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WO1997031869A1 - Sealing glass suspension - Google Patents

Sealing glass suspension

Info

Publication number
WO1997031869A1
WO1997031869A1 PCT/US1997/002544 US9702544W WO1997031869A1 WO 1997031869 A1 WO1997031869 A1 WO 1997031869A1 US 9702544 W US9702544 W US 9702544W WO 1997031869 A1 WO1997031869 A1 WO 1997031869A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
glass
vehicle
sealing
frit
material
Prior art date
Application number
PCT/US1997/002544
Other languages
French (fr)
Inventor
Paul B. Dohn
Edward J. Fewkes
Robert Morena
Frances M. Smith
Lung-Ming Wu
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10Frit compositions, i.e. in a powdered or comminuted form containing lead
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C03C8/245Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders containing more than 50% lead oxide, by weight

Abstract

A sealing glass material comprising a sealing glass frit and a vehicle, the vehicle being an aqueous solution of a cellulosic polymer, and a method of preparing the sealing glass material.

Description

SEALING GLASS SUSPENSION

FIELD OF THE INVENTION

A suspension of a sealing glass frit in a vehicle free of volatile organic compounds.

BACKGROUND OF THE INVENTION

Glasses that melt at relatively low temperatures have long been used to join metal, glass and ceramic components by a fusion seal. Initially, such seals were vitreous in nature. Lead glasses, particularly lead zinc borates, were commonly used.

The sealing art was revolutionized by discovery that such glasses could be crystallized in a controlled manner by thermal treatment. This combined the virtues of a low melting glass with a strong seal in the crystalline state. More recently, non-lead glasses, composed essentially of tin, zinc, and phosphorous oxides, have been proposed as a substitute for the traditional lead zinc borate glasses. United States Patent No. 5,246,890 (Aitken et al.) discloses examples of such phosphate glasses.

In forming a seal with such sealing glasses, it has become customary to use the glass in a particle form known as glass frit. The glass frit is mixed with a vehicle and binder to form a suspension, or paste. This mixture is applied to a sealing surface, for example, by extrusion.

Numerous organic vehicles and binders have been proposed. A combination of nitrocellulose and amyl acetate is commonly used in commercial cathode ray tube production. Numerous organic vehicles and binders have been proposed. A combination of nitrocellulose and amyl acetate is commonly used in commercial cathode ray tube production.

Recently, environmental concerns have made it desirable to avoid the use of volatile organic compounds (VOCs) where possible. A prominent area of concern is sealing glass paste used in such diverse applications as LCD panels, cathode ray tubes, and lighting products.

It is a purpose of the present invention to provide a sealing glass suspension that avoids the use of volatile organic compounds while meeting current process specifications for paste dispersibility, seal strength, electrical characteristics, and hermeticity in a seal. It is a further purpose to provide such a suspension having a smooth consistency. Another purpose is to provide a sealing glass material having Theological characteristics that provide good flow and easy dispensing. Still another purpose is to provide a sealing glass material that has acceptable electrical characteristics when fired to form a seal. In considering the present invention, it is necessary to distinguish between volatile and non-volatile organic compounds. The former characteristically vaporize at or near ambient temperature, thus entering the atmosphere in gaseous, organic form.

The latter, which are acceptable, do not vaporize in organic form. Rather, the only material volatilized is water.

SUMMARY OF THE INVENTION

The present invention resides in part in a sealing glass material that is free of volatile organic compounds, and that comprises a sealing glass frit and an aqueous solution of a cellulosic polymer.

The invention further resides in a fusion glass seal that is the fired product of the sealing glass material. BRTEF DESCRIPTION OF THE DRAWINGS

The single FIGURE in the accompanying drawing is a graphical representation illustrating characteristics of the inventive materials.

PRIOR ART

Literature of possible relevance is listed and supplied separately.

DESCRIPTION OF THE INVENTION

The present invention arose from efforts to eliminate the need for volatile organics in producing a fusion sealing material. It was recognized that any substitute would necessarily have to be compatible with the glass frits currently available. Further, it would be necessary to maintain comparable rheological characteristics in order to permit application of the material with present procedures and equipment.

We have found that the desired end can be accomplished by using a water-soluble, cellulosic binder with water or methanol as a solvent. While any soluble cellulosic binder may be employed, we have worked with a side chain functional type supplied by Alpha Metals (AMV). This material contains about 1.25% polymeric solids dispersed in water as solvent.

A sealing paste is readily prepared by adding a low melting glass frit to the aqueous cellulosic vehicle. The term "low melting" glass frit is understood in the art to mean a mid-temperature sealing glass that softens to wet a sealing surface and form a seal therewith at a sealing temperature of about 400-450°C. The glass has a softening point on the order of 400-450°C.

Commercial usage has grown up around lead borosilicate glasses, generally containing zinc oxide. Such glasses may consist essentially of 70-80% PbO, 10-14% ZnO, 6-12% B203, 0-3% Si02 and 0-3% BaO. A typical glass is Code 7590, available from Corning Incorporated and having a composition of about 75% PbO, 12% ZnO, 9%

B2Oj, 2% Si02 and 2% BaO. Recently, non-lead glasses have been proposed. A family of SnO-ZnO-P20s glasses is disclosed, for example, in the Aitken et al. patent referred to earlier. These glasses are lead-free and have compositions containing 25-50 mole % P20, and SnO and ZnO in amounts such that the mole ratio of SnO:ZnO is in the range of 1 : 1 to 5: 1. They may further contain up to 20 mole % of modifying oxides including up to 5 mole % SiOj, up to 20 mole % B203, up to 5 mole % alkaline earth metal oxide, and up to 5 ole % A120}; also one or more crystallization promoters selected from 1 to 5 mole % zircon and or zirconia and 1-15 mole % R20 and a seal adherence promoter selected from up to 5 mole % W03, up to 5 mole % Mo03, up to 0.10 mole % Ag metal and mixtures. The present invention has been developed for use with lead borosilicate glasses.

However, it has also been shown to be effective for use with non-lead glasses, such as those disclosed in the Aitken et al. patent.

A paste can be readily prepared by adding glass frit to the vehicle. The frit may be dispersed in the vehicle by mixing in a Hobart shaker, although a high speed mixer may be used to form a smoother paste. The ratio of glass frit to vehicle has been varied between

6: 1 and 10: 1 with a smooth paste resulting after mixing.

It is then necessary to consider the rheological characteristics necessary for dispensing the paste onto a sealing surface. For dispensing onto a narrow surface, such as the rim of a CRT panel, it is common practice to extrude the paste through a small opening. This may be pressure applied through an orifice, a syringe, or an automatic dispenser.

The rheological characteristics of a paste, that is, the viscosity or flow characteristics for dispensing purposes, are measured by employing a Rheometrics Dynamic analyzer. This is a parallel plate mechanism in which one of the plates is oscillated. A material sample is placed between the plates and viscosity is measured as the oscillation rate is increased.

The single FIGURE in the accompanying drawing is a graphical representation of viscosity measurements made on the dynamic analyzer. Viscosity is plotted in log poises on the vertical axis; oscillatory frequency is plotted on the horizontal axis in radians/second (rad/s). Curve A displays the rheology of a paste prepared by mixing six parts of Code 7590 glass to one part of the cellulosic vehicle as received. It will be observed that the paste has a high value initially. This decreases as shear is applied, thus indicating a thinner, more fluid paste. Similar measurements were made on a current commercial paste in which the glass frit is dispersed in a vehicle of nitrocellulose dissolved in amyl acetate. This curve was substantially lower than curve A, thus indicating different viscosity characteristics. It was apparent that the material of curve A could not dispense properly using the practice employed for the present commercial material.

This created a need to modify the paste in some manner to fit present application practice. Initially, attempts were made to dilute the paste by adding more vehicle. This addition of vehicle showed no significant effect. Rheology curves, corresponding to those shown as curve A, were obtained on the modified materials. They showed no significant change.

Further study revealed that the desired lowering of the Theological curve of the paste of curve A can be achieved. Surprisingly, this is accomplished by prediluting the vehicle with solvents such as methanol or water. In effect, this reduces the ratio of polymeric solids in the vehicle to less than one part per hundred. Doubling the amount of solvent, which reduces the polymeric solids to about 0.6% of the vehicle, has been found to produce a paste having a rheology close to that of the present paste. Curve C is based on measurements on a paste prepared with a vehicle diluted with water. The amount of solvent in the vehicle was doubled so that the vehicle contained 0.6% solids in the form of cellulosic polymer. The paste prepared with this diluted vehicle was composed of six parts Code 7590 glass frit and one part of the diluted vehicle. A corresponding mixture in which the vehicle was diluted with methanol rather than water, provided a curve similar in shape to curve C, but slightly higher. Curve D is based on a paste containing ten parts glass frit to one part vehicle. In this case, the vehicle is diluted with methanol to provide 0.6% polymeric solids in the vehicle.

A further consideration in producing a fusion seal is the color of the fired seal. A dark color indicates the possible presence of reduced lead. Consequently, a yellow or orange color is deemed desirable, and may be used as a qualitative process control. When a paste with a 6: 1 frit-vehicle ratio was fired, the color of the seal was a drab olive. Electrical testing showed acceptable properties. Nevertheless, it appeared necessary to allay fears by improving the seal color.

It was found that higher frit-vehicle ratios gave an improved color. Also, various oxidants can be added in minor amount to improve color. These include peroxides, persulphates, and sulfates. We prefer to use potassium persulphate.

We have found that the rheology of the paste can be further adjusted by the addition of a gelling agent to the vehicle before adding the glass frit. In particular, this permits modifying a material to have a higher viscosity at low shear, while still thinning out to a very low viscosity at higher shear. This is highly desirable as it allows easy dispensing of the paste while causing it to set up quickly so that it does not flow or drip after being deposited on a sealing surface. Thus, the rheology of the present paste can be tailored to closely match present practice.

A material containing a clay gelling agent has been prepared in the following manner. 100 grams of vehicle, as received, was diluted with 100 grams of water. To this diluted vehicle was then added 7.7 grams of a clay-type rheology modifier. This modifier is available from Rheox, Inc. under the designation Bentone LT. The mixture was then heated at 38°C and mixed with a high-speed disperser for about 90 minutes to produce a homogeneous pregel blend. The sealing paste was then prepared by adding 14.28 grams of the pregel to 36.26 grams of the diluted vehicle. This was stirred rapidly for approximately 20 minutes. To this mixture, 500 grams of Code 7590 frit was then added in small additions. Following addition of the frit, the mixture was stirred to a creamy consistency preparatory to being used for sealing purposes. A series of tests were carried out to determine the effectiveness of the invention in conjunction with non-lead, SnO-ZnO-P205 glass frits. A glass was selected having the following composition on a molar basis: 31.5% P2Os, 1.5% B2Oj, 14.6% ZnO, 51.2% SnO and 0.7% A120, and 0.5% WO,. Four blends of 74 grams glass frit, 6 grams alumina and 20 grams of zircon each were prepared. Two of the batches were mixed with the cellulose vehicle as received to form pastes. The frit:vehic!e was 4.8: 1 in one mixture and 6.7: 1 in the other. The other two blends were each mixed with vehicle diluted on a 1 : 1 basis with water to form pastes. In each paste the frit:vehicle ratio was 4.8: 1.

The Theological characteristics of the four pastes thus produced were analyzed as described above employing the Rheometrics Dynamic analyzer. The two pastes containing vehicle as received produced viscosity curves comparable to those shown by curve A in the drawing. The other two pastes, prepared with the diluted vehicle produced viscosity curves comparable to those shown as curves C and D in the drawing. This demonstrated that the benefits of the invention were obtainable with both traditional lead borate frits and the newer non-lead frits.

Claims

WE CLAIM:
1. A sealing glass material comprising a sealing glass frit and a vehicle, the vehicle being an aqueous solution of a cellulosic polymer.
2. A sealing glass material in accordance with claim 1 wherein the glass frit is a lead borosilicate.
3. A sealing glass material in accordance with claim 1 wherein the glass frit consists essentially of, as calculated from the batch on an oxide basis in weight percent, 70-80%
PbO, 10-14% ZnO, 6-12% B20„ 0-3% Si02 and 0-3% BaO.
4. A sealing glass material in accordance with claim 3 wherein the glass frit consists essentially of 75% PbO, 12% ZnO, 9% B20„ 2% Si02 and 2% BaO.
5. A sealing glass material in accordance with claim I wherein the glass frit is a non- lead, SnO-ZnO-P2Os glass.
6. A sealing glass material in accordance with claim 5 wherein the glass frit consists essentially of 25-50 mole % P20, and SnO and ZnO in amounts such that the mole ratio is in the range of 1:1 to 5:1.
7. A sealing glass material in accordance with claim 1 wherein the material comprises the glass frit and the vehicle in a weight ratio between 5: 1 and 10: 1.
8. A sealing glass material in accordance with claim 1 wherein the cellulose porymer solids content in the vehicle is less than 1%.
9. A sealing glass material in accordance with claim 8 wherein the solids content in the vehicle is about 0.6%.
10. A sealing glass material in accordance with claim 1 which additionally contains a gelling agent.
11. A sealing glass material in accordance with claim 10, wherein the gelling agent is a clay.
12. A method of producing the sealing glass material of claim 1 which comprises preparing, as a vehicle, a solution of a water-soluble cellulosic polymer in which the solids content of the cellulosic polymer in the vehicle is less than 1%, and adding to the vehicle a sealing glass frit in an amount such that the frit-to-vehicle ratio is at least 6: 1 , but not over
12:1.
13. A method in accordance with claim 12 wherein an aqueous solution of a cellulosic polymer containing about 1.2% solids is diluted with water or methanol to a solids content less than 1%.
14. A method in accordance with claim 13 wherein the solids content is approximately halved by diluting with water or methanol.
15. A method in accordance with claim 13 wherein a pregel is prepared by adding a gelling agent to a portion of the diluted vehicle, dispersing the clay in the vehicle, adding the pregel to the vehicle with mixing, and adding the glass frit to the mixture of pregel and vehicle.
16. A method in accordance with claim 15 wherein the gelling agent is a clay.
PCT/US1997/002544 1996-02-27 1997-02-19 Sealing glass suspension WO1997031869A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US1233096 true 1996-02-27 1996-02-27
US60/012,330 1996-02-27

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19970906665 EP0883580A4 (en) 1996-02-27 1997-02-19 Sealing glass suspension
JP53099297T JP2000505414A (en) 1996-02-27 1997-02-19 Sealing glass suspension

Publications (1)

Publication Number Publication Date
WO1997031869A1 true true WO1997031869A1 (en) 1997-09-04

Family

ID=21754458

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/002544 WO1997031869A1 (en) 1996-02-27 1997-02-19 Sealing glass suspension

Country Status (4)

Country Link
EP (1) EP0883580A4 (en)
JP (1) JP2000505414A (en)
CA (1) CA2247019A1 (en)
WO (1) WO1997031869A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812810A2 (en) * 1996-06-13 1997-12-17 Corning Incorporated Optical device comprising substrate of betaeucryptite or fused silico, an optical component and a fusion seal comprising a low melting glass frit and a mill addition
EP0889010A1 (en) * 1997-06-30 1999-01-07 Fry's Metals, Inc. Sealing glass paste for cathode ray tubes
US5926599A (en) * 1996-06-13 1999-07-20 Corning Incorporated Optical device and fusion seal
US6603900B1 (en) 1998-11-06 2003-08-05 Corning Incorporated Athermal optical waveguide grating device

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070002554A (en) 2005-06-30 2007-01-05 엘지.필립스 엘시디 주식회사 Liquid crystal display device and fabricating the same
JP4564472B2 (en) * 2006-07-11 2010-10-20 エルジー ディスプレイ カンパニー リミテッド The liquid crystal display device and manufacturing method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038091A (en) * 1972-04-21 1977-07-26 Owens-Illinois, Inc. Sealing glass vehicle and composition and method for making same
US4099977A (en) * 1972-04-21 1978-07-11 Owens-Illinois, Inc. Sealing glass vehicle and composition and method for making same
US4260406A (en) * 1978-08-17 1981-04-07 Corning Glass Works Gelled solder glass suspensions for sealing glass or ceramic parts
US4521251A (en) * 1982-05-17 1985-06-04 Daicel Chemical Industries, Ltd. Low-melting glass paste and cellulose nitrate therefor
US5246890A (en) 1992-08-03 1993-09-21 Corning Incorporated Non-lead sealing glasses
US5470804A (en) * 1994-08-03 1995-11-28 Corning Incorporated Mill additions for sealing glasses
US5516733A (en) * 1994-03-31 1996-05-14 Corning Incorporated Fusion seal and sealing mixtures

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57170838A (en) * 1981-04-15 1982-10-21 Matsushita Electric Works Ltd Water-base glass coating composition
GB2118928A (en) * 1982-04-21 1983-11-09 Geoffrey Cooke Enamelling process
JPS59141141A (en) * 1983-01-31 1984-08-13 Matsushita Electric Works Ltd Sealing method by glass frit
EP0617702B1 (en) * 1991-12-17 1996-02-07 Aqualon Company High productivity ceramic glaze
GB9500798D0 (en) * 1995-01-16 1995-03-08 Cookson Group Plc Sealing glass paste

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038091A (en) * 1972-04-21 1977-07-26 Owens-Illinois, Inc. Sealing glass vehicle and composition and method for making same
US4099977A (en) * 1972-04-21 1978-07-11 Owens-Illinois, Inc. Sealing glass vehicle and composition and method for making same
US4260406A (en) * 1978-08-17 1981-04-07 Corning Glass Works Gelled solder glass suspensions for sealing glass or ceramic parts
US4521251A (en) * 1982-05-17 1985-06-04 Daicel Chemical Industries, Ltd. Low-melting glass paste and cellulose nitrate therefor
US5246890A (en) 1992-08-03 1993-09-21 Corning Incorporated Non-lead sealing glasses
US5516733A (en) * 1994-03-31 1996-05-14 Corning Incorporated Fusion seal and sealing mixtures
US5470804A (en) * 1994-08-03 1995-11-28 Corning Incorporated Mill additions for sealing glasses

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0883580A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812810A2 (en) * 1996-06-13 1997-12-17 Corning Incorporated Optical device comprising substrate of betaeucryptite or fused silico, an optical component and a fusion seal comprising a low melting glass frit and a mill addition
EP0812810A3 (en) * 1996-06-13 1998-09-09 Corning Incorporated Optical device comprising substrate of betaeucryptite or fused silico, an optical component and a fusion seal comprising a low melting glass frit and a mill addition
US5926599A (en) * 1996-06-13 1999-07-20 Corning Incorporated Optical device and fusion seal
US6122430A (en) * 1996-06-13 2000-09-19 Corning Incorporated Optical device and fusion seal
EP0889010A1 (en) * 1997-06-30 1999-01-07 Fry's Metals, Inc. Sealing glass paste for cathode ray tubes
US6183871B1 (en) 1997-06-30 2001-02-06 Fry's Metals, Inc. Sealing glass paste for cathode ray tubes
US6603900B1 (en) 1998-11-06 2003-08-05 Corning Incorporated Athermal optical waveguide grating device

Also Published As

Publication number Publication date Type
JP2000505414A (en) 2000-05-09 application
EP0883580A1 (en) 1998-12-16 application
EP0883580A4 (en) 1999-03-31 application
CA2247019A1 (en) 1997-09-04 application

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