CN101234854A - Infrared shielding film-coated glass plate and production process therefor - Google Patents
Infrared shielding film-coated glass plate and production process therefor Download PDFInfo
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- CN101234854A CN101234854A CNA2007100063602A CN200710006360A CN101234854A CN 101234854 A CN101234854 A CN 101234854A CN A2007100063602 A CNA2007100063602 A CN A2007100063602A CN 200710006360 A CN200710006360 A CN 200710006360A CN 101234854 A CN101234854 A CN 101234854A
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- infrared rays
- blocking layer
- sheet glass
- rays blocking
- glass
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- 239000011521 glass Substances 0.000 title abstract description 51
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- 239000005357 flat glass Substances 0.000 abstract description 77
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000758 substrate Substances 0.000 abstract description 21
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011164 primary particle Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract 3
- 230000000903 blocking effect Effects 0.000 description 77
- 239000006185 dispersion Substances 0.000 description 55
- 239000007788 liquid Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 36
- 239000012298 atmosphere Substances 0.000 description 24
- 230000004888 barrier function Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 229920001709 polysilazane Polymers 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 18
- -1 silica gel silicon compound Chemical class 0.000 description 17
- 150000003377 silicon compounds Chemical class 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000010936 titanium Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- 150000003609 titanium compounds Chemical class 0.000 description 13
- 208000037656 Respiratory Sounds Diseases 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
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- RUXCEUCWDRGJCD-UHFFFAOYSA-J [Ti+4].CCC(=O)CC([O-])=O.CCC(=O)CC([O-])=O.CCC(=O)CC([O-])=O.CCC(=O)CC([O-])=O Chemical compound [Ti+4].CCC(=O)CC([O-])=O.CCC(=O)CC([O-])=O.CCC(=O)CC([O-])=O.CCC(=O)CC([O-])=O RUXCEUCWDRGJCD-UHFFFAOYSA-J 0.000 description 10
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- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
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- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910018540 Si C Inorganic materials 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
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- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical class [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
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- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 239000003446 ligand Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241001515806 Stictis Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- DVZKARSJEWBIEA-UHFFFAOYSA-N [Ti].C(C)C(C[O])CCCC Chemical compound [Ti].C(C)C(C[O])CCCC DVZKARSJEWBIEA-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 229940008099 dimethicone Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
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- 125000006606 n-butoxy group Chemical group 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides an infrared shielding film-coated glass plate and production process therefor, which has high visible light transmittance, high radiowave transmittance and low infrared transmittance and which can be applied to a site where mechanical durability is highly required such as a window glass plate for an automobile. The infrared shielding film-coated glass plate has an infrared shielding film having a thickness of 100-1,500 nm on the surface of a glass substrate, wherein the infrared shielding film comprises fine ITO particles having an average primary particle diameter of <=100 and dispersed in a matrix containing silicon oxide and titanium oxide.
Description
Technical field
The present invention relates to sheet glass and manufacture method thereof with the infrared rays blocking layer.
Background technology
In recent years, vehicle with glass or glass for building purposes in, to block the infrared rays that is incident upon in Che Nei or the buildings, to alleviate that temperature in Che Nei or the buildings rises, the load of air-cooling system is a purpose, adopted glass (for example patent documentation 1) with the infrared rays barrier film.In addition, for dual-purpose glass of car or glass for building purposes, in order to ensure the security and the visual field, many requirements have high visible light transmissivity.
So far, proposed much to make the additional infrared rays barrier properties of sheet glass to improve the method for invisible heat block.For example, propose and beginning is actual uses, make the scheme of the additional infrared rays barrier properties of sheet glass itself, perhaps scheme by adding the infrared rays barrier properties at glass baseplate surface formation conducting film by the ion that in glass, adds infrared ray-absorbable.
But, for the ionic sheet glass that in glass, adds infrared ray-absorbable, be difficult to when keeping transmission of visible light higher, improve infrared ray-absorbable, also be difficult to improve the ultrared block of medium wavelength in addition to wavelength 1.5 μ m～2.7 μ m.In addition, for the method that forms conducting film in glass pane surface, owing to the reason electric wave of conducting film can not see through glass, and along with the electric wave-transparent that requires peristome gradually of popularizing of mobile communication in recent years, so also be unfavorable.Therefore, it is very difficult making the sheet glass that has the transparency, infrared rays block and electric wave-transparent simultaneously.
In order to address the above problem, Indium sesquioxide (ITO) particulate that has proposed that doping (dope) and show the stannic oxide of high IR line block in tackiness agent, disperse and tunicle be coated on the surface of glass substrate, form method (patent documentation 2,3) with the sheet glass of infrared rays barrier film.For this method, can when keeping higher visible rays transmissivity, give the infrared rays block, simultaneously as the electroconductibility of film because the existence of tackiness agent is suppressed, so also can give electric wave-transparent.
In this is general tackiness agent be the organic system tackiness agent or inorganic be tackiness agent, but be to use the tunicle of organic system tackiness agent gained to lack mechanical endurance, existence can not be used the problem that requires the position of mechanical endurance at for example automobile door sheet glass etc.On the other hand, as inorganic be tackiness agent, use carried out with the material of sol-gel method as representative more, but for make reach can as the good tunicle of the weather resistance used of the above-mentioned position that requires mechanical endurance, must be in higher temperature, for example more than 400 ℃, be preferably under the temperature more than 500 ℃ and heat-treat.
But the ITO electrical conductor is the semi-conductor of oxygen defect type, if be positioned in the presence of oxygen under the temperature more than 300 ℃, then unbound electron is owing to oxidation disappears, and infrared rays block as a result disappears.Therefore, to guarantee infrared rays block, the good tunicle of mechanical endurance in order making, need to heat-treat under non-oxidizing atmosphere that this is very disadvantageous on cost, anti-ITO zone of oxidation perhaps is covered on the surface of the tunicle with infrared rays block.Make method in also in atmosphere, not heat-treating at present, particularly the method for making by 1 film-forming process with the sheet glass of high competent infrared rays barrier film simple and cheaply.Particularly not do not require the sheet glass and the manufacture method thereof with the infrared rays barrier film at the position of high mechanical endurance applicable to window glass for automobile plate etc.
In recent years, in patent documentation 4, proposed to obtain in visible light permeability, the method for good sheet glass with the invisible heat barrier film aspect transparent by 1 film-forming process.Should contain 2 kinds of alkalimetal oxides in the invisible heat barrier film at least by making with in the sheet glass of invisible heat barrier film, prevent the oxidation of invisible heat barrier film.But on the other hand,, therefore have to be applied to the position that automobile door sheet glass or window glass plate etc. are placed in harsh outside atmosphere for a long time because the chemical resistant properties of the film of alkali metal containing oxide compound is lower.Wish to develop more recently to have the block of high IR line, electric wave-transparent concurrently, and machinery and the good sheet glass with the infrared rays barrier film of chemical durability.
[patent documentation 1] Japanese patent laid-open 10-279329 communique (claims)
[patent documentation 2] Japanese patent laid-open 7-70482 communique (claims)
[patent documentation 3] Japanese patent laid-open 8-41441 communique (claims)
[patent documentation 4] international No. 2004/046057 international publication text (brochure) that disclose
Summary of the invention
The purpose of this invention is to provide the transmission of visible light height, the infrared transmission rate is low, electric wave-transparent is high, and go for the sheet glass to machinery, the demanding position of chemical durability such as window glass for automobile plate with the infrared rays blocking layer, and in containing the atmosphere of aerobic, can make this manufacture method with the sheet glass on infrared rays blocking layer by 1 time simple and cheap film-forming process.
The invention provides sheet glass with the infrared rays blocking layer, it is characterized in that, it is the infrared rays blocking layer of 100～1500nm that bed thickness is arranged on glass substrate, and this infrared rays blocking layer has the structure that is dispersed with the ITO particulate below the average primary particle diameter 100nm in the substrate (matrix) of silicon oxide-containing and titanium oxide.
In addition, the invention provides manufacture method with the sheet glass on infrared rays blocking layer, it is characterized in that, be included on the surface of glass substrate, coating contains average primary particle diameter behind the dispersion liquid of the ITO particulate below the 100nm, the silicon compound that can form silica gel, the titanium compound that can form titanium oxide gel and organic solvent, make it dry, form the operation of the ITO microparticulate layer that contains this silicon compound and this titanium compound and/or their gelation thing; The sheet glass that will be formed with above-mentioned layer is in the operation of carrying out roasting under the oxygen containing atmosphere under glass sheet temperatures reaches 400～750 ℃ temperature.
The transmission of visible light height of the sheet glass with the infrared rays blocking layer of the present invention, the infrared transmission rate is low, electric wave-transparent is high, and mechanical endurance and chemical resistant properties are good.In addition, manufacturing method according to the invention, can carry out intensive treatment under the atmosphere of aerobic, containing and obtain the sheet glass with the infrared rays blocking layer of the present invention when carrying out high-temperature molding processing under the atmosphere of aerobic containing, particularly in the manufacturing of window glass for automobile plate etc., can simplify manufacture method, reduce manufacturing cost.
Description of drawings
The sectional view of the sheet glass of having the infrared rays blocking layer of [Fig. 1] one embodiment of the present invention.
[explanation of symbol]
10 glass substrates
20 infrared rays blocking layers
Embodiment
Below describe formation main points of the present invention in detail.
In infrared rays of the present invention blocking layer (20 among Fig. 1), the ITO particulate of average primary particle diameter below 100nm is the textural element that shows the infrared rays block, and average primary particle diameter is very important below 100nm.If particle diameter more than this, then because on the surface of glass substrate after the film forming scattering and occur bluring (turbidity, haze), therefore undesirable.Consider that from the aspect of keeping the transparency particle diameter is 5～65nm more fortunately in addition.
Use with respect to the expression of the phosphide atom number (In/Sn) of tin atom number, show the stannic oxide in the ITO particulate of infrared rays block and the mixture ratio of Indium sesquioxide and need be In/Sn=2～20, particularly preferably In/Sn=3～10.
The effect of the wedding agent of above-mentioned ITO particulate is played in the substrate that contains silicon oxide and titanium oxide, has improved by film hardness, has the effect of infrared rays blocking layer to the adherence of glass substrate face of giving.In addition, the titanium oxide selective adsorption has the effect of the contraction of the film of mitigation when roasting described later on the surface of ITO particulate.As a result, show the effect of the appearance of crackle in sheet glass perk when preventing roasting, the film.
Since the excellent conductivity of ITO particulate own, the person if the ITO particulate is not combined closely in tunicle continuously, and then tunicle performance electroconductibility itself is brought detrimentally affect to electric wave-transparent.And the substrate that contains titanium oxide and silicon oxide has limited and has been in contact with one another between the ITO particulate, plays preventing that tunicle itself from becoming the effect of conducting film, is the important textural element that makes tunicle performance electric wave-transparent.At this, for silicon oxide and titanium oxide, there is no need is the SiO of stricti jurise
2And TiO
2, get final product so long as contain the base material of Si-O-Si key, Ti-O-Ti key or Si-O-Ti key.This base material better is to be the complex metal oxides that main constituting atom forms homogeneous with Siliciumatom, titanium atom and Sauerstoffatom.In addition, also can be the surface that the partial oxidation titanium is the ITO particulate partially.In addition, also can contain in the base material and Si, Ti bonded nitrogen-atoms.That is, the part of the silicon oxide in the base material, titanium oxide can become silicon oxynitride, oxynitriding titanium.At this moment, carry out roasting described later after, be preferably and compare this nitrogen-atoms with Sauerstoffatom and be a small amount of (for example, being illustrated in about 5% below), be the amount that deliberately importing it would be better to say that the degree of sneaking into as impurity with mass ratio.In addition, in base material, can contain, can exemplify as C, Sn, Zr, Al, B, P, Nb, Ta etc. as the formation element except that Si, Ti, O, N that is limited to the minor constituent about 5% by quality ratio.
The ITO particulate in the infrared rays blocking layer and the containing ratio of substrate are preferably [ITO particulate]/[substrate]=20/80～50/50 by quality ratio.By making above-mentioned ratio, also keep electric wave-transparent in addition easily in the adherence and the hardness that can guarantee tunicle below 50/50.On the other hand, by making above-mentioned ratio, can fully show the infrared rays block more than 20/80.Better is [ITO particulate]/[substrate]=20/80～40/60.
In addition, the containing ratio of the silicon oxide/titanium oxide in the infrared rays blocking layer is preferably [SiO by quality ratio
2]/[TiO
2]=45/55～85/15.By making above-mentioned ratio in the adherence that can fully obtain more than 45/55 with sheet glass.On the other hand, by making above-mentioned ratio below 85/15, the perk of the caused sheet glass of contraction in the time of can fully being inhibited by roasting and the effect of crackle, and can prevent from the ITO particulate to supply with oxygen and the ITO particulate that causes is oxidized, fully show effect as the oxygen barrier film.Its reason is also indeterminate, but thinks more by the containing ratio that makes the titanium oxide in the substrate, thereby titanium oxide plays effect as the reductive agent that suppresses the ITO oxidation.Be more preferably above-mentioned ratio at [SiO
2]/[TiO
2In the scope of]=50/50～80/20.
The bed thickness on infrared rays of the present invention blocking layer is formed 100～1500nm.Bed thickness less than 100nm can not show the infrared rays block fully, on the other hand, occurs crackle and transmission of visible light decline in the time of might forming tunicle if bed thickness surpasses 1500nm.If bed thickness in the scope of 250～1000nm, then obtains having stable infrared rays block easily, the infrared rays blocking layer that transmission of visible light is also good, therefore comparatively desirable, particularly preferably bed thickness is in the scope of 300～900nm.
The above-mentioned infrared rays of adjacency blocking layer constitutes the sheet glass with the infrared rays blocking layer of the present invention on the surface of sheet glass.
In addition, when using as the window glass for automobile plate, because the difference at position requires high visible light transmissivity sometimes, therefore, as the transmission of visible light of above-mentioned sheet glass with the infrared rays blocking layer more fortunately more than 70%.This transmission of visible light be meant by the calculating formula of JIS-R3212 (1998) regulation calculate transmission of visible light.
In addition, there is no particular limitation to glass substrate (10 among Fig. 1) that the present invention uses, but the sheet glass that example forms as the glass material by inorganic system, the sheet glass that forms by the glass material of organic system.The sheet glass that better uses the glass material by inorganic system to form in the window usefulness, particularly windshield glass of automobile, sliding window time spent.As the glass material of inorganic system, can exemplify as glass materials such as general soda-lime glass, pyrex, non-alkali glass, silica glasss.
Glass material as inorganic system also can use absorption ultraviolet ray, ultrared glass.As glass substrate, specifically, if use by the transmission of visible light of JIS-R3212 (1998) regulation more than 70%, the optical transmission rate of wavelength 1.0 μ m below 30% and the optical transmission rate of wavelength 2.0 μ m be the sheet glass that 40～70% the glass material by inorganic system forms, then effect is high especially.Because the infrared rays barrier film among the present invention is very not high near the block of the near infrared range the 1.0 μ m, therefore by will be near the barrier properties of the light of the wavelength 1.0 μ m high sheet glass as glass substrate, can make it that whole infra-red range is all had good infrared rays block.
The following operation can be made the sheet glass with the infrared rays blocking layer of the present invention, that is,
1) on the surface of glass substrate the coating contain average primary particle diameter be below the 100nm the ITO particulate, can form silica gel silicon compound (below, also abbreviate silicon compound as), can form titanium oxide gel titanium compound (below, also abbreviate titanium compound as) and the dispersion liquid of organic solvent, carry out drying, formation contains the ITO microparticulate layer of this silicon compound and this titanium compound and/or their gelation thing
2) glass substrate that will be formed with above-mentioned layer is carrying out roasting under the oxygen containing atmosphere under the glass substrate temperature reaches 400～750 ℃ temperature.
Because the state of aggregation in the state of aggregation of the ITO particulate in the ITO microparticulate layer after the roasting reflection dispersion liquid, therefore the transparency and the electric wave-transparent in order to keep tunicle must make the ITO particulate disperse at the dispersion liquid camber.As dispersion state, better be number average the aggegation particle diameter below the 500nm, be more preferably below the 200nm, be more preferably the monodisperse status below the 100nm again.For the kind of the organic solvent that becomes dispersion medium, so long as can the dissolves silicon compound and titanium compound just there is no particular limitation.Specifically, can exemplify as aliphatic hydrocarbon, aromatic hydrocarbons, ketone, ester, ethers, halogenated hydrocarbon etc.These organic solvents can use separately also can mix use.As making it the dispersive method, can adopt known method, can utilize medium mixing tanks such as ultrasonic irradiation, clarifixator, ball mill, ball mill, sand mill, paint shaker, and jet-type mixing machine, nanometer high pressure homogenizer high pressure such as (nanomizer) impact mixing machine etc.
At this, the ITO particulate in the dispersion liquid can use known ITO particulate, for crystal system, if use base material of the present invention, then except general cube brilliant ITO, can also use general for the relatively poor hexagonal crystal ITO of infrared rays block.Wherein, better use among the present invention in the xy tristimulus coordinates of trying to achieve by 2 ° of visuals field of JIS-Z8701 (1999) c light source the powder look as the x value more than 0.3, the y value is at the ITO more than 0.33.The ITO particulate of this tone, the electroconductibility of powder itself is low, do not show the block of high IR line.That is, the number of the oxygen defect of expression ITO intracell is little.This ITO particulate since only by the precursor powder that will get by coprecipitation method etc. in atmosphere or in the general rare gas element such as nitrogen roasting just can make, do not need as the ITO particulate that in the past used, will to follow and dangerous carrying out roasting under the reducing atmospheres such as hydrogen or under the nonactive atmosphere of pressurizeing, therefore have the advantage of low cost, safe manufacturing with the block of high IR line.Even the manufacture method of the sheet glass with the infrared rays blocking layer of the present invention such as above-mentioned owing to use low, the low-cost ITO particulate of infrared rays barrier properties, also can make the sheet glass with sufficient infrared rays blocking layer, therefore also good aspect productive.
The silicon compound that can form silica gel is meant through heating can become the composition that has as the silica-based end of the siloxane bond of silicon oxide (below, be also referred to as the siloxanes bottom material).The siloxanes bottom material is carry out three-dimensional nettedization through adding thermosetting siloxane bond (Si-O-Si), can become the compound at hard, the transparent silica-based end, specifically can exemplify as the alkoxyl silicone alkanes that utilizes in the sol-gel method, this organoalkoxysilane sector of breakdown hydrolyzate, this organoalkoxysilane sector of breakdown hydrolytic condensate, water glass, polysilazane etc.In addition, also can use the silicone oil that under the temperature of calcining process described later, can become the silica-based end, silicone resin etc.Wherein, be preferably the partial hydrolystate of polysilazane, tetraalkoxysilane, tetraalkoxysilane, the partial hydrolysis condenses of tetraalkoxysilane, particularly preferably polysilazane.
Polysilazane is to have-SiR
1 2-NR
2-SiR
1 2-(R
1, R
2Represent hydrogen or alkyl respectively independently, a plurality of R
1Also can be different) shown in the wire of structure or the general name of ring compound, be through heating or hydrolysis reaction Si-NR
2-Si key decomposes and the cancellated material of formation Si-O-Si.With the silicon oxide by gained such as tetraalkoxysilanes is that tunicle is compared, and is that tunicle has high mechanical endurance and gas barrier by the silicon oxide of polysilazane gained.Think in addition, contain a spot of nitrogen-atoms in the silicon oxide by the polysilazane gained, a part wherein generates silicon oxynitride.Silicon oxide among the present invention can be this silicon oxide that contains nitrogen-atoms.In addition, the above-mentioned mass ratio (mass ratio [SiO that contains the silicon oxide of nitrogen-atoms for this
2]/[TiO
2] etc.) be as the Siliciumatom of silicon oxide and the numerical value (being converted into the numerical value of silicon oxide) that calculates with whole Siliciumatoms.
As the polysilazane among the present invention, better adopt R in the above-mentioned chemical formula
1=R
2The perhydro polysilazane of=H, R
1Alkyl such as=methyl, R
2The part of=H the polysilazane that organises, R
1A part be alkyl, other R such as methyl
1Be hydrogen atom, R
2The part of=H organise polysilazane and their mixture.Since use the oxygen block height on the infrared rays blocking layer of these polysilazanes formation, therefore very desirable.Be preferably in addition, in the dispersion liquid amount of polysilazane with respect to the overall mass ratio of dispersion liquid below 20%.
As the alkoxyl silicone alkanes, be preferably general formula R
aSiX
4-a(X be carbon number at the alkoxyl group below 4, R is a carbon number at the alkyl below 6, carbon number at the thiazolinyl below 6 or carbon number at the aryl below 6, a is 0～2 integer) shown in organoalkoxysilane.Be preferably methoxyl group and oxyethyl group as above-mentioned alkoxyl group, be preferably methyl and ethyl, be preferably vinyl, be preferably phenyl as above-mentioned aryl as above-mentioned thiazolinyl as abovementioned alkyl.Specifically can exemplify as tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, dimethyldimethoxysil,ne, dimethyldiethoxysilane, phenyltrimethoxysila,e and dimethoxydiphenylsilane etc.
In containing the of the present invention dispersion liquid of polysilazane, can also contain other siloxanes bottom material as required as silicon compound.As other siloxanes bottom material is above-mentioned silicon compound beyond the polysilazane, wherein, better adopts alkoxyl silicone alkanes or its partial hydrolystate or its partial hydrolysis condenses, and silicone oil, silicone resin.
In addition, as with the silicon compound of polysilazane and usefulness, if use the silicon compound that contains the Si-C key, then obtain the sheet glass with the infrared rays blocking layer of excellent optical characteristics easily, therefore comparatively desirable.To its reason and indeterminate, but think owing to contain the silicon compound of Si-C key by use, when carrying out calcining process described later, can prevent that the crosslinking structure in the infrared rays blocking layer from becoming closely, can fully remove chelating ligand that contains in the above-mentioned titanium compound etc.As the silicon compound that contains the Si-C key, can exemplify as a in the above-mentioned chemical formula is 1 or 2 alkoxyl silicone alkanes, dimethicone oils or methylphenyl siloxane wet goods silicone oil, silicone resins such as dimethyl silicone resin, aminomethyl phenyl silicone resin.As a is 1 or 2 alkoxyl silicone alkanes, can exemplify as methyltrimethoxy silane, Union carbide A-162, dimethyldimethoxysil,ne, dimethyldiethoxysilane, phenyltrimethoxysila,e, dimethoxydiphenylsilane etc.
As the above-mentioned silicon compound that contains the Si-C key, particularly preferably use phenyltrimethoxysila,e, dimethoxydiphenylsilane and methylphenyl siloxane oil.Its reason is that to have a big more substituting group of volume then sterically hindered big more, and the effect of removing above-mentioned chelating ligand etc. is improved.As methylphenyl siloxane oil, be preferably ratio with respect to the total number phenyl number of methyl and phenyl (mole %) and be 5～50% methylphenyl siloxane oil.
In addition, the amount of the above-mentioned silicon compound beyond the polysilazane is preferably with respect to the whole silicon compounds that contain polysilazane below 50 quality %.
In addition, contain the titanium compound that can form titanium oxide gel in the dispersion liquid of the present invention.As this titanium compound, better use organic titanic compound.Organic titanic compound is because in calcining process described later, the high effect that suppresses that has to polysilazane is crosslinked when shrinking in film crackle, therefore by adding organic titanic compound, can show good oxygen block, mechanical endurance, and can form thicker tunicle.As organic titanic compound, can exemplify as four alkoxy titanium compounds, titanium chelate, acidylate titanium, titanic acid ester is coupling agent etc., as titanium compound of the present invention, is preferably four alkoxy titanium compounds, titanium chelate.As four alkoxy titanium compounds, be preferably general formula Ti (OR ')
4(R ' be the alkyl of carbon number 1～8), be specially four titanium n-butoxide, tetraisopropoxy titanium, tetramethoxy titanium, purity titanium tetraethoxide, four (2-ethylhexyl oxygen) titanium etc.Be preferably the inner complex of titan-alkoxide as titanium chelate, diisopropoxy two (methyl aceto acetate) titanium, two n-butoxy two (methyl aceto acetate) titaniums, diisopropoxy two (methyl ethyl diketone (acetylacetonato)) titanium, two n-butoxies two (methyl ethyl diketone (acetylacetonato)) titanium, four titanium acetylacetones etc. are specifically arranged.Aspect from the property handled is preferably titanium chelate as titanium compound of the present invention, wherein, and from the viewpoint of the stability of dispersion liquid, particularly preferably diisopropoxy two (methyl aceto acetate) titanium and four titanium acetylacetones.In addition, can make the back at dispersion liquid and add titanium compound, also can when making dispersion liquid, add.
The dispersion liquid of coating gained like this on the surface of glass substrate, the dry ITO microparticulate layer that forms.メ ニ ス カ ス コ one ト method), known method such as mould Tu Fa there is no particular limitation to coating process, can adopt dip coating, spin-coating method, spraying method, flexographic printing method, silk screen print method, intaglio plate coating method, rolling method, Mai Shi coating method (Japanese:.In addition, drying temperature is preferably less than 400 ℃.In the drying process, main purpose is to remove solvent composition in the striping etc., even rise to this above temperature, special expectation can not be arranged to the raising of effect.Be preferably 30 seconds time of drying～about 2 hours.Atmosphere when dry can be also can be non-oxidizing atmosphere under the atmosphere, but can not expect that special effect is arranged under non-oxidizing atmosphere.In addition, in this drying process, Heating temperature can be risen interimly for example 200 ℃, 300 ℃, 350 ℃ etc.
In addition, this drying process also can under reduced pressure carry out.Final vacuum is 10kN/m
2～0.10kN/m
2About, the treatment time is 10 seconds～30 minutes.
Be preferably after as above on glass-board surface, forming ITO microparticulate layer, under the temperature of sheet glass reaches temperature more than 400 ℃, carry out roasting, tunicle is solidified, formation infrared rays blocking layer.Roasting time is generally 30 seconds～about 10 hours.Atmosphere during this roasting can be the medium oxygen-containing atmosphere of common atmosphere, and this is a less expensive.Particularly, when making the chilled glass that uses as window glass for automobile, temperature near 600～700 ℃ in being warming up to atmosphere is shaped afterwards, according to circumstances implement air cooling again and carry out intensive treatment, even infrared rays of the present invention blocking layer is used for the deterioration that the infrared rays barrier properties does not appear in the roasting of intensive treatment yet, therefore can utilize the pyritous heat of this reinforcement operation to carry out roasting, can make with the automobile usefulness on infrared rays blocking layer, chilled glass for building efficiently, economically with high-durability.In addition, as mentioned above, above-mentioned dispersion liquid contains titanium compound, is the dispersion liquid that is particularly suitable for heat-treating at high temperature the situation (even also being difficult to occur because film shrinks the crackle that causes in heat) that forms the infrared rays blocking layer, therefore when thermal treatment temp be glass sheet temperatures when reaching 400～750 ℃ temperature, bring into play this feature easily.This high-temperature heat treatment is called roasting in the present invention.Maturing temperature particularly preferably glass sheet temperatures is 600～750 ℃ a temperature.Can form fine and close more infrared rays blocking layer by roasting.
Below, exemplify embodiments of the invention and describe, the invention is not restricted to these embodiment.In addition, utilize the observation of transmission electron microscope (TEM) to estimate the median size of marking the ITO particulate in the gained infrared rays blocking layer, following evaluation gained is with the sheet glass on infrared rays blocking layer.
[evaluation]
1) bed thickness: (Hitachi's system: S-800) section of film is observed, the observation by gained looks like to obtain bed thickness [nm] to utilize scanning electronic microscope.
2) form in the layer:, In, Si, Ti are measured the composition distribution (being converted into the mass ratio of oxide compound) of the depth direction on the infrared rays blocking layer after the roasting by x-ray photoelectron spectroscopy (XPS).
3) crackle:, judge crackle in aspect, whether to occur by the infrared rays blocking layer after naked eyes and the roasting of metal microstructure sem observation.Do not occur being designated as zero, naked eyes do not see, but can observedly be designated as △ with microscope, can observe with the naked eye be designated as *.
4) transmission of visible light (Tv): by spectrophotometer (Hitachi's system: U-3500) measure 380～780nm transmissivity down, according to JIS-R3212 (1998) calculating transmission of visible light [%] with the glass of infrared rays barrier film.
5) insolation transmissivity (Te): by spectrophotometer (Hitachi's system: U-3500) measure 300～2100nm transmissivity down, according to JIS-R3106 (1998) calculating insolation transmissivity [%] with the glass of infrared rays barrier film.In addition, middle infrared (Mid-IR) barrier properties of the present invention is by the performance performance of insolation transmissivity.
6) wearability: use the wear-resistant trier of Taber formula according to the described method of JIS-R3212 (1998), carry out 1000 wearing tests of changeing with the CS-10F abrasion wheels, the extent of damage before and after the test is measured by turbidity, estimated with the increasing amount [%] of turbidity.
7) chemical resistant properties: the sulphuric acid soln of 0.05 mol and the sodium hydroxide solution of 0.1 mol are dripped to tunicle washing after 25 ℃ are placed 24 hours, the outward appearance before and after the tracking test, the variation of characteristic.Sight, the characteristic variations of not regarding sb. as an outsider for qualified.
[example 1]
The powder look of measuring on the xy tristimulus coordinates that contains under 30 quality %c light sources, the 2 ° of visuals field is the dimethylbenzene dispersion liquid A 0.43g of the ITO particulate of 55nm for the primary particle size of (x, y)=(0.353,0.374), contains 20 quality % chemical formula-SiR
1 2-NR
2-SiR
1 2-middle R
1=H and methyl, R
2The part of=H organise polysilazane (AZ-エ レ Network ト ロ ニ Star Network マ テ リ ア Le ズ society system, trade(brand)name: xylene solution B 0.90g ア Network ア ミ カ NN-310), and diisopropoxy two (methyl aceto acetate) titanium (this pharmacy of pine society system, trade(brand)name: TC-750) 0.67g, after they are at room temperature mixed, stir and obtained dispersion liquid C in 10 minutes.
High invisible heat on the surface through cleaning absorbs green glass (the optical transmission rate of Tv:72.8%, Te:45.2%, wavelength 2.0 μ m: 47.1%, vertical 10cm, horizontal 10cm, thick 3.5cm, Asahi Glass society system, common name UVFL) goes up the dispersion liquid C that is coated with gained by spin-coating method, in atmosphere after 155 ℃ make it dry 10 minutes kinds, roasting to glass sheet temperatures reaches 700 ℃ in maintaining 755 ℃ the electric furnace of air atmosphere, obtains the sheet glass with the infrared rays blocking layer.Roasting time is about 3 minutes.
The characteristic of gained being had the sheet glass on infrared rays blocking layer is shown in table 1.At this moment, carry out the compositional analysis on infrared rays blocking layer by 2 secondary ion mass spectroscopy, the result determines that principal constituent is for containing TiO
2Si oxide, few for containing the silicon oxynitride of nitrogen.
In addition, the increasing amount of the turbidity of measuring through aforesaid method is 1.8%, is lower value.
[example 2]
Measure the above-mentioned dispersion liquid A of 0.52g, the above-mentioned solution B of 1.51g and the above-mentioned diisopropoxy two of 0.91g (methyl aceto acetate) titanium, after they are at room temperature mixed, stir and obtained dispersion liquid D in 10 minutes afterwards.
Except use dispersion liquid D replace dispersion liquid C, according to the bed thickness that changes the infrared rays blocking layer after the roasting shown in the table 1, operate equally with example 1, obtain having the sheet glass on infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
[example 3]
Measure the above-mentioned dispersion liquid A of 0.48g, the above-mentioned solution B of 1.51g and the above-mentioned diisopropoxy two of 0.99g (methyl aceto acetate) titanium, after they are at room temperature mixed, stir and obtained dispersion liquid E in 10 minutes.
Except use above-mentioned dispersion liquid E replace dispersion liquid C, according to the bed thickness that changes the infrared rays blocking layer after the roasting shown in the table 1, operate equally with example 1, obtain having the sheet glass on infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
[example 4]
Measure the above-mentioned dispersion liquid A of 0.62g, the above-mentioned solution B of 1.41g and the above-mentioned diisopropoxy two of 0.85g (methyl aceto acetate) titanium, after they are at room temperature mixed, stir and obtained dispersion liquid F in 10 minutes.
Except use above-mentioned dispersion liquid F replace dispersion liquid C, according to the bed thickness that changes the infrared rays blocking layer after the roasting shown in the table 1, operate equally with example 1, obtain having the sheet glass on infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
[example 5]
Except bed thickness according to the outside line blocking layer after the roasting of variation shown in the table 1, operate equally with example 4, obtain sheet glass with the infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
[example 6]
Measure the above-mentioned dispersion liquid A of 0.83g, the above-mentioned solution B of 0.93g and the above-mentioned diisopropoxy two of 1.04g (methyl aceto acetate) titanium, after they are at room temperature mixed, stir and obtained dispersion liquid G in 10 minutes.
Except use above-mentioned dispersion liquid G replace dispersion liquid C, according to the bed thickness that changes the infrared rays blocking layer after the roasting shown in the table 1, operate equally with example 1, make sheet glass with the infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
[example 7]
Measure the above-mentioned dispersion liquid A of 0.62g, the above-mentioned solution B of 1.52g and the above-mentioned diisopropoxy two of 0.73g (methyl aceto acetate) titanium, after they are at room temperature mixed, stir and obtained dispersion liquid H in 10 minutes.
Except use above-mentioned dispersion liquid H replace dispersion liquid C, according to the bed thickness that changes the infrared rays blocking layer after the roasting shown in the table 1, operate equally with example 1, make the sheet glass with the infrared rays blocking layer, the evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
[example 8 (comparative example)]
Except bed thickness according to the infrared rays blocking layer after the roasting of variation shown in the table 1, operate equally with example 7, make sheet glass with the infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
According to the result of table 1 as can be known, have in the infrared rays blocking layer above the example 8 of the bed thickness of 1500nm and crackle occurs, the insolation transmissivity also decreases.
[example 9 (comparative example)]
Measure above-mentioned dispersion liquid A of 0.62g and the above-mentioned solution B of 2.17g, after they are at room temperature mixed, stir and obtained dispersion liquid I in 10 minutes.
Except use above-mentioned dispersion liquid I replace dispersion liquid C, according to the bed thickness that changes the infrared rays blocking layer after the roasting shown in the table 1, operate equally with example 1, make sheet glass with the infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 1.
In the infrared rays blocking layer, in the not titaniferous example 7, become fine and close, present black by roasting infrared rays blocking layer.Its reason thinks that dispersion agent that dispersion liquid A contains not have to volatilize through roasting and by the cause of charing.Confirm that simultaneously transmission of visible light and insolation transmissivity in the example 9 significantly reduce, the oxidation of ITO is remarkable.
[table 1]
| Bed thickness | Form ITO/SiO in the layer 2/TiO 2 | Crackle | Tv | Te | |
| Example 1 | 650 | 30/42/28 | ○ | 70.3 | 41.0 |
| Example 2 | 850 | 25/49/26 | ○ | 70.2 | 40.6 |
| Example 3 | 1000 | 23/49/28 | △ | 70.2 | 40.8 |
| Example 4 | 683 | 30/45/25 | ○ | 70.4 | 40.8 |
| Example 5 | 635 | 30/45/25 | ○ | 71.1 | 41.1 |
| Example 6 | 627 | 40/30/30 | ○ | 70.7 | 42.1 |
| Example 7 | 544 | 30/49/21 | ○ | 71.6 | 41.9 |
| Example 8 | 1600 | 30/49/21 | × | 70.4 | 40.4 |
| Example 9 | 719 | 30/70/0 | × | 19.7 | 23.5 |
In addition, the chemical resistant properties test-results is that example 1～9 is all qualified.Hence one can see that obtains the very good sheet glass with the infrared rays blocking layer of chemical durability.
[example 10]
Measure the above-mentioned dispersion liquid A of 0.77g, the above-mentioned solution B of 1.97g and the above-mentioned diisopropoxy two of 0.83g (methyl aceto acetate) titanium, after they are at room temperature mixed, stir and obtained dispersion liquid J in 10 minutes.
By spin-coating method, gained dispersion liquid J is coated on the used identical high invisible heat of example 1 absorbs on the green glass, in atmosphere, make it dry 10 minutes in 155 ℃.Reach 700 ℃ in electric kiln roasting to the glass sheet temperatures that maintains 755 ℃ air atmosphere again, obtain sheet glass with the infrared rays blocking layer.Roasting time is about 3 minutes.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 2.
[example 11]
Measure the above-mentioned dispersion liquid A of 0.48g, the above-mentioned solution B of 1.01g, above-mentioned diisopropoxy two (methyl aceto acetate) titanium of 0.43g and 0.19g phenyltrimethoxysila,e, after they are at room temperature mixed, stir and obtained dispersion liquid K in 10 minutes.
Except using above-mentioned dispersion liquid K to replace operating equally with example 10 the dispersion liquid J, make sheet glass with the infrared rays blocking layer.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 2.
[table 2]
| Bed thickness | Form ITO/SiO in the layer 2/TiO 2 | Crackle | Tv | Te | |
| Example 10 | 500 | 30/51/19 | ○ | 72.1 | 41.5 |
| Example 11 | 500 | 30/54/16 | ○ | 71.7 | 41.5 |
In addition, the result of chemical resistant properties test is that example 10 and example 11 are all qualified.Hence one can see that can obtain the very good sheet glass with the infrared rays blocking layer of chemical durability.
[example 12]
Measure the above-mentioned dispersion liquid A of 0.50g, the above-mentioned solution B of 0.85g, 0.28g four titanium acetylacetones (the Virahol evaporation in the aqueous isopropanol [this pharmacy of pine society system, trade(brand)name: TC-401] that contains four titanium acetylacetones, 65 quality % being got) and 0.08g methylphenyl siloxane oil (siloxanes society of GE Toshiba system by vaporizer, the mole number of the mole number/methyl of trade(brand)name: TSF437, phenyl=27/73=0.37), they are at room temperature mixed, stir and obtained dispersion liquid L in 10 minutes.
By spin-coating method,, in atmosphere, make it dry 10 minutes in 155 ℃ absorbing the dispersion liquid L of coating gained on the green glass with the used same high invisible heat of example 1.Reach 700 ℃ in electric kiln roasting to the glass sheet temperatures of keeping 755 ℃ air atmosphere again, obtain sheet glass with the infrared rays blocking layer.Roasting time is about 3 minutes.The evaluating characteristics of gained being had the sheet glass on infrared rays blocking layer the results are shown in table 3.
[table 3]
| Bed thickness | Form ITO/SiO in the layer 2/TiO 2 | Crackle | Tv | Te | |
| Example 12 | 400 | 31/53/16 | ○ | 71.5 | 41.2 |
In addition, the result of chemical resistant properties test is that example 12 is also qualified.Hence one can see that, obtains the very good sheet glass with the infrared rays blocking layer of chemical durability.
Sheet glass with the infrared rays blocking layer of the present invention has good infrared rays block and visible light permeability, and can be applied to the position that door sheet glass equal altitudes that automobile uses requires machinery, chemical durability.In addition, by manufacture method of the present invention, can pass through 1 film-forming process, make the sheet glass have good infrared rays block and visible light permeability concurrently at low cost, therefore be particularly suitable for the manufacturing of automotive glass plate, building materials with sheet glass etc. with the infrared rays blocking layer.
Claims (12)
1. the sheet glass of having the infrared rays blocking layer, it is characterized in that, having bed thickness on the surface of glass substrate is the infrared rays blocking layer of 100～1500nm, and described infrared rays blocking layer has the structure that is dispersed with the ITO particulate of average primary particle diameter below 100nm in the substrate of silicon oxide-containing and titanium oxide.
2. the sheet glass with the infrared rays blocking layer as claimed in claim 1 is characterized in that the ITO particulate in the described infrared rays blocking layer and the containing ratio of substrate are expressed as [ITO particulate]/[substrate]=20/80～50/50 with mass ratio.
3. the sheet glass with the infrared rays blocking layer as claimed in claim 1 is characterized in that the containing ratio of the silicon oxide/titanium oxide in the described infrared rays blocking layer is expressed as [SiO with mass ratio
2]/[TiO
2]=45/55～85/15.
4. the sheet glass with the infrared rays blocking layer as claimed in claim 1 is characterized in that the containing ratio of the silicon oxide/titanium oxide in the described infrared rays blocking layer is expressed as [SiO with mass ratio
2]/[TiO
2]=50/50～80/20.
5. the sheet glass with the infrared rays blocking layer as claimed in claim 1 is characterized in that, by the transmission of visible light of JIS-R3212 (1998) regulation more than 70%.
6. have the manufacture method of the sheet glass on infrared rays blocking layer, it is characterized in that, comprise,
On the surface of glass substrate coating contain the ITO particulate of average primary particle diameter below 100nm, can form silica gel silicon compound, can form the titanium compound of titanium oxide gel and the dispersion liquid of organic solvent, carry out drying, form the operation of the ITO microparticulate layer that contains described silicon compound and described titanium compound and/or their gelation thing;
The glass substrate that will be formed with described layer reaches the operation of carrying out roasting under 400～750 ℃ the temperature in the glass substrate temperature under oxygen containing atmosphere.
7. the manufacture method of having the sheet glass on infrared rays blocking layer as claimed in claim 6 is characterized in that described silicon compound is a polysilazane.
8. the manufacture method of having the sheet glass on infrared rays blocking layer as claimed in claim 7 is characterized in that described silicon compound also contains alkoxyl silicone alkanes or its partial hydrolystate or its partial hydrolysis condenses.
9. the manufacture method of having the sheet glass on infrared rays blocking layer as claimed in claim 8, it is characterized in that, the amount of described alkoxyl silicone alkanes or its partial hydrolystate or its partial hydrolysis condenses with respect to the whole silicon compounds that contain polysilazane below 50 quality %.
10. the manufacture method of having the sheet glass on infrared rays blocking layer as claimed in claim 7 is characterized in that described silicon compound also uses the silicon compound that contains the Si-C key.
11. the manufacture method of having the sheet glass on infrared rays blocking layer as claimed in claim 10, it is characterized in that, the amount of described alkoxyl silicone alkanes or its partial hydrolystate or its partial hydrolysis condenses with respect to the whole silicon compounds that contain polysilazane below 50 quality %.
12. the manufacture method of having the sheet glass on infrared rays blocking layer as claimed in claim 6 is characterized in that described titanium compound is four alkoxy titanium compounds or titanium chelate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006024506 | 2006-02-01 | ||
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| JP2006282630 | 2006-10-17 |
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| CN101234854A true CN101234854A (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2007100063602A Pending CN101234854A (en) | 2006-02-01 | 2007-01-31 | Infrared shielding film-coated glass plate and production process therefor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003216A (en) * | 2010-07-28 | 2013-03-27 | 法国圣戈班玻璃厂 | Glazing panel |
| CN103619771A (en) * | 2011-06-30 | 2014-03-05 | 旭硝子欧洲玻璃公司 | Temperable and non-temperable transparent nanocomposite layers |
| CN108033688A (en) * | 2017-12-26 | 2018-05-15 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of silica based super hydrophobic coating and preparation method thereof |
| CN112297543A (en) * | 2020-10-20 | 2021-02-02 | 福耀玻璃工业集团股份有限公司 | Heat-insulating laminated glass and manufacturing method thereof |
-
2007
- 2007-01-31 CN CNA2007100063602A patent/CN101234854A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003216A (en) * | 2010-07-28 | 2013-03-27 | 法国圣戈班玻璃厂 | Glazing panel |
| CN103003216B (en) * | 2010-07-28 | 2015-08-12 | 法国圣戈班玻璃厂 | Window glass |
| CN103619771A (en) * | 2011-06-30 | 2014-03-05 | 旭硝子欧洲玻璃公司 | Temperable and non-temperable transparent nanocomposite layers |
| CN108033688A (en) * | 2017-12-26 | 2018-05-15 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of silica based super hydrophobic coating and preparation method thereof |
| CN108033688B (en) * | 2017-12-26 | 2020-08-28 | 中建材蚌埠玻璃工业设计研究院有限公司 | Silicon oxide-based super-hydrophobic coating and preparation method thereof |
| CN112297543A (en) * | 2020-10-20 | 2021-02-02 | 福耀玻璃工业集团股份有限公司 | Heat-insulating laminated glass and manufacturing method thereof |
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