Coated substrate for transparent assembly with high selectivity

COVERED BASE FOR HIGH SELECTIVITY TRANSPARENT SYSTEM

The present invention relates to a coated base, in particular to a transparent coated sheet which provides a high selectivity system, ie with a high light to power transmission ratio.

Laminate systems comprising coated base sheets and constituting high selectivity systems have become widely used in vehicle glazing, especially for automobiles and train carriages. These functions address the need to provide adequate light transmission, in many cases as defined by legal regulations, and at the same time to protect vehicle occupants from solar radiation. Desirably, the glass should also have a pleasant color for both vehicle occupants and passers-by.

Several of the terms used for the properties of a coated base have precise meanings defined by an appropriate standard. Those used herein include those given below, most of which are as defined by the International Commission on Illumination Commission Inlernalionale de l'Eclairage (“CIE”).

In the present specification, two standard illuminants are used: Illuminant C and Illuminant A, as defined by the CIE. Illuminant C represents average daylight with a color temperature of 6,700 K. Illuminant A represents radiation from a Planck radiator at a temperature of about 2,856 K. This illuminant represents light emitted by the headlights and is essentially used to evaluate the optical properties of motor vehicle glass panels.

The term "light transmittance" (TLA) used herein is as defined by the CIE, namely the light flux transmitted through a base as a percentage of the illuminant incident light flux A.

The term "energy transmission" (TE) used herein is as defined by the CIE, namely it represents the total energy transmitted directly through a base without changing wavelength. Excludes energy absorbed (AE), ie energy that is absorbed by the base.

The term "selectivity" (SE) used herein is the relationship between light transmission (TLA) and energy transmission (TE).

The term "color purity" used herein refers to the excitation purity measured with illuminant C as defined by the CIE International Lighting Vocabulary 1987, pages 87 and 89. Purity is specified on a linear scale, whereby a defined white light source has a purity of zero and the pure color has a purity of 100%. For motor vehicle window panes, the purity of the coated base is measured on the side where the exterior surface of the window is to be formed.

The dominant wavelength (λ₀) is the peak wavelength in the range transmitted or reflected by the coated base.

The terms "refractive index" and "spectral absorption index" are defined in the CIE International Lighting Vocabulary, 1987, pages 127, 138 and 139.

The base is usually made of a glassy material, such as glass, but may be made of another rigid transparent material, such as polycarbonate or polymethyl methacrylate.

For various reasons, many related to sound or heat transmission considerations, or safety in case of fracture, the system typically comprises two or more laminated sheets. A standard laminate system comprises, in sequence, a first layer of glass, a clear glue layer such as polyvinyl butyral (PVB) and a second layer of glass. The thickness of each layer of glass is usually within the range of

1.6 to 3 mm. The average refractive index of the system, ignoring the effect of the coating layers, is usually 1.5. The coating is generally applied to the inner face (ie the glue contacting face) of the sheet which in use will form the outer sheet of the system, but may alternatively be applied to the inner face of the sheet which in use will form the inner sheet of the system. system.

A laminate system has different optical properties than a single sheet of glass. The differences are mainly the result of using multiple sheets. Thus, the properties required for and obtained by a laminate system differ from those of a single sheet of glass. Therefore, great care must be taken in the manufacture of a laminate system, in the aspect of proper selection of the respective materials, thickness and coatings, to ensure that the required end properties are obtained.

- 4 For motor vehicle windows, the legal requirements for the light transmission (TLA) of windscreen glass are at least 70% in the United States and at least 75% in Europe. With regard to solar radiation, the totality of directly transmitted energy (TE) is desirably adequate below 50%. Another factor is the color of the coated base, which should provide a pleasing appearance. A pink color may be considered attractive and a green color may be even more attractive. Thus, obtaining the desired color from the coating while maintaining light transmission at the required high level and low energy transmission is an additional problem.

The requirements for train carriage window glass are similar to the above, although all cases are not as well regulated by law. The need generally remains for high light transmission and low power transmission.

For vehicle applications, the reflected color purity is preferably low. It has been found that it is particularly difficult to achieve both a high level of light transmission and a low level of power transmission.

The application of various coating layers to glass sheets is becoming increasingly popular, which are known as the "stack" in order to modify their transmission and reflective properties. Previous proposals have been made based on the principle of metal and metal oxide layers in very different combinations to function as a coating pile, to impart the selected properties to the glass. A recent combination of attention-grabbing layers has been called the “five-layer stack”, the

Which normally comprises three layers of metal oxide alternatively applied with two layers of metal.

U.S. Patent No. 4,965,121 relates to a battery for a vehicle windscreen which comprises sequentially from the substrate: a first layer of dielectric material; a second layer of partially reflective metal material; a third layer of dielectric material; a fourth layer of partially reflective metal material; and a fifth layer of dielectric material. Dielectric material is required with a refractive index of 1.7 to 2.7. The first and fifth layers are about the same optical thickness, but are 33-45% of the optical thickness of the third layer. The second and fourth layers have thicknesses ranging within the range of 75-100% of each other. The claimed battery typically provides high light transmission and a practically neutral reflective visible light color.

French Patent Specification 2708926-A1 also refers to a five layer stack, in this case for transmitting to the vehicle or building glass a combination of high selectivity, ie a light transmission ratio for power transmission as high as possible while retaining a pleasantly reflective visual aspect. This aim is achieved by a stack comprising sequentially from the substrate: a first layer of dielectric material; a first layer of metallic material with infrared reflective properties; a second layer of dielectric material; a second metal layer with infrared reflective properties; and a third layer of dielectric material. The first infrared reflective layer has a thickness of 55-57% of the second infrared reflective layer.

We have found that the required combination of optical properties sought by the invention can be obtained, as well as other advantages, through a five-layer multi-coated base, wherein the coating layers are formed from certain materials. with certain thickness limits and with certain ratios to the thicknesses of certain layers.

According to the invention, there is provided a coated sheet for use in a laminate system with a high level of light transmission and a low level of energy transmission, characterized in that it comprises a transparent base which would support two metallic layers of silver or a silver alloy and three layers of a non-absorbent transparent dielectric material which are sequentially from the base: non-absorbent (1) / metal (1) / non-absorbent (2) / metal (2) / non-absorbent (3), where the total geometric thickness of the metal layers varies between 16,5 and 22 nm, the optical thickness the non-absorbent layer (1) ranges from 50 to 56 nm, the total optical thickness of the non-absorbent layers ranges from 220 to 260 nm and the non-absorbent (2): non-absorbent (1) thickness ratio ranges from 2, 1: 1 and 2.8: 1.

The present invention further provides a process for producing a coated sheet for use in a laminate system with a high level of light transmission and a low level of energy transmission, characterized by the deposition on a transparent base of two metal layers of silver or silver alloy and three layers of a transparent dielectric non-absorbent material, which are sequentially from the base: non-absorbent (1) / metal (1) / non-absorbent (2) / metal (2) / non-absorbent (3), where the total geometric thickness of the metal layers varies between 16,5 and 22 nm, the optical thickness of the non-absorbent layer (1) ranges from 50 to 56 nm, the total optical thickness of the non-absorbent layers ranges from 220

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and 260 nm and the non-absorbent (2): non-absorbent (1) thickness ratio ranges from 2.1: 1 to 2.8: 1.

The clear (or neutral) bases coated according to the invention provide laminated systems with the advantageous combination of a light transmission of at least 75% and a power transmission of less than 42%. Indeed, with certain types of clear glass bases, the power transmission can be reduced to less than 40% while maintaining a light transmission of over 75%. These transmission properties make these highly advantageous systems windscreen for vehicles.

Another desired quality for all glass systems used in vehicle window glass is low energy absorption, which must be much lower than the power transmission and energy reflection of the system.

The laminate system according to the present invention also provides a pleasing color appearance in the reflection range from pink at the lower end (2.10 to 2.40: 1) of the thickness ratio defined for nonabsorbent (2): non-absorbent (1) to bluish at the upper end (2.70 to 2.80: 1). Near the center of the gamma (2.45 to 2.65: 1), the color is greenish, provided that the non-absorbent (3): non-absorbent (1) thickness ratio ranges from 0.85 to 1.10 :1. This condition is based on the fact that coloration is also affected by the ratio of non-absorbent (3): non-absorbent (1) thicknesses.

For window glass of a vehicle of the type which includes a screen-applied black peripheral band, there is a tendency for a narrow pink band to appear in an adjacent reflection zone near the edge

- 8 peripheral. This strip, which appears due to the light interference between the coating and the screen edge, can be prevented by increasing the oxide layer thickness by about 10%.

For a given non-absorbent ratio value (2): non-absorbent ratio (1) within the central greenish zone (2.45 to 2.65: 1) and for a given non-absorbent ratio value (3): no absorber (1) within the defined range (0.85 to 1.10: 1), the dominant wavelength of the laminate system increases, ie the color moves towards yellow when the thickness of the metal layer ( 1) increases in relation to the metal layer (2).

The present invention thus provides the additional advantage of providing the normally preferred green color for vehicle window panes while satisfying the requirements of high light transmission and low power transmission.

Although the use of a clear base material is required to achieve the required European levels of 75% light transmission in vehicle windshields, the invention includes within its scope the use of at least one base sheet which It is itself colored. For example, for light transmissions slightly less than 70% specified for windshields in the United States, the systems according to the present invention comprise at least one colored glass sheet that can reduce power transmission to less than that 37%. These systems are also suitable for use on automotive front side window panes. For rear window and rear side window applications of motor vehicles, systems according to the present invention comprising at least one colored glass sheet provide the combination of a light transmission of at least 30% and

- 9 out of a power transmission of less than 25%.

The systems according to the present invention further provide low levels of light reflection, with a maximum reflection of 10% of incident light. These low levels of reflection are advantageous in both vehicles and architectural applications. High levels of reflected light are uncomfortable for an observer, and in the case of car window panes they can pose a danger to drivers of other vehicles.

In some cases, the coating is most conveniently applied during the glass forming step, for example to a flat glass sheet in or after the float glass chamber. For vehicle glass panels, which generally need to be bent to the shape imposed by the vehicle body shape, the coating may be applied after or before the base has been formed and bent to the required shape and size. For vehicle glass panels that are coated while flat and then bent to the desired shape, care must be taken to ensure that the bending action does not damage the coating. Said care should comprise slightly altering the composition or structure of the coating to make it more capable of withstanding the folding action.

The low thickness of the respective layers of the invention provide operational advantages in terms of the short time taken in applying the layers and the economical use of the respective materials.

The total geometric thickness of the metal layers preferably ranges between 16.5 and 20 nm.

The coating is preferably applied to one side of the sheet.

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base that will form an interior surface of the laminate system.

The metal layers comprise silver or a silver alloy, such as platinum or palladium silver alloys.

The term "non-absorbent material" used herein refers to a material having a refractive index (η (λ)] greater than the value of the spectral absorption index [k (X) J over the entire spectrum). visible (380 to 780 nm) It is advantageous for the non-absorbent material of the invention to have a refractive index greater than 10 times the spectral absorption index.

Preferably, the non-absorbent material has a refractive index, measured at 550 nm, between 1.85 and 2.2, advantageously between 1.9 and 2.1.

Suitable non-absorbent materials may be oxides such as tin oxide (S11O2) and zinc oxide (ZnO), nitrides such as silicon nitride (Si3N4) or a mixture thereof, or a complex of non-absorbent materials such as zinc stannate. (Zn₂SnO₄). Zinc oxide is a particularly preferred material because of its high deposition rate, its refractive index - which is well suited to the requirements of the invention - and its beneficial effect on silver layer passivation.

Each complete non-absorbent layer may include more than one of these materials and each layer may be a composite layer formed of successive subsidiary layers of different composition, for example a zinc oxide layer divided into two or more sub-layers. by one or more layers of another non-absorbent material such as tin oxide. The sub-layers may be deposited simultaneously and / or successively. Not essential for metal and oxygen or nitrogen of the

II layer be present in stoichiometric proportions.

A combination of tin oxide and zinc oxide is generally advantageous, either in admixture or in successive sub-layers. This appears to be the result of having very similar refractive indices.

The coated base according to the invention may further comprise, as part of a non-absorbent layer, a thin layer of a sacrificial material disposed above (ie subsequently deposited) and in contact with each metal layer. The purpose of the sacrificial material is to protect the silver and silver alloy during the deposition of the next non-absorbent layer. Suitable sacrificial materials may be titanium and zinc. Titanium is generally preferred because it is readily oxidizable.

The total optical thickness of the sacrificial material, ie the total layers of sacrificial material in the respective nonabsorbent layers, shall not be greater than 15 nm. After the coating process has been completed, all of the sacrificial material remains present as oxide.

The coating layers are preferably applied by cathodic deposition. This can be accomplished by introducing the base into a processing chamber containing an appropriate magnetron deposition source, and having gas inlet and outlet valves, a base conveyor, power sources and inlets and deposition gas evacuation outlets. The base is transported past the activated deposition source and the cold deposit is passed through an appropriate atmosphere (oxygen gas in case of oxide coating) to provide the desired layer on the base. The process is repeated for each layer of

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coating.

When employing this method, the use of a sacrificial material is highly desirable in order to protect the metal layer against oxidation during subsequent deposition of a nonabsorbent oxide layer. If, however, the non-absorbent material is a nitride rather than an oxide, the layer is deposited under a nitrogen atmosphere and the use of a sacrificial material layer is no longer required.

Because silicon nitride is deposited using a silicon cathode which has been activated, for example with aluminum, nickel, boron, phosphorus and / or tin, the activating element (s) may be present in the layer. of non-absorbent material.

The coating layers may be completed with a protective layer (2-5 nm) that protects the coating without significant modification of the optical properties of the product. Otherwise, the third non-absorbent layer is usually an exposed layer. Suitable materials for the additional protective layer exposed to tin are silicon oxides, nitrides and oxynitides. The silica (SiO₂) is the generally preferred material. This layer provides the coated base with improved chemical and / or mechanical durability with little or no resultant change in its optical properties.

Glass panels comprising the laminate systems of the present invention may be installed in single or multi-glazed units, for example double-glazed units or vehicle windshields.

A multi-window unit version for a vehicle

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comprises a laminate system according to the present invention positioned face to face with respect to a sheet of transparent glassy material having a gas space which is bounded by a spacer extending peripherally between said system and the leaf. In this unit, the coated surface faces the gas space.

A laminated glass unit may comprise at least two sheets of transparent glassy material fixed together with the aid of an intermediate film made of a polymeric adhesive material, wherein at least one of the sheets is a coated base according to the present invention. wherein the coated surface faces the polymeric adhesive. When employing the coated base in such a structure, it is desirable to employ a thin protective layer, as noted above, to protect the coating and to preserve it from delamination.

The invention will now be described in more detail with reference to the following non-limiting examples.

The properties of the coated base cited in the following Examples were measured on the basis of a laminate system, which comprises in sequence a sheet of ordinary soda lime glass having a thickness of 2.1 mm, a coating on said sheet, an adhesive layer. polyvinyl butyral (pvb) with a thickness of 0.76 mm and a second soda lime glass with a thickness of 2.1 mm.

Examples 1-10

Samples of a 2.1 mm glass base sheet were passed through an ongoing process deposition apparatus comprising two vacuum deposition chambers (at a pressure of 0.3 Pa), a carrier for the base , power sources and gas inlet valves. Each deposition chamber contained magnetron deposition cathodes, deposition gas inlets and an evacuation outlet, the deposition being obtained by passing the base sample several times under the cathodes.

The first chamber comprised cathodes provided with zinc and tin wafers, and was employed for the deposition of non-absorbent zinc oxide and tin oxide layers in an oxygen atmosphere. The second chamber comprised a silver cathode and a titanium cathode and was employed in the deposition of these metals in an inert atmosphere (argon), the titanium being necessary for the deposition of a sacrificial layer. Each base sample was subjected to several passes to obtain the desired succession and thickness for the coating layers.

The glass used as a base was soda lime glass with a thickness of 2.1 mm and other properties shown below:

<td>Glass type</td><td>TLA (%)</td><td>TE (%)</td><td>λ_η (nm)</td><td>Purity (%)</td>

<td>Sure (I)</td><td> 90,6</td><td> 87,8</td><td> 571</td><td> 0,5</td>

<td>Colorful (II)</td><td> 84,4</td><td> 67,6</td><td> 508</td><td> 1,3</td>

<td>Colorful (III)</td><td> 80,2</td><td> 59,5</td><td> 509</td><td> 1,8</td>

<td>Color (IV)</td><td> 57,0</td><td> 44,6</td><td> 503</td><td> 3,4</td>

In each case, it was applied to the base:

a first non-absorbent layer (Ox-1) of zinc oxide and tin oxide, a first silver layer (Ag-1), a second non-absorbent layer (Ox-2) of zinc oxide and tin oxide

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tin and titanium oxide, where the latter has an optical thickness of 7.5 nm and is in contact with the first silver metal layer (Ag-1), a second silver layer (Ag-2), a third non-absorbent layer (Ox-3) of zinc oxide, tin oxide and titanium oxide, the latter having an optical thickness of

7.5 nm and is in contact with the second silver metal layer (Ag-2).

The sheets thus coated were formed into laminated panels comprising the aforementioned laminate system of the coated sheet, a polyvinyl butyral adhesive layer and a second 2.1 mm glass sheet. In Examples 1 to 7, both sheets were clear glass (type I). In Examples 8 to 10, at least one of the sheets was colored glass (types II, III or IV).

Further details of each of the non-absorbent layers (Ox-1, Ox-2 and Ox-3) and silver layers (Ag-1 and Ag-2) of the coated sheet and the resulting properties of the coating pile thus formed. are shown in the following tables.

Table A shows the constituent materials of the nonabsorbent layers of the coating stack and their geometric thicknesses. Examples 1 to 4 and 8 to 10 show an Ox-1 layer having equal SnO thicknesses.₂ and from ZnO. Examples 5 to 7 show an Ox-1 layer always having 10 nm SnO 2, the remainder of the thickness of said layer being ZnO. The Ox-2 layer of each example is made of the succession of TiO.₂/ ZnO / SnO₂/ ZnO / SnO₂/ ZnO, where the thicknesses of the extreme ZnO sublayers are equal, as well as those of the two SnO sublayers₂these thicknesses being about half that of the central ZnO sublayer. The Ox-3 layer of each example has 2.5 nm TiO₂ and 10 to 13 nm SnO₂the remainder of the thickness of said layer being ZnO.

0 Table Β shows for Examples 1 to 7 the optical thicknesses of each layer, the total optical thickness of the non-absorbent layers (Ox-I + Ox-2 + Ox-3), the ratio of optical thicknesses of the first and the non-absorbent second layers (0x-2: 0x-1), the ratio of the optical thicknesses of the first and third non-absorbent layers (0x-3: 0x-1), and, for the resulting laminated panel, the light transmission Illuminant A (TLA), power transmission (TE), the dominant wavelength λ₀, the purity and, where appropriate, the resulting color. Table C shows data similar to those in Table B, for Examples 8 to 10 and further shows the types of glass employed.

The panels of Examples 1 to 7 are well suited for use as a vehicle windscreen. The panel of Example 8 is suitable for use on a vehicle front side window and those for Examples 9 and 10 are suitable for use on a vehicle rear or side rear windows.

TABLE A

<td>Example</td><td>Ox-1 SnO₂/ ZnO (mu)</td><td>Ox-2 Uncle₂/ ZnO / SnO₂/ ZnO / SnO₂/ ZnO (nm)</td><td>Ox-3 Uncle₂/ ZnO / SnO₂(nm)</td>

<td> 1.</td><td> 13,1/13,1</td><td> 2,5/10/10/23/10/10</td><td> 2,5/13/13</td>

<td> 2.</td><td> 14,0/14,0</td><td>2.5 / 11/11 / 22.5 / 11/11</td><td> 2,5/11,25/11,25</td>

<td>·&gt; J.</td><td> 13,4/13,4</td><td> 2,5/11/11/22,5/11/11</td><td> 2,5/10/10</td>

<td> 4.</td><td> 13,0/13,0</td><td> 2,5/10/10/22/10/10</td><td> 2,5/11/11</td>

<td> 5.</td><td> 10,0/17,0</td><td> 2,5/11/11/22/11/11</td><td> 2,5/22/10</td>

<td> 6.</td><td> 10,0/15,0</td><td> 2,5/10/11/20,5/11/10</td><td> 2,5/20/10</td>

<td> 7.</td><td> 10,0/15,6</td><td> 2,5/11/11/21/11/11</td><td> 2,5/11/10</td>

<td> 8.</td><td> 14,5/14,5</td><td> 2,5/11/12/24/12/11</td><td> 2,5/15/10</td>

<td> 9.</td><td> 14,5/14,5</td><td> 2,5/11/12/24/12/11</td><td> 2,5/15/10</td>

<td> 10.</td><td> 14,5/14,5</td><td> 2,5/11/12/24/12/11</td><td> 2,5/15/10</td>

<td colspan="4">PAINTING</td><td colspan="3">β</td>

<td>Example</td><td>Ox-1 ZnO / SnO₂(nm)</td><td>Ag-I (nm)</td><td>Ox-2 ZnO / SnO? (nm)</td><td>Ag-2 (nm)</td><td>Ox-3 ZnO / SnO₂(nm)</td><td>Total Ox (nm)</td>

<td> 1.</td><td> 52,4</td><td> 8,9</td><td> 132,0</td><td> 8,9</td><td> 58,7</td><td> 243,1</td>

<td> 2.</td><td> 56,0</td><td> 9,0</td><td> 140,7</td><td> 9,0</td><td> 51,3</td><td> 248,0</td>

<td>O 3</td><td> 53,4</td><td> 8,8</td><td> 134,7</td><td> 8,0</td><td> 46,3</td><td> 234,3</td>

<td> 4.</td><td> 51,6</td><td> 9,6</td><td> 130,1</td><td> 8,0</td><td> 50,3</td><td> 232,0</td>

<td> 5.</td><td> 54,0</td><td> 8,8</td><td> 138,3</td><td> 8,8</td><td> 70,3</td><td> 262,6</td>

<td> 6.</td><td> 50,0</td><td> 8,8</td><td> 131,3</td><td> 8,8</td><td> 66,3</td><td> 247,6</td>

<td> 7.</td><td> 51,2</td><td> 8,8</td><td> 136,1</td><td> 8,8</td><td> 48,5</td><td> 235,8</td>

<td>Ex.</td><td>Relationship Ox-2.Ox-1</td><td>Relationship Ox-3: Ox-1</td><td>TLA (%)</td><td>YOU (%)</td><td>7-d (nm)</td><td>Purity (%)</td><td>Color</td>

<td> 1.</td><td> 2,52</td><td> 1,12</td><td> 76,1</td><td> 41,3</td><td> -493</td><td> 2</td><td>reddish</td>

<td> 2.</td><td> 2,51</td><td> 0,96</td><td> 76,2</td><td> 41,0</td><td> 487</td><td> 7</td><td>blue greenish</td>

<td> 3.</td><td> 2,52</td><td> 0,88</td><td> 75,5</td><td> 40,7</td><td> 495</td><td> 2</td><td>bluish green</td>

<td> 4.</td><td> 2,52</td><td> 0,99</td><td> 75,0</td><td> 40,6</td><td> 581</td><td> 5</td><td>yellow greenish</td>

<td> 5.</td><td> 2,56</td><td> 1,30</td><td> 76,1</td><td> 41,1</td><td> -554</td><td> 4</td><td>red bluish</td>

<td> 6.</td><td> 2,63</td><td> 1,33</td><td> 75,5</td><td> 40,5</td><td> -542</td><td> 4</td><td>red bluish</td>

<td> 7.</td><td> 2,66</td><td> 0,95</td><td> 75,1</td><td> 39,9</td><td> 486</td><td> 9</td><td>greenish blue</td>

- 18 TABLE C

<td>Example</td><td>Glass Exterior</td><td>Sticker</td><td>Ox-1 (nm)</td><td>Ag-1 (nm)</td><td>Ox-2 (nm)</td><td>Ag-2 (nm)</td><td>Ox-3 (nm)</td>

<td> 8.</td><td>(D</td><td>pvb</td><td> 58,4</td><td> 9,5</td><td> 146,4</td><td> 9,5</td><td> 55,9</td>

<td> 9.</td><td>(III)</td><td>pvb</td><td> 58,4</td><td> 9,5</td><td> 146,4</td><td> 9,5</td><td> 55,9</td>

<td> 10.</td><td>(IV)</td><td>pvb</td><td> 58,4</td><td> 9,5</td><td> 146,4</td><td> 9,5</td><td> 55,9</td>

<td>Example</td><td>Total Ox</td><td>Relationship Ox-2: Ox-1</td><td>Glass Interior</td><td>TLA (%)</td><td>YOU (%)</td><td>Color</td>

<td> 8.</td><td> 260,7</td><td> 2,51</td><td>(II)</td><td> 70,9</td><td> 35,6</td><td>green</td>

<td> 9.</td><td> 260,7</td><td> 2,51</td><td>(III)</td><td> 55,0</td><td> 23,3</td><td>green</td>

<td> 10.</td><td> 260,7</td><td> 2,51</td><td>(IV)</td><td> 30,3</td><td> 14,1</td><td>green</td>

Lisbon, March 19, 1997

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Official Industrial Property Agent

VICTOR CORDON STREET, 14 1200 LISBON

-1CLAIMS