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WO2006035112A1 - Bande fibreuse enduite et son procede de fabrication - Google Patents

Bande fibreuse enduite et son procede de fabrication Download PDF

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Publication number
WO2006035112A1
WO2006035112A1 PCT/FI2005/000417 FI2005000417W WO2006035112A1 WO 2006035112 A1 WO2006035112 A1 WO 2006035112A1 FI 2005000417 W FI2005000417 W FI 2005000417W WO 2006035112 A1 WO2006035112 A1 WO 2006035112A1
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WO
WIPO (PCT)
Prior art keywords
electrically conductive
conductive polymer
pigment
weight
approximately
Prior art date
Application number
PCT/FI2005/000417
Other languages
English (en)
Inventor
Jukka Perento
Soili Peltonen
Kirsi Immonen
Hannu Mikkonen
Original Assignee
Panipol 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 Panipol Oy filed Critical Panipol Oy
Priority to EP05794627A priority Critical patent/EP1794364A1/fr
Publication of WO2006035112A1 publication Critical patent/WO2006035112A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • 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
    • 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
    • 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
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads

Definitions

  • the present invention relates to a coated fibrous web in accordance with the preamble of Claim 1
  • a fibrous web such as this usually comprises a base web, at least one surface of which comprises a pigment-bearing coating layer.
  • the present invention also relates to a method of manufacturing coated fibrous web, according to the preamble of Claim 13.
  • electrostatic phenomena cost the electronics industry several billion euros every year. As components increase their speeds and their sizes decrease, their vulnerability to electrostatic charging and discharging (hereafter also abbreviated as "ESD”) increases, too. Moreover, these ESD phenomena affect the productivity and the functionality of products in almost all fields of the electronic industry. Managing ESD is important in clean room applications and in the graphics industry, too.
  • One way to decrease ESD is to incorporate electrically conductive components in the packages of electronic products, in floor coverings or underlay coatings.
  • conductive components are metal powders, graphite and electrically conductive polymers. These polymers are arousing more and more interest because, among other things, it is possible to flexibly modify their properties and in turn, for example, adjust the electrical conductivity to a desired level depending on whether ESD protection or antistatic properties are desired. This has led to electrically conductive polymers being used, among other things, in antistatic packages and in products which protect against electromagnetic radiation. Due to their properties these polymers are also suitable for use as electrodes of primary or secondary batteries and also for security paper application.
  • Microwave packages comprising electrically conductive polymers, in turn, are known from US Patent Specification 5,211,810. Electrically conductive polymers have been incorporated in the above-mentioned products which comprise cellulosic fibres, by mixing the polymers with the fibres or by polymerizing the polymers onto the surface of the fibres.
  • the acid modifies for instance the amorphous areas of the cellulose, lowers the strength, keratinizes the fibre and decreases the water retention capacity of the fibre. Keratinized fibre also demands considerably more grinding energy. The effect of a low pH-treatment is almost equivalent to drying the cellulose.
  • a method of manufacturing wallpaper which protects against electromagnetic radiation is also known.
  • ordinary wallpaper is coated with a mixture that comprises a matrix polymer, an electrically conductive polymer and additives mixed with these (EP Published Patent Application 1,139,710).
  • the affixing of the electrically conductive polymer onto the paper surface represents an additional treatment step, one that is intended to create a separate surface layer which otherwise would not exist in the structure of the paper.
  • It is an aim of the present invention is to eliminate the disadvantages associated with the known technology and to generate a new fibre web comprising an electrically conductive polymer and a method for its production.
  • the present invention is based on the idea that a paper or cardboard product, the production costs of which are competitive, and which comprises electrically conductive polymer, is produced most suitably in such a way that the electrically conductive polymer is brought onto the surface of the fibre web in association with an ordinary coating process.
  • the electrically conductive polymer-bearing layer is spread, i.e. applied onto the surface of the paper or cardboard surface, to form a coating layer.
  • a coated fibrous web which has at least a first layer comprising cellulosic and/or lignocellulosic fibres, and a second layer comprising a coating layer which is on the top of the fibrous web and which comprises synthetic electrically conductive polymer mixed into a binding agent and light scattering pigments.
  • the electrically conductive polymer is brought onto the surface of the pigments and at least partially attached to them.
  • the coating layer on the surface of the fibrous web is conductive or it must be made conductive at least in part of the coating layer.
  • the invention can be used to bring the conductive polymer onto the surface of the paper or cardboard using a conventional coating technique, hi this way, additional process steps can be avoided.
  • the conductive polymer is placed on the surface of the base paper and being completely incorporated in the coating layer, it does not disturb the existing main functions of the paper. Rather, the surface of the paper or cardboard can, for example, be used as a surface for printing and at the same time the cellulosic or lignocellulosic matrix of the base paper gives the product the desired strength properties.
  • the polymer can be incorporated into one or several coating layers. If it is added only in the precoating layer, it is possible to hide the conductive layer under the surface coating. This is advantageous if it is desired to hide the colour of the polymer in the product surface, such as the green colour in the case of polyaniline.
  • the electrically conductive polymer can be used in one single or in several surface coating layers, if it is desirable that the conductive layer is as close to the surface as possible.
  • the place at which the polymer is added can also be chosen according to the pigment.
  • an acidic pH-value is advantageous for the conductivity of the polymer, in which case an acid-stable pigment is preferably chosen as the pigment for a layer which comprises electrically conductive polymer. In a way which is known per se the pigments of the coating used in the precoating can be different from those in the surface coating, in which case a less acid-stable pigment can be used in the layer containing no electrically conductive polymer.
  • An electrically conductive polymer in the coating layer can provide several different functions; also, it is not directly visible to the consumer.
  • the conductive polymer can be utilized for example for equipping the product with additional information or for checking the authenticity of the product. No contact is needed for measuring conductivity. Non- contact measurement, for instance capacitive measurement, can be carried out at a short distance.
  • the amount of the electrically conductive polymer it is possible to reach a selected conductivity level, which is, for example, 10 4 -10 ⁇ ohm/square, typically approximately 10 -10 ohm/square.
  • a selected conductivity level which is, for example, 10 4 -10 ⁇ ohm/square, typically approximately 10 -10 ohm/square.
  • the product can easily be distinguished from non-conductive products.
  • a conductive network into the paper or cardboard it is possible to provide the surface with several different functions which, depending on the conductivity level, are associated with antistatic applications, storage of identification data, security marks, etc.
  • the present invention provides a novel fibrous product having an electrical conductivity, one which is maintained over extended periods of time. When attached to the pigment which, in turn, is mixed into the binder, the polymer is evenly and homogeneously distributed throughout the whole web surface.
  • Another special advantage which is attained with pigment coating is that it is easy to adjust the amount of the electrically conductive polymers by changing the amount of the coating to be applied.
  • the EP Published Patent Application 1,010,733 describes a polymer composition which is suitable for coatings and which has a good refractivity, conductivity and translucency.
  • the composition comprises mainly C 1 -C 3 alcohol and amide with dissolved polytiophene-based conductive polymer, high refractivity inorganic sol, resin binders and dopant comprising a sulphonic acid group.
  • a composition such as this can be used to coat the outer surface of a CRT tube by means of spin or spray coating.
  • the references disclose no statements about the fact that the described compositions would be used to coat fibrous webs. In known solutions, no references to usability of products generated in this way, for instance in the production of security products, can be found either.
  • the fibrous web comprises a base paper or corresponding uncoated web which consists of cellulosic or lignocellulosic fibres.
  • the cellulosic or lignocellulosic fibres can be sourced from mechanical, chemi-mechanical or chemical pulp which is produced from plant fibres (one-year or perennial fibres).
  • the fibrous web comprises a conventional paper or cardboard web which is produced from paper or cardboard pulp made of wood based fibres.
  • non-woven products and fabrics can be coated, too.
  • the latter can be made of natural fibres or synthetic fibres, or combinations of these.
  • a coating layer comprising a synthetic electrically conductive polymer which is mixed into the binder that forms the binder matrix.
  • matrix is meant a polymer network or layer, one which is at least partially continuous in such a way that it is capable of forming continuous surfaces and layers.
  • the second layer is at least partially electrically conductive or it can be rendered electrically conductive.
  • the surface resistivity of a second layer is in the electrically conductive form approximately 10 2 -10 n ohm, preferably approximately 10 3 -10 10 ohm, in particular approximately 10 4 -10 9 ohm. In the examples below, a surface resistivity of 10 5 -10 9 ohm was reached.
  • the grammage of the web to be coated is generally approximately 5-700 g/m 2 , typically approximately 20-500 g/m 2 , for instance approximately 30-150 g/m 2 in the case of paper, and 80-300 g/m 2 with cardboard.
  • the total grammage of the product is generally 10-1500 g/m 2 , typically approximately 40-1000 g/m 2 .
  • the bottom web can comprise one layer or comprise a two or more layer web which is made using for instance a "layer webbing technique" - for example as used with a multilayer headbox - or by laminating.
  • a coating colour according to the invention contains 10-100 parts by weight of at least one pigment or a mixture of pigments, 0.1-30 parts by weight of at least one binder, 0.1-50 parts by weight of an electrically conductive polymer and 1-10 parts by weight of other additives known per se.
  • a more preferable coating mixture comprises a conventional pigment and a pigment coated with conductive polymer with a weight ratio of 100: 1...100:50.
  • a pigment coated with an electrically conductive polymer comprises an electrically conductive polymer which is 1-30 % by weight of the pigment weight.
  • composition of a precoating mixture is as follows:
  • Water balance Water is added to the precoating mixture so that the solids content is generally from 40 to 70 %.
  • composition of the surface-coat mixture or single coat mixture is for example as follows:
  • Water is added to such a coating mixture so that the dry solids content is typically from 50 to 75 %.
  • pigments that have a steep particle size distribution, which means that a maximum of 35 % of the pigment particles are smaller than 0.5 ⁇ m, preferably at maximum 15 % are smaller than 0.2 ⁇ m.
  • the present invention can be applied to any pigment, particularly light-scattering pigments, and typically mineral or synthetic pigments.
  • pigments are precipitated calcium carbonate, ground calcium carbonate, calcium sulphate, calcium oxalate, aluminium silicate, kaolin (hydrous aluminium silicate), aluminium hydroxide, magnesium silicate, talc (hydrous magnesium silicate), titanium dioxide and barium sulphate, and mixtures of them.
  • synthetic pigments too.
  • the main pigments are kaolin, calcium carbonate, precipitated calcium carbonate and gypsum, which in general constitute over 50 % of the dry solids in the coating mix.
  • Calcined kaolin, titanium dioxide, satin white, aluminium hydroxide, sodium silicoaluminate and plastics pigments are additional pigments, and their amounts are in general less than 25 % of the dry solids in the mix.
  • special pigments special-quality kaolins and calcium carbonates, as well as barium sulphate and zinc oxide, should be mentioned.
  • the present invention is applied, in particular, to mineral pigments selected from aluminium silicate and aluminium hydroxide, magnesium silicate, titanium dioxide and/or barium sulphate, as well as mixtures thereof.
  • spherical Hollow Pigment which is marketed by, among others, Roehm & Haas (e.g. under their brand name "Ropaque”)- Dow Chemical has corresponding products, too (HS - Hollow Sphere Plastic Pigments).
  • This pigment is synthetic and comprises a hollow latex ball approximately 0.1-10 ⁇ m in size; typically its average particle size is approximately 0.5-2 ⁇ m.
  • the Ropaque product comprises styrene-acryl polymer, its void volume is over 50 % and density 1.02 g/cm 3 . Characteristically, therefore, it possesses a large surface in relation to its weight and, as a result, the surface weight of the coating can be decreased because the pigment gives a good coverage.
  • the amount of the electrically conductive polymer can be decreased. Because at least part of the pigment is flattened during the coating process, part of which is the IR drying and the following calendering, the conductive polymer that is attached to the surface of the pigment is able to form, even when used at low volumes, a continuous and conductive surface on the top of the fibrous web.
  • Hollow Pigment has high glass transition point, tg, which is close to the tg of conductive polymer.
  • the pigments are easy to use and it is possible to achieve a high conductivity even when using a pigment which is coated with 10-12 % by weight of electrically conductive polymer in the coating paste.
  • Hollow Pigment coated with conductive polymer can be used not only for coating paper and cardboard but also for modifying paints.
  • binders in the coating mixture it is possible to use any known binders generally employed in paper production. Besides individual binders, it is also possible to use mixtures of binders.
  • typical binders include synthetic latexes made of polymers or copolymers of ethylenically unsaturated compounds, for instance copolymers of the butadienestyrene type, which possibly also have a comonomer containing a carboxyl group, such as acrylic acid, itaconic acid or maleic acid, and polyvinyl acetate having comonomers that contain carboxyl groups.
  • binders for example, the water-soluble polymers, starch, CMC, hydroxyethyl cellulose and polyvinyl alcohol.
  • additives and auxiliary agents such as dispersants (e. g. sodium salt of polyacrylic acid), agents affecting the viscosity and water retention of the mix (e.g. CMC, hydroxyethyl cellulose, polyacrylates, alginates, benzoate), lubricants, hardeners used for improving water-resistance, optical auxiliary agents, anti- foaming agents, pH control agents, and preservatives, in the coating composition.
  • dispersants e. g. sodium salt of polyacrylic acid
  • agents affecting the viscosity and water retention of the mix e.g. CMC, hydroxyethyl cellulose, polyacrylates, alginates, benzoate
  • lubricants e.g. CMC, hydroxyethyl cellulose, polyacrylates, alginates, benzoate
  • hardeners used for improving water-resistance
  • optical auxiliary agents e.g., anti- foaming agents, pH control agents, and preservatives, in the coating composition
  • Examples of lubricants include sulphonated oils, esters, amines, calcium or ammonium stearates; an example of agents improving water resistance is glyoxal; examples of optical auxiliary agents are diaminostilbene disulphonic acid derivatives; examples of anti- foaming agents are phosphate esters, silicones, alcohols, ethers, vegetable oils; examples of pH control agents are sodium hydroxide, ammonia, sulphuric acid, acetic acid and sulphonic acids; and finally examples of preservatives are formaldehyde, phenol, quaternary ammonium salts.
  • the coating mix can be applied to the material web in a manner known per se.
  • the method according to the present invention for coating paper and/or cardboard can be carried out with a conventional coating apparatus, i.e. by blade coating, or film coating or spray application or curtain coating.
  • the conductivity of the electrically conductive polymer is adjusted using an acid or, correspondingly, an alkali, as described in detail below. Because a high level of conductivity is usually achieved in a clearly acidic pH area, it is advisable to choose the components of the coating material mix in accordance with the above in order to allow the coating layer to function well in different conditions. This means that many of the binders mentioned above are alkaline, for example. They must be neutralized if it is desirable to bring the conductive polymer into the coating layer in a conductive form. Certainly it is possible to apply the layer comprising electrically conductive polymer in an alkaline form and change it to a conductive form after the coating, for example during the printing stage.
  • an electrically conductive polymer which is an inherently electrically conductive polymer and which can be "doped" to generate charge carriers, and the polymer in question is attached to pigments.
  • Electrode conductive polymers means inherently electrically conductive polymers (ICP), which are "doped” (furnished, processed) in order to generate charge carriers (holes and electrons). Common to all electrically conductive polymers are the conjugated double bonds of the backbone chain (alternate single and double bonds, delocalized silicon electron system), which enable the movement of the charge carriers. Electrically conductive polymers have both ionic and electronic conductivity, which can be utilized in various applications. The conductivity of electrically conductive polymers can fluctuate and be regulated within the whole conductivity range, from insulant to metallic conductor. Generally, a polymer is considered to be electrically conductive if its maximum resistance is 10 11 ohm (as surface resistivity).
  • electrically conductive polymer can be present in the binding agent layer both in an electrically conductive and in an electrically non-conductive form. Consequently, the term "electrically conductive polymer” in the claims presented below also means a polymer that is non-conductive at the time of reference, but which, however, can be brought to an electrically conductive state, for instance by using a suitable doping agent treatment.
  • One of the advantages when using inherently conductive polymers is, among others, that by using doping the coated product can be equipped with desired electrically conductive patterns.
  • Polyaniline, polypyrrol, polyacetylene, polyparaphenyl or polytiophene, or derivatives or mixtures of them, are used as electrically conductive polymers.
  • the derivatives the alkyd and aryl derivatives and the chlorine and bromine-substituted derivatives of the polymers mentioned above are particularly worth mentioning.
  • electrically conductive particles such as graphite or carbon black can be added, too.
  • Polyaniline is more preferable in the present invention.
  • the monomer in the aniline polymer is aniline or a derivative of that, and the nitrogen atom of the monomer is in most cases bonded to the para-position carbon of the benzene ring of the next unit.
  • the unsubstituted polyaniline can be in different forms, among which the emeraldine form, which as a salt is characterized by a clear, emerald-green colour, hence its name, is generally used for conductive polymer applications.
  • the electrically neutral polyaniline can be converted into a conductive polyaniline-complex.
  • the doping agents used in the present invention can vary widely and they are generally employed when conjugated polymers are doped into an electrically conductive or semiconductive form.
  • Protonic acids are known doping agents in the field of inherent conductive polymers, as can be seen from the references by J. -C. Chiang and Alan G. MacDiarmid, and in the W. R. Salaneck citation: o Chiang et al., Synth. Metals (1986) 13: 193-205 o MacDiarmid et al., Papers from the 6th European Physical Society Industrial
  • Such doping agents comprise inorganic or organic acids, and their derivatives, among which mineral acids, sulphonic acids, picric acid, n-nitrobenzene acid, dichloric acetic acid and polymer acids are typical examples. If desired, more than one doping agent can be used.
  • a functional acid is used for doping, such as a sulphonic acid, particularly an aromatic sulphonic acid, which comprises one aromatic ring, or two fused rings, in which case at least one ring may have a polar or a non-polar cyclic substituent, such as a functional group (for instance a hydroxyl group) or a hydrocarbon chain, such as an alkyl chain with 1-20 carbons.
  • a functional group for instance a hydroxyl group
  • hydrocarbon chain such as an alkyl chain with 1-20 carbons.
  • PSAs phenol sulphonic acids or hydroxybenzene sulphonic acids
  • PPA phenyl phosphine acids
  • Polystyrene (PSSA) polystyrene
  • polyolefins polyethylene oxide
  • polyvinyls polystyrene
  • polysulphonated polyparaphenylenes and sulphonated aromatic polyamides and similar substances are noteworthy examples of polymeric acids.
  • Preferred acids are dodecylbenzene sulphonic acid (DBSA), camphor sulphonic acid, para- toluene sulphonic acid and phenol sulphonic acid.
  • DBSA dodecylbenzene sulphonic acid
  • camphor sulphonic acid para- toluene sulphonic acid
  • phenol sulphonic acid phenol sulphonic acid.
  • Oxidizing agents are generally used to polymerize a monomelic compound into a corresponding electrically conductive polymer.
  • Preferred oxidizing agents are polyatomic metallic salts such as iron( ⁇ i) salts and per-compounds like peroxides, peracids, persulphates, perborates, permanganates, perchlorates and chlorates, nitrates and quinones.
  • the amount of oxidizing agent in relation to the monomer is generally from 10: 1 to 1 : 1, more preferably from approximately 5:1 to 2:1 (parts by weight) or from 4:1 to 1:1 as mole fractions (oxidant/monomer).
  • the electrically conductive polymer is incorporated in the coating composition by mixing it with a binder, for example in dispersion form, or - preferably - by first polymerizing it on the surface of the pigment after which the pigment coated with the electrically conductive polymer is mixed in a way known per se with the other components of the binder and the coating mixture.
  • a binder for example in dispersion form, or - preferably - by first polymerizing it on the surface of the pigment after which the pigment coated with the electrically conductive polymer is mixed in a way known per se with the other components of the binder and the coating mixture.
  • polyaniline can be used as a water paste in the case of aqueous binding agents.
  • concentration of polyaniline ranges, for instance, from 0.1 to 25 % by weight, preferably from approximately 0.5 to 20 % by weight and, particularly, from 5 to 17 % by weight. It is most suitable if the polyaniline is in a conductive form, in which case the previously mentioned concentration includes the amount of the doping agent.
  • concentration of polyaniline (without the doping agent) ranges generally from approximately 0.1 to 15 % by weight.
  • organic solvents for example toluene
  • the electrically conductive polymer is integrated into the compound already polymerized onto the surface of the pigment particles.
  • the coated pigments are produced by bringing the pigments into close contact with the monomer which forms the electrically conductive polymer, in an intermediate agent, preferably an aqueous intermediate agent. Besides water and aqueous solutions it is possible to use organic, polar and non-polar solvents.
  • close contact means that the pigments and the slurry comprising the monomeric pre-stage of polymer and/or the polymer doping agent are briskly mixed so that the monomer and/or the doping agent are well distributed among the pigments. It is possible to proceed as described in detail in the examples, that is by using the counter-ion and the monomer corresponding to the polymer to form a dispersion, to which the pigment to be coated is added and which is mixed to form a homogeneous dispersion, after which the oxidant is added in order to start the polymerization.
  • an aqueous intermediate agent means both water and aqueous solutions in which the pigments are elutriated.
  • the consistency of the aqueous slurry is 0.1-50 % (weight/weight), preferably approximately 0.5-30 and especially approximately 0.7-20 %.
  • the counter-ion of the electrically conductive material to be polymerized or a corresponding monomer can be dissolved in the aqueous phase.
  • the quantity of the doping agent varies according to the amount of the monomers. Generally, the monomer percentage is approximately 0.1-200 % of the quantity of the doping agent/pigment, typically approximately 1-150 % by weight, preferably approximately 5-120 % by weight and especially approximately 10-100 % by weight.
  • the amount of the counter-ions can be equimolar to the amount of the monomers, but it can also be approximately the same as the number of moles of the monomer ⁇ 30 %.
  • the temperature is generally above 0 0 C, but below room temperature. Typically, the temperature is approximately 1-18 °C, preferably approximately 2-15 0 C.
  • the counter-ion is acidic and in the pairing of the fibres and the polymer/monomer the pH-value of the aqueous phase is most suitably clearly acidic, preferably the pH is below 5, typically approximately 2 + 1.
  • the monomer amount (without the doping agent) is approximately 0.1-50 % by weight of the amount of pigment, most suitably approximately 1-30 % by weight, especially approximately 2-20 % by weight.
  • the present invention provides a binding agent compound in which the percentage of the electrically conductive polymer (doping agent) is approximately 0.01-20 %, preferably approximately 0.05-15 %, most suitably approximately 0.1-10 % of the total weight of the compound.
  • the percentage of the electrically conductive polymer of the coating layer formed by a compound like this is approximately 0.1-15 % by weight, preferably approximately 0.2-10 % by weight, typically approximately 0.5-7 % by weight, after the drying of the layer.
  • the electrically conductive polymer is at least partially bound to the binder, part of it can be dispersed or otherwise mixed into the binder, but typically at least 20 % by weight, preferably at least 50 % by weight, most suitably at least 75 % by weight of the electrically conductive polymer is attached to the surface of the pigment.
  • the present invention also includes the case in which practically all the electrically conductive polymer is bound to the pigment.
  • the pH value of the compound should preferably be kept on the acidic side, if the electrically conductive polymer is introduced (dispersed or attached to the pigment) in an electrically conductive form and there is no intention to change its electrical conductivity.
  • a suitable pH value is 1-6.5, more preferebly approximately 1.5-5.
  • the coating mix can be applied to the material web in a manner known per se.
  • the method according to the present invention to coat paper and/or cardboard can be carried out with a conventional coating apparatus, i.e. by blade coating, or film coating or spray application.
  • a coating layer is formed having a grammage of 5 to 30 g/m 2 .
  • the uncoated side can be treated by, for example, surface sizing.
  • the coated product in accordance with the present invention can be used to accommodate the introduction of electronic information as well as for communication and creating security symbols.
  • it is beneficial that the conductivity of the electrically conductive polymer in the coating layer has been changed locally to form an electrically conductive pattern or a non-conductive pattern, respectively.
  • the electric conductivity of the polymer is changed by means of doping a non-conductive polymer or dedoping an electrically conductive polymer, respectively.
  • a non-conductive polymer is doped by treating the polymer layer with an acid solution, which is used to paint the desired pattern onto the surface of the paper or cardboard product.
  • the electrically conductive polymer is dedoped by treating the polymer layer with an alkali solution, which is used to paint the desired pattern on the surface of the paper or cardboard product.
  • Doping or dedoping, respectively can be achieved by printing the desired pattern on the surface of a paper or a cardboard product by using printing ink capable of doping or dedoping the electrically conductive polymer. If the layer comprising the electrically conductive polymer is coated with another, non-conductive layer, the doping/dedoping reaction can be generated through the non-conductive layer, too.
  • acid solutions are suitable for doping or dedoping.
  • acid solutions the same acids as in the doping of the electrically conductive polymer can be used (see above) or, alternatively, different acids can be used.
  • Conventional hydroxides and carbonates alkali metal and alkali earth metal hydroxides and carbonates
  • different kinds of amines can be used as alkalis.
  • Sodium hydroxide, potassium hydroxide and sodium carbonate are common alkalis.
  • acids and alkalis are used as relatively dilute solutions (approximately 0.01 to 5 N, for example approximately 0.1 to 1 N solutions) to avoid brittleness of the fibre matrix.
  • the surface of the coating layer can be provided with a visual mark indicating the layer which contains the electrically conductive polymer. This mark discloses what kind of information is contained in the layered product.
  • the surface of the paper or cardboard product is provided with a printed pattern, which indicates how the electrical conductivity of the second layer can be detected.
  • ESD packages which are especially suitable for the needs of the electronics industry.
  • packages made of coated cardboard blanks can be used in any application where for instance a dust-free surface or a safety mark is technically or economically advantageous.
  • Such applications are packaging for food and similar products (in these instances, it is preferable that a barrier sheet such as a polyethylene sheet) is fitted between the coated surface and the contents.
  • the polymerization was carried out as follows. The acid used was added to the quantity of water described in the table. Mixing was carried out for approximately 10 minutes. The aniline was added (over a period of 5 minutes) and in some cases phenylene diamine and mixing was carried out for a period of 15 minutes. Next, the titanium dioxide powder was added followed by a mixing for a period of 15 minutes. The APS was dissolved in water and this APS solution was added to the reactor over the period and at the temperature shown in the table.
  • the reaction continued according to the time shown in the table. The reaction mixture was then allowed to settle over night. If it was impossible to decant the solution, the reaction mixture was centrifuged and washed with water until the pH was > 3. The product was then either air-dried or freeze- dried.
  • Table 2 shows the material quantities and the reaction conditions for the bench-scale tests. The polymerizations were carried out by using five different counter-ions in the reaction.
  • PSA Sulphocarbolic acid
  • the polymerization was carried out as described in tests 1-4.
  • tests 5, 8, 9 and 10 the separation of the product was carried out by letting the product settle and decanting water from the surface, after which the product was washed with water and left to settle.
  • the product was separated and the water was washed by suction filtering.
  • test 6 the reaction mixture was left to settle using an ethanol-water mixture (1:1), then suction filtered and washed with water. Before drying, the pH of the products was 2.5-3.5.
  • the powder preparation in tests 5 and 6 was carried out by drying the product in a heating chamber (37 0 C) and grinding it to powder using a mill.
  • tests 7, 8, 9 and 10 the product was dried to a powder using a spray-dryer.
  • a sheet was prepared on cardboard by applying the reaction mixture using a metallic spiral rod (rod number 4), after which the sheet was dried in a heating chamber at 105 0 C for 10 minutes.
  • a sample was prepared by first mixing the powdery product with the binder, namely a polyvinyl alcohol-water solution (dry solids 10 %), and then applying the mixture onto the cardboard surface using a metallic rod, and, finally, drying the cardboard in a heating chamber at 105 0 C for 10 minutes.
  • the surface resistivity of the dry sheet on the cardboard surface was measured by using an instrument which measures the electric resistance between two parallel 6.5 cm metal bars placed on the surface of the sample. The distance between the bars is 4 cm.
  • the measurement voltage is 10 V in the conductive area ⁇ 10 5 ohm and 100 V in the area >10 5 ohm.
  • the polymerization was carried out in the same way as in Example 1 above and using material quantities, reaction temperature and reaction times described in Table 3.
  • the product was separated by ethanol precipitation (ethanol 1/3 of the reaction mixture quantity) and followed by filtering the sediment generated.
  • the sediment was washed twice with an ethanol- water solution (1:1 v/v), then dried first at room temperature and finally in a heating chamber at 30 0 C.
  • Hollow Pigment latex (200 g) was diluted with water by adding a volume of water equivalent to half of the weight of the latex.
  • the pH of the diluted latex was adjusted with 0.1 M sulphuric acid (22 ml) to pH 7 and the reaction mixture was diluted to 500 ml.
  • 3.0 g of aniline was added over a period of 15 minutes and thereafter 10.5 g of DBSA over a period of approximately 0.5 h.
  • the reaction mixture was cooled to approximately 10 0 C and the APS solution (15 g APS in 25 g of water) was added over a period of approximately 0.5 h. After that, the temperature of the reaction mixture was kept below 10 0 C for approximately 2 h and thereafter it was allowed to warm up to room temperature over a period of approximately 4 h.
  • the resulting product was a homogeneous dispersion.
  • the polymerization was carried out by using material amounts described in Table 4.
  • the Hollow Pigment latex was diluted with water by adding a volume of water equivalent to half of the weight of the latex.
  • the pH of the diluted latex was adjusted with 0.1 M sulphuric acid to pH 7.
  • the aniline was mixed in water and DBSA was added to the mixture over a period of approximately 1 h and the mixing was continued until the emulsion was homogeneous.
  • the aniline/DBSA emulsion was added into the latex over a period of approximately 1 h and the reaction mixture was cooled to approximately 10 0 C.
  • the APS solution was added over the period of time described in the table and the reaction continued after the addition for a period of time shown in the table.
  • the temperature was allowed to increase to the temperature described in the table.
  • the resulting product was a homogeneous dispersion.
  • the aniline was polymerized onto the surface of Hollow Pigment as follows. 1.6 kg of Hollow Pigment latex (dry solids 32 %) were diluted by adding 1.4 kg of water to it. The pH of the latex was adjusted with 0.1 M sulphuric acid to pH 7. The aniline was mixed into 4 kg of water and DBSA was added while briskly stirring the solution for approximately 1 h. The emulsion generated continued to be mixed for a further 1 h, after which it was added to the Hollow Pigment latex over a period of approximately 1 h. The reaction mixture was then cooled to ⁇ 10 0 C.
  • APS 120 g was dissolved into 200 g of water and added to the reaction mixture over a period of 3 h, keeping the temperature at 8-10 0 C. After the addition, the cooling was stopped and the mixture continued to be mixed for another 2 h, and the temperature was allowed to increase to 16 0 C.
  • the resulting product was a homogeneous green dispersion, the conductivity of which was at the level of E+5, measured as surface resistivity.
  • the dispersion can be cleaned by centrifuging the sediment and washing it with water, until the pH of the washing solution has increased to the desired level.
  • the colour of the dispersion was dark green and the conductivity of the reaction mixture, measured as surface resistivity, was E+5 ohm/square.
  • the product was cleaned by adding to the reaction mixture ethanol 1/3 of the amount of the reaction mixture (ETAX A 10, Primalco Oy) and, as a result, the product was precipitated.
  • the product was then filtered, i.e. washed with water using the filter?, until the pH of the filtrate was > 4.
  • the product was then dried in a heating chamber at 50 0 C.
  • the amount of dry product was 749 g.
  • Cotton fabric was treated according to the dispersion described in Example 4, Test 1.
  • the fabrics were dried either at room temperature or at 130 0 C.
  • the conductivities of the fabrics, measured as surface resistivity were 0.9 x E+6 and 0.5 x E+6 when the amount of dispersion applied during the treatment was 7.5 % of the amount of fabric.
  • the electrically conductive pigment can be attached to the surface of the fabric using different binding agents, too, to improve the coating's resistance to wear.
  • a paper coating paste was prepared at the KCL laboratory as follows. The components of the paste were: 88.7 parts of basic pigment (SPS), 11.3 parts of electrically conductive polymer product bonded to Hollow Pigment, 10 parts of latex (DOW-966) and 0.8 parts of carboxy-methyl cellulose (CMC-10). The paste was prepared using 60 % dry solids. The paste was applied to the cardboard surface and dried. Surface resistivity was used to measure the electrical conductivity of the coating. The coating was not conductive. When a conductive pigment was added as a supplementary addition to the said paste, a conductive pigment percentage of 20 % generated a coating the surface resistivity value of which was E+6...E+7 ohm/square.
  • SPS basic pigment
  • DOW-966 electrically conductive polymer product bonded to Hollow Pigment
  • CMC-10 carboxy-methyl cellulose
  • Paper was coated with a 6.5 % mixture dispersion, comprising 90.4 % of the product according to Example 4, Test 2 above and 9.6 % of Acram ALW binder latex.
  • the mixture was applied to a cardboard surface and the cardboard was dried at 130 0 C.
  • the surface resistivity measured from the coating was E+5 ohm/square.
  • the dried coating could be recoated.
  • a polymeric coating was applied onto the first coating using a 5 % Mowital BH 45 ethanol solution, the conductivity remained at the level of E+5 ohm/square.
  • a 26 % mixed dispersion was prepared comprising 12.7 % of the product according to
  • Example 4 Test 2 and 87.3 % of starch polymer.
  • the mixed dispersion was applied onto a paper surface and the coated paper was dried at 130 0 C.
  • the surface resistivity measured from the coating was E+6 ohm/square.

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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)
  • Paper (AREA)

Abstract

Cette invention concerne un produit fibreux enduit et son procédé de fabrication. Le produit est composé d'une bande, formé de fibres de cellulose ou de lignocellulose, à la surface de laquellle se trouve une couche d'enduction comprenant un liant ainsi que des pigments de diffusion de la lumière. La couche d'enduction est constituée d'un polymère synthétique et électriquement conducteur mélangé au liant, et au moins partiellement attaché aux pigments; ainsi la couche d'enduction peut être rendue électriquement conductrice. La présente invention permet d'appliquer un polymère électroconducteur sur une surface de papier ou de carton, au moyen d'une technique d'enduction classique, ce qui permet d'éviter des étapes de traitement additionnelles, par exemple dans la production de matériaux d'emballage antistatiques.
PCT/FI2005/000417 2004-09-30 2005-09-30 Bande fibreuse enduite et son procede de fabrication WO2006035112A1 (fr)

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EP05794627A EP1794364A1 (fr) 2004-09-30 2005-09-30 Bande fibreuse enduite et son procede de fabrication

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FI20041272A FI20041272L (fi) 2004-09-30 2004-09-30 Päällystetty kuiturata ja menetelmä sen valmistamiseksi
FI20041272 2004-09-30

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011098656A1 (fr) * 2010-02-11 2011-08-18 Dinoto Oy Revêtement
CN109047321A (zh) * 2018-09-10 2018-12-21 山东大学 一种基于聚苯胺辅助电极的多电极系统电动修复土壤方法
FR3078341A1 (fr) * 2018-02-26 2019-08-30 Association Pour Les Transferts De Technologies Du Mans Primaire antistatique en base aqueuse, et procede pour la mise en peinture de substrats electriquement isolants
US11056250B1 (en) * 2011-08-29 2021-07-06 University Of New Brunswick Conductive surface coating based on modified and unmodified particles and method of preparation thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887496A (en) * 1972-08-02 1975-06-03 Dow Chemical Co Quaternary ammonium electroconductive resin coating compositions
US4007148A (en) * 1974-12-19 1977-02-08 The Dow Chemical Company Electroconductive coatings having excellent coating holdout properties
EP0905560A1 (fr) * 1997-09-29 1999-03-31 Eastman Kodak Company Couche électroconductrice comprenant de l'argile pour des éléments photographiques
EP1081548A1 (fr) * 1999-08-30 2001-03-07 Eastman Kodak Company Composition de revêtement comprenant du polythiophène et un mélange de solvants
US20030062510A1 (en) * 2001-03-29 2003-04-03 Agfa-Gevaert Aqueous composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and a non-newtonian binder
WO2003048229A1 (fr) * 2001-12-04 2003-06-12 Agfa-Gevaert Composition renfermant un polymere ou un copolymere d'un 3,4-dialcoxythiophene et un solvant non aqueux

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887496A (en) * 1972-08-02 1975-06-03 Dow Chemical Co Quaternary ammonium electroconductive resin coating compositions
US4007148A (en) * 1974-12-19 1977-02-08 The Dow Chemical Company Electroconductive coatings having excellent coating holdout properties
EP0905560A1 (fr) * 1997-09-29 1999-03-31 Eastman Kodak Company Couche électroconductrice comprenant de l'argile pour des éléments photographiques
EP1081548A1 (fr) * 1999-08-30 2001-03-07 Eastman Kodak Company Composition de revêtement comprenant du polythiophène et un mélange de solvants
US20030062510A1 (en) * 2001-03-29 2003-04-03 Agfa-Gevaert Aqueous composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and a non-newtonian binder
WO2003048229A1 (fr) * 2001-12-04 2003-06-12 Agfa-Gevaert Composition renfermant un polymere ou un copolymere d'un 3,4-dialcoxythiophene et un solvant non aqueux

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011098656A1 (fr) * 2010-02-11 2011-08-18 Dinoto Oy Revêtement
US11056250B1 (en) * 2011-08-29 2021-07-06 University Of New Brunswick Conductive surface coating based on modified and unmodified particles and method of preparation thereof
FR3078341A1 (fr) * 2018-02-26 2019-08-30 Association Pour Les Transferts De Technologies Du Mans Primaire antistatique en base aqueuse, et procede pour la mise en peinture de substrats electriquement isolants
CN109047321A (zh) * 2018-09-10 2018-12-21 山东大学 一种基于聚苯胺辅助电极的多电极系统电动修复土壤方法

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FI20041272L (fi) 2006-03-31
FI20041272A0 (fi) 2004-09-30

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