WO2011098656A1 - Revêtement - Google Patents

Revêtement Download PDF

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Publication number
WO2011098656A1
WO2011098656A1 PCT/FI2010/050092 FI2010050092W WO2011098656A1 WO 2011098656 A1 WO2011098656 A1 WO 2011098656A1 FI 2010050092 W FI2010050092 W FI 2010050092W WO 2011098656 A1 WO2011098656 A1 WO 2011098656A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
binding agent
coating according
particles
coated
Prior art date
Application number
PCT/FI2010/050092
Other languages
English (en)
Inventor
Harri Repo
Original Assignee
Dinoto Oy
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 Dinoto Oy filed Critical Dinoto Oy
Priority to PCT/FI2010/050092 priority Critical patent/WO2011098656A1/fr
Publication of WO2011098656A1 publication Critical patent/WO2011098656A1/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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a coating which is of the type set forth in the preamble portion of appended claim 1.
  • Coatings have been developed for various purposes with desired electrical conductivity levels, that is, they differ from pure insulating materials. Conductive particles mixed with a polymeric binding agent are commonly used in such coatings to provide electrical conductivity. Depending on the level of conductivity one can speak about static dissipative or ESD (electrostatic discharge) shielding.
  • ESD electrostatic discharge
  • xylene-soluble acryl copolymers (of PMMA type) aiming principally at hardness are known.
  • Organic solvents like xylene that are used in manufacture of the coatings cause problems of toxicity and fire safety, which are generally recognized as problems that should be eliminated.
  • coatings based on an intrinsically conducting polymer, aniline are known, the main problem of which is poor folding resistance.
  • the coating is primarily characterized in what is presented in the characterizing portion of appended claim 1.
  • the coating comprises the following components essential for its functionality:
  • aqueous dispersion based film-forming elastic acrylic copolymer as binding agent, and electrically conducting particles mixed with the binding agent in such an amount that the surface resistivity of the coating is at the level of 1x10E3 - 1x10E1 1 ohm/square (10 3 - 10 11 ohm/square),
  • the surface resistivity of the coating is 1 x10E6 - 1x10E8 ohm/square fulfilling ESD demands set on packages.
  • the water-based acrylic copolymer provides a certain degree of elasticity to the coating, which has clear advatages when flexible and foldable materials are coated especially in view of packaging applications, because the coating persisists without cracking and thus retains the desired level of electric conductivity.
  • the coating must withhold creasing, when a folding boxboard coated with it is made to a package. Creasing is a well-known operation where a surface pattern is made in a folding boxboard blank to facilitate later folding and it interrupts the smooth surface of the carboard material and therefore easily creates points of discontimuity in the coating.
  • binding agent under tradename "PRIMALTM ECO-16” (Rohm and Haas), which is a nonionic, self- crosslinking acrylic copolymer (methyl methacrylate - ethyl acrylate copolymer), which can be applied on a substrate as an aqueous emulsion.
  • grades “PRIMALTM ECO-36” (self-crosslinking, anionic) and “PRIMALTM ECO-8” (sel- crosslinking, nonionic) may also be used.
  • MMA/EA copolymers corresponding polymer producs from other manufacturers may also be used.
  • EAA ethylene acrylic acid copolymer
  • TECSEAL E-799/45 Trub Emulsions Chemie
  • an ethylene-acrylic acid dispersion solids content 45%, Tg 4°C
  • Acrylic copolymers of different types with differing mechanical properties may be blended with each other to achieve the desired final properties of the coating.
  • the advantages of the acryl copolymers can be summarized as
  • Styrene-butadiene latexes and polyurethane latexes can also be used in the coating compositions as aqueous film-forming polymer binding agents in mixture with the above-mentioned acrylic copolymers.
  • the proportion of these additional polymers should be kept moderate. They can be present in an amount not exceeding 50 wt-%, preferably at the most 20 wt-% of the total dry weight of the film- forming polymers in the mixture.
  • Styrene-acrylates still one group of acryl copolymers, are useful alone or especially as blends where a "hard” and “soft” polymer is combined to provide a creasable and at the same time block resistant surface for different packaging materials.
  • the elasticity can be increased through the addition of a compatible polurethane dispersion.
  • a compatible polurethane dispersion For example NeoCryl XK-188 (DSM), an acryl ic-styrene emulsion, blended with NeoRez-1007 (DSM), a polyurethane dispersion, is a sufficiently stable mixture for production scale.
  • the binding agent of the coating should not occlude the particles so that the electric conductivity is maintained. Because of this requirement, the binding agent of the coating is not crosslinked in coating conditions.
  • the binding agent is crosslinkable, it is dried, after being applied onto the substrate in admixture with the conductive particles, in such a temperature - time profile where crosslinking has no time to take place.
  • the drying after spreading of the coating may be conducted in such a way that crosslinking occurs at the interface of the fibrous substrate and the coating while the outer layer of the coating remains unaffected.
  • the elasticity of the above-mentioned aqueous dispersion based acrylic copolymer binding agent or an aqueous dispersion based binding agent composition containing the acrylic copolymer as main constituent is preferably at such a level that a dry film made of it has minimum elongation at break above 300 %, and optimally above 600 %.
  • the amount of electrically conductive particles in the coating is preferably 5-60 wt-% of the total mass of the coating (on dry weight), more preferably 10-40 wt-%.
  • any electrically conductive particles can be used that have sufficiently small size (average diameter) to be able to disperse uniformly in the liquid coating composition and to form, upon drying of the coating, a uniform network of interconnecting particles at least in the immediate vicinity of the top face of the coating, preferably in the interface of the coating, even in cases where the coating is relatively thin, only of the order of 1 ,5 to 15 g/m 2 as expressed in square weight of the coating when applied wet on the substrate in one or several steps.
  • the amount of coating may be in the range of 1 - 10 g/m 2 .
  • the conductive particles do not increase the opacity of the coating, a property which is quite contrary to the requirements of the common coating compositios of paper and cardboard products. Electrically conductive particles whose colour is close to white (i.e. they do nor absorb light) and which have a small particle size should be used. In the following, types of particles that are particularly suitable for the coating are discussed.
  • the conductive particles are transparent particles.
  • Transparent particles are meant to be particles that do not raise, in concentrations required for conductivity, the light absorbency of the clear elastic coating based on acrylic copolymer to such an extent that they would block the impression or the original substrate surface from being visible through the thickness of the coating once the coating has dried, that is, they are light-coloured and "colour-neutral".
  • the original non-printed packaging material surface may be visible through the transparent coating, which in turn is provided with impression (printed) on its top surface.
  • Particularly suitable particles with optical properties for achieving a transparent coating in combination with the polymeric binder are for example mineral particles that are coated to be electrically conductive. These are typically mineral particles having a metal oxide coated or metal coated (metallized) surface.
  • conductive pigment sold under trade name "Minatec” by Merck. This pigment consists of mica particles coated with (Sn/Sb)O 2 , tin oxide doped with antimony.
  • Suitable grades are for example "Minatec® 40 CM” and "Minatec® 31 CM Transparent". Both grades provide for transparency of the coating, if the binding agent is transparent.
  • the particle size of both grades is under 15 m as determined by laser diffraction measurement. By transparency is meant that the coating may not necessarily be clear but it may have some color.
  • the transparency of the coating retains the original colour of the dye and does not distort it or change its hue, thus, the coating has "clear" colour.
  • An important component in the coating composition is dispersion aid (dispersant) which helps to distribute the particles uniformly in a coating composition that upon application and drying results even in a relatively thin coating.
  • dispersion aid for example isopropanol optionally supplemented with propylene glycol may be used.
  • the amount of the dispersion aid is preferably 1 -5 wt-% in the aqueous coating composition.
  • the coating composition based on the above-mentioned acryl copoymers in aqueous dispersions and conductive particles is an improvement over resin technology.
  • Aqueous acryl copolymer dispersions and their best compatibility with various printing machines and coating machines can be utilized directly without any intermediary resin step or solvent based premixture of the pigment.
  • the aqueous polymer dispersion can be used directly in preparing the coating composition to be applied to the substrate, by mixing desired components into it.
  • the coating process is environmentally friendly resulting only in release of water vapour and negligent amounts of alcohol vapours (dispersion aids) when the coating is dried.
  • Coating compositions that on drying (evaporation of the water) form the coating, can be applied onto a substrate by many different methods, such as flexographic, gravure coating, silk screen printing, roll coating, size press coating and blade coating methods.
  • the substrate may be cardboard, paper or plastic.
  • packaging materials are suitable for substrates.
  • the coating can be provided with glue (for example to make glue lines on the surfaces of package blanks), printed (in which case the impression is on top of the coating) and it can be coated with a topcoat, according to need.
  • Paper and carboard are preferred substrates and the coating can be applied with methods generally used for coating these substrates.
  • the paper or cardboard surface to be coated may be previously coated with a coating improving the printability, provided that this coating is compatible with the coating composition of the invention.
  • the substrate can also be a plastic film, where the elasticity properties of the coating are important, and materials that can be coated with the coating composition of the invention include various polyolefins, such as LDPE, HDPE, PP, OPP (oriented polypropylene), MDPE and LLDPE.
  • the substrate can also be a layered substrate.
  • plastic films consisting of two or more polymer layers and paper or carboard laminates coated with one or more polymer layers may be used.
  • the surface of such a layered substrate to be coated with the composition may be a polyolefin, for example some of the above-mentioned polyolefins.
  • the polymer surface may be pretreated by known methods, for example by corona treatment.
  • the substrate can also be a laminate where the coating composition is applied on the paper or carton surface and one or several additional layers are on the reverse side in relation to the surface where the coating composition is applied.
  • One aspect of the invention is thus to provide a coating composition that can be spread on the substrate as an aqueos composition containing all components that are part of the final solid elastic coating permanently attached to the surface of the substrate.
  • the carrier of the coating composition water, evaporates, as do solvents used as dispersants, leaving behind a finished coating consisting mainly of the acrylic copolymer and the particles.
  • the film-forming elastic acrylic copolymer binder is in form of dispersion (emulsion) in the aqueous carrier that contains the other components of the coating composition such as the electrically conductive particles and the dispersant. It is possible to coat the substrate in form of a continuous web when it runs past a coating station that is arranged to apply the coating composition in one of the above-mentioned methods.
  • the coating can be applied on a paper or board substrate in a paper or board machine that manufactures paper or board from water-based fibrous pulp, or in a separate paper or board coater (finishing machine) spreading a coating on a paper or board previously manufactured. In both alternatives the coating on the web is dried in the same machine subsequently to the coating station.
  • the paper or cardboard substrates suitable to be coated with the compositions described above are preferably uncoated paper and cardboard (i.e. uncoated on the surface to be coated with the coating composition), such as uncoated liner, board, and paper, including products made of recycled fibre. These substrates may be printed or non-printed.
  • the board was one-side blade-coated Tambrite, which was coated on both sides twice with the composition, top side (coated side of the board): 1.6 + 1.4 g/m2 wet, and back side: 1.8 + 1.8 g/m2 (wet weight), and dried.
  • the coating was transparent due to the transparent nature of the pigment used as the conducting particles.
  • the surface resisitivity of the dry coating was measured with Perell ohm/square measuring device, with the following results: top side 1x10E6 ohm/sq, back side 1x10E7 ohm/sq.
  • the board was one-side blade-coated Tambrite, which was coated on top side once and back side twice with the composition, top side: 1.7 g/m2 wet, and back side: 1.7 + 1.7 g/m2 (wet weight), and dried.
  • the surface resisitivity of the dry coating was measured with Perell ohm/square measuring device, with the following results: top side 1x10E3 ohm/sq, back side 1x10E5 ohm/sq.
  • Example 2a When the composition of Example 2a was used together with PRIMAL ECO 16 in a ratio 50/50 in a Flexo application to form a single layer of 1.8 g/m 2 (wet weight), the resulting value for the dry coating was 1x10E10 ohm/sq.
  • the board was printed board, which was coated using one gravure unit on top side once the composition, 1.5 g/m2 wet, to obtain maximal transparency, and dried. The impression remained visible through the coating due to the transparent nature of the pigment.
  • the surface resisitivity of the dry coating was measured with Perell ohm/square measuring device, with the result of 1 x10E8 ohm/sq.
  • the substrate coated was machine-glazed paper, which was blade- coated on one side with the composition in an amount of 12 g/m2 wet, and dried.
  • the surface resisitivity of the dry coating was measured with Perell ohm/square measuring device, with the result of 1 x10E5 ohm/sq.
  • the surface of the coating had sufficient conductivity despite the talc used as nonconductive filler.
  • the transparency was not affected by the minor amout of talc used as assistant filler which gave the surface a matt appearance and a greiyish hue for the coating, but it did not hide the background surface colouration.
  • This coated product is suitable for printing on it, because it is optically similar to conventional printing papers while having surface conductivity.
  • the coating composition may contain conventional non-conductive fillers as one fraction of particle material to adjust the optical properties for printing on the coating.
  • Assistant fillers that can be used in addition to the transparent conductive fillers can be talc (for example Talc de Luzenac with average particle diameter of 15 ⁇ ) or silica (for example Degussa Aerosil 200 silica).
  • the assintant fillers whose amount is preferably lower that of the conductive pigments in the composition, can be used to adjust the surface mattness of the coating and increase the abrasion resistance of the coating surface.
  • the mechanical properties of the coating are influenced also by the glass transition temperature, Tg of the polymer used as binding agent alone or in mixture with other polymers.
  • the polymers in the above compositions have the following Tgs: Primal ECO 8 -14°C, Primal ECO 16 +33°C, and Primal ECO 36 -12°C.
  • the preferable packaging materials where the invention can be used are those that are made to packages of electronic industry, for example by folding (preferably preceded by creasing of the package blank) or deep-drawing, where the coating continues uninterrupted over the folds of folded material or bends of the deep-drawn article.
  • the heat sealing properties of the dried coating can be used in sealing the package.
  • the invention is not imited to the above examples.
  • the coating that is formed of the composition need not exist as uniform uninterrupted coating on the substrate, but it can also form areas, between which the original substrate remains exposed after the coating operation.
  • the coating can thus form patterns, which may have functionality because of the electrical properties of the coating.

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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)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne un revêtement comprenant un copolymère acrylique élastique filmogène aqueux en tant qu'agent liant et des particules conductrices d'électricité mélangées avec l'agent liant en quantité telle à ce que la résistivité superficielle du revêtement séché soit de l'ordre de 1 x 10E3 à 1 x 10E1 ohm/sq., le mélange constitué de l'agent liant et des particules conductrices d'électricité formant un revêtement transparent.
PCT/FI2010/050092 2010-02-11 2010-02-11 Revêtement WO2011098656A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/FI2010/050092 WO2011098656A1 (fr) 2010-02-11 2010-02-11 Revêtement

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/FI2010/050092 WO2011098656A1 (fr) 2010-02-11 2010-02-11 Revêtement

Publications (1)

Publication Number Publication Date
WO2011098656A1 true WO2011098656A1 (fr) 2011-08-18

Family

ID=44367320

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2010/050092 WO2011098656A1 (fr) 2010-02-11 2010-02-11 Revêtement

Country Status (1)

Country Link
WO (1) WO2011098656A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6286066A (ja) * 1985-10-14 1987-04-20 Sumitomo Chem Co Ltd 透明導電性塗料
US5494609A (en) * 1992-04-15 1996-02-27 Kulkarni; Vaman G. Electrically conductive coating compositions and method for the preparation thereof
US5536770A (en) * 1993-10-16 1996-07-16 Merck Patent Gesellschaft Mit Beschrankter Haftung Conductive coating formulation
US20050214526A1 (en) * 2004-03-25 2005-09-29 Dagmar Klein Transparent, electrically conductive, coated polyester film, process for its production, and its use
WO2006035112A1 (fr) * 2004-09-30 2006-04-06 Panipol Oy Bande fibreuse enduite et son procede de fabrication
US20080113195A1 (en) * 2006-10-25 2008-05-15 Bayer Materialscience Ag Silver-containing aqueous formulation and its use to produce electrically conductive or reflective coatings
WO2009018261A2 (fr) * 2007-08-01 2009-02-05 Honeywell International Inc. Matériaux conducteurs à rhéologie régulée, procédés de production et utilisation de ceux-ci

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6286066A (ja) * 1985-10-14 1987-04-20 Sumitomo Chem Co Ltd 透明導電性塗料
US5494609A (en) * 1992-04-15 1996-02-27 Kulkarni; Vaman G. Electrically conductive coating compositions and method for the preparation thereof
US5536770A (en) * 1993-10-16 1996-07-16 Merck Patent Gesellschaft Mit Beschrankter Haftung Conductive coating formulation
US20050214526A1 (en) * 2004-03-25 2005-09-29 Dagmar Klein Transparent, electrically conductive, coated polyester film, process for its production, and its use
WO2006035112A1 (fr) * 2004-09-30 2006-04-06 Panipol Oy Bande fibreuse enduite et son procede de fabrication
US20080113195A1 (en) * 2006-10-25 2008-05-15 Bayer Materialscience Ag Silver-containing aqueous formulation and its use to produce electrically conductive or reflective coatings
WO2009018261A2 (fr) * 2007-08-01 2009-02-05 Honeywell International Inc. Matériaux conducteurs à rhéologie régulée, procédés de production et utilisation de ceux-ci

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