JP6959566B2 - Glass plate - Google Patents

Description

The present invention relates to a glass plate for producing a glass-resin composite by compositely integrating with a resin plate, and particularly to a glass plate used for a glass-resin composite suitable for windshields and door glasses of automobiles.

Generally, laminated glass in which a plurality of soda lime glass plates are compositely integrated with an organic resin intermediate layer is used for window glass of a vehicle or the like, and a plurality of soda lime glass plates are used for the purpose of weight reduction. A glass resin composite in which the resin plate and the resin plate are compositely integrated with an organic resin intermediate layer may be used (see Patent Documents 1 to 4).

The soda lime glass plate used for the window glass of vehicles, etc. has the function of attenuating the collision energy of the scattered pieces by deforming the tip shape of the scattered pieces such as stepping stones during running and increasing the impact resistance. Have.

However, it cannot be said that the soda lime glass plate has a sufficient effect of increasing the impact resistance of the scattered pieces. At present, the thickness of the soda lime glass plate is increased or the number of laminated sheets is increased to increase the impact resistance of the scattered pieces, but this has led to an increase in the thickness and weight of the window glass.

Therefore, in order to increase the impact resistance of the scattered pieces, it is considered to use a crystallized glass plate instead of the soda lime glass plate. _{For example, a crystal formed by precipitating a Li 2} O-Al ₂ O _{3 -SiO 2} system crystal such as a β-quartz solid solution (Li ₂ O · Al ₂ O ₃ · nSiO ₂ [however, n ≧ 2]) as a main crystal. A glass-ceramic plate is being considered.

Japanese Unexamined Patent Publication No. 2012-144217 Japanese Unexamined Patent Publication No. 2004-196184 Japanese Unexamined Patent Publication No. 2001-151539 Jikkenhei No. 1-8821

By the way, if the crystallinity of the crystallized glass is increased, the hardness of the crystallized glass is increased and the collision energy of the scattered pieces can be attenuated. It cannot be applied to the front glass of automobiles. Further, the collision energy of the scattered pieces can be attenuated by increasing the thickness of the crystallized glass, but in this case, the weight of the window glass may increase and the transparency may be impaired.

Therefore, the present invention has been made in view of the above circumstances, and its technical problem is that it is excellent in bending workability and can effectively attenuate the collision energy of scattered pieces even if the thickness and crystallinity are small. It is to create a glass plate.

The present inventors have found that the above technical problems can be solved by strictly regulating the glass composition range of the glass plate, and propose the present invention. That is, the glass plate of the present invention is to composite integrated with the resin plate, a glass plate for making glass resin composite, as a glass composition, in _{mol%, SiO 2 45~80%, Al} 2 O _{3 5~30%, Li 2 O +} Na 2 O + K 2 O 0~20%, MgO 3~35%, characterized in that it contains 0~15% CaO + SrO + BaO. Here, "Li ₂ O + Na ₂ O + K ₂ O" refers to the total amount of _{Li 2} O, Na ₂ O and K _{2 O.} "CaO + SrO + BaO" refers to the total amount of CaO, SrO and BaO.

The glass plate of the present invention is a glass plate for producing a glass-resin composite by compositely integrating with a resin plate. In the glass-resin composite, the glass plate is a material that has transparency and enhances impact resistance. The resin plate is a material that cushions the impact caused by the collision of the scattered pieces and prevents the glass pieces from scattering due to the impact of the scattered pieces. By providing both, it becomes easy to secure the impact resistance performance.

FIG. 1 is a schematic view for explaining an example of a glass resin composite. The glass-resin composite 10 has a glass plate 11, a glass plate 12, and a resin plate 13 in this order from the outside, and these have a three-dimensionally curved curved surface shape and are not shown. It is compositely integrated by an organic resin intermediate layer. The glass plate 11 has a glass composition of SiO ₂ 45 to 80%, Al ₂ O _{3 to} 30%, Li ₂ O + Na ₂ O + K ₂ O 0 to 20%, MgO 3 to 35%, CaO + SrO + BaO 0 to 0 in terms of glass composition. Similarly, the glass plate 12 contains 15%, and the glass composition is mol%, SiO ₂ 45 to 80%, Al ₂ O ₃ 5 to 30%, Li ₂ O + Na ₂ O + K ₂ O 0 to 0. It contains 20%, MgO 3 to 35%, and CaO + SrO + BaO 0 to 15%. The resin plate 13 is polycarbonate.

When the present inventors analyzed the collision of the scattered pieces in detail, it was found that the glass plate was first damaged by the shock wave caused by the collision of the scattered pieces, and then the scattered pieces penetrated the inside of the glass plate. Then, it was found that by dispersing the shock wave due to the collision of the scattered pieces, the collision energy of the scattered pieces can be attenuated and the penetration of the scattered pieces can be prevented. Further analysis of the shock wave in detail shows that when the shock wave is dispersed and attenuated with respect to the traveling direction of the scattered pieces and the direction perpendicular to the traveling direction, the speed of the shock wave increases in proportion to the Young's modulus of the glass plate. Therefore, since the glass plate of the present invention has the above glass composition, it contains 3 mol% or more of MgO in the glass composition, so that the Young's modulus can be increased. As a result, when the collision of the scattered pieces is received, the dispersion region of the shock wave is widened, the energy absorption of the shock wave is increased, and the velocity of the scattered pieces themselves can be effectively reduced. As a result, it becomes difficult for the scattered pieces to penetrate the inside of the glass plate.

Further, the glass plate of the present invention preferably has a Young's modulus of 80 GPa or more. In this way, since the velocity of the shock wave is increased in the glass plate, the dispersed region of the shock wave is widened, and the collision energy of the scattered body can be greatly attenuated. Here, "Young's modulus" refers to a value measured by a well-known resonance method.

Further, the glass plate of the present invention preferably has a crack resistance of 500 gf or more. In this way, the glass plate is less likely to be scratched, so that it is possible to prevent a decrease in strength due to scratches. In addition, it is possible to prevent a decrease in transparency due to scratches. Here, the "crack resistance" is a load at which the crack occurrence rate is 50%. The "crack occurrence rate" is a value measured as follows. First, in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C., a Vickers indenter set to a predetermined load is driven into the glass surface (optically polished surface) for 15 seconds, and 15 seconds later, it is generated from the four corners of the indentation. Count the number of cracks (up to 4 per indentation). In this way, the indenter is driven 20 times to obtain the total number of cracks generated, and then the total number of cracks generated / 80 is calculated.

Further, the glass plate of the present invention preferably has a crystallinity of 30% or less. By doing so, the bending workability of the glass plate can be improved. Here, the "crystallinity" is determined after calculating the area of the halo corresponding to the mass of amorphous material and the area of the peak corresponding to the mass of the crystal by measuring XRD by the powder method. Peak area] x 100 / [Peak area + Hello area] (%) indicates the value obtained by the formula.

Further, the glass plate of the present invention preferably has a plate thickness of 3 to 15 mm.

Further, the glass plate of the present invention preferably has a curved surface shape that is three-dimensionally curved. In this way, it becomes easy to apply to the windshield of an automobile or the like.

It is the schematic for demonstrating an example of a glass resin composite.

The glass plate of the present invention has a glass composition, in _{mol%, SiO 2 45~80%, Al} 2 O 3 5~30%, Li 2 O + Na 2 O + K 2 O 0~20%, MgO 3~35%, CaO + SrO + BaO Contains 0-15%. The reasons for restricting the content range of each component as described above are shown below. In the description of the content range of each component, the% indication shall indicate mol%.

SiO ₂ is a component that forms a network of glass. The content of SiO ₂ is preferably 45 to 80%, 52 to 75%, and particularly 58 to 72%. If _{the content of SiO 2} is too small, it becomes difficult to vitrify and the weather resistance tends to decrease. On the other hand, if _{the content of SiO 2} is too large, the meltability and moldability tend to decrease, and the coefficient of thermal expansion becomes too low, making it difficult to match the coefficient of thermal expansion of the resin plate or the organic resin intermediate layer.

Al ₂ O ₃ is a component that enhances Young's modulus and weather resistance. The content of Al ₂ O ₃ is preferably 5 to 30%, 9 to 25%, 15 to 24%, and particularly 18 to 23%. If _{the content of Al 2} O ₃ is too small, Young's modulus and weather resistance tend to decrease. On the other hand, if _{the content of Al 2} O ₃ is too large, the meltability, moldability and devitrification resistance tend to decrease.

Li ₂ O, Na ₂ O and K ₂ O are components that reduce high-temperature viscosity and enhance meltability, moldability and bendability. The _{total amount of Li 2} O, Na ₂ O and K ₂ O is preferably 0 to 20%, 1 to 15%, and particularly 5 to 12%. The respective contents of Li ₂ O and K ₂ O are preferably 0 to 15%, 0 to 3%, and particularly less than 0 to 1%. The content of Na ₂ O is preferably 0 to 15%, 1 to 12%, and particularly 3 to 10%. If _{the contents of Li 2} O, Na ₂ O and K ₂ O are too large, crack resistance and weather resistance tend to decrease.

MgO is a component that significantly increases Young's modulus and crack resistance, and is a component that lowers high-temperature viscosity and enhances meltability, moldability, and bendability. The content of MgO is preferably 3 to 35%, 8 to 33%, 12 to 32%, and particularly 15 to 30%. If the content of MgO is too small, it becomes difficult to enjoy the above effect. On the other hand, if the content of MgO is too large, the devitrification resistance tends to decrease.

CaO, SrO and BaO are components that reduce high-temperature viscosity and enhance meltability, moldability and bendability. The total amount of CaO, SrO and BaO is preferably 0 to 15%, 0 to 5%, particularly less than 0 to 1%. The respective contents of CaO, SrO and BaO are preferably 0 to 12%, 0 to 5%, 0 to 2%, particularly less than 0 to 1%. If the contents of CaO, SrO and BaO are too large, the devitrification resistance, Young's modulus, crack resistance and the like tend to decrease.

From the viewpoint of increasing Young's modulus and crack resistance, the molar ratio MgO / (MgO + CaO + SrO + BaO) is preferably 0.5 or more, 0.7 or more, 0.8 or more, and particularly 0.9 or more. In addition, "MgO / (MgO + CaO + SrO + BaO)" is a value obtained by dividing the content of MgO by the total amount of MgO, CaO, SrO and BaO.

In addition to the above components, for example, the following components may be added.

B ₂ O ₃ is a component that forms a network of glass, but is a component that lowers Young's modulus and weather resistance. Therefore, _{the content of B 2} O ₃ is preferably 0 to 20%, 0 to 10%, 0 to 1%, and particularly less than 0 to 0.1%.

TiO ₂ is a component that enhances weather resistance, but is a component that colors glass. Therefore, _{the content of TiO 2} is preferably 0 to 0.5%, particularly less than 0 to 0.1%.

ZrO ₂ is a component that increases Young's modulus and weather resistance, but is a component that lowers devitrification resistance. Therefore, _{the content of ZrO 2} is preferably 0 to 0.5%, particularly less than 0 to 0.1%.

As a clarifying agent, _{one or more selected from the group of SnO 2} , Cl, SO ₃ , and CeO ₂ (preferably the group of SnO ₂ , SO ₃ ) may be added in an amount of 0.05 to 0.5%. ..

Fe ₂ O ₃ is a component that is inevitably mixed with the glass raw material as an impurity and is a coloring component. Therefore, _{the content of Fe 2} O ₃ is preferably 0.5% or less, particularly 0.01 to 0.07%.

V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO are coloring components. Therefore, _{the content of each of V 2} O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO is preferably 0.1% or less, particularly less than 0.01%.

Rare earth oxides such as Nd ₂ O ₃ and La ₂ O ₃ are components that increase Young's modulus. However, the cost of the raw material itself is high, and if a large amount is added, the devitrification resistance tends to decrease. Therefore, the total amount of rare earth oxides is preferably 3% or less, 1% or less, 0.5% or less, and particularly 0.1% or less.

From the viewpoint of the environment, it is preferable that _{the glass composition does not substantially contain As 2} O ₃ , Sb ₂ O ₃ , Pb O _{, Bi 2 O 3 and F.} Here, "substantially free of ~" means that although an explicit component is not positively added as a glass component, it is allowed to be mixed as an impurity. It means that the content is less than 0.05%.

The glass plate of the present invention preferably has the following characteristics.

Young's modulus is preferably 80 GPa or more, 85 GPa or more, 90 GPa or more, and particularly 95 to 150 GPa. If the Young's modulus is too low, the velocity of the shock wave due to the collision of the scattered pieces becomes slow, so that the shock wave spreads only in a narrow region, and it becomes difficult to attenuate the collision energy of the scattered pieces.

The crack resistance is preferably 500 gf or more, 800 gf or more, 1000 gf or more, and particularly preferably 1200 to 5000 gf. If the crack resistance is too low, the glass plate is likely to be scratched, and the scratches tend to reduce the strength and transparency of the glass plate.

The crystallinity is preferably 30% or less, 10% or less, 5% or less, 1% or less, particularly 0%, that is, amorphous. If the crystallinity is too high, the bending workability tends to decrease.

The thickness of the glass plate is preferably 15 mm or less, 12 mm or less, 10 mm or less, particularly 8 mm or less, preferably 1.5 mm or more, 3 mm or more, 4 mm or more, 5 mm or more, 6 mm or more, and particularly 7 mm or more. If the thickness of the glass plate is too small, it becomes difficult to secure impact resistance. On the other hand, if the thickness of the glass plate is too large, it becomes difficult to make the window glass thin, and the visibility tends to decrease. In addition, the weight of the window glass increases, and the fuel consumption of automobiles and the like rises.

The glass plate of the present invention is a glass plate for producing a glass-resin composite by compositely integrating with a resin plate. In the glass-resin composite, it is preferable that the number of glass plates is plurality. When a plurality of glass plates are contained in the glass resin composite, a glass plate other than the glass plate of the present invention (for example, a soda glass plate) may be included, but from the viewpoint of accurately enjoying the effect of the present invention. Therefore, it is preferable that all the glass plates are the glass plates of the present invention.

In the glass-resin composite, a plurality of resin plates may be used, but one is preferable from the viewpoint of improving visibility. Various resins such as acrylic and polycarbonate can be used as the resin plate, but polycarbonate is particularly preferable from the viewpoint of transparency, impact mitigation, and weight reduction.

The thickness of the resin plate is preferably 10 mm or less, 8 mm or less, 7 mm or less, 6 mm or less, particularly 5 mm or less, preferably 0.5 mm or more, 0.7 mm or more, 1 mm or more, 2 mm or more, and particularly 3 mm or more. .. If the thickness of the resin plate is too small, it becomes difficult to alleviate the impact when the scattered pieces collide. On the other hand, if the thickness of the resin plate is too large, it becomes difficult to make the window glass thinner, and the visibility of the window glass tends to decrease.

In the glass-resin composite, it is preferable that the glass plates are compositely integrated with each other by an organic resin intermediate layer. The thickness of the organic resin intermediate layer is preferably 0.1 to 2 mm, 0.3 to 1.5 mm, 0.5 to 1.2 mm, and particularly 0.6 to 0.9 mm. If the thickness of the organic resin intermediate layer is too small, the energy of the shock wave tends to propagate to the indoor side when the scattered pieces collide. On the other hand, if the thickness of the organic resin intermediate layer is too large, the visibility of the window glass tends to decrease.

The coefficient of thermal expansion of the organic resin intermediate layer is preferably equal to or greater than the coefficient of thermal expansion of the glass plate and less than or equal to the coefficient of thermal expansion of the resin plate. In this way, when the window glass is heated by direct sunlight, the glass plate and the resin plate are less likely to be separated and deformed. The "coefficient of thermal expansion" refers to the average coefficient of linear thermal expansion in the temperature range of 0 to 300 ° C.

Various organic resins can be used as the organic resin intermediate layer, for example, polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin (PMA), poly. Vinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cellulose acetate (CA), diallyl phthalate resin (DAP), urea resin (UP), melamine resin (MF), unsaturated polyester (UP) , Polyvinylbutyral (PVB), Polyvinylformal (PVF), Polyvinyl alcohol (PVAL), Vinyl acetate resin (PVAc), Ionomer (IO), Polymethylpentene (TPX), Vinylidene chloride (PVDC), Polysulphon (PSF), Vinylidene fluoride (PVDF), methacrylic-styrene copolymer resin (MS), polyarate (PAR), polyallyl sulfone (PASF), polybutadiene (BR), polyether sulfone (PESF), polyether ether ketone (PEEK), etc. Can be used. Among them, EVA and PVB are preferable from the viewpoint of transparency and adhesiveness, and PVB is particularly preferable because it can impart sound insulation.

A colorant may be added to the organic resin intermediate layer, or an absorbent that absorbs specific wavelength rays such as infrared rays and ultraviolet rays may be added.

As the organic resin intermediate layer, a combination of a plurality of types of the above organic resins may be used. For example, when a two-layer organic resin intermediate layer is used for the composite integration of the glass plate and the resin plate, the glass plate and the resin plate are fixed by different organic resins, so that the warp of the window glass can be easily reduced.

The total plate thickness of the glass resin complex is preferably 55 mm or less, 45 mm or less, 40 mm or less, preferably 4 mm or more, 5 mm or more, 7 mm or more, and particularly 10 mm or more. If the total plate thickness of the glass-resin composite is too small, the impact resistance performance of the window glass tends to deteriorate. On the other hand, if the total thickness of the glass-resin composite is too large, the weight of the window glass becomes heavy, and the visibility of the window glass tends to decrease.

A glass plate can be produced as follows.

First, a glass raw material prepared to have a predetermined glass composition is put into a continuous melting furnace, melted by heating at 1500 to 1700 ° C., clarified and stirred, and then supplied to a molding apparatus to be molded into a plate shape. By cooling, a glass plate can be produced.

It is preferable to adopt the float method as a method for molding the glass plate. The float method is a method capable of producing a glass plate at low cost.

In addition to the float method, the overflow down draw method may be adopted. The overflow down draw method is a method capable of producing a large number of thin glass plates with the surface unpolished. If the surface is unpolished, the manufacturing cost of the glass plate can be reduced.

The glass plate is preferably chamfered, if necessary. In that case, it is preferable to perform C chamfering with a # 800 metal bond grindstone or the like. In this way, the end face strength can be increased. If necessary, it is also preferable to etch the end face of the glass plate to reduce the crack source existing on the end face.

Next, the obtained glass plate is subjected to curved surface processing as necessary. Various methods can be adopted as the method for processing the curved surface. In particular, it is preferable to press-mold the glass plates one by one or by laminating them with a mold, and it is preferable to pass the glass plates through the heat treatment furnace with the glass plates sandwiched between the molds having a predetermined shape. In this way, the dimensional accuracy of the curved surface shape can be improved. Further, after the glass plates are arranged one by one or laminated on a mold having a predetermined shape, a part or the whole of the glass plates is heat-treated to soften the glass plates by their own weight along the shape of the mold. A method of deforming is also preferable. By doing so, the efficiency of curved surface processing can be improved.

Next, a glass resin composite can be produced by compositely integrating a glass plate (preferably a plurality of glass plates) and a resin plate with an organic resin intermediate layer. As a method of composite integration, a method of injecting an organic resin between glass plates or between glass plates and a resin plate and then curing the organic resin, a method of arranging an organic resin sheet between glass plates or between glass plates and a resin plate, and then pressurizing and heating. Examples include a method of processing (heat crimping). The former method can suppress the deformation of the resin plate due to the expansion mismatch between the glass plate and the resin plate. The latter method is easier to integrate.

Further, after the composite integration, a functional film such as a hard coat film, an infrared reflection film, or a heat ray reflection film may be formed on the outer surface of the outermost glass plate. Further, a functional film such as a hard coat film, an infrared reflection film, or a heat ray reflection film may be formed on the inner surface of the outermost glass plate before the composite integration.

Hereinafter, the present invention will be described in detail based on Examples. The following examples are merely examples. The present invention is not limited to the following examples.

Table 1 shows Examples (Samples Nos. 1 to 6) and Comparative Examples (Samples Nos. 7 to 9) of the present invention.

A glass plate was produced as follows. The glass raw materials were prepared so as to obtain the glass plates shown in Table 1. Next, the prepared glass batch was put into a continuous melting furnace, melted at 1600 ° C. for 20 hours, clarified and stirred to obtain homogeneous molten glass, and then formed into a plate having a thickness of 8.0 mm. Molded. Young's modulus, crack resistance, glass transition temperature and crystallinity were evaluated for the obtained glass plate. In addition, sample No. The glass plates according to 1 to 6 have an _{impure amount of Fe 2} O ₃ mixed in 0.05 mol%, and an impurity amount of V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO mixed in 0.01 mol, respectively. Was less than%.

Young's modulus is a value measured by a well-known resonance method.

The crack resistance is a load at which the crack occurrence rate is 50%. The crack occurrence rate was measured as follows. First, in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C., a Vickers indenter set to a predetermined load is driven into the glass surface (optically polished surface) for 15 seconds, and 15 seconds later, it is generated from the four corners of the indentation. Count the number of cracks (up to 4 per indentation). In this way, the indenter was driven 20 times to obtain the total number of cracks generated, and then the total number of cracks generated was calculated by the formula (total number of cracks generated / 80) × 100.

The glass transition temperature is a value measured using a dilatometer.

The crystallinity is determined by measuring the XRD by the powder method, calculating the area of the halo corresponding to the mass of the amorphous substance and the area of the peak corresponding to the mass of the crystal, respectively, and then [peak area] ×. It refers to the value obtained by the formula of 100 / [peak area + halo area] (%).

As can be seen from Table 1, Samples Nos. 1 to 6 have high Young's modulus, low glass transition point and low crystallinity, so that they have high impact resistance and are easy to bend. Therefore, the sample No. It is considered that 1 to 6 are suitable as a glass plate for producing a glass resin composite by compositely integrating with the resin plate. On the other hand, sample No. Since 7 to 9 have a low Young's modulus, it is considered that the impact resistance performance is low.

Next, sample No. By passing the glass plate according to No. 1 in a state of being sandwiched between molds having a predetermined shape and passing through the heat treatment furnace, a curved surface in which the entire plate width direction is curved in an arc shape and the entire length direction is curved in an arc shape. The curved surface was processed into a shape. Then, the end face of the glass plate after the curved surface was chamfered and polished with a # 800 metal bond grindstone.

Subsequently, a polycarbonate plate (plate thickness 4.0 mm) having a curved surface shape similar to that of the glass plate was prepared.

Finally, from the outside (atmosphere side), the sample No. Glass plate (outer layer glass plate) according to No. 1, polyvinyl butyral (PVB) having a thickness of 0.8 mm, sample No. The glass plate (inner layer glass plate), polyvinyl butyral (PVB) having a thickness of 0.8 mm, and polycarbonate plate according to No. 1 were compositely integrated by autoclave treatment in this order, and sample No. The glass resin composite according to No. 1 was obtained. Sample No. The same experiment was performed for 2 to 6 and sample No. The glass resin composites according to 2 to 6 were obtained.

The glass plate of the present invention is suitable as a glass plate for producing a glass-resin composite by compositely integrating with a resin plate, and the glass-resin composite is suitable for window glass of automobiles, railways, aircraft, etc. In addition to that, it is also suitable for window glass of buildings such as high-rise buildings.

10 Glass resin complex 11 Glass plate 12 Glass plate 13 Resin plate

Claims (5)

It is a glass plate for producing a glass resin composite by compositely integrating with a resin plate.
As the glass composition, in mol%, SiO ₂ 45 to 80%, Al ₂ O _{3 to} 30%, Li ₂ O + Na ₂ O + K ₂ O 0 to 20%, Na ₂ O 0 to 10%, MgO 8 to 35%, CaO + SrO + BaO containing 0-15% molar ratio MgO / (MgO + CaO + SrO + BaO) is Ri der 0.5 or higher,
A glass plate characterized by having a curved surface shape that is three-dimensionally curved. The glass plate according to claim 1, wherein the Young's modulus is 80 GPa or more. The glass plate according to claim 1 or 2, wherein the crack resistance is 800 gf or more. The glass plate according to any one of claims 1 to 3, wherein the crystallinity is 30% or less. The glass plate according to any one of claims 1 to 4, wherein the plate thickness is 3 to 15 mm.

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