Method for effectively contacting manganese-activated zinc silicate phosphor with antimony oxide during phosphor coating, and resulting lamp

Claim 2

A fluorescent lamp having a predetermined correlated color temperature and combined high efficacy and good color rendition, said lamp comprising a sealed elongated light-transmitting envelope having electrodes operatively positioned therein proximate the ends thereof and enclosing a discharge-sustaining filling comprising mercury and a small charge of inert ionizable starting gas which when energized generates a discharge comprising ultraviolet radiations and a limited proportion of visible radiations, phosphor means comprising a predetermined amount of a first phosphor layer carried on the inner surface of said envelope and a predetermined amount of a second phosphor layer coated on and carried on said first phosphor layer so that said second phosphor layer is positioned nearer to said discharge than said first phosphor layer; said first phosphor layer principally comprising finely divided apatite-structured calcium halophosphate activated by predetermined proportions of antimony and manganese, said first phosphor layer when excited by said discharge, emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp, said first phosphor layer having been applied in predetermined amount by flowing over the envelope interior surface a phosphor coating paint comprising a liquid vehicle and organic binder having said first phosphor suspended therein as a slurry, said coating paint also including a small predetermined amount of finely divided antimony oxide, and said applied coating paint having been lehred at a temperature sufficient to volatilize the organic binder therefrom but insufficient to volatilize more than a minor proportion of said antimony oxide; and said second phosphor layer substantially comprising a mixture of predetermined amounts and relative proportions of finely divided narrow-band blue-emitting phosphor activated by divalent europium having an emission substantially confined to the wavelength range of from 430 nm to 485 nm, finely divided green-emitting phosphor comprising manganese-activated zinc silicate, and finely divided red-orange-emitting trivalent-europium-activated yttrium oxide, the predetermined amounts and relative proportions of said mixed phosphors comprising said second phosphor layer when excited by said discharge emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp, said second phosphor layer having been applied in predetermined amount by flowing over said lehred first phosphor layer a second phosphor coating paint comprising a liquid vehicle and organic binder having said phosphors of said second layer mixed and suspended therein as a slurry, and said second layer applied coating paint having been lehred at a temperature sufficient to drive organic binder therefrom and also sufficient to volatilize an appreciable portion of residual antimony oxide in said first phosphor layer to cause said volatilized antimony oxide to contact said manganese-activated zinc silicate.

Claim 3

The lamp as specified in claim 1, wherein said antimony oxide is in the form of antimony trioxide, and said antimony trioxide is added to said first coating paint in amount sufficient to deposit with said first layer phosphor an amount of antimony trioxide which is equal to about 0.1% to about 0.5% by weight of the predetermined amount of the total phosphor which is to be included in said first and second phosphor layers.

Claim 4

The lamp as specified in claim 2, wherein said antimony trioxide is added to said first layer coating paint in predetermined amount sufficient to deposit with said first phosphor layer an amount of antimony trioxide which is equal to about one-quarter percent by weight of the total phosphor which is to be included in said first and second phosphor layers.

Claim 5

The lamp as specified in claim 2, wherein said first phosphor layer has a coating weight of from about 1 mg/cm 2 to about 3.5 mg/cm 2 , said second phosphor layer has a coating weight of from about 1 mg/cm 2 to about 3 mg/cm 2 , and the combined coating weights of said first phosphor layer and said second phosphor layer fall within the range of from about 3.1 mg/cm 2 to about 5.5 mg/cm 2 .

Claim 6

The lamp as specified in claim 2, wherein said lamp has a correlated color temperature of about 3000° K., said first phosphor layer principally comprises a mixture of predetermined amounts and relative proportions of apatite-structured calcium fluorophosphate activated by antimony and manganese and yttrium oxide activated by trivalent europium, said antimony activator constituting from 0.4 to 1 weight percent and said manganese activator constituting from 1 to 1.5 weight percent of said apatite-structured calcium fluorophosphate phosphor, said europium activator constituting from 2 to 13 weight percent of said yttrium oxide first layer phosphor, said apatite-structured calcium fluorophosphate phosphor having a broad band emission of visible radiations, said yttrium oxide first layer phosphor having a narrow emission in the red-orange region of the visible spectrum, and the predetermined amounts and relative proportions of said apatite-structured calcium fluorophosphate phosphor and said yttrium oxide first layer phosphor being such that the composite emission of said first phosphor layer has a correlated color temperature of approximately 3000° K.

Claim 7

The lamp as specified in claim 5, wherein said apatite-structured calcium fluorophosphate phosphor and said yttrium oxide first layer phosphor are uniformly mixed as said first phosphor layer, with the relative weight proportions of said apatite-structured calcium fluorophosphate phosphor and said yttrium oxide first layer phosphor being about 79:21, and said second phosphor layer utilizes strontium chlorophosphate activated by divalent europium as the narrow-band blue-emitting phosphor and the weight ratio of red-orange to green to blue-emitting phosphors of said second phosphor layer respectively is about 72:24:4.

Claim 8

The fluorescent lamp as specified in claim 2, wherein said lamp has a correlated color temperature of about 4100° K., said first phosphor layer is a mixture of finely divided bluish-white apatite-structured calcium fluorochlorophosphate activated by antimony and manganese, apatite-structured calcium fluorophosphate activated by antimony and manganese, and yttrium oxide activated by from 2 to 13 wt.% trivalent europium, with the weight ratio of said calcium fluorochlorophosphate to said calcium fluorophosphate to said yttrium oxide phosphor in said first phosphor layer being about 56:40:4, and the relative weight ratio of said red-orange-emitting phosphor to said green-emitting phosphor to said blue-emitting phosphor in said second phosphor layer is about 57:29:14.

Claim 9

The fluorescent lamp as specified in claim 2, wherein said lamp has a correlated color temperature of about 5000° K., said first phosphor layer is a mixture of finely divided bluish-white apatite-structured calcium fluorochlorophosphate activated by antimony and manganese and apatite-structured calcium fluorophosphate activated by antimony and manganese, the weight ratio of said calcium fluorochlorophosphate to said calcium fluorophosphate phosphor in said first phosphor layer is about 77:23, and the relative weight ratio of said red-orange-emitting phosphor to said green-emitting phosphor to said blue-emitting phosphor in said second phosphor layer is about 50:35:15.

Claim 10

The lamp as specified in claim 2, wherein said first applied phosphor coating paint is lehred at a temperature of less than 600° C., and said second applied phosphor coating paint is lehred at a temperature greater than 600° C.

Claim 11

The lamp as specified in claim 9, wherein said first applied phosphor coating paint is lehred at a temperature of about 550° C., and said second applied phosphor coating paint is lehred at a temperature of about 650° C.

Claim 12

A fluorescent lamp having a predetermined correlated color temperature and combined high efficacy and good color rendition, said lamp comprising a sealed elongated light-transmitting envelope having electrodes operatively positioned therein proximate the ends thereof and enclosing a discharge-sustaining filling comprising mercury and a small charge of inert ionizable starting gas which when energized generates a discharge comprising ultraviolet radiations and a limited proportion of visible radiations, phosphor means comprising a predetermined amount of a first phosphor layer carried on the inner surface of said envelope, a predetermined amount of a second phosphor layer coated on and carried on said first phosphor layer, and a predetermined amount of a third phosphor layer coated on and carried on said second phosphor layer so that said third phosphor layer is positioned nearest to said discharge; said first phosphor layer principally comprising finely divided apatite-structured calcium halophosphate activated by predetermined proportions of antimony and manganese, said first phosphor layer when excited by said discharge emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp, said first phosphor layer having been applied in predetermined amount by flowing over the envelope interior surface a phosphor coating paint comprising a liquid vehicle and organic binder having said first phosphor suspended therein as a slurry, said coating paint also including a small predetermined amount of finely divided antimony oxide, and said applied coating paint having been lehred at a temperature sufficient to volatilize the organic binder therefrom but insufficient to volatilize more than a minor proportion of said antimony oxide; and said second phosphor layer substantially comprising a mixture of predetermined amounts and relative proportions of finely divided narrow-band blue-emitting phosphor activated by divalent europium and having an emission substantially confined to the wavelength range of from 430 nm to 485 nm, finely divided green-emitting manganese-activated zinc silicate, and finely divided red-orange-emitting trivalent-europium-activated yttrium oxide, the predetermined amounts and relative proportions of said mixed phosphors comprising said second phosphor layer when excited by said discharge emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp, said second phosphor layer having been applied in predetermined amount by flowing over said lehred first phosphor layer a second phosphor coating paint comprising a liquid vehicle and organic binder having said phosphors of said second layer mixed and suspended therein as a slurry, and said second layer applied coating paint having been lehred at a temperature sufficient to drive organic binder therefrom and also sufficient to volatilize an appreciable portion of residual antimony oxide in said first phosphor layer to cause said volatilized antimony oxide to contact said manganese-activated zinc silicate; and said third phosphor layer substantially comprising a mixture of predetermined amounts and relative proportions of finely divided narrow-band blue-emitting phosphor activated by divalent europium and having an emission substantially confined to the wavelength range of from 430 nm to 485 nm, finely divided green-emitting magnesium aluminate activated by cerium and terbium, and finely divided red-orange-emitting trivalent-europium-activated yttrium oxide, and the predetermined amounts and relative proportions of said mixed phosphors comprising said third layer when excited by said discharge emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp.

Claim 13

A fluorescent lamp having a predetermined correlated color temperature and combined high efficacy and good color rendition, said lamp comprising a sealed elongated light-transmitting envelope having electrodes operatively positioned therein proximate the ends thereof and enclosing a discharge-sustaining filling comprising mercury and a small charge of inert ionizable starting gas which when energized generates a discharge comprising ultraviolet radiations and a limited proportion of visible radiations, phosphor means comprising a predetermined amount of a first phosphor layer carried on the inner surface of said envelope, a predetermined amount of a second phosphor layer coated on and carried on said first phosphor layer, and a predetermined amount of a third phosphor layer coated on and carried on said second phosphor layer so that said third phosphor layer is positioned nearest to said discharge; said first phosphor layer principally comprising finely divided apatite-structured calcium halophosphate activated by predetermined proportions of antimony and manganese, said first phosphor layer when excited by said discharge emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp, said first phosphor layer having been applied in predetermined amount by flowing over the envelope interior surface a phosphor coating paint comprising a liquid vehicle and organic binder having said first phosphor suspended therein as a slurry, said coating paint also including a small predetermined amount of finely divided antimony oxide, and said applied coating paint having been lehred at a temperature sufficient to volatilize the organic binder therefrom but insufficient to volatilize more than a minor proportion of said antimony oxide; and said second phosphor layer substantially comprising a mixture of predetermined amounts and relative proportions of finely divided narrow-band blue-emitting phosphor activated by divalent europium and having an emission substantially confined to the wavelength range of from 430 nm to 485 nm, finely divided green-emitting manganese-activated zinc silicate, and finely divided red-orange-emitting trivalent-europium-activated yttrium oxide, the predetermined amounts and relative proportions of said mixed phosphors comprising said second phosphor layer when excited by said discharge emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp, said second phosphor layer having been applied in predetermined amount by flowing over said lehred first phosphor layer a second phosphor coating paint comprising a liquid vehicle and organic binder having said phosphors of said second layer mixed and suspended therein as a slurry, and said second layer applied coating paint having been lehred at a temperature sufficient to drive organic binder therefrom and also sufficient to volatilize an appreciable portion of residual antimony oxide in said first phosphor layer to cause said volatilized antimony oxide to contact said manganese-activated zinc silicate; and said third phosphor layer substantially comprising a mixture of predetermined amounts and relative proportions of finely divided narrow-band blue-emitting phosphor activated by divalent europium and having an emission substantially confined to the wavelength range of from 430 nm to 485 nm, finely divided green-emitting magnesium aluminate activated by cerium and terbium, and finely divided red-orange-emitting trivalent-europium-activated yttrium oxide, and the predetermined amounts and relative proportions of said mixed phosphors comprising said third layer when excited by said discharge emitting visible radiations of a color which approximates said predetermined correlated color temperature of said lamp.

Claim 14

The lamp as specified in claim 11, wherein said antimony oxide is in the form of antimony trioxide, and said antimony trioxide is added to said first coating layer in amount sufficient to deposit with said first layer phosphor an amount of antimony trioxide which is equal to about 0.1% to about 0.5% by weight of the predetermined amount of the total phosphor which is to be included in said first and second phosphor layers.

Claim 15

The lamp as specified in claim 12, wherein said antimony trioxide is added to said first layer coating paint in predetermined amount sufficient to deposit with said first phosphor layer an amount of antimony trioxide which is equal to about one-quarter percent by weight of the predetermined amount of the total phosphor which is to be included in said first and second phosphor layers.

Claim 16

The lamp as specified in claim 12, wherein said first phosphor layer has a coating weight of from about 1 mg/cm 2 to about 3.5 mg/cm 2 , said second phosphor layer has a coating weight of from about 1 mg/cm 2 to about 3 mg/cm 2 , said third phosphor layer has a coating weight of from about 0.15 mg/cm 2 to about 0.7 mg/cm 2 , and the combined coating weights of said first and second and third phosphor layers fall within the range of from about 3.1 mg/cm 2 to about 6.2 mg/cm 2 .

Claim 17

The lamp as specified in claim 12, wherein said lamp has a correlated color temperature of about 3000° K., said first phosphor layer principally comprises a mixture of predetermined amounts and relative proportions of apatite-structured calcium fluorophosphate activated by antimony and manganese and yttrium oxide activated by trivalent europium, said antimony activator constituting from 0.4 to 1 weight percent and said manganese activator constituting from 1 to 1.5 weight percent of said apatite-structured calcium fluorophosphate phosphor, said europium activator constituting from 2 to 13 weight percent of said yttrium oxide first layer phosphor, said apatite-structured calcium fluorophosphate phosphor having a broad band emission of visible radiations, said yttrium oxide first layer phosphor having a narrow emission in the red-orange region of the visible spectrum, and the predetermined amounts and relative proportions of said apatite-structured calcium fluorophosphate phosphor and said yttrium oxide first layer phosphor being such that the composite emission of said first phosphor layer has a correlated color temperature of approximately 3000° K.

Claim 18

The lamp as specified in claim 15, wherein said apatite-structured calcium fluorophosphate phosphor and said yttrium oxide first layer phosphor are uniformly mixed as said first phosphor layer, with the relative weight proportions of said apatite-structured calcium fluorophosphate phosphor and said yttrium oxide first layer phosphor being about 79:21, said second phosphor layer utilizes strontium chlorophosphate activated by divalent europium as the narrow-band blue-emitting phosphor and the weight ratio of red-orange to green to blue-emitting phosphors of said second phosphor layer respectively is about 72:24:4, and said third phosphor layer utilizes strontium chlorophosphate activated by divalent europium as the narrow-band blue-emitting phosphor and the weight ratio of red-orange to green to blue-emitting phosphors of said third phosphor layer respectively is about 71:27:2.

Claim 19

The fluorescent lamp as specified in claim 12, wherein said lamp has a correlated color temperature of about 4100° K., said first phosphor layer is a mixture of finely divided bluish-white apatite-structured calcium fluorochlorophosphate activated by antimony and manganese, apatite-structured calcium fluorophosphate activated by antimony and manganese, and yttrium oxide activated by from 2 to 13 wt.% trivalent europium, with the weight ratio of said calcium fluorochlorophosphate to said calcium fluorophosphate to said yttrium oxide phosphor in said first phosphor layer being about 56:40:4, the relative weight ratio of said red-orange-emitting phosphor to said green-emitting phosphor to said blue-emitting phosphor in said second phosphor layer is about 57:29:14, and the relative weight ratio of said red-orange-emitting phosphor to said green-emitting phosphor to said blue-emitting phosphor in said third phosphor layer is about 57:33:10.

Claim 20

The fluorescent lamp as specified in claim 12, wherein said lamp has a correlated color temperature of about 5000° K, said first phosphor layer is a mixture of finely divided bluish-white apatite-structured calcium fluorochlorophosphate activated by antimony and manganese and apatite-structured calcium fluorophosphate activated by antimony and manganese, the weight ratio of said calcium fluorochlorophosphate to said calcium fluorophosphate phosphor in said first phosphor layer is about 77:23, the relative weight ratio of said red-orange-emitting phosphor to said green-emitting phosphor to said blue-emitting phosphor in said second phosphor layer is about 50:35:15, and the relative weight ratio of said red-orange-emitting phosphor to said green-emitting phosphor to said blue-emitting phosphor in said third phosphor layer is about 50:39:11.

Claim 21

The lamp as specified in claim 11, wherein said first applied phosphor coating paint is lehred at a temperature of less than 600° C., and said second applied phosphor coating paint is lehred at a temperature greater than 600° C.

Claim 22

The lamp as specified in claim 19, wherein said first applied phosphor coating paint is lehred at a temperature of about 550° C., and said second applied phosphor coating paint is lehred at a temperature of about 650° C.

Claim 25

The method as specified in claim 21, wherein said first phosphor means coating paint is lehred at a temperature less than 600° C., and said second phosphor means coating paint is lehred at a temperature greater than 600° C.

Claim 26

The method as specified in claim 22, wherein said first phosphor means coating paint is lehred at a temperature of about 550° C., and said second phosphor means coating paint is lehred at a temperature of about 650° C.

Claim 27

The method as specified in claim 21, wherein said antimony oxide is in the form of antimony trioxide, said antimony trioxide content in said first phosphor means coating paint is predetermined to deposit with said first phosphor means layer an amount of antimony trioxide which is equal to about 0.1 to about 0.5% by weight of the total phosphor which is to be included in said first and second phosphor means layers.

Claim 28

The method as specified in claim 24, wherein said antimony trioxide content is added to said first phosphor means coating paint is predetermined amount to deposit with said first phosphor means layer an amount of antimony trioxide which is equal to about one-quarter percent by weight of the total phosphor which is to be included in said first and second phosphor means layers.