JP2019198981A - Glass resin composite and method for producing the same - Google Patents

Abstract

To provide a glass resin composite that can limit the range in which cracks spread in collision with a flying piece, and a method for producing the same.SOLUTION: A glass resin composite 1 has a glass plate 2A,2B, a segment layer 3 containing a plurality of glass segments 3a,3b, and a resin plate 4. The plurality of glass segments contain glass segments having different compositions. The plurality of glass segments in the segment layer include a plurality of kinds of glasses having different Young's moduli, and the difference between them is set to 5 GPa or more and the difference in crack resistance is set to 100 gf or more, so that the impact wave occurring in collision with a flying piece can be effectively attenuated.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a glass resin composite suitably used for window glass such as an automobile windshield and door glass, and a method for producing the same.

  In general, laminated glass made by combining and integrating multiple soda lime glass plates with an organic resin intermediate layer is used for window glass for vehicles, etc. For the purpose of weight reduction, multiple soda lime glass plates are used. A glass resin composite in which a resin plate and a resin plate are combined and 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. is the movement of the scattered pieces at the time of collision by deforming the shape of the tip of the flying pieces such as stepping stones while running and increasing the impact resistance. It has a function to attenuate energy.

JP 2012-144217 A JP 2004-196184 A JP 2001-151539 A Japanese Utility Model Publication No. 1-8821

  However, even the conventional window glass as described above cannot be said to have sufficient ability to increase the impact resistance of the scattering pieces.

  According to the investigation by the present inventors, a crack is formed in the glass plate due to the collision of the scattering piece, and when another scattering piece collides so as to overlap the part where the crack is formed, the shock wave propagates through the glass plate. Thus, it was found that cracks propagate over a wide range of the glass plate. When the scattered pieces repeatedly collide with the glass plate in this way and cracks are formed in a wide range, the scattered pieces may penetrate the glass plate.

  In order to suppress the penetration of the glass plate by the scattered pieces, it is conceivable to increase the thickness dimension of the glass plate or increase the number of glass plates. However, this increases the weight of the glass resin composite, When used as a window glass, it results in reduced mobility and poor fuel consumption.

  In order to suppress the penetration of the glass plate by the scattering pieces without increasing the weight of the glass resin composite, it is necessary to limit the progress range so that cracks that cause the spread do not progress in a wide range.

  This invention is made | formed in view of said situation, and it aims at providing the glass resin composite which can restrict | limit the progress range of the crack by collision of a scattering piece, and its manufacturing method.

  The present invention is for solving the above-mentioned problems. In a glass resin composite used for a window glass, the glass resin composite includes a glass plate, a segment layer including a plurality of glass segments, and a resin plate, and includes a plurality of glass segments. Is characterized by comprising glass segments having different compositions.

  According to such a configuration, the segment layer is composed of glass segments having different compositions, thereby attenuating the shock wave generated when the scattering pieces collide with the glass resin composite due to the difference in Young's modulus due to the difference in composition between the segments. Can be made. Thereby, it is possible to limit as much as possible the range in which the crack caused by the collision progresses according to the propagation of the shock wave.

  The glass plate includes a first glass plate located on the outer layer side and a second glass plate located on the inner layer side of the first glass plate, and the second glass plate is a crack-resistant glass plate (crack resistance). Refers to a glass plate of 300 gf or more. Thereby, the crack resistance of a glass resin composite can be improved.

  The plurality of glass segments in the segment layer may include a first glass segment and a second glass segment having different Young's moduli, and the difference between the Young's moduli of the first glass segment and the second glass segment may be 5 GPa or more. Thus, by making the Young's modulus of the first glass segment and the second glass segment different, the shock wave generated by the collision of the scattering pieces can be effectively attenuated. Here, the “Young's modulus” can be measured by a known resonance method or the like.

  Alternatively, the plurality of glass segments may include a first glass segment and a second glass segment having different crack resistances, and the difference between the crack resistances of the first glass segment and the second glass segment may be 100 gf or more. Thus, by making the crack resistances of the first glass segment and the second glass segment different, the shock wave generated by the collision of the scattering pieces can be effectively attenuated.

  Here, “crack resistance” refers to a load at which the crack occurrence rate is 50%. “Crack occurrence rate” refers to 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 (optical polishing surface) for 15 seconds, and 15 seconds later, it is generated from the four corners of the indentation. Count the number of cracks (maximum 4 per indentation). After indenting the indenter 20 times in this manner to determine the total number of cracks generated, the crack resistance is determined by the formula (total number of cracks generated / 80) × 100.

  Alternatively, the plurality of glass segments include a first glass segment and a second glass segment having different refractive indexes, and the difference between the refractive index of the first glass segment and the second glass segment is 0.3 or less. Good. Thereby, the suitable visibility of a window glass is securable. Here, “refractive index” refers to a measured value for d-line (587.6 nm) of a helium lamp using KPR-2000 manufactured by Shimadzu Corporation.

Alternatively, the plurality of glass segments include a first glass segment and a second glass segment having different thermal expansion coefficients, and the difference between the thermal expansion coefficient of the first glass segment and the thermal expansion coefficient of the second glass segment is 20 × 10. ⁻⁷ / ° C. or less. Thereby, when forming a segment layer, a 1st glass segment and a 2nd glass segment can be joined suitably. Here, “the thermal expansion coefficient of glass” refers to an average linear thermal expansion coefficient in a temperature range of 0 to 300 ° C.

  The glass resin composite may have a curved shape that is three-dimensionally curved. Thereby, a glass resin composite can be used conveniently as a window glass of a vehicle.

  The present invention is for solving the above problems, and is a method for producing a glass resin composite comprising a glass plate, a segment layer, and a resin plate, wherein the first glass segment and the second glass composition are different from each other. A joining step of joining the two glass segments to form a segment layer is provided, and in the joining step, the first glass segment and the second glass segment are thermally fused.

  According to such a configuration, the first glass segment and the second glass segment can be joined without using the organic resin intermediate layer, so that the thermal processability of the segment layer can be improved.

  The present invention is for solving the above problems, and is a method for producing a glass resin composite comprising a glass plate, a segment layer, and a resin plate, wherein the first glass segment and the second glass composition are different from each other. It comprises a joining step of joining two glass segments to form a segment layer, the joining step comprising a step of stacking a plurality of glass bodies adjacent to the first glass segment, and heating the glass bodies And a heating step of forming a second glass segment fused to the first glass segment by melting and integrating.

  According to such a configuration, the first glass segment and the second glass segment can be joined without using the organic resin intermediate layer, so that the thermal processability of the segment layer can be improved.

  The present invention is for solving the above problems, and is a method for producing a glass resin composite comprising a glass plate, a segment layer, and a resin plate, wherein the first glass segment and the second glass composition are different from each other. A joining step of joining two glass segments to form a segment layer is provided, and the joining step is characterized in that the first glass segment and the second glass segment are joined by optical contact. Here, “optical contact” means that the end surface molecules of the first glass segment and the end surface molecules of the second glass segment are fanned when the end surfaces of the smoothly formed glass segments are brought into contact with each other. It means that the first glass segment and the second glass segment are firmly adhered by being bonded by a Delwars force.

  According to such a configuration, the first glass segment and the second glass segment can be joined without using the organic resin intermediate layer, so that the thermal processability of the segment layer can be improved.

  According to the present invention, it is possible to limit the progress range of cracks due to collision of scattered pieces.

It is a perspective view of the glass resin composite which concerns on 1st embodiment. It is sectional drawing of a glass resin composite. It is a top view of a segment layer. It is sectional drawing which shows 1 process of the manufacturing method which concerns on a glass resin composite. It is sectional drawing of the glass resin composite which shows the process in which a crack generate | occur | produces. It is sectional drawing of the glass resin composite which shows the process in which a crack generate | occur | produces. It is sectional drawing of the glass resin composite which shows the process in which a crack generate | occur | produces. It is sectional drawing of the glass resin composite which concerns on 2nd embodiment. It is sectional drawing of the glass resin composite which concerns on 3rd embodiment. It is sectional drawing of the glass resin composite which concerns on 4th embodiment. It is a top view which shows the segment layer of the glass resin composite which concerns on 5th embodiment. It is sectional drawing which shows 1 process of the manufacturing method of the glass resin composite which concerns on 6th embodiment. It is sectional drawing which shows 1 process of the manufacturing method of the glass resin composite which concerns on 7th embodiment.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. 1 to 7 show a first embodiment of a glass resin composite according to the present invention. In this embodiment, although the transparent glass resin composite used for the window glass of a motor vehicle is illustrated, the use of a glass resin composite is not limited to this.

  As shown in FIGS. 1 and 2, a glass resin composite 1 (glass resin laminate) according to this embodiment includes glass plates 2A and 2B and a segment layer 3 including a plurality of transparent glass segments 3a and 3b. The resin plate 4 is mainly provided. In the glass resin composite 1, the glass plates 2A and 2B and the segment layer 3, and the glass plate 2B and the resin plate 4 are joined by organic resin intermediate layers 5a to 5c. The glass resin composite 1 has been subjected to curved surface processing and has a curved surface shape that is curved three-dimensionally. Not only this but the glass resin composite 1 may be comprised by flat form.

  The total plate thickness of the glass resin composite 1 is preferably 70 mm or less, 65 mm or less, 60 mm or less, particularly 55 mm or less, preferably 7 mm or more, 11 mm or more, 12 mm or more, particularly 15 mm or more. If the total plate thickness of the glass resin composite 1 is too small, the impact resistance performance tends to be lowered. On the other hand, if the total plate thickness of the glass resin composite 1 is too large, the glass resin composite 1 becomes heavy and the visibility tends to decrease.

  The first glass plate 2A constituting the outermost layer (outer surface) of the window glass and the second glass plate 2B constituting the inner layer have transparency and are intended to increase the impact resistance of the flying pieces (or flying objects). It is.

  The first glass plate 2A and the second glass plate 2B (hereinafter also referred to as glass plates 2A and 2B) are preferably made of crack-resistant glass having a crack resistance of 300 gf or more. The crack resistance of the crack resistant glass 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 plates 2A and 2B are likely to be scratched, and the scratch resistance and transparency of the glass plates 2A and 2B are liable to be reduced.

  The crack resistant glass is preferably composed of aluminosilicate glass. Aluminosilicate glass tends to have high crack resistance. Since aluminosilicate glass has good devitrification resistance, it can be easily formed into a plate shape.

The crack resistant glass has a glass composition of mol%, SiO ₂ 45-80%, Al ₂ O ₃ 5-30%, Li ₂ O + Na ₂ O + K ₂ O (Li ₂ O, Na ₂ O and K ₂ O. Total amount) It is preferable to contain 0 to 20%, MgO 2 to 25%, CaO + SrO + BaO 0 to 15%. The reason why the content range of each component is regulated as described above is shown below. In addition, in description of the containing range of each component,% display shall show mol%.

SiO ₂ is a component that forms a network of glass. The content of SiO ₂ is preferably 45 to 80%, 50 to 75%, particularly 55 to 70%. When the content of SiO ₂ is too small, it becomes difficult to vitrify. On the other hand, if the content of SiO ₂ is too large, the meltability and moldability tend to decrease, and the thermal expansion coefficient becomes too low, matching the thermal expansion coefficients of the resin plate 4 and the organic resin intermediate layers 5a to 5c. It becomes difficult to let you.

Al ₂ O ₃ is a component that improves weather resistance and crack resistance. The content of Al ₂ O ₃ is preferably 5 to 30%, 10 to 30%, 15 to 25%, particularly 18 to 23%. When the content of Al ₂ O ₃ is too small, weather resistance and cracking resistance tends to decrease. On the other hand, when the content of Al ₂ O ₃ is too large, the melting properties, formability, and resistance to devitrification tends to drop.

Li ₂ O, Na ₂ O, and K ₂ O are components that lower the high-temperature viscosity and improve the meltability, moldability, and thermal processability. The total amount of Li ₂ O, Na ₂ O and K ₂ O is preferably 0-20%, 1-15%, in particular 5-12%. The respective contents of Li ₂ O, Na ₂ O and K ₂ O are preferably 0-15%, 1-12%, in particular 3-10%. Li ₂ O, when the content of Na ₂ O and K ₂ O is too large, cracks resistance and weather resistance tends to decrease.

  MgO is a component that increases crack resistance, and is a component that lowers the high-temperature viscosity and improves meltability, moldability, and thermal processability. The content of MgO is preferably 2 to 25%, 3 to 15%, particularly 5 to 16%. When there is too much content of MgO, devitrification resistance will fall easily.

  CaO, SrO, and BaO are components that lower the high-temperature viscosity and increase the meltability, moldability, and thermal processability. The total amount of CaO, SrO and BaO is preferably 0 to 15%, 0 to 10%, particularly 0 to 5%. The respective contents of CaO, SrO and BaO are preferably 0 to 12%, 0 to 5%, particularly 0 to 2%. When there is too much content of CaO, SrO, and BaO, devitrification resistance and crack resistance will fall easily.

  From the viewpoint of increasing 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. “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, and is a component that increases crack resistance, but is a component that decreases weather resistance. Therefore, the content of B ₂ O ₃ is preferably 0 to 20%, 1 to 15%, particularly 5 to 10%.

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

ZrO ₂ is a component that increases weather resistance, but is a component that decreases devitrification resistance. Therefore, the content of ZrO ₂ is preferably 0 to 0.5%, particularly 0 to less than 0.1%.

As a fining agent, 0.05 to 0.5% of one or more selected from the group of SnO ₂ , Cl, SO ₃ and CeO ₂ (preferably a group of SnO ₂ and SO ₃ ) may be added. .

Fe ₂ O ₃ is a component that is inevitably mixed as an impurity in the glass raw material, 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 respective contents of V ₂ O ₅ , Cr ₂ O ₃ , CoO ₃ and NiO are 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 expensive in the raw materials themselves, and when added in a large amount, devitrification resistance tends to decrease. Therefore, the total amount of the rare earth oxide is preferably 3% or less, 1% or less, 0.5% or less, particularly 0.1% or less.

From the environmental consideration, it is preferable that the glass composition does not substantially contain As ₂ O ₃ , Sb ₂ O ₃ , PbO, Bi ₂ O ₃ and F. Here, “substantially does not contain” means that the glass component does not positively add an explicit component, but allows a case where it is mixed as an impurity. It indicates that the content is less than 0.05%.

The first glass plate 2A and the second glass plate 2B may be made of glass having the same composition or may be made of glass having different compositions. Further, when the first glass plate 2A is used as the outermost layer of the window glass, the above-mentioned crack-resistant glass may be used, but it is preferable to use soda lime glass from the viewpoint of manufacturing cost. Soda-lime glass is generally in _{mol%, SiO 2 68~78%, Al} 2 O 3 0~3%, CaO 6~15%, 0~10% MgO, Na 2 O 10~20%, K ₂ O 0 to 3%, Fe ₂ O ₃ 0 to 1% are contained.

  The Young's modulus of each glass plate 2A, 2B 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 speed of the shock wave W due to the collision of the scattering pieces becomes slow, so that the shock wave W spreads only in a narrow region and it becomes difficult to attenuate the collision energy of the scattering pieces. It is preferable that the Young's modulus of the first glass plate 2A and the Young's modulus of the second glass plate 2B are set to different values.

  The crystallinity of each glass plate 2A, 2B is preferably 30% or less, more preferably 10% or less, particularly preferably less than 1%, that is, an amorphous glass. If the crystallinity is too high, it is difficult to bend the glass plates 2A and 2B. Here, the “crystallinity” is calculated by measuring the XRD by a powder method to calculate the area of the halo corresponding to the mass of the amorphous and the area of the peak corresponding to the mass of the crystal, respectively. Peak area] × 100 / [peak area + halo area] (%) is a value determined by the formula.

  The thickness of each glass plate 2A, 2B is preferably 15 mm or less, 12 mm or less, 10 mm or less, particularly 8 mm or less, preferably 3 mm or more, 4 mm or more, 5 mm or more, 6 mm or more, particularly 7 mm or more. If the plate thickness of the glass plates 2A and 2B is too small, it will be difficult to ensure impact resistance. On the other hand, if the plate thickness of the glass plates 2A and 2B is too large, it is difficult to make the glass resin composite 1 thinner, and the visibility is likely to be lowered. Moreover, the weight of the glass resin composite 1 increases, and the fuel efficiency of an automobile or the like increases.

  The segment layer 3 is for limiting the range in which the crack CR generated by the collision of the scattering pieces propagates. The segment layer 3 is disposed between the first glass plate 2A and the second glass plate 2B. The segment layer 3 is formed in a plate shape by joining a plurality of glass segments 3a and 3b to each other. The plurality of glass segments 3a and 3b include a first glass segment 3a and a second glass segment 3b which are configured by different compositions. The segment layer 3 has a configuration in which first glass segments 3a and second glass segments 3b are alternately arranged. The first glass segment 3a and the second glass segment 3b are integrated by thermal fusion.

  The thickness of the segment layer 3 is preferably 15 mm or less, 12 mm or less, 10 mm or less, particularly 8 mm or less, preferably 3 mm or more, 4 mm or more, 5 mm or more, 6 mm or more, particularly 7 mm or more. If the thickness of the segment layer 3 is too small, it will be difficult to ensure the limiting function of the progress range of the crack CR. On the other hand, when the thickness of the segment layer 3 is too large, it is difficult to reduce the thickness of the glass resin composite 1 and the visibility is likely to be lowered.

  As shown in FIG.2 and FIG.3, each glass segment 3a, 3b is comprised by elongate rod shape or plate shape in planar view. Each glass segment 3a, 3b has a rectangular cross section. In the present embodiment, the glass segments 3a and 3b having the same shape and the same length and width are used, but are not limited to this configuration. The segment layer 3 can be constituted by a combination of a plurality of glass segments 3a and 3b having different dimensions.

  It is preferable that each glass segment 3a, 3b is comprised by said crack-resistant glass. The glass segments 3a and 3b have the same composition, crystallinity, Young's modulus, and the like as the glass plates 2A and 2B.

  In this embodiment, the segment layer 3 is different in composition, Young's modulus, crack resistance, refractive index, and thermal expansion coefficient between the first glass segment 3a and the second glass segment 3b.

  The difference between the Young's modulus of the first glass segment 3a and the Young's modulus of the second glass segment 3b is preferably 5 GPa or more, more preferably 10 GPa or more.

  The difference between the crack resistance of the first glass segment 3a and the crack resistance of the second glass segment 3b is preferably 100 gf or more, particularly 300 gf or more.

  The difference between the refractive index (nd) of the first glass segment 3a and the refractive index (nd) of the second glass segment 3b is preferably 0.3 or less, 0.2 or less, particularly 0.1 or less.

The difference between the coefficient of thermal expansion of the first glass segment 3a and the coefficient of thermal expansion of the second glass segment 3b is preferably 20 × 10 ⁻⁷ / ° C. or less, particularly 10 × 10 ⁻⁷ / ° C. or less.

  The resin plate 4 has transparency, is for reducing the impact caused by the collision of the scattered pieces, and for preventing the glass plates 2A and 2B from being scattered by the impact of the scattered pieces. The resin plate 4 is configured as an innermost layer (layer facing the vehicle compartment side) of the window glass (glass resin composite 1). A plurality of resin plates 4 may be used, but one is preferable from the viewpoint of improving visibility. As the resin plate 4, various resin plates such as an acrylic plate and a polycarbonate plate can be used. Among these, a polycarbonate plate is particularly preferable from the viewpoints of transparency, impact relaxation, and weight reduction.

  The thickness of the resin plate 4 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, particularly 3 mm or more. is there. If the thickness of the resin plate 4 is too small, it will be difficult to mitigate the impact when the scattered pieces collide. On the other hand, if the thickness of the resin plate 4 is too large, it is difficult to reduce the thickness of the window glass, and the visibility is likely to deteriorate.

  The organic resin intermediate layers 5a to 5c are a first organic resin intermediate layer 5a that joins the first glass plate 2A and the segment layer 3, and a second organic resin intermediate layer that joins the second glass plate 2B and the segment layer 3. 5b and a third organic resin intermediate layer 5c that joins the second glass plate 2B and the resin plate 4 to each other.

  The thickness of each organic resin intermediate layer 5a to 5c 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 layers 5a to 5c is too small, when the scattering pieces collide, the impact absorbability tends to be lowered, and the stickiness tends to vary, and the second glass plate 2B and the resin plate 4 Each glass plate 2A, 2B and the segment layer 3 become easy to peel. On the other hand, if the thicknesses of the organic resin intermediate layers 5a to 5c are too large, the visibility of the glass resin composite 1 is likely to be lowered.

  It is preferable that the thermal expansion coefficient of each organic resin intermediate | middle layer 5a-5c is more than the thermal expansion coefficient of glass plate 2A, 2B, and below the thermal expansion coefficient of the resin board 4. FIG. If it does in this way, when the glass resin composite 1 is heated by direct sunlight, the 2nd glass plate 2B and the resin plate 4 will become difficult to isolate | separate and deform | transform.

  Various organic resins can be used as the organic resin intermediate layers 5a to 5c. For example, polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin ( PMA), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cellulose acetate (CA), diallyl phthalate resin (DAP), urea resin (UP), melamine resin (MF), unsaturated Polyester (UP), polyvinyl butyral (PVB), polyvinyl formal (PVF), polyvinyl alcohol (PVAL), vinyl acetate resin (PVAc), ionomer (IO), polymethylpentene (TPX), vinylidene chloride (PVDC), polysulfone (P F), polyvinylidene fluoride (PVDF), methacryl-styrene copolymer resin (MS), polyarate (PAR), polyallyl sulfone (PASF), polybutadiene (BR), polyether sulfone (PESF), or polyether ether ketone ( PEEK) or the like can be used. Among these, EVA and PVB are preferable from the viewpoint of transparency and adhesiveness, and PVB is particularly preferable because it can provide sound insulation.

  A colorant may be added to each of the organic resin intermediate layers 5a to 5c, or an absorber that absorbs light of a specific wavelength such as infrared rays or ultraviolet rays may be added.

  For each of the organic resin intermediate layers 5a to 5c, a combination of a plurality of organic resins may be used. For example, when a two-layer organic resin intermediate layer is used for the composite integration of the second glass plate 2B and the resin plate 4, the second glass plate 2B and the resin plate 4 are fixed with different organic resins. It becomes easy to reduce the curvature of 1.

  Hereinafter, a method for producing the glass resin composite 1 having the above configuration will be described.

  First, a glass raw material prepared so as to have a predetermined glass composition is put into a continuous melting furnace and heated at 1500 to 1700 ° C. to produce a molten glass. After the molten glass is clarified and stirred, the glass plates 2A and 2B can be produced by supplying the molding glass to a molding apparatus, molding it into a plate shape, and slowly cooling it.

  As a method for forming glass into a flat plate shape, it is preferable to employ an overflow down draw method. The overflow down draw method is a method in which high-quality glass plates 2A and 2B can be produced in large quantities and the large glass plates 2A and 2B can be easily produced while the surface is not polished. If the surface is unpolished, the manufacturing cost of the glass plates 2A and 2B can be reduced.

  In addition to the overflow downdraw method, it is also preferable to form the glass plates 2A and 2B by a float method or a rollout method. In particular, the float method is a method capable of producing large glass plates 2A and 2B at low cost.

  The glass plates 2A and 2B are preferably chamfered as necessary. In that case, it is preferable to perform C chamfering with a # 800 metal bond grindstone or the like. If it does in this way, end face strength can be raised. It is also preferable to reduce the crack sources existing on the end surfaces by etching the end surfaces of the glass plates 2A and 2B as necessary.

  Next, curved surface processing is performed on the obtained glass plates 2A and 2B as necessary. Various methods can be employed as a method of processing the curved surface. In particular, a method in which the glass plates 2A and 2B are press-molded one by one or by stacking them with a mold is preferable, and it is preferable to pass through a heat treatment furnace with the glass plates 2A and 2B sandwiched between molds having a predetermined shape. . In this way, the dimensional accuracy of the curved surface shape can be increased. In addition, after the glass plates 2A and 2B are arranged on a mold having a predetermined shape, the glass plates 2A and 2B are self-weighted along the shape of the mold by heat-treating part or all of the glass plates 2A and 2B. A method of softening and deforming with is also preferable. If it does in this way, the efficiency of curved surface processing can be raised.

  Further, by cutting the glass plates 2A and 2B formed as described above, a plurality of glass segments 3a and 3b are produced. If the composition of the first glass plate 2A and the second glass plate 2B is different, the first glass segment 3a and the second glass segment 3b having different compositions can be easily obtained by cutting the glass plates 2A and 2B. Can be made.

  In this method, the process (joining process) of joining the 1st glass segment 3a and the 2nd glass segment 3b is implemented. In the joining step, first, as shown in FIG. 4A, first glass segments 3a and second glass segments 3b are alternately arranged. And as shown in FIG.4 (b), each glass segment 3a, 3b is arrange | positioned in the heat-resistant formwork 6 in the state which the end surface of the 1st glass segment 3a and the end surface of the 2nd glass segment 3b contacted each other. (Installation process). Thereafter, the heat-resistant mold 6 is passed through a heat treatment furnace (heating process). Thereby, the end surface of the 1st glass segment 3a and the end surface of the 2nd glass segment 3b are integrated by heat fusion, and the plate-shaped segment layer 3 is obtained as shown in FIG.4 (c). Thereafter, the segment layer 3 is processed into a curved surface similarly to the glass plates 2A and 2B.

  Next, the first glass plate 2A, the segment layer 3, the second glass plate 2B, and the resin plate 4 are combined and integrated by the organic resin intermediate layers 5a to 5c. In this case, a method of curing after injecting an organic resin between the glass plates 2A, 2B and the segment layer 3 and between the second glass plate 2B and the resin plate 4, the organic resin sheet is made into each glass plate 2A, For example, a method of pressurizing and heating (thermocompression bonding) between 2B and the segment layer 3 and between the second glass plate 2B and the resin plate 4 is used. The former method can suppress deformation of the resin plate 4 due to expansion mismatch between the second glass plate 2 </ b> B and the resin plate 4. The latter method is easy for complex integration.

  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 first glass plate 2A. Moreover, you may form functional films, such as a hard-coat film | membrane, an infrared reflective film, and a heat ray reflective film, on the inner surface of the first glass plate 2A before complex integration.

  FIG. 5 thru | or FIG. 7 shows the formation process of the crack CR when a scattering piece collides with the glass resin composite 1 which concerns on this embodiment. As shown in FIG. 5, when the scattering pieces collide with the first glass plate 2A as the outermost layer (the collision position is indicated by the symbol CP), the shock wave W generated by this collision propagates radially through the first glass plate 2A. Cracks CR generated in the first glass plate 2A due to the collision of the scattered pieces propagate radially inside the first glass plate 2A along the direction of propagation of the shock wave W (see FIG. 6).

  When another scattering piece collides so as to overlap the collision position CP of the scattering piece, the crack CR previously formed further develops inside the first glass plate 2A due to the shock wave W. When such collision of scattered pieces is repeated, the crack CR may propagate to the segment layer 3 in some cases. As shown in FIG. 7, the crack CR propagates inside the second glass segment 3b. However, the difference in Young's modulus and the difference in crack resistance between the second glass segment 3b and the adjacent first glass segment 3a. As a result, the shock wave W is attenuated. Thereby, the crack CR can be prevented from progressing from the second glass segment 3b where the crack CR is formed to the first glass segment 3a. Therefore, even if this crack CR progresses to the second glass plate 2B, the range is limited.

  As described above, by restricting (suppressing) the progress range of the crack CR that is going to progress radially according to the propagation of the shock wave W by the segment layer 3, the durability of the glass resin composite 1 is greatly improved and the crack is A reduction in the visibility of the glass resin composite 1 due to CR can also be suppressed. In addition, the first glass segment 3a and the second glass segment 3b are integrated by thermal fusion to constitute the segment layer 3, which is compared with the case of integrating (joining) using the organic resin intermediate layer. Thus, the thermal workability of the segment layer 3 can be greatly improved.

  FIG. 8 shows a second embodiment of the glass resin composite. The glass resin composite 1 according to the present embodiment is different from the first embodiment in the configuration of the segment layer 3. The segment layer 3 includes a plurality of first glass segments 3a and second glass segments 3b having a triangular cross section. The segment layer 3 is configured in a plate shape by causing the slope of the first glass segment 3a and the slope of the second glass segment 3b to face each other and joining the slopes by thermal fusion. The segment layer 3 is bonded to the first glass plate 2A and the second glass plate 2B via the first organic resin intermediate layer 5a and the second organic resin intermediate layer 5b. Other configurations in the present embodiment are the same as those in the first embodiment.

  FIG. 9 shows a third embodiment of the glass resin composite. In this embodiment, the aspect of the joining process which forms the segment layer 3 differs from 1st embodiment. In this embodiment, a joining process produces the segment layer 3 by joining the 1st glass segment 3a and the 2nd glass segment 3b with an optical contact.

  The close contact with the optical contact tends to be stronger when the smoothness of the surface (end face) of each glass segment 3a, 3b is high. Therefore, the arithmetic average roughness Ra of the surface can be used to firmly bond the two. It is desirable to be as small as possible. Therefore, the arithmetic average roughness Ra concerning the surface of each glass segment 3a, 3b is preferably 0.1 to 20 nm, particularly 0.2 to 15 nm.

  When manufacturing the glass resin composite 1 which concerns on this embodiment, in the process (joining process) which joins each glass segment 3a, 3b, end surface (smooth surface) of each glass segment 3a, 3b is normal temperature (-10-10). (40 ° C). As a result, a plate-like segment layer 3 is formed in which the first glass segment 3a and the second glass segment 3b are alternately and directly bonded (optical contact).

  The glass resin composite 1 including the segment layer 3 according to the present embodiment reflects and attenuates the shock wave W propagating through the segment layer 3 by the interface between the first glass segment 3a and the second glass segment 3b. Can do.

  FIG. 10 shows a fourth embodiment of the glass resin composite. The glass resin composite 1 according to this embodiment includes a segment layer 3 formed by separating a plurality of glass segments 3a and 3b. The plurality of glass segments 3a and 3b are alternately arranged between the first glass plate 2A and the second glass plate 2B and are spaced apart at equal intervals. Therefore, a space S is formed between the adjacent first glass segment 3a and second glass segment 3b.

  In this embodiment, in order to form the segment layer 3 between the first glass plate 2A and the second glass plate 2B, for example, each glass segment 3a, 3b is placed on one surface of the first glass plate 2A with the first organic resin. It joins via the intermediate | middle layer 5a. Then, this 1st glass plate 2A is piled up on the 2nd glass plate 2B, and the 2nd glass plate 2B and each glass segment 3a, 3b are joined via the 2nd organic resin intermediate | middle layer 5b. Other configurations according to the present embodiment are the same as those of the first embodiment.

  FIG. 11 shows a fifth embodiment of the glass resin composite (segment layer). The segment layer 3 according to the present embodiment is obtained by integrating a plurality of glass segments 3a and 3b having a triangular shape in plan view. The segment layer 3 is formed in a plate shape by joining the hypotenuses of the glass segments 3a and 3b by thermal fusion.

  FIG. 12 shows a sixth embodiment of the glass resin composite (segment layer). In this embodiment, the aspect of the joining process which forms a segment layer differs from 1st embodiment. In the bonding step according to the present embodiment, a part of the segment layer (second glass segment) is formed by an integration method. The stacking method is a method of stacking glass bodies on the heat-resistant form 6 and heat-treating them to fuse the glass bodies together.

  Specifically, a joining process fuses to the 1st glass segment 3a by accumulating the integration | stacking process which integrates the several glass body 7 so that the 1st glass segment 3a may be adjoined, and heating the glass body 7. A heating step of forming the second glass segment 3b. The glass body 7 may be crystallized by heating.

  In the stacking process, as shown in FIG. 12 (a), a plurality of first glass segments 3a configured in a rod shape are arranged on the heat-resistant form 6 at regular intervals, and then shown in FIG. 12 (b). Thus, the space between the first glass segments 3 a is filled with a plurality of glass bodies 7. Thereby, the several glass body 7 is integrated | stacked so that it may adjoin each 1st glass segment 3a arrange | positioned spaced apart.

  Thereafter, the glass body 7 is melted and fused with each other by housing the heat-resistant form 6 in a heating furnace and heating it. At this time, the glass body 7 in contact with the side surface of the first glass segment 3a is also fused to the side surface. When all the glass bodies 7 are melted and integrated, the second glass segment 3b formed integrally with the first glass segment 3a is formed (see FIG. 12C). Then, the plate-shaped segment layer 3 is produced by cooling the 1st glass segment 3a and the 2nd glass segment 3b (cooling process).

  FIG. 13 shows a seventh embodiment of the glass resin composite (segment layer). In this embodiment, the aspect of the joining process which forms a segment layer differs from 1st embodiment.

  In the joining step, first, as shown in FIG. 13 (a), a plurality of first glass segments 3a configured in a rod shape are arranged on the heat-resistant form 6 at a predetermined interval (installation step).

  Next, as shown in FIG.13 (b), the several glass plate 8 which is the raw material of the 2nd glass segment 3b is laminated | stacked in the space between the 1st glass segments 3a. Thereafter, the raw glass plate 8 is melted by heating the heat-resistant form 6 in a heating furnace (heating step). The plurality of glass plates 8 are melted, integrated, and cooled, whereby the second glass segment 3b formed by integration (thermal fusion) with the first glass segment 3a is formed. Thereby, as shown in FIG.13 (c), the plate-shaped segment layer 3 formed by alternately integrating the 1st glass segment 3a and the 2nd glass segment 3b is produced.

  In addition, this invention is not limited to the structure of the said embodiment, It is not limited to an above-described effect. The present invention can be variously modified without departing from the gist of the present invention.

  In the above embodiment, the glass resin composite 1 including the two glass plates 2A and 2B has been exemplified, but the present invention is not limited to this configuration. The glass resin composite 1 may include one or three or more glass plates. Moreover, although the glass resin composite 1 was provided with the segment layer 3 of one layer, it can be provided with the segment layer 3 of two or more layers.

  In the above embodiment, the segment layer 3 formed by alternately joining the first glass segment 3a and the second glass segment 3b having different compositions, Young's modulus, crack resistance, refractive index, and thermal expansion coefficient is exemplified. The present invention is not limited to this configuration. In addition to the 1st glass segment 3a and the 2nd glass segment 3b, the segment layer 3 containing other glass segments, such as the 3rd glass segment from which a composition differs, a 4th glass segment, etc. is employable.

1 glass resin composite 2A first glass plate 2B second glass plate 3a first glass segment 3b second glass segment 3 segment layer 4 resin plate 7 glass body

Claims (10)

In the glass resin composite used for the window glass,
A glass plate, a segment layer including a plurality of glass segments, and a resin plate,
The glass resin composite, wherein the plurality of glass segments include glass segments having different compositions. The glass plate includes a first glass plate located on the outer layer side, and a second glass plate located on the inner layer side than the first glass plate,
The glass resin composite according to claim 1, wherein the second glass plate is a crack-resistant glass plate. The plurality of glass segments include a first glass segment and a second glass segment having different Young's moduli,
The glass resin composite according to claim 1 or 2, wherein a difference between the Young's modulus of the first glass segment and the Young's modulus of the second glass segment is 5 GPa or more. The plurality of glass segments include a first glass segment and a second glass segment having different crack resistances,
The glass resin composite according to claim 1 or 2, wherein a difference between the crack resistance of the first glass segment and the crack resistance of the second glass segment is 100 gf or more. The plurality of glass segments include a first glass segment and a second glass segment having different refractive indices (nd),
The glass resin according to claim 1 or 2, wherein a difference between the refractive index (nd) of the first glass segment and the refractive index (nd) of the second glass segment is 0.3 or less. Complex. The plurality of glass segments include a first glass segment and a second glass segment having different thermal expansion coefficients,
3. The glass resin according to claim 1, wherein a difference between the thermal expansion coefficient of the first glass segment and the thermal expansion coefficient of the second glass segment is 20 × 10 ⁻⁷ / ° C. or less. Complex.   The glass resin composite according to any one of claims 1 to 6, wherein the glass resin composite has a curved shape that is three-dimensionally curved. A method of producing a glass resin composite comprising a glass plate, a segment layer, and a resin plate,
Comprising a joining step of joining the first glass segment and the second glass segment having different compositions to form the segment layer;
In the joining step, the first glass segment and the second glass segment are heat-sealed. A method of producing a glass resin composite comprising a glass plate, a segment layer, and a resin plate,
Comprising a joining step of joining the first glass segment and the second glass segment having different compositions to form the segment layer;
The joining step includes fusing to the first glass segment by accumulating a plurality of glass bodies so as to be adjacent to the first glass segment and heating and integrating the glass bodies. And a heating step of forming the second glass segment. A method of producing a glass resin composite comprising a glass plate, a segment layer, and a resin plate,
Comprising a joining step of joining the first glass segment and the second glass segment having different compositions to form the segment layer;
In the joining step, the first glass segment and the second glass segment are joined by optical contact.

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