FI85460B

Coatings on glass

Abstract

This record has no abstract on file.

FI85460B, drawing sheet 1 — Sheet 1 of 13

Term

Term ended

Expired 22 December 2007, 18.8 years ago.

9 claims: 6 independent, 3 dependent

1
Patenttivaatimukset 1. Menetelmä pohjustuskerroksen muodostamiseksi lasin pinnalle, tunnettu siitä, että johdetaan kuumalle lasipinnalle lämpötilassa 600 - 750°C silaanin, tyydyttymättömän hiilivedyn ja hiilidioksidin kaasumaista seosta, jolloin lasin pinnalle saostuu läpinäkyvä piitä ja happea sisältävä kerros.
2
Patenttivaatimuksen 1 mukainen menetelmä, tunnettu siitä, että pohjustuskerrokselle levitetään lisäksi kerros, joka on herkkä alkalimetalliionien kulkeutumiselle lasista.
3
Patenttivaatimuksen 1 mukainen menetelmä, tunnettu siitä, että pohjustuskerrokselle muodostetaan lisäksi infrapunasäteilyä heijastava ja/tai sähköä johtava kerros.
4
Minkä tahansa edeltävän patenttivaatimuksen mukainen menetelmä, tunnettu siitä, että pohjustuskerroksen saostamisessa käytettävä tyydyttymätön hiilivety-yhdiste on olefiini, joka sisältää 2-4 hiiliatomia.
5
Patenttivaatimuksen 4 mukainen menetelmä, tunnettu siitä, että tyydyttymätön hiilivety-yhdiste on eteeni.
6
Minkä tahansa edeltävän patenttivaatimuksen mukainen menetelmä, tunnettu siitä, että pohjustuskerroksen saostamiseen käytettävässä kaasuseoksessa olevien kaasukomponenttien osuudet ja kaasuseoksen virtausnopeus kuumalla lasipinnalla säädetään siten, että saostuu pohjustuskerros, jonka paksuus on 60 - 80 nm ja taitekerroin 1,6 - 1,8.
7
Minkä tahansa edeltävän patenttivaatimuksen mukainen menetelmä, tunnettu siitä, että pohjustuskerroksen saostamiseen käytettävässä kaasuseoksessa olevien kaasukomponenttien osuudet ja kaasuseoksen virtaus21 nopeus kuumalla lasipinnalla säädetään siten, että saostuu pohjustuskerros, jonka paksuus ja taitekerroin ovat sellaiset, että pohjustuskerroksella päällystetyn lasin valonläpäisykyky poikkeaa korkeintaan 2 % päällystämättö5 män lasin valonläpäisykyvystä, ja joka toimii tehokkaana sulkuna alkalimetalli-ionien kulkeutumiselle lasista.
8
Minkä tahansa edeltävän patenttivaatimuksen mukainen menetelmä, tunnettu siitä, että pohjustuskerroksen saostamiseen käytettävässä kaasuseoksessa tyy- 10 dyttymättömän hiilivedyn tilavuussuhde silaaniin on alueella 2:1 - 5:1.
9
Minkä tahansa edeltävän patenttivaatimuksen mukainen menetelmä, tunnettu siitä, että pohjustuskerroksen saostamiseen käytettävässä kaasuseoksessa hii- 15 lidioksidin tilavuussuhde silaaniin on alueella 2:1 8:1.

Independent claims9

272 paragraphs in 2 sections, as filed

A method of forming a priming layer on a glass surface

This invention relates to coatings and in particular to the production of primer layers useful in reducing iridescence and protecting alkali metal ion sensitive coatings from the migration of such ions from the underlying glass surface.

GB 2,031,756 discloses thin transparent infrared reflective semiconductor coatings which are useful in improving the insulating properties of windows and, because they are electrically conductive, can act as resistance heaters, for example to remove ice or condensed water from windows. According to GB Patent 2,031,756, the use of such coatings is limited by the presence of iridescent colors, especially in reflected light; these iridescence phenomena are generally considered to be aesthetically unsatisfactory, and the problem is exacerbated by the variation of the iridescent color which occurs with little variation in coating thickness, GB 2,031,756 proposes in the range of 1.7 to 1.8 and a thickness of 64 to 80 nm. According to GB 2,031,756, primer layers can be produced by co-precipitating a mixture of components which is calculated to provide the required refractive index, for example a mixture containing 84 + 3% silicon nitride with the remainder being silica and called silicon oxide nitride.

Such silicon oxynitride layers can be formed by chemical vapor deposition from a silicon source (e.g., SiH4, (CH3)2SiH2, (C2B5)2SiH2, (CH 2 Si, SiCl4,

SiBr4), an oxygen source (e.g. O2, H2O, OF2°) tYP from the source (e.g. N2H4, NH 4, HN 2, CH3NHNH2, (CH3)2NNH2) or from a combined source of oxygen and nitrogen: - 35 (NO, NHLOH, N 2 HH-O) for hot glass at

500 - 600 ° C.

Although a suitable primer-reducing primer layer is required, the primer layers proposed in GB Patent 2,031,756 have not, however, been used to a significant extent commercially. This may be due to the difficulties encountered in producing primer layers of sufficiently good quality and thickness by known methods, in particular the long precipitation time required.

GB Application 2,163,146 discusses barrier coating compositions on the glass surface to prevent alkali metal ions from migrating to an alkali metal ion sensitive overlay coating, for example an inium dinoxide coating. It describes the preparation of transparent barrier coatings with good light transmission and excellent barrier properties by pyrolyzing a silane on a hot glass surface at a temperature above 600 ° C in the presence of a gaseous electron donating compound; the presence of an electron donating compound has been found to lead to the entry of oxygen from the glass into the coating, forming a transparent barrier coating with a thickness of up to • 50 nm on the surface of the glass.

The electron donating compounds that can be used in the method of GB Application 2,163,146 are compounds that contain, either bound or free electrons, electrons that can be donated to the electron structure of suitable acceptor molecules. The use of an electron donating compound has been found to lead to the incorporation of oxygen from the glass. Although the mechanism is not understood, the adsorption of an electron-donating compound associated with the. on the glass surface is assumed. It is preferred to use an oxygen-free electron donating compound, for example ethylene, or a compound which is generally considered to be reducing, even if it contains some oxygen, for example carbon monoxide and alcohols.

Because transparent barrier coatings can be made in the absence of free oxygen and compounds generally considered oxidizers, barrier coatings can be applied to a flat glass strip as it progresses over the surface of the metal melt bath in which it is formed without the unnecessary risk of metal melt oxidation.

While the use of an anaerobic electron donating compound reduces the risk of the silane oxidizing before reaching the glass surface and the reagent gas oxidizing the metal melt bath on which the glass strip floats, there is unfortunately too little oxygen from the glass to reduce the thickening iridescent agents recommended in GB 2,031,756. Although thicker layers can be produced using oxygen-containing electron donating compounds, it has been found that the use of a combination of silane and carbon dioxide results in either thin coatings of poor durability or, if attempting to make thicker coatings, a white turbid layer.

In addition, when attempting to produce highly transparent barrier coatings (e.g., those having a light transmittance of up to 2% less than a glass pane) using a combination of silane and ethylene according to GB Application 2,163,146, the barrier properties of the coatings have also been found to be insufficiently uniform for some applications.

There is a need for a method suitable for industrial production on a flat glass production line for preparing the irradiation reducing primer recommended in GB Patent 2,031,756. In addition, there is a need to provide a method suitable for commercial production on a flat glass production line for the production of coatings that are efficient4 ίο

Ef r 25 barriers for the transport of alkali metal ions from the glass and with very good transparency.

It has now been found that these needs can be met by a method in which a gaseous mixture of silane, ethylenically unsaturated hydrocarbon and carbon dioxide is applied to a hot glass surface, whereby a coating containing silicon and oxygen is deposited on the glass surface.

According to the present invention, there is provided a method of forming a useful primer layer on a glass surface, comprising applying to the hot glass surface at 600 to 750 ° C a gaseous mixture of silane, an unsaturated hydrocarbon compound and carbon dioxide to form a transparent layer of silicon and oxygen on the glass surface.

The primer layers prepared by the method of this invention act as barriers to the migration of alkali metal ions from the glass and are useful when a surface layer sensitive to the migration of alkali metal ions from the glass is applied directly or indirectly to the primer layer. According to a further aspect of the present invention, the method further comprises the step of applying a layer sensitive to the migration of alkali metal ions from the glass to the primer layer.

To produce a less iridescent infrared reflective and / or electrically conductive coating, an infrared reflective and / or electrically conductive layer is formed on top of the primer layer. According to a further aspect of the invention, the method thus includes the step of forming the infrared reflecting and / or electrically conducting layer over the primer layer. This surface layer can be a semiconductor metal oxide, for example tin-doped indium oxide or doped tin oxide, in particular fluorine-doped tin oxide.

Both the primer layer and the top layer can be applied to the flat glass on its production line. The surface layer may in this case be fluorine-doped tin oxide: ··: 35 which is deposited by pyrolytic decomposition from a solid source (e.g. as described in GB 2,156,386), a liquid source (e.g. as described in GB 1,523,991) or a vapor source (e.g. gaseous) (IV) chloride in the presence of water vapor and hydrogen fluoride). Decomposition can be done at the inlet of the glass cooling furnace.

When the coating is to be used as an infrared reflective coating, the thickness of the IR reflective layer is generally in the range of 200 to 500 nm. Thicker layers, for example up to 1000 nm, can be used if desired, but are generally unnecessary due to the iridescent-reducing properties of the primer layer. When the coating is to conduct an electric current, for example in a resistance heater or a liquid crystal display, the thickness of the coating depends on the required electrical conductivity, but is typically in the range of 100 to 1000 nm.

The silane is preferably a monosilane (SiH4), although other gaseous substituted or unsubstituted silanes, such as dimethylsilane (CH3)2SiH4 and disilane Si2B6, can be used if desired.

The unsaturated hydrocarbon may be an ethylenically unsaturated hydrocarbon compound, an acetylenically unsaturated compound (e.g. acetylene) or an aromatic compound (e.g. toluene), although in general it is most convenient to use a gaseous unsaturated hydrocarbon under ambient conditions. The unsaturated hydrocarbon is preferably an olefin, with an olefin having 2 to 4 carbon atoms being convenient. Ethylene is particularly preferred.

The ratios of the gas components present in the gas mixture and the flow rate of the gas mixture on the glass can be adjusted so as to obtain a primer layer of the desired thickness and refractive index.

Carbon dioxide acts as a source of oxygen, so that although oxygen from the surface of the glass is only available to a limited extent, it is easy to achieve in the GB patent publication

031 756 described transparent layers with a thickness of up to 80 nm. By further adjusting the ratios of the gas components present, a primer layer having a refractive index as described in GB 2,031,756 of 1.7 to 1.8 can be obtained. According to a preferred aspect of the present invention, in accordance with for forming the undercoat layer in a gas mixture of gas components ratios and gas mixture flow rate over the hot glass is adjusted so that precipitates primer layer having a thickness and refractive index are such that the primer layer coated glass valonläpäisevyvs differs by no more than 2% of the uncoated glass light transmittance, and which forms an effective barrier to the migration of alkali metal ions from the glass. The light transmittance of the coated glass preferably differs by at most 1% from the light transmittance of the base glass. By the term effective barrier is meant that when tested by the method described herein, the primer layer allows a maximum of 100 (preferably a maximum of 60) / Ug of sodium Na2Expressed as 0 per dm ^ per glass.

In general, the higher the ratio of unsaturated hydrocarbon to silane, the thinner the coatings, and the lower the refractive index of the coating. It is generally preferred to use a volume ratio of unsaturated hydrocarbon to silane of 2: 1 to 5: 1, although ratios outside this range, for example 1: 1 to 8: 1 (or even higher), may be used. The unsaturated hydrocarbon is assumed to act by adsorption on the glass surface, so that the more strongly the unsaturated hydrocarbon is adsorbed on the glass, the lower the ratio of unsaturated hydrocarbon to silane is generally required to achieve a certain effect. The volume ratio of carbon dioxide: silane is preferably in the range of 2: 1 to 8: 1, although ratios outside this range, for example 1: 1 to 20: 1 (or even higher), may be used. Higher ratios are usually used only when supplied with very low silane contents.

The gas mixture used generally contains an inert carrier gas, for example nitrogen, in a proportion of, for example, 10 to 90% by volume in the gas mixture.

An increase in the total flow rate of a gas mixture of a certain composition leads, as expected, to an increase in the thickness of the primer layer. It has also been found to lead to a primer layer with a higher refractive index.

The temperature of the glass is preferably 630 to 720 ° C.

The method of the present invention facilitates the on-line preparation of iridescent-reducing primer layers and primer layers that act as a barrier to the transport of alkali metal ions and transmit very visible light. In addition, since the reagents used are not strongly oxidizing, the method can be applied to a flat glass strip as it proceeds with the metal melt bath in which it is formed, without the unnecessary risk of oxidation of the molten metal.

The following examples illustrate, but do not limit, the invention. In the examples, all percentages are by volume unless otherwise indicated, and gas flow rates are measured at 69 kPa (10 psi) and approximately 20 ° C. The refractive index and thickness of the primer layer are calculated by applying thin film theory from the wavelength and magnitude of the maximum reflection of the primer layer. The light transmittance of coated glass is expressed as dT, which is the difference between the percentage light transmittance of coated glass and the percentage light transmittance of uncoated glass. The effectiveness of the primer layers as barrier layers against the migration of alkali metal ions was determined by the following procedure: Two coated glass samples, both squares with a side length of 10 cm, were fastened together with a ring-shaped silicone rubber seal with an inner diameter of 8.5 cm. a cylindrical cell bounded by coated glass surfaces and the inner surface of a sili8 conical rubber ring. The cell was filled with deionized water through a hole in the rubber ring, the hole was sealed, and the sealed cell was immersed in a water bath at 96 ° C for 48 hours. The solution was removed and analyzed by sodium flame emission spectroscopy. Extracted sodium was determined and expressed in micrograms of Na2O per dm of glass surface under the influence of water in the cell.

Example A 1 mm thick flat glass strip advancing in an oven at 322 m / h was coated with a primer layer by applying a gas mixture to the top surface of the glass as the glass progressed in a melt bath at a glass temperature of about 645 ° C. The gas mixture contained 11% monosilane, 23% ethylene, 23% carbon dioxide and 44% nitrogen as a carrier gas. The gas mixture was made to flow parallel to the glass surface in the glass flow direction under laminar flow conditions using the apparatus described in GB 1,507,966, which was modified so that the distance traveled by the gas mixture on the glass surface increased to about 0.2 m. The gas mixture flow rate was 22 1 / min per 1 m of coated width.

A clear, approximately turbidity-free primer layer having a thickness of 76.1 nm and a refractive index of 1.77 formed on the surface of the glass.

Examples 2 and 3

The procedure of Example 1 was repeated using a higher ethylene to carbon dioxide flow ratio. This led to a small decrease in the thickness and refractive index of the formed layer. The conditions used and the results obtained are shown in Table 1, which shows the corresponding details for Example 1 for comparison.

Examples 4-8

The procedure of Example 1 was repeated using different gas mixtures and varying the ratio of ethylene to carbon dioxide, keeping both the ratio of monosilane to the total amount of ethylene and carbon dioxide and the total gas flow rate constant. The conditions used and the results obtained are shown in Table 2.

The use of a high ethylene-silane ratio, as in Examples 4 and 5, results in a very thin priming layer (less than 55 nm). Decreasing the ethylene-silane ratio and increasing the carbon dioxide-silane ratio initially results in an increase in the thickness of the primer layer (Examples 6 and 7), but the thickness of the primer layer decreases as the carbon dioxide-silane ratio increases to 8: 1.

Examples 9-13

The procedure of Example 1 was repeated using a gas mixture containing 10% monosilane, 25% ethylene, 25% carbon dioxide and 40% nitrogen, and various total flow rates. The results are shown in Table 3 (Examples 9-11). It is observed that the thickness and refractive index of the primer layer increase with increasing total flow rate.

The procedure of Example 9 was repeated using the same silane, ethylene and carbon dioxide flow rates, but increasing the nitrogen flow rate. The flow rates used and the properties of the primer layers produced are shown in Table 3 (Examples 9, 12 and 13). It was found that as the nitrogen flow increased, the thickness of the primer layer decreased, while its refractive index increased.

Examples 14 to 19

In these examples, which were carried out in the same manner as in Example 1, primer layers were prepared on 6 mm thick flat glass under the conditions shown in Table 4, and it was found that their refractive indices and thicknesses were shown in said table. Fluorine-doped tin oxide layers were then deposited on the flat glass strip on top of the primer layer as the glass strip entered the furnace by chemical vapor deposition of a gaseous mixture of tin (IV) chloride, water and hydrogen fluoride.

The thicknesses of the tin oxide layers were measured, and the color coordinates of the light reflected from the coated side of the glass were determined. (CIE Illuminant C) and, in the case of Examples 14 to 17, were compared with the color coordinates of the light reflected from similar fluorine-doped tin oxide coatings without a primer layer. (The use of color coordinates to define colors is described in RS Hunter in The Measurement of Appearances, John Wiley & Sons, 1975.) The results obtained are shown in Table 5.

It has been found that the primer layers have a damping effect on the reflective color of the tin oxide layers.

Examples 20-23

The procedure of Example 1 was repeated using a gas mixture containing 10% silane, 20% ethylene, 30% carbon dioxide and 40% nitrogen and fed at a rate of 50 l / min per 1 m of coated glass width to a glass strip of 2.1 other thickness which progressed. in the oven at a speed of 1130 m / h. The gas mixture was fed to the glass at a temperature of about 645 ° C.

The glass was found to be covered with a layer with good transparency; the light transmittance of coated glass was only 1.1% lower than that of uncoated glass. The effectiveness of the layer as a barrier against the transport of alkali metal ions was measured to be 90 μg Na2O: a / dm glass (see above). The procedure was repeated using different gas compositions and 6 and 4 mm thick glasses. The temperature of the glass at the coating point, the rate of advance of the glass strip in the furnace, the gas composition used and the flow rate as well as the properties of the coated product are given in Table 6. Comparing Examples 21 and 22, it is found that the increase in glass temperature and silane content and the decrease in ethylene to carbon dioxide to silane ratios were more than sufficient to compensate for the decrease in gas flow (from 55 to 24 l / min) so that the coating in Example 22 was twice as thick. than the coating of Example 21. Barrier properties of all coatings

<td></td><td>were good, but the light transmittance of the coating of Example 22 was the highest (relative to the light transmittance of the uncoated glass). Examples 24-30</td>

<td> 5</td><td>These examples illustrate the use of butene as an unsaturated hydrocarbon in combination with silane and carbon dioxide to make the color reducing primer and barrier layers of this invention. The examples are carried out following the procedure of Example 1,</td>

<td> 10</td><td>but by coating only a narrow strip of glass from the edge of the strip. The glass was 6 mm thick, progressed at a speed of 360 m / h and was coated at a temperature of 685 ° C. Conditions used, gas composition and gas flow rates, and properties of primers prepared</td>

<td> 15</td><td>are shown in Table 7. Examples 25 to 27 produced satisfactory color-reducing layers with a thickness of 60 to 80 nm and a refractive index of 1.6 to 1.8 (in Example 24 the values were just outside these ranges). Examples 28 to 30,</td>

<td> 20</td><td>which were implemented using lower gas flow rates resulted in thinner coatings with excellent barrier properties when the light transmittance of the coated glass was close to that of uncoated glass. Comparing Examples 24 to 30 to the previous ones</td>

<td> 25</td><td>for examples, it has been found that apparently a higher total gas flow was required to produce layers of the same thickness. This is thought to be due, at least in part, to the fact that the method of Examples 24-30 was carried out using a narrower strip of glass, with</td>

<td> 30</td><td>gas escaped significantly from the edges of the strip to be coated. Examples 31-36 Stationary flat glass samples (thickness 3 mm, 10 x 10 cm) was coated in the laboratory by heating</td>

<td> : 35</td><td>glass in a silica tube furnace to a temperature of about 650 ° C and by applying to the hot glass surface a coating gas which was</td>

a mixture of silane, carbon dioxide, unsaturated hydrocarbon and nitrogen. The gas compositions and treatment times used are shown in Table 8, as are the results obtained when measuring the light transmittance and barrier properties of the coated products. Each unsaturated hydrocarbon gas used provided good barrier properties and good transparency (differs by no more than 1% from the transparency of uncoated glass).

Examples 37 to 40

The procedure of Example 1 was repeated using a gas coil containing silane, ethylene and carbon dioxide under nitrogen to coat a 2 mm flat glass which was advanced in an oven at 1,100 m / h.

The light transmittance of the glass was measured and compared with the light transmittance of uncoated glass to obtain a difference dT, and the barrier properties of the glass were measured as described above. The thickness of the coatings was too small to be measured by the optical method described above, and the measurement was made by the argon ion etching method.

The coating conditions and the results obtained are shown in Table 9.

Examples 37 to 40 illustrate the preparation of barrier layers such that the light transmittance of the coated glass differs by no more than 1.5% from the light transmittance (dT) of the uncoated glass. The last comparative example shows that in the absence of carbon dioxide the light transmittance is significantly lower (dT = 2.3%), although the primer layer is in fact thinner than those prepared in Examples 38 and 40. A comparison of Examples 37 and 38 shows that increasing the ratio of dopants (ethylene and carbon dioxide) to silane has reduced the thickness of the primer layer, resulting in increased light transmittance but reduced barrier properties. A slight reduction in the ratio of dopants to silane (cf. Examples 37 and 19) has impaired light transmittance without changing the thickness and barrier properties. Reducing the amount of ethylene and substantially increasing the amount of carbon dioxide (Example 40) results in a decrease in thickness and an improvement in light transmittance, but at the same time a substantial decrease in barrier properties.

The above examples show that by controlling the proportions of the gas components in the gas mixture used in the process of the present invention and the flow rate of the gas mixture on the hot glass surface, primer layers of the desired thickness and refractive index can be prepared. Thus, the process of the invention is not only useful for preparing color-reducing primer layers such as those described in GB 2,031,756, but can also be used to prepare other color-reducing primer layers known in the art as well as primer layers with good transparency due to their barrier properties.

Table

(fl

CM

nJ H + J (0 o 0 M co <d

Ό · ®

O d * nJ

4-> Ö | Q Ή Q <U) g nJ »8 j» -1 § · § nJ • 5 (fl r0 ►q

(fl ω nJ ω (fl • H a

Φ Qi

I

r- c * ·. r ** r * r **

CM CM CM CM CM m cm m <r cn m <rm cm m (Λ M1 A (N r ** r * r * »r *. R **

*? ΐΛ \ O r * 00

Table

tO H

• · ·

Table

The gas was prepared by feeding nitrogen through a liquid unsaturated hydrocarbon, and the amount of unsaturated hydrocarbon in the gas mixture was calculated from the known vapor pressure of the liquid assuming a bubbler efficiency of 50%, i.e., the nitrogen fed through the liquid hydrocarbon became saturated with 50% saturation.

Contents2

49 members in 26 offices

This recordMember, by publication datePriority claim16 more offices are in the list below

Priority claims4

Priority claims
Document	Office	Kind	Date
8630918	United Kingdom	A	1986-12-24
8630918	United Kingdom	A	1986-12-24
8630918	–	–	–
GB19860030918	–	–	–

Members49

Family members, oldest first
Document	Office	Kind
GB8630918D0	United Kingdom	D0	1987-02-04
NO875344D0	Norway	D0	1987-12-21
FI875657A0	Finland	A0	1987-12-22
DK685687D0	Denmark	D0	1987-12-23
PT86460A	Portugal	A	1988-01-01
GB8729171D0	United Kingdom	D0	1988-01-27
ZA879553B	South Africa	B	1988-06-16
IE873482L	Ireland	L	1988-06-24
DK685687A	Denmark	A	1988-06-25
FI875657A	Finland	A	1988-06-25
FI875657L	Finland	L	1988-06-25
NO875344L	Norway	L	1988-06-27
AU8288587A	Australia	A	1988-06-30
GB2199848A	United Kingdom	A	1988-07-20
EP0275662A1	European Patent Office (EPO)	A1	1988-07-27
BR8707035A	Brazil	A	1988-08-02
KR880007390A	Republic of Korea	A	1988-08-27
CN87101283A	China	A	1988-09-28
DE275662T1	Germany	T1	1988-11-24
ES2003853A4	Spain	A4	1988-12-01
DD264911A5	German Democratic Republic (until 1990)	A5	1989-02-15
US4828880A	United States of America	A	1989-05-09
JPH01201046A	Japan	A	1989-08-14
AU593966B2	Australia	B2	1990-02-22
TR23524A	Türkiye	A	1990-03-01
CS978987A2	Czechoslovakia (until 1993)	A2	1990-09-12
EP0275662B1	European Patent Office (EPO)	B1	1990-11-07
AT58114T	Austria	T	1990-11-15
ATE58114T1	Austria	T1	1990-11-15
PT86460B	Portugal	B	1990-11-20
DE3766095D1	Germany	D1	1990-12-13
CS274417B2	Czechoslovakia (until 1993)	B2	1991-04-11
GB2199848B	United Kingdom	B	1991-05-15
ES2003853B3	Spain	B3	1991-06-01
FI85460BThis record	Finland	B	1992-01-15
IN170516B	India	B	1992-04-04
FI85460C	Finland	C	1992-04-27
CN1018636B	China	B	1992-10-14
GR3002521T3	Greece	T3	1993-01-25
NO171970B	Norway	B	1993-02-15
NO171970C	Norway	C	1993-05-26
RU1830053C	Russian Federation	C	1993-07-23
MX170772B	Mexico	B	1993-09-14
CA1327143C	Canada	C	1994-02-22
IE60946B1	Ireland	B1	1994-09-07
JPH0674158B2	Japan	B2	1994-09-21
KR950002332B1	Republic of Korea	B1	1995-03-16
DK170066B1	Denmark	B1	1995-05-15
UA11076A	Ukraine	A	1996-12-25

Coatings on glass

Abstract

Term

CM

I

Priority claims4

Members49

Events

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Titles2

Classification