CN110194590A

CN110194590A - The manufacturing method of glass, the protective glass for having used the glass and glass

Info

Publication number: CN110194590A
Application number: CN201910299038.6A
Authority: CN
Inventors: 村田隆; 齐藤敦己
Original assignee: Nippon Electric Glass Co Ltd
Current assignee: Nippon Electric Glass Co Ltd
Priority date: 2014-04-03
Filing date: 2015-04-01
Publication date: 2019-09-03
Also published as: JP2019112303A; KR102563271B1; KR20210142775A; JP6691315B2; KR102332532B1; CN106132889A; KR20160141737A; JP2016102045A; JP7183108B2; KR20230117626A; CN113998884A; CN115448593A; WO2015152342A1; JP7472925B2; JP2022060313A; CN115448592A; JP2024071784A

Abstract

The purpose of the present invention is be put forward for the first time even if without ion-exchange treatment, do not tend to have that scratch, drop impact strength be high and the glass and its manufacturing method of light weight.For glass of the invention, forms, in mass, contain: SiO as glass₂50~70%, Al₂O₃0~20%, B₂O₃15~30%, Li₂O+Na₂O+K₂O 0~3%, MgO+CaO+SrO+BaO 0~12%.

Description

The manufacturing method of glass, the protective glass for having used the glass and glass

The cross reference of related application

The application is to enter on 09 30th, 2016 National Phase in China, national application number 201580018105.2, hair It is bright it is entitled " glass, used the glass protective glass and glass manufacturing method " divisional application.

Technical field

The present invention relates to glass, the protective glass of the glass and the manufacturing method of glass have been used, in particular to To mobile phone, digital camera, PDA (portable terminal), solar battery, chip size packages (CSP), charge coupled cell (CCD), the protective glass of the protective glass of equimultiple proximity type solid-state image pickup element (CIS), particularly touch-screen display is applicable in Glass and glass manufacturing method.

Background technique

The equipment such as mobile phone, digital camera, PDA have the tendency that more more and more universal.At these on the way, at ion exchange Tempered glass after reason is used as the protective glass (referring to patent document 1, non-patent literature 1) of touch-screen display.

All the time, for tempered glass, to carry out at ion exchange after glass plate is cut into predetermined shape in advance The mode of so-called " strengthen before cutting " of reason makes, but in recent years, have studied to large-scale reinforcing with glass plate carry out from After sub- exchange processing, the films such as touch sensor are formed, and cut into so-called " cutting off after reinforcing " of predetermined size.If carried out strong It is cut off after change, then the manufacture efficiency of equipment improves by leaps and bounds.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2006-83045 bulletin

Non-patent literature

Non-patent literature 1: the thorough youth of spring paddy etc., " novel glass and its physical property ", the first edition, enterprise management system research institute, August in 1984 20 days, p.451-498

Summary of the invention

The technical problem to be solved by the invention

However, being needed for protective glass: (1) it is high not tend to have scratch, (2) drop impact strength.Existing protective glass In order to meet the characteristic of above-mentioned (1), (2), by ion-exchange treatment, the tempered glass that surface has compressive stress layers is obtained.

But ion-exchange treatment keeps the manufacturing cost of protective glass surging.

In addition, the compressive stress layers for being present in surface become obstacle and therefore cut in the case where cutting off after being strengthened When disconnected, tempered glass is easy breakage, meanwhile, after cutting, there is no the regions of compressive stress layers to expose in end face, therefore, end face Intensity is easy decline.In the case where further forming the films such as touch sensor on the surface of tempered glass, the face of tempered glass Interior intensity is easy decline.

Further, it is studying in large-scale tv also using protective glass, is being used in the protective glass in recent years Tempered glass.But existing tempered glass is not yet light enough, nor facilitating the lightweight of large scale equipment.

The present invention is completed in view of above-mentioned item, and technical task is to be put forward for the first time at without ion exchange Reason does not tend to have scratch, drop impact strength height and the glass of light weight, the protective glass for having used the glass and its manufacturer yet Method.

For technical means to solve problem

Various experiments are repeated in the present inventor, as a result, it has been found that, by the way that glass compositing range is limited in preset range, from And it is able to solve above-mentioned technical problem, and propose as the present invention.That is, being formed as glass, in glass of the invention with quality Meter, contains SiO₂50~70%, Al₂3 0~20%, B₂O₃15~30%, Li₂O+Na₂O+K₂O 0~3%, MgO+CaO+ SrO+BaO 0~12%.Herein, Li₂O+Na₂O+K₂O refers to Li₂O、Na₂O and K₂The total amount of O.MgO+CaO+SrO+BaO refers to The total amount of MgO, CaO, SrO and BaO.

Glass of the invention contains B in glass composition₂O₃For 15 mass % or more.In such manner, it is possible to improve resistance to marring, Crack resistance.Further, since Young's modulus declines, it also can be improved drop impact.Further, glass of the invention makes Li in glass composition₂O+Na₂O+K₂The content of O is 3 mass % hereinafter, making the 12 mass % of content of MgO+CaO+SrO+BaO Hereinafter, preferably 8 mass % or less.In this way, density is easy decline, as a result, being easy to make protective glass lightweight.

In addition, glass of the invention is preferred are as follows: form, in mass, contain: SiO as glass₂58~70%, Al₂O₃ 7~20%, B₂O₃18~30%, Li₂O+Na₂O+K₂O 0~1%, MgO+CaO+SrO+BaO 0~10%.

In addition, glass of the invention is preferred are as follows: form, in mass, contain: SiO as glass₂50~70%, Al₂O₃ 0~15%, B₂O₃15~30%, Li₂O+Na₂O+K₂O 0~3%, MgO+CaO+SrO+BaO 0~8%.

In addition, glass of the invention is preferred are as follows: B₂O₃(MgO+CaO+SrO+BaO) is 5 mass % or more.Herein, “B₂O₃(MgO+CaO+SrO+BaO) " refers to, from B₂O₃Content in subtract the total content of MgO, CaO, SrO and BaO after Value.

For example, 200 μm of film-like glass below of plate thickness the case where, light weight and coiled to help to be wound is needed The small radius of curvature of shape is bent.Therefore, if using above-mentioned composition, it is easy to get the glass of low-density and low Young's modulus, It is suitable as film-like glass material.

In addition, glass of the invention is preferred are as follows: by quality ratio, (SrO+BaO)/(MgO+CaO) is 1 or less.Herein, (SrO+BaO)/(MgO+CaO) refers to value obtained from total content of the total content of SrO and BaO divided by MgO and CaO.

If being easy to get the glass of low-density using above-mentioned composition, it is suitable as film-like glass material.

In addition, glass of the invention is preferred are as follows: in terms of quality standard, B₂O₃Content ratio Al₂O₃Content it is more (that is, B₂O₃- Al₂O₃More than 0 mass %).

If being easy to get the glass of low Young's modulus using above-mentioned composition, it is suitable as film-like glass material.

In addition, glass of the invention is preferred are as follows: liquid phase viscosity 10^5.0DPas or more.Herein, " liquid phase viscosity " refers to It is worth obtained from the viscosity of glass when measuring liquidus temperature with platinum ball czochralski method." liquidus temperature ", which refers to, passes through standard screen 30 Mesh (500 μm) but the glass powder for remaining in 50 mesh (300 μm) is put into platinum boat, and kept for 24 hours in temperature gradient furnace, it surveys Value obtained from the temperature of crystallization is precipitated is determined.

In addition, glass of the invention is preferred are as follows: density 2.40g/cm³(especially 2.30g/cm below³30 below) ,~ Thermal expansion coefficient within the temperature range of 380 DEG C is 25~40 × 10^-7/ DEG C, strain point is 610 DEG C or less and Young's modulus is 66GPa or less (especially 65GPa or less).Herein, " density " can be measured by well known Archimedes method." 30~380 DEG C Within the temperature range of thermal expansion coefficient " refer to using dilatometer measure average value." strain point " refers to according to ASTM C336 Method measurement value." Young's modulus " refers to the value measured by well known resonance method.

In addition, glass of the invention is preferred are as follows: be molded with by overflow downdraw.Herein, " overflow downdraw " is to make Melten glass is overflowed from the two sides of the water guide tubular structure object of heat resistance, and makes the melten glass overflowed in water guide tubular structure object Lower end interflow, and extend downward the method to make glass plate of molding.

In addition, glass of the invention is preferred are as follows: be used for protective glass.

In addition, glass of the invention is preferred are as follows: do not carry out ion-exchange treatment.In such manner, it is possible to make the manufacture of protective glass It is cost-effective.

However, in the case where using glass of the invention as protective glass etc., spot caused by the attachment of fingerprint etc. It is not easy to become problem.In such a situation it is preferred to have photocatalyst particles in glass surface load.

According to such composition, the fingerprint etc. for removing and being attached to surface can be decomposed by the effect of photocatalyst particles Spot.

In addition, largely containing B₂O₃Glass split-phase tendency it is strong, even if especially sometimes without heat treatment, surface It also can split-phase.If implementing acid processing to such glass, surface portion becomes cellular, can be readily derived specific surface The big glass of product.

In addition, glass of the invention is preferred are as follows: glass surface is cellular.Herein, " surface is cellular " refers to only table Face is cellular, and in other words, particle is not integrally porous body." cellular " refers to the state there are millions of holes, but unrequired It wants to be connected between hole.

If a large amount of photocatalyst particles can be loaded in glass surface using above-mentioned composition, and can will be a large amount of Organic matter is adsorbed on photochemical catalyst body surface face, therefore, can greatly improve photochemical catalyst function.

In addition, glass of the invention is preferred are as follows: photocatalyst particles are TiO 2 particles.

If using above-mentioned composition, once irradiation sunlight etc. includes the light of ultraviolet light, in the organic matters quilt such as spot, bacterium Fast decoupled can obtain excellent antifouling, antibacterial, antimycotic and other effects.

Protective glass of the invention includes the glass of aforementioned present invention.

Protective glass of the invention is preferred are as follows: glass surface is cellular, and load has photocatalyst particles.

The protective glass of above-mentioned composition can remove the fingerprint for being attached to surface by effect, the decomposition of photocatalyst particles Etc. spots, therefore be easy to maintain clean state.

The manufacturing method of glass of the invention is will to form as glass, contain in mass to become: SiO₂50~ 70%, Al₂O₃0~20%, B₂O₃15~30%, Li₂O+Na₂O+K₂O 0~3%, MgO+CaO+SrO+BaO 0~12% The fusing of feed proportioning that the mode of glass is prepared for, molding method.Contain in mass it is further preferred that being prepared into: SiO₂58~70%, Al₂O₃7~20%, B₂O₃18~30%, Li₂O+Na₂O+K₂O 0~1%, MgO+CaO+SrO+BaO 0 ~10% glass contains in mass: SiO₂50~70%, Al₂O₃0~15%, B₂O₃15~30%, Li₂O+Na₂O +K₂The feed proportioning of the mode of the glass of O 0~3%, MgO+CaO+SrO+BaO 0~8%.

In addition, the manufacturing method of the present invention is preferred are as follows: further contain photochemical catalyst ingredient in glass surface coating Solution, then, carrying out heat treatment makes glass surface loaded optic catalyst particle.

If, can be easily in glass surface loaded optic catalyst particle using above-mentioned composition.

In addition, the manufacturing method of the present invention is preferred are as follows: after carrying out sour processing to glass surface, coating contains photocatalysis The solution of agent ingredient.

If the surface of the glass as substrate is cellular using above-mentioned composition, it is capable of increasing specific surface area, therefore energy Enough load a large amount of photocatalyst particles.

In addition, the manufacturing method of the present invention is preferred are as follows: as the solution containing photochemical catalyst ingredient, using being dispersed with dioxy Change the solution of titanium particle.

If can easily be coated with the organic matters such as rapid decomposable spot, bacterium in glass surface using above-mentioned composition TiO 2 particles.

Invention effect

According to the present invention, as described above, glass composition is specified to specific range, to even if hand over without ion Processing is changed, is also capable of providing and does not tend to have scratch, drop impact strength height and the glass of light weight, the protection glass for having used the glass Glass and its manufacturing method.

Specific embodiment

In glass of the invention, the reasons why limiting the content of each ingredient as above, is as follows.It should be noted that for following % indicate, unless otherwise instructed, then refer to quality %.

SiO₂Content be 50~70%, preferably 53~70%, 55~70%, 58~70%, 60~70%, 62~ It 69%, is particularly preferably 62~67%.If SiO₂Content it is very few, then density is easy to get higher.On the other hand, if SiO₂'s Content is excessive, then high temperature viscosity is got higher, meltability declines, in addition, the defects of being easy to happen devitrification crystallization (cristobalite) in glass.

Al₂O₃It is any ingredient, but if its content is very few, then resistance to marring, crack resistance, heat resistance are easy decline.Separately Outside, split-phase causes transmitance to be easy decline.Therefore, Al₂O₃Lower range be 0% or more, preferably 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, particularly preferred 9% or more.On the other hand, Al₂O₃ It is improved the ability of Young's modulus, but if its content is excessive, then Young's modulus becomes excessively high, and impact resistant strength is easy decline. In addition, in the case where film-like glass, it is difficult to reduce radius of curvature.Moreover, if Al₂O₃Content it is excessive, then liquidus temperature It gets higher, devitrification resistance is easy decline.Therefore, Al₂O₃Upper range be 20% hereinafter, preferably 19% or less, 18% or less, 17% or less, 15% or less, less than 13%, 12% hereinafter, particularly preferred 11% or less.

B₂O₃It is the ingredient of raising resistance to marring, crack resistance, and is the ingredient for declining Young's modulus.Still make density The ingredient of decline.In addition, being the ingredient for reducing dielectric loss, vibration loss.It is further the ingredient for being easy to induce split-phase.Such as Split-phase occurs for fruit glass, then leads to peracid treatment and be easy to make Glass Surface Modification at cellular, loaded optic catalyst particle can obtain To the photocatalyst activity function of height.B₂O₃Content be 15~30%.If B₂O₃Content it is very few, then resistance to marring, anti- Fragility is easy decline, in addition, Young's modulus is got higher, impact resistance is easy decline.In addition, in the case where film-like glass, it is difficult to Reduce radius of curvature.Further, insufficient as the ability of fluxing agent, high temperature viscosity gets higher, steeps the easy decline of quality.It is difficult To further realize low-density.Therefore, B₂O₃Lower range be 15% or more, preferably 18% or more, 20% or more, it is big In 20%, 22% or more, 24% or more, especially 25% or more.On the other hand, if B₂O₃Content it is excessive, then heat resistance, Chemical durability is easy decline, and split-phase causes transmitance to be easy decline.Therefore, B₂O₃Upper range be 30% hereinafter, preferably 28% or less, 27% or less.

B₂O₃- Al₂O₃Preferably greater than 0%, more preferable 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, particularly preferred 10% or more.The value is bigger, the easier decline of Young's modulus, Therefore, it is easy to improve drop impact strength.In addition, being easy to reduce radius of curvature in the case where film-like glass.It needs to illustrate , " B₂O₃- Al₂O₃" refer to from B₂O₃Content in subtract Al₂O₃Content after amount.

Alkali metal oxide is the ingredient for improving meltability, mouldability, but if its content is excessive, then density gets higher, is resistance to Aqueous decline, thermal expansion coefficient are exceedingly got higher, and thermal shock resistance decline is difficult to integrate with the thermal expansion coefficient of periphery material. In addition, alkali metal oxide in the case where making area load photocatalyst particles, makes photocatalyst activity function reduction.Cause This, Li₂O+Na₂O+K₂The content of O is 0~3%, preferably 0~2%, 0~1%, 0~0.5%, 0~0.2%, 0~0.1%, Particularly preferred 0~less than 0.1%.Li₂O、Na₂O and K₂The respective content of O is preferably 0~3%, 0~2%, 0~1%, 0~ 0.5%, 0~0.2%, 0~0.1%, particularly preferred 0~less than 0.1%.It should be noted that if alkali metal oxide Content is few, then does not need SiO₂The alkali barrier films such as film.

Alkaline-earth metals oxide is the ingredient for reducing liquidus temperature, making to be difficult to generate crystallization foreign matter in glass, is still mentioned The ingredient of high meltability, mouldability.The content of MgO+CaO+SrO+BaO is 0~12%, preferably 0~10%, 0~8%, 0~ 7%, 1~7%, 2~7%, 3~9%, particularly preferred 3~6%.If the content of MgO+CaO+SrO+BaO is very few, can not Give full play to the ability as fluxing agent, meltability decline, in addition, devitrification resistance is easy decline.On the other hand, if MgO+ The content of CaO+SrO+BaO is excessive, then density rises, it is difficult to the lightweight of glass is realized, in addition, thermal expansion coefficient exceedingly becomes Height, thermal shock resistance are easy decline.In addition, the split-phase of glass is deteriorated.Further, Young's modulus is got higher, in film-like glass In the case where, it is difficult to reduce radius of curvature.

If mass ratio (MgO+CaO+SrO+BaO)/Al₂O₃Too small, then devitrification resistance declines, it is difficult to pass through overflow down draw Method formed glass plate.On the other hand, if mass ratio (MgO+CaO+SrO+BaO)/Al₂O₃It is excessive, then worry density, thermal expansion Coefficient exceedingly rises.Therefore, mass ratio (MgO+CaO+SrO+BaO)/Al₂O₃Preferably 0.1~1.2,0.2~1.2,0.3~ 1.2,0.4~1.1, particularly preferred 0.5~1.0.It should be noted that (MgO+CaO+SrO+BaO)/Al₂O₃Refer to MgO+CaO+ The content of SrO+BaO is divided by Al₂O₃The obtained value of content.

Mass ratio (SrO+BaO)/B₂O₃Preferably 0.1 or less, 0.05 or less, 0.03 hereinafter, particularly preferably 0.02 with Under.In this way, being easy to improve resistance to marring, crack resistance.It should be noted that SrO+BaO refers to the total amount of SrO and BaO.In addition, (SrO+BaO)/B₂O₃Refer to the content of SrO+BaO divided by B₂O₃The obtained value of content.

In addition, mass ratio B₂O₃/ (SrO+BaO) is preferably 10 or more, 20 or more, 30 or more, 40 or more, particularly preferred 50 More than.In this way, being easy to improve resistance to marring, crack resistance.It should be noted that B₂O₃/ (SrO+BaO) refers to the content of SrO+BaO Divided by B₂O₃The obtained value of content.

B₂O₃(MgO+CaO+SrO+BaO) be preferably 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 11% or more, particularly preferred 12% or more.In this way, density is easy decline, therefore, the light weight of equipment easy to accomplish Change.In addition, Young's modulus becomes smaller.

MgO is to reduce high temperature viscosity with not making strain point decline, improves the ingredient of meltability, and be alkaline-earth metal oxygen The ingredient of density effect is most reduced in compound.Or improve the ingredient of crack resistance.In addition, and be easy induce split-phase at Point.If split-phase occurs for glass, being easy logical peracid treatment makes Glass Surface Modification at cellular, loaded optic catalyst particle, It can obtain the photocatalyst activity function of height.The content of MgO is preferably 0~12%, 0~10%, 0~8%, 0.1~ 6%, 0.5~3%, particularly preferred 1~2%.But if the content of MgO is excessive, liquidus temperature rises, and devitrification resistance is held It tends to decrease.In addition, glass is easy split-phase, the transparency is easy decline.

CaO is to reduce high temperature viscosity with not making strain point decline, significantly improves the ingredient of meltability, meanwhile, in the present invention Glass composition system in, be to improve the big ingredient of devitrification resistance effect.Therefore, the suitable lower range of CaO be 0% with Upper, 0.1% or more, 1% or more, 2% or more, 3% or more, especially 4% or more.On the other hand, if the content mistake of CaO More, then thermal expansion coefficient, density exceedingly rise, damage the ingredient balance of glass composition, in addition, devitrification resistance is easy decline. Therefore, the suitable upper range of CaO is 12% or less, 10% or less, 8% or less, 7% or less, 6% hereinafter, especially 5% Below.

SrO is the ingredient for reducing high temperature viscosity, improving meltability with not making strain point decline, but if SrO's contains quantitative change More, then resistance to marring, crack resistance are easy decline.Therefore, the content of SrO be preferably 0~3%, 0~2%, 0~1.5%, 0~ 1%, 0~0.5%, particularly preferred 0~0.1%.

BaO is to reduce high temperature viscosity with not making strain point decline, improves the ingredient of meltability, but if the content of BaO Become more, then resistance to marring, crack resistance are easy decline.Therefore, the content of BaO be preferably 0~3%, 0~2%, 0~1.5%, 0~ 1%, 0~0.5%, particularly preferred 0~less than 0.1%.

Mass ratio (SrO+BaO)/(MgO+CaO) is preferably 1 or less, 0.8 or less, 0.5 hereinafter, particularly preferred 0.3 or less. If mass ratio (SrO+BaO)/(MgO+CaO) is excessive, the density of glass becomes excessive.

Other than mentioned component, following component can also be introduced into glass composition.

ZnO is the ingredient for improving meltability, but if making largely to contain in glass composition, glass is easy devitrification, close Degree is also easy to rise.Therefore, the content of ZnO be preferably 0~5%, 0~3%, 0~0.5%, 0~0.3%, particularly preferred 0~ 0.1%.

ZrO₂It is the ingredient for improving Young's modulus.ZrO₂Content be preferably 0~5%, 0~3%, 0~0.5%, 0~ 0.2%, particularly preferred 0~0.02%.If ZrO₂Content it is excessive, then liquidus temperature rises, and the crystallization of the devitrification of zircon is easy It is precipitated.

TiO₂It is to reduce high temperature viscosity, improves the ingredient of meltability, and is the ingredient of inhibition overexposure, but if Largely contain in glass composition, then glass coloration, transmitance is easy decline.Therefore, TiO₂Content be preferably 0~5%, 0~ 3%, 0~1%, 0~0.1%, particularly preferred 0~0.02%.

P₂O₅It is the ingredient for improving devitrification resistance, but if largely containing in glass composition, then glass is easy split-phase, becomes cream White, in addition, worrying that water resistance is remarkably decreased.Therefore, P₂O₅Content be preferably 0~5%, 0~1%, 0~0.5%, especially It is preferred that 0~0.1%.

SnO₂It is the ingredient that there is good clarification in high-temperature area, and is the ingredient for declining high temperature viscosity. SnO₂Content be preferably 0~1%, 0.01~0.5%, 0.05~0.3, particularly preferred 0.1~0.3%.If SnO₂Content Excessively, then SnO₂Devitrification crystallization be easy be precipitated in glass.

As described above, adding SnO in glass of the invention₂It is suitable as clarifying agent, but as long as not damaging glass spy Property, as clarifying agent, up to 1% CeO can also be added₂、SO₃, C, metal powder (such as Al, Si etc.).

As₂O₃、Sb₂O₃, F, Cl also effectively play a role as clarifying agent, glass of the invention is not excluded for containing these Ingredient, but from environmental consideration, the content of these ingredients is preferably respectively smaller than 0.1%, particularly preferably less than 0.05%.

Glass of the invention preferably has following characteristic.

Density is preferably 2.40g/cm³Below, 2.35g/cm³Hereinafter, particularly preferred 2.30g/cm³Below.If density mistake Height is then difficult to realize the lightweight of glass.

Thermal expansion coefficient within the temperature range of 30~380 DEG C is preferably 25~40 × 10^-7/ DEG C, 30~38 × 10^-7/ DEG C, particularly preferred 32~36 × 10^-7/℃.If thermal expansion coefficient is too low, it is difficult to the thermal expansion coefficient with various periphery materials Integration, glass plate are easy warpage.On the other hand, if thermal expansion coefficient is excessively high, thermal shock resistance is easy decline.

Strain point is preferably 610 DEG C or less, 600 DEG C or less, 590 or less, 580 DEG C hereinafter, particularly preferred 570 DEG C or less. If the viscosity, particularly strain point of glass are low, in the case where the object fallen from eminence strikes glass, pass through glass Deformation, be easy to mitigate the stress of collision, be easy to mitigate the impact fallen.

10^2.5Temperature when dPas is preferably 1650 DEG C or less, 1620 DEG C or less, 1600 DEG C hereinafter, particularly preferred 1580 DEG C or less.Bubble quality not only influences the yield rate of glass, also influences the yield rate of touch sensor.Therefore, reduce high temperature viscosity, Bubble quality is improved to be important.Herein, " 10^2.5Temperature when dPas " is the value using the measurement of platinum ball czochralski method.

Young's modulus be preferably 66GPa or less, 65GPa or less, 63GPa or less, 61GPa hereinafter, particularly preferably 60GPa with Under.If reducing Young's modulus, stress caused by each certain deflection can reduce.In addition, falling from eminence In the case that object collides glass, glass is easy to happen elastic deformation, therefore, easy to mitigate the impact fallen.As a result, It is suitble to the deflection of glass to be limited at small-scale purposes, is particularly suitable for protective glass.In addition, being shaped to film-like glass In the case of, Young's modulus is lower, can be more rolled into a roll with small radius of curvature.

Liquidus temperature is preferably 1180 DEG C or less, 1150 DEG C or less, 1130 DEG C or less, 1110 DEG C or less, 1090 DEG C hereinafter, Particularly preferred 1070 DEG C or less.Liquid phase viscosity is preferably 10^5.0DPas or more, 10^5.2DPas or more, 10^5.3DPas with Above, 10^5.5DPas or more, particularly preferably 10^5.7DPas or more.In this way, devitrification crystallization is not susceptible to when molding, therefore, It is easy through formed glasses plates such as overflow downdraws, while improving the surface quality of glass plate.

Scratch resistance is preferably 5N or more, 7N or more, 10N or more, 12N or more, 15N or more.If scratch resistance is low, Trace brought by crackle is difficult to enter glass.Herein, " scratch resistance ", which refers to, is scratched with Knoop pressure head with the speed of 0.4mm/s After glass surface, with scratch the vertical direction in direction generate length be scratch 15% or more overall length, width be 2 times of scratch The load of above crackle.It should be noted that scratch test uses the friction wear testing machine UMT-2 of Bruker company, It keeps carrying out in the constant temperature and humidity cabinet of humidity 30%, temperature 25%.

Cracking preferably 200gf or more, 500gf or more, 700gf or more, 900gf or more, 1200gf or more, 1500gf Above, 2000gf or more, 2500gf or more, 3000gf or more, particularly preferred 35000gf or more.If cracking low, glass On be easy scratch.Herein, " cracking " refers to load when crackle generation rate reaches 50%.In addition, " crackle generation rate " is Refer to the value measured as follows.Firstly, predetermined load will be set as in holding humidity 30%, 25 DEG C of temperature of constant temperature and humidity cabinet Vickers indenter throw glass surface (optical grinding face) into 15 seconds, calculate this after 15 seconds from the number of the crackle of 4 jiaos of impression generations 4) amount (for 1 impression, is up to.It squeezes into this way pressure head 50 times, and after finding out total crackle and generating number, passes through total crackle The formula for generating number/200 × 100 (%) is found out.

Dielectric loss angle tangent when 1MHz frequency be preferably 0.01 or less, 0.05 hereinafter, particularly preferably 0.001 with Under.

Internal friction is preferably 0.01 or less, 0.002 or less, 0.001 hereinafter, particularly preferably 0.0008 or less.

Glass of the invention can be melted by the way that the preparing glass charge for being deployed into scheduled glass composition is put into continuous glass Furnace carries out heating fusing to the preparing glass charge, after clarifying obtained melten glass, is supplied to molding machine, so After be shaped to writing board shape etc., to make.

Glass of the invention is preferably formed by overflow downdraw.In such manner, it is possible to not ground and surface quality is good Glass plate.In the case where overflow downdraw, the face that should become surface of glass plate does not connect with tubulose (Japanese: Gutter shape) refractory material Touching, with the state forming of Free Surface, therefore, can be improved the surface quality of glass plate.The devitrification resistance of glass of the invention It is excellent, and have and be suitble to molding viscosity characteristics, it therefore, being capable of expeditiously formed glass plate by overflow downdraw.

For glass of the invention, other than overflow downdraw, various forming methods can also be used.For example, can be with Using salivation drop-down (slot down) method, float glass process, offset the forming methods such as (roll out) method.

Glass of the invention preferably has writing board shape, that is to say, that preferably glass plate, plate thickness are preferably 0.6mm or less, 0.5mm or less, 0.4mm are hereinafter, particularly preferred 0.05~0.3mm.If it is writing board shape, then it is easily applied to Protective glass.In addition, plate thickness is smaller, it is easier by glass plate lightweight, equipment also easier lightweight.

In addition, glass of the invention is preferably membranaceous.At this point, its plate thickness is preferably 200 μm or less, 100 μm or less, 50 μm Hereinafter, particularly preferred 30 μm or less.

Glass of the invention preferably has various functional membranes on the surface.As functional membrane, preferably for example, being led for assigning Electrical transparent conductive film, for reducing the antireflection film of reflectivity, for assigning anti-dazzle function, improving identification, improve touching Anti-dazzling film (anti-dazzling film), the anti-soil film for preventing fingerprint attachment, assigning waterproofness, grease proofness for touching the writing sense of pen etc. Deng.Transparent conductive film is played a role as touch sensor with electrode, such as being preferably formed in should be as display apparatus side Surface.As transparent conductive film, such as use the indium oxide (ITO) of tin dope, tin-oxide (FTO), the Sb doped of Fluorin doped Tin oxide (ATO) etc..In particular, the resistance of ITO is low, therefore preferably.ITO can for example be formed by sputtering method.In addition, FTO, ATO can be formed by CVD (Chemical Vapor Deposition) method.Antireflection film is formed on to become and see The surface of the person of examining side.In addition, protective glass also preferably should be being become in the case where having gap between touch screen and protective glass The inside side (with display apparatus side opposite side) surface formed antireflection film.Antireflection film is for example preferably by refractive index phase Multilayer dielectric film after alternately laminated to low low-index layer and the relatively high high refractive index layer of refractive index.Antireflection film is for example It can be formed by sputtering method, CVD method etc..For anti-dazzling film in the case where being used as protective glass, observer should be become by being formed in The surface of side.Anti-dazzling film preferably has sag and swell.Sag and swell is also possible to partly cover the island on the surface of glass Construction.In addition, sag and swell does not preferably have systematicness.Based on this, anti-dazzle function can be improved.Anti-dazzling film for example can SiO is enough coated with by spray-on process₂Equal translucent materials, make it dry, to be formed.Anti-soil film is the case where being used as protective glass Under, it is formed in the surface that should become observer side.Anti-soil film preferably comprises fluoropolymer siliceous in main chain.As fluorine-containing poly- Object is closed, the polymer preferably in main chain with-O-Si-O- unit and side chain with fluorine-containing waterproofness functional group.It is fluorine-containing poly- Closing object for example can be by carrying out dehydrating condensation to silanol to synthesize.In the case where forming antireflection film and anti-soil film, It is preferred that forming anti-soil film on antireflection film.In the case where further forming anti-dazzling film, preferably it is initially formed anti-dazzle Light film is formed on antireflection film and/or anti-soil film.

In addition, glass of the invention or having used the protective glass of glass of the invention preferably in area load photochemical catalyst Particle.The particle comprising a variety of materials can be used in photocatalyst particles.TiO 2 particles, oxidation tungsten particle can be used for example Son etc..The TiO 2 particles of particularly preferred Detitanium-ore-type.It is preferred that the reasons why anatase titanium dioxide, is, with rutile-type or The titanium dioxide of brookite type is compared, and the reactivity as photochemical catalyst is high.The average grain diameter of photocatalyst particles is preferably 1nm Above, 2nm or more, particularly preferred 3nm or more, additionally, it is preferred that for 200nm or less, 100nm or less, 50nm or less, 30nm with Under, 20nm hereinafter, particularly preferably 10nm or less.

In addition, except above-mentioned ultraviolet light response type, N doping type TiO 2 particles, cupric oxide doped also can be used The photochemical catalyst of the visible-light response types such as type TiO 2 particles, cupric oxide doped type tungsten oxide particle.If using the type Photochemical catalyst, then indoor environment can also obtain the effect of photochemical catalyst.In addition, existing if used in the field environment The advantages of luminous energy being able to use more than ultraviolet light response type.

In order to make a large amount of photocatalyst particles of area load, preferably glass surface is cellular.As keeping surface porous The method of shape, can be using the method for carrying out sour processing to glass surface.That is, glass composition of the present invention has It is easy the property, in most cases of split-phase, surface split-phase.Therefore, if carrying out sour processing to surface, containing many boric acid at Point acid resistance it is low mutually melts out, the acid resistance containing many silicon it is high mutually remain in surface.As a result, glass surface at For cellular, specific surface area is dramatically increased.It should be noted that inside glass is not easy split-phase, therefore, even if acid processing, becomes Cavernous is also glass surface.It should be noted that the thickness (depth) for becoming cavernous surface (porous layer) is preferred It is 10 μm or less.If the thickness for becoming cavernous surface is excessively thin, the effect for increasing specific surface area becomes smaller.If surface Thickness is blocked up, then organic matter etc. is deposited in inside, and the function as photochemical catalyst is possible to decline.

Then, the method for making above-mentioned glass-loaded photocatalyst particles is illustrated.

Firstly, preparing the glass with above-mentioned composition.For the glass of preparation, split-phase it is important.Contain in glass Some split-phase particles are preferably sized to 1nm or more, 2nm or more, 3nm or more, 5nm or more, particularly preferred 10nm or more, separately Outside, preferably 100nm or less, 80nm are hereinafter, particularly preferably 60nm or less.Such glass is able to use overflow downdraw progress Production.It should be noted that the features such as the composition of glass, characteristic are as previously mentioned, omit the description herein.

As pre-treatment, sour processing preferably has been carried out to the surface of glass.By carrying out sour processing to surface in advance, thus The surface of glass can be modified as to cellular, increase specific surface area.As the method for acid processing, for example, can use glass Glass is immersed in acid solution.Alternatively, it is also possible to make acid solution be sprayed at glass.As acid, it is, for example, possible to use hydrochloric acid, nitric acid, Sulfuric acid etc..

Then, the solution containing photocatalyst particles is coated with to the surface of glass.Coating method does not limit.For example, can Make photocatalyst particles dispersion, the method by glass-impregnated in the solution to use.Furthermore it is possible to be that will contain photochemical catalyst grain The solution of son is sprayed to glass surface.

Then, glass is heat-treated.By heat treatment, photocatalyst particles can be fixed on glass surface.Make For heating temperature, preferably 250 DEG C or more, 410 DEG C or more, particularly preferred 420 DEG C or more.Heating temperature is higher, can more incite somebody to action Photocatalyst particles are securely fixed in glass surface.It should be noted that if heating temperature is excessively high, Glass Transition, hole Hole is blocked, and surface area occurs sometimes reduces such unfavorable condition.Therefore, heating temperature is preferably 650 DEG C or less.

In this wise, the glass that area load has photochemical catalyst body can be obtained.

Then, the preferred embodiment of example glass of the invention.

(1) a kind of glass forms as glass, in mass, contains: SiO₂55~70%, Al₂O₃3~15%, B₂O₃ 18~30%, Li₂O+Na₂O+K₂O 0~1%, MgO+CaO+SrO+BaO 0~7%.

(2) a kind of glass forms as glass, in mass, contains: SiO₂55~70%, Al₂O₃3~12%, B₂O₃ 20~30%, Li₂O+Na₂O+K₂O 0~0.5%, MgO+CaO+SrO+BaO 0~6%, and density is 2.28g/cm³With Under, strain point is 610 DEG C or less and Young's modulus is 66GPa or less.

(3) a kind of glass forms as glass, in mass, contains: SiO₂58~70%, Al₂O₃7~20%, B₂O₃ 18~30%, Li₂O+Na₂O+K₂O 0~1%, MgO+CaO+SrO+BaO 0~6%, also, Young's modulus is 63GPa or less.

(4) a kind of glass, density 2.40g/cm³Hereinafter, the thermal expansion coefficient within the temperature range of 30~380 DEG C is 36 ×10^-7/ DEG C hereinafter, strain point is 610 DEG C hereinafter, also, Young's modulus is 63GPa or less.

(5) a kind of glass, density 2.30g/cm³Hereinafter, the thermal expansion coefficient within the temperature range of 30~380 DEG C is 25 ~36 × 10^-7/ DEG C, strain point is 610 DEG C hereinafter, and Young's modulus is 63GPa or less.

(6) a kind of glass, density 2.30g/cm³Hereinafter, the thermal expansion coefficient within the temperature range of 30~380 DEG C is 25 ~40 × 10^-7/ DEG C, strain point is 610 DEG C hereinafter, and Young's modulus is 65GPa or less.

Embodiment 1

Hereinafter, the present invention is described in detail according to embodiment.It should be noted that following embodiment is only to show Example.The present invention is not limited to the following examples.

Table 1~6 shows the embodiment of the present invention (sample No.1~42).It should be noted that not indicating [] not survey in table It is fixed.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

Sample No.1~42 are made as follows.Firstly, the glass raw material that the glass being deployed into table forms is put into platinum earthenware Crucible, and after being melted 24 hours at 1600 DEG C, it flows out on carbon plate, is shaped to tabular.Then, for obtained each sample, Evaluate density p, thermalexpansioncoefficientα, strain point Ps, annealing point Ta, softening point Ts, 10⁴Temperature when dPas, 10³When dPas Temperature, 10^2.5Temperature, Young's modulus E, liquidus temperature TL when dPas, liquid phase viscosity log η TL, scratch resistance (scratch resistance Property) and it is cracking (crack resistance).It should be noted that, as clarifying agent, having used SnO in the present embodiment₂, but can also To use SnO₂Clarifying agent in addition.In addition, defoaming is good if passing through the adjustment of melting condition, ingredient, then can not also make Use clarifying agent.

Density p is the value measured using well known Archimedes method.

Thermalexpansioncoefficientα is the value measured using dilatometer, is the average value within the temperature range of 30~380 DEG C.

Strain point Ps, annealing point Ta and softening point Ts are the values measured according to the method for ASTM C336, C338.

10^4.0Temperature when dPas, 10^3.0Temperature when dPas and 10^2.5Temperature when dPas is using platinum The value of ball czochralski method measurement.

Young's modulus E is the value measured using resonance method.Young's modulus is bigger, specific Young's modulus (Young's modulus/density) It more tends to get bigger, if it is writing board shape, self weight causes glass to be difficult to be bent.

Liquidus temperature TL is to pass through 30 mesh of standard screen (500 μm) but remain in the glass powders of 50 mesh (300 μm) to be put into Platinum boat, and kept for 24 hours in temperature gradient furnace, determine value obtained from the temperature that crystallization is precipitated.

Liquid phase viscosity log η TL is when determining liquidus temperature TL using platinum ball czochralski method obtained from the viscosity of glass Value.

For resistance to marring (scratch resistance), when scratching glass surface with Knoop pressure head with the speed of 0.4mm/s, measurement exists It is the negative of crackle that scratch 15% or more overall length, that width is scratch 2 times or more that the direction vertical with direction is scratched, which generates length, The situation that the load reaches 10N or more is evaluated as " A ", will be evaluated as " B " less than the case where 10N by lotus.Scratch test uses The friction wear testing machine UMT-2 of Bruker society is carried out in the constant temperature and humidity cabinet for remaining humidity 30%, temperature 25%.

Crack resistance (cracking) is value obtained from measuring the load of crackle generation rate arrival 50%.Crackle generation rate is as follows Ground measurement.Firstly, the Vickers pressure of predetermined load will be set as remaining humidity 30%, in 25 DEG C of temperature of constant temperature and humidity cabinet Head throws glass surface (optical grinding face) into 15 seconds, calculates the quantity after 15 seconds from the crackle of 4 jiaos of impression generations (for 1 4) a impression, is up to.Squeeze into this way pressure head 50 times, and after finding out total crackle and generating number, by total crackle generate number/ The formula of 200 × 100 (%) is found out.

The dielectric loss angle tangent when frequency of 1MHz is using well known plane-parallel capacitor method with 1MHz, 25 DEG C of condition Measurement.

Internal friction is measured using well known half-breadth method (half value width method).

Embodiment 2

The material of sample No.4 that table 1 is recorded, 5 are melted in test melting furnace, after obtaining melten glass, use overflow The glass plate of glass tube down-drawing molding plate thickness 0.3mm.As a result, the warpage of glass plate is 0.075% hereinafter, bending (WCA) is 0.15 μ M or less (cutting fh:0.8mm, fl:8mm), surface roughness (Ry) are(cutting λ c:9 μm) below.When molding, suitably Adjust the speed of traction roller, the speed of chill roll, the temperature of heating device difference, the temperature of melten glass, melten glass stream Amount, plate pull speed, revolving speed of blender etc., to adjust the surface quality of glass plate.It should be noted that " warpage " refers to Glass plate is placed on optics fixed board, the value measured using the clearance meter recorded in JIS B-7524." bending " refers to Using the surface-profile measuring instrument of contact pin type, measures the WCA (bending of filter center line) recorded in JIS B-0610 and obtain Value, the measurement install SEMI STD D15-1296 " measuring method of the surface curvature of FPD glass substrate "." average surface is thick Rugosity (Ry) " refers to the value measured according to SEMI D7-94 " measuring method of the surface roughness of FPD glass substrate ".

Embodiment 3

By the glass processing for the No.5 being made in embodiment 2 at 100mm × 100mm × 0.3mm size, to prepare Glass specimen.The glass specimen is impregnated 10 minutes in the HCl of 80 DEG C of -5wt%, surface is modified as cellular.Then, will Treated that glass specimen impregnates 10 minutes in ethanol water for acid, and cleans.

Then, it is dispersed in titanium dioxide (anatase titanium dioxide) particle of average grain diameter 5nm in 2- propanol solution with 2wt%, it will Glass specimen impregnates 5 minutes in obtained solution, and titanium particle is made to be attached to glass specimen surface.

Then, glass specimen is put into the annealing furnace (annealer) for remaining 500 DEG C, after heat treatment 2 hours, is taken Out, to obtain the glass specimen that area load has TiO 2 particles.Ultraviolet light is irradiated to the sample obtained in this way, it is then sharp It being capable of decomposing organic matter with the photochemical catalyst function of TiO 2 particles.

Embodiment 4

By the material of the sample No.19 recorded in table 3 test melting furnace in melt, after obtaining melten glass, with overflow Flow down the film-like glass that daraf(reciprocal of farad) forms 100 μm of plate thickness.The film-like glass can be wound into the web-like of radius of curvature 60mm.

Although describing the invention in detail referring to ad hoc fashion, those skilled in the art are illustrated, and are not departing from In the case where the spirit and scope of the present invention, various modifications may be made and amendment.

It should be noted that the application based on and require on April 3rd, 2014 propose Japanese patent application (Patent 2014- 076596), the Japanese patent application (Patent 2014-087828) of proposition on April 22nd, 2014, on May 23rd, 2014 propose Japanese patent application (the Patent 2014- that Japanese patent application (Patent 2014-106847), on October 23rd, 2014 propose 216332) priority and right of the Japanese patent application (Patent 2014-230599) proposed on November 13rd, 2014, passes through Reference, quotes entire contents.In addition, entire contents are hereby incorporated by, as reference.

Industrial applicability

Glass of the invention is suitable as protective glass, but in addition to this, and it is aobvious also to be suitable as liquid crystal display, organic EL Show the imaging sensors such as the flat-panel monitors such as device substrate, CSP, CCD, CIS substrate, touch sensor substrate.In addition, In the case where so that photocatalyst particles is carried on surface, can unvaryingly maintain its anti-pollution function, therefore, in addition to such use with Outside, for example, can also be used as glass for building purposes use.

Claims

1. a kind of glass, which is characterized in that

It forms, in mass, contains: SiO as glass₂50~70%, Al₂O₃0~20%, B₂O₃15~30%, B₂O₃? Al₂O₃6% or more, Li₂O+Na₂O+K₂O 0~3%, MgO+CaO+SrO+BaO 0~12%.

2. glass according to claim 1, which is characterized in that

It forms, in mass, contains: SiO as glass₂58~70%, Al₂O₃7~20%, B₂O₃18~30%, B₂O₃? Al₂O₃6% or more, Li₂O+Na₂O+K₂O 0~1%, MgO+CaO+SrO+BaO 0~10%.

3. glass according to claim 1, which is characterized in that

It forms, in mass, contains: SiO as glass₂50~70%, Al₂O₃0~15%, B₂O₃15~30%, B₂O₃? Al₂O₃6% or more, Li₂O+Na₂O+K₂O 0~3%, MgO+CaO+SrO+BaO 0~8%.

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

B₂O₃(MgO+CaO+SrO+BaO) is 5 mass % or more.

5. glass described in any one of claim 1 to 3, which is characterized in that

By quality ratio, (SrO+BaO)/(MgO+CaO) is 1 or less.

6. glass described in any one of claim 1 to 3, which is characterized in that

By quality ratio, (MgO+CaO+SrO+BaO)/Al₂O₃It is 0.1~1.2, (SrO+BaO)/B₂O₃It is 0.1 or less.

7. glass described in any one of claim 1 to 3, which is characterized in that

It is formed as glass, in terms of quality %, also containing 0~5% ZnO, 0~5% ZrO₂, 0~5% TiO₂, 0~5% P₂O₅, 0~1% SnO₂, As₂O₃Less than 0.1%, Sb₂O₃Less than 0.1%, F less than 0.1%, Cl less than 0.1%.

8. glass described in any one of claim 1 to 3, which is characterized in that

The density of the glass is 2.40g/cm³Hereinafter, thermal expansion coefficient within the temperature range of 30~380 DEG C be 25~40 × 10^-7/ DEG C, strain point is 610 DEG C hereinafter, and Young's modulus is 66GPa or less.

9. glass described in any one of claim 1 to 3, which is characterized in that

Liquid phase viscosity is 10^5.0DPas or more.

10. glass described in any one of claim 1 to 3, which is characterized in that

10^2.5Temperature when dPas be 1650 DEG C hereinafter, liquidus temperature be 1180 DEG C hereinafter, Young's modulus be 66GPa hereinafter, Scratch resistance is 5N or more, and cracking is 200gf or more, and dielectric loss angle tangent when 1MHz frequency is 0.01 hereinafter, internal Friction is 0.01 or less.

11. glass described in any one of claim 1 to 3, which is characterized in that

The glass is molded with by overflow downdraw.

12. glass described in any one of claim 1 to 3, which is characterized in that the glass is used for protective glass.

13. glass described in any one of claim 1 to 3, which is characterized in that

The glass does not carry out ion-exchange treatment.

14. glass described in any one of claim 1 to 3, which is characterized in that

There are photocatalyst particles in the area load of the glass.

15. glass according to claim 14, which is characterized in that

Glass surface is cellular.

16. glass according to claim 14, which is characterized in that

Photocatalyst particles are TiO 2 particles.

17. glass described in any one of claim 1 to 3, which is characterized in that

With writing board shape, plate thickness is 0.6mm or less.

18. a kind of protective glass, which is characterized in that

Glass according to any one of claims 1 to 3 is used.

19. a kind of manufacturing method of glass, which is characterized in that

It will form as glass, contain in mass to become: SiO₂50~70%, Al₂O₃0~20%, B₂O₃15~ 30%, B₂O₃- Al₂O₃6% or more, Li₂O+Na₂O+K₂The side of the glass of O 0~3%, MgO+CaO+SrO+BaO 0~12% The feed proportioning that formula is prepared for is melted, is formed.

20. the manufacturing method of glass according to claim 19, which is characterized in that

Further, it is then heat-treated in solution of the glass surface coating containing photochemical catalyst ingredient, makes glass surface Loaded optic catalyst particle.

21. the manufacturing method of glass according to claim 20, which is characterized in that

After carrying out sour processing to glass surface, it is coated with the solution containing photochemical catalyst ingredient.

22. the manufacturing method of the glass according to claim 20 or 21, which is characterized in that as contain photochemical catalyst ingredient Solution, use the solution for being dispersed with TiO 2 particles.