DE2010920A1 - - Google Patents

Description

'PATENT LAWYERS Γ -

OH.iNG.H.NEGEifDA] VK · bipl-ing. M. Εί AitTCK β1ρϊ. Ρηυ8. W. SCHMITZ

HAMBURG-MUNICH 0 Π 1 Π Q 9 Π

DELIVERY ADDRESS HAMBURG 36 · NEUER WALL 41

TBt. 3β74 28 AND 364119 'TEXEOB. NBGEDAPATBNtHAMBOBG

"MÜNCHEN-15 · MOZARTSTH. 23;

'OWMS-IIiLIIiOXS, DTO. . .in."""""*-

, OhiO 43601 / USÄ. TB ₁ BGB-NBGBDAPATBNTMuNCHEN

March 5, 1970

Composition based on a polymer and method for coating a substrate

so :

The invention relates to one based on a polymer Composition that is excellent for coating a specific substrate, ζ. B. for decorative purposes, for Protection and / or suitable for sealing, and their manufacture. It also relates to a method of applying this composition to a selected substrate.

Inorganic coating materials in the form of solid particles get wet in the Hegel, i.e. in a binder-solvent system dispersed, applied to the substrate. Such processes make the mixing of binders, Solvent and inorganic material required to to obtain a paste or slurry which is then applied to the surface. The viscosity of the pastes changes with temperature and with the particle size distribution of the inorganic material. So quality control is difficult, and the solution-binder 'technique is

009839/2121

material and time consuming.

The wet coating is commonly used for soldering glass or ceramic parts such. B. in the manufacture of a cathode ray tube in which the ätirnplatte is placed on the funnel. In this ball , the paste, which contains solder glass distributed in the binder-solvent system, is applied to the edges of a part in the form of a binder

^ upset. The other part is then brought into contact with the paste and the ^ lance heated to remove the solvent, burn out the binder and melt the solder glass. Although this method is widely used, quality control is cumbersome and expensive because it leaves a carbonaceous or carbonaceous residue that cannot be removed by evaporation or incineration during heating. Likewise, when a solvent evaporates, changes in the viscosity and / or the thixotropic properties of the system occur

^ f on what can have harmful effects, such as B. Occurrence of the xipf elsinenschelleneffektes, the formation of iischaugen etc., especially with smooth surfaces. To overcome the difficulties associated with applying a coating or a sealant to oubstrate by means of a

are connected, binder-solvent system / bypass, one has dry Coating compositions which contain a polymer as a binder are used and aas as ieststoffpartikel existing coating material evenly in the binder

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distributed. These compositions were then formed into films which were applied to the substrate to be coated and then heated to burn out the binder and a coating of the inorganic material, usually molten or sintered form. The presence of the carbonaceous residue is also a problem here.

For the dry coatings polymethacrylate and polyisobutylene ■ were used which have been found to be not quite ^v satisfying because built on these polymers compositions can not be deformed as usual into a film. Films of these compositions are formed by casting, which includes many of the disadvantages inherent in the binder-solvent system. Upon decomposition, the polymethacrylate and polyisobutylene binder leave a noticeable carbonaceous residue. This residue prevents polymers from being used for many important purposes. When heated, the carbonaceous residue present as oxide reduces to LIetalle% elemental state, ie to the metal tfenn the coated material for electrical devices is used, the absence of an electrically conductive L-etalifilmes is disadvantageous. Tt & xm ζ. B. the organic coating material is a soldering glass, which usually contains lead oxide, the carbonaceous residue acts as a reducing agent and reduces aas lead oxide to lead. If this metallic

009839/2121

SADORfGlNAl

If lead is present in a cathode ray tube solder joint, it conducts electricity and the tube is unusable. Also, the presence of free metals in the coating reduces the aesthetic value of the coated part, which affects the use of such films for glazing.

It is therefore an object of the present invention to provide a coating composition which has the above does not bring the disadvantages mentioned. This ρ task is achieved by a composition consisting of finely divided inorganic solid particles, which in a liquid polymer of low molecular weight, which is pyrolyzed at a relatively low temperature, dispersed. The composition can also be cyclical include isoprenoid solvent.

Thus, according to the invention, the disadvantages listed above become apparent avoided by producing a composition based on a polymer that is used for coating or for Forming a film on a substrate is suitable without evaporation a solvent and without changing the viscosity and / or the thixotropic properties, which leads to the damaging ■ Effects such as appearance of the orange peel effect, the Formation of fish eyes and the like, especially on smooth surfaces.

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BAD ORlGfNAt

A polymer composed of a polymer is described in more detail Composition prepared which disperses finely divided inorganic solid particles in a polymer contains, -which is liquid, a low molecular weight and has low vapor pressure, a relatively constant viscosity and relatively, constant thixotropic properties during the Composition heating cycle and watch

relatively low temperatures completely in gaseous form Products decompose without forming a noticeable carbonaceous or similar residue and / or to S that has direct or indirect harmful effects, e.g. Bo direct influence on the decorative or

(Adhesive) - ■

connecting / properties of the composition by the Backing up and / or transferring easily reducible metal ■

oxides to the metal through the residue. The composition can also include a cyclic isoprenoid solvent, e.g. Turpentine, particularly cyclic isoprenoid solvents such as saturated and unsaturated, monocyclic and bicyclic terpenes including diterpenes, triterpenes, % sesquiterpenes and isoprene.

Typical monocyclic terpenes considered as solvents are dipentene, para-cymene, oL -terpinene, para-menthenes, para-methane, terpinolene, 2,4 (8) -para-iuenthadiene, thymol, limonene, pulegon, menthol, cJü - Terpineol, β- terpineol,, Gis-ijS-terpin hydrate, anethole, etc. Typical solvents

00 9839/2121

Bicyclic terpenes under consideration are oC pinene,

-Pinen, Camphene, Camphor, Fenchon, Sabinol, Bornylen, etc. as well as mixtures thereof. Mixtures of monocyclic and bicyclic terpenes can be used.

Although the boiling point of the terpene can be in the range up to about 300 ⁰ C, terpenes with a lower boiling point, z. B. below about 230 ⁰ G, preferably below 200 ⁰ C, as more suitable preferred.

In the particular embodiment of this invention it has been found that polystyrene and / or PoIyCoC -substituierte-) Low molecular weight styrenes, below about 1000, especially are suitable because such polymers are liquid over a relatively wide temperature range, e.g. 3rd of Such polymers are from room temperature to about 300 ° C. initially when the composition is made in a liquid state and remain so until the polymerizate pyrolyzed and the coating or film on the substrate, e.g. B. by melting or solid attachment of the dispersed Solid particles, forms. 3-at the same time have such polymers a low vapor pressure and relatively constant viscosity and / or thixotropic properties.

In a preferred embodiment of this invention, the polymer is an oly (OL> -substituted) styrene of the general formula below

_ 7 -

009839/2121

-C- CH ₂ -

in which η is an integer greater than 1 and R is a Alkyl with up to 6 carbon atoms, ζ. B. methyl, ethyl, propyi, butyl, leobutyl, isopropyl, ethyl, isopentyl, ueopentyl, Hexyl etc.

Some finely divided particulate inorganic Coating material can be incorporated into the composition will. Under "finely divided particulate inorganic Coating material "is an inorganic, Understand conductive and / or non-conductive material in finely divided form, as a substrate in Porm a Coating which can be melted, sintered or particulate can be applied. the Choice of such materials is largely unlimited. Suitable materials, which are only mentioned here as an example and do not represent a limitation of the invention, are oxides, such as Silicon dioxide, aluminum oxide and boron oxide decorative G-glazes, which are glassy compositions contain low melting points Compounds or fluxes, such as the alkali metal oxides, Boron oxide and lead oxide j electron-emitting compounds, such as

009839/212 1

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the carbonates of barium, strontium and calcium! Metals and metallic alloys such as copper, gold, silver, nickel, platinum, etc. $ glasses and thermally crystallizable glasses; Solder glasses and mixtures thereof.

In a preferred embodiment of this invention the inorganic coating material is a soldering glass · soldering glass are well known and are used for soldering glass or ceramic surfaces to glass, ceramic or metallic ^ Share used. They are also used to coat substrates, especially electrical parts such as micro-rectifiers (microcircuits) used. Vitreous and devitrifiable solder glasses are known and are commercially available. Either type of solder glass can be used to practice the invention. Examples of solder glasses used in this Invention are disclosed in the United States patents listed below: 2,866,298? 2,931,142 $

2,936,923; 3,061,664; 3,063,198; 3,080,328} 3,088,833;

3,086,634; 3,066,835; 3,127,278; 3 250 631, 3 291 586 and

W 3 366 024. The applicant is the owner of the patents listed above. The soldering glass can be used alone or mixed with other inorganic material, for example a glass ceramic.

Exemplary particular solder glass compositions that have been used with success in practicing the invention, contained in Jew.- ;; about: 70 to 80 PbO, 16 to 8 ZnO,

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- Q _

■ 10 Mg 7 B ₂ O ₅ , 1 to 4 SiO ₂ , O to 1 BaO and O Ms 1 ₂ Such solder glasses are used alone and / or in conjunction with 1 to about 15% by weight of a glass or a glass-ceramic composition.

The coating composition can be of any suitable one Substrate which has any geometric configuration or shape can be applied. All the advantages of this Invention, however, are obtained when the composition is applied to a substantially smooth surface, e.g. B. I. on a glass plate. However, such surface can have notches, depressions or other irregularities, which the Adhesion of the coating to your substrate increases.

The substrate can be made of any magnetic or non-magnetic material including glass, ceramic, Glass-ceramic, metal, carbon, plastic and mixtures thereof, such as ceramic-metallic compositions, i.e. Cermets. Metal, as the word is used here, includes

Metalloids as well as metals and metalloid oxides * examples are silicon, aluminum, titanium, zircon, etc. as well as Alloys and oxides thereof. If plastic is used as a substrate, it must be able to withstand the heat treatment endure, such plastics are z. B. the high temperature resistant Polyaromatics. ■

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The quantitative ratio of pyrolyzable polymer and dispersed inorganic material can vary within a wide range, depending on the intended use and the required viscosity of the coating composition. In general, the pyrolysable polymer is used in an amount which is at least sufficient to serve as a carrier for the Ivlenge particles which is required for the particular application, in order to have good coating properties in the raw state, ie before melting and sintering, if to ensure the particles are applied to the substrate.

The coating composition contains about 90 to about 2% by weight of the pyrolyzable polymer and about 10 to about 98% by weight of the dispersed, finely divided, particulate inorganic coating material. If solvents, cyclic isoprenoids, are used, then the composition consists of about 90 to about 2% by weight of solvent and pyrolyzable polymer and about 1 to about 98% by weight of the dispersed, finely divided, particulate inorganic coating material, wherein the weight ratio of solvent to polymer is in the range from about 5 1 to about 1:10, in particular 1: 1. The viscosity of the resulting composition before the application of heat and pyrolysis of the polymer is in the range between good flowability, e.g. B ₀ a viscosity,

009839/2121 - 11 -

in which the composition can be sprayed, and one Thickness, like that of a paste or a putty, for example one Viscosity of about 50,000 cps at ^ room temperature »

In addition, the coating composition can include others Components ^ such as wetting agents and / or leveling agents, which pyrolyze cleanly.

Although the composition of this invention as a Coating and / or film-forming composition is described, the terms "coating" and / or "film-forming" a variety of uses and is not limited to decorating and / or protecting a surface alone. That is, the coating composition according to the invention is for application to any substrate, the one continuous or discontinuous layer or a PiIm needed, suitable · So the composition for a Variety of uses can be used, e.g. B »around one dielectric or conductive layer or lines (continuous or discontinuous), in electronic systems and parts, for decorative and / or protective layers, for sealing or adhesive layers for joining two substrates together, and the like can be used.

In a particular embodiment of the invention, the Composition used to manufacture small electronic components (electronic dual in line parts), e.g. B. to

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double-sided layers or lamination of an electronic microcircuit, consisting of a small (e.g. 6.35 to 19.05 mm) notched alumina substrate comprising a layer of a glazed coating composition of thickness Contains 8 to 10 HiI.

In another particular embodiment of the invention the coating composition is measured to be 127 x 165 x 6.35 mm large glass plate of a gas discharge indicator and storage device upset. The coating is applied to the substrate as a continuous layer, e.g. B. so that a dielectric coating is formed on it, or as continuous or interrupted conductive thin lines, z. B. such that they represent electrodes on it.

Multiple gas discharge indicator and / or storage disks of the kind with which the present invention is concerned, are characterized by an ionizable gaseous medium, which is usually a mixture of two gases at a suitable gas pressure, in a thin gas chamber or a space between a pair of opposing dielectric charge storage bodies, which on the rear side with conductors (electrodes), a series of thin lines or dots. The ones on the back of each opposing dielectric Body arranged conductors are aligned transversely so that they delimit a plurality of discrete discharge spaces and form a discharge unit. In some

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Plates are the discharge units 'additionally' bounded by surrounding or restricting physical structures such as cells or openings in perforated glass plates and the like, so that the units are physically isolated from one another. For example, the dielectric body and the conductor are applied to a glass substrate carrying them with two spaced apart substrates which are suitably joined together so that they make up the plate. The coating composition according to the invention can be used to apply the dielectric and / or the conductive electrode to the substrate

'the · ■ ·

and also, around the edges around / joined, in the distance to seal arranged substrates.

The coating composition can be applied by any of the known methods, for example by extrusion, with a Meyer rod, with a blade, by spraying, dipping, or printing, e.g., screen printing thin lines on a substrate, eg. B ₀ as the electrode lines, in the form of finely divided, molten conductive material such as gold or silver on the glass substrate and a Gasentladungsanzeige- memory device.

Although the coating composition can be applied to the substrate in a single step, Z ₉ B ", by any of the aforementioned techniques, it should be noted that

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that such a step can be repeated to build up the thickness of the layer on the substrate. Thus, the invention is in an off guide die deposited the coating composition to the substrate, suitable dried and the whole process several times, for example. 2 to 8 times, repeated until a desired thickness of the fresh coating is reached, e.g. B. a thickness of about 0.1016 to 0.5080 mm (4 to 20 mils). The built-up coating (a plurality of dried layers) is then cured by heating, e.g. B. in one or more ovens, so that the polymer

pyrolyzes and the inorganic material melts. With such coatings, the drying of the applied coating best done by radiant heat, e.g. B. by irradiation with infrared such that the upper, exposed Part of the coating dries without melting the inorganic material.

The conditions under which the single layer or layers of inorganic material are melted or sintered are a puncture of the material and the purpose for which the coated substrate is used. For example, the flatness, e.g. B. a glazed surface coating, determined by the length of time that is required for melting or sintering

If the solid inorganic material is a crystallizable one Solder glass is and the coated substrate is then with

009839/2121

is

glued to another surface by heating the coating then the solder glass coating is first melted onto the substrate at a temperature below the crystallization temperature of the solder glass The substrate is then reheated, and the glassy solder glass coating becomes crystallized during the following soldering stage

The particle size of the solid inorganic material can be vary within wide limits, e.g. from very fine to very

rough. The finer the particles, the larger the M

Surface and all the more pyrolysable liquid polymer is required.

Although the pyrolyzable liquid polymers that come into consideration here can easily be prepared, they are also commercially available. ^{5 for} the Hamen Dow "" Resins 276-V2 and 276-V9. The properties of these two resins are summarized in Table I below. "^

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M>

properties

Color ■

Color (iodine standard)

Boiling range ( $ 5 - 90 &) at 5 mm Hg., C.

Specific weight at 60/60 ⁰ C kg / 1 at 25 ⁰ C viscosity at 60 ⁰ C, cps flash point (approx.), ⁰ C focal point, ⁰ C volatility -100 hours at 100 ⁰ C, <fo refractive index at 60 ⁰ C acid number

Iodine number

Dielectric constant (10 ^ cps) dielectric loss factor (10 cps) viscosity at 60 ⁰ C, cps Dow Resin
276-V2 276-V9

clear as water clear as water .0.85 0.85 150-300 150-300 1 .01 1.04 1.008 1.039 100-200 700-1000 166 182 182 207 28-32 18-20 1.58 1.57 40.1 * 0.1 <4.0. <4.0 2.56 2.60 0.0001 0.0005 100-200 700-1000

According to a further embodiment of this invention, you can Polymers of different molecular weights «are mixed with one another in a suitable manner, so that the special desired viscosity and / or thixotropic properties can be obtained.

009839/2121 - 16 -

Although not listed in the table above, the molecular weight of poly ( ch -methyl) styrene can range from about 250 to about 1000.

The following examples illustrate preferred embodiments of the invention.

EXAMPLE I ■ .- '. ■ ·

A rating based on a polymer Beschichtungszusammen- M reduction was prepared by dispersing 50 g of an inorganic material in 50 g of liquid poly-Cc ^ / - methyl) styrenes.

The inorganic material consisted of finely divided glassy particles about the same size or smaller than about 400 mesh. The glassy particles were produced by melting and fritting the glassware, which consisted essentially of 73.3% by weight PbO, _{13.4 B 2} O ₃ and 13.3% by weight SiO ₂ . The polymer

was DOW 276-V2. ■ "™

The composition was obtained as a 0.381 mm (15 mil) layer applied with a Meyer rod to the surface of a glass substrate with a size of 127 χ 165.1 x 6.35 mm. That the The composition-bearing substrate was then left for 2 to 4 hours heated to 621 0 to form a very transparent dielectric layer approximately 0.0508 mm thick. The hardened one

- 17 - ' 0 0 98 3 9 / -21 21

bchicht was characterized by an unusual smoothness of the surface

The above procedure was repeated using 30 g and 70 g of inorganic material polymer, but the results were not as good, ie, the surface did not have the smoothness as the composition 50 t 50th

EXAMPLE II

A coating composition was prepared by dispersing 600 grams of finely divided inorganic material in 50 grams of cyclic isoprenoid solvent and 50 grams of liquid poly ( cL- -methyl) styrene.

The inorganic material consisted of about 95 weights-5 ^ vitreous

5
Particles and about / wt.-fc glass-ceramic. 74% by weight of the particles were approximately equal to or smaller than 400 mesh. Jer! Lest of the particles ranged up to about 100 mesh (0.147 mm).

The composition of the inorganic material consisted essentially of> a by weight: 5.37 SiO ₂ , 0.15 Ea ₂ G, 71.00 PbO, 12.3 ZnO, 7.78 B ₂ O ₅ , 0.06 K ₂ O, 0.18 BaO, 1.17 Al ₂ O ₅ , 0.23 Li ₂ O, and 5.0 glass-ceramic.

The polymer was DOW 276-V2. The solvent was HiiÄCüLiiS T'erpineol 3I0 and consisted of 55 to 60 wt .-, *

009839/2121 _ ₁₆ _

BATH ORIGINAL

2Ö10S20

-lerpinöol. " 1? up to 22% by weight -> ρ -Terpineol * 20% by weight of other tertiary alcohols with boiling points in the range of o (y -lerpineol, and 3% by weight of terpene hydrocarbons and dineol. The solvent had a boiling temperature in an absolute atmosphere of about 220 ⁰ C, a specific gravity of 0.939 »a refractive index of 1.482, a flash point (determined in an open crucible according to Cleveland) of 88 G and an eauri-butanol solution value of over 500 *

When applied to a suitable substrate by the screen printing method, and heated j, v / urde complete burn and curing the composition reached at about 300 ⁰ C *

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0098 397 21 2 1

Claims (1)

Claims 1. Composition based on a polymer, characterized in that it contains finely divided inorganic pesticide particles dispersed in a polymer, which is liquid, low molecular weight and low vapor pressure, has a relatively constant viscosity and has relatively constant thixotropic properties and completely gaseous products "at a Temperature below the sintering or melting temperature of the ^ Inorganic material decomposes or pyrolyses without the formation of a carbonaceous or similar residue. 2. Composition according to claim 1, characterized in that that aas inorganic material in two polymers of different molecular weight, so mixed together are that the 3-egg the particular viscosity desired and / or has thixotropic properties, φ is dispersed. 3. Composition according to claim 1, characterized in that that the polymer is polystyrene or a poly (o6 -alkyl) Styrene is. 4. Composition according to claim 3, characterized in that the polymer has a molecular weight below about 1000, 009839/2121 -20- Ιλ 5. Composition according to claim. 1, characterized; that they are inherited from about 90 to about 2 wt. fo pyr ο Iy si
Polymerisats and about 1.0 to 98 wt .- $ inorganic
Mate.rials consists. 6. The composition according to claim 1, characterized in that the polymer is poly-C oC-alkyl) styrene, wherein
the AlkyIresi "has at most 6 G-atoms. 7. Composition according to claim 1, characterized in that that the polymer is poly (e £ / ″ - methyl) styrene. 8. Composition according to claim 7, characterized in that the inorganic material is solder glass. 9. Composition according to claim 7, characterized in that that the inorganic material copper, gold, silver,
Mckel or platinum is. 10. Composition according to claim 7, characterized in that the inorganic material is a thermally crystallizable one Glass is. 11. Composition according to claim 8, characterized in that that the solder glass is glassy and essentially consists from about, given in weight _r $ 70 to 80 PbO, 16 to 8 ZnO, 009839/212 1 - 3f - is 10 Ms 7 B ₂ O ₅ , 1 to 4 SiO ₂ , 0 to 1 BaO and 0 to 1 SnO ₂ . 12. The composition according to claim 11, characterized in that the solder glass together with about 1 to about 15 wt. - "/ <>
thermally crystallizable glass or glass ceramic is used. 13. Composition according to claim 1, characterized in that it contains a cyclic isoprenoid solvent, White and the inorganic material in this solvent
and the liquid polymer is dispersed. H. Composition according to claim 13 »characterized in that the cyclic isoprenoid solvent from
karine stock comes from. 15. Composition according to claim 13, characterized in that the solvent is selected from saturated A or unsaturated, monocyclic or bicyclic
Terpenes and mixtures thereof. 16. The composition of claim 13 »characterized in that the solvent has a boiling point below about 300 ⁰ G at an absolute pressure of 1 atmosphere. 17. Composition according to claim 13, characterized in that the solvent has a boiling point below about 230 g. 009839/212 1 - 22 - 18. A method for coating a substrate with a A composition according to any one of claims 1 to providing the substrate with a layer of one inorganic material, characterized in that the composition according to any of the known Methods such as brushing, spraying, dipping or silk-screen printing are applied because * the composition The supporting substrate is heated to a temperature sufficient to evaporate the solvent if necessary and to pyrolyze the polymer without melting or sintering the inorganic material and then further is heated to a temperature sufficient to "melt or" melt the inorganic material on the substrate to sinter. 009839/2121