PT1368200E - Composições marcáveis por laser e processo de formação de imagem por laser - Google Patents

Composições marcáveis por laser e processo de formação de imagem por laser Download PDF

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Publication number
PT1368200E
PT1368200E PT02706945T PT02706945T PT1368200E PT 1368200 E PT1368200 E PT 1368200E PT 02706945 T PT02706945 T PT 02706945T PT 02706945 T PT02706945 T PT 02706945T PT 1368200 E PT1368200 E PT 1368200E
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Portugal
Prior art keywords
laser
binder
aom
substrate
image
Prior art date
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PT02706945T
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English (en)
Inventor
Nazir Khan
Original Assignee
Datalase Ltd
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26245843&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=PT1368200(E) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from GBGB0106603.4A external-priority patent/GB0106603D0/en
Priority claimed from GB0108360A external-priority patent/GB0108360D0/en
Application filed by Datalase Ltd filed Critical Datalase Ltd
Publication of PT1368200E publication Critical patent/PT1368200E/pt

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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09D7/61—Additives non-macromolecular inorganic
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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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    • B05D5/00—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
    • 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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    • 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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    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
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    • C09D11/00—Inks
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    • C09D127/00—Coating compositions 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 a halogen; Coating compositions based on derivatives of such polymers
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    • C09D127/04—Coating compositions 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C09D129/00—Coating compositions 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; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
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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
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Description

ΕΡ 1 368 200 /PT
DESCRIÇÃO "Composições marcáveis por laser e processo de formação de imagem por laser"
Campo do invento
Este invento refere-se a composições marcáveis por laser e a processos de formação de imagem por laser.
Antecedentes do invento Têm sido feitas várias propostas de modo a conseguir uma impressão eficaz sobre um substrato, provocando uma modificação de cor no substrato sobre o qual a impressão vai aparecer. Têm sido propostos vários pigmentos, que podem ser utilizados para marcar um substrato sob aplicação de energia de laser. Algumas destas propostas podem ser encontradas em, por exemplo, WO-A-O0/43456, JP-A-11001065, EP-A-0522370, EP-A-0797511, US-A-5053440, US-A-5350792 (uma composição de molde de plásticos que compreende um polioximetileno e carvão animal), US-A-5928780, US-A-6017972 e US-A-6019831. Em US-A-5489639 e US-A-5884079 revela-se que o hidroxifosfato de cobre é um material marcável por laser. O octamolibdato de amónio, tendo a fórmula (ΝΗ4)4Μθ8θ26 e aqui abreviado para AOM, é um material facilmente disponível que possui propriedades retardadoras de fogo. Para este propósito tem sido formulado com polímeros tais como policloreto de vinilo (PVC). Por exemplo, cabos contendo PVC podem conter AOM como um agente supressor de fumo.
Sumário do invento
Verificou-se que o AOM em combinação com ligantes de polímero absorve no comprimento de onda da luz laser de C02 (10600 nm) e sofre uma modificação de cor devido a uma alteração no estado de oxidação, mas não é afectado por luz ultravioleta (utilizada normalmente para cura de polímeros) ou pelas temperaturas, tipicamente cerca de 200-300°C, utilizadas em extrusão. 0 AOM é assim eficazmente selectivo para o laser, e proporciona um material muito adequado para 2
ΕΡ 1 368 200 /PT utilização em tintas destinadas a aplicação em superfícies que podem ter de sofrer um tratamento térmico ou para incorporação em extrusões de polímero, e ser marcadas pela aplicação de luz laser.
De acordo com um aspecto do presente invento, uma tinta de impressão ou um verniz de revestimento transparente, corado ou pigmentado compreende um ligante e AOM. Outro aspecto do presente invento é uma formulação adesiva que compreende um ligante e AOM.
Ainda outro aspecto do invento é um processo para proporcionar uma imagem sobre um substrato, que compreende a aplicação ao substrato de uma composição marcável por laser que compreende um ligante e AOM, seguida por irradiação na forma de imagem com um laser, pelo que o AOM sofre uma modificação de cor.
Um aspecto adicional do presente invento para proporcionar uma imagem sobre um substrato, compreende a extrusão em fusão de uma composição que compreende um ligante e AOM, seguida de irradiação na forma de imagem com um laser, pelo que o AOM sofre uma modificação de cor.
Descrição das concretizações preferidas 0 AOM é adequado para utilização neste invento porque está prontamente disponível, e é selectivo para um laser de CO2 robusto e de baixa energia, operando a cerca de 10600 nm.
Uma formulação de tinta a ser utilizada no invento pode ser baseada em água, baseada em solvente, ou curável por UV, e pode ser uma solução ou dispersão. A formulação pode incluir um componente carregável, para utilização numa impressora de jacto de tinta. 0 ligante e o AOM são misturados intimamente com o solvente que pode ser seleccionado entre os habitualmente utilizados para tintas e vernizes, e.g. água, etanol, acetato de etilo, álcool isopropílico, hidrocarbonetos, etc. Os componentes podem estar presentes em solução e/ou dispersão. A quantidade de AOM na tinta é tipicamente de 1 to 90% em 3
ΕΡ 1 368 200 /PT peso. 0 ligante é tipicamente polimérico, e pode ser seleccionado de polímeros comercialmente disponíveis incluindo acrílicos, celuloses, PVOH, poliésteres, etc. O ligante preferivelmente inclui um grupo lábil tal como hidroxilo, acetoxi, acetal de éter ou halogéneo e este tem a função de sofrer uma reacção de eliminação, para originar uma entidade formadora de cor (ver também WO 02/068205) . O AOM pode ser incorporado em vários sistemas de polímeros e triturado, utilizando um moinho de esferas, até um tamanho de partícula desejado, sem qualquer dificuldade técnica. Exemplos de sistemas de polímeros em que o AOM tem sido incorporado e triturado com sucesso incluem solução de nitrocelulose em álcool/acetato de etilo, solução de acetatopropionato de celulose em álcool/acetato de etilo, solução de polivinilbutiral em álcool/acetato de etilo, resina de poliuretano baseada em solvente, resina de epóxido baseada em solvente, resina de poliéster baseada em solvente, resina acrílica baseada em água, resina de poliéster baseada em água, resina de poliuretano baseada em água, monómeros e oligómeros curáveis por luz ultravioleta sem solvente, poliamidas baseadas em solvente, poliimidas baseadas em solvente, poliamidas baseadas em água, poliimidas baseadas em água, revestimentos e vernizes de epoxi/vinil/poliéster baseados em solvente, e resinas de siloxano.
Podem ser incorporados pigmentos orgânicos e inorgânicos em tintas/revestimentos de AOM sem qualquer efeito adverso sobre a capacidade de marcação por laser das tintas/ revestimentos de AOM. Além disso, as tintas/revestimentos de AOM contendo os pigmentos orgânicos e inorgânicos podem ser trituradas até ao tamanho de partícula desejado sem dificuldade ou efeito adverso sobre a capacidade de marcação por laser das tintas/revestimentos de AOM. O componente AOM pode em alternativa ser incorporado fundido em polímeros extrudíveis, ou pode ser incorporado em formulações de monómero de cura por UV. Uma película ou laminado de camadas que inclui um componente marcável por laser proporciona um produto à prova de violação. Polímeros extrudíveis que podem ser utilizados no invento incluem nylon, poliésteres, poliamida, policarbonato, poliacrilato, 4
ΕΡ 1 368 200 /PT polimetacrilato, polímeros com enxerto de ABS, poliolefinas tais como polietileno ou polipropileno, poliestireno, policloreto de vinilo, polioximetileno, poliimida, poliéteres e poliétercetonas, elastómeros termoplásticos, poliuretano termoplástico que podem ser utilizados individualmente ou como uma mistura de vários polímeros, são adequados como matriz de polímero. A quantidade de AOM que é incorporada é tipicamente de 0,1 a 5% em peso do extrudado. O AOM ou seu análogo deve ser selectivo para o laser, pelo que se pretende afirmar que absorve energia a um comprimento de onda, e.g. de -1064 nm ou -10600 nm, para o qual pode ser escolhido um laser em conformidade, de modo que sofre uma modificação na cor. A modificação de cor será tipicamente o resultado de uma mudança no estado de valência e/ou a formação de produtos não estequiométricos, embora possa ocorrer também alguma reacção com o ligante. O laser que é utilizado pode operar num modo de matriz por pontos ou num modo de gravação em onda contínua. O substrato pode ser cartão, e.g. cartolina. A embalagem para utilização no invento pode, em alternativa, estar na forma de uma película polimérica, tal como polipropileno ou polietileno, e que pode ser laminado e utilizado, por exemplo, para embrulhar chocolate. Se é utilizado um material de embalagem em multi-camada, o invento é aplicável a qualquer camada em que a tinta esteja presente.
Qualquer pigmento que é utilizado no invento pode ser convencional. Pode ser preferido um pigmento branco, proporcionando não apenas contraste com, digamos, códigos de barras a negro mas também opacidade. Outras cores podem ser escolhidas, conforme desejado. Pigmentos típicos incluem CaC03, ZnO, TÍO2 e talco.
Uma formulação do invento também pode incluir componentes convencionais que estão presentes para proporcionar a imagem. Tipicamente, estes incluem um material que absorve luz laser incidente; este material pode ele próprio modificar a cor na absorção, ou pode reagir com outro material para proporcionar uma mudança de cor. Os reagentes típicos incluem fenóis, resinas fenólicas, ácidos carboxílicos juntamente com um formador de cor, e.g. lactona de violeta cristal. Os agentes de absorção típicos incluem argilas, micas, T1O2, carbonatos, 5
ΕΡ 1 368 200 /PT óxidos, talco, silicatos e aluminossilicatos.
Para que o invento possa ser mais facilmente entendido, é feita referência aos Exemplos seguintes, que se pretende serem ilustrativos do invento, mas não destinados a limitar o seu âmbito.
Exemplos 1 a 7
Foram formuladas com octamolibdato de amónio (AOM) tintas baseadas em solvente, baseadas em água e curáveis por UV. Foram produzidos vernizes nas proporções mostradas, aplicados como revestimento sobre cartolina e secos. Foram depois marcados utilizando um laser de CO2 de exploração, com um diâmetro de feixe de 0,3 mm e uma velocidade de exploração de 1000 mm.s-1. As quantidades utilizadas e os resultados são mostrados na Tabela 1.
Exemplo 8
Misturaram-se 197 g de homopolimero de polipropileno com 3 g de uma mistura 4:1 de AOMrlriodin 805, através de mistura completa num Optiblender 2000 (Moulinex). A mistura foi compostada e paletizada num extrusor FOS axon 11502 a temperaturas de 190°C, 200°C, 210°C, 220°C e 225°C nas cinco zonas respectivas. O polímero moldado podia ser marcado com um laser de CO2.
Exemplos 9 e 10
Foi seguido o procedimento do Exemplo 8, mas utilizando HDPE e HIPS, respectivamente. Os polímeros moldados puderam ser satisfatoriamente marcados com lasers Nd-YAG e CO2, respectivamente.
Exemplo 11
Formulou-se um verniz, compreendendo jPolicloreto de vinilo 30% : Octamolibdato de amónio 15% Álcool etílico balanço 6
ΕΡ 1 368 200 /PT
Este foi aplicado como revestimento em folha de alumínio utilizando uma barra Meyer e seco. O revestimento semi-opaco foi depois exposto a um feixe laser de C02 de 0,3 mm de diâmetro, explorando a 1000 mm/segundo a uma potência de saída de 3W, para produzir uma imagem negra.
Tabela 1 EXEMPLO LIGANTE QUAN TIDADE <g) ADITIVO í QUAN TIDADE <g) \ SOLVENTE QUAN TIDADE (g) MARCAÇÃO POR S LASER ΐ POTÊNCIAíCOR DAÍ (W) jj IMAGEM j 1 Álcool polivinilico (Gohsenol GH17) 1, 1 AOM ΐ 1 í Água ; 9 3 Negro § 2 Alcotex 395B (26%) 12 AOM | 2 íMetanol/acetato i; § de metilo jj - 3 Negro 5 3 Etilcelulose 2 AOM | 2 § Etanol jj 15 3 Negro * 4 Klucel (hidroxi-propilcelulose) 2 AOM | 2 § Água 15 3 Negro § 5 Mowital B30H 2 AOM | 2 | Etanol S 10 3 Negro 5 6 PVC Vycar 577E 15 AOM | 3 5 Água ·: 9 3 Negro 5 7 Ebecryl 657 3,5 AOM j 3 $ Irgacure 651 i; 0, 7 3 Negro 5 Ebecryl 1608 3,5 Γ § (Fotoiniciador) i; 1
Gohsenol foi obtido era CIBA Speciality Chemicals
Alcotex foi obtido em Harlow Chemicals
Klucel foi obtido em Hercules
Mowital foi obtido em Hoechst
Vycar foi obtido em B.F. Goodrich
Ebecryl foi obtido em UCB Chemicals
Lisboa

Claims (10)

  1. ΕΡ 1 368 200 /PT 1/1 REIVINDICAÇÕES 1. Tinta de impressão ou verniz de revestimento transparente, corado ou pigmentado, que compreende um ligante e octamolibdato de amónio.
  2. 2. Formulação adesiva que compreende um ligante e octamolibdato de amónio.
  3. 3. Produto de acordo com a reivindicação 1, em que o ligante compreende um grupo lábil.
  4. 4. Produto de acordo com qualquer reivindicação precedente, em que o ligante é um polímero.
  5. 5. Produto de acordo com qualquer reivindicação precedente, que compreende adicionalmente um pigmento branco.
  6. 6. Produto de acordo com a reivindicação 5, em que o pigmento é CaCC>3, ZnO, TÍO2 ou talco.
  7. 7. Processo para proporcionar uma imagem sobre um substrato, que compreende a aplicação ao substrato de uma composição marcável por laser, a qual compreende um ligante e octamolibdato de amónio, seguida de irradiação na forma de imagem com um laser, pelo que o octamolibdato de amónio sofre uma modificação de cor.
  8. 8. Processo de acordo com a reivindicação 7, em que a composição é uma tinta ou verniz de acordo com a reivindicação 1.
  9. 9. Processo de acordo com a reivindicação 7, em que a composição é aplicada por moldação com solvente, para formar uma película sobre o substrato.
  10. 10. Processo para proporcionar uma imagem sobre um substrato, que compreende a extrusão em fusão de uma composição que compreende um ligante e octamolibdato de amónio, seguida de irradiação na forma de imagem com um laser, pelo que o octamolibdato de amónio sofre uma modificação de cor. Lisboa
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AU2002241108A1 (en) 2002-10-03
JP3913680B2 (ja) 2007-05-09
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US7485403B2 (en) 2009-02-03
CY1106395T1 (el) 2011-10-12
EP1657072B1 (en) 2009-07-01
ATE348712T1 (de) 2007-01-15
EP1368200B1 (en) 2006-12-20
WO2002074548A2 (en) 2002-09-26
DE60216898D1 (de) 2007-02-01
DK1368200T4 (da) 2011-10-10
ES2327662T5 (es) 2013-09-20
ES2278008T5 (es) 2011-11-18
EP1657072B2 (en) 2013-07-10
US20060147842A1 (en) 2006-07-06
EP1657072A3 (en) 2006-07-26
US8936901B2 (en) 2015-01-20
JP2004522631A (ja) 2004-07-29
DK1368200T3 (da) 2007-04-30
DE60216898T2 (de) 2007-07-26
DE60216898T3 (de) 2012-04-26
EP1657072B3 (en) 2016-08-31
ATE435123T1 (de) 2009-07-15
EP1368200A2 (en) 2003-12-10
US20030180660A1 (en) 2003-09-25
ES2278008T3 (es) 2007-08-01
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US8753791B2 (en) 2014-06-17
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US20140242290A1 (en) 2014-08-28
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EP1657072A2 (en) 2006-05-17
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