METHOD FOR MANUFACTURING COLOR COATED PLATE GLASS

Abstract

A method of producing a colored film-attached glass sheet includes a step of obtaining a colored film-forming coating solution by mixing the following components: (a) a reaction product obtained by reacting an amino group-containing silane compound with at least one boron compound selected from the group consisting of H.sub.3BO.sub.3 and B.sub.2O.sub.3; (b) a metal alkoxide and/or a metal alkoxide condensate; (c) a synthetic resin; (d) a triazine-based UV absorber; (e) a solvent substantially consisting of a non-aqueous solvent having an SP value of 8 to 11.5 (cal/cm.sup.3).sup.1/2; and (f) a pigment. The colored film-forming coating solution contains the UV absorber in an amount of 5 to 12% by mass relative to the total solids content and the pigment in an amount equal to 0.02 to 0.50 times the amount of the UV absorber by mass ratio.

Claims

1. A method of producing a colored film-attached glass sheet including a glass sheet and a colored film formed on at least one surface of the glass sheet, the method comprising: a step of obtaining a colored film-forming coating solution by mixing the following components: (a) a reaction product obtained by reacting an amino group-containing silane compound represented by R.sup.1.sub.4-nSi(OR.sup.2).sub.n [1] wherein R.sup.1 represents an organic group containing an amino group, R.sup.2 represents a methyl, ethyl, or propyl group, and n represents an integer selected from 1 to 3, with at least one boron compound selected from the group consisting of H.sub.3BO.sub.3 and B.sub.2O.sub.3; (b) a metal alkoxide and/or a metal alkoxide condensate; (c) a synthetic resin; (d) a triazine-based UV absorber having an SP value of 10 to 13.5 (cal/cm.sup.3).sup.1/2; (e) a solvent substantially consisting of a non-aqueous solvent having an SP value of 8 to 11.5 (cal/cm.sup.3).sup.1/2; and (f) a pigment; a coating step of coating a surface of the glass sheet with the colored film-forming coating solution to form a coating thereon; and a curing step of heating the glass sheet after the coating step to cure the coating to form the film, wherein the colored film-forming coating solution contains the UV absorber in an amount of 5 to 12% by mass relative to the total solids content and the pigment in an amount equal to 0.02 to 0.50 times the amount of the UV absorber by mass ratio, and the colored film has a thickness of 1.5 to 8 m.

2. The method of producing a colored film-attached glass sheet according to claim 1, wherein the reaction product is obtained by reacting the boron compound with the amino group-containing silane compound at a ratio of 0.02 to 0.8 mol of the boron compound to 1 mol of the amino group-containing silane compound.

3. The method of producing a colored film-attached glass sheet according to claim 1, wherein the reaction product is a reaction product obtained by reacting the amino group-containing silane compound with the boron compound, without hydrolysis by adding water.

4. The method of producing a colored film-attached glass sheet according to claim 1, wherein the metal alkoxide is tetramethoxysilane and/or tetraethoxysilane, and is added in an amount of 10 or less mol relative to 1 mol of the amino group-containing silane compound.

5. The method of producing a colored film-attached glass sheet according to claim 1, wherein the film-forming coating solution includes microparticles of a conductive material.

6. The method of producing a colored film-attached glass sheet according to claim 1, wherein the glass sheet has an absorbance per mm thickness of 0.10 or less at the maximum in a wavelength range of 380-780 nm.

7. The method of producing a colored film-attached glass sheet according to claim 2, wherein the reaction product is a reaction product obtained by reacting the amino group-containing silane compound with the boron compound, without hydrolysis by adding water.

Description

EXAMPLES

[0085] The following describes methods of evaluating the colored film-attached glass sheets obtained in examples and comparative examples of the present invention. The present invention is not limited to these examples.

[Presence or Absence of SiOB Bond in Film]

[0086] A portion of the film of the resulting colored film-attached glass sheet was scraped off, and the solid-state .sup.11B-NMR and the solid-state .sup.29Si-NMR of the piece were measured to determine the presence or absence of an SiOB bond in the film.

[Film Thickness]

[0087] The thickness of the film of the colored film-attached glass sheet was measured using Surf-corder ET-4000A available from Kosaka Laboratory Ltd.

[Appearance]

[0088] Cracking, coloring, and white cloudiness (non-uniform dispersion of the UV absorber in the film due to agglomeration or the like) of the film of the colored film-attached glass sheet were visually observed for appearance defects.

[Haze Value]

[0089] The haze value of the colored film-attached glass sheet was measured using a haze meter NDH 2000 available from Nippon Denshoku Industries Co., Ltd. When the haze value of the resulting colored film-attached glass sheet is less than 3.0%, the colored film-attached glass sheet has good transparency in practical use. A lower haze is considered to indicate higher transparency.

[UV Transmittance]

[0090] The UV transmittance TUV of the colored film-attached glass sheet was calculated in accordance with ISO 9050-1990 using a spectrophotometer U-4100 available from Hitachi, Ltd. The colored film-attached glass sheet having a TUV of less than 1% was regarded as acceptable.

[Color Difference]

[0091] The L*a*b* values of the colored film-attached glass sheet was determined in accordance with ISO 11664-4. The colored film-attached glass sheet was regarded as acceptable when its color difference E was less than 5 before and after each of a moisture resistance test, a heat resistance test, and a weather resistance test described below.

[Moisture Resistance Test]

[0092] In accordance with JIS R 3212, the colored film-attached glass sheet was stored in an environment at 50 C. with 95% RH for 500 hours, and the appearance and the color difference after the test were observed. When no appearance defects were found after the test and the color difference before and after the test was 5 or less, the colored film-attached glass sheet has good moisture resistance in practical use. A smaller color difference is considered to indicate higher moisture resistance.

[Heat Resistance Test]

[0093] The colored film-attached glass sheet was stored in an environment at 80 C. for 500 hours, and the appearance and the color difference after the test were observed. When no appearance defects are found after the test and the color difference before and after the test is 5 or less, the colored film-attached glass sheet has good heat resistance in practical use. A smaller color difference is considered to indicate higher heat resistance.

[Weather Resistance Test]

[0094] In accordance with JIS R 3212, a glass surface (uncoated side) of the colored film-attached glass was irradiated with light for 1000 hours at a black panel temperature of 83 C. using a sunshine weather meter SX80 available from Suga Test Instruments Co., Ltd., and the appearance and the color difference after the test were observed. When no appearance defects are found after the test and the color difference before and after the test is 5 or less, the colored film-attached glass sheet has good weather resistance in practical use. A smaller color difference is considered to indicate higher weather resistance.

[Wear Resistance Test]

[0095] In accordance with JIS R 3212, the colored film-attached glass sheet was placed on a rotating table with the coated side facing up, and an abrasive wheel (C180 OXF available from Daiwa Kasei Industry Co., Ltd.) with a load of 4.9 N was rotated 1000 times against the coated side. The haze value difference of the portion for the test before and after the test was calculated. When the haze value difference is less than 5%, the colored film-attached glass sheet has good wear resistance in practical use. A smaller color difference is considered to indicate higher wear resistance.

Example 1

[0096] Step of Obtaining a Colored Film-Forming Coating Solution

[0097] In a reaction vessel, 2.73 g of boric acid (H.sub.3BO.sub.3) powder as the component (b) was added to 16.30 g of a 3-aminopropyltriethoxysilane solution as the component (a) (the component (b) was added in an amount of 0.6 mol per mol of the component (a)), followed by stirring at 23 C. for 5 minutes. Subsequently, 29.15 g of tetramethoxysilane as the component (c) was added (the amount of the component (c) was 2.6 mol per mol of the component (a)), and 5.35 g of epoxy resin CY232 (Nagase ChemteX Corporation) as the component (d) was added (the amount of the component (d) was 18% by mass relative to the total solids content). Subsequently, the mixture was reacted at 60 C. for 120 hours. Thus, a viscous liquid was formed.

[0098] To this liquid was added 33.27 g of 2-heptanone (SP value: 8.5 (cal/cm.sup.3).sup.1/2) as a solvent, 8.79 g of 3-methoxy-3-methylbutanol (SP value: 10.5 (cal/cm.sup.3).sup.1/2) as a glycol ether, 2.61 g of triazine-based UV absorber TINUVIN 460 (SP value: 10.9 (cal/cm.sup.3).sup.1/2) (BASF) as a UV absorber, 0.52 g of a light stabilizer TINUVIN 292, and 1 g of a pigment dispersant (solid content concentration: 10%; phthalocyanine blue Pigment Blue 15:4 as a blue pigment; D.sub.50: 114 nm). Thus, a film-forming coating solution having a solid content concentration of 29% by mass was obtained.

[0099] The solvent in the coating solution has an SP value of 9.0 (cal/cm.sup.3).sup.1/2. The produced coating solution was colorless, and no white cloudiness due to agglomeration or the like was observed. The UV absorber (TINUVIN 460) and the phthalocyanine blue Pigment Blue 15:4 were uniformly dispersed in the coating solution. All the coating solutions produced in this example and other examples were colorless, and no white cloudiness due to agglomeration or the like was observed. The UV absorber and the phthalocyanine blue were uniformly dispersed in these coating solutions. In this example, the colored film-forming coating solution contained the UV absorber in an amount of 7.7% by mass relative to the total solids content and the pigment in an amount equal to 0.03 times the amount of the UV absorber by mass ratio.

Coating Step

[0100] An amount of 5 g of the coating solution was spin-coated to a float glass sheet (length: 10 cm; width: 10 cm; thickness: 3 mm; visible light transmittance in accordance with ISO 9050: 90.5%; solar transmittance in accordance with JIS R 3106: 86.0%; UV transmittance in accordance with ISO 9050: 59.6%; absorbance per mm thickness in a wavelength range of 380-780 nm: 0.013 or less; high-transmission glass sheet). The thickness of each film used in the examples and the comparative examples was adjusted by the rotation speed of the spin coating.

Leveling Step

[0101] The glass sheet coated with the coating solution was placed horizontally at room temperature for 10 minutes. Pre-heating step

[0102] After the leveling step, the glass sheet coated with the coating solution was heated in a hot air circulation furnace at 180 C. for 5 minutes.

Curing Step

[0103] After the pre-heating, the glass sheet coated with the coating solution was exposed to superheated steam at 180 C. for 10 minutes using a superheated steam generator available from Shinnetsu Co., Ltd. Thus, a colored film-attached glass sheet was obtained. The colored film had a thickness of 4.4 m. Table 1 shows the evaluation results of the colored film-attached glass sheet.

TABLE-US-00001 TABLE 1 Durability test of the colored film-attached glass sheet Evaluation of the resulting colored film-attached glass sheet Wear resistance Film Haze Moisture Heat Weather Difference thickness value TUV resistance resistance resistance in haze value [m] Appearance [%] [%] L* a* b* Appearance E Appearance E Appearance E [% ] Example 1 4.4 No defects 0.3 0.5 90.4 5.32 5.59 No defects 0.6 No defects 0.6 No defects 1.6 4.3 Example 2 4.3 No defects 0.3 0.5 90.6 5.8 6.05 No defects 0.5 No defects 0.8 No defects 1.8 4.2 Example 3 4.5 No defects 0.3 0.4 90.6 8.84 3.92 No defects 0.5 No defects 0.5 No defects 1.7 4.1 Example 4 4.3 No defects 0.4 0.4 94.9 12.9 26.3 No defects 0.6 No defects 1.0 No defects 1.4 4.0 Example 5 4.5 No defects 0.5 0.4 89.3 10.5 4.4 No defects 0.3 No defects 1.0 No defects 2.4 3.9 Example 6 4.8 No defects 0.2 0.4 86.6 2.3 1.44 No defects 0.3 No defects 1.0 No defects 0.8 4.0 Example 7 4.7 No defects 0.3 0.4 90.8 23.8 5.06 No defects 0.6 No defects 0.5 No defects 1.6 4.1 Comparative 4.5 No defects 0.5 0.1 89.1 6.62 5.47 No defects 9.1 4.0 Example 1 Comparative 4.5 No defects 0.5 0.6 89.8 12.4 5.93 No defects 5.5 4.2 Example 2

Example 2

[0104] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that the component (c) was tetraethoxysilane, and the colored film-forming coating solution contained the UV absorber in an amount of 7.7% by mass relative to the total solids content and the pigment in an amount equal to 0.03 times the amount of the UV absorber by mass ratio. The colored film obtained in this example had a thickness of 4.3 m. Table 1 shows the evaluation results of the colored film-attached glass sheet.

Example 3

[0105] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that the UV absorber was a triazine-based UV absorber TINUVIN 477 (SP value: 11.4 (cal/cm.sup.3).sup.1/2) available from BASF, and the colored film-forming coating solution contained the UV absorber in an amount of 7.7% by mass relative to the total solids content and the pigment in an amount equal to 0.03 times the amount of the UV absorber by mass ratio. The colored film obtained in this example had a thickness of 4.5 m. Table 1 shows the evaluation results of the colored film-attached glass sheet.

Example 4

[0106] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that a yellow pigment Pigment Yellow 150 (D.sub.50: 125 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 7.8% by mass relative to the total solids content and the pigment in an amount equal to 0.17 times the amount of the UV absorber by mass ratio. The colored film obtained in this example had a thickness of 4.3 m. Table 1 shows the evaluation results of the colored film-attached glass sheet.

Example 5

[0107] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that a red pigment

[0108] Pigment Red 202 (D.sub.50: 120 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 7.6% by mass relative to the total solids content and the pigment in an amount equal to 0.08 times the amount of the UV absorber by mass ratio. The colored film obtained in this example had a thickness of 4.5 m. Table 1 shows the evaluation results of the colored film-attached glass sheet.

Example 6

[0109] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that a black pigment Pigment Black 26 (D.sub.50: 65 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 7.6% by mass relative to the total solids content and the pigment in an amount equal to 0.13 times the amount of the UV absorber by mass ratio. The colored film obtained in this example had a thickness of 4.8 m. Table 1 shows the evaluation results of the colored film-attached glass sheet.

Example 7

[0110] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that a green pigment Pigment Green 36 (D.sub.50: 135 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 7.7% by mass relative to the total solids content and the pigment in an amount equal to 0.33 times the amount of the UV absorber by mass ratio. The colored film obtained in this example had a thickness of 4.7 m. Table 1 shows the evaluation results of the colored film-attached glass sheet.

Comparative Example 1

[0111] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that the UV absorber was a benzophenone-based UV absorber SEESORB 106 (SP value: 13.0 (cal/cm.sup.3).sup.1/2) available from Shipro Kasei Kaisha, Ltd., a red pigment Pigment Red 202 (D.sub.50: 120 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 8.2% by mass relative to the total solids content and the pigment in an amount equal to 0.07 times the amount of the UV absorber by mass ratio. The colored film obtained in this comparative example had a thickness of 4.5 m. The colored film-attached glass sheet showed a significant change, E=9.1, in the weather resistance test.

Comparative Example 2

[0112] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that the UV absorber was a benzotriazole-based UV absorber TINUVIN 109 (SP value: 11.1 (cal/cm.sup.3).sup.1/2) available from BASF, a red pigment Pigment Red 202 (D.sub.50: 120 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 9.3% by mass relative to the total solids content and the pigment in an amount equal to 0.06 times the amount of the UV absorber by mass ratio. The colored film obtained in this comparative example had a thickness of 4.5 m. The colored film-attached glass sheet showed a significant change, E=5.5, in the weather resistance test.

Comparative Example 3

[0113] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that a red pigment Pigment Red 202 (D.sub.50: 120 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 7.6% by mass relative to the total solids content and the pigment in an amount equal to 0.08 times the amount of the UV absorber by mass ratio. The colored film obtained in this comparative example had a thickness of 11 m. This colored film-attached glass sheet showed good coloration, but the film cracked in the weather resistance test.

Comparative Example 4

[0114] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that a yellow pigment Pigment Yellow 150 (D.sub.50: 125 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 7.4% by mass relative to the total solids content and the pigment in an amount equal to 0.55 times the amount of the UV absorber by mass ratio. The colored film obtained in this comparative example had a thickness of 1.3 m. The colored film-attached glass sheet showed a haze value difference of 5.5% before and after the wear resistance test, and the film had low wear resistance.

Comparative Example 5

[0115] A colored film-attached glass sheet was obtained by the same manner as in Example 1, except that a yellow pigment Pigment Yellow 150 (D.sub.50: 125 nm) was used. In this comparative example, the colored film-forming coating solution contained the UV absorber in an amount of 12.6% by mass relative to the total solids content and the pigment in an amount equal to 0.10 times the amount of the UV absorber by mass ratio. The colored film had a thickness of 5.6 m. In the resulting colored film-attached glass sheet, a solid was precipitated on the surface of the film in the moisture resistance test.

Comparative Example 6

[0116] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that the colored film-forming coating solution contained the UV absorber in an amount of 7.7% by mass relative to the total solids content and the same pigment as used in Example 1 in an amount equal to 0.01 times the amount of the UV absorber by mass ratio. The colored film obtained in this comparative example had a thickness of 5.2 m. The colored film-attached glass sheet had poor coloration.

Comparative Example 7

[0117] A colored film-attached glass sheet was obtained by the same method as in Example 1, except that a red pigment pigment Red 202 (D.sub.50: 120 nm) was used, and the colored film-forming coating solution contained the UV absorber in an amount of 7.6% by mass relative to the total solids content and the pigment in an amount equal to 0.57 times the amount of the UV absorber by mass ratio. The colored film obtained in this comparative example had a thickness of 5.3 m. The colored film-attached glass sheet had low transparency with an initial haze of 3.5%. The colored film-attached glass sheet showed a color difference AE of 6.8 before and after the weather resistance test. Thus, discoloration of the film was significant.