ES2278008T3 - Composiciones que pueden marcarse por laser y procedimiento de formacion de imagenes por laser. - Google Patents
Composiciones que pueden marcarse por laser y procedimiento de formacion de imagenes por laser. Download PDFInfo
- Publication number
- ES2278008T3 ES2278008T3 ES02706945T ES02706945T ES2278008T3 ES 2278008 T3 ES2278008 T3 ES 2278008T3 ES 02706945 T ES02706945 T ES 02706945T ES 02706945 T ES02706945 T ES 02706945T ES 2278008 T3 ES2278008 T3 ES 2278008T3
- Authority
- ES
- Spain
- Prior art keywords
- laser
- binder
- aom
- substrate
- ammonium octamolybdate
- 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.)
- Expired - Lifetime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- 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
- B05D5/065—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 having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
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- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
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- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/267—Marking of plastic artifacts, e.g. with laser
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
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Abstract
Laca de revestimiento o tinta de impresión transparente, teñida o pigmentada que comprende un aglutinante y octamolibdato de amonio.
Description
Composiciones que pueden marcarse por láser y
procedimiento de formación de imágenes por láser.
La presente invención se refiere a composiciones
que pueden marcarse por láser y procedimientos de formación de
imágenes por láser.
Se han realizado varias propuestas, con el fin
de conseguir una impresión eficaz sobre un sustrato, provocando un
cambio de color en el sustrato sobre el que va a aparecer la
impresión. Se han propuesto varios pigmentos, que pueden utilizarse
para marcar un sustrato en la aplicación de energía láser. Algunas
de estas propuestas pueden encontrarse, por ejemplo, en los
documentos WO-A-00/43456,
JP-A-11001065,
EP-A-0522370,
EP-A-0797511,
US-A-5053440,
US-A-5350792 (una composición de
moldeo de plásticos que comprende un polioximetileno y carbón
animal), US-A-5928780,
US-A-6017972 y
US-A-6019831. Los documentos
US-A-5489639 y
US-A-5884079 dan a conocer que el
hidroxifosfato de cobre es un material que puede marcarse por
láser.
El octamolibdato de amonio, que presenta la
formula (NH_{4})_{4}Mo_{8}O_{26} y que se abrevia en
la presente memoria como AOM, es un material fácilmente disponible
que presenta propiedades ignífugas. Para este propósito, se ha
formulado con polímeros tal como poli(cloruro de vinilo)
(PVC). Por ejemplo, los cables que contienen PVC pueden contener
AOM como un agente supresor del humo.
Se ha encontrado que el AOM en combinación con
aglutinantes de polímero absorbe a la longitud de onda de la luz de
láser de CO_{2} (10.600 nm) y experimenta un cambio de color
debido a un cambio en el estado de oxidación, pero no se ve
afectado por la luz ultravioleta (utilizada comúnmente para el
curado de polímeros) o por las temperaturas, normalmente de
alrededor de 200-300ºC, utilizadas en la extrusión.
Así, el AOM es realmente selectivo para láser, y proporciona un
material muy adecuado para utilizarse en tintas previstas para
aplicarse a superficies que puede requerirse que se sometan a un
tratamiento térmico o para la incorporación en extrusiones de
polímeros, y se marcan mediante la aplicación de luz láser.
Según un aspecto de la presente invención, una
laca de revestimiento o tinta de impresión transparente, teñida o
pigmentada comprende un aglutinante y AOM. Otro aspecto de la
presente invención es una formulación adhesiva que comprende un
aglutinante y AOM.
Aún otro aspecto de la invención es un
procedimiento para proporcionar una imagen sobre un sustrato, que
comprende aplicar al sustrato de una composición que puede marcarse
por láser que comprende un aglutinante y AOM, seguido por una
irradiación cómo una imagen con un láser, mediante el cual el AOM
experimenta un cambio de color.
Un aspecto adicional de la presente invención,
para proporcionar una imagen sobre un sustrato, comprende extruir
en fundido una composición que comprende un aglutinante y AOM,
seguido de una irradiación como una imagen con un láser, mediante
el cual AOM experimenta un cambio de color.
El AOM es adecuado para su utilización en esta
invención porque está fácilmente disponible, y es selectivo para un
láser de CO_{2} robusto y de baja potencia que funciona a
aproximadamente 10.600 nm.
Una formulación de tinta que puede utilizarse en
la invención puede presentar base acuosa, base de disolvente, o
curable por UV, y puede ser una disolución o una dispersión. La
formulación puede incluir un componente que puede cargarse, para su
utilización en una impresora de chorro de tinta.
El aglutinante y el AOM se mezclan íntimamente
con el disolvente que puede seleccionarse de aquellos que se
utilizan normalmente para tintas y lacas, por ejemplo, agua, etanol,
acetato de etilo, alcohol isopropílico, hidrocarburos, etc. Los
componentes pueden estar presentes en disolución y/o dispersión. La
cantidad de AOM en la tinta es normalmente del 1% al 90% en peso.
El aglutinante es normalmente polimérico, y puede seleccionarse de
polímeros comercialmente disponibles incluyendo acrílicos,
celulosas, PVOH, poliésteres, etc. El aglutinante incluye
preferentemente un grupo lábil tal como hidroxilo, acetoxilo, éter
acetal o halógeno, y éste presenta la función de experimentar una
reacción de eliminación, para dar una entidad formadora de color
(véase también el documento WO 02/068205).
El AOM puede incorporarse en varios sistemas de
polímeros y molerse, utilizando un molino de bolas, hasta un tamaño
de partícula deseado, sin ninguna dificultad técnica. Ejemplos de
sistemas de polímeros en los que el AOM se ha incorporado
satisfactoriamente y se ha molido incluyen disolución de
nitrocelulosa en alcohol/acetato de etilo, disolución de acetato
propionato de celulosa en alcohol/acetato de etilo, disolución de
polivinilbutiral en alcohol/acetato de etilo, resina de poliuretano
con base de disolvente, resina epoxídica con base de disolvente,
resina de poliéster con base de disolvente, resina acrílica con base
acuosa, resina de poliéster con base acuosa, resina de poliuretano
con base acuosa, monómeros y oligómeros curables con luz
ultravioleta sin disolvente, poliamidas con base de disolvente,
poliimidas con base de disolvente, poliamidas con base acuosa,
poliimidas con base acuosa, revestimientos y lacas de
epoxi/vinil/poliéster con base de disolvente, y resinas de
siloxano.
Pueden incorporarse pigmentos orgánicos e
inorgánicos a las tintas/revestimientos de AOM sin ningún efecto
adverso en la marcabilidad por láser de las tintas/revestimientos de
AOM. Además, las tintas/revestimientos de AOM que contienen los
pigmentos orgánicos e inorgánicos pueden molerse hasta el tamaño de
partícula deseado sin dificultad o efecto adverso en marcabilidad
por láser de las tintas/revestimientos de AOM.
El componente AOM puede incorporarse
alternativamente en fundido en polímeros extrudibles, o puede
incorporarse a formulaciones de monómeros curables por UV. Una
película o laminado de capas que incluye un componente que puede
marcarse por láser proporciona un producto a prueba de
falsificaciones. Polímetros extrudibles que pueden utilizarse en la
invención incluyen nylon, poliésteres, poliamida, policarbonato,
poliacrilato, polimetacrilato, polímeros de injerto de ABS
(acrilonitrilo butadieno estireno), poliolefinas tales como
polietileno o polipropileno, poliestireno, poli(cloruro de
vinilo), polioximetileno, poliimida, poliéteres y polietercetonas
elastómeros termoplásticos, poliuretano termoplástico que pueden
utilizarse individualmente o como una mezcla de varios polímeros,
son adecuados como matriz polimérica. La cantidad de AOM que se
incorpora es normalmente del 0,1% al 5% en peso del extrudido.
El AOM o análogo del mimo suele ser selectivo
por láser, lo que quiere decir que absorbe energía a una longitud
de onda, por ejemplo, de \sim1.064 nm o \sim10.600 nm, para las
que puede elegirse un láser en consecuencia, de tal manera que
experimenta un cambio de color. Normalmente, el cambio de color
puede ser el resultado de un cambio en el estado de valencia y/o a
la formación de productos no estequiométricos, aunque también puede
existir algo de reacción con el aglutinante. El láser que se utiliza
puede funcionar tanto en el modo de matriz de puntos pulsado como
el modo de trazado, de onda continua.
El sustrato puede ser un tablero, por ejemplo,
de cartón. El envoltorio que puede utilizarse en la invención puede
estar alternativamente en forma de película polimérica, tal como
propileno o polietileno, y que puede laminarse y utilizarse, por
ejemplo para envolver chocolate. Si se utiliza un material de
envoltura de múltiples capas, la invención puede aplicarse a
cualquier capa en la que la tinta esté presente.
Cualquier pigmento que se utiliza en la
invención puede ser convencional. Puede preferirse un pigmento
blanco, que proporciona no solo contraste con, por ejemplo, códigos
de barras negros, sino también opacidad. Pueden seleccionarse otros
colores, según se desee. Pigmentos típicos incluyen CaCO_{3}, ZnO,
TiO_{2} y talco.
Una formulación de la invención también puede
incluir componentes convencionales que están presentes con el fin
de proporcionar la imagen. Normalmente, incluyen un material que
absorbe la luz láser incidente; este material puede cambiar de
color por si mismo con la absorción, o puede reaccionar con otro
material para proporcionar un cambio de color. Reactivos típicos
incluyen fenoles, resinas fenólicas, ácidos carboxílicos junto con
un formador de color, por ejemplo, lactona violeta cristal. Agentes
de absorción típicos incluyen arcillas, micas, TiO_{2},
carbonatos, óxidos, talco, silicatos y alumnosilicatos.
Para que la invención pueda entenderse más
fácilmente, se hace referencia a los siguientes ejemplos, que
pretenden ilustrar la invención, pero no limitar su alcance.
Ejemplos de 1 a
7
Se formularon tintas con base de disolvente,
acuosa y de curado por UV con octamolibdato de amonio (OAM). Se
fabricaron lacas en las proporciones que se muestran, que se
aplicaron como revestimiento sobre cartón y se secaron. Después se
marcaron utilizando un láser de CO_{2} de barrido, con un diámetro
de haz de 0,3 mm y una velocidad de barrido de 1.000
mm\cdots^{-1}. Las cantidades utilizadas, y los resultados se
muestran en la tabla 1.
Se combinaron 197 g de homopolímero de
polipropileno con 3 g de una mezcla 4:1 de AOM:Iriodin 805,
mezclándolos bien con un Optiblender 2000 (Moulinex). Se preparó la
combinación y se granuló en una prensa extrusora FOS axon 11502 a
temperaturas de 190ºC, 200ºC, 210ºC, 220ºC y 225ºC en las cinco
zonas respectivas. El polímero moldeado pudo marcarse con un láser
de CO_{2}.
Ejemplos 9 y
10
Se siguió el procedimiento del ejemplo 8, pero
utilizando HDPE (polietileno de alta densidad) y HIPS (poliestireno
de alto impacto), respectivamente. Los polímeros moldeados pudieron
marcarse satisfactoriamente con láser de Nd-YAG y
CO_{2}, respectivamente.
Se formuló una laca, que comprende:
Poli(cloruro de vinilo) | 30% |
Octamolibdato de amonio | 15% |
Alcohol etílico | resto |
Se aplicó como revestimiento sobre una lámina de
aluminio, utilizando una barra Mayer, y se secó. Entonces se expuso
el revestimiento semiopaco a un haz de láser de CO_{2} de 0,3 mm
de diámetro, que barría a 1.000 mm/segundo con una potencia de
salida de 3 W, para producir una imagen negra.
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Claims (10)
1. Laca de revestimiento o tinta de impresión
transparente, teñida o pigmentada que comprende un aglutinante y
octamolibdato de amonio.
2. Formulación adhesiva que comprende un
aglutinante y octamolibdato de amonio.
3. Producto según la reivindicación 1, en el
que el aglutinante comprende un grupo lábil.
4. Producto según cualquiera de las
reivindicaciones anteriores, en el que el aglutinante es un
polímero.
5. Producto según cualquiera de las
reivindicaciones anteriores, que comprende asimismo un pigmento
blanco.
6. Producto según la reivindicación 5, en el
que el pigmento es CaCO_{3}, ZnO, TiO_{2} o talco.
7. Procedimiento para proporcionar una imagen
sobre un sustrato, que comprende aplicar al sustrato una
composición que puede marcarse por láser que comprende un
aglutinante y octamolibdato de amonio, seguido de irradiación como
una imagen con un láser, experimentando el octamolibdato de amonio
un cambio de color.
8. Procedimiento según la reivindicación 7,
en el que la composición es una tinta o laca según la reivindicación
1.
9. Procedimiento según la reivindicación 7,
en el que la composición se aplica mediante colada de disolvente,
para formar una película sobre el sustrato.
10. Procedimiento para proporcionar una imagen
sobre un sustrato, que comprende extruir en fundido una composición
que comprende un aglutinante y octamolibdato de amonio, seguido de
una irradiación como una imagen con un láser, experimentando el
octamolibdato de amonio un cambio de color.
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GB0108360 | 2001-04-03 | ||
GB0108360A GB0108360D0 (en) | 2001-04-03 | 2001-04-03 | Laser printing on packaging |
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Publication Number | Publication Date |
---|---|
ES2278008T3 true ES2278008T3 (es) | 2007-08-01 |
ES2278008T5 ES2278008T5 (es) | 2011-11-18 |
Family
ID=26245843
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ES02706945T Expired - Lifetime ES2278008T5 (es) | 2001-03-16 | 2002-03-18 | Composiciones que pueden marcarse por láser y procedimiento de formación de imágenes por láser. |
ES06000946.1T Active ES2327662T7 (es) | 2001-03-16 | 2002-03-18 | Procedimiento de obtención de imágenes por láser |
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Application Number | Title | Priority Date | Filing Date |
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ES06000946.1T Active ES2327662T7 (es) | 2001-03-16 | 2002-03-18 | Procedimiento de obtención de imágenes por láser |
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US (3) | US7485403B2 (es) |
EP (2) | EP1657072B3 (es) |
JP (2) | JP3913680B2 (es) |
AT (2) | ATE435123T1 (es) |
AU (1) | AU2002241108A1 (es) |
CY (1) | CY1106395T1 (es) |
DE (2) | DE60232829D1 (es) |
DK (2) | DK1657072T6 (es) |
ES (2) | ES2278008T5 (es) |
PT (1) | PT1368200E (es) |
WO (1) | WO2002074548A2 (es) |
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EP2121821B1 (en) * | 2006-12-19 | 2013-11-13 | Siltech Limited | Improvements relating to laser marking |
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- 2002-03-18 AT AT06000946T patent/ATE435123T1/de not_active IP Right Cessation
- 2002-03-18 AT AT02706945T patent/ATE348712T1/de not_active IP Right Cessation
- 2002-03-18 DK DK02706945.9T patent/DK1368200T4/da active
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2006
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