WO2015184166A1 - Compositions d'encre durcissable par uv - Google Patents

Compositions d'encre durcissable par uv Download PDF

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Publication number
WO2015184166A1
WO2015184166A1 PCT/US2015/033026 US2015033026W WO2015184166A1 WO 2015184166 A1 WO2015184166 A1 WO 2015184166A1 US 2015033026 W US2015033026 W US 2015033026W WO 2015184166 A1 WO2015184166 A1 WO 2015184166A1
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WO
WIPO (PCT)
Prior art keywords
ink composition
curable ink
less
hydroxy
acrylate
Prior art date
Application number
PCT/US2015/033026
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English (en)
Inventor
Katsuya Ono
Original Assignee
3M Innovative Properties Company
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
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to JP2016569958A priority Critical patent/JP2017524751A/ja
Publication of WO2015184166A1 publication Critical patent/WO2015184166A1/fr

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Classifications

    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • the present application relates to UV-curable ink compositions, methods of using and applying these compositions, and articles to which these compositions are applied.
  • the present application relates to UV-curable ink compositions that can be printed using an ink jet printer.
  • Advertising and promotional displays often include graphic images appearing on structural surfaces such as truck sides, awnings, and/or free-hanging banners.
  • the graphic image is formed on an adhesive-backed image receptor medium, sometimes referred to as a graphic marking film, which is then adhered to the desired substrate.
  • the image is formed on a plasticized polymeric (e.g., vinyl) film which may be subsequently used as a banner, awning, or the like.
  • Plasticizers are additives that increase the plasticity or fluidity of a material. Plasticizers have long been used to control the processability of polymers (e.g., polyvinyl chloride) used for graphic films and banners. Plasticizers can be monomeric or polymeric in nature. The most common plasticizers used in PVC are monomeric plasticizers, such as dioctyl phthlate. Other plasticizer chemistries in addition to phthlate esters include sebacates, adipates, terephthalates, dibenzoates, gluterates, and azelates. One disadvantage of inclusion of these (monomeric) plasticizers is that they may, over time, migrate towards the surface, where they can produce surface tackiness or stickiness.
  • plasticizers may migrate into layers adjacent to the film (e.g., into the adhesive that joins them to a substrate).
  • Plasticizer migration is often expedited by high temperatures, such as, for example, those caused by exposure to sunlight or during UV curing.
  • the plasticizer migration can also cause plasticizer depletion of the polymer layer, which reduces its elasticity significantly over time, so that the layers become brittle, which produces cracks in the film.
  • the migration of the plasticizer can thus reverse or erode the key properties of the polymer layer - including, for example, sealing against moisture, flexibility, and aging stability.
  • plasticizers in plasticized polymeric films also migrate into the inks that make up the graphic images.
  • plasticizer migration causes undesirable effects for the ink and ink/film combination including, for example, decreased ink adhesion, film embrittlement, and/or increased tackiness of the ink over time.
  • Some or all of these undesirable properties are increased when the substrate onto which the ink is applied is repeatedly folded (e.g., when used as a tarpaulin).
  • Some or all of these undesirable properties are increased where the ink is cured at a high temperature, which can undesirably increase plasticizer migration.
  • Some embodiments of the present disclosure relate to a UV-curable ink composition including (1) at least 12 wt% N-isopropyl acrylamide; (2) 25 wt% or less hydroxy acrylate; and (3) N- vinylcaprolactam.
  • the composition is applied to a substrate that is a polymer film including a plasticizer.
  • the polymeric film includes PVC.
  • Some embodiments of the present disclosure relate to methods for applying a UV-curable ink composition to a substrate comprising: providing a substrate; providing a UV-curable ink composition comprising (1) at least 12wt% N-isopropyl acrylamide; (2) 25 wt% or less hydroxy acrylate; and (3) N- vinylcaprolactam; and applying the UV-curable ink composition to the substrate.
  • the composition is applied to a substrate that is a polymer film including a plasticizer.
  • the polymeric film includes PVC.
  • Some embodiments of the present disclosure relate to an article comprising a polymeric substrate including a plasticizer having thereon a UV-curable ink composition, comprising: at least 12wt% N- isopropyl acrylamide; 25 wt% or less hydroxy acrylate; and N-vinylcaprolactam.
  • the polymeric film includes PVC.
  • the UV-curable ink composition includes at least 15 wt% N-isopropyl acrylamide. In some embodiments, the UV-curable ink composition includes between about 12 wt% and about 25 wt% N-isopropyl acrylamide.
  • the UV-curable ink composition includes less than 20 wt% hydroxyl acrylate. In some embodiments, the UV-curable ink composition includes less than 15 wt% hydroxy acrylate. In some embodiments, the UV-curable ink composition includes between about 5 wt% and about 25 wt% hydroxy acrylate.
  • the UV-curable ink composition includes less than 20 wt% N- vinylcaprolactam. In some embodiments, the UV-curable ink composition includes less than 10 wt% N- vinylcaprolactam. In some embodiments, the UV-curable ink composition includes between about 5 wt% and about 15 wt% N-vinylcaprolactam.
  • ink compositions with a predicted Tg of about 46° C or less have better crack-resistant properties and thus do not crack when applied to substrates that are folded (e.g., tarpaulin).
  • substrates that are folded e.g., tarpaulin
  • Such inks are preferably highly flexible, since many substrates (e.g. tarpaulin) are repeatedly folded during use, storage, processing, and/or application.
  • the UV-curable ink composition has a Tg by the Fox equation between about 30° C and about 46° C.
  • the viscosity of the UV-curable ink composition is less than or equal to 15 milliPascal- seconds at 60 ° C.
  • a UV-curable ink composition of the type described herein includes (1) at least 12 wt% N- isopropyl acrylamide; (2) 25 wt% or less hydroxy acrylate; and (3) N-vinylcaprolactam.
  • the resulting composition exhibits an excellent combination of flexibility, adhesion, and no tackiness after time.
  • the resulting ink composition also exhibits excellent plasticizer resistance when placed directly adjacent to or on a polymer substrate that includes a plasticizer.
  • the UV-curable ink composition is excellent in applications where the plasticizer-containing substrate to which the ink composition adheres or is applied is folded or flexed during use, application, transport, manufacturing, etc.
  • the resulting UV-curable ink composition can be applied, for example, to various substrates including, for example, those used as a tarpaulin, a barrier, a banner, and/or a wrapping film.
  • preferred UV-curable inks exhibit (1) minimal tackiness (initially and over time); (2) excellent ink adhesion; (3) pass the folding test; and (4) have a Tg by the Fox equation that is below 46° C when the ink is applied to a plasticized (in other words, plasticizer-containing) material, especially plasticized vinyl (e.g., PVC) materials.
  • the UV-curable ink composition includes at least 12 wt%, at least 15 wt%, at least 17wt%, at least 20 wt%, at least 22 wt%, at least 24 wt%, and about 25 wt% N-isopropyl acrylamide.
  • One advantage of use of this specific acrylamide is that has more desirable toxicity properties (e.g., is less toxic) than other acrylamides such as, for example, dimethylacrylamide.
  • the UV-curable ink composition includes about 25 wt% or less, about 24 wt% or less, about 23 wt% or less, about 22 wt% or less, about 21 wt% or less, about 20 wt% or less, about 18 wt% or less, about 16 wt% or less, about 14 wt% or less, about 12 wt% or less, about 10 wt% or less, or about 8 wt% or less hydroxy acrylate.
  • Some exemplary hydroxy acrylates include 4-hydroxy butyl acrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1 ,4-cyclohexanedimethanol monoacrylate.
  • the UV-curable ink compositions include between about 5 wt% to about 15 wt% N-vinylcaprolactam. [0020] In some embodiments, the UV-curable ink compositions are applied with a thickness of about 5- 30 um.
  • Sensitizers, co-initiators, and amine synergists can, optionally, be included in UV-curable ink compositions of the present disclosure in order to improve the curing rate.
  • examples include
  • UV-curable ink compositions of the present disclosure may, optionally, include one or more colorants.
  • Useful colorants include dyes and pigments, which may be used alone or in any combination.
  • Useful dyes and pigments may be of any color, and are well known in the art, for example, as described in U.S. Pat. Nos. 6,294,592 (Herrmann et al.) and 6, 1 14,406 (Caiger et al.), both of which are incorporated in their entirety herein.
  • the colorant comprises at least one pigment.
  • the amount of optional colorant(s) used in UV-curable ink compositions of the present disclosure is typically less than 25 volume percent based on the total volume of the ink composition, although higher volume percentages may be used.
  • the colorant(s), if present is in an amount in a range of from 0.1 percent by volume to 15 percent by volume, based on the total volume of the ink composition.
  • UV-curable ink compositions of the present disclosure may, optionally, contain solvent.
  • Solvent may consist of one or more non-reactive diluent materials that may serve, for example, to lower the viscosity of UV-curable ink composition, lower the surface tension of the UV-curable ink composition, and/or dissolve components in the UV-curable ink composition. Any amount of solvent may be utilized. In some embodiments of the present disclosure, small quantities of solvent may be added as described, for example, in PCT Publication No. WO 02/38687 Al (Ylitalo et al.), published May 16, 2002, incorporated in its entirety herein.
  • the amount of optional solvent incorporated is kept to a minimum, preferably essentially none (for example, less than one weight percent).
  • exemplary solvents include water; alcohols such as isopropyl alcohol (IP A) or ethanol; ketones such as methyl ethyl ketone, cyclohexanone, or acetone; aromatic hydrocarbons; isophorone;
  • butyrolactone N-methyl pyrrolidone; tetrahydrofuran; ethers such as lactates, acetates, and the like; ester solvents such as propylene glycol monomethyl ether acetate (PM acetate), diethylene glycol ethyl ether acetate (DE acetate), ethylene glycol butyl ether acetate (EB acetate), dipropylene glycol monomethyl acetate (DPM acetate), iso-alkyl esters, isohexyl acetate, isoheptyl acetate, isooctyl acetate, isononyl acetate, isodecyl acetate, isododecyl acetate, isotridecyl acetate or other iso-alkyl esters; combinations of these, and the like.
  • ester solvents such as propylene glycol monomethyl ether acetate (PM acetate), diethylene glycol e
  • additives may be incorporated into UV-curable ink compositions of the present disclosure.
  • exemplary additives may, for example, include one or more of colorants, slip modifiers, thixotropic agents, foaming agents, antifoaming agents, flow or other rheology control agents, waxes, oils, plasticizers, binders, antioxidants, stabilizers, electrical conductive agents, fungicides, bactericides, organic and/or inorganic filler particles, leveling agents, opacifiers, antistatic agents, and/or dispersants.
  • UV-curable ink compositions of the present disclosure may be cured, for example, by exposure to actinic radiation (that is, radiation having a wavelength in the ultraviolet or visible region of the spectrum).
  • actinic radiation that is, radiation having a wavelength in the ultraviolet or visible region of the spectrum.
  • Suitable sources of actinic radiation include mercury lamps, xenon lamps, carbon arc lamps, tungsten filament lamps, lasers, electron beam energy, sunlight, microwave driven lamps, light emitting diodes, and the like.
  • the source of radiation is a medium pressure mercury lamp or light emitting diodes.
  • Images may be created using the inks described herein by one of several known methods, such as screen printing, flexographic printing, lithographic printing, gravure printing, and ink jet printing.
  • the inks can be applied as a coating using techniques such as knife coating and roll coating.
  • the inks of the present disclosure are not tacky after cure and do not become tacky (often a sign of undesirable plasticizer migration) over time after cure. Excessively tacky inks undesirably pick up dirt, degrading the image quality and appearance of the graphics. Also, in instances where the graphic film is rolled into a roll, the ink could stick to the portion of the graphic sheet directly adjacent to the ink. In other words, the graphic film would stick to itself when rolled. When unrolled, the ink on a single-side printed graphic film may transfer to the unprinted backside of the graphic film, thereby destroying the image. And in severe cases, this can result in destruction of the sheeting in the affected area and potentially the entire roll. The inks and articles and method of the present disclosure prevent or minimize these undesirable events by eliminating or minimizing undesirable tackiness after cure.
  • the inks, methods, and articles of the present disclosure exhibit excellent flexibility.
  • the inks do not crack when the graphic film is rolled, bent, or folded. This permits easier installation, storage, and manufacturing.
  • the inks, methods, and articles of the present disclosure also exhibit excellent ink adhesion.
  • Premasks are often applied to graphic films to assist during the installation process. The premask is then peeled off the graphic film before installation is complete. It is essential that the ink on the graphic film remain in the desired and intended position during and after the premask is removed.
  • the inks and methods and articles of the present disclosure exhibit excellent adhesion throughout the life of the graphic film.
  • Tackiness coated tarpaulin samples were prepared as described in Comparative Examples A-N and Examples 1 - 14, below.
  • a tackiness test (initial) was performed by placing a user's index finger on the samples. The user then attributed a category to each sample, wherein (A) meant no tackiness was felt by the user; (B) meant a slight tackiness was felt; and (C) meant a strong tackiness was felt.
  • the coated samples were then put in an oven heated to a temperature of about 65°C for three days. The samples were subsequently removed from the oven and allowed to cool down to room temperature. The tackiness test was performed for the heat aged samples.
  • Ink adhesion test a cutter knife was used to scrape a Crosshatch pattern on a portion of the ink layer of the coated tarpaulin samples.
  • An adhesive tape obtained under the trade designation
  • Tg predicted glass transition temperature
  • a and B monomer or oligomer
  • Tg glass transition temperature of a copolymer formed from A and B
  • WA and WB Weight fractions of A and B
  • Tg A and Tg B Tg values of the homopolymers of A and B
  • HPA Hydroxy propyl acrylate (HPA) Tg -7 °C Osaka Organic Chemical
  • LIGNOSTAB 1 198 1 -Piperidinyloxy, 4-hydroxy-2,2,6,6-tetramethyl-, BASF
  • Comparative examples A-N were prepared by coating PVC tarpaulin (obtained under the trade designation SPC-0448, from Mimaki Engineering) with the ink compositions listed in Tables 1 and 2, below.
  • the ink compositions were coated using a Meyer wirebar number 7 and subsequently cured by 385 nm UV LED (303 mW/cm 2 , 360 mJ/cm 2 ) (model LN-517VL385-FNEDTKHI, obtained from CCS Inc.).
  • Comparative Ink Compositions A-N were prepared by mixing monomers, oligomers, and light stabilizers using a mixer for 60 minutes at room temperature and at a speed of 2000 rpm. Then, a pigment (millbase which comprised cyan pigment, dispersant and IBOA) was added to the mixture and stirred for about 30 minutes.
  • Comparative Ink Compositions (CI) A-N are listed in Tables 1 and 2, below, wherein the amount of each material is expressed in weight percent (wt%) based on the total weight of the composition.
  • Examples 1-14 were prepared as described in Comparative Examples A-N, except that ink compositions used are listed in Tables 3 and 4, below, wherein the amount of each material is expressed in weight percent (wt%) based on the total weight of the composition.
  • Comparative Examples A-N and Examples 1- 14 were submitted to qualitative tackiness, folding and ink adhesion tests, using the procedures described above. In addition, Tg of each composition was calculated using Fox equation as explained above. Results are reported in Table 5.
  • Example 1 A A OK 0 34
  • Samples coated with ink compositions comprising at least 12 wt% NIPAM, about 25 wt% or less hydroxy acrylate, and NVC did not show tackiness increase after aging at 65° C for three days.
  • a tackniness increase could be due to, for example, plasticizer migration from the substrate (e.g. , tarpaulin) to the ink layer.
  • Compositions with a predicted Tg of 46° C or less have better crack-resistant properties, as observed in the folding test.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

La présente invention concerne des compositions d'encre durcissable par UV, un procédé d'utilisation et d'application de ces compositions, et des articles sur lesquels ces compositions sont appliquées. Selon certains modes de réalisation, les compositions d'encre durcissable par UV peuvent être imprimées au moyen d'une imprimante à jet d'encre. Selon certains modes de réalisation, la composition d'encre durcissable par UV comprend (1) au moins 12 % en poids d'acrylamide de N-isopropyle ; (2) 25 % en poids ou moins d'hydroxyacrylate ; et (3) du N-vinylcaprolactame. Certains modes de réalisation au moins de ces compositions d'encre durcissable par UV réduisent au minimum l'incidence ou les effets indésirables de la migration de plastifiant dans la couche d'encre.
PCT/US2015/033026 2014-05-29 2015-05-28 Compositions d'encre durcissable par uv WO2015184166A1 (fr)

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US62/004,420 2014-05-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019031357A1 (fr) * 2017-08-08 2019-02-14 サカタインクス株式会社 Composition d'encre durcissable par un rayonnement d'énergie active pour impression par jet d'encre
EP3421554A4 (fr) * 2016-02-23 2019-10-16 Sakata INX Corporation Composition d'encre photodurcissable pour l'impression par jet d'encre
CN112534007A (zh) * 2018-08-10 2021-03-19 爱克发有限公司 可辐射固化的喷墨油墨

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4263218A1 (fr) * 2020-12-18 2023-10-25 3M Innovative Properties Company Stratifié comprenant une couche contenant un plastifiant et une couche d'encre, et encre durcissable par rayonnement

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114406A (en) 1996-02-21 2000-09-05 Coates Brothers Plc Radiation curable ink composition
US6294592B1 (en) 1997-06-30 2001-09-25 Basf Aktiengesellschaft Pigment preparations with radiation curable binder suitable for ink jet printing method
WO2002038687A1 (fr) 2000-11-09 2002-05-16 3M Innovative Properties Company Encres et autres compositions incorporant des quantites limitees de solvant utilisees avantageusement dans des applications par jets d'encre
US20130033039A1 (en) 2010-01-21 2013-02-07 Echenique Gordillo Inigo Balance wave energy-electricity generation system
EP2644664A1 (fr) * 2012-03-29 2013-10-02 Fujifilm Corporation Composition d'encre de type durcissant au rayonnement actinique, procédé d'enregistrement à jet d'encre, feuille décorative, produit moulé en feuille décorative, procédé de production d'article moulé dans un moule, et article moulé dans un moule
JP2013203845A (ja) * 2012-03-28 2013-10-07 Fujifilm Corp インクジェットインク組成物
EP2705953A1 (fr) * 2012-08-31 2014-03-12 Fujifilm Corporation Cartouche d'encre

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114406A (en) 1996-02-21 2000-09-05 Coates Brothers Plc Radiation curable ink composition
US6294592B1 (en) 1997-06-30 2001-09-25 Basf Aktiengesellschaft Pigment preparations with radiation curable binder suitable for ink jet printing method
WO2002038687A1 (fr) 2000-11-09 2002-05-16 3M Innovative Properties Company Encres et autres compositions incorporant des quantites limitees de solvant utilisees avantageusement dans des applications par jets d'encre
US20130033039A1 (en) 2010-01-21 2013-02-07 Echenique Gordillo Inigo Balance wave energy-electricity generation system
JP2013203845A (ja) * 2012-03-28 2013-10-07 Fujifilm Corp インクジェットインク組成物
EP2644664A1 (fr) * 2012-03-29 2013-10-02 Fujifilm Corporation Composition d'encre de type durcissant au rayonnement actinique, procédé d'enregistrement à jet d'encre, feuille décorative, produit moulé en feuille décorative, procédé de production d'article moulé dans un moule, et article moulé dans un moule
EP2705953A1 (fr) * 2012-08-31 2014-03-12 Fujifilm Corporation Cartouche d'encre

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3421554A4 (fr) * 2016-02-23 2019-10-16 Sakata INX Corporation Composition d'encre photodurcissable pour l'impression par jet d'encre
US10767068B2 (en) 2016-02-23 2020-09-08 Sakata Inx Corporation Photocurable inkjet printing ink composition
WO2019031357A1 (fr) * 2017-08-08 2019-02-14 サカタインクス株式会社 Composition d'encre durcissable par un rayonnement d'énergie active pour impression par jet d'encre
CN112534007A (zh) * 2018-08-10 2021-03-19 爱克发有限公司 可辐射固化的喷墨油墨

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