose, nitrocellulose, ethylcellulose, vinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyethylene oxide, and polyester, and these are used alone or Can be used as a mixture.

  In step (ii), for example, the coating film 12 can be formed by applying a coating liquid on the first main surface 11a of the glass plate 11 and drying and solidifying the formed coating film. Since the coating liquid is produced by dissolving the material constituting the coating film 12 in a solvent, it can be appropriately prepared according to the coating film 12 to be formed. Therefore, the components of the coating liquid are not particularly limited. Examples of the coating liquid application method include dip coating, flow coating, curtain coating, spin coating, spray coating, bar coating, roll coating, and brush coating. The coating liquid is applied to the surface of the glass plate 11 and the coating liquid is smoothed by the surface tension before the solvent is volatilized and dried to form a coating film having a uniform wet thickness. It is preferable to leave the membrane and the glass plate 11 as they are and dry them. Here, “standing still” means that the applied wet coating film has a uniform thickness using the surface tension of the coating liquid and is dried in that state. If it is about / min, it will be substantially left still even if it conveys a base material.

  It is desirable that step (ii) is performed after step (i). Thereby, it can prevent that the coating film 12 is accidentally damaged in the middle of process (i).

  Moreover, you may further include the process of softening the glass plate 11 and shape | molding between process (i) and process (ii). In order to soften the glass plate 11, it is necessary to heat the glass plate 11 to the softening point or higher (for example, 650 ° C. or higher). However, by performing a molding step before the step (ii), It is possible to use a functional material having poor heat resistance. That is, in the case where the glass plate 11 is softened and molded, the width of the functional material used for the coating film 12 can be increased by performing the process between the process (i) and the process (ii). it can. Further, this forming step can also serve as a step of subjecting the material for forming the mark 13 to a sufficiently high temperature heat treatment, and the durability of the mark 13 can be enhanced. Moreover, the process which softens the glass plate 11 and shape | molds may include the process which wind-cools strengthens the glass plate 11. FIG. Thereby, the glass plate 11 can be strengthened together with the molding.

(Embodiment 2)
In FIG. 2, sectional drawing of the coating glass plate 2 with a mark of Embodiment 2 is shown. The coating glass plate 2 is provided with a coating film (second coating film) 14 on the second main surface 11 b with the mark 13 of the glass plate 11. The coating glass plate 2 has the same configuration as the coating glass plate 1 of Embodiment 1 except that the coating film 14 is further provided. Therefore, only the coating film 14 will be described here.

  The coating film 14 has a thickness of 0.3 μm or less. By setting the thickness of the coating film 14 to 0.3 μm or less, even if the coating film is formed on the second main surface 11b with the mark 13, the thickness of the coating film 14 due to the bulge of the mark 13 from the glass surface. Unevenness is unlikely to occur. Therefore, the coated glass plate 2 of the present embodiment can also realize excellent transparency with little distortion, like the coated glass plate 1 of the first embodiment. In order to more reliably improve the perspective distortion, it is desirable that the thickness of the coating film 14 is 0.1 μm or less.

  As with the coating film 12, the type of the coating film 14 can be appropriately selected according to the function required of the coating glass plate 2, and is not particularly limited. The coating film 14 can also be implemented similarly to the coating film 12 described in the first embodiment, and can be appropriately selected from known coating films. The coating film 14 may be a film having the same function as the coating film 12, or may be a film having a different function such as a water repellent function.

  The method for manufacturing the coated glass plate 1 described in Embodiment 1 can be applied to the method for manufacturing the coated glass plate 2. However, in the manufacturing method of the coating glass plate 1, it is necessary to further implement the process of forming the coating film 14 on the 2nd main surface 11b after process (i).

  EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited to a following example, unless the summary of this invention is exceeded.

Example 1
In Example 1, the coated glass plate 1 shown in FIG. 1 was produced. A glass plate having a thickness of 3.1 mm, which is commercially available as a float plate glass for construction, was cleaved to a size of 100 mm × 100 mm with a wheel cutter, and a glass plate having a chamfered edge with abrasive sand having a particle size of # 100 was prepared. This glass plate was used as the glass plate 11. Next, a black ceramic color for glass printing was screen printed on one main surface (second main surface 11b) of the glass plate 11 using a screen (polyester screen: 355 mesh, coat thickness (thickness of the mark 13). A): 20 μm, tension: 20 Nm, squeegee hardness: 80 degrees, mounting angle: 75 °, printing speed: 300 mm / s). This black ceramic color for glass printing has a viscosity suitable for screen printing, black pigment, glass frit for heat fusion with a glass plate to express mechanical strength, an organic binder that can be removed by firing. And an organic solvent such as pine oil. The screen used in this example was made so that the letter “L” (a Gothic body with a character height of 5 mm and a line thickness of 250 μm) could be printed. After printing, drying for 10 minutes at 150 ° C. in a drying oven removes the organic solvent of the printed ceramic color, lowers the fluidity, and deformation due to flow of the printed pattern before firing Etc. were prevented. After drying, the glass plate 11 was tempered with air cooling. This air-cooling strengthening treatment was performed by holding the glass plate 11 in an electric furnace set at 700 ° C. for 180 seconds and heating it, and then rapidly cooling the heated glass plate 11 by blowing air at room temperature. The organic binder contained in the printed ceramic color is baked and removed by heating in this air-cooling strengthening treatment, and at the same time, the glass frit is melted and thermally fused to the glass plate, and “L” made of black pigment and glass frit. Was formed as a mark 13 having a thickness of 20 μm on the second main surface 11 b of the glass plate 11. The cooling rate in this rapid cooling was about 80 to 100 K per second in the temperature range of 650 to 550 ° C. Separately, the ultraviolet shielding film forming solution used in Example A1 described in paragraph [0086] of International Publication No. 2012/107968 was prepared as a coating solution. Using this coating liquid, flow coating is performed on the first main surface 11a of the glass plate 11 on which the mark 13 is not formed by the method described in paragraph [0087] of International Publication No. 2012/107968. A coating film 12 having a thickness of 2 μm was formed.

  About the obtained coating glass plate 1 of Example 1, the surface roughness Ra of the coating film 12 was measured using an atomic force microscope (“SPI3700”, manufactured by Seiko Instruments Inc.). The surface roughness Ra was less than 2 nm. Further, it was confirmed by visual observation that no see-through distortion occurred around the mark 13 of the coated glass plate 1 of Example 1.

(Example 2)
In Example 2, the coated glass plate 2 shown in FIG. 2 was produced. On the 2nd main surface 11b of the coating glass plate of Example 1, the coating film 14 was further formed so that the mark 13 might be covered, and the coating glass plate 2 of Example 2 was obtained. The water repellent coating solution of Example 1 described in WO99 / 63022 was prepared as a coating solution. Using this coating solution, the method for applying and drying the water-repellent coating solution of Example 1 described in International Publication No. 99/63022 on the second main surface 11b on which the mark 13 of the glass plate 11 is formed Thus, a coating film 14 having a thickness of 0.1 μm was formed. It was confirmed by visual observation that no see-through distortion occurred around the mark 13 of the coated glass plate 2 of Example 2.

(Comparative Example 1)
In Comparative Example 1, the same film as the coating film 12 formed on the first main surface 11a in Example 1 was formed so as to cover the mark 13 on the second main surface 11b instead of on the first main surface 11a. A coated glass plate was produced in the same manner as in Example 1 except for the above. In Comparative Example 1, when the coating solution for forming the ultraviolet shielding film was flow-coated, the flow of the solution became non-uniform due to the marks 13, and the formed coating film had thickness unevenness. When the obtained coated glass plate of Comparative Example 1 was visually confirmed, perspective distortion was confirmed around the mark 13.

  The coated glass plate of the present invention can be suitably used for various coated glass plates that are required to be marked, and can be suitably used for, for example, buildings and vehicle window glass.

1, 2 coating glass plate with mark 11 glass plate 11a first main surface 11b second main surface 13 mark 12 coating film (first coating film)
21 Coating film (second coating film)

Claims (5)

A manufacturing method of a coated glass plate with a mark,
The marked coated glass plate is
A glass plate having a first main surface and a second main surface facing each other;
A first coating film provided on the first main surface of the glass plate;
A mark formed by a thin film made of an opaque material provided on the second main surface of the glass plate;
A second coating film provided on a surface constituted by the second main surface of the glass plate and the surface of the mark;
Including
In the marked coated glass plate,
The first coating film has an outer surface having a thickness of 1.5 μm or more and a surface roughness Ra of 1 μm or less,
The mark has a thickness of 5 to 50 μm, and
The second coating film has a thickness of 0.3 μm or less,
The manufacturing method includes:
(I) preparing the glass plate having the first main surface and the second main surface facing each other, and forming the mark on the second main surface of the glass plate;
(Ii) forming the first coating film on the first main surface;
Including
Wherein step (i) later than the said second further comprising the step of forming the second coating layer on the main surface, a manufacturing method with mark coated glass plate.
However, the surface roughness Ra is an arithmetic average roughness obtained in accordance with JIS B 0601 (2001). The step (ii) is performed after the step (i).
The manufacturing method of the coated glass plate with a mark of Claim 1 . Between the step (i) and the step (ii),
Further comprising the step of softening and molding the glass plate,
The manufacturing method of the coated glass plate with a mark of Claim 2 . The manufacturing method of the coating glass plate with a mark of Claim 3 with which the process of softening the said glass plate includes the process which air-cooling strengthens the said glass plate. In the step (ii),
Applying a coating liquid on the first main surface of the glass plate, and drying and solidifying the formed coating film, thereby forming the first coating film;
The manufacturing method of the coating glass plate with a mark of any one of Claims 1-4 .

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