EP1077471A1 - Coloured light emitting device with a lamp coated with a pigmented layer - Google Patents
Coloured light emitting device with a lamp coated with a pigmented layer Download PDFInfo
- Publication number
- EP1077471A1 EP1077471A1 EP00202907A EP00202907A EP1077471A1 EP 1077471 A1 EP1077471 A1 EP 1077471A1 EP 00202907 A EP00202907 A EP 00202907A EP 00202907 A EP00202907 A EP 00202907A EP 1077471 A1 EP1077471 A1 EP 1077471A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pigment
- lamp
- layer
- pigments
- red
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V3/00—Globes; Bowls; Cover glasses
- F21V3/04—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
- F21V3/10—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/38—Devices for influencing the colour or wavelength of the light
- H01J61/40—Devices for influencing the colour or wavelength of the light by light filters; by coloured coatings in or on the envelope
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01K—ELECTRIC INCANDESCENT LAMPS
- H01K1/00—Details
- H01K1/28—Envelopes; Vessels
- H01K1/32—Envelopes; Vessels provided with coatings on the walls; Vessels or coatings thereon characterised by the material thereof
Definitions
- the invention relates to a colored light, in particular a colored signal light for Automobile equipped with a lamp and a lamp cover in which the lamp a piston with a coating with a layer containing an organic pigment, Has.
- Colored lights are used in various places in automobiles, for example for brake lights, indicators and fog lamps.
- conventional colored lights is the bulb of the lamp made of clear glass and the lamp under a colored, mostly red or yellow lamp cover arranged.
- a more recent development is going for colored ones Shine colored lamps under a colorless or neutral colored cover to use. This allows different colored signal lamps as a lamp ensemble a uniform fluorescent cover.
- Lights with colored lamps under a colorless or neutral colored cover have the advantage that they have a flexible, visually appealing design for integrated Allow front and rear lights. They are also cheaper than lights with multi-colored ones Housing or multi-colored covers. These lights are also even safer to drive, because the difference between on and off lighting in daylight on luminaires with colored lamps and colorless or neutral colored Luminaire cover is more recognizable.
- the object is achieved by a colored lamp equipped with a lamp and a lamp cover in which the lamp has a bulb coating with a first pigment-containing layer, which is a pigment selected from the group of Perylene pigments, perinone pigments, isoindoline pigments and the thioindigo pigments contains, has.
- a first pigment-containing layer which is a pigment selected from the group of Perylene pigments, perinone pigments, isoindoline pigments and the thioindigo pigments contains, has.
- a lamp with such a lamp has a long lifespan. It is caused by UV light, Moisture and road salt are not attacked and are resistant to temperatures between 250 and 350 ° C. Colored lights with bulb coatings with these pigments alone or together with other pigments for color correction Color standards for automotive lights, such as those for Europe by the E.C.E. and for USA by the S.A.E. are defined.
- the first pigment-containing layer additionally contains an iron oxide pigment.
- An iron oxide pigment in the layer corrects the color value the organic pigment, for example in the bluish area, e.g. from yellow to amber or from orange-red to red. In the event that the lamp in the lamp exposed to temperatures above 250 ° C for a long time, this lamp still has emergency running properties.
- the first pigment-containing layer is an iron oxide pigment and contains a silicon-oxygen compound. Such a layer adheres very well the glass of the lamp bulb.
- a second pigment-containing layer is arranged on the first pigment-containing layer, which contains an iron oxide pigment. If the lamp is too strong and too frequent This embodiment is also exposed to changes in temperature and the top layer flakes off the emergency running properties of the lamp.
- the lamp has a transparent cover layer, which is a silicon-oxygen compound contains, has to the scratch resistance of the pigmented coating to increase
- the invention also relates to a lamp with a bulb with a coating a layer containing a pigment selected from the group of perylene pigments, perinone pigments, Contains isoindoline pigments and the thioindigo pigments.
- a colored lamp according to the invention is with a lamp and a lamp cover equipped in which the lamp has a bulb with a coating of a Layer containing a pigment selected from the group of perylene pigments, perinone pigments, Has isoindoline pigments and which contains thioindigo pigments.
- the colored lamp can still be used with other components, e.g. Attachment means the lamp in the lamp, means of protection against dust, damage and Moisture and the components necessary for energy supply, e.g. Versions, Lines, ballasts, starters, ignition devices and connecting terminals equipped his.
- a desired light distribution and glare limitation can be achieved by optical reflectors, clear or cloudy cover trays, grid made of metal or plastic, Scatter glasses and prism reflectors can be achieved.
- the invention comprises the lamp two or more colored lamps under a common Luminaire cover that is colorless or neutral colored.
- Perylene, perinone, isoindoline or thioindigo pigments are used for the first pigment-containing layer on the flask.
- the pigments used are polycyclic Pigments that have long been known for dyeing textile fibers.
- the pigments are subsequently based on their chemical constitution or the Color Index (C.I.), by the Society of Dyers and Colorists together with the American Association of Textile Chemists and Colorists is published.
- Perinones [CAS4424-06-0 (trans-Perinon), CAS 4216-02-8 (cis-Perinon)) are derivatives the 1,4,5,8-naphthaline tetracarboxylic acid. Cis and trans perinone are obtained as a cis / trans isomer mixture by heating 1,4,5,8-naphthalene tetracarboxylic acid in the form of the Monoanhydrides, e.g. in glacial acetic acid at 120 ° C, with o-phenylenediamine. If you look at the isomers separates, the trans-perinone is obtained with a pure orange-yellow color and the cis-perinon with red hue.
- the perylene pigments are derivatives of 3,4,9,10-perylenetetracarboxylic acid.
- the perylene pigments are made from 3,4,9,10-perylenetetracarboxylic anhydride by reaction with primary aliphatic amines or substituted anilines, optionally in the presence of a catalyst.
- PY 139 (CAS 36888-99-0) with the summation formula C 16 H 9 N 5 O 6 has an orange color and is very thermally stable.
- PY 185 (CAS 76199-85-4) has a yellow color and is also very good thermal resistance.
- the thioindigo pigments are especially those with chlorine and / or with methyl groups substituted derivatives suitable for the invention.
- Tetrachlorothioindigo PR 88 (CAS 14295-43-3) has a red-violet color, which is used to adjust other red pigments suitable is.
- the perylene, perinone, isoindoline or thioindigo pigments are preferred in finely divided, colloidal shape with a grain size of 2nm ⁇ d ⁇ 200 nm used to make transparent To get layers.
- the first pigment-containing Layer in addition to the perylene, perinone, isoindoline and thioindigo pigments contain an iron oxide pigment.
- Iron oxide pigments have a wide range of colors from yellow to orange to red, brown and black.
- the natural and synthetic iron oxide pigments used consist of well-defined compounds with a known crystal structure.
- ⁇ -Fe 2 O 3 hematite
- ⁇ -Fe 2 O maghemite
- ⁇ -FeOOH triasporic structure
- ⁇ -FeOOH boethite
- ⁇ -FeOOH boehmite structure changes its color from yellow to orange with increasing particle size.
- These iron oxides are iron (III) oxides.
- the red-violet to black Fe 3 O 4 (magnetite) with spinel structure is only suitable in exceptional cases.
- the transparent iron oxide pigments are preferably used in finely divided, colloidal form with a grain size of 2 ⁇ d ⁇ 15 nm in order to obtain transparent layers.
- Transparent yellow iron oxide CI PY 42: 77492 is ⁇ -FeOOH (goethite) with a diasporic structure. When heated, it changes into the preferred transparent brown-red ⁇ -Fe 2 O 3 (hematite) CI PR 101: 77491. Orange nuances develop with a shorter temperature treatment. They can also be obtained by mixing yellow and red pigments.
- the iron oxide pigments with a grain size of 2 nm ⁇ d ⁇ 200 nm are preferred.
- the first pigment-containing layer is a silicon-oxygen compound contains, e.g. amorphous or crystalline silicon dioxide, quartz, a silica gel or a Silica or a silicate, i.e. Salts or esters of silicas, especially tetraethyl orthosilicate (TEOS), a silicone or a siloxane.
- a silicon-oxygen compound contains, e.g. amorphous or crystalline silicon dioxide, quartz, a silica gel or a Silica or a silicate, i.e. Salts or esters of silicas, especially tetraethyl orthosilicate (TEOS), a silicone or a siloxane.
- TEOS tetraethyl orthosilicate
- the pigments and the silicon-oxygen compounds can be in a single color layer be applied.
- the colored piston coating also have a variable multilayer structure. It always includes a first colored layer, which is a pigment selected from the group of perylene pigments, perinone pigments, isoindoline pigments and which contains thioindigo pigments.
- a layer containing iron oxide can first be placed on the Lamp bulb be applied.
- the iron oxide-containing layer can either be the iron oxide contained as a finely divided pigment or as a precipitate from a sol-gel process.
- the iron oxide is applied as a pigment, it comes as a manufacturing process both a dry, e.g. electrostatic deposition, as well as wet application, e.g. as an aqueous suspension - by dipping or spraying.
- the multilayer structure for the coating of the lamp bulb is such that an iron oxide-containing layer is first applied to the inside or outside of the lamp bulb.
- the iron oxide can be applied either as a fine pigment or in a sol-gel process.
- a temperature-resistant, transparent protective layer which contains a silicon-oxygen compound, for example an SiO 2 or a quartz glass layer, is applied over the layer containing iron oxide.
- the pigment-containing layer is in turn applied to this.
- the multi-layer structure for the Coating the lamp bulb so that between the bulb and the first pigmented Layer a transparent layer that contains a silicon-oxygen compound contains is arranged.
- a temperature-resistant, transparent cover layer can be arranged over the pigment-containing layers.
- the cover layer contains a silicon-oxygen compound, for example amorphous or crystalline silicon dioxide, quartz, a silica gel or a silica or a silicate, ie salts or esters of silica, in particular tetraethylorthosilcat (TEOS).
- TEOS tetraethylorthosilcat
- this additional top layer can also be a temperature-resistant, transparent, colorless or dye-containing lacquer or a transparent ceramic layer, for example made of Al 2 O 3 or enamel. If the coatings are applied to the inside of the flask, the top layer prevents chemical changes in the pigments. If the coating is applied on the outside, the cover layer forms a scratch-resistant surface, which facilitates further processing of the bulb in lamp production.
- a cover layer with a suitable refractive index is preferably used, which has the Scattering of the pigment-containing layers is reduced.
- conventional Processes for coating complex shaped substrates can be used. These include the wet coating processes such as Spraying, dipping and brushing on. Dry coating processes, e.g. electrostatically assisted dusting are suitable for applying the pigment-containing coating to the lamp bulb.
- the pigments For wet coating processes, the pigments must be dispersed in water, an organic solvent or a binder preparation, optionally together with a dispersant, a surfactant and an antifoam.
- Suitable for binder preparations for a lamp according to the invention are organic or inorganic binders which can withstand an operating temperature of 250 ° C to 350 ° C without decomposition, embrittlement or discoloration.
- a layer thickness of 0.5 to 2.0 ⁇ m can be sufficient.
- Binder-containing layers generally have a layer thickness of 1 to 50 ⁇ m.
- the pigment coated lamps were subjected to an accelerated thermal stress test in which the lamps were kept at 300 ° C permanently. The color location changed only minimally within a period of 150 hours within the range specified by the ECE and the SAE for the color specification. Even with regular lamp operation over a period of 500 h, the color point remained within the ECE color specification.
- a very suitable iron oxide pigment is hematite.
- a coating is obtained in particular together with a mixture. which has a very good color point saturation in the red area and good light transmission.
- a surfactant for example a polyether-modified polysiloxane, can also be added to the dispersion.
- the cleaned and heated lamp bulbs are immersed in this dispersion and then baked at 250 ° C.
- 180 g of tetraethyl orthosilicate are mixed with 2077 g of ethanol, 146 g in hydrochloric acid and 27 ml of an anionic surfactant.
- the pre-coated lamp bulbs are dipped into this mixture and briefly heated at 300 ° C in order to convert tetraethyl orthosilicate into a silicon dioxide layer.
- a very suitable iron oxide pigment is hematite.
- an organic red pigment which is applied as the first layer in a temperature-resistant silicone resin, a coating is obtained which has very good color point saturation in the red area and good light transmission.
- a dispersion of 15% by weight of transparent iron oxide pigment PR 101, 3% by weight of a 25% solution of sodium in a polycarboxylic acid as a dispersing agent, 0.075% by weight of potyethylene propylene oxide as an anti-foaming agent is first wet with water in a stirred mill milled until the agglomerated pigment is dispersed. The dispersion is filtered to remove contaminants and hard agglomerates.
- a surfactant for example a polyether-modified polysiloxane
- the dispersion is diluted to a pigment concentration of 8.7% by weight.
- the cleaned and heated lamp bulbs are immersed in this dispersion, dried and then baked at 450 ° C.
- a transparent hematite layer approximately 0.5 ⁇ m thick is obtained.
- Another pigment dispersion is obtained by grinding the organic red pigment Dimethylperylimide PR 179 in a ball mill. 6% by weight of pigment in one Solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a Dispersing agent ground until the pigment agglomerates are dispersed.
- a dispersant a pigment-affine block copolymer in a concentration of 18% by weight based on the amount of pigment used.
- the dispersion is filtered and with a Siliconhar solution mixed.
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the silicone resin solution has a polymer content of 50% by weight in a solvent mixture like this has already been used to grind the pigment.
- the ready-to-use mixture contains 32% by weight silicone and 12% by weight dimethylperylimide pigment PR 179.
- the already Lamp droppings covered with a hematite layer are sprayed with the pigment containing dimethylperylimide Silicone resin solution covered.
- the solvent is evaporated and crosslinked the silicone resin at 250 ° C.
- a red, 8 to 10 ⁇ m thick silicone resin layer is obtained as the outer cover layer of the lamp.
- the two-layer hematite coating and dimethylperylimide PR 179 results in a transparent red coating on the lamp, which complies with the ECE and SAE standards for red signal lamps.
- a very suitable iron oxide pigment is hematite.
- an organic yellow pigment which is applied as the first layer in a temperature-resistant silicone resin, a coating is obtained which has very good color point saturation in the amber area and good light transmission.
- the hematite layer to be applied first to the lamp bulb is obtained by grinding the iron oxide pigment PR101 in water as described in Example 2.
- the ground hematite dispersion is diluted to 5.5% by weight of pigment.
- the lamp bulb is coated by dipping.
- the dried and baked hematite layer at 450 ° C has a thickness of 0.3 ⁇ m.
- the layer is transparent and colored red-brown. The color point does not yet meet the ECE standard for amber-colored signal lamps.
- the isoindoline pigment PY 139 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant.
- the grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment.
- the yellow pigment dispersion and the silicone resin solution described in working example 2 are mixed in a ratio. that the concentration of isoindoline yellow pigment is 1.6% by weight and that of silicone is 35% by weight.
- the lamp bulb which is already covered with a hematite layer, is covered by spraying with the silicone resin solution containing isoindoline pigment.
- the solvent is evaporated and the silicone mixture is crosslinked at 250 ° C.
- An approximately 10-15 ⁇ m thick transparent yellow silicone resin coating is obtained on the hematite-coated lamp, which shifts the color point of the lamp into the ECE standard range for amber-colored signal lamps.
- a very suitable mixture of two organic pigments is the use of an organic red pigment (PR 149, bis-dimethylphenylperylimide) and an organic yellow pigment (PY139, isoindoline yellow pigment) in a silicone resin.
- PR 149 bis-dimethylphenylperylimide
- PY139 isoindoline yellow pigment
- a coating is obtained which has very good color point saturation in the amber region and good light transmission.
- the yellow isoindoline pigment PY 139 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment.
- the yellow pigment dispersion and a 50% by weight silicone resin solution which is a mixture of 80 parts of reactive methylphenyl silicone and 20 parts of reactive polyester-modified methylphenyl silicone, are mixed in a ratio such that the concentration of isoindoline yellow pigment 2.4 % By weight and 35% by weight of silicone.
- the red bis-dimethylphenylperylimide pigment PR149 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment.
- the red pigment dispersion and a 50% by weight silicone resin solution which is a mixture of 80 parts of reactive methyl-phenyl silicone and 20 parts of reactive polyester-modified methyl-phenyl silicone, are mixed in a ratio such that the concentration of red bis-dimethylphenylperylimide Pigment is 0.8% by weight and 35% by weight of silicone.
- the two pigment dispersions are mixed in equal proportions and applied to the lamp bulb by spraying.
- the solvent is evaporated and the silicone resin crosslinked at 250 ° C. A transparent, amber-colored silicone resin layer with a thickness of 10 to 15 ⁇ m is obtained, which corresponds to the ECE standard for signal lamps.
- a coating is obtained which has very good color point saturation in the red color range and good light transmission when the organic red pigment bis-dimethylphenylperylimide pigment PR149 is used in a silicone resin.
- the red bis-dimethylphenylperylimide pigment PR149 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment.
- the red pigment dispersion and a 50% by weight silicone resin solution are mixed in a ratio such that the concentration of red bisdimethylphenylperylimide pigment is 2.9% by weight and that of silicone 33% by weight.
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the lamp bulb is sprayed with the red, pigment-containing silicone resin solution.
- the solvent is evaporated and the silicone resin crosslinked at 250 ° C.
- An approximately 15 ⁇ m thick transparent red silicone resin coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
- a particularly hard and scratch-resistant coating is obtained which has a very good color saturation in the red color range and good light transmission if a layer of the organic red pigment bis-dimethylphenylperylimide PR149 is covered with a silicon dioxide sol-gel layer.
- a dispersion of 10% by weight bis-dimethylphenylperylimide PR14), 10% by weight of a 40% aqueous solution of a pigment-affine block copolymer as a dispersant, 0.075% by weight polyethylene propylene oxide as an antifoam with water in a ball mill is first used milled until the agglomerated pigment is dispersed. The dispersion is filtered to remove contaminants and hard agglomerates.
- a surfactant for example a polyether-modified polysiloxane
- a surfactant can be added to improve the wetting of the lamp bulb.
- the cleaned and heated lamp bulbs are immersed in this dispersion, dried and then baked at 250 ° C.
- a transparent pigment layer approximately 1.5 ⁇ m thick is obtained.
- 180 g of tetraethyl orthosilicate are mixed with 2077 g of ethanol, 146 g in hydrochloric acid and 27 ml of an anionic surfactant.
- the pre-coated lamp bulbs are dipped into this mixture and briefly heated at 300 ° C in order to convert tetraethyl orthosilicate into a silicon dioxide layer.
- a scratch-resistant, transparent red coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
- a coating is obtained which has very good color point saturation in the red area and good light transmission if a mixture of the very suitable iron oxide pigment hematite with the organic red pigment dimethylperylimide PR179 is used.
- a pigment dispersion of the organic red pigment dimethylperylimide PR 179 is obtained by grinding in a ball mill. For this purpose, 6% by weight of pigment is ground in a solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a dispersant until the pigment agglomerates are dispersed.
- a pigment-affine block copolymer in a concentration of 18% by weight, based on the amount of pigment, is used as the dispersant.
- a further pigment dispersion is obtained by grinding iron oxide pigment PR 101.
- the solvent is a mixture of xylene and cyclohexanone (ratio 5: 1).
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the pigment dispersions are filtered to remove contaminants and hard agglomerates and mixed with a silicone resin solution.
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the mixture suitable for spray coating contains 42% by weight of silicone, 2.2% by weight of dimethylperylimide pigment and 2.8% by weight of iron oxide pigment PR 101.
- the lamp bulb is sprayed with the red, pigment-containing silicone resin solution.
- the solvent is evaporated and the silicone resin crosslinked at 250 ° C.
- An approximately 15 to 20 ⁇ m thick transparent red silicone resin coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
- a coating is obtained which has very good color point saturation in the red area and good light transmission if a mixture of the very suitable transparent iron oxide pigment Hematite PR101 with the isoindoline yellow pigment PY139 is used.
- 15% by weight of transparent iron oxide pigment PR 101 and 3.75% by weight of a pigment-affine block copolymer as a dispersant are ground in a 25% by weight solution of a phenyl-methyl-silicone resin in a ball mill.
- the solvent is a mixture of xylene and cyclohexanone (ratio 5: 1).
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- Another pigment dispersion is obtained by grinding a yellow isoindoline pigment, PY 139, in a ball mill. For this purpose, 6% by weight of pigment is ground in a solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a dispersant until the pigment agglomerates have been dispersed. A pigment-affine block copolymer in a concentration of 18% by weight, based on the amount of pigment, is used as the dispersant. The dispersions are filtered and mixed with a silicone resin solution.
- the silicone resin is a reactive phenyl-methyl silicone, which is dissolved in a solvent mixture of xylene and cyclohexanone (ratio 5: 1).
- the mixture suitable for spray coating contains 35% by weight of silicone, 2.8% by weight of iron oxide pigment PR 101 and 1.6% by weight of isoindoline yellow pigment PY 139.
- the lamp bulb is spray-coated with the pigment-containing silicone resin solution.
- the solvent is evaporated and the silicone resin crosslinked at 250 ° C.
- a transparent, amber-colored silicone resin layer approximately 15 ⁇ m thick is obtained, which corresponds to the ECE standard for signal lamps.
- a coating is obtained which has very good color saturation in the amber color range and good Lichuransmission when using the organic isoindoline yellow pigment PY185.
- the yellow isoindoline pigment PY185 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment.
- the yellow pigment dispersion and a 50% by weight silicone resin solution are mixed in a ratio such that the concentration of yellow isoindoline pigment is 2.9% by weight and that of silicone 33% by weight.
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the lamp bulb is sprayed with the yellow, pigment-containing silicone resin solution covered.
- the solvent is evaporated and the silicone resin crosslinked at 250 ° C.
- An approximately 20 ⁇ m thick transparent yellow coating is obtained which has a color point which complies with the ECE and SAE standards for amber-colored signal lamps.
- a coating is obtained which has very good color point saturation in the red color range and good light transmission when using the red pigment dichlorodiketopyrrolo-pyrrole PR254.
- the red pigment dichloro-diketopyrrolo-pyrrole (PR254) is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method specified in Example 5.
- the red pigment dispersion and a 50% by weight silicone resin solution are mixed in a ratio such that the concentration of red dichloro-diketopyrrolo-pyrrole pigment is 2.9% by weight and that of silicone is 33% by weight.
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the lamp bulb is sprayed with the red, pigment-containing silicone resin solution.
- the solvent is evaporated and the silicone resin crosslinked at 250 ° C.
- An approximately 15 to 20 ⁇ m thick transparent red coating is obtained, which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
- a coating is obtained which has very good color point saturation in the red area and good light transmission when a mixture of the very suitable iron oxide pigment Hematite PR101 with the organic red pigment tetrachlorothioindigo PR88 is used.
- a pigment dispersion of the organic red pigment tetrachlorothioindigo PR88 is obtained by grinding in a ball mill. For this purpose, 8.5% by weight of pigment is ground in a solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a dispersant until the pigment agglomerates are dispersed.
- a pigment-affine block copolymer in a concentration of 15% by weight, based on the amount of pigment, is used as the dispersant.
- a further pigment dispersion is obtained by grinding iron oxide pigment PR 101. 15% by weight of transparent iron oxide pigment PR 101 and 3.75% by weight of a pigment-affine block copolymer are used as dispersing agents in a 25% by weight solution of a phenyl-methyl-silicone resin in one Ball mill ground.
- the solvent is a mixture of xylene and cyclohexanone (ratio 5: 1).
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the pigment dispersions are filtered to remove contaminants and hard agglomerates and mixed with a silicone resin solution.
- the silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
- the mixture suitable for spray coating contains 37% by weight of silicone, 3.2% by weight of tetrachlorothioindigo PR88 and 2.8% by weight of iron oxide pigment PR 101.
- the lamp bulb is sprayed with the red, pig-containing silicone resin solution.
- the solvent is evaporated and the silicone resin crosslinked at 250 ° C.
- An approximately 15 ⁇ m thick transparent red coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
Abstract
Description
Die Erfindung betrifft eine farbige Leuchte, insbesondere eine farbige Signalleuchte für Automobile, ausgestattet mit einer Lampe und einer Leuchtenabdeckung, in der die Lampe einen Kolben mit einer Beschichtung mit einer Schicht, die ein organisches Pigment enthält, hat.The invention relates to a colored light, in particular a colored signal light for Automobile equipped with a lamp and a lamp cover in which the lamp a piston with a coating with a layer containing an organic pigment, Has.
Farbige Leuchten finden in Automobilen an verschiedenen Stellen Verwendung, beispielsweise für Bremslichter, Blinker und Nebellampen. In konventionellen farbigen Leuchten ist der Kolben der Lampe aus klarem Glas und die Lampe unter einer farbigen, meist roten oder gelben Leuchtenabdeckung angeordnet. Eine neuere Entwicklung geht dahin, für farbige Leuchten farbige Lampen unter einer farblosen oder neutral eingefärbten Abdeckung zu verwenden. Dies erlaubt es, verschiedenfarbige Signallampen als Lampenensemble unter einer einheitlichen Leuchrenabdeckung einzubauen.Colored lights are used in various places in automobiles, for example for brake lights, indicators and fog lamps. In conventional colored lights is the bulb of the lamp made of clear glass and the lamp under a colored, mostly red or yellow lamp cover arranged. A more recent development is going for colored ones Shine colored lamps under a colorless or neutral colored cover to use. This allows different colored signal lamps as a lamp ensemble a uniform fluorescent cover.
Leuchten mit farbigen Lampen unter einer farblosen oder neutral gefärbten Abdeckung haben den Vorteil, daß sie ein flexibles, optisch ansprechendes Design für integrierte Front- und Heckleuchten erlauben. Außerdem sind sie billiger als Leuchten mit mehrfarbigen Gehäuse oder mehrfarbigen Abdeckungen. Diese Leuchten sind zudem noch verkehrssicherer, weil der Unterschied zwischen eingeschalteter und ausgeschalteter Beleuchtung bei Tageslicht an Leuchten mit farbigen Lampe und farbloser oder neutral eingefärbter Leuchtenabdeckung besser erkennbar ist.Lights with colored lamps under a colorless or neutral colored cover have the advantage that they have a flexible, visually appealing design for integrated Allow front and rear lights. They are also cheaper than lights with multi-colored ones Housing or multi-colored covers. These lights are also even safer to drive, because the difference between on and off lighting in daylight on luminaires with colored lamps and colorless or neutral colored Luminaire cover is more recognizable.
Für die farbige, pigmenthaltige Kolbenbeschichtung von farbigen Lampen kann man grundsätzlich anorganische oder organische Farbpigmente verwenden. Die bekannten roten und gelben anorganische Farbpigmente sind langzeitstabil, haben aber keine optimalen Farbwerte. Kolbenbeschichtungen mit organische Farbpigmente, z.B. die aus der JP-A-60 116958 bekannten Beschichtungen mit roten Pigmenten aus der Gruppe der Anthrachinon-Pigmente lassen sich in Bezug auf die Farbkoordinaten optimieren, vergilben jedoch mit der Zeit.For the colored, pigmented bulb coating of colored lamps you can Always use inorganic or organic color pigments. The well-known red and yellow inorganic color pigments are long-term stable, but do not have optimal ones Color values. Piston coatings with organic color pigments, e.g. the from the JP-A-60 116958 known coatings with red pigments from the group of Anthraquinone pigments can be optimized in terms of color coordinates, yellow with time, however.
Wie in vielen anderen Industriezweigen geht auch bei Automobillampen der Trend in Richtung zu einer immer weiteren Miniaturisierung. Man versucht, die Größe der Beleuchtungskörper am Automobil insgesamt zu reduzieren und beispielsweise die Signalleuchten in die Scheinwerfer zu integrieren. In derartigen Beleuchtungskörpern sind die Lampen jedoch erhöhten thermischen Belastungen ausgesetzt.As in many other branches of industry, the trend is also in automotive lamps Towards an ever more miniaturization. One tries the size of the lighting fixtures on the automobile as a whole and, for example, the signal lights to integrate into the headlights. In such lighting fixtures However, lamps are exposed to increased thermal loads.
Es ist die Aufgabe der vorliegenden Erfindung, eine farbige Leuchte, ausgestattet mit einer Lampe und einer Leuchtenabdeckung, in der die Lampe einen Kolben mit einer Beschichtung mit einer Schicht, die ein organisches Farbpigment enthält hat, zu schaffen, die eine lange Lebensdauer auch bei erhöhten Umgebungstemperaturen sowie optimale Farbkoordinaten hat und die für eine Automobilbeleuchtung geeignet ist.It is the object of the present invention to provide a colored light fitting Lamp and a lamp cover in which the lamp has a bulb with a coating with a layer that has an organic color pigment to create the one long service life even at high ambient temperatures as well as optimal color coordinates and which is suitable for automotive lighting.
Erfindungsgemäß wird die Aufgabe gelöst durch eine farbige Leuchte, ausgestattet mit einer Lampe und einer Leuchtenabdeckung, in der die Lampe eine Kolbenbeschichtung mit einer ersten pigmenthaltigen Schicht, die ein Pigment ausgewählt aus der Gruppe der Perylen-Pigmente, Perinon-Pigmente, Isoindolin-Pigmente und der Thioindigo-Pigmente enthält, hat.According to the invention the object is achieved by a colored lamp equipped with a lamp and a lamp cover in which the lamp has a bulb coating with a first pigment-containing layer, which is a pigment selected from the group of Perylene pigments, perinone pigments, isoindoline pigments and the thioindigo pigments contains, has.
Eine Leuchte mit einer derartigen Lampe hat eine lange Lebensdauer. Sie wird durch UV-Licht, Feuchtigkeit und Streusalz nicht angegriffen und ist beständig gegen Temperaturen zwischen 250 und 350°C. Farbige Leuchten mit Kolbenbeschichtungen mit diesen Pigmenten allein oder zusammen mit weiteren Pigmenten zur Farbkorrektur erfüllen die Farbnormen für Automobilleuchten, wie sie für Europa durch die E.C.E. und für USA durch die S.A.E. definiert sind.A lamp with such a lamp has a long lifespan. It is caused by UV light, Moisture and road salt are not attacked and are resistant to temperatures between 250 and 350 ° C. Colored lights with bulb coatings with these pigments alone or together with other pigments for color correction Color standards for automotive lights, such as those for Europe by the E.C.E. and for USA by the S.A.E. are defined.
Nach einer bevorzugten Ausführungsform enthält die erste pigmenthaltige Schicht zusätzlich ein Eisenoxidpigment. Ein Eisenoxidpigment in der Schicht korrigiert den Farbwert des organischen Pigmentes beispielsweise in den blaustichigen Bereich, z.B. von gelb nach bernsteinfarben oder von orangerot nach rot. Für den Fall, daß die Lampe in der Leuchte längere Zeit Temperaturen oberhalb von 250°C ausgesetzt ist, hat diese Lampe noch Notlaufeigenschaften.According to a preferred embodiment, the first pigment-containing layer additionally contains an iron oxide pigment. An iron oxide pigment in the layer corrects the color value the organic pigment, for example in the bluish area, e.g. from yellow to amber or from orange-red to red. In the event that the lamp in the lamp exposed to temperatures above 250 ° C for a long time, this lamp still has emergency running properties.
Es kann bevorzugt sein, daß die erste pigmenthaltige Schicht ein Eisenoxidpigment und eine Silicium-Sauerstoff-Verbindung enthält. Eine derartige Schicht haftet sehr gut auf dem Glas des Lampenkolbens.It may be preferred that the first pigment-containing layer is an iron oxide pigment and contains a silicon-oxygen compound. Such a layer adheres very well the glass of the lamp bulb.
Nach einer weiteren bevorzugten Ausführungsform der Erfindung ist zwischen dem Kolben und der ersten pigmenthaltigen Schicht eine zweite pigmenthaltige Schicht angeordnet, die ein Eisenoxidpigment enthält. Wenn die Lampe zu starken und zu häufigen Temperaturwechseln ausgesetzt ist und die oberste Schicht abplatzt, hat auch diese Ausführungsform der Leuchte Notlaufeigenschaften.According to a further preferred embodiment of the invention is between the piston and a second pigment-containing layer is arranged on the first pigment-containing layer, which contains an iron oxide pigment. If the lamp is too strong and too frequent This embodiment is also exposed to changes in temperature and the top layer flakes off the emergency running properties of the lamp.
Zwischen dem Kolben und der ersten pigmenthaltigen Schicht kann eine transparente Schicht, die eine Silicium-Sauerstoff-Verbindung enthält, angeordnet sein. Dadurch wird die mechanische Festigkeit des Beschichtungsaufbaus erhöht.There can be a transparent layer between the piston and the first pigment-containing layer Layer containing a silicon-oxygen compound can be arranged. This will increases the mechanical strength of the coating structure.
Es ist auch möglich, daß die Lampe eine transparente Deckschicht, die eine Silicium-Sauerstoff-Verbindung enthält, hat, um die Kratzfestigkeit der pigmenthaltigen Beschichtung zu erhöhenIt is also possible that the lamp has a transparent cover layer, which is a silicon-oxygen compound contains, has to the scratch resistance of the pigmented coating to increase
Die Erfindung betrifft auch eine Lampe mit einem Kolben mit einer Beschichtung mit einer Schicht, die ein Pigment ausgewählt aus der Gruppe der Perylen-Pigmente, Perinon-Pigmente, Isoindolin-Pigmente und der Thioindigo-Pigmente enthält. The invention also relates to a lamp with a bulb with a coating a layer containing a pigment selected from the group of perylene pigments, perinone pigments, Contains isoindoline pigments and the thioindigo pigments.
Nachfolgend wird die Erfindung anhand von drei Ausführungsbeispielen wettet erläutert.In the following, the invention is explained on the basis of three exemplary embodiments.
Eine farbige Leuchte nach der Erfindung ist mit einer Lampe und einer Leuchtenabdeckung ausgestattet, in der die Lampe einen Kolben mit einer Beschichtung mit einer Schicht, die ein Pigment ausgewählt aus der Gruppe der Perylen-Pigmente, Perinon-Pigmente, Isoindolin-Pigmente und der Thioindigo-Pigmente enthält, hat.A colored lamp according to the invention is with a lamp and a lamp cover equipped in which the lamp has a bulb with a coating of a Layer containing a pigment selected from the group of perylene pigments, perinone pigments, Has isoindoline pigments and which contains thioindigo pigments.
Je nach Bauform der Lampe kann die Beschichtung auf einer oder mehreren Wänden des Lampenkolbens - sowohl auf der Außenseite als auch an der Innenseite des Kolbens - an-gebracht sein.Depending on the design of the lamp, the coating on one or more walls of the Lamp bulb - both on the outside and on the inside of the bulb - attached his.
Die farbige Leuchte kann weiterhin noch mit anderen Bauteilen, z.B. Mittel zur Befestigung der Lampe in der Leuchte, Mittel zum Schutz gegen Staub, Beschädigung und Feuchtigkeit sowie die zur Energieversorgung notwendigen Bestandteile, z.B. Fassungen, Leitungen, Vorschaltgeräte, Starter, Zündeinrichtungen und Anschlußlklemmen ausgerüstet sein. Eine erwünschte Lichrverteilung und eine Blendungsbegrenzung kann durch optische Reflektoren, klare oder getrübte Abschlußwannen, Raster aus Metall oder Kunststoff, Streugläser und Prismenreflektoren erreicht werden. Nach einer Ausführungsform der Erfindung umfaßt die Leuchte zwei oder mehrere farbige Lampen unter einer gemeinsamen Leuchtenabdeckung, die farblos oder neutral eingefarbt ist.The colored lamp can still be used with other components, e.g. Attachment means the lamp in the lamp, means of protection against dust, damage and Moisture and the components necessary for energy supply, e.g. Versions, Lines, ballasts, starters, ignition devices and connecting terminals equipped his. A desired light distribution and glare limitation can be achieved by optical reflectors, clear or cloudy cover trays, grid made of metal or plastic, Scatter glasses and prism reflectors can be achieved. According to one embodiment the invention comprises the lamp two or more colored lamps under a common Luminaire cover that is colorless or neutral colored.
Für die erste pigmenthaltige Schicht auf dem Kolben werden Perylen-, Perinon-, Isoindolin- oder Thioindigo-Pigmente verwendet. Die verwendeten Pigmente sind polycyclische Pigmente, die schon länger zum Farben von Textilfasern bekannt sind. Die Pigmente werden nachfolgend gemäß ihrer chemischen Konstitution oder dem Colour Index (C.I.), der von der Society of Dyers and Colourists gemeinsam mit der American Association of Textile Chemists and Colorists publiziert wird, bezeichnet.Perylene, perinone, isoindoline or thioindigo pigments are used for the first pigment-containing layer on the flask. The pigments used are polycyclic Pigments that have long been known for dyeing textile fibers. The pigments are subsequently based on their chemical constitution or the Color Index (C.I.), by the Society of Dyers and Colorists together with the American Association of Textile Chemists and Colorists is published.
Perinone [CAS4424-06-0 (trans-Perinon), CAS 4216-02-8 (cis-Perinon)) sind Derivate der 1,4,5,8-Naphtralintetracarbonsäure. Man erhält cis- und trans-Perinon als cis/trans-Isomerengemisch durch Erhitzen von 1,4,5,8-Naphtalintetracarbonsäure in Form des Monoanhydrids, z.B. in Eisessig bei 120°C, mit o-Phenylendiamin. Wenn man die Isomeren auftrennt, erhält man das trans-Perinon mit einem reinen orangegelben Farbton und das cis-Perinon mit Rotton.Perinones [CAS4424-06-0 (trans-Perinon), CAS 4216-02-8 (cis-Perinon)) are derivatives the 1,4,5,8-naphthaline tetracarboxylic acid. Cis and trans perinone are obtained as a cis / trans isomer mixture by heating 1,4,5,8-naphthalene tetracarboxylic acid in the form of the Monoanhydrides, e.g. in glacial acetic acid at 120 ° C, with o-phenylenediamine. If you look at the isomers separates, the trans-perinone is obtained with a pure orange-yellow color and the cis-perinon with red hue.
Die Perylen-Pigmente sind Derivate der 3,4,9,10-Perylentetracarbonsäure. Bevorzugt verwendet werden können die Rotgelb bzw. Rotpigmente Perylentetracarbonsäurebis(methylimid) PR 179 (CAS 5521-31-3), Perylentetracarbonsäuredianhydrid PR 224 (CAS 3049-71-6), Bis-dimethylphenylperylimid PR 149 und Perylentetracarbonsäurediimid) PV 29 (CAS 81-33-4). Allgemein werden die Perylenpigmente aus dem 3,4,9,10-Perylentetracarbonsäureanhydrid durch Umsetzung mit primären aliphatischen Aminen oder substituierten Anilinen, ggf. in Gegenwart eines Katalysators, hergestellt.The perylene pigments are derivatives of 3,4,9,10-perylenetetracarboxylic acid. Prefers the red yellow or red pigments perylene tetracarboxylic acid bis (methylimide) can be used PR 179 (CAS 5521-31-3), perylene tetracarboxylic dianhydride PR 224 (CAS 3049-71-6), bis-dimethylphenylperylimide PR 149 and perylenetetracarboxylic acid diimide) PV 29 (CAS 81-33-4). In general, the perylene pigments are made from 3,4,9,10-perylenetetracarboxylic anhydride by reaction with primary aliphatic amines or substituted anilines, optionally in the presence of a catalyst.
Die Isoindolin-Pigmente enthalten als zentrales Strukturelement einen Isoindolinring, der über eine C=C - Doppelbindung mit verschiedenen Substituenten substituiert sein kann. Je nach Substituent sind die Isoindolin-Pigmente gelb, orange oder rot gefärbt. PY 139 (CAS 36888-99-0) mit der Summenforrnel C16H9N5O6 hat eine orange Färbung und ist thermisch sehr beständig. PY 185 (CAS 76199-85-4) hat eine gelbe Färbung und ist ebenfalls thermisch sehr gut beständig.The central structural element of the isoindoline pigments is an isoindoline ring, which can be substituted with various substituents via a C = C double bond. Depending on the substituent, the isoindoline pigments are colored yellow, orange or red. PY 139 (CAS 36888-99-0) with the summation formula C 16 H 9 N 5 O 6 has an orange color and is very thermally stable. PY 185 (CAS 76199-85-4) has a yellow color and is also very good thermal resistance.
Von den Thioindigo-Pigmenten sind besonders die mit Chlor und/oder mit Methylgruppen substituierten Derivate für die Erfindung geeignet. Tetrachlorthioindigo PR 88 (CAS 14295-43-3) hat eine rotviolette Farbe, die zur Einstellung von anderen Rotpigmenten geeignet ist.The thioindigo pigments are especially those with chlorine and / or with methyl groups substituted derivatives suitable for the invention. Tetrachlorothioindigo PR 88 (CAS 14295-43-3) has a red-violet color, which is used to adjust other red pigments suitable is.
Bevorzugt werden die Perylen-, Perinon-, Isoindolin- oder Thioindigo-Pigmente in feinteiliger, kolloider Form mit einer Korngröße 2nm <d <200 nm verwendet, um transparente Schichten zu erhalten. The perylene, perinone, isoindoline or thioindigo pigments are preferred in finely divided, colloidal shape with a grain size of 2nm <d <200 nm used to make transparent To get layers.
Nach einer bevorzugten Ausführungsform der Erfindung kann die erste pigmenthaltige Schicht zusätzlich zu den Perylen-, Perinon-, Isoindolin- und Thioindigo-Pigmenten ein Eisenoxidpigment enthalten.According to a preferred embodiment of the invention, the first pigment-containing Layer in addition to the perylene, perinone, isoindoline and thioindigo pigments contain an iron oxide pigment.
Eisenoxid-Pigmente haben ein breites Farbenspektrum von gelb über orange zu rot, braun und schwarz. Die verwendeten natürlichen und synthetischen Eisenoxid-Pigmente bestehen aus gut definierten Verbindungen mit bekannter Kristallstruktur. α-Fe2O3 (Hämatit) mit Korundstruktur verändert seine Farbe mit Partikelgröße und Kristallform von Hellrot bis Dunkelviolett. γ-Fe2O, (Maghemit) mit Spinellstruktur ist braun gefärbt. α-FeOOH (Goethit) mit Diaspor-Struktur verändert seine Farbe mit zunehmender Partikelgröße von hellgelb bis braungelb. γ-FeOOH (Lepidocrocit) mit Boehmit-Struktur verändert seine Farbe mit zunehmender Partikelgröße von Gelb nach Orange. Diese Eisenoxide sind Eisen(III)oxide. Das rotviolette bis schwarze Fe3O4 (Magnetit) mit Spinellstruktur ist nur in Ausnahmefällen geeignet. Bevorzugt werden die transparenten Eisenoxid-Pigmente in feinteiliger, kolloider Form mit einer Korngröße 2 < d < 15 nm verwendet, um transparente Schichten zu erhalten.Iron oxide pigments have a wide range of colors from yellow to orange to red, brown and black. The natural and synthetic iron oxide pigments used consist of well-defined compounds with a known crystal structure. α-Fe 2 O 3 (hematite) with corundum structure changes its color with particle size and crystal form from light red to dark violet. γ-Fe 2 O, (maghemite) with a spinel structure is colored brown. α-FeOOH (goethite) with a diasporic structure changes its color with increasing particle size from light yellow to brownish yellow. γ-FeOOH (lepidocrocite) with a boehmite structure changes its color from yellow to orange with increasing particle size. These iron oxides are iron (III) oxides. The red-violet to black Fe 3 O 4 (magnetite) with spinel structure is only suitable in exceptional cases. The transparent iron oxide pigments are preferably used in finely divided, colloidal form with a grain size of 2 <d <15 nm in order to obtain transparent layers.
Transparentes gelbes Eisenoxid C. I. PY 42:77492 ist α-FeOOH (Goethit) mit Diaspor-Struktur. Beim Erhitzen wandelt es sich in das bevorzugt verwendete transparente braunrote α-Fe2O3 (Hämatit) C.I. PR 101: 77491 um. Orange Zwischentöne entwickeln sich bei einer kürzeren Temperaturbehandlung. Sie können auch durch Mischen von gelben und roten Pigmenten erhalten werden. Bevorzugt werden die Eisenoxid-Pigmente mit einer Korngröße 2 nm < d < 200 nm.Transparent yellow iron oxide CI PY 42: 77492 is α-FeOOH (goethite) with a diasporic structure. When heated, it changes into the preferred transparent brown-red α-Fe 2 O 3 (hematite) CI PR 101: 77491. Orange nuances develop with a shorter temperature treatment. They can also be obtained by mixing yellow and red pigments. The iron oxide pigments with a grain size of 2 nm <d <200 nm are preferred.
Es ist auch möglich, daß die erste pigmenthaltige Schicht eine Silicium-Sauerstoff-Verbindung enthält, z.B. amorphes oder kristallines Siliciumdioxid, Quarz, ein Kieselgel oder eine Kieselsäure oder ein Silicat, d.h. Salze oder Ester der Kieselsäuren, insbesondere Tetraethylorthosilicat (TEOS), ein Silicon oder ein Siloxan. It is also possible for the first pigment-containing layer to be a silicon-oxygen compound contains, e.g. amorphous or crystalline silicon dioxide, quartz, a silica gel or a Silica or a silicate, i.e. Salts or esters of silicas, especially tetraethyl orthosilicate (TEOS), a silicone or a siloxane.
Die Pigmente und die Silicium-Sauerstoff-Verbindungen können in einer einzigen Farbschicht aufgetragen werden.The pigments and the silicon-oxygen compounds can be in a single color layer be applied.
Nach einer anderen Ausführungsform der Erfindung kann die farbige Kolbenbeschichtung auch einen variablen Vielschichtaufbau haben. Er umfaßt immer eine erste farbige Schicht, die ein Pigment ausgewählt aus der Gruppe der Perylen-Pigmente, Perinon-Pigmente, Isoindolin-Pigmente und der Thioindigo-Pigmente enthält.According to another embodiment of the invention, the colored piston coating also have a variable multilayer structure. It always includes a first colored layer, which is a pigment selected from the group of perylene pigments, perinone pigments, isoindoline pigments and which contains thioindigo pigments.
Unter der ersten farbigen Schicht kann zuerst eine Eisenoxid - haltige Schicht auf dem Lampenkolben aufgebracht sein. Die Eisenoxid-haltige Schicht kann das Eisenoxid entweder als feinteiliges Pigment oder als Niederschlag aus einem Sol-Gel-Verfahren enthalten. Wenn das Eisenoxid als Pigment aufgebracht wird, kommt als Herstellungsverfahren sowohl eine trockene, z.B. elektrostatische Abscheidung, als auch eine nasse Auftragung, z.B. als wässrige Suspension- durch Tauchen oder Sprühen in Betracht.Under the first colored layer, a layer containing iron oxide can first be placed on the Lamp bulb be applied. The iron oxide-containing layer can either be the iron oxide contained as a finely divided pigment or as a precipitate from a sol-gel process. When the iron oxide is applied as a pigment, it comes as a manufacturing process both a dry, e.g. electrostatic deposition, as well as wet application, e.g. as an aqueous suspension - by dipping or spraying.
In einer anderen Ausführungsform der Erfindüng sieht der Vielschichtaufbau für die Beschichtung des Lampenkolbens so aus, daß zuerst eine eisenoxidhaltige Schicht auf den Lampenkolben innen oder außen aufgebracht wird. Für diese Schicht kann das Eisenoxid entweder als feinteiliges Pigment oder in einem Sol-Gel-Verfahren aufgebracht werden. Über die eisenoxidhaltige Schicht wird eine temperaturbeständige, transparente Schutzschicht, die eine Silicium-Sauerstoff-Verbindung enthält, z.B. eine SiO2-oder eine Quarzglas-Schicht, aufgebracht. Auf dieser wird wiederum die pigmenthaltige Schicht aufgebracht.In another embodiment of the invention, the multilayer structure for the coating of the lamp bulb is such that an iron oxide-containing layer is first applied to the inside or outside of the lamp bulb. For this layer, the iron oxide can be applied either as a fine pigment or in a sol-gel process. A temperature-resistant, transparent protective layer which contains a silicon-oxygen compound, for example an SiO 2 or a quartz glass layer, is applied over the layer containing iron oxide. The pigment-containing layer is in turn applied to this.
In einer weiteren Ausführungsform der Erfindung sieht der Vielschichtaufbau für die Beschichtung des Lampenkolbens so aus, daß zwischen dem Kolben und der ersten pigmenthaltigen Schicht eine transparente Schicht, die eine Silicium-Sauerstoff-Verbindung enthält, angeordnet ist. In a further embodiment of the invention, the multi-layer structure for the Coating the lamp bulb so that between the bulb and the first pigmented Layer a transparent layer that contains a silicon-oxygen compound contains, is arranged.
Über den pigmenthaltigen Schichten kann eine temperaturbeständige, transparente Deckschicht, angeordnet sein. Die Deckschicht enthält eine Silicium-Sauerstoff-Verbindung, z.B. amorphes oder kristallines Siliciumdioxid, Quarz, ein Kieselgel oder eine Kieselsäure oder ein Silicat, d.h. Salze oder Ester der Kieselsäuren, insbesondere Tetraethylorthosilcat (TEOS). Alternativ kann diese zusätzliche Deckschicht auch ein temperaturbestandiger, transparenter farbloser oder farbstoffhaltiger Lack oder eine transparente Keramikschicht z.B. aus Al2O3 oder Emaille sein. Wenn die Beschichtungen innen im Kolben aufgetragen sind, verhindert die Deckschicht eine chemische Veränderung der Pigmente. Ist die Beschichtung außen aufgetragen, bildet die Deckschicht eine kratzfeste Oberfläche, die die weitere Verarbeitung des Kolbens in der Lampenproduktion erleichtert.A temperature-resistant, transparent cover layer can be arranged over the pigment-containing layers. The cover layer contains a silicon-oxygen compound, for example amorphous or crystalline silicon dioxide, quartz, a silica gel or a silica or a silicate, ie salts or esters of silica, in particular tetraethylorthosilcat (TEOS). Alternatively, this additional top layer can also be a temperature-resistant, transparent, colorless or dye-containing lacquer or a transparent ceramic layer, for example made of Al 2 O 3 or enamel. If the coatings are applied to the inside of the flask, the top layer prevents chemical changes in the pigments. If the coating is applied on the outside, the cover layer forms a scratch-resistant surface, which facilitates further processing of the bulb in lamp production.
Bevorzugt wird eine Deckschicht mit einem geeigneten Brechungsindex eingesetzt, der die Streuung der pigmenthaltigen Schichten vermindert.A cover layer with a suitable refractive index is preferably used, which has the Scattering of the pigment-containing layers is reduced.
Als Verfahren zum Aufbringen der Beschichtung auf den Lampenkolben können herkömmliche Verfahren zur Beschichtung komplex geformter Substrate verwendet werden. Diese schließen die nassen Beschichtungsverfahren wie z.B. Sprühen, Tauchen und Pinseln ein. Auch Trockenbeschichtungsverfahren, z.B. elektrostatisch unterstütztes Bestauben sind geeignet, um die pigmenthaltige Beschichtung auf den Lampenkolben aufzubringen.As a method for applying the coating on the lamp bulb, conventional Processes for coating complex shaped substrates can be used. These include the wet coating processes such as Spraying, dipping and brushing on. Dry coating processes, e.g. electrostatically assisted dusting are suitable for applying the pigment-containing coating to the lamp bulb.
Für Naßbeschichtungsverfahren müssen die Pigmente in Wasser, einem organischen Lösemittel
oder einer Bindemittelzubereitung, gegebenenfalls zusammen mit einem Dispergiermittel,
einem Tensid und einem Antischaummittel, dispergiert werden. Geeignet für Bindemittelzubereitungen
für eine Leuchte nach der Erfindung sind organische oder anorganische
Bindemittel, die einer Betriebstemperatur von 250°C bis 350 °Cohne Zersetzung,
Versprödung oder Verfarbung überstehen.
Für bindemittelfreie, pigmenthaltige Schichten kann eine Schichtdicke von 0.5 bis 2.0 µm
ausreichend sein. Bindemittelhaltige Schichten haben im allgemeinen eine Schichtdicke
von 1 bis 50 µm.
Die pigmentbeschichteten Lampen wurden einem beschleunigten Temperaturbelastungstest
ausgesetzt, bei dem die Lampen permanent auf 300 °C gehalten wurden. Der Farbort
veränderte sich in einem Zeitraum von 150 h nur minimal innerhalb des durch die E.C.E
und die S.A. E. festgelegten Bereichs für die Farbspezifikation. Auch bei einem regulären
Lampenbetrieb über einen Zeitraum von 500 h blieb der Farbpunkt innerhalb der E.C.E.
Farbspezifikation.For wet coating processes, the pigments must be dispersed in water, an organic solvent or a binder preparation, optionally together with a dispersant, a surfactant and an antifoam. Suitable for binder preparations for a lamp according to the invention are organic or inorganic binders which can withstand an operating temperature of 250 ° C to 350 ° C without decomposition, embrittlement or discoloration.
For binder-free, pigment-containing layers, a layer thickness of 0.5 to 2.0 µm can be sufficient. Binder-containing layers generally have a layer thickness of 1 to 50 μm.
The pigment coated lamps were subjected to an accelerated thermal stress test in which the lamps were kept at 300 ° C permanently. The color location changed only minimally within a period of 150 hours within the range specified by the ECE and the SAE for the color specification. Even with regular lamp operation over a period of 500 h, the color point remained within the ECE color specification.
Ein sehr geeignetes Eisenoxidpigment ist Hämatit. Insbesondere gemeinsam mit einem
Gemisch erhält man eine Beschichtung. die eine sehr gute Farbpunktsättigung im roten
Bereich und eine gute Lichttransmission aufweist.
Zur Herstellung der Kolbenbeschichtung wird zunächst eine Dispersion aus 7.5 Gew.-%
cis/trans-Perinon-Pigment VR 54 und 7.5 Gew.-% transparentem Eisenoxidpigment PR
101, 0.75 Gew.-% Natriumpolyacrylat als Dispergiermittel, 0.075 Gew.-% Polyethylen-propylenoxid
als Antischaurmmittel mit Wasser in einer Rührwerksmühle naß gemahlen,
solange bis das agglomerierte Pigment dispergiert sind. Der Dispersion kann weiterhin ein
Tensid z.B. ein polyether-modifiziertes Polysiloxan zugesetzt werden. Die gereinigten und
ausgeheizten Lampenkolben werden in diese Dispersion getaucht und anschließend bei
250°C eingebrannt.
180 g Tetraethylorthosilikat werden mit 2077 g Ethanol, 146 g in Salzsäure und 27 ml
eines anionischen Tensid gemischt. In diese Mischung werden die vorbeschichteten Lampenkolben
getaucht und kurzzeitig bei 300°C ausgeheizt, um Tetraethylorthosilikat in eine
Siliciumdioxidschicht umzuwandeln.A very suitable iron oxide pigment is hematite. A coating is obtained in particular together with a mixture. which has a very good color point saturation in the red area and good light transmission.
To produce the piston coating, a dispersion of 7.5% by weight cis / trans-perinone pigment VR 54 and 7.5% by weight transparent iron oxide pigment PR 101, 0.75% by weight sodium polyacrylate as a dispersant, 0.075% by weight polyethylene propylene oxide as anti-foaming agent wet-ground with water in an agitator mill until the agglomerated pigment is dispersed. A surfactant, for example a polyether-modified polysiloxane, can also be added to the dispersion. The cleaned and heated lamp bulbs are immersed in this dispersion and then baked at 250 ° C.
180 g of tetraethyl orthosilicate are mixed with 2077 g of ethanol, 146 g in hydrochloric acid and 27 ml of an anionic surfactant. The pre-coated lamp bulbs are dipped into this mixture and briefly heated at 300 ° C in order to convert tetraethyl orthosilicate into a silicon dioxide layer.
Ein sehr geeignetes Eisenoxidpigment ist Hämatit. Insbesondere mit einem organischen
Rotpigment, das als erste Schicht in einem temperaturbeständigem Siliconharz aufgetragen
wird, erhält man eine Beschichtung, die eine sehr gute Farbpunktsättigung im roten Bereich
und eine gute Lichttransmission aufweist.
Zur Herstellung der Lampenbeschichtung wird zunächst eine Dispersion aus 15 Gew.-%
transparentem Eisenoxidpigment PR 101, 3 Gew.-% einer 25 %igen Lösung eines Natriumsatzes
einer Polycarboxylsäure als Dispergiermittel, 0.075 Gew.-% Potyethylenpropylenoxid
als Antischaummittel mit Wasser in einer Rührwerksmühle naß gemahlen, solange
bis das agglomerierte Pigment dispergiert ist. Die Dispersion wird filtriert, um Verunreinigungen
und harte Agglomerate zu entfernen. Zur besseren Benetzung des Lampenkolbens
wird ein Tensid z.B. ein polyether-modifiziertes Polysiloxan zugesetzt. Die Dispersion wird
auf eine Pigmentkonzentrarion von 8.7 Gew.% verdünnt. Die gereinigten und ausgeheizten
Lampenkolben werden in diese Dispersion getaucht, getrocknet und anschließend bei
450°C eingebrannt. Man erhält eine transparente Hämatitschicht von ca. 0.5 µm Dicke.A very suitable iron oxide pigment is hematite. In particular with an organic red pigment, which is applied as the first layer in a temperature-resistant silicone resin, a coating is obtained which has very good color point saturation in the red area and good light transmission.
To produce the lamp coating, a dispersion of 15% by weight of transparent iron oxide pigment PR 101, 3% by weight of a 25% solution of sodium in a polycarboxylic acid as a dispersing agent, 0.075% by weight of potyethylene propylene oxide as an anti-foaming agent is first wet with water in a stirred mill milled until the agglomerated pigment is dispersed. The dispersion is filtered to remove contaminants and hard agglomerates. For better wetting of the lamp bulb, a surfactant, for example a polyether-modified polysiloxane, is added. The dispersion is diluted to a pigment concentration of 8.7% by weight. The cleaned and heated lamp bulbs are immersed in this dispersion, dried and then baked at 450 ° C. A transparent hematite layer approximately 0.5 µm thick is obtained.
Eine weitere Pigmentdispersion erhält man durch Mahlen des organischen Rotpigments Dimethylperylimid PR 179 in einer Kugelmühle. Dazu wird 6 Gew.-% Pigment in einem Lösungsmittelgemisches aus Xylol und Cyclohexanon (Verhältnis 5:1) unter Zusatz eines Dispergiermittels gemahlen bis die Pigmentagglomerate dispergiert sind. Als Dispergiermittel wird ein pigmentaffines Blockcopolymer in einer Konzentration von 18 Gew.% bezogen auf die Pigmentmenge verwendet. Die Dispersion wird filtriert und mit einer Siliconharlösung gemischt. Das Siliconharz ist ein reaktives Phenyl-Methyl-Silicon, das thermisch vernetzt wird und dann bis zu Temperaturen von 500°C stabil ist. Die Siliconharzlösung hat einen Polymeranteil von 50 Gew.% in einem Lösungsmittelgemisch wie es bereits zum Mahlen des Pigmentes verwendet wurde. Die gebrauchsfertige Mischung enthält 32 Gew.% Silicon und 12 Gew.% Dimethylperylimid-Pigment PR 179. Der bereits mit einer Hämatitschicht bedeckte Lampenkotben wird durch Sprühen mit der Dimethylperylimid-pigmenthaltigen Siliconharzlösung bedeckt. Das Lösungsmittel wird verdampft und das Siliconharz bei 250°C vernetzt. Man erhält eine rote, 8 bis 10 µm dicke Siliconharzschicht als äußere Deckschicht der Lampe. Die zweilagige Beschichtung aus Hämatit und Dimethylperylimid PR 179 ergibt eine transparente rote Beschichtung auf der Lampe, die den ECE und SAE Normen für rote Signallampen entspricht.Another pigment dispersion is obtained by grinding the organic red pigment Dimethylperylimide PR 179 in a ball mill. 6% by weight of pigment in one Solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a Dispersing agent ground until the pigment agglomerates are dispersed. As a dispersant a pigment-affine block copolymer in a concentration of 18% by weight based on the amount of pigment used. The dispersion is filtered and with a Siliconhar solution mixed. The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C. The silicone resin solution has a polymer content of 50% by weight in a solvent mixture like this has already been used to grind the pigment. The ready-to-use mixture contains 32% by weight silicone and 12% by weight dimethylperylimide pigment PR 179. The already Lamp droppings covered with a hematite layer are sprayed with the pigment containing dimethylperylimide Silicone resin solution covered. The solvent is evaporated and crosslinked the silicone resin at 250 ° C. A red, 8 to 10 μm thick silicone resin layer is obtained as the outer cover layer of the lamp. The two-layer hematite coating and dimethylperylimide PR 179 results in a transparent red coating on the lamp, which complies with the ECE and SAE standards for red signal lamps.
Ein sehr geeignetes Eisenoxidpigment ist Hämatit. Insbesondere mit einem organischen
Gelbpigment, das als erste Schicht in einem temperaturbeständigem Siliconharz aufgetragen
wird, erhält man eine Beschichtung, die eine sehr gute Farbpunktsättigung im amberfarbenen
Bereich und eine gute Lichttransmission aufweist.
Die auf den Lampenkolben zuerst aufzutragende Hamatitschicht erhält man durch Mahlen
des Eisenoxidpigmentes PR101 in Wasser wie es in Ausführungsbeispiel 2 beschrieben ist.
Die gemahlenen Hämatitdispersion wird auf 5.5 Gew.% Pigmentanteil verdünnt. Der
Lampenkolben wird durch Tauchen beschichret. Die getrocknete und bei 450°C eingebrannte
Hämatirschicht hat eine Dicke von 0.3 µm. Die Schicht ist transparent und rotbraun
gefärbt. Der Farbpunkt genügt noch nicht der ECE Norm für amberfarbene Signallampen.
Deshalb ist eine weitere Beschichtung mit einem geeigneten Gelbpigment notwendig,
um eine Farbpunktkorrektur entsprechend der ECE Norm vorzunehmen.
Das Isoindolinpigment PY 139, wird in einem Lösungsmittelgemisch unter Zusatz eines
pigmentaffinen Blockcopolymers als Dispergiermittel gemahlen. Die Mahlung erfolgt nach
der in Ausführungsbeispiel 2 angegebenen Methode für das Dimethylperylimid-Pigment.
Die gelbe Pigmentdispersion und die in Ausführungsbeispiel 2 beschriebene Siliconharzlösung
werden in einem Verhältnis gemischt. dass die Konzentration an Isoindolin-Gelbpigment
1.6 Gew.% und an Silicon 35 Gew.% beträgt. Der bereits mit einer Hämatitschicht
bedeckte Lampenkolben wird durch Sprühen mit der Isoindolin -pigmenthaltigen
Siliconharzlösung bedeckt. Das Lösungsmittel wird verdampft und das Siliconhatz bei
250°C vernetzt. Man erhält eine etwa 10 - 15 µm dicke transparente gelbe Siliconharzbeschichtung
auf der Hämatit beschichteten Lampe, die den Farbpunkt der Lampe in den
ECE Normbereich für amberfarbene Signallampen verschiebt.A very suitable iron oxide pigment is hematite. In particular with an organic yellow pigment, which is applied as the first layer in a temperature-resistant silicone resin, a coating is obtained which has very good color point saturation in the amber area and good light transmission.
The hematite layer to be applied first to the lamp bulb is obtained by grinding the iron oxide pigment PR101 in water as described in Example 2. The ground hematite dispersion is diluted to 5.5% by weight of pigment. The lamp bulb is coated by dipping. The dried and baked hematite layer at 450 ° C has a thickness of 0.3 µm. The layer is transparent and colored red-brown. The color point does not yet meet the ECE standard for amber-colored signal lamps. Therefore, a further coating with a suitable yellow pigment is necessary to make a color point correction in accordance with the ECE standard.
The isoindoline pigment PY 139 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment. The yellow pigment dispersion and the silicone resin solution described in working example 2 are mixed in a ratio. that the concentration of isoindoline yellow pigment is 1.6% by weight and that of silicone is 35% by weight. The lamp bulb, which is already covered with a hematite layer, is covered by spraying with the silicone resin solution containing isoindoline pigment. The solvent is evaporated and the silicone mixture is crosslinked at 250 ° C. An approximately 10-15 µm thick transparent yellow silicone resin coating is obtained on the hematite-coated lamp, which shifts the color point of the lamp into the ECE standard range for amber-colored signal lamps.
Eine sehr geeignete Mischung von zwei organischen Pigmenten ist die Verwendung von
einem organischen Rotpigment (PR 149, Bis-dimethylphenylperylimid) und einem organischen
Gelbpigment (PY139, Isoindolin-Gelbpigment) in einem Siliconharz. Man erhält
eine Beschichtung, die eine sehr gute Farbpunktsättigung im amberfarbenen Bereich und
eine gute Lichrtransmission aufweist.
Das gelbe Isoindolinpigment PY 139, wird in einem Lösungsmittelgemisch unter Zusatz
eines pigmentaffinen Blockcopolymers als Dispergiermittel gemahlen. Die Mahlung erfolgt
nach der in Ausführungsbeispiel 2 angegebenen Methode für das Dimethylperylimid-Pigment.
Die gelbe Pigmentdispersion und eine 50 Gew.%ige Siliconharzlösung, die eine
Mischung aus 80 Teilen reaktivem Methyl-Phenyl-Silicon und 20 Teilen reaktivem polyestermodifiziertem
Methyl-Phenyl-Silicon ist, werden in einem Verhältnis gemischt, dass
die Konzentration an Isoindolin-Gelbpigment 2.4 Gew.% und an Silicon 35 Gew.% beträgt.
Das rote Bis-dimethylphenylperylimid-Pigment PR149 wird in einem Lösungsmittelgemisch
unter Zusatz eines pigmentaffinen Blockcopolymers als Dispergiermittel gemahlen.
Die Mahlung erfolgt nach der in Ausführungsbeispiel 2 angegebenen Methode für das
Dimethylperylimid-Pigment. Die rote Pigmentdispersion und eine 50 Gew.%ige Siliconharzlösung,
die eine Mischung aus 80 Teilen reaktivem Methyl-Phenyl-Silicon und 20
Teilen reaktivem polyestermodifiziertem Methyl-Phenyl-Silicon ist, werden in einem
Verhältnis gemischt, dass die Konzentration an rotem Bis-dimethylphenylperylimid-Pigment
0.8 Gew.% und an Silicon 35 Gew.% beträgt.
Die beiden Pigmentdispersionen werden zu gleichen Anteilen gemischt und durch Sprühen
auf den Lampenkolben aufgetragen. Das Lösungsmittel wird verdampft und das Siliconharz
bei 250°C vernetzt. Man erhält eine transparente, amberfarbene Siliconharzschicht
von 10 bis 15 µm Dicke, die der ECE Norm für Signallampen entspricht.A very suitable mixture of two organic pigments is the use of an organic red pigment (PR 149, bis-dimethylphenylperylimide) and an organic yellow pigment (PY139, isoindoline yellow pigment) in a silicone resin. A coating is obtained which has very good color point saturation in the amber region and good light transmission.
The yellow isoindoline pigment PY 139 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment. The yellow pigment dispersion and a 50% by weight silicone resin solution, which is a mixture of 80 parts of reactive methylphenyl silicone and 20 parts of reactive polyester-modified methylphenyl silicone, are mixed in a ratio such that the concentration of isoindoline yellow pigment 2.4 % By weight and 35% by weight of silicone.
The red bis-dimethylphenylperylimide pigment PR149 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment. The red pigment dispersion and a 50% by weight silicone resin solution, which is a mixture of 80 parts of reactive methyl-phenyl silicone and 20 parts of reactive polyester-modified methyl-phenyl silicone, are mixed in a ratio such that the concentration of red bis-dimethylphenylperylimide Pigment is 0.8% by weight and 35% by weight of silicone.
The two pigment dispersions are mixed in equal proportions and applied to the lamp bulb by spraying. The solvent is evaporated and the silicone resin crosslinked at 250 ° C. A transparent, amber-colored silicone resin layer with a thickness of 10 to 15 µm is obtained, which corresponds to the ECE standard for signal lamps.
Man erhält eine Beschichtung, die eine sehr gute Farbpunktsättigung im roten Farbbcreich
und eine gute Lichttransmission aufweist bei Verwendung des organischen Rotpigments
Bis-dimethylphenylperylimid-Pigment PR149 in einem Siliconharz.
Das rote Bis-dimethylphenylperylimid-Pigment PR149 wird in einem Lösungsmittelgemisch
unter Zusatz eines pigmentaffinen Blockcopolymers als Dispergiermittel gemahlen.
Die Mahlung erfolgt nach der in Ausführungsbeispiel 2 angegebenen Methode für das
Dimethylperylimid-Pigment. Die rote Pigmentdispersion und eine 50 Gew.%ige Siliconharzlösung
werden in einem Verhältnis gemischt, dass die Konzentration an rotem Bisdimethylphenylperylimid-Pigment
2.9 Gew.% und an Silicon 33 Gew.% beträgt. Das Siliconharz
ist ein reaktives Phenyl-Methyl-Silicon, das thermisch vernetzt wird und dann bis
zu Temperaturen von 500°C stabil ist.
Der Lampenkolben wird durch Sprühen mit der roten, pigmenthaltigen Siliconharzlösung
bedeckt. Das Lösungsmittel wird verdampft und das Siliconharz bei 250°C vernetzt. Man
erhält eine etwa 15 µm dicke transparente rote Siliconharzbeschichtung, die einen Farbpunkt
aufweist, der den ECE und SAE Normen für rote Signallampen entspricht.A coating is obtained which has very good color point saturation in the red color range and good light transmission when the organic red pigment bis-dimethylphenylperylimide pigment PR149 is used in a silicone resin.
The red bis-dimethylphenylperylimide pigment PR149 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment. The red pigment dispersion and a 50% by weight silicone resin solution are mixed in a ratio such that the concentration of red bisdimethylphenylperylimide pigment is 2.9% by weight and that of silicone 33% by weight. The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
The lamp bulb is sprayed with the red, pigment-containing silicone resin solution. The solvent is evaporated and the silicone resin crosslinked at 250 ° C. An approximately 15 µm thick transparent red silicone resin coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
Man erhält eine besonders harte und kratzfeste Beschichtung, die eine sehr gute Farbpunktsättigung
im roten Farbbereich und eine gute Lichttransmission aufweist, wenn eine
Schicht des organischen Rotpigments Bis-dimethylphenylperylimid PR149 mit einer Siliciumdioxid
Sol-Gel-Schicht bedeckt wird.
Zur Herstellung der Lampenbeschichtung wird zunächst eine Dispersion aus 10 Gew.-%
Bis-dimethylphenylperylimid PR14), 10 Gew.-% einer 40 %igen wässrigen Lösung eines
pigmentaffinen Blockcopolymers als Dispergiermittel, 0.075 Gew.-% Polyethylenpropylenoxid
als Antischaummittel mit Wasser in einer Kugelmühle gemahlen, solange bis das
agglomerierte Pigment dispergiert ist. Die Dispersion wird filtriert, um Verunreinigungen
und harte Agglomerate zu entfernen. Zur besseren Benetzung des Lampenkolbens kann ein
Tensid z.B. ein polyether-modifiziertes Polysiloxan zugesetzt werden.
Die gereinigten und ausgeheizten Lampenkolben werden in diese Dispersion getaucht, getrocknet
und anschließend bei 250°C eingebrannt. Man erhält eine transparente Pigmentschicht
von etwa 1.5 µm Dicke.
180 g Tetraethylorthosilikat werden mit 2077 g Ethanol, 146 g in Salzsäure und 27 ml
eines anionischen Tensid gemischt. In diese Mischung werden die vorbeschichteten Lampenkolben
getaucht und kurzzeitig bei 300°C ausgeheizt, um Tetraethylorthosilikat in eine
Siliciumdioxidschicht umzuwandeln. Man erhält eine kratzfeste, transparente rote Beschichtung,
die einen Farbpunkt aufweist, der den ECE und SAE Normen für rote Signallampen
entspricht.A particularly hard and scratch-resistant coating is obtained which has a very good color saturation in the red color range and good light transmission if a layer of the organic red pigment bis-dimethylphenylperylimide PR149 is covered with a silicon dioxide sol-gel layer.
To produce the lamp coating, a dispersion of 10% by weight bis-dimethylphenylperylimide PR14), 10% by weight of a 40% aqueous solution of a pigment-affine block copolymer as a dispersant, 0.075% by weight polyethylene propylene oxide as an antifoam with water in a ball mill is first used milled until the agglomerated pigment is dispersed. The dispersion is filtered to remove contaminants and hard agglomerates. A surfactant, for example a polyether-modified polysiloxane, can be added to improve the wetting of the lamp bulb.
The cleaned and heated lamp bulbs are immersed in this dispersion, dried and then baked at 250 ° C. A transparent pigment layer approximately 1.5 μm thick is obtained.
180 g of tetraethyl orthosilicate are mixed with 2077 g of ethanol, 146 g in hydrochloric acid and 27 ml of an anionic surfactant. The pre-coated lamp bulbs are dipped into this mixture and briefly heated at 300 ° C in order to convert tetraethyl orthosilicate into a silicon dioxide layer. A scratch-resistant, transparent red coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
Man erhält eine Beschichtung, die eine sehr gute Farbpunktsättigung im roten Bereich und
eine gute Lichtrransmission aufweist, wenn ein Gemisch des sehr geeigneten Eisenoxidpigments
Hämatit mit dem organischen Rotpigment Dimethylperylimid PR179 verwendet
wird.
Eine Pigmentdispersion des organischen Rotpigments Dimethylperylimid PR 179 erhält
man durch Mahlen in einer Kugelmühle. Dazu wird 6 Gew.-% Pigment in einem Lösurtgsmittelgemisch
aus Xylol und Cyclohexanon (Verhältnis 5:1) unter Zusatz eines
Dispergiermittels gemahlen bis die Pigmentagglomerate dispergiert sind. Als Dispergiermittel
wird ein pigmentaffines Blockcopolymer in einer Konzentration von 18 Gew.%
bezogen auf die Pigmentmenge verwendet.
Eine weitere Pigmentdispersion erhält man durch Mahlen von Eisenoxidpigment PR 101.
Es werden 15 Gew.-% transparentes Eisenoxidpigment PR 101 und 3.75 Gew.-% eines
pigmentaffinen Bockcopolymers als Dispergiermittel in einer 25 Gew.-%igen Lösung eines
Phenyl-Methyl-Siliconharzes in einer Kugelmühle gemahlen. Das Lösungsmittel ist ein
Gemisch aus Xylol und Cyclohexanon (Verhältnis 5:1). Das Siliconharz ist ein reaktives
Phenyl-Methyl-Silicon, das thermisch vernetzt wird und dann bis zu Temperaturen von
500°C stabil ist.
Die Pigmentdispersionen werden filtriert, um Verunreinigungen und harte Agglomerate zu
entfernen und mit einer Siliconharzlösung gemischt. Das Silconharz ist ein reaktives Phenyl-Methyl-Silicon,
das thermisch vernetzt wird und dann bis zu Temperaturen von 500°C
stabil ist. Die zum Sprühbeschichten geeignete Mischung enthält 42 Gew.% Silicon, 2.2
Gew.% Dimethylperylimid-Pigment und 2.8 Gew.% Eisenoxidpigment PR 101.
Der Lampenkolben wird durch Sprühen mit der roten, pigmenthaltigen Siliconharzlösung
bedeckt. Das Lösungsmittel wird verdampft und das Siliconharz bei 250°C vernetzt. Man
erhält eine etwa 15 bis 20 µm dicke transparente rote Siliconharzbeschichtung, die einen
Farbpunkt aufweist, der den ECE und SAE Normen für rote Signallampen entspricht.A coating is obtained which has very good color point saturation in the red area and good light transmission if a mixture of the very suitable iron oxide pigment hematite with the organic red pigment dimethylperylimide PR179 is used.
A pigment dispersion of the organic red pigment dimethylperylimide PR 179 is obtained by grinding in a ball mill. For this purpose, 6% by weight of pigment is ground in a solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a dispersant until the pigment agglomerates are dispersed. A pigment-affine block copolymer in a concentration of 18% by weight, based on the amount of pigment, is used as the dispersant.
A further pigment dispersion is obtained by grinding iron oxide pigment PR 101. 15% by weight of transparent iron oxide pigment PR 101 and 3.75% by weight of a pigment-affine block copolymer are used as dispersants in a 25% by weight solution of a phenylmethyl silicone resin ground in a ball mill. The solvent is a mixture of xylene and cyclohexanone (ratio 5: 1). The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
The pigment dispersions are filtered to remove contaminants and hard agglomerates and mixed with a silicone resin solution. The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C. The mixture suitable for spray coating contains 42% by weight of silicone, 2.2% by weight of dimethylperylimide pigment and 2.8% by weight of iron oxide pigment PR 101.
The lamp bulb is sprayed with the red, pigment-containing silicone resin solution. The solvent is evaporated and the silicone resin crosslinked at 250 ° C. An approximately 15 to 20 μm thick transparent red silicone resin coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
Man erhält eine Beschichtung, die eine sehr gute Farbpunktsättigung im roten Bereich und
eine gute Lichttransmission aufweist, wenn ein Gemisch des sehr geeigneten transparenten
Eisenoxidpigments Hämatit PR101 mit dem Isoindolin-Gelbpigment PY139 verwendet
wird.
Es werden 15 Gew.-% transparentes Eisenoxidpigment PR 101 und 3.75 Gew.-% eines
pigmentaffinen Blockcopolymers als Dispergiermittel in einer 25 Gew.%igen Lösung eines
Phenyl-Methyl-Siliconharzes in einer Kugelmühle gemahlen. Das Lösungsmittel ist ein
Gemisch aus Xylol und Cyclohexanon (Verhältnis 5:1). Das Siliconharz ist ein reaktives
Phenyl-Methyl-Silicon, das thermisch vernetzt wird und dann bis zu Temperaturen von
500°C stabil ist.
Eine weitere Pigmentdispersion erhält man durch Mahlen von einem gelben Isoindolinpigment,
PY 139, in einer Kugelmühle. Dazu wird 6 Gew.-% Pigment in einem Lösungsmittelgemisch
aus Xylol und Cyclohexanon (Verhältnis 5:1) unter Zusatz eines Dispergiermittels
gemahlen bis die Pigmentagglomerate dispergiert sind. Als Dispergiermittel wird
ein pigmentaffines Blockcopolymer in einer Konzentration von 18 Gew.% bezogen auf die
Pigmentmenge verwendet.
Die Dispersionen werden filtriert und mit einer Siliconharzlösung gemischt. Das Siliconharz
ist ein reaktives Phenyl-Methyl-Silicon, das in einem Lösungsmittelgemisch aus Xylol
und Cyclohexanon (Verhältnis 5:1) gelöst ist. Die zum Sprühbeschichten geeignete
Mischung enthält 35 Gew.% Silicon, 2.8 Gew.% Eisenoxidpigment PR 101 und 1.6
Gew.% Isoindolin-Gelbpigment PY 139.
Der Lampenkolben wird durch Sprühen mit der pigmenthaltrigen Siliconharzlösung bedeckt.
Das Lösungsmittel wird verdampft und das Siliconharz bei 250°C vernetzt. Man
erhält eine transparente, amberfarbene Siliconharzschicht von etwa 15 µm Dicke, die der
ECE Norm für Signallampen entspricht.A coating is obtained which has very good color point saturation in the red area and good light transmission if a mixture of the very suitable transparent iron oxide pigment Hematite PR101 with the isoindoline yellow pigment PY139 is used.
15% by weight of transparent iron oxide pigment PR 101 and 3.75% by weight of a pigment-affine block copolymer as a dispersant are ground in a 25% by weight solution of a phenyl-methyl-silicone resin in a ball mill. The solvent is a mixture of xylene and cyclohexanone (ratio 5: 1). The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
Another pigment dispersion is obtained by grinding a yellow isoindoline pigment, PY 139, in a ball mill. For this purpose, 6% by weight of pigment is ground in a solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a dispersant until the pigment agglomerates have been dispersed. A pigment-affine block copolymer in a concentration of 18% by weight, based on the amount of pigment, is used as the dispersant.
The dispersions are filtered and mixed with a silicone resin solution. The silicone resin is a reactive phenyl-methyl silicone, which is dissolved in a solvent mixture of xylene and cyclohexanone (ratio 5: 1). The mixture suitable for spray coating contains 35% by weight of silicone, 2.8% by weight of iron oxide pigment PR 101 and 1.6% by weight of isoindoline yellow pigment PY 139.
The lamp bulb is spray-coated with the pigment-containing silicone resin solution. The solvent is evaporated and the silicone resin crosslinked at 250 ° C. A transparent, amber-colored silicone resin layer approximately 15 µm thick is obtained, which corresponds to the ECE standard for signal lamps.
Man erhält eine Beschichtung, die eine sehr gute Farbpunktsattigung im amberfarbenen
Farbbereich und eine gute Lichuransmission aufweist bei Verwendung des organischen
Isoindolin-Gelbpigments PY185.
Das gelbe Isoindolinpigments PY185 wird in einem Lösungsmittelgemisch unter Zusatz
eines pigmentaffinen Blockcopolymers als Dispergiermittel gemahlen. Die Mahlung erfolgt
nach der in Ausführungsbeispiel 2 angegebenen Methode für das Dimethylperylimid-Pigment.
Die gelbe Pigmentdispersion und eine 50 Gew.%ige Siliconharzlösung werden in
einem Verhältnis gemischt, dass die Konzentration an gelbem Isoindolinpigment 2.9
Gew.% und an Silicon 33 Gew.% beträgt. Das Siliconharz ist ein reaktives Phenyl-Methyl-Silicon,
das thermisch vernetzt wird und dann bis zu Temperaturen von 500°C stabil ist. A coating is obtained which has very good color saturation in the amber color range and good Lichuransmission when using the organic isoindoline yellow pigment PY185.
The yellow isoindoline pigment PY185 is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method given in Example 2 for the dimethylperylimide pigment. The yellow pigment dispersion and a 50% by weight silicone resin solution are mixed in a ratio such that the concentration of yellow isoindoline pigment is 2.9% by weight and that of silicone 33% by weight. The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
Der Lampenkolben wird durch Sprühen mit der gelben, pigmenthaltigen Siliconharzlösung bedeckt. Das Lösungsmittel wird verdampft und das Siliconharz bei 250°C vernetzt. Man erhält eine etwa 20 µm dicke transparente gelbe Beschichtung, die einen Farbpunkt aufweist, der den ECE und SAE Normen für amberfarbene Signallampen entspricht.The lamp bulb is sprayed with the yellow, pigment-containing silicone resin solution covered. The solvent is evaporated and the silicone resin crosslinked at 250 ° C. An approximately 20 μm thick transparent yellow coating is obtained which has a color point which complies with the ECE and SAE standards for amber-colored signal lamps.
Man erhält eine Beschichtung, die eine sehr gute Farbpunktsättigung im roten Farbbereich
und eine gute Lichttransmission aufweist bei Verwendung des Rotpigments Dichlorodiketopyrrolo-pyrrol
PR254.
Das rote Pigment Dichloro-diketopyrrolo-pyrrol (PR254) wird in einem Lösungsmittelgemisch
unter Zusatz eines pigmentaffinen Blockcopolymers als Dispergiermittel gemahlen.
Die Mahlung erfolgt nach der in Ausführungsbeispiel 5 angegebenen Methode. Die
rote Pigmentdispersion und eine 50 Gew.%ige Siliconharzlösung werden in einem Verhältnis
gemischt, dass die Konzentration an rotem Dichloro-diketopyrrolo-pyrrol- Pigment 2.9
Gew.% und an Silicon 33 Gew.% beträgt. Das Siliconharz ist ein reaktives Phenyl-Methyl-Silicon,
das thermisch vernetzt wird und dann bis zu Temperaturen von 500°C stabil ist.
Der Lampenkolben wird durch Sprühen mit der roten, pigmenthaltigen Siliconharzlösung
bedeckt. Das Lösungsmittel wird verdampft und das Siliconharz bei 250°C vernetzt. Man
erhält eine etwa 15 bis 20 µm dicke transparente rote Beschichtung, die einen Farbpunkt
aufweist, der den ECE und SAE Normen für rote Signallampen entspricht.A coating is obtained which has very good color point saturation in the red color range and good light transmission when using the red pigment dichlorodiketopyrrolo-pyrrole PR254.
The red pigment dichloro-diketopyrrolo-pyrrole (PR254) is ground in a solvent mixture with the addition of a pigment-affine block copolymer as a dispersant. The grinding is carried out according to the method specified in Example 5. The red pigment dispersion and a 50% by weight silicone resin solution are mixed in a ratio such that the concentration of red dichloro-diketopyrrolo-pyrrole pigment is 2.9% by weight and that of silicone is 33% by weight. The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C. The lamp bulb is sprayed with the red, pigment-containing silicone resin solution. The solvent is evaporated and the silicone resin crosslinked at 250 ° C. An approximately 15 to 20 µm thick transparent red coating is obtained, which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
Man erhält eine Beschichtung, die eine sehr gute Farbpunktsättigung im roten Bereich und
eine gute Lichttransmission aufweist, wenn ein Gemisch des sehr geeigneten Eisenoxidpigments
Hämatit PR101 mit dem organischen Rotpigment Tetrachloro-thioindigo PR88
verwendet wird.
Eine Pigmentdispersion des organischen Rotpigments Tetrachloro-thioindigo PR88 erhält
man durch Mahlen in einer Kugelmühle. Dazu wird 8.5 Gew.-% Pigment in einem Lösungsmittelgemisch
aus Xylol und Cyclohexanon (Verhältnis 5:1) unter Zusatz eines
Dispergiermittels gemahlen bis die Pigmentagglomerate dispergiert sind. Als Dispergiermittel
wird ein pigmentaffines Blockcopolymer in einer Konzentration von 15 Gew.%
bezogen auf die Pigmentmenge verwendet.
Eine weitere Pigmentdispersion erhäit man durch Mahlen von Eisenoxidpigment PR 101.
Es werden 15 Gew.-% transparentes Eisenoxidpigment PR 101 und 3.75 Gew.-% eines
pigmentaffinen Bockcopolymers als Dispergiermttrel in einer 25 Gew.%igen Lösung eines
Phenyl-Methyl-Siliconharzes in einer Kugelmühle gemahlen. Das Lösungsmittel ist ein
Gemisch aus Xylol und Cyclohexanon (Verhältnis 5:1). Das Siliconharz ist ein reaktives
Phenyl-Methyl-Silicon, das thermisch vernetzt wird und dann bis zu Temperaturen von
500°C stabil ist.
Die Pigmentdispersionen werden filtriert, um Verunreinigungen und harte Agglomerate zu
entfernen und mit einer Siliconharzlösung gemischt. Das Siliconharz ist ein reaktives Phenyl-Methyl-Silicon
das thermisch vernetzt wird und dann bis zu Temperaturen von 500°C
stabil ist. Die zum Sprühbeschichten geeignete Mischung enthält 37 Gew.% Silicon, 3.2
Gew.% Tetrachloro-thioindigo PR88 und 2.8 Gew.% Eisenoxidpigment PR 101.
Der Lampenkolben wird durch Sprühen mit der roten, pigmenrhaltigen Siliconharzlösung
bedeckt. Das Lösungsmittel wird verdampft und das Siliconharz bei 250°C vernetzt. Man
erhält eine etwa 15 µm dicke transparente rote Beschichtung, die einen Farbpunkt aufweist,
der den ECE und SAE Normen für rote Signallampen entspricht.A coating is obtained which has very good color point saturation in the red area and good light transmission when a mixture of the very suitable iron oxide pigment Hematite PR101 with the organic red pigment tetrachlorothioindigo PR88 is used.
A pigment dispersion of the organic red pigment tetrachlorothioindigo PR88 is obtained by grinding in a ball mill. For this purpose, 8.5% by weight of pigment is ground in a solvent mixture of xylene and cyclohexanone (ratio 5: 1) with the addition of a dispersant until the pigment agglomerates are dispersed. A pigment-affine block copolymer in a concentration of 15% by weight, based on the amount of pigment, is used as the dispersant.
A further pigment dispersion is obtained by grinding iron oxide pigment PR 101. 15% by weight of transparent iron oxide pigment PR 101 and 3.75% by weight of a pigment-affine block copolymer are used as dispersing agents in a 25% by weight solution of a phenyl-methyl-silicone resin in one Ball mill ground. The solvent is a mixture of xylene and cyclohexanone (ratio 5: 1). The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C.
The pigment dispersions are filtered to remove contaminants and hard agglomerates and mixed with a silicone resin solution. The silicone resin is a reactive phenyl-methyl silicone that is thermally cross-linked and then stable up to temperatures of 500 ° C. The mixture suitable for spray coating contains 37% by weight of silicone, 3.2% by weight of tetrachlorothioindigo PR88 and 2.8% by weight of iron oxide pigment PR 101.
The lamp bulb is sprayed with the red, pig-containing silicone resin solution. The solvent is evaporated and the silicone resin crosslinked at 250 ° C. An approximately 15 µm thick transparent red coating is obtained which has a color point which corresponds to the ECE and SAE standards for red signal lamps.
Claims (7)
dadurch gekennzeichnet,
daß die erste pigmenthaltige Schicht zusätzlich ein Eisenoxidpigment enthält.Colored lamp according to claim 1,
characterized,
that the first pigment-containing layer additionally contains an iron oxide pigment.
dadurch gekennzeichnet,
daß die erste pigmenthaltige Schicht ein Eisenoxidpigment und eine Silicium-Sauerstoff-Verbindung enthält.Colored lamp according to claim 1,
characterized,
that the first pigment-containing layer contains an iron oxide pigment and a silicon-oxygen compound.
dadurch gekennzeichnet,
daß zwischen dem Kolben und der ersten pigmenthaltigen Schicht eine zweite pigmenthaltige Schicht angeordnet ist, die ein Eisenoxidpigment enthält.Colored lamp according to claim 1,
characterized,
that a second pigment-containing layer is arranged between the piston and the first pigment-containing layer, which contains an iron oxide pigment.
dadurch gekennzeichnet,
daß zwischen dem Kolben und der ersten pigmenthaltigen Schicht eine transparente Schicht, die eine Silicium-Sauerstoff-Verbindung enthält, angeordnet ist. Colored lamp according to claim 1,
characterized,
that a transparent layer containing a silicon-oxygen compound is arranged between the piston and the first pigment-containing layer.
dadurch gekennzeichnet,
daß die Lampe eine transparente Deckschicht, die eine Silicium-Sauerstoff-Verbindung enthält, hat.Colored lamp according to claim 1,
characterized,
that the lamp has a transparent cover layer containing a silicon-oxygen compound.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19938700A DE19938700A1 (en) | 1999-08-14 | 1999-08-14 | Colored lamp with pigment-coated lamp |
DE19938700 | 1999-08-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1077471A1 true EP1077471A1 (en) | 2001-02-21 |
Family
ID=7918489
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00202907A Withdrawn EP1077471A1 (en) | 1999-08-14 | 2000-08-07 | Coloured light emitting device with a lamp coated with a pigmented layer |
Country Status (6)
Country | Link |
---|---|
US (1) | US6520664B1 (en) |
EP (1) | EP1077471A1 (en) |
JP (1) | JP2001101996A (en) |
KR (1) | KR20010021280A (en) |
CN (1) | CN1288250A (en) |
DE (1) | DE19938700A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1119020A2 (en) * | 2000-01-18 | 2001-07-25 | Philips Patentverwaltung GmbH | Warm colour fluorescent lamp |
EP1125998A2 (en) * | 2000-02-18 | 2001-08-22 | Ichikoh Industries Limited | Coloring coating agent and colored bulb |
WO2004044486A2 (en) * | 2002-11-14 | 2004-05-27 | Koninklijke Philips Electronics N.V. | Light-transmitting substrate provided with a light-absorbing coating |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003346516A (en) * | 2002-05-30 | 2003-12-05 | Koito Mfg Co Ltd | Vehicle lamp |
US20050024874A1 (en) * | 2003-07-28 | 2005-02-03 | Yu-Peng Liu | Decorative bulbs |
US7345414B1 (en) * | 2006-10-04 | 2008-03-18 | General Electric Company | Lamp for night vision system |
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JPS52135582A (en) * | 1976-05-06 | 1977-11-12 | Matsushita Electronics Corp | Red lamp |
JPS6067545A (en) * | 1983-09-26 | 1985-04-17 | Dainichi Seika Kogyo Kk | Manufacture of decorative material |
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US5143443A (en) * | 1990-08-31 | 1992-09-01 | Integrated Systems Engineering, Inc. | Light permeable, color adding, self-securing stressed covers for large display light-emitting devices, and methods |
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JPH09124976A (en) * | 1995-10-27 | 1997-05-13 | Koito Mfg Co Ltd | Coloring coating agent for turn signal lamp and turn signal lamp |
JPH09320545A (en) * | 1996-05-30 | 1997-12-12 | Toshiba Lighting & Technol Corp | Color lamp and display device |
WO1999016847A1 (en) * | 1997-09-29 | 1999-04-08 | Minnesota Mining And Manufacturing Company | Fluorescent dye blends |
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DE2908890A1 (en) * | 1979-03-07 | 1980-09-18 | Patra Patent Treuhand | MERCURY VAPOR LOW PRESSURE DISCHARGE LAMP |
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-
1999
- 1999-08-14 DE DE19938700A patent/DE19938700A1/en not_active Withdrawn
-
2000
- 2000-08-07 EP EP00202907A patent/EP1077471A1/en not_active Withdrawn
- 2000-08-11 KR KR1020000046660A patent/KR20010021280A/en not_active Application Discontinuation
- 2000-08-11 JP JP2000243630A patent/JP2001101996A/en active Pending
- 2000-08-11 CN CN00130600A patent/CN1288250A/en active Pending
- 2000-08-14 US US09/638,552 patent/US6520664B1/en not_active Expired - Fee Related
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JPS52135582A (en) * | 1976-05-06 | 1977-11-12 | Matsushita Electronics Corp | Red lamp |
JPS6067545A (en) * | 1983-09-26 | 1985-04-17 | Dainichi Seika Kogyo Kk | Manufacture of decorative material |
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US5143443A (en) * | 1990-08-31 | 1992-09-01 | Integrated Systems Engineering, Inc. | Light permeable, color adding, self-securing stressed covers for large display light-emitting devices, and methods |
WO1997012000A1 (en) * | 1995-09-29 | 1997-04-03 | Minnesota Mining And Manufacturing Company | Fluorescent dye blends |
JPH09124976A (en) * | 1995-10-27 | 1997-05-13 | Koito Mfg Co Ltd | Coloring coating agent for turn signal lamp and turn signal lamp |
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DATABASE WPI Section Ch Week 197751, Derwent World Patents Index; Class L03, AN 1977-91329Y, XP002155005 * |
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PATENT ABSTRACTS OF JAPAN vol. 1998, no. 04 31 March 1998 (1998-03-31) * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1119020A2 (en) * | 2000-01-18 | 2001-07-25 | Philips Patentverwaltung GmbH | Warm colour fluorescent lamp |
EP1119020A3 (en) * | 2000-01-18 | 2003-02-12 | Philips Corporate Intellectual Property GmbH | Warm colour fluorescent lamp |
EP1125998A2 (en) * | 2000-02-18 | 2001-08-22 | Ichikoh Industries Limited | Coloring coating agent and colored bulb |
EP1125998A3 (en) * | 2000-02-18 | 2002-07-03 | Ichikoh Industries Limited | Coloring coating agent and colored bulb |
WO2004044486A2 (en) * | 2002-11-14 | 2004-05-27 | Koninklijke Philips Electronics N.V. | Light-transmitting substrate provided with a light-absorbing coating |
WO2004044486A3 (en) * | 2002-11-14 | 2004-07-29 | Koninkl Philips Electronics Nv | Light-transmitting substrate provided with a light-absorbing coating |
Also Published As
Publication number | Publication date |
---|---|
DE19938700A1 (en) | 2001-05-23 |
KR20010021280A (en) | 2001-03-15 |
CN1288250A (en) | 2001-03-21 |
JP2001101996A (en) | 2001-04-13 |
US6520664B1 (en) | 2003-02-18 |
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