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EP0298604A2 - Dekorative Gegenstände mit Mehrfarbeffekten - Google Patents

Dekorative Gegenstände mit Mehrfarbeffekten Download PDF

Info

Publication number
EP0298604A2
EP0298604A2 EP88305170A EP88305170A EP0298604A2 EP 0298604 A2 EP0298604 A2 EP 0298604A2 EP 88305170 A EP88305170 A EP 88305170A EP 88305170 A EP88305170 A EP 88305170A EP 0298604 A2 EP0298604 A2 EP 0298604A2
Authority
EP
European Patent Office
Prior art keywords
color
pigment
absorption
interference
colorant
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.)
Granted
Application number
EP88305170A
Other languages
English (en)
French (fr)
Other versions
EP0298604A3 (en
EP0298604B1 (de
Inventor
Louis Armanini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Catalysts LLC
Original Assignee
Mearl Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22092636&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0298604(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Mearl Corp filed Critical Mearl Corp
Publication of EP0298604A2 publication Critical patent/EP0298604A2/de
Publication of EP0298604A3 publication Critical patent/EP0298604A3/en
Application granted granted Critical
Publication of EP0298604B1 publication Critical patent/EP0298604B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects

Definitions

  • interference pigments are an outgrowth of nacreous pigments, that is, pigments which simulate the effect of natural pearls.
  • the pigments are composed of thin platelets which are transparent in the visible region of the spectrum. The platelets are very smooth and part of the light which strikes the platelets is reflected and part is transmitted through the platelet. That part of the light which is trans­mitted is subsequently reflected by other layers of platelets. The result is that there are multiple re­flections from many layers and it is this which gives rise to a depth of sheen since the eye cannot focus on one particular layer.
  • the reflection which takes place is specular in that the angle of incidence equals the angle of reflection.
  • the amount of light reflected at non-­specular angles is small and the amount of light re­flected diminishes very quickly as the specular angle is passed.
  • the result is that nacreous pigments are extremely sensitive to the angle of viewing.
  • the platelets In order for the maximum amount of light to be reflected, the platelets must be extremely smooth. Any surface rough­ness causes light to be scattered in a non-specular manner and diminishes the lustrous effect.
  • the platelets must be aligned parallel to each other and to the substrate for maximum reflectivity. If not so aligned, light will be re­flected randomly and again, luster will diminish. The amount of light which is reflected depends on the index of refraction of the platelets. The greater the index of refraction, the greater the amount of light reflect­ed. Since in most cases, the platelets are imbedded in film forming mediums which have an index of refraction of approximately 1.5, it is necessary that the index of refraction of the platelets be considerably greater than 1.5.
  • the layers of reflecting material are composed of calcium carbon­ate interspersed between layers of an organic material.
  • Synthetic nacreous pigments have been made by growing crystals of basic lead carbonate and bismuth oxy­chloride. Both of these substances can be grown into crystals which are extremely smooth and flat.
  • titanium dioxide which per se has not been grown into flat crystals has been coated on thin smooth platelets of mica which act as a carrier.
  • the mica platelets are ideally from 5 to 50 microns in length.
  • the coatings of titanium dioxide which are applied generally range from 60 nanometers to 160 nanometers in thickness.
  • titanium dioxide can be used as the coating on mica. These include ZrO2, SnO2, ZnO, Fe2O3, Cr2O3, V2O5 and the hydrous forms thereof.
  • the oxides can be present in various crystal­line forms.
  • TiO2 can be anatase or rutile or mixtures of the two.
  • Combinations of oxides of two or more metals can be used as can their different crys­talline forms.
  • Interference pigments if composed of the correct thickness, can reflect any color of the visible spectrum. These colors can range from a yellow to a red to a blue and a green. Shadings between these are also possible. Because the reflected colors are pro­duced by an interference effect, the complementary colors are produced by transmission. Thus if a red color is produced by reflection from an interference pigment, a green color will be seen if the pigment is viewed in transmission.
  • interference pigments are incorporated into film formers and coated on white backgrounds, then two colors can be seen depending on the angle of view­ing. At near specular angles, the reflected color can be observed. At other angles, the transmission color can be observed.
  • absorption pigments In order to enhance the reflection color, absorption pigments have been added to interference pigments. In most cases, the absorption pigments have been precipitated onto the interference pigments so that they form an integral part of the platelets. Thus, for example, if Fe2O3 which has a yellow to red color depending on its particle size is precipitated upon a yellow interference color, an enhancement of the yellow color will be produced. The yellow of the Fe2O3 adds to the yellow of the interference color producing a rich lustrous yellow color. Those pigments which have an absorption pigment added to an interference pigment resulting in enhanced color intensity are called combination pigments.
  • a colored oxide is used for the coating on mica, that color will combine with the added colorant and will modify the final absorption color. If a col­orless oxide is used for the coating on mica, the ab­sorption color will not be modified.
  • the concentration of the absorption pigments is adjusted so that the color intensity produced is of the same order of magnitude as the interference colors. If the concentration of the colorants is too great, the absorption colorant will obscure the interference color and no enhancement will take place. In order for this enhancement to take place, the colorants are added at a concentration between about 2% and 5% in the case of TiO2 coated mica pigments, based upon the weight of titanium dioxide coated mica.
  • the absorption pigment of the same color as the interference color can be added but difversferent absorption colorants can be added to different interferences colors.
  • it is possi­ble to add a red absorption pigment (carmine) to a blue interference pigment.
  • the combination pigments When the combination pigments are dispersed in a film-forming medium and coated over a white back­ground, two distinct colors can be observed depending on the angle of viewing. At the normal angle of view­ing, the reflection color of the interference pigment is seen. At the diffuse angle or the grazing angle, the reflection color of the interference pigment is no longer observed and the color of the absorption pigment is now seen. Thus by changing the angle of viewing from the normal to a grazing angle, the color changes from the reflection color of the interference to the color of the absorption pigment. Very beautiful and esthetically pleasing color effects can be seen.
  • Combination pigments have been used in applications such as coating on white, grey or black substrates or incorporating them into formulations used for cosmetic applications such as eye shadow, etc. where such color changes would be desirable.
  • interference pigments made from titanium diox­ide coated mica were used as base substrates.
  • Four interference colors were used. They were yellow, red, blue and green.
  • the absorption pigments which were used were a yellow (Fe2O3), a red (carmine), a blue (iron blue) and a green (Cr2O3).
  • Each of the absorp­tion colorants was precipitated upon the interference pigments forming a total of 16 samples.
  • the concentra­tion of the colorants ranged between 2% and 5%. Other colorants may be used in place of the colorants speci­fied in these examples.
  • the combination pigments were incorporated at 3% concentration into a nitrocellulose lacquer having a solids content of 9.5%.
  • Films of the combination pigments dispersed in the nitrocellulose lacquer were formed on glass slides using a Bird Film Applicator. This formed a wet film of approximately 0.003 inch. The films were allowed to dry so that the platelets were aligned parallel to the film.
  • the dried films were viewed visually in daylight by observing the specular reflection color at normal incidence, by observing the color at a diffuse or grazing angle and finally by observing the color by transmission.
  • the observer stood with daylight at his back and the slide held so that the light struck the surface and was specularly reflected back to the ob­server.
  • the slide was held toward the light so that the light fell upon the sur­face at a grazing angle and then was reflected to the observer.
  • For transmission the slides were held to the light.
  • the colors which were observed were record­ed and the results of these observations are shown in Table I.
  • Table I For comparison, the observations made on the interference pigments which contained no absorption pigments are also set forth. The combinations which exhibited the most distinct three-color effects are indicated by an asterisk.
  • the combination pigments which have been used in the Table to demonstrate third color effects had the absorption pigments precipitated directly on the sur­faces. Similar results can be achieved by dispersing the absorption colorants and the interference pigments separately in the film former. In this case, the ab­sorption colorant is dispersed throughout the film rather than being concentrated upon each platelet. Similar, though not exactly equivalent, results are produced. As can be expected, different concentrations of colorant will be needed and these can be easily determined by a few routine experiments.
  • any object which is transparent or semi-­transparent and which will allow some of the light to pass through and which can be coated with the combina­tion pigments or have them incorporated therein can be used.
  • a combination pigment of a yellow absorption colorant and a red interference pigment was dispersed in a water base acrylic polymer emulsion.
  • the disper­sion was made by taking 3.0 g of the combination pig­ment, adding approximately 3 g of the emulsion and stirring in thoroughly. Then 94 g of the emulsion was slowly added with stirring to form a 3% concentration of the combination pigment in the emulsion.
  • This pig­mented emulsion was then applied by brush to a clear transparent acrylic sheet, one quarter inch in thick­ness, and the emulsion allowed to dry. Small sections were then cut from this sheet. Each of the sections when viewed at the specular angle showed a red inter­ference color, a yellow color at the glancing angle and by transmission, a yellow-green color.
  • a combination pigment of a red absorption colorant on a blue interference pigment was dispersed in a clear thermosetting acrylic enamel (AT56 Rohm & Haas Co.) and diluted in a ratio of 2:1 with xylene.
  • the dispersion was made by taking 3.0 g of the combina­tion pigment and adding approximately 3 g of the thermosetting acrylic which was stirred in thoroughly. Then 94 g of the acrylic enamel was added with stir­ring.
  • the pigmented acrylic enamel was applied to a large transparent glass bowl approximately 24 inches in diameter.
  • the coating was applied using a conventional air spray gun. Two layers were applied. The coating was then cured in an oven at 120°C for 30 minutes. Viewing the bowl directly a blue reflection color was seen. The sides of the bowl displayed a red absorption color and the rear of the bowl where the transmission color could be seen displayed an orange color.
  • the colors blended one into the other and a pleasing artis­tic effect was produced which was a delight to the eye.
  • the components of the combination pigment of Example 2 were introduced separately into the acrylic lacquer of that example.
  • the red colorant was first dispersed followed by the blue interference pigment.
  • the color play in the coated bowl was similar to that seen in Example 2.
  • a combination pigment of a red absorption pigment on a yellow interference pigment was dispersed in a nitrocellulose lacquer.
  • the dispersion was made by mixing 3.0 g of the pigment with 3 g of a nitrocel­lulose lacquer having a solids content of 9.5%. After thorough mixing, an additional 94 g of the nitrocellu­lose lacquer was added with stirring. Films of the dispersed particles in the nitrocellulose lacquer were formed on glass slides by using a Bird Film Applicator. This formed a wet film of approximately 0.003 inch. The films were allowed to air dry. The glass slides were then cut into rectangular sections, 2 inches by 3 inches, and provision made so the slides could be hung by a wire or string.
  • a combination pigment of a blue colorant and green interference pigment was dispersed in a low den­sity polyethylene. 950 g of Tenite 1925F made by Eastman Chemicals was put into a Banbury Mixer. The plastic was mixed until melted. 50 g of the combina­tion pigment were then added slowly to the melted plas­tic and mixing was continued for 10 minutes. After the mixing cycle was complete, the pigmented plastic was dumped into a pan and taken immediately to a Boling Steward hot roll machine where the pigmented plastic was pressed between the 2 hot rolls to form a slab 1 ⁇ 4 to 1 ⁇ 2 inch in thickness and 10 inches wide. It was scored with a razor knife, allowed to cool, and broken into small pieces.
  • the combination pigments can be ap­plied to a substrate by methods which are known in the art.
  • the coating methods include brush, roll, knife, pressure-roll, engraving roll, dipping, air blade, air spray, electrostatic spray, airless spray, fluidized bed and other similar methods.
  • the pigmented plastics can also be molded by any of the known processes which include compression molding, injection molding, extru­sion, or blow molding. They may also be cast by vari­ous processes.
  • thermoplastics which can be used include cellulose acetate, cellulose acetate butyrate, poly­carbonate, polyethylene, polypropylene, polystyrene, and similar materials.
  • thermosetting plastics include epoxy resins, phenol-formaldehyde acrylic, polyesters, polystyrene, polyurethanes and similar products.

Landscapes

  • Cosmetics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Laminated Bodies (AREA)
  • Adornments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP88305170A 1987-07-06 1988-06-07 Dekorative Gegenstände mit Mehrfarbeffekten Expired - Lifetime EP0298604B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7002287A 1987-07-06 1987-07-06
US70022 1987-07-06

Publications (3)

Publication Number Publication Date
EP0298604A2 true EP0298604A2 (de) 1989-01-11
EP0298604A3 EP0298604A3 (en) 1990-10-10
EP0298604B1 EP0298604B1 (de) 1994-05-18

Family

ID=22092636

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88305170A Expired - Lifetime EP0298604B1 (de) 1987-07-06 1988-06-07 Dekorative Gegenstände mit Mehrfarbeffekten

Country Status (6)

Country Link
EP (1) EP0298604B1 (de)
JP (1) JPH0777840B2 (de)
AT (1) ATE105787T1 (de)
CA (1) CA1324241C (de)
DE (1) DE3889592T2 (de)
ES (1) ES2051849T3 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2249974A (en) * 1990-11-20 1992-05-27 Swintex Coloured material
EP1200250A1 (de) * 1999-06-14 2002-05-02 CPFilms, Inc. Lichstabile, gefärbte transparente verbundfilme
EP1047371B1 (de) * 1998-06-24 2006-03-29 Color Access, Inc. Kosmetische zusammensetzung für natürliches aussehen
US7064897B2 (en) * 2002-12-31 2006-06-20 3M Innovative Properties Company Optical polarizing films with designed color shifts
US20110118384A1 (en) * 2008-05-09 2011-05-19 Basf Se Pearlescent pigments coated with a metal oxide/hydroxide layer and an acrylic copolymer
KR102123940B1 (ko) * 2019-10-16 2020-06-17 이윤정 옻칠 스크린인쇄 및 자개를 이용한 장식패널 및 그 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087828A (en) * 1961-06-28 1963-04-30 Du Pont Nacreous pigment compositions
GB1141981A (en) * 1966-01-21 1969-02-05 Dow Chemical Co Iridescent bodies and coating compositions and composite structures comprising them
DE2313331A1 (de) * 1973-03-17 1974-09-19 Merck Patent Gmbh Eisenhaltige glimmerschuppenpigmente
EP0075755A2 (de) * 1981-09-23 1983-04-06 MERCK PATENT GmbH Perlglanzpigmente mit verbesserter Lichtechtheit, Verfahren zur Herstellung und Verwendung
EP0211351B1 (de) * 1985-08-07 1990-10-24 MERCK PATENT GmbH Eisenoxidbeschichtete Perlglanzpigmente

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087828A (en) * 1961-06-28 1963-04-30 Du Pont Nacreous pigment compositions
GB1141981A (en) * 1966-01-21 1969-02-05 Dow Chemical Co Iridescent bodies and coating compositions and composite structures comprising them
DE2313331A1 (de) * 1973-03-17 1974-09-19 Merck Patent Gmbh Eisenhaltige glimmerschuppenpigmente
EP0075755A2 (de) * 1981-09-23 1983-04-06 MERCK PATENT GmbH Perlglanzpigmente mit verbesserter Lichtechtheit, Verfahren zur Herstellung und Verwendung
EP0211351B1 (de) * 1985-08-07 1990-10-24 MERCK PATENT GmbH Eisenoxidbeschichtete Perlglanzpigmente

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2249974A (en) * 1990-11-20 1992-05-27 Swintex Coloured material
GB2249974B (en) * 1990-11-20 1994-10-12 Swintex Coloured material
EP1047371B1 (de) * 1998-06-24 2006-03-29 Color Access, Inc. Kosmetische zusammensetzung für natürliches aussehen
EP1200250A1 (de) * 1999-06-14 2002-05-02 CPFilms, Inc. Lichstabile, gefärbte transparente verbundfilme
EP1200250A4 (de) * 1999-06-14 2005-05-25 Cpfilms Inc Lichstabile, gefärbte transparente verbundfilme
US7229684B2 (en) 1999-06-14 2007-06-12 Cpfilms, Inc. Light-stable colored transparent composite films
US7064897B2 (en) * 2002-12-31 2006-06-20 3M Innovative Properties Company Optical polarizing films with designed color shifts
US7256936B2 (en) 2002-12-31 2007-08-14 3M Innovative Properties Company Optical polarizing films with designed color shifts
US7744987B2 (en) 2002-12-31 2010-06-29 3M Innovative Properties Company Optical polarizing films
US20110118384A1 (en) * 2008-05-09 2011-05-19 Basf Se Pearlescent pigments coated with a metal oxide/hydroxide layer and an acrylic copolymer
US8772371B2 (en) * 2008-05-09 2014-07-08 Basf Se Pearlescent pigments coated with a metal oxide/hydroxide layer and an acrylic copolymer
KR102123940B1 (ko) * 2019-10-16 2020-06-17 이윤정 옻칠 스크린인쇄 및 자개를 이용한 장식패널 및 그 제조방법

Also Published As

Publication number Publication date
JPS6424800A (en) 1989-01-26
EP0298604A3 (en) 1990-10-10
ES2051849T3 (es) 1994-07-01
JPH0777840B2 (ja) 1995-08-23
CA1324241C (en) 1993-11-16
ATE105787T1 (de) 1994-06-15
DE3889592T2 (de) 1994-09-01
EP0298604B1 (de) 1994-05-18
DE3889592D1 (de) 1994-06-23

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