CN109476538A - Laminated glass for use in vehicles - Google Patents

Abstract

Laminated glass for use in vehicles of the invention be outside strengthening glass sheets and inside strengthening glass sheets via organic resin middle layer it is integrated made of laminated glass for use in vehicles, it is characterized in that, the plate thickness of outside strengthening glass sheets is 2.0mm or less, outside strengthening glass sheets have the surface compression stressor layers as brought by ion exchange, the compression stress value of the surface compression stressor layers of outside strengthening glass sheets is 350MPa or more, and stress depth is 15~100 μm.

Description

Laminated glass for use in vehicles

Technical field

The present invention relates to laminated glass for use in vehicles, in particular to are suitable for the laminated glass for use in vehicles of windshield.

Background technique

The windshield of automobile has used two glass sheets via laminated glass made of organic resin middle layer integration. Laminated glass has an advantage that breakage, which occurs, even if a part of glass plate can also ensure that the good visual field, in addition, sending out Even if glass sheet breakage when making trouble former, it can also rely on the retractility of organic resin middle layer and prevent passenger from flying out outside vehicle.

For example, patent document 1 discloses a kind of laminated glass, organic resin middle layer is in airbag deployment in order to prevent Occur to be broken and the ratio between the thickness by the thickness of inner glass plate relative to outboard-side glass plate is set as 0.6 or more and 0.9 or less.This Outside, patent document 2 discloses a kind of laminated glass, in order to improve guarding against theft etc. and by outboard-side glass plate and inner glass plate Thickness difference be set as 1.0mm or more, and make outboard-side glass plate plate thickness be greater than inner glass plate plate thickness.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2003-55007 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2001-39743 bulletin

Summary of the invention

Subject to be solved by the invention

In recent years, in automobile industry, it is strongly required to improve fuel efficiency by the lightweight of car body.Thus, it is desirable that The lightweight of the relevant component of automobile is improved to more than existing level.Requirement to laminated glass is no exception.Realizing interlayer In the light-weighted situation of glass, the slimming of glass plate is effective, but from the viewpoint of safety etc., is not easy to realize and be somebody's turn to do Slimming.Status is, in order to realize the slimming of laminated glass, imagines as glass plate and uses very thin physical strengthening glass Glass.

But to be difficult to formation temperature poor for very thin physical strengthening glass its surface and inside in heat treatment, therefore hardly possible To increase the stress depth of compressive stress layers.As a result, being difficult to maintain the intensity of laminated glass.

In addition, the windshield to automobile uses the point punching in the case where physical strengthening glass, existed due to small stone etc. It hits and a possibility that physical strengthening glass breakage granulates, and due to the tiny fragment, human body is damaged.

Thus, present invention is made in view of the above circumstances, and technical task is, creation can take into account it is high-intensitive and The dangerous laminated glass for use in vehicles of slimming and injury of human when can be effectively prevented from breakage.

The method used for solving the problem

The inventors of the present invention's discovery, by the way that by the board stacking integration of two panels strengthened glass, further corresponding to becomes on the outside of vehicle Glass plate carries out chemical strengthening, and the compression stress value for compressing it stressor layers and stress depth limit within the specified scope, can Above-mentioned technical task is solved, to propose the present invention.That is, laminated glass for use in vehicles of the invention be outside strengthening glass sheets with Inside strengthening glass sheets are via laminated glass for use in vehicles made of organic resin middle layer integration, which is characterized in that outside is strong Change glass plate plate thickness be 2.0mm hereinafter, outside strengthening glass sheets have the surface compression stressor layers as brought by ion exchange, The compression stress value of the surface compression stressor layers of outside strengthening glass sheets is 350MPa or more, and stress depth is 15~100 μm. Herein, " compression stress value " and " stress depth " is by using surface stress meter (such as the FSM- that the former production of folding is manufactured 6000) the item number for, observing interference fringe and its interval are to calculate.

The plate thickness of the outside strengthened glass of laminated glass for use in vehicles of the invention is restricted to 2.0mm hereinafter, compression stress The compression stress value of layer is restricted to 350MPa or more, and stress depth is restricted to 15~100 μm.It is not easy as a result, because of gravel Point etc. tiny flying object impacts and breakage occurs for outside strengthening glass sheets.In addition, laminated glass for use in vehicles of the invention will Two panels strengthening glass sheets are via organic resin middle layer integration.Passenger flies out outside vehicle when thereby, it is possible to prevent accident from occurring.

Fig. 1 is the skeleton diagram for illustrating laminated glass for use in vehicles of the invention.Laminated glass for use in vehicles 10 has inside Strengthening glass sheets 11, plate thickness 2.0mm outside strengthening glass sheets 12 below and be clipped in inside strengthening glass sheets 11 and outside it is strong Change the organic resin middle layer 13 between glass plate 12.Outside strengthening glass sheets 12 are pressed with the surface as brought by ion exchange Stress under compression layer, compression stress value is 300MPa or more, and stress depth is 15~60 μm.Also, laminated glass for use in vehicles 10 In, so that outside 12 side of strengthening glass sheets is become protrusion, the integrally bending of plate width direction is at arc-shaped, and the Integral bending of length direction Song is at arc-shaped.

In addition, the tensile stress values of the inside of the preferred outside strengthening glass sheets of laminated glass for use in vehicles of the invention are 70MPa or less.

In addition, the preferred outside strengthening glass sheets of laminated glass for use in vehicles of the invention are formed as glass and are contained in terms of quality % There is SiO₂40~80%, Al₂O₃3~30%, B₂O₃0~10%, Na₂O 5~20% and K₂O 0~5%.

In addition, the compression of the surface compression stressor layers of the preferred inside strengthening glass sheets of laminated glass for use in vehicles of the invention is answered Force value is 350MPa or more, and stress depth is 15~100 μm.Point punching is being applied to inside strengthening glass sheets from car as a result, When hitting, inside strengthening glass sheets also not cracky.

In addition, the tensile stress values of the preferred inside strengthening glass sheets of laminated glass for use in vehicles of the invention are 70MPa or less.

In addition, the preferred inside strengthening glass sheets of laminated glass for use in vehicles of the invention are formed as glass and are contained in terms of quality % There is SiO₂40~80%, Al₂O₃3~30%, B₂O₃0~10%, Na₂O 5~20% and K₂O 0~5%.

In addition, the poplar of the preferred outside strengthening glass sheets of laminated glass for use in vehicles of the invention and/or inside strengthening glass sheets Family name's modulus is 76GPa or less.Strengthening glass sheets become easy flexure as a result, therefore can be improved the impact absorbing of laminated glass Effect.

In addition, laminated glass for use in vehicles of the invention preferably outside strengthening glass sheets and/or inside strengthening glass sheets is strong Cracking frequency before change processing is 80% or less.Here, " cracking frequency " is the value measured in the following way.Firstly, It is being maintained at humidity 30%, in 25 DEG C of temperature of constant temperature and humidity cabinet, the Vickers indenter indentation glass table of load 800gf will be set as Face (optical grinding face) 15 seconds, this is counted after 15 seconds, and from the quantity of the crackle of 4 jiaos of generations of impression, (every 1 impression is up to 4).It is pressed into pressure head 50 times in this manner, after finding out total crackle generation number, passes through (number/200 occur for total crackle) × 100 Formula is found out.The indentation of Vickers indenter can use full-automatic Vickers (such as Future-Tech FLC-50VX) It carries out.But due to cracking frequency is according to the moisture state of glass surface and numerical value changes, it is therefore desirable for before the assay With the temperature range of (Ps-350 DEG C)~(Ps-150 DEG C) carry out 1 hour it is annealed above, come glass caused by eliminating because of room epidemic disaster The difference of the moisture state on glass surface.It should be noted that Ps refers to strain point.

In addition, the preferred organic resin layer of laminated glass for use in vehicles of the invention is by vinyl-vinyl acetate copolymer or gathers Vinyl butyral is constituted.

In addition, laminated glass for use in vehicles of the invention preferably has the curve form of three-dimensional bending.

In addition, laminated glass for use in vehicles of the invention is preferred for the windshield of automobile.

In addition, laminated glass for use in vehicles of the invention is preferred for the glass pane of rail truck.Rail truck and automobile phase It is faster than travel speed, therefore the point impact that glass pane applies is tended to get bigger.Therefore, laminated glass for use in vehicles of the invention is to this It is advantageous for purposes.

Detailed description of the invention

Fig. 1 is the skeleton diagram for showing an example of laminated glass for use in vehicles of the invention.

Specific embodiment

Laminated glass for use in vehicles of the invention has outside strengthening glass sheets and inside strengthening glass sheets.These strengthened glass Plate has compressive stress layers on surface.As the method for forming compressive stress layers on surface, there are physical strengthening processing and chemistry strong Change handles (ion-exchange treatment), and outside strengthening glass sheets carry out chemical intensification treatment.On the other hand, inside strengthening glass sheets can To carry out any intensive treatment.

Chemical intensification treatment is imported by ion exchange to glass surface at the strain point temperature below of glass plate The method of the big basic ion of ionic radius.If chemical intensification treatment, even if then also can in the case where the plate thickness of glass plate is small It is properly formed compressive stress layers.Physical strengthening processing is, near the softening point of glass plate at a temperature of be heat-treated after, Especially near the softening point of glass plate at a temperature of carry out Machining of Curved Surface after glass chilling is answered to form compression on surface The method of power layer.If physical strengthening processing, then the stress depth of compressive stress layers is capable of increasing.

In laminated glass for use in vehicles of the invention, the plate thickness of outside strengthening glass sheets be preferably 2.0mm or less, 1.5mm with Under, 1.3mm hereinafter, particularly preferably 1.0mm hereinafter, particularly preferably 0.8mm hereinafter, preferably 0.3mm or more, 0.4mm with Upper, 0.5mm or more, 0.6mm or more, 0.7mm or more, particularly preferably 1.0mm or more.The plate thickness of inside strengthening glass sheets is preferred For 1.5mm or less, 1.2mm or less, 1.1mm or less, 1.0mm hereinafter, particularly preferably 0.8mm hereinafter, preferably 0.3mm with Upper, 0.4mm or more, 0.5mm or more, 0.6mm or more, particularly preferably 0.7mm or more.If especially by outside strengthening glass sheets It is limited to 1.0~1.5mm, inside strengthening glass sheets is limited to 0.3~1.1mm, be then easy flexibly to absorb mechanical punching Power is hit, therefore is applied to not allow easy damaged in the case where the windshield of automobile.

In laminated glass for use in vehicles of the invention, outside strengthening glass sheets have the surface compression as brought by ion exchange Stressor layers, the compression stress value of compressive stress layers are preferably 350MPa or more, 400MPa or more, 500MPa or more, 550MPa More than, particularly preferably 600MPa or more.Compression stress value is bigger, then the intensity of outside strengthening glass sheets becomes higher.It is another Aspect, if forming great compression stress on surface, exist inside tensile stress become high, outside strengthening glass sheets because A possibility that point conflicts and autoclasis occurs.Thus, the compression stress value of compressive stress layers is preferably 1000MPa or less, 800MPa Hereinafter, particularly preferably 650MPa or less.

The stress depth of the compressive stress layers of outside strengthening glass sheets is preferably 15 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, particularly preferably 50 μm or more.Stress depth is bigger, even if then bringing due to impacting to outside strengthening glass sheets Deep scar, outside strengthening glass sheets are also more not easily broken, and strength variance also becomes smaller.On the other hand, if stress is deep Degree becomes excessive, then exist inside tensile stress become that autoclasis occurs due to conflicting for high, outside strengthening glass sheets can It can property.Thus, stress depth be preferably 100 μm or less, 90 μm or less, 80 μm or less, 75 μm or less, 70 μm or less, 65 μm with Under, particularly preferably 60 μm or less.

The tensile stress values of the inside of outside strengthening glass sheets are preferably 70MPa hereinafter, particularly preferably 10~60MPa. If internal tensile stress values are excessive, there is a possibility that outside strengthening glass sheets autoclasis due to conflict.It needs to illustrate It is that internal tensile stress values refer to the value calculated by following mathematical expressions.

[mathematical expression 1]

Internal tensile stress values=(compression stress value × stress depth)/(plate thickness -2 × stress depth)

In laminated glass for use in vehicles of the invention, inside strengthening glass sheets have surface compression stressor layers, the compression stress The compression stress value of layer is preferably 350MPa or more, 400MPa or more, 500MPa or more, 550MPa or more, particularly preferably 600MPa or more.Compression stress value is bigger, then the intensity of inside strengthening glass sheets is more got higher.On the other hand, if being formed on surface Great compression stress, then exist inside tensile stress become high, inside strengthening glass sheets autoclasis occur due to conflicting A possibility that.Therefore, the compression stress value of compressive stress layers is preferably 1000MPa or less, 800MPa hereinafter, particularly preferably 650MPa or less.

The stress depth of the compressive stress layers of inside strengthening glass sheets is preferably 15 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, particularly preferably 50 μm or more.Stress depth is bigger, even if then bringing depth to inside strengthening glass sheets because of impact Deep scar, inside strengthening glass sheets are also more difficult to rupture, and the deviation of intensity is also easier becomes smaller.On the other hand, if stress is deep Degree becomes excessive, then exist inside tensile stress become that autoclasis occurs due to conflicting for high, inside strengthening glass sheets can It can property.Therefore, stress depth be preferably 100 μm or less, 90 μm or less, 80 μm or less, 75 μm or less, 70 μm or less, 65 μm with Under, particularly preferably 60 μm or less.

The tensile stress values of the inside of inside strengthening glass sheets are preferably 70MPa hereinafter, particularly preferably 10~50MPa. If internal tensile stress values are excessive, there is a possibility that due to conflicting autoclasis occurs for inside strengthening glass sheets.

In laminated glass for use in vehicles of the invention, strengthening glass sheets (outside strengthening glass sheets and/or inside strengthened glass Plate) preferably alkali alumina silicate glass, alkali borosilicate glass, soda-lime glass, particularly preferred alkali alumina silicate glass.Alkali manosil AS Salt glass can form desired compression stress due to ion-exchange performance height with the chemical intensification treatment of short time Layer.And devitrification resistance is good, therefore is easily shaped into plate.

Strengthening glass sheets (outside strengthening glass sheets and/or inside strengthening glass sheets) are formed preferably as glass with quality % Meter contains SiO₂40~80%, Al₂O₃3~30%, B₂O₃0~10%, Na₂O 5~20% and K₂O 0~5%.It is such as above-mentioned The as described below the reasons why containing range of each ingredient is limited like that.It should be noted that in the explanation containing range of each ingredient In, this statement of % indicates quality %.

SiO₂It is the ingredient to form glass network.SiO₂Content be preferably 40~80%, 45~75%, 52~73%, 55 ~71%, 57~68%, particularly preferably 58~67%.If SiO₂Content it is very few, then be difficult to vitrifying, in addition thermal expansion system Number becomes excessively high, and thermal shock resistance is easily reduced.On the other hand, if SiO₂Content it is excessive, then meltbility, formability be easy drop Low, in addition thermal expansion coefficient becomes too low, it is difficult to be matched with the thermal expansion coefficient of organic resin middle layer.

Al₂O₃It is the ingredient for improving ion-exchange performance, in addition, being the ingredient for improving strain point, Young's modulus.If Al₂O₃ Content it is very few, then generate a possibility that being unable to give full play ion-exchange performance.Therefore, Al₂O₃Lower range be preferably 3% or more, 8% or more, 12% or more, 16% or more, 16.5% or more, 17.1% or more, 17.5% or more, 18% or more, Particularly preferably 18.5% or more.On the other hand, if Al₂O₃Content it is excessive, then in glass be easy be precipitated devitrification crystallization, it is difficult to Plate is configured to using overflow downdraw etc..In addition, acid resistance reduces, it is difficult to be suitable for acid treatment process.In addition, high temperature is viscous Property is got higher, and meltbility is easily reduced.Therefore, Al₂O₃Upper range be preferably 30% or less, 28% or less, 26% or less, 24% or less, 23.5% or less, 22% or less, 21% hereinafter, particularly preferably 20.5% or less.

B₂O₃It is the ingredient for reducing liquidus temperature, cracking frequency, high temperature viscosity and density, in addition, being to make stabilization The ingredient for making crystallization be difficult to be precipitated.B₂O₃Lower range be preferably 0% or more, 0.1% or more, 1% or more, 2% or more, it is special It You Xuanwei 3% or more.But if B₂O₃Content it is excessive, then the glass surface referred to as burnt occurs because of ion exchange Perhaps water resistance reduces or stress depth is easy to become smaller for coloring.Therefore, B₂O₃Upper range be preferably 10% or less, 6% Below, 5% hereinafter, particularly preferably less than 4%.

Na₂O is ion exchange ingredient, in addition, being the ingredient for reducing high temperature viscosity, improving meltbility and formability.In addition, Na₂O still improves the ingredient of devitrification resistance.If Na₂The content of O is very few, then meltbility, ion-exchange performance are easily reduced.Cause This, Na₂The content of O is preferably 5% or more, more than 7.0%, 10% or more, 12% or more, 13% or more, particularly preferably 14% or more.On the other hand, if Na₂The content of O is excessive, then thermal expansion coefficient becomes excessively high, and thermal shock resistance reduces, or is difficult to It is matched with the thermal expansion coefficient of organic resin middle layer.In addition, strain point excessively reduces, or the ingredient of shortcoming glass composition is flat Weighing apparatus, devitrification resistance reduces sometimes instead.Therefore, Na₂The content of O is preferably 20% or less, 19% or less, 17% or less, 16.3% or less, 16% hereinafter, particularly preferably 15% or less.

K₂O is the ingredient for promoting ion exchange, is the ingredient of stress depth easy to increase among alkali metal oxide.Separately It outside, is the ingredient for reducing high temperature viscosity, improving meltbility, formability.In addition, still improving the ingredient of devitrification resistance.But if K₂The content of O is excessive, then thermal expansion coefficient becomes excessively high, and thermal shock resistance reduces, it is difficult to be matched with organic resin middle layer Thermal expansion coefficient.In addition, there are the ingredient balances of glass composition, and impaired, devitrification resistance drops instead if strain point is excessively reduced Low tendency.Therefore, K₂The upper range of O is preferably 5% or less, 4% or less, less than 2%, especially less than 1%.It needs It is bright, add K₂In the case where O, additive amount is preferably 0.1% or more, 0.3% or more, particularly preferably 0.5% or more.

In addition to the above ingredients, ingredient for example below can also be added.

Li₂O is ion exchange ingredient, in addition, being the ingredient for reducing high temperature viscosity, improving meltbility, formability, is simultaneously Improve the ingredient of Young's modulus.In addition, among alkali metal oxide, Li₂The effect of the raising compression stress value of O is big, but Include 5% or more Na₂In the glass system of O, if Li₂The content of O becomes extremely more, then there is the tendency that compression stress value reduces instead. In addition, if Li₂The content of O is excessive, then on the basis of liquid phase viscosity reduces, glass is easy devitrification, thermal expansion coefficient became High, thermal shock resistance reduces, or is difficult to be matched with the thermal expansion coefficient of organic resin middle layer.In addition, low temperature viscometric property excessively drops It is low, it is easy to happen stress relaxation, compression stress value reduces sometimes instead.Therefore, Li₂The content of O is preferably 0~4%, 0~ 2%, 0~1.5%, 0~1%, 0% more than and less than 1.0%, 0~0.5%, 0~0.1%, particularly preferably 0.01~ 0.05%.

MgO is the ingredient for reducing high temperature viscosity, raising meltbility, formability, strain point and Young's modulus, in alkaline-earth metal It is the big ingredient of the effect of raising ion-exchange performance among oxide.Thus, the lower range of MgO be preferably 0% or more, 0.5% or more, 1% or more, 1.2% or more, 1.3% or more, particularly preferably 1.4% or more.But the if content mistake of MgO More, then density and thermal expansion coefficient are easy to get higher, and in addition glass is easy devitrification.Therefore, the upper range of MgO be preferably 9% with Under, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2.3% Hereinafter, particularly preferably 2.2% or less.

CaO is to reduce high temperature viscosity compared with other ingredients, and improve meltbility, formability, strain point and Young mould The ingredient measured and reduced without devitrification resistance.But if the content of CaO is excessive, density, thermal expansion coefficient are got higher, in addition The ingredient balance of glass composition is impaired, and glass is easy devitrification instead, and perhaps ion-exchange performance reduces or is easy to hand over ion Change solution deterioration.Therefore, the content of CaO be preferably 0~6%, 0~5%, 0~4%, 0~3.5%, 0~3%, 0~2%, 0% more than and less than 1%, 0~0.5%, particularly preferably 0~0.1%

SrO and BaO is the ingredient for reducing high temperature viscosity, and improving meltbility, formability, strain point and Young's modulus. But if the content of SrO and BaO is excessive, on the basis of ion-exchange reactions is easy to be hindered, density, thermal expansion system Number is got higher or glass is easy devitrification.Therefore, the content of SrO and BaO is respectively preferably 0~2%, 0~1.5%, 0~1%, 0 ~0.5%, 0~0.1%, particularly preferably 0% more than and less than 0.1%.

If the total amount of MgO, CaO, SrO and BaO are excessive, got higher there are density, thermal expansion coefficient or glass devitrification, Or the tendency that ion-exchange performance reduces.Thus, the total amount of MgO, CaO, SrO and BaO are preferably 0~9.9%, 0~8%, 0 ~6%, particularly preferably 0~5%.

TiO₂It is the ingredient for improving ion-exchange performance and whitening resistance, in addition, be the ingredient for reducing high temperature viscosity, if but Its content is excessive, then glass is easy coloring or easy devitrification.Therefore, TiO₂Content be preferably 0~4.5%, 0.01~ 0.5%, particularly preferably 0.05~0.3%.

ZrO₂Be improve ion-exchange performance ingredient, and be improve liquid phase viscosity near viscosity, strain point at Point.But if ZrO₂Content it is excessive, then there is a possibility that devitrification resistance significant decrease, in addition, there is also density to become A possibility that high.Thus, ZrO₂Content be preferably 0~5%, 0~3%, 0% more than and less than 1%, particularly preferably 0.001~0.5%.

ZnO is the ingredient for improving ion-exchange performance, the big ingredient of the effect of especially raising compression stress value.In addition, It is the ingredient for reducing high temperature viscometrics without making low temperature viscometric property reduction.But if the content of ZnO is excessive, there are glass phase-separating or The tendency that person's devitrification resistance reduces or density is got higher or stress depth becomes smaller.Therefore, the content of ZnO be preferably 0~ 6%, 0~3%, 0~1%, particularly preferably 0~0.1%.

P₂O₅It is the ingredient for improving ion-exchange performance, the especially ingredient of increasing stress depth.P₂O₅Suitable lower limit model Enclosing is 0% or more, 1% or more, 3% or more, 5% or more, especially more than 7%.But if P₂O₅Content it is excessive, then glass Split-phase or water resistance are easily reduced.Therefore, P₂O₅Content suitable upper range be 20% or less, 18% or less, 15% with Under, 13% or less, 10% hereinafter, especially 7% or less.

SnO₂Have the effect of improving ion-exchange performance.Thus, SnO₂Content be preferably 0~3%, 0.01~3%, 0.05~3%, 0.1~3%, particularly preferably 0.2~3%.

As clarifying agent, can add 0~3% selected from Cl, SO₃、CeO₂Group (preferably Cl, SO₃Group) in one Kind is two or more.

Fe₂O₃Be by with TiO₂And deposit to improve the ingredient of Ultraviolet Light, if but content it is excessive, then, it is seen that Light transmission is easily reduced.Therefore, Fe₂O₃Content be preferably 10ppm or more (0.001% or more), 30ppm or more, 50ppm Above, 100ppm or more, particularly preferably 200ppm or more.In addition, Fe₂O₃Content be preferably smaller than 1000ppm and (be less than 0.1%), it is less than 800ppm, is less than 600ppm, is less than 400ppm, especially less than 300ppm.In turn, it is preferred that inciting somebody to action Fe₂O₃Content provide to above range on the basis of, by molar ratio Fe₂O₃/(Fe₂O₃+SnO₂) provide to 0.8 or more, 0.9 More than, it particularly preferably provides to 0.95 or more.Thereby, it is possible to improve total light under the conditions of 400~770nm of wavelength, plate thickness 1mm Transmissivity (for example, 90% or more).

Nd₂O₃、La₂O₃Equal rare-earth oxides are the ingredients for improving Young's modulus.But raw material itself is at high cost, this Outside, if a large amount of additions, devitrification resistance are easily reduced.Therefore, the total amount of rare-earth oxide be preferably 3% or less, 2% with Under, 1% or less, 0.5% hereinafter, particularly preferably 0.1% or less.

From the considerations of environment, is formed as glass, be preferably substantially free of As₂O₃、Sb₂O₃、PbO、Bi₂O₃And F.? This, the purport of " being substantially free of~" refers to: although not adding the ingredient write exactly energetically as glass ingredient, allowing its work It is mixed into for impurity, specifically, referring to the component content write exactly less than 0.05%.

As strengthening glass sheets, above-mentioned alkali alumina silicate glass is suitable, but from the viewpoint of manufacturing cost, can also To use soda-lime glass.Soda-lime glass is formed usually as glass contains SiO in terms of quality %₂65~75%, Al₂O₃0~ 3%, CaO 5~15%, MgO0~15%, Na₂O 10~20%, K₂O 0~3% and Fe₂O₃0~3%.

Strengthening glass sheets (outside strengthening glass sheets and/or inside strengthening glass sheets) before intensive treatment do not strengthen glass The cracking frequency of glass plate is 90% hereinafter, preferably 80% or less.Or cracking frequency is excellent as 80% load below It is selected as 500gf or more, particularly preferably 800gf or more.If cracking frequency is excessive, there are flying object and strengthening glass sheets to rush When stress that is prominent and generating part, a possibility that being easy to produce crackle in strengthening glass sheets, laminated glass caused integrally to destroy.Separately Outside, if cracking frequency is that 80% load below is too small, conflict there are flying object with strengthening glass sheets and generate local When stress, a possibility that crackle is easy to produce in strengthening glass sheets, laminated glass is caused integrally to destroy.

The density of strengthening glass sheets (outside strengthening glass sheets and/or inside strengthening glass sheets) is preferably 2.60g/cm³With Under, 2.55g/cm³Below, 2.50g/cm³Below, 2.48g/cm³Below, 2.46g/cm³Hereinafter, particularly preferably 2.45g/cm³ Below.If density is excessive, strengthening glass sheets are difficult to lightweight, and laminated glass is also difficult to lightweight.It should be noted that " close Degree " is measured using Archimedes method.

Within the temperature range of 25~380 DEG C of strengthening glass sheets (outside strengthening glass sheets and/or inside strengthening glass sheets) Thermal expansion coefficient be preferably 100 × 10^-7/ DEG C or less, 95 × 10^-7/ DEG C or less, 90 × 10^-7/ DEG C hereinafter, particularly preferably 85 ×10^-7/ DEG C or less.If the thermal expansion coefficient of strengthening glass sheets is excessively high, it is difficult to be matched with the thermal expansion of organic resin middle layer Coefficient, strengthening glass sheets and organic resin middle layer are easy to happen removing.It should be noted that " 25~380 DEG C of temperature range Interior thermal expansion coefficient " is the average value using dilatometer measurement.

The liquidus temperature of strengthening glass sheets (outside strengthening glass sheets and/or inside strengthening glass sheets) be preferably 1200 DEG C with Under, 1150 DEG C or less, 1100 DEG C or less, 1080 DEG C or less, 1050 DEG C or less, 1020 DEG C hereinafter, particularly preferably 1000 DEG C with Under.Liquid phase viscosity is preferably 10^4.0DPas or more, 10^4.4DPas or more, 10^4.8DPas or more, 10^5.0DPas or more, 10^5.3DPas or more, 10^5.5DPas or more, 10^5.7DPas or more, 10^5.8DPas or more, particularly preferably 10^6.0DPas or more.If liquidus temperature and liquid phase viscosity become outside above range, glass is easy devitrification when shaping.It needs Bright, " liquidus temperature " refers to following numerical value: by 30 mesh of standard screen (sieve pore is 500 μm) and will remain in 50 mesh (sieve pores Be 300 μm) glass powder investment platinum boat after, is kept for 24 hours in temperature gradient furnace, measurement crystallization precipitation temperature and obtain Value." liquid phase viscosity " refers to the glass viscosity under liquidus temperature is measured using platinum ball czochralski method obtained by value.

The Young's modulus of strengthening glass sheets (outside strengthening glass sheets and/or inside strengthening glass sheets) be preferably 76GPa with Under, 74GPa or less, 72GPa be hereinafter, particularly preferably 70GPa or less.If Young's modulus is excessively high, strengthening glass sheets are difficult to scratch The impact absorbency of song, laminated glass is easily reduced.It should be noted that " Young's modulus " is surveyed using resonance method etc. It is fixed.

In laminated glass for use in vehicles of the invention, the thickness of organic resin middle layer be preferably 0.1~2mm, 0.3~ 1.5mm, 0.5~1.2mm, particularly preferably 0.6~0.9mm.If the thickness of organic resin middle layer is too small, impact absorbency It is easily reduced, in addition, anchorage is easy to produce deviation, strengthening glass sheets are easily peeled off with organic resin middle layer.On the other hand, If the thickness of organic resin middle layer is excessive, the observation of laminated glass is easily reduced.

As organic resin middle layer, various organic resins can be used, such as polyethylene (PE), ethylene-can be used Vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin (PMA), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), cellulose ethanoate (CA), neighbour Dially phthalate resin (DAP), carbamide resin (UP), melamine resin (MF), unsaturated polyester (UP) (UP), polyvinyl alcohol Butyral (PVB), polyvinyl formal (PVF), polyvinyl alcohol (PVAL), vinyl acetate resin (PVAc), ionomer (IO), polymethylpentene (TPX), vinylidene chloride (PVDC), polysulfones (PSF), Kynoar (PVDF), methacrylic acid- Styrene copolymerized resin (MS), polyarylate (PAR), polyallyl sulfone (PASF), polybutadiene (BR), polyether sulfone (PESF) or poly- Ether ether ketone (PEEK) etc..Wherein, from the viewpoint of the transparency and anchorage, it is suitably for EVA, PVB, especially, PVB can be assigned Sound-proofing is given, therefore preferably.

Colorant can be added into organic resin middle layer, can also add that absorb infrared ray, ultraviolet light etc. specific The absorbent of wavelength light.

For organic resin middle layer, the organic resin middle layer that above-mentioned organic resin composition is a variety of can be used.Example Such as, if using two layers of organic resin middle layer, outside strengthening glass sheets and the different organic resin of inside strengthening glass sheets Fixation, therefore when stacking integration, it is easy to reduce the warpage of laminated glass.

According to following operation, laminated glass for use in vehicles of the invention can be made.

Firstly, glass raw material made of being deployed in the way of becoming regulation glass and forming is put into continuous fusion furnace, With 1500~1700 DEG C of progress heating meltings, after clarification, stirring, supply is configured to plate to forming device, carries out slow cooling, by This can make glass plate.

As the method for being configured to writing board shape, it is preferred to use overflow downdraw.Overflow downdraw be can surface not The glass plate of high-quality, and the method that can easily make large glass plate are largely made in the state of ground.It needs It is bright, if surface free is ground, the manufacturing cost of glass plate can be made cheaper.

Other than overflow downdraw, glass plate further preferably is configured to using float glass process.Float glass process is inexpensively to make The method of large glass plate.

Then, Machining of Curved Surface is carried out as needed for obtained glass plate.As the method for Machining of Curved Surface, can adopt With various methods.It is particularly preferred to carry out stamping method to glass plate using mold, more preferably regulation shape is being utilized Mold clamp glass plate in the state of make it through heat-treatment furnace.Thereby, it is possible to improve the dimensional accuracy of curve form.This Outside, further preferably following methods: after configuring glass plate on the mold of regulation shape, a part to glass plate or it is whole into Row heat treatment, to make method of glass plate due to self weight along the shape generation softening transform of mold.Thereby, it is possible to improve song The efficiency of face processing.

Then, intensive treatment is carried out to the glass plate after Machining of Curved Surface, obtains two panels strengthened glass.From improving, point impact is strong From the perspective of degree, chemical intensification treatment is carried out to outside strengthening glass sheets.The condition of chemical intensification treatment is not particularly limited, Viscosity characteristics, purposes, thickness, the tensile stress of inside, change in size of glass etc. is considered to select optimum condition.Example Such as, it can be carried out by impregnating 1~8 hour in 390~490 DEG C of fuse salt.Especially, if by the K ion in fuse salt Ion exchange is carried out with the Na ingredient in glass, then compressive stress layers can be efficiently formed in glass surface.As fuse salt, Various fuse salts can be used, it is, for example, possible to use KNO₃With NaNO₃Mixed melting salt.In this case, NaNO₃Concentration it is excellent It is selected as 5~20 mass %.

Multiple (preferably twice) chemical intensification treatment can be carried out for a glass plate.If repeatedly carrying out chemical strengthening Processing, then can be such that the distribution curve of the K ion concentration of depth direction be bent, can make the compression stress values of compressive stress layers with Stress depth increases, and reduces the total amount of the tensile stress of internal accumulation.It, can in the case where carrying out chemical intensification treatment twice Heat treatment procedure to be arranged between chemical intensification treatment.As a result, by fuse salt, the pressure on surface to depth direction can be made Stress under compression curve is efficiently bent.And then the time of first time ion-exchange treatment can be shortened.

Physical strengthening processing can be carried out for inside strengthening glass sheets.The condition of physical strengthening processing does not limit especially It is fixed, after being preferably heated to the temperature near the softening point of glass plate, chilling is carried out by air injection etc..It can be in other approach Heat treatment procedure in carry out physical strengthening processing, but from the viewpoint of manufacture efficiency, preferably by will be after Machining of Curved Surface Glass plate chilling carries out.

And then integration is laminated via organic resin middle layer in two panels strengthening glass sheets, laminated glass is made.As Integrated method is laminated, can enumerate: keeping organic resin cured after injecting organic resin between two panels strengthening glass sheets Method；The method etc. that pressurized, heated processing (thermo-compression bonding) is carried out after organic resin sheet is configured between two panels strengthening glass sheets, after It is integrated thus preferred that the method for person is easy stacking.

In addition, when pressurized, heated processing (thermo-compression bonding), it, can be in being configured at according to the thermal expansion coefficient of strengthening glass sheets The heating temperature of the heater of side and outside sets difference.In this case, it is preferred that improving the heater of the strengthening glass sheets side of low bulk Heating temperature, reduce the heating temperature of the heater of the strengthening glass sheets side of high expansion.It is flexible between strengthening glass sheets as a result, Amount is easy matching, can reduce the warpage of laminated glass.

After obtaining laminated glass, preferably the organic resin middle layer overflowed from the end face of laminated glass is removed, in order to anti- Only chamfer machining can be carried out from the end face breakage of laminated glass.It, can strengthened glass on the outside in addition, after obtaining laminated glass The surface of plate or inside strengthening glass sheets forms hardcoat film, infrared reflection film.

(embodiment 1)

Hereinafter, based on embodiment come the present invention will be described in detail.It should be noted that embodiment below is simple example Show.The present invention is not limited to the following embodiments completely.

Firstly, containing SiO in terms of quality % according to obtaining forming as glass₂61.5%, Al₂O₃18.0%, B₂O₃ 0.5%, Na₂O 14.5%, K₂O 2.0%, MgO 3.0% and SnO₂The mode of 0.5% glass deploys glass raw material.It connects , the glass raw material deployed is put into continuous fusion furnace, melting, clarification, stirring, after obtaining the melten glass of homogeneous, In supply to formed body, plate is configured to using overflow downdraw.

Various characteristics, fruit density 2.45g/cm are evaluated for obtained glass plate³, thermal expansion coefficient be 91 × 10^-7/ DEG C, Young's modulus 71GPa, liquidus temperature is 970 DEG C, liquid phase viscosity 10^6.3DPas, cracking frequency 65%.? This, density is the value using the measurement of well known Archimedes method.Thermal expansion coefficient is to measure 25~380 DEG C using dilatometer It is worth obtained by mean thermal expansion coefficients in temperature range.Young's modulus is the value using the measurement of well known resonance method.Liquid phase temperature Degree refers to following numerical value: passing through 30 mesh of standard screen (sieve pore is 500 μm) and remains in the glass on 50 mesh (sieve pore is 300 μm) It after powder puts into platinum boat, is kept for 24 hours in temperature gradient furnace, is worth obtained by the temperature that measurement crystallization is precipitated.Liquid phase viscosity is It is measured using platinum ball czochralski method and is worth obtained by the glass viscosity under liquidus temperature.Cracking frequency refers to following numerical value: firstly, Be maintained in 200 DEG C of temperature of electric furnace and kept for 1 hour, keep the moisture state on surface constant, thereafter, be maintained at humidity 30%, In the constant temperature and humidity cabinet that 25 DEG C of temperature, the Vickers indenter for being set as load 800gf is pressed into glass surface 15 seconds, this is after 15 seconds The quantity (every 1 impression maximum is set as 4) for counting the crackle from 4 jiaos of generations of impression, is pressed into further according to this mode First 50 times, find out the value after number occurs for total crackle, found out by the formula that number/200 × 100 occur for total crackle.

Next, using fuse salt recorded in table 1, being recorded in table 1 after carrying out optical grinding to two surfaces of glass plate Under conditions of carry out ion-exchange treatment, obtain each strengthening glass sheets (sample No.1~4).Then, for obtained reinforcing Glass plate, according to the item number for the interference fringe for using surface stress meter (the manufactured FSM-6000 of the former production of folding) observation and therebetween Every the compression stress value CS and stress depth DOL of surface compression stressor layers being calculated, further by above-mentioned mathematical expression 1, in calculating The tensile stress values CT in portion.When calculating, the refractive index of each sample is set as 1.5, Photoelasticity constant and is set as 29.5 [(nm/ cm)/MPa].It the results are shown in table 1.

[table 1]

For obtained strengthening glass sheets evaluation point impact strength.Point impact strength is found out in accordance with the following methods: in flower 1 strengthening glass sheets is placed on the precision surface plate of Gang Yan, on it by the abrasive grain face of sand paper (grain size number P100, abrasive grain SiC) It after placing towards strengthening glass sheets side, falls the stainless steel ball of 66.8g naturally from upper direction sand paper, it is broken to find out strengthening glass sheets The height of damage.Measurement number is set as 15 times, and mean intensity is calculated by steel ball weight × acceleration of gravity × breakage height, together also Calculate Weibull modulus.Their result is shown in table 1.

As shown in Table 1, the tensile stress values of sample No.1,2 plate thickness, compression stress value CS, stress depth DOL and inside CT is appropriate, therefore it is high to put impact strength.On the other hand, the stress depth DOL of sample No.3 is excessive, therefore it is low to put impact strength. The stress depth DOL of sample No.4 is too small, therefore it is low to put impact strength.

(embodiment 2)

Firstly, containing SiO in terms of quality % according to obtaining forming as glass₂61.5%, Al₂O₃18.0%, B₂O₃ 0.5%, Na₂O 14.5%, K₂O 2.0, MgO 3.0% and SnO₂The mode of 0.5% glass deploys glass raw material.Then, The glass raw material deployed is put into continuous fusion furnace, melting, clarification, stirring, after obtaining the melten glass of homogeneous, supply To formed body, plate is configured to overflow downdraw in the way of obtaining plate thickness as 1.1mm.

Then, it for obtained glass plate, is made it through in the state of sandwiching each sample with the mold of regulation shape Heat-treatment furnace, so that Machining of Curved Surface is at the integrally bending in board width direction at arc-shaped and the integrally bending Cheng Yuan of length direction The curve form of arcuation.

For the glass plate after Machining of Curved Surface, mixed melting salt (KNO is used₃87.43 mass %, NaNO₃12.57 matter Measure %), with 480 DEG C of progress, 2 hours ion-exchange treatments, strengthened glass plate.After further preparing two panels Machining of Curved Surface Strengthening glass sheets, and using the organic resin middle layer (PVB) of thickness 0.7mm, they are handled into layer by pressurized, heated Folded integration, obtains the laminated glass with curve form.Think that the laminated glass can take into account high-intensitive and slimming, and energy Enough it is effectively prevented from the danger of injury of human when breakage.

(embodiment 3)

For the glass plate (sample No.5~11) recorded in table 2, pass through the method march recorded in 2 one column of embodiment After the processing of face, intensive treatment is carried out, strengthened glass plate.It should be noted that the density of each sample, thermal expansion coefficient, poplar Family name's modulus, liquidus temperature, liquid phase viscosity and cracking frequency are measured by the measuring method recorded in 1 one column of embodiment.

For sample No.5~7,9~11, ion-exchange treatment has been carried out according to the condition recorded in 2 one column of embodiment, The compression stress value CS of surface compression stressor layers is 400MPa or more, and stress depth DOL is 40~90 μm.For sample No.8, By the chilling after Machining of Curved Surface, surface compression stressor layers are formed, compression stress value CS is 50MPa, and stress depth DOL is 200μm。

[table 2]

Then, for the sample No.1 (outside strengthening glass sheets) of table 1,2 and sample No.2 (inside strengthening glass sheets), examination Expect No.1 (outside strengthening glass sheets) and sample No.5 (inside strengthening glass sheets), sample No.2 (outside strengthening glass sheets) and examination Expect No.5 (inside strengthening glass sheets), two panels sample No.6, two panels sample No.7, sample No.1 (outside strengthening glass sheets) and examination Expect No.8 (inside strengthening glass sheets), two panels sample No.9, two panels sample No.10, two panels sample the No.11, (outside sample No.9 Strengthening glass sheets) with the combination of sample No.8 (inside strengthening glass sheets), the method by being recorded in 2 one column of embodiment, respectively Make laminated glass.

Industrial availability

Laminated glass for use in vehicles of the invention is suitable for the windshield of automobile, be also suitable for automobile wind shield glass wind shield, Door glass, roof glass.In addition, being also adapted to the glass pane of rail truck.

Description of symbols

10 laminated glass for use in vehicles

11 outside strengthening glass sheets

12 inside strengthening glass sheets

13 organic resin middle layers

Claims (12)

1. a kind of laminated glass for use in vehicles is outside strengthening glass sheets and inside strengthening glass sheets via organic resin middle layer Laminated glass for use in vehicles made of integration, which is characterized in that

The plate thickness of outside strengthening glass sheets be 2.0mm hereinafter,

Outside strengthening glass sheets have the surface compression stressor layers as brought by ion exchange,

The compression stress value of the surface compression stressor layers of outside strengthening glass sheets be 350MPa or more, and stress depth be 15 μm~ 100μm。

2. laminated glass for use in vehicles according to claim 1, which is characterized in that

The tensile stress values of the inside of outside strengthening glass sheets are 70MPa or less.

3. laminated glass for use in vehicles according to claim 1 or 2, which is characterized in that

Outside strengthening glass sheets are formed as glass contains SiO in terms of quality %₂40%~80%, Al₂O₃3%~30%, B₂O₃0%~10%, Na₂O 5%~20% and K₂O 0%~5%.

4. laminated glass for use in vehicles described in any one of claim 1 to 3, which is characterized in that

The compression stress value of the surface compression stressor layers of inside strengthening glass sheets be 350MPa or more, and stress depth be 15 μm~ 100μm。

5. laminated glass for use in vehicles according to any one of claims 1 to 4, which is characterized in that

The tensile stress values of inside strengthening glass sheets are 70MPa or less.

6. laminated glass for use in vehicles according to any one of claims 1 to 5, which is characterized in that

Inside strengthening glass sheets are formed as glass contains SiO in terms of quality %₂40%~80%, Al₂O₃3%~30%, B₂O₃0%~10%, Na₂O 5%~20% and K₂O 0%~5%.

7. laminated glass for use in vehicles according to claims 1 to 6, which is characterized in that

The Young's modulus of outside strengthening glass sheets and/or inside strengthening glass sheets is 76GPa or less.

8. laminated glass for use in vehicles according to any one of claims 1 to 7, which is characterized in that

Cracking frequency before the intensive treatment of outside strengthening glass sheets and/or inside strengthening glass sheets is 80% or less.

9. laminated glass for use in vehicles described according to claim 1~any one of 8, which is characterized in that

Organic resin layer is made of vinyl-vinyl acetate copolymer or polyvinyl butyral.

10. laminated glass for use in vehicles according to claims 1 to 9, which is characterized in that

Curve form with three-dimensional bending.

11. laminated glass for use in vehicles described according to claim 1~any one of 10, which is characterized in that

Windshield for automobile.

12. laminated glass for use in vehicles described according to claim 1~any one of 10, which is characterized in that

Glass pane for rail truck.