EP3720816A1 - Composition de pigment composite - Google Patents

Composition de pigment composite

Info

Publication number
EP3720816A1
EP3720816A1 EP18819452.6A EP18819452A EP3720816A1 EP 3720816 A1 EP3720816 A1 EP 3720816A1 EP 18819452 A EP18819452 A EP 18819452A EP 3720816 A1 EP3720816 A1 EP 3720816A1
Authority
EP
European Patent Office
Prior art keywords
pigment composition
composite pigment
weight
silicates
aluminium
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP18819452.6A
Other languages
German (de)
English (en)
Inventor
Sakari Saastamoinen
Sirpa SAASTAMOINEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Keusik Oy
Original Assignee
Keusik 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 Keusik Oy filed Critical Keusik Oy
Publication of EP3720816A1 publication Critical patent/EP3720816A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/13—Silicon-containing compounds
    • 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
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • 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
    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • 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
    • D21H19/64—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the present invention relates to a composite pigment composition which comprises titanium dioxide and at least one precipitated porous pigment.
  • the in- vention also relates to the use of such a composite pigment composition as a pig ment providing opacity and/or brightness. Further, the invention relates to the use of the composite pigment composition according to the invention as a titanium di- oxide substitute without impairment of the optical properties. The invention also re- lates to a method for preparing the composite pigment composition of the inven- tion.
  • Titanium dioxide is commonly used as a white pigment in paints, fillers of paper, carton, plastic, rubber, laminate and printing inks as well as in different kinds of coatings.
  • the most important properties achived by the use of titanium di- oxide are opacity, coverage, brightness, tintability and L-value.
  • T1O2 is the most ef- fective and very expensive pigment providing optical properties.
  • White titanium di- oxide is commercially available as anatase crystals and rutile crystals. Both anatase and rutile crystals are non-amorphous and widely commercially available. There are also amorphous forms of T1O2 but these are not commercially widely available.
  • extenders are typi- cally added to titanium dioxide to substitute part of the required amount of titanium dioxide.
  • Extenders are pigments or fillers, which are substantially cheaper than tita nium dioxide and which can be used to separate physically the crystals of titanium dioxide from each other and have the distances of the crystals more fitted for light scattering.
  • extenders should, however, be kept low, since the high refrac- tive index of T1O2 (about 2.49 - 2.61 ) gives finally the highest light scattering effi ciency and bigger amounts of extenders diminish the light scattering efficiency.
  • at most 25% by weight of titanium dioxide can be replaced in different appli- cations without losing the optical properties achvieved with titanium dioxide, es- pcially opacity.
  • the producers of titanium dioxide commonly coat titanium dioxide with different organic and/or inorganic precipitation or polymer products of chemicals in an amount of 1 -20% based on the weight of the pigment.
  • Patent publication WO 2009/109705 discloses replacing ti- tanium dioxide partly with calsium carbonate.
  • Patent publication WO 2015/007954 discloses compositions comprising titanium dioxide and addi- tives, which can be used for substitution of at least part of the titanium dioxide in said composition.
  • the first additive comprises a composite pigment comprising a shell-forming component and an optical pigment
  • a second additive comprises a reactive polymer.
  • the shell-forming component is preferably an inorganic corn- pound having a low water solubility, such as precipitated calcium carbonate, calcium sulphate, barium sulphate, magnesium carbonate, magnesium silicate, aluminium hydroxide or aluminium silicate.
  • An object of the present invention is to provide a composite pigment compo- sition, which comprises titanium dioxide and at least one precipitated porous pig ment.
  • the composite pigment composition according to the invention is suited to be used in fillers of paper, carton, plastic, rubber, laminate and printing inks, in coating compositions for coating paper, carton, plastic, rubber, concrete, metal, composites and wood as well as in decor papers and paints.
  • An object of the pre- sent invention is to provide a composite pigment composition, which comprises ti- tanium dioxide and at least one precipitated porous pigment for use as a pigment providing opacity and/or brightness.
  • an object of the present invention is the use of a composite pigment composition comprising titanium dioxide and at least one precipitated porous pigment as a titanium dioxide substitute without im- pairment of the optical properties.
  • An object of the present invention is also to pro- vide a method for preparing the composite pigment composition.
  • the invention is directed to a composite pigment composition comprising tita- nium dioxide and at least one precipitated porous pigment, which composition is suitable to be used in fillers of paper, carton, plastic, rubber, laminate and printing inks, in coatings of paper, carton, plastic, rubber, concrete, metal, composites and wood, as well as in paints.
  • the invention is directed to a use of the composite pig ment compostion as a pigment providing opacity and brightness.
  • the pre- sent invention is directed to the use of the composite pigment composition of the invention as a titanium dioxide substitute without impairment of the optical proper- ties.
  • the invention is also directed to a method for producing the composite pig ment composition of the invention.
  • the refractive index of air is about 1
  • the refractive indexes of other substances such as plastics, fibers, rubbers and the most of pigments and fillers, are in the range of 1.4 -1.8
  • the small average particle size of the pigments - optimum half of the wave- lenght of the light visible light is in the range of 400-780 nm.
  • CPVC Critical Pigment Volume Concentration
  • titanium dioxide can be replaced partly (about 1 % by weight, 1-5% by weight, 5-15% by weight, 10-25% by weight ,at least 25% by weight, 25-50% by weight, 50-75% by weight, 75-100% by weight) or totally (100% by weight) with the composite pigment composition of the invention as a pigment providing optical properties (opacity and brightness) without imparing the optical properties provided to the produced material.
  • the raw material expenses of coated and uncoated materials can be reduced because of the excellent light-scattering ability and low cost of the compo- site pigment composition of the invention, or the materials can be thinned down without imparing the optical properties.
  • the invention works best when the average particle size of the composite pigment composition is about half of the wavelenght of light. It is advantageous to the invention that the pores of the pigment are full of air after the drying.
  • the composite pigment composition according to the invention comprises ti- tanium dioxide and at least one precipitated porous pigment selected from alumin- ium silicates, calcium silicates, magnesium silicates, aluminium magnesium sili- cates, aluminium calcium silicates, aluminium calcium magnesium silicates, zinc silicates, aluminium zinc silicates, calcium zinc silicates, calcium magnesium sili cates, aluminium calcium zinc silicates, aluminium calcium magnesium zinc sili- cates, aluminium magnesium zinc silicates, a combination/mixture of any other al- uminium, magnesium, calcium and/or zinc silicate, silicas or any mixture thereof.
  • alumin- ium silicates calcium silicates, magnesium silicates, aluminium magnesium sili- cates, aluminium calcium silicates, aluminium calcium magnesium silicates, zinc silicates, aluminium zinc silicates, calcium zinc silicates, calcium magnesium sili cates, aluminium magnesium zinc silicates, a combination/mixture of any other al- uminium, magnesium
  • the composite pigment composition according to the in- vention comprises titanium dioxide and at least one precipitated porous pigment selected from the group consisiting of aluminium silicates, calcium silicates, mag- nesium silicates, aluminium magnesium silicates, aluminium calcium silicates, alu- minium calcium magnesium silicates, zinc silicates, aluminium zinc silicates, cal- cium zinc silicates, calcium magnesium silicates, aluminium calcium zinc silicates, aluminium calcium magnesium zinc silicates, aluminium magnesium zinc silicates, a combination/mixture of any other aluminium, magnesium, calcium and/or zinc sil icate, silicas or any mixture thereof.
  • the composite pigment composition con- sists of titanium dioxide and at least one precipitated porous pigment selected from aluminium silicates, calcium silicates, magnesium silicates, aluminium mag- nesium silicates, aluminium calcium silicates, aluminium calcium magnesium sili- cates, zinc silicates, aluminium zinc silicates, calcium zinc silicates, calcium mag- nesium silicates, aluminium calcium zinc silicates, aluminium calcium magnesium zinc silicates, aluminium magnesium zinc silicates, a combination/mixture of any other aluminium, magnesium, calcium and/or zinc silicate, silicas or any mixture thereof, optionally Na-, K-, L-, S0 4 -, SO3-, P0 4 -, BO3-, B-, PO3-, NO2-, NO3-, F-, carbonic acid-, carboxylic acid-, zinc-, manganese-, iron-, zirkonium-, nickel-, cobolt-, chrome-, barium-, sulphur-,
  • the composite pigment composition comprises titanium dioxide and at least one precipitated porous pigment selected from aluminium silicates, calcium silicates, magnesium silicates, zinc silicates, alu- minium magnesium silicates, aluminium calcium silicates, aluminium zinc silicates, silicas, or any mixture thereof.
  • the composite pigment composition comprises titanium dioxide and at least one precipitated po- rous pigment selected from aluminium silicates, calcium silicates, magnesium sili cates, aluminium magnesium silicates, aluminium calcium silicates, aluminium cal- cium magnesium silicates, silicas, or any mixture thereof.
  • the composite pigment composition comprises titanium dioxide and at least one precipitated porous pigment selected from aluminium silicates, mag- nesium silicates and/or aluminium magnesium silicates. In one embodiment of the invention, the composite pigment composition comprises titanium dioxide and at least one precipitated porous pigment selected from calcium silicates, aluminium silicates and/or aluminium calcium silicates. In one embodiment of the invention, the composite pigment composition comprises titanium dioxide and at least one precipitated porous pigment selected from aluminium silicates, zinc silicates and/or aluminium zinc silicates.
  • the precipitated porous pigments of the invention may contain Na-, K-, L-, S0 4 -, SO3-, P0 4 -, BO3-, B-, PO3-, NO2-, NO3-, F-, carbon acid-, car- boxylic acid-, zinc-, manganese-, iron-, zirkonium-, nicel-, cobolt-, chrome-, barium-, sulphur-, strontium-, carbon-, Cl-residues and/or residues of other ele- ments.
  • the type of these residues and/or elements depends on the starting mate- rials and/or other compounds used in the manufacture of the pigment composition.
  • the composite pigment composition of the invention does not contain poly- mers as additives.
  • the composite pigment composition of the invention does not contain any shell structures.
  • the composite pigment composition of the invention contains at most 50% titanium dioxide by weight based on the weight of the final composite pigment composition.
  • the composite pigment composi- tion contains titanium dioxide about 50% by weight based on the weight of the final composite pigment composition.
  • the compo- site pigment composition contains titanium dioxide about 30% by weight based on the weight of the final composite pigment composition.
  • the composite pigment composition contains titanium dioxide about 15% by weight based on the weight of the final composite pigment composition.
  • the composite pigment composition contains titanium dioxide about 10% by weight based on the weight of the final composite pigment composition.
  • the composite pigment composi- tion contains titanium dioxide about 5% by weight based on the weight of the final composite pigment composition.
  • the compo- site pigment composition contains titanium dioxide about 5-50% by weight based on the weight of the final composite pigment composition. In one embodiment of the invention, the composite pigment composition contains titanium dioxide about 10-50% by weight based on the weight of the final composite pigment composi- tion. In one embodiment of the invention, the composite pigment composition con- tains titanium dioxide about 15-50% by weight based on the weight of the final composite pigment composition. In one embodiment of the invention, the compo- site pigment composition contains titanium dioxide about 15-30% by weight based on the weight of the final composite pigment composition.
  • the composite pigment composition of the invention can be used for provid- ing opacity and/or brightness in applications where organic binders are used in such amounts that they create a uniform film with the pigments. In these cases, CPVC-value is not attained.
  • Applications of this kind include decor-paper, gloss paints, semi-gloss paints and outdoor paints.
  • the composite pigment composition of the invention may also contain addi- tives, such as stabilizing agents, dispersing agents, biocides and/or surfactants.
  • addi- tives such as stabilizing agents, dispersing agents, biocides and/or surfactants.
  • the type of the additive depends on the purpose of use of the composite pigment composition.
  • the particles of the composite pigment composition of the invention are ag- gregates, which have a cluster-type formation made up of primary/ultimate parti- cles.
  • Aggregates have a definite pattern of molecules formed of primary (ele- mental) particles by an irreversible process and they cannot be broken by me- chanical forces. As a result of the process, the specific surface area of an aggre- gate is smaller than the sum of its primary particles.
  • Agglomerates consist of pri mary particles and/or aggregates which are joined loosely together e.g. at the cor- ners or edges and can be broken by mechanical forces.Thus agglomerates can change their size and shape.
  • the average particle size of the composite pigment composition of the inven- tion is at most 10 pm (0-10 pm), determined by laser measurement. In one em- bodiment, the average particle size of the pigment composition of the invention is below 10 pm, determined by laser measurement. In one embodiment of the inven- tion, the average particle size of the composite pigment composition is in the range of 0.1-10 pm or in the range of 0.2-10 pm, determined by laser measure- ment. In one embodiment of the invention, the average particle size of the compo- site pigment composition is in the range of 1-10 pm, determined by laser meas- urement. In one embodiment, the average particle size of the composite pigment composition of the invention is at most 5 pm (0-5 pm), determined by laser meas- urement.
  • the average particle size of the composite pigment composition of the invention is below 5 pm, determined by laser measurement. In one embodiment of the invention, the average particle size of the composite pig ment composition is in the range of 0.1-5 pm or in the range of 0.2-5 pm, deter- mined by laser measurement. In one embodiment of the invention, the average particle size of the composite pigment composition is in the range of 1-5 pm, de- termined by laser measurement. In one embodiment, the average particle size of the pigment composition of the invention is at most 2 pm (0-2 pm), determined by laser measurement. In one embodiment, the average particle size of the compo- site pigment composition of the invention is below 2 pm, determined by laser measurement.
  • the average particle size of the composite pigment composition is in the range of 0.1- 2 pm or in the range of 0.2- 2 pm. In one embodiment of the invention, the average particle size of the compo- site pigment composition is 1-2 pm, determined by laser measurement. In one embodiment, the average particle size of the composite pigment composition of the invention is at most 1 pm (0-1 pm), determined by laser measurement. In one embodiment, the average particle size of the composite pigment composition of the invention is below 1 pm, determined by laser measurement. In one embodi- ment of the invention, the average particle size of the composite pigment composi- tion is in the range of 0.1-1 pm or in the range of 0.2-1 pm determined by laser measurement. In one embodiment of the invention, the average particle size of the composite pigment composition is 0.1-0.6 pm or 0.2-0.6 pm, determined by laser measurement.
  • the average particle size of the composite pigment corn- position of the invention after the precipitation step and before any grinding step is at most 10 pm (0-10 pm). In one embodiment, the average particle size of the composite pigment composition of the invention after the precipitation step and be- fore any grinding step is below 10 pm, determined by laser measurement. In one embodiment of the invention, the average particle size of the composite pigment composition after the precipitation and before grinding is in the range of in the range of 0.1-10 pm, 0.2-10 pm or 1-10 pm, determined by laser measurement. In one embodiment, the average particle size of the composite pigment composition of the invention after the precipitation and before grinding is at most 5 pm (0-5 pm), determined by laser measurement.
  • the average particle size of the composite pigment composition of the invention after the precipitation and before grinding is below 5 pm, determined by laser measurement.
  • the average particle size of the composite pigment corn- position after the precipitation and before grinding is in the range of in the range of 0.1-5 pm, 0.2-5 pm or 1-5 pm, determined by laser measurement.
  • the average particle size of the composite pigment composition after the precipitation and before grinding is at most 2 pm (0-2 pm), determined by laser measurement.
  • the average particle size of the pigment corn- position after the precipitation and before grinding is below 2 pm, determined by laser measurement.
  • the average particle size of the composite pigment composition after the precipitation and before grinding is in the range of 0.1-2 miti, 0.2-2 miti or 1-2 miti, determined by laser measurement. In one embodiment, the average particle size of the composite pigment composi- tion after the precipitation and before grinding is at most 1 pm (0-1 pm), deter- mined by laser measurement. In one embodiment, the average particle size of the composite pigment composition after the precipitation and before grinding is below 1 pm, determined by laser measurement. In one embodiment of the invention, the average particle size of the composite pigment composition after the precipitation and before grinding is in the range of 0.1-1 pm or 0.2-1 pm determined by laser measurement. In one embodiment of the invention, the average particle size of the composite pigment composition after the precipitation and before grinding is in the range of 0.1-0.6 pm or 0.2-0.6 pm, determined by laser measurement.
  • the average particle size and/or the par- ticle size distribution of the composite pigment composition is determined by laser diffraction technique. In one embodiment of the invention, the average particle size and/or the particle size distribution of the composite pigment composition is deter- mined by laser diffraction technique using equipment which is able to determine particle sizes in the range of 0.02-2000 pm. In one embodiment of the invention, the average particle size and/or the particle size distribution of the composite pig ment composition is determined with Malvern 2000-analyzer. The pore volume of the composite pigment composition of the invention is typically in the range of 0.15- 0.20 cm 3 /g.
  • the composite pigment composition of the invention is not subjected to a grinding step after the precipitation. Grinding the precipitated composite pigment composition after the precipitation may break the structure of the pigment and thus affect harmfully to the light scattering ability of the pigment.
  • the composite pigment composition of the invention is prepared using a wet method of production.
  • the air pores of the precipitated pig ments are kept empty after the drying, wherein the difference between the refrac- tive index of the air in the pores (about 1 ) and the refractive index of the pigment (1 .4-1 .8) can be utilized as light scattering, which is shown as better opacity and brightness.
  • the composite pigment composition of the invention is suited to be used as a pigment in fillers of paper, carton, plastic, rubber and printing inks.
  • filler compositions of this kind also contain conventional manufactur- ing agents and additives of fillers.
  • the composite pigment composition of the invention is suited to be used as a pigment in coating composition which are used for coating paper, carton, plastic, rubber, laminate, concrete, metal, composites and wood.
  • coating compositions of this kind also contain also conven- tional manufacturing agents and additives of coating compositions.
  • the composite pigment composition of the invention is suited to be used as a raw material in any material wherein high light scattering is needed.
  • the composite pigment composition of the invention is suited to be used as a pigment in decor-papers.
  • Decor-papers of this kind also contain, in addition to the pigment, manufacturing agents and additives known to a person skilled in the art.
  • the pigment composition of the invention is suited to be used as a pigment in paints.
  • paints of this kind also contain conventional manufacturing agents and additives of paints. Titanium dioxide, other pigments, binders, rheological modifiers, adhesives and other necessary additives depending on the application can be used with the composite pigment composition of the in- vention.
  • the composite pigment composition is suited to be used as a pigment providing opacity and/or brightness.
  • the composite pigment composition is suited to be used to replace titanium dioxide without impairing the optical charac- teristics.
  • the composite pigment composition of the invention is suited to be used as a substitute for titanium dioxide in fillers of paper, carton, plastic, rubber, lami- nate and printing inks.
  • the composite pigment composition of the in- vention is suited to be used as a substitute for titanium dioxide in coating composi- tions which are used as coatings in paper, carton, plastic, rubber, concrete, metal, composites and wood, and as a pigment in paints and decor-papers.
  • titanium dioxide can be replaced with the composite pigment composition of the invention without any detectable impairment in the op- tical characteristics.
  • 5 -100% by weight, 10- 100% by weight, 15-100% by weight of titanium dioxide can be replaced with the composite pigment composition of the invention without any detectable impairment in the optical characteristics.
  • 25 -100% by weight of titanium dioxide can be replaced with the composite pigment composi- tion of the invention without any detectable impairment in the optical characteris- tics.
  • 50 -100% by weight of titanium dioxide can be replaced with the composite pigment composition of the invention without any detectable impairment in the optical characteristics.
  • 75-100 % by weight of titanium dioxide can be replaced with the compo- site pigment composition of the invention without any detectable impairment in the optical characteristics.
  • about 25% by weight, about 50% by weight, about 75% by weight, about 85% by weight, about 95% by weight or about 100% by weight of titanium dioxide can be replaced with the com- posite pigment composition of the invention without any detectable impairment in the optical characteristics.
  • about 100% by weight of titanium dioxide can be replaced with the composite pigment composi- tion of the invention without any detectable impairment in the optical characteris- tics.
  • titanium dioxide can be replaced partially or totally with the composite pigment composition of the invention, remarkable savings in raw material costs can be achieved.
  • an equivalent light-scattering ability is achieved more advantageously than with tita- nium dioxide.
  • the materi- als to be produced can be thinned and/or lightened without weakening the attaina- ble light-scattering ability (brightness and opacity) compared to the use of titanium dioxide.
  • the basis weight of paper or carton is enabled, the number of coating layers can be reduced, coating layers from multilayer structures can be removed as unnecessary, or the coating layers, paint or laminate can be thinned without weakening the spreading capacity and/or brightness and opacity.
  • the present invention also relates to a method for producing the described composite pigment composition, which method comprises the following steps: a) optionally providing and/or adding at least one compound containing mag- nesium and/or at least one compound containing calcium and/or at least one corn- pound containing zinc in a liquid form, or optionally bringing at least one corn- pound containing magnesium and/or at least one compound containing calcium and/or at least one compound containing zinc into a liquid form,
  • the method steps a), b), c), d) and/or e) can be performed in any order. Selection of the order of performing the method steps belongs to the knowledge of a skilled person and depends, among other things, on the compounds and reaction conditions to be used.
  • the method for producing the composite pigment composition does not contain a step of grinding the precipitated pigment (step h).
  • the compounds used in the method steps a), b), c) and/or d) can be pro- vided and/or added at once or in several portions during the precipitation.
  • the compounds used in the method of the invention can be added simultaneously or separately. In the method of the invention, several compounds can be used. Typi- cally, the reactions of the method take place in a solution.
  • The“at least one corn- pound containing magnesium” can be any compound that is suitable for the method, such as magnesium hydroxide, magnesium carbonate, magnesium sul- phate and/or magnesium chloride.
  • The“at least one compound containing cal- cium” can be any compound that is suitable for the method, such as calcium hy- droxide, calcium carbonate, calcium sulphate and/or calcium chloride.
  • The“at least one compound containing zinc” can be any compound that is suitable for the method, such as zinc sulphate, zinc chlorate, zinc chloride, zinc nitrate and/or zinc oxide.
  • The“at least one compound containing aluminium” can be any compound that is suitable for the method, such as aluminium sulphate, polyaluminium chlo- ride and/or sodiumaluminate.
  • The“at least one compound containing silicon” can be any compound that is suitable for the method, such as Na-, K- and/or L-silicate.
  • the composite pigment composition of the invention can be produced with an industrially applicable method, wherein mixing having peripheral speed of at least 1 m/s is utilized at least once in at least one method step.
  • the peripheral speed is 1 - 500 m/s.
  • the peripheral speed is 1 - 250 m/s.
  • the mixing is performed preferably with mixers operating with rotor-rotor and/or rotor-stator techniques. In the mixing, a shock mixer, rotors rotating into op- posite directions, rotors rotating into the same direction with big relative speed dif- ference, dropping, a pin mill, strikes and/or counter strikes can be exploited.
  • the mixing elements are pins, wings, plates with holes, furrows or other corresponding bodies of different forms.
  • the speed difference between the circles of rotors rotating to opposite directions or to the same direction or the cir cles of the adjacent rotors and stators is typically in the range of 5-400 m/s, pref- erably in the range of 5-200 m/s. Consequently, the material is subjected to very strong turbulence, shear and impact forces during processing (disintegration and atomization).
  • the preparation of the pigment sample was started with adding T1O2 solutions of magnesium hydroxide and aluminium sulphate into the medium of the reactor. A temperature above the freezing point of water and uniform mixing were used in the preparation. Dilute aluminium sulphate and sodium silicate were added into this so- lution so that the target pH was kept constant. Sodium silicate was used at least in an amount which is required for the stoichiometric reaction of magnesium and alu- minium. Rotor-rotor-mixing with peripheral speed of at least 1 m/s is was utilized along during the preparation. Finally before dispersing the filter cake into an aque- ous slurry, the pigment sample was filtrated and washed with water. The pigment sample thus obtained is called OPA2.
  • OPA2 comprised 30.1 % Ti0 2 by weight and 69.9% precipitated aluminium magnesium silicate by weight. The average particle size of OPA2 was 0.44 pm.
  • the preparation of the pigment sample was started with adding T1O2 to a dilute solution of sodium silicate. A temperature above the freezing point of water and uniform mixing were used in the preparation. Dilute sulphuric acid was added into this solution so that the target pH was kept constant and sodium silicate was stoi- chiometrically reacted into silica (S1O2). Rotor-rotor-mixing with peripheral speed of at least 1 m/s was utilized along during the preparation. Finally before dispersing the filter cake into an aqueous slurry, the pigment sample was filtrated and washed with wa- ter. This composite pigment contained 15.7% Ti0 2 by weight and 84.3% precipitated sil ica (S1O2) by weight. The average particle size of this composite pigment was 0.77 pm.
  • the pore sizes and the pore size distributions of pigment samples OPA1 , OPA2, Ti02A ja Ti02C were determined based on the measurements of isothermal adsoption-desorption points in a temperature of liquid nitrogen and the computa- tional handling of thus received adsoption-desorption isoterms.
  • the pigment sam- ples were analysed with N2-sorption at -196 C (TriStar 3000, Micromeritics).
  • the porocity of the pigments of the pigment samples OPA1 , Ti02A and Ti02C (Kronos 2971) is shown in Table 1. Sample Ti02A contained 6.5% in- organic finishing. Sample Ti02C contains no finishing.
  • a paint paste was prepared from the pigment dispersion prepared in Example 1.
  • the paste contained 5% dried pigment and 5% latex (Acronal S728, BASF) based on the amount of dry pigment.
  • the pH of this aquoeus slurry was kept above pH- value 8.3 with the additions of lye while adding a thickener (Sterocoll FS, BASF) until the viscosity of the dispersion of 800 - 850 cp (Brookfield, 100 rpm, Spindle LV-4) was achieved.
  • the opacity and tone of the coatings of both 2.5 g/m 2 and 5 g/m 2 were meas- ured with an opacimeter (Rhopoint Novoshade Duo+).
  • the coating was spread with standard rods nos. 4 and 7 (K Bar) of the rod coating method (RK101 Control Coater) onto a plastic film (Leneta 1 mm, clear polyester sheets).
  • the pigments used were OPA1 , OPA2 and Ti02A (SR5, Venator). The results are shown in Table 2.
  • the pigments OPA2 and Ti02A were tested also in an un- coated fine paper.
  • Tha pulp contained bleached pine and bleached eucalyptus (40:60) refined to the value SR30.
  • the tests were done in a dynamic sheet former so that the targets for basis weight and ash were 80 g/m 2 and 20%. These target values were achieved by adjusting the amount of furnish and the retention aid (PAM) in the dynamic sheet former.
  • the papers pro- prised were machine caelered and dried in a drying drum before the conditioning of paper and testing. The results are shown in Table 3.
  • the sheets of the previous example were HPL-laminated which is needed for the preparation of decor-paper.
  • Decor-paper is laminated with resins using temperature above 120°C and pressure of 5 mPa. Lamination takes normally 40-50 minutes.
  • the optical characteristics of laminated paper are usually called“wet opacity” and L-value, since the pigment is surrounded by the resin.
  • the results of the laminated papers are presented in Table 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une composition de pigment composite qui comprend du dioxyde de titane et au moins un pigment poreux précipité. L'invention concerne également l'utilisation d'une telle composition de pigment composite comme pigment conférant opacité et luminosité. En outre, l'invention concerne l'utilisation de la composition de pigment composite selon l'invention en tant que substitut de dioxyde de titane sans altération des propriétés optiques.
EP18819452.6A 2017-12-05 2018-12-05 Composition de pigment composite Withdrawn EP3720816A1 (fr)

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FI20176092A FI20176092A1 (fi) 2017-12-05 2017-12-05 Komposiittipigmenttikoostumus
PCT/FI2018/050879 WO2019110871A1 (fr) 2017-12-05 2018-12-05 Composition de pigment composite

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US3510335A (en) * 1965-10-22 1970-05-05 Du Pont Titanium pigment production
US3945965A (en) * 1974-05-24 1976-03-23 Scm Corporation Mixtures of titanium dioxide and porous synthetic magnesium silicate in opacified emulsion paints
FI124696B (fi) 2008-03-07 2014-12-15 Fp Pigments Oy Pigmenttipartikkelikoostumus, menetelmä sen valmistamiseksi sekä sen käyttö
US9120074B2 (en) * 2011-10-28 2015-09-01 The Chemours Company Tt, Llc Laminate paper treated with inorganic pigments having improved dispersability
JP6242812B2 (ja) * 2012-01-16 2017-12-06 ザ ケマーズ カンパニー ティーティー リミテッド ライアビリティ カンパニー 改善された光学性能を有するデコール紙を製造するための、処理された無機粒子から調製された分散体
FI126409B (en) 2013-07-16 2016-11-15 Fp-Pigments Oy Composition with interactive elements
KR20170126998A (ko) * 2015-03-10 2017-11-20 크로노스 인터내셔널, 인코포레이티드 수산화알루미늄을 포함하는 복합 안료 및 이의 제조 방법

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