WO2008062229A2 - Vitres imprimées - Google Patents

Vitres imprimées Download PDF

Info

Publication number
WO2008062229A2
WO2008062229A2 PCT/GB2007/050705 GB2007050705W WO2008062229A2 WO 2008062229 A2 WO2008062229 A2 WO 2008062229A2 GB 2007050705 W GB2007050705 W GB 2007050705W WO 2008062229 A2 WO2008062229 A2 WO 2008062229A2
Authority
WO
WIPO (PCT)
Prior art keywords
silver
printed
alloy
ink
heating
Prior art date
Application number
PCT/GB2007/050705
Other languages
English (en)
Other versions
WO2008062229A3 (fr
Inventor
Michael Lyon
Michael Robert Greenall
Original Assignee
Pilkington Group Limited
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
Application filed by Pilkington Group Limited filed Critical Pilkington Group Limited
Publication of WO2008062229A2 publication Critical patent/WO2008062229A2/fr
Publication of WO2008062229A3 publication Critical patent/WO2008062229A3/fr

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass

Definitions

  • the present invention relates to compositions of inks used for printing onto glass, in particular, ink used to print electrical circuits onto glass used in automotive glazings.
  • Automotive glazings are often provided with heating circuits to enable the glazing to be demisted in humid, wet or cold weather conditions.
  • the circuits may be provided by heating wires embedded in the interlayer material, or by printing on one of the inner surfaces of the plies of glass forming the laminated structure.
  • heating circuits are printed onto the side of the glazing which will face into the vehicle when fitted.
  • Heating circuits are printed using a high-silver content ink. Although elemental silver is virtually unreactive, the printed lines making up the heating circuit may be corroded by acid or alkaline cleaning agents, or by voltage dependent diffusion. However, the largest cause of failure of heating circuits is mechanical damage of the lines in the circuit. This can occur by scratching with sharp or blunt objects, or by abrasion. For example, in a hatchback vehicle, if the parcel shelf is removed, the boot may be overfilled with objects such as shopping, suitcases, building materials, garden waste. Alternatively, items such as keys and coats may be placed on the parcel shelf when it is in position. In both situations, objects come into contact with the printed heating circuit, and may damage the heating lines by scratching and abrasion. Aside from corrosion by cleaning materials, cleaning the inside of the glazing may also cause damage by scratching, for example, contact with cufflinks, watches and other jewellery, or if grit or other dirt is present on the cloth being used to clean.
  • the scratch or abrasion made to the surface of the heating line may be complete, causing a break in the heating line, or partial, causing surface damage or partial breakage. If there is a break in the heating line, no current will flow, even at maximum voltage, due to the effectively infinite resistance of the line. If the break is partial, such that it is possible to obtain a resistance value, it often results in the silver being "blown out” or removed at a low initial voltage, with no further response, even at maximum voltage. As current flow along a conductor is constant, any small break in the heating line causes a restriction, such that localised heating takes place, damaging the printed line.
  • Figures Ia, Ib and Ic are photographs that illustrate the situation where an AC voltage is applied to the heating line.
  • Figure Ia shows an incomplete break in the heating line.
  • Figure Ib shows the sudden failure when the voltage is applied, causing the ink to melt and vaporise.
  • Figure Ic shows the heating line after failure, where a large portion of the ink has been removed.
  • Figures 2a and 2b show the initial break before and just after application of the DC voltage.
  • a wave front of molten silver can be seen moving away from the break. As the voltage applied increases, this wave front progresses further and further away from the break in Figures 2d, 2e and 2f. The wave front travels towards the positive terminal, and leaves a gap in the heating line at the position of the original break.
  • the present invention aims to address these problems by providing an autmotive glazing having an electrical circuit printed thereon, wherein the ink used to print the electrical circuit contains an alloy of silver and at least one other metal.
  • the alloy has an annealed hardness on the Rockwell 15T of at least 50.
  • the alloy has an electrical conductivity of at least 80% IACS.
  • the alloy comprises silver and copper. More preferably the alloy comprises an amount of copper in the range 0.01%wt to 28.0wt%. Even more preferably, the alloy comprises 92.5% wt% silver and 7.5 wt% copper.
  • Figure Ia is a photograph showing a partial break in a heating line prior to testing with AC voltages
  • Figure Ib (referred to above) is a photograph showing a partial break in a heating line after testing with AC voltages
  • Figure Ic (referred to above) is a photograph showing a partial break in a heating line after testing with AC voltages
  • Figure 2a (referred to above) is a photograph showing a partial break in a heating line prior to testing with DC voltages
  • Figure 2b (referred to above) is a photograph showing a partial break in a heating line during testing with DC voltages
  • Figure 2c (referred to above) is a photograph showing a partial break in a heating line during testing with DC voltages
  • Figure 2d (referred to above) is a photograph showing a partial break in a heating line during testing with DC voltages
  • Figure 2e is a photograph showing a partial break in a heating line during testing with DC voltages
  • Figure 2f (referred to above) is a photograph showing a partial break in a heating line during testing with DC voltages.
  • FIG. 3 is a schematic diagram showing the printed glass samples used for testing purposes.
  • Typical inks for printing electric circuits on the surfaces of automotive glazings comprise between 50 and 83wt% of elemental silver in powdered form (as either particles or flakes), 3-6% glass frit, 1-12% other additives (colour improvers), and small amounts of oils, polymers and flow agents.
  • silver has high electrical conductivity (104% IACS - International Annealed Copper Standard), it is relatively soft, having a hardness, when annealed, of 30 on the Rockwell 15T scale.
  • Alloying silver with other metals increases the hardness of the alloy, compared with elemental silver, when annealed.
  • Suitable metals include copper, cadmium, palladium, gold and nickel.
  • Particularly suitable are silver-copper alloys, having up to 28wt% copper. Table 1 below shows the electrical conductivity (on the IACS scale) and annealed hardness (on the Rockwell 15T scale) of three silver-copper alloys:
  • test samples were prepared using two ink compositions in order to compare the scratch resistance behaviour:
  • Composition 1 SP1773, available from Ferro Corporation, 1000 Lakeside Avenue, Cleveland, Ohio 44114-1147, USA
  • Composition 2 SP1773 containing sterling silver in place of elemental silver, composition: 92.5% wt% silver and 7.5% wt% copper.
  • FIG. 3 is a schematic diagram showing the printed glass samples used for testing purposes.
  • Two broad lines 1, 2, both 89mm in length and 12mm in width were printed along opposite edges of the upper surface of the glass 3, with eight evenly spaced lines 4, 60mm long and ending in a 4mm diameter circle 5 were printed between the broad lines 1, 2.
  • the samples were fired at 650°C.
  • Table 2 The physical properties of the printed lines are summarised in Table 2 below:
  • Table 2 physical properties of printed lines for initial testing.
  • Table 3 shows the results of both of these tests for each ink composition given above (all figures other than percentages are in Ohms, percentages are given to the nearest whole number):
  • Table 3 Initial resistance and resistance after 2ON, 30N Erichsen Pen or razor blade tests in ⁇ .
  • Table 4 Initial resistance and resistances after razor blade tests for ink compositions 1 and 2. From the above results it is seen that including a silver alloy in the ink composition, rather than elemental silver, reduces the change in resistance in the printed line if the line is scratched. Consequently, ink compositions containing such alloys exhibit a higher resistance to scratching than other ink compositions containing elemental silver.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Encre électro-conductrice pour impression sur des vitres d'automobile, qui présente une résistance accrue au rayage et autres dégâts après cuisson. L'encre contient un alliage d'argent et d'au moins un autre élément métallique en lieu et place d'argent élémentaire. La conductivité électrique de l'alliage est suffisante pour que l'encre convienne pour l'impression de circuits chauffants.
PCT/GB2007/050705 2006-11-22 2007-11-21 Vitres imprimées WO2008062229A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0623278.9 2006-11-22
GB0623278A GB0623278D0 (en) 2006-11-22 2006-11-22 Printed glazings

Publications (2)

Publication Number Publication Date
WO2008062229A2 true WO2008062229A2 (fr) 2008-05-29
WO2008062229A3 WO2008062229A3 (fr) 2008-07-10

Family

ID=37636312

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2007/050705 WO2008062229A2 (fr) 2006-11-22 2007-11-21 Vitres imprimées

Country Status (2)

Country Link
GB (1) GB0623278D0 (fr)
WO (1) WO2008062229A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11445577B2 (en) 2016-06-17 2022-09-13 Swansea University Glass laminate structure
WO2023107355A1 (fr) * 2021-12-09 2023-06-15 Corning Incorporated Articles, encre conductrice et procédés de fabrication d'articles

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2200087A (en) * 1938-09-14 1940-05-07 Westinghouse Electric & Mfg Co Electrical contact member
US4973446A (en) * 1990-06-07 1990-11-27 United Precious Metal Refining Co., Inc. Silver alloy compositions
US5782945A (en) * 1995-09-05 1998-07-21 Cookson Matthey Ceramics Plc Method for forming silver tracks on glass
US20040124401A1 (en) * 2001-10-23 2004-07-01 Murata Manufacturing Co., Ltd. Conductive paste
EP1218891B1 (fr) * 1999-10-08 2004-09-15 E.I. Du Pont De Nemours And Company Composition conductrice

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2200087A (en) * 1938-09-14 1940-05-07 Westinghouse Electric & Mfg Co Electrical contact member
US4973446A (en) * 1990-06-07 1990-11-27 United Precious Metal Refining Co., Inc. Silver alloy compositions
US5782945A (en) * 1995-09-05 1998-07-21 Cookson Matthey Ceramics Plc Method for forming silver tracks on glass
EP1218891B1 (fr) * 1999-10-08 2004-09-15 E.I. Du Pont De Nemours And Company Composition conductrice
US20040124401A1 (en) * 2001-10-23 2004-07-01 Murata Manufacturing Co., Ltd. Conductive paste

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11445577B2 (en) 2016-06-17 2022-09-13 Swansea University Glass laminate structure
WO2023107355A1 (fr) * 2021-12-09 2023-06-15 Corning Incorporated Articles, encre conductrice et procédés de fabrication d'articles

Also Published As

Publication number Publication date
GB0623278D0 (en) 2007-01-03
WO2008062229A3 (fr) 2008-07-10

Similar Documents

Publication Publication Date Title
US6886403B2 (en) Sensor with amorphous electrode
EP2117022A1 (fr) Element de contact electrique, son procede de fabrication et contact electrique
JP2013189703A (ja) 電子部品用金属材料及びその製造方法
US7015406B2 (en) Electric contact
TW495769B (en) Electrically conductive metal band and plug connection
WO2014054190A1 (fr) Matériau métallique pour composants électroniques et son procédé de production
JP2002202179A (ja) 摺動式検出器
CN100460835C (zh) 液面检测装置
JP6172811B2 (ja) Ａｇ−Ｓｎ合金めっき液及び電子部品の製造方法
WO2014054189A1 (fr) Matériau métallique pour composants électroniques et son procédé de production
JP4771316B2 (ja) 電気プラグ接点とその製造のための半製品
US9851237B2 (en) Contact material suitable for slider for fuel sender, and slider for fuel sender
US20160168741A1 (en) Contact element with gold coating
WO2008062229A2 (fr) Vitres imprimées
JP5306870B2 (ja) 嵌合型端子用錫めっき付き銅合金板材
CN101208762A (zh) Ag-氧化物系电触点材料以及使用该材料的继电器、交流通用继电器、汽车用继电器
JPH11238413A (ja) 導電性の金属帯板および金属帯板から作製されたコネクタ
Long et al. Contact resistance behavior of the 60 Pd-40 Ag alloy in tarnishing environments
JP5230284B2 (ja) 液面レベル検出装置
JP7023890B2 (ja) 高伝導卑金属電極と合金ローオームチップ抵抗の作製方法
GB2449174A (en) Printed automotive glazing
JP2000030558A (ja) 電気接触子用材料とその製造方法
KR102566570B1 (ko) 표면 피복층 부착 구리 또는 구리 합금 판조
US4334929A (en) Use of nickel-cobalt sintered materials for electric relay contacts
KR102641071B1 (ko) 전도성 페이스트 조성물 및 이의 용도

Legal Events

Date Code Title Description
NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07824917

Country of ref document: EP

Kind code of ref document: A2