DE1061979B - Curved sheet of glass bearing a metal oxide coating of uneven thickness on one side of the glass and process for its manufacture - Google Patents

Description

GERMAN

PATENT OFFICE

kl. 32 b 6/50

INTERNAT. KL. C 03 C

P 16305 IVc / 32 b

REGISTRATION DATE: MAY 19, 1956

NOTICE.
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: JULY 23, 1959

The present invention relates to an improved method of making coatings uneven thickness on glass, ceramic or other heat-resistant see-through parts that form a heat or light protection, whose Al) -sorption. properties according to a desired Patterns are variable, and on such objects made of glass or the like with the coatings mentioned.

The primary object of the present invention is a curved sheet of glass with a strip of composite metal oxide films for the absorption of heat and light for that part of the glass pane that is near the roof of vehicles or that is in the roof extends into it. For rear windows of passenger cars that have a single glazing If the pane of tempered glass has, it is desirable to have a clear in the lower part of this pane To have vision, however, to apply a film in the upper part that the sun rays and excessive Keep away from exposure to light. The same applies to side window glazing of such vehicles. Protective screens on the front of the vehicles also require a strip of heat and light absorbing Coatings in the upper part of these discs.

Windshields have already been made that have absorbent strips in the upper part and at which the thickness of the coatings gradually decreased downwards. To make these disks colored an intermediate plastic layer between two panes of glass of different thicknesses. The ones used for this However, organic dyes decompose or have been used for a certain period of time faded. Metal oxide films of the type described below are significantly more durable as well easier to apply to the panes to be hardened or to individual panes that are then closed Laminated glass panes processed.

The present invention relates to curved glass panes in which the novelty lies in the fact that a heat absorbing strip made by a metal oxide coating on a surface of the glass is. The present invention also relates to a method for producing metal oxide films of the type mentioned of different thickness over the area of the glass pane.

In particular, the procedure for producing the above-mentioned coating films is to heat a pane to a temperature which is above the temperature required for film formation, but below that at which the carrier melts, then takes the pane out of the oven and sets it immediately a spray of a film-forming mixture which has at least one dense area and one sparse area. This creates a relative movement between the curved glass pane,

which have a metal oxide coating

of uneven thickness

on one side of the glass,

and methods of making them

Applicant:

Pittsburgh Plate Glass Company,
Pittsburgh, Pa. (V. St. A.)

Representative: Dr. W. Beil, lawyer,
Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority:
V. St. v. America May 19, 1955

Leigthon E. Orr, Tarentum, Pa.,

William O. Lytle, New Kensington, Pa.,

and Arnold E. Saunders, Saxonburg, Pa. (V. St. A.),

have been named as inventors

see the wearer and the spray jet at such a speed that a coherent film on the support is created with a cross-sectional image corresponding to the pattern of those formed on the support Spray jet strength. Since, however, with each deposition on the carrier along the axis of the Relative movement occurs as a result of the contact with the spray jet, each additional cooling must be carried out Part of the contact with the beam can be removed before the temperature of any part of the Precipitation drops below the lowest film-forming temperature. If it is not removed in time, so the film tends to deviate from its diversity across the axis of movement.

Examples of metal oxide films obtained by spraying suitable metal compounds onto a can produce preheated base from heat-resistant material, are in the USA. patent 2,564,708. The metal oxide films of the present invention enable non-uniform Passage of heat or light due to their uneven strength in the area of the Pane of glass. The main value of the invention lies primarily in the ability of these films to produce a

909 578 / .95

Part of the heat and light to shield that when sprayed on a heated heat-resistant otherwise it would go through the glass window, which would serve as a base on the surface of the window transparent closure is used. In the case of motor vehicle colored metal oxide films, Glazing in which the glass extends into the car - The ones listed in Table I below

Extending into this, it is especially important that 5 solutions provide films of uniform thickness. the roof part of the glass has a strong coating, but these films can be made in different locations and that its strength decreases along an axis, starches apply when using the spray liquid which sprays from the roof to the hood of the vehicle in an uneven distribution and which stretches in order to achieve a graduated shielding effect. Duration of the impact time of the heated glass base give. It may also be desirable to have the shielding effect according to the teachings of the present invention is bordered at the lowest end of the glass.

amplify to absorb light and heat, which As can be seen from Figs. 1 and 2, a force

reflecting off the road and the hood of the vehicle windshield 30, which are made of an or. Side windows of buses preferably have several panes of glass with a thermoplastic, dark upper and lower stripe to protect 15 intermediate layer, according to the present earth passengers receive a coating against direct and reflected reflection, the strength of which is sunlight, while a clear colorless surface in between an axis transverse to the direction of the relative's rule allows the strip an unobstructed view of the movement between the central axis of the spray landscape. and the glass can change, making one of the

These are the main objects of the invention; other 20 quers after graduated color depth generated if the are used in the following description ati hand the panel is used in a vehicle. The concentration Drawings become apparent; of these is the sprayed-on coating on the windbreak

Fig. 1 is a perspective view of the method disk of a motor vehicle is approximately the same along for making a sheet of glass according to the invention, each horizontal axis coinciding with the axis the pane with a film at the end completely preventing the relative movement between the pane of glass and the shrinking spray Strength is provided that is required for beam coincidences.

the achievement of various types of permeability The disc 30 has a central portion 32 which

properties is; extend across the motor vehicle and at his

Fig. 2 is a schematic section through one of the two outermost longitudinal ends in side parts 34 over disk along the line VIII-VIII in Fig. 1, which can go in this way, extending from the central part in sinking treated is as shown in Fig. 1; right planes roughly perpendicular to the tangential FIG. 3 is a section along the lines IX-IX of the plane er-FIG. 1 transverse to the axis of the spray jet; stretch. The upper end of the middle part is curved, Fig. 4 is a cross-section through a disc which forms a roof part 36, which is an edge of the shows how it is oriented so that one film will last 35 automobile roofs. It is desirable that of very vanishing strength on it arises when the roof part is rather opaque and the it is treated according to a special spray pattern will; Coating is provided, the thickness of which is downwards. Fig. 5 is a section through a disc which gradually decreases until it is approximately halfway up has been treated by a special procedure, disappears completely by 40, so that a colorless, clear sub-unit transparent coating of uneven part 35 remains, which extends horizontally under the upper part

"" "" "'33 is dragging on.

Such a pane can be made by heating a pane of glass in the same way as 45 as described above for producing transparent electrically conductive coatings, and then they immediately sprayed with a solution of such a metal salt, which has a metal oxide coating with heat-shielding Effect. If you have the disc

Create starch on their surface;

Fig. 6 is a cross section showing another method of spraying glass sheets according to the invention shows, and

FIG. 7 is a longitudinal section taken along the line XIII-XIII in FIG. 6.

Various metal oxide films can produce these desired effects. By spraying on

1 f .. .11 1 1 * * _ 1 · · 1 Tf- *. .

g g

of metal salt solutions, which are arranged for the generation * of these 50 30 when spraying so that their convex metal oxide films or certain mixtures thereof surface is exposed to the spray jet, one can also use films according to the invention with the fact that the relative position of the Disc and certain, locally different transparency of the spray jet to each other is so that the roof part produce. in the dense zone 23 of the jet and the next. The most suitable metal oxide coatings for this 55 strip 33 in the zone 25 of the weaker spray purpose are those which come with tin oxide, indium oxide, and cadneous oxide, while the lower, colorless desired mium oxide or mixtures of it, mixtures of tin part 35 completely out of contact with the spray jet and antimony oxide with or without minor additions of remains (Fig. 1, 2 and 3). But you can also use the oxides of bismuth, iron, zinc, copper, Vana spray guns opposite the test arranged he; Move dins, chromium, manganese, cobalt or mixtures of heated glass panes so as to contain the required metals, as well as to produce iron oxide films with gentle relative motion. In any case, or without small amounts of tinoxycJ, titanium oxide, it is necessary to apply fifme and kboaftoxycMime for each layer of application. Special solutions, which allow the spray syrup to act on the disk 30 for a limited time for the composition of the spray jets. However, this action must be reversed, which in contact with the heated glass cease in good time before the temperature of the applicators, metal oxide films form, are listed in Table I on a layer below the minimum level for film formation. However, the invention is not particularly limited to this, so that the spray solutions by separating the spray are limited, since the principles of mixture on the preheated base for the formation of unevenly thick films are applicable to every standing metal oxide film in the desired, film-forming starting liquid, which ranks 70 Shape is obtained.

Table I.

Solution misalignment Metal oxide + L + E Durable paint (Salts + solvents) ° / o Vo Vo of the film I-l 73.2 g Sn Sl ₄ SnO ₂ 71.2 10 19.5 Dark blue 27 g SbCl ₃ Sb ₂ O ₃ 28.8 75.6gH ₂ O 10 g HCl 1-2 73.2 g SnCl ₄ SnO ₂ 80.9 20th 25th Dark blue purple 15.5 g SbCl ₃ Sb ₂ O ₃ 19.1 70.6 g H ₂ O 15 g of H Cl 1-3 73.2 g SnCl ₄ SnO ₂ 95.4 59 39 Light Blue 3.3 g SbCl ₃ Sb ₂ O ₃ 4.6 70.6 g H ₂ O 15 g of H Cl 1-4 73.2 g Sn Cl ₄ SnO, 82.6 27 15th Blue black 6.9 g Sb Cl ₃ Sb ₂ O ₃ 7.6 completely neutral 6.8 g Bi Cl ₃ Bi ₂ O ₃ 9.8 70.6 g U ₂ O 15gHCl I 5 73.2 g SnCl ₄ SnO ₂ 74.7 24 22nd Olive green to brown 7.7 g Sb Cl ₃ Sb ₂ O ₃ 8.7 12SgBiCl ₃ Bi ₂ O ₃ 16.6 70.6 g H ₂ O 15 g of H Cl 1-6 132 g SnCl ₄ SnO ₂ 75 26th 25th Neutral teal 36, IgSbCl ₃ Sb ₂ O ₃ 22.7 7.8 g FeCl ₃ 6H ₂ O Fe ₂ O ₃ 2.3 70.6 g H ₂ O 15 g of H Cl 1-7 132 g SnCl ₄ SnO ₂ 62.9 55 42 Light green, more iron creates stains 36, IgSbCl ₃ Sb ₂ O ₃ 19.2 73.5 g Fe Cl ₃ 6H ₂ O FeO ₃ 17.9 70.6 g H ₂ O 15 g of H Cl 1-8 45 g FeCl ₃ -6 H ₂ O 47 48 Amber in the Review 45 g of methanol Avoid this film change review through strong reflection 1-9 45 g Fe ₂ O ₃ 6H ₂ O Fe ₂ O ₃ 86 5 51 46 Amber colored 3 g SnCl ₄ SnO ₂ 13.5 45 g of methanol 5 g HCl I-IO 3OgIi Cl ₄ TiO ₂ 100 62 60 Amber in 70 g of methanol the review, silvery reflection I 11 20 g cobalt acetate · 4H ₂ O CoO 100 9 28 Amber colors 2OgH ₂ O

+ L is the light transmission, determined with the Weston light meter, Corporation, Newark, NJ (USA)

+ E is the total energy, determined by a »radiomatic head«, lator Company, Minneapohas, Minn (USA)

that from Weston Electric Instrument
from the company Minneapolis Honeywell Regu-

One must also take care of the influence of the off the front and rear disc edges, which is disclosed in U.S. Pat. No. 2,724,658, dated 16 2 1950 is described This can be done by extending the dwell time of the spray jet the front and rear edges of the heated glass substrate compared to the dwell time for the achieve intermediate coats, either by moving the front and back rear disc edge slowed down through the spray jet or by using the spray gun in the same direction as the movement of the disc

through the beam something rotates The duration, however, that one exposes such a single coating layer strip of the pane to the beam, has to pass through time the above conditions remain limited

Since the strength of the spray jet affects the degree of

determines the transparency of the resulting film, a coating with a tightness pattern is created, which is roughly in the direction of the relative movement between Disc and spray jet remain unchanged, but transverse to the axis of this relative movement changes when the density of such a film because of the above No restrictions on the spraying time

is sufficient, the spraying can be repeated by adding the once coated disc, heated again, sprayed a second time. If more than a single coating is required to achieve adequate To achieve density of the film, one can get more uniform coatings in the direction of relative movement obtained by the direction of movement of the disc relative to the spray jet when second pass reverses

Another method of making a film of graded staike is by using the Brings the windshield in an inverted position (FIG. 4), such that the roof part 36 lies below, and the concave Obei side of the disc 30 to the spray jet exposed to act in the manner shown in FIG let the sparse zone 25 so that the dense jet zone 23 hits the roof strip 36 of the pane dtn stripe 33 and the stripe 35 remains out of range of the beam

The film produced in this way lies on the inside of the windshield and is therefore not exposed to the weather and other influences that damage the film

Example I.

A previously cut flat sheet of glass, 350 mm wide, 1070 mm long and 6.35 mm thick, was on a glass bending mold of the type with latticework matnze placed, the upper surfaces of which corresponded in outline and height to the shape desired for the glass The disc and mold were placed on a cart and placed in a horizontal oven Maintained for 5.5 minutes, during which time the heated glass sank by its weight in the middle and to the shaping surface of the bending form The glass bent in this way was then led immediately horizontally under the jet of a spray gun through it, which is directed downwards at a 30 ° angle and was directed across the horizontal path of movement of the glass opposite the spray gun.

ίο The density of the jet was thereby graduated and the jet was directed so that its strongest zone struck along one long edge of the curved glass pane, while the bevelled edge of the weaker spray zone of the jet was aimed at the part of the pane where the coating was supposed to stop Glass was fed past the aligned spray gun at a distance of 10 cm, measured in the center axis of the jet. The air pressure in the spray gun was about 4.2 kg / cm ² , and the spray solution flowed through the gun by its own weight to

The spray solution formed an oxide coating which mainly consisted of a mixture of antimony oxide and tin oxide, with the antimony making up 20% by weight of the total weight formed from tin plus antimony.The composition of the spray liquid was the following 151 g H ₂ O, 30 g concentrated HCl, 146 g SnCl _4, 31 g of SbCl ₃ were the percentages of light transmission at various points of the sprayed washer along various longitudinal axes of the following

Table II

Front margin, ° / o 6th Upper margin, ° / o 8th 14th 20th Rear
Edge, »/ 0 10 20th 15th 31 32 30th 40 60 46 68 74 46 77 79 70 74 82 78 85 87 81 83 85 82 89 87 87 87 87 85 89 87

Lower margin

The film formation was on the rear edge of the disc not as strong as at the front edge or in the middle. This result shows that one is running out of time the disk on the rear edge must be longer exposed to the hammer-producing jet when coating large panes according to the present invention This can be done either by rotating the spray gun in the direction of movement reach the disc or by slowing down the relative movement of the rear edge of the disc compared to the spray jet those lowest permissible speed through the Run through the beam, in which each layer of coating in front of it leaves the steel before the tempe temperature of part of it has dropped below the lowest temperature at which the film is formed

The same result can of course also be achieved by covering the one covered with the film Trager warmed up again and a second Sprayed times, with the trailing edge from applying the first coating the leading edge for the second Coating is, that is, the direction of movement of the disc is reversed compared to the spray jet

Another usefulness of the invention for Requires production of non-uniformly dense coatings working with a dumbbell-shaped spray jet, in order to create such a spray pattern on a pane of glass, the one made of spaced-apart densely sprayed and intermediate thinly sprayed Such a spray pattern is shown in FIG. 5, where a pane of glass 40 after being heated in an oven except for one far above the temperature required for film formation taken out of the oven and moved by a dumbbell-shaped spray jet The upper one Strip of the disc 40 is so with a relatively Dense coating 44 is provided, which over a medium-thick coated strip 45 in a central strip 46 of the disc passes over, which is only a moderate weak coating wears The thickness of the coating then takes over again downwards the intermediate strip 47 to the floor strip 48. This spray pattern is created by the Strips 44 and 48 of the disc 40 on the densely sprayed areas and the central portion 46 of the disc aligns with the sparsely sprayed area while the dumbbell-shaped beam during the limited, above-described radiation duration on the window 40 moving past under him is directed

Example II

A solution of 72.2 g of SnCl ₄ , 75.6 g of H ₂ O, 10 g of HCl and 27 g of SbCl _{3 was} prepared, corresponding to a 30 weight percent antimony concentration based on the total weight of antimony and tin in the solution. Glass panes were attached After heating for about 8 minutes, the panes (460 x 460 x 6.35 mm) were removed from the oven and passed through a spray jet containing the solution described above was attached along an axis perpendicular to the plane of the heated pane, sent a split spray pattern, similar to a dumbbell, on both sides of the axis of the beam The following table shows typical percentages of the visible and total light transmittance obtained with a Weston light meter he and a "radiomatic head" were measured

Table III Sheet HI-I

Stripes

Visible permeability, ° / o total energy transmittance, ° / o

44
45
46
47
48

20th
27
47
23
17th

18th
22nd
41
20th
16

Sheet III-2 30
38
47
37
29

28
36
44
32
26th

33 37 44 36 31

Stripes 10 Visible permeability, ° / o 10 17th Total energy transfer, ° / o 19th 44 13th 15th 22nd 24 45 26th 29 31 34 46 8th 12th 17th 19th 47 6th 8th 16 18th 48 7th 17th 10 21 26th 31 6th 17th 5 15th

Example III

Two spray guns that can deliver a jet, as shown in Fig. 3, were above the trajectory of glass panes attached to horizontally arranged glass bending molds, which according to have concave lattice form surfaces open at the top, the shapes of which correspond to those of the glass panes to be bent The pistols were in one Angle of 30 ° directed downwards from the horizontal and aimed in opposite directions with zones 23 denser spraying on the directed elongated edges of the discs and zones 25 with sparse spraying on the inner zones of the slices that were passed by The discs were in one for 572 minutes horizontal duct furnace heated to 680 ° C During the warming up the flat glass panes sank, until they rested on the top of the bending form immediately the panes were sprayed after they were removed from the oven. The two spray guns were aimed in such a way that the dense zone of the beam from one pistol hit the one long end of it The curved sheet of glass was aimed and the dense zone of the beam from the other pistol was aimed at the other long end The guns were about 10 cm from the target, measured on the axis of the spray jet

A total of four disks were bent and sprayed.The first disk was passed under the spray guns only once, the second was reheated and passed through again under the pistols.The third and fourth disks were also reheated and sprayed twice, the same shape as the last two Discs carried, but was turned over from end to end before the second warm-up and spraying. The speed of passage of the discs through the jet was 0.18 m / sec. Disc IV 3 was ^{sprayed under a pressure of 4.2 kg / cm 2} and disc IV -4 under 3.2 kg / cm ² in order to increase its light transmittance in relation to the disc IV-3. The percentages of transmittances were determined with the Weston light meter, from one long edge to the other and from the front to the rear Edge of the disks They are given in Table IV

Table IV

Front Margin, ° / o 32 Upper margin, ° / o 31 Rear
Rand, Vo 34 20th 44 56 45 60 48 58 70 62 74 58 62 70 70 76 60 52 53 70 63 56 26th 35 52 38 28 42 26th 42 59 59 51 30th

Lower margin 909 578/195

Disk IV

Front Rand, Vo Upper margin, V 9 13th ο 24 Rear
Rand, Vo 12th 10 27 36 59 50 40 45 .— 60 71 84 63 59 51 54 62 86 66 58 22nd 27 33 74 55 39 11 11 17th 44 24 13th 24

Lower margin

Disk IV-3

Front margin, ° / o 18th 14th 10 Upper margin, Vo 10 10 14th Rear
Rand, Vo 18th 16 14th 14th 14th 18th 18th 24 26th 22nd 24 22nd 24 24 42 30th 24 26th 26th 32 30th 40 28 24 26th 24 27 42 24 18th 18th 16 15th 16 40 14th 14th 10 10 10 12th 22nd 14th

Lower margin

Disk IV-4

Front margin, Vo 26th Upper margin, Vo 27 26th 27 Rear
Rand, Vo 32 28 36 30th 35 35 31 49 35 56 49 56 60 47 55 57 60 60 58 64 67 65 63 60 56 60 62 73 63 61 51 45 54 50 70 52 47 38 38 38 39 63 41 36 41

Lower margin

The disks thus coated can be used are used for glazing windows or for making laminated glass panes in the latter case you have to put at least two panes of glass in the desired one Bend shape, a coating in the manner described above on at least one of the glass sheets and place the two discs on both sides of a transparent plastic film ζ Β made of polyvinyl butyral

You can of course use the technique described here still change in various ways, as far as it is in the Is within the scope of the following claims

59

Claims (9)

Claims 1 curved sheet of glass containing a metal oxide cover of uneven thickness on one side Side of the glass is characterized in that the metal oxide coating (33) is only part of it the pane of glass covered while the rest of the top flat of the disc is relatively clear and allows a completely clear view and that the The thickness of the coating gradually increases outwards from the clear part of the disc 2 glass pane according to claim 1, characterized in that the glass pane (30) both in the longitudinal as well as 111 the transverse direction curved is 3 pane of glass according to claim 1 and 2, characterized in that the glass is hardened 4 pane of glass according to claim 1 to 3, characterized in that the metal oxide film on the Surface of the disc (30) in the transverse direction is different in its thickness, such that it is on strongest in the area of the shoulder (36) in the longitudinal direction of the disc and the rest of relatively even strength in Direction of all long axes of the disk is 5 pane of glass according to claim 4, wherein the glass pane has a main part in the middle, then strongly curved areas at the two outer ends in the longitudinal direction and wing ends, which extend in two mutually parallel planes approximately at right angles to the center of the main part it thereby characterized in that the thickness of the metal oxide coating decreases along an axis (AA) transverse to the longitudinal axis (BB) of the plane to be coated, which extends between the two end parts (34), but that the coating along each longitudinal axis on the surface of the disc (30 ) is almost equally strong 6 pane of glass according to claim 5, wherein the main part near the one longitudinal side of the pane staik is curved so that it has a roof part which extends in a direction from the main part at an approximately right angle to the end parts extending plane, characterized in that the metal oxide coating its largest Has strength in the area of this latter curved disc part (36). 7. Process for the production of metal oxide films on bent glass sheets for production of window glazing according to claims 1 to 5, characterized in that the curved Disc heated to over 200 ° C, but not up to the melting temperature of the glass, that one A spray of such a composition is generated which results in the formation of a metal oxide film suitable, the strength of this coating from an outside of the disc to the others decrease in such a way that stripes are created according to a predetermined pattern, and that the spray of each of the sections of decreasing coating thickness on the heated Glass pane breaks after such a time, which leads to the formation of a coherent film with the desired pattern in the cross direction sufficient, but before any part of the applied layer is below that required for film formation Temperature has cooled down. 8. The method of claim 6 for coating a surface of a curved one in the longitudinal direction Glass pane with a metal oxide film that follows a certain pattern in the The transverse direction of the disc has decreasing coating thickness, characterized in that the The spray jet aligns with its central axis transversely to the longitudinal axis of the disc and a relative movement between the heated disc and the beam in such a way that the to be coated parts of the carrier along its longitudinal axis successively the transverse pattern of the Exposed to the beam. 9. Glazing, characterized in that at least one with a coating according to claim 1 to 5 provided curved disc (30) with another, matching in the curvature Disc with at least one transparent thermoplastic plastic film in between is combined into a composite unit. 1 sheet of drawings © 909 578/195 7.