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
  • 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
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
• • 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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/66—Salts, e.g. alums
• • 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
  • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31779—Next to cellulosic
  • Y10T428/31783—Paper or wood
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/3188—Next to cellulosic
  • Y10T428/31895—Paper or wood

Definitions

• the present invention consists in implementing certain rheological additives which make it possible both to regulate the viscosity of the medium so as to avoid any problem of destabilization, and which also make it possible to advantageously improve the water retention of the sauce.
• the inkjet printing technique allows printing of a carrier paper by means of ink droplets.
• the latter are ejected or propelled from different mechanical means to a paper medium, on which they form dots that create the corresponding text or image.
• This coating is called “coating color”: it is an aqueous formulation typically containing water, at least one mineral filler, one or more binders and various additives.
• coating colors intended for inkjet-type printing it is possible to introduce either inorganic or organic salts or cationic species whose primary function is to fix the ink as it reaches the surface. paper in the form of droplets.
• the documents WO 2009/110910, WO 2010/068193 and WO 2011/008218 give examples of such formulations containing salts, whereas the document WO 2007/112013 relates to coating sauces containing cationic species, all of these documents being relating to inkjet technology.
• the mineral filler introduced into the coating color is conveyed in the form of an aqueous suspension.
• this filler is a calcium carbonate suspended in water by means of a dispersing agent.
• the most widespread dispersing agents are anionic polymers of low molecular weight (less than 10,000 g / mol) which are homopolymers of acrylic acid.
• weakly anionic dispersants which are low molecular weight copolymers of acrylic acid with a methoxy or oxyalkylated hydroxy monomer; examples of these are found in WO 01/096007.
• the introduction of the salt or of the cationic compound may give rise to a problem during the additional introduction of a rheology agent whose the function is to regulate the viscosity and improve the water retention of said sauce.
• rheology agents are generally anionic polymers which have been observed that their introduction into inkjet sauces containing salts or a cationic compound causes a violent flocculation reaction, reflected by a sharp increase in viscosity, without any noticeable improvement in water retention.
• the Applicant has developed the use of weakly anionic polymer additives in these coating sauces, additives which, surprisingly, provide the desired sis thick function while substantially improving the water retention.
• additives are water-soluble polymers characterized in that they consist of, expressed in% by weight of each of their monomers: a) 5% to 40, preferably 5% to 20% of (meth) acrylic acid,
• R is a polymerizable function selected from methacrylate and methacrylurethane function
• EO and OP respectively denote oxides of ethylene and propylene
• m and n are 2 integers of which at least one is nonzero and are understood in a broad sense between 0 and 100
• R 'de denotes hydrogen or an alkyl group having 1 to 4 carbon atoms.
• a first object of the present invention is a method of manufacturing a coating color for an inkjet printing paper, comprising the steps of:
• R is a polymerizable function chosen from the methacrylate and methacrylurethane function
• EO and OP respectively denote the ethylene and propylene oxides arranged in a regular or random manner
• m and n are 2 integers, at least one of which is not no and are understood in the broad sense between 0 and 100
• R 'de notes hydrogen or an alkyl group having from 1 to 4 carbon atoms
• a second object of the present invention resides in the use, as stabilizing agent of a coating color for an inkjet printing paper, containing water, at least one inorganic filler in aqueous suspension in the presence of a dispersing agent, at least one binder, at least one inorganic or organic salt or a cationic compound, of at least one water-soluble polymer consisting of, expressed in% by weight of each of its monomers: a) 5% to 40% preferably 5% to 20% of (meth) acrylic acid, b) 60% to 95%, preferably 80% to 95% of at least one monomer of formula (I):
• R - (OE) m - (OP) n - R '(I) where R is a polymerizable function chosen from methacrylate and methacrylurethane function, EO and OP respectively denote oxides of ethylene and propylene, m and n are 2 whole, one of which less is non-zero and is understood in the broad sense between 0 and 100, R 'denotes hydrogen or an alkyl group having 1 to 4 carbon atoms.
• a third object of the present invention resides in a coating color for an inkjet printing paper containing water, at least one mineral filler in aqueous suspension in the presence of a dispersing agent, at least one binder at least one mineral salt or an organic salt or a cationic compound, and at least one water-soluble polymer consisting of, expressed in% by weight of each of its monomers: a) 5% to 40, preferably 5% to 20% of (meth) acrylic acid, b) 60% to 95, preferably 80% to 95% of at least one monomer of formula (I):
• R - (OE) m - (OP) n - R '(I) where R is a polymerizable function chosen from methacrylate and methacrylurethane function, EO and OP respectively denote oxides of ethylene and propylene, m and n are 2 at least one of which is non-zero and is understood in the broad sense between 0 and 100, R 'denotes hydrogen or an alkyl group having from 1 to 4 carbon atoms.
• the water-soluble polymer in question is totally or partially neutralized.
• its weight-average molecular weight is between 10,000 g / mol and 10,000,000 g / mol.
• so-called "low molecular weight” polymers of between 10,000 g / mol and 100,000 g / mol are used.
• high molecular weight polymers of between 1,000,000 g / mol and 10,000,000 g / mol are used.
• salt is meant a substance which is in ionic form composed of cations and anions forming a neutral product without neutral charge.
• Mineral salts classically come from rocks; organic salts contain carbon, hydrogen and oxygen.
• inorganic salts are calcium chloride, magnesium chloride, sodium chloride, potassium chloride, calcium bromide, sodium sulfate or mixtures of these salts.
• organic salts are sodium acetate, potassium acetate, sodium citrate, calcium citrate or mixtures of these salts.
• the coating color contains at least one mineral salt which is calcium chloride.
• cationic compound according to the present invention is meant a compound having a positive charge and having the function of fixing the ink on the surface of the paper.
• the coating color contains a cationic compound which is chosen from polydadmac, polymadquat or polyamine.
• binder is meant a compound having the function of bonding the inorganic filler particles (or pigments) together and keeping the layer on the surface of the paper.
• water-soluble binders such as CMC, PVOH, starch and / or synthetic latices (styrene-butadiene, styrene-acrylic, polyvinyl acetate).
• the inorganic filler is chosen from a natural, synthetic or chemically modified calcium carbonate.
• the mineral filler is a natural calcium carbonate.
• calcium carbonate includes ground calcium carbonate (GCC), that is, calcium carbonate obtained from natural sources, such as limestone, marble, calcite or lime, and that precipitated calcium carbonate (PCC), that is to say a synthesized substance, generally obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous environment or by precipitation a source of calcium and carbonate in water.
• GCC ground calcium carbonate
• PCC precipitated calcium carbonate
• chemically modified calcium carbonate is meant a carbonate of which at least one of the surface properties has been modified by a treatment from a chemical agent.
• the slurry suspensions of calcium carbonate are suspensions of insoluble solids in a liquid medium which is generally a mixture of water and at least one additive.
• the dispersant is chosen from an anionic or cationic dispersant.
• the skilled person can add in the coating sauce all the additives he deems necessary, chosen in a non-exhaustive manner from optical brighteners, anti -mosses and biocides.
• This example illustrates the manufacture of a coating color for inkjet printing paper, said sauce containing a cationic compound.
• This example illustrates the effects of various polymeric additives used on the rheology of said sauce as well as its water retention.
• a coating color is prepared by premixing an anionically dispersed aqueous suspension of calcium carbonate and marketed by Omya under the name Omyajet TM 5020 Me.
• a cationic polymer marketed by Coatex TM under the name Topsperse TM 67 K is added in an amount equal to 7.5 parts by dry weight per 100 parts by dry weight of calcium carbonate.
• the sauces are made with a solids content of 45.5% and have a pH adjusted to 8.5.
• the water retention is determined by a device of the AAGWR type marketed by GRADEK TM.
• This device consists of a measuring chamber in which there is a test paper called “Test Blotter Paper”, covered by a perforated plastic cloth called “Test Filter PCTE", the paper and canvas being marketed by the company GRADEK TM.
• the size of the perforations is 2 ⁇ .
• the AAGWR apparatus exerts some pressure on the coating color, driving all or part of the water and water-soluble substances contained in the sauce through the perforated plastic web and migrating into the test paper.
• a pressure of 1.5 bar is applied for 90 seconds.
• This test illustrates the invention and uses 0.8 parts by dry weight of a copolymer consisting of, expressed in% by weight of each of its monomers: a) 8% of acrylic acid, 2.5% of methacrylic acid,
• R is the methacrylate function
• EO and OP respectively denote oxides of ethylene and propylene
• This test illustrates the invention and uses 0.8 parts by dry weight of a copolymer consisting of, expressed in% by weight of each of its monomers: a) 6% of acrylic acid, 1.8% of methacrylic acid,
• R is the methacrylate function
• EO and OP respectively denote oxides of ethylene and propylene
• This test illustrates the invention and uses 1.2 parts by dry weight of the copolymer according to test No. 12.
• This test illustrates the invention and uses 0.8 parts by dry weight of the copolymer according to test No. 10, but with a weight average molecular weight of 4,200,000 g / mol.
• This example illustrates the manufacture of a coating color for an inkjet printing paper, said sauce containing a salt.
• This example illustrates the effects of various polymeric additives used, on the rheology of said sauce as well as on its retention of water.
• a coating color is produced by mixing an aqueous suspension containing 78% by dry weight of calcium carbonate, containing an anionic dispersant and marketed by Omya TM under the name Hydrocarb TM. 90 and 10 parts by dry weight of calcium chloride.
• the Resyn TM binder 1190 is then introduced.
• the mixture is made in such a way as to have 100 parts by dry weight of calcium carbonate per 10 parts by dry weight of binder.
• the polymer additive to be tested is then introduced into the sauce; the quantity used as well as its composition are given further.
• the sauces are made with a solids content of 60% and have a pH adjusted to 8.5.
• its Brookfield TM viscosity is then determined at 25 ° C. and at 100 rpm according to the technique well known to those skilled in the art, as is the value of its water retention, determined according to the protocol described. previously.
• This test illustrates the invention and uses 1 part by dry weight of the copolymer according to tests 14 and 15.
• This test illustrates the invention and uses 0.5 parts by dry weight of the copolymer according to tests 14, 15 and 17, and 0.2 parts by dry weight of the copolymer according to test No. 18.
• This test illustrates the invention and uses 1 part by dry weight of the copolymer according to tests 12 and 13.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Paper (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (13)

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• 2011
  • 2011-11-18 FR FR1103520A patent/FR2982887B1/fr active Active
• 2012
  • 2012-10-08 ES ES12779121.8T patent/ES2565527T3/es active Active
  • 2012-10-08 SI SI201230483T patent/SI2780508T1/sl unknown
  • 2012-10-08 WO PCT/FR2012/052272 patent/WO2013072586A1/fr not_active Ceased
  • 2012-10-08 CN CN201280055511.2A patent/CN103930620B/zh not_active Expired - Fee Related
  • 2012-10-08 JP JP2014541725A patent/JP6143770B2/ja not_active Expired - Fee Related
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  • 2012-10-08 EP EP12779121.8A patent/EP2780508B1/fr not_active Not-in-force
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