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WO2009144372A1 - Process for forming a pigment product from a cellulose derivative - Google Patents

Process for forming a pigment product from a cellulose derivative Download PDF

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Publication number
WO2009144372A1
WO2009144372A1 PCT/FI2009/050434 FI2009050434W WO2009144372A1 WO 2009144372 A1 WO2009144372 A1 WO 2009144372A1 FI 2009050434 W FI2009050434 W FI 2009050434W WO 2009144372 A1 WO2009144372 A1 WO 2009144372A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
pigment product
cellulose derivative
cellulose
product
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.)
Ceased
Application number
PCT/FI2009/050434
Other languages
French (fr)
Inventor
Sami Turunen
Nina PYKÄLÄINEN
Tarja Sinkko
Kaisa Putkisto
Hannu Mikkonen
Soili Peltonen
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.)
UPM Kymmene Oy
Original Assignee
UPM Kymmene 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 UPM Kymmene Oy filed Critical UPM Kymmene Oy
Priority to EP09754025.6A priority Critical patent/EP2291408A4/en
Publication of WO2009144372A1 publication Critical patent/WO2009144372A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/005—Crosslinking of cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic 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
    • D21H19/52—Cellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/26—Cellulose ethers
    • C08J2301/28—Alkyl ethers
    • 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

Definitions

  • the invention relates to the process for forming a pigment product from a cellulose derivative as defined in the preamble of claim 1, to the pigment product as defined in the preamble of claim 14 and to the use of a pigment product as defined in the pream- ble of claim 15.
  • Known from the prior art is the formation of organic pigments from starch-based materials and pure cellulose. In these cases, the pigment is usually present in a mixture with some other material or in a dispersion.
  • Also known from the prior art is the production of organic pigments from oil-based materials. As mineral fillers and coating pigments are replaced by materials of organic origin either partly or completely, the environmental load can be reduced.
  • fillers or pigments of organic origin e.g. in papermaking, the recycling of paper is enhanced and the deinking sludge is easier to process further or dispose of. This allows the application of used paper e.g. in the production of biofuels.
  • the strength of paper can be improved by organic fillers, and smoothness of the paper surface during calendering can be improved by organic pigments .
  • a problem with oil-based organic pigments is their price which follows the development of the oil price, and high production costs.
  • the objective of the invention is to disclose a novel process for producing a pigment product from a cellulose derivative. Another objective of the invention is to provide an industrially applicable process for industrial production of a cellulose-based pigment product .
  • the invention is based on a process for pro- ducing an organic pigment product from a cellulose derivative.
  • a selected cellulose derivative containing at least one OH group is crosslinked by a hydroxyl-active crosslinker to form a substantially insoluble pigment product.
  • the pigment product may be in the form of particles, a particle cluster, a dispersion or a foam.
  • a pigment product refers to a material or agent providing a substrate or a surface with color or other optical property.
  • the pigment may be translucent or opaque.
  • the provided pigment product is pulverized to microparticles .
  • microparticles refer to micro- or nanoscale particles in the size class of preferably less than 50 ⁇ m, more preferably less than 10 ⁇ m.
  • the particles may be of any shape, e.g. spherical.
  • the microparticles are formed substantially in connection with the production of the pigment product. In one embodiment, the microparticles are formed substantially after the production of the pigment product.
  • pulverization refers to any pulverization, grinding, crushing or disintegration of a material to a desired particle size.
  • Operation of the pulverizing devices, preferably mills, is typically based on application of pressure, cutting, rubbing, compression and/or the effect of an impact provided by blowing, or an equivalent principle of operation. Most mills operate as a combination of many principles of operation.
  • Pulverization may be performed by any suitable process known per se.
  • the pig- ment product is pulverized by air jet pulverization, preferably an air jet mill.
  • the pulverization is performed as Cryo-pulverization.
  • the pulverization may be performed as wet or dry pulverization.
  • the cellulose derivative is cellulose ether.
  • the cellulose derivative is hydroxy propyl cellulose (HPC) .
  • the cellulose derivative is selected from the group of hydroxy ethyl cellulose and carboxy methyl cellulose.
  • the cellulose derivative is selected so as to be solu- ble in water.
  • the cellulose derivative has substantially high molecular weight.
  • the cellulose derivative may be a mixture of a number of cellulose compounds.
  • the cellulose derivative may contain small amounts of compounds which are not cellulose- based.
  • the crosslinker is selected from the group of divinyl sul- phones, dianhydrides, dialdehydes, formaldehydes, gly- oxal, diisocyanates, ethylene glycol, diglycidyl ether, oxalic and citric acids and inorganic salts, e.g. aluminum sulphate.
  • the solubility of the cellulose derivative may be adjusted by crosslinkers .
  • the crosslinkers are preferably selected so as to obtain a substantially insoluble pigment product, preferably insoluble in water, with a cellulose derivative.
  • the crosslinker is used in an amount of 4 to 15% by weight of the amount of cellulose derivative.
  • the crosslinking reaction is activated by at least one activator selected from the group of heat, pH, catalyst, drying and radiation.
  • the catalyst is an aluminum sulphate catalyst.
  • metal catalysts such as inorganic salts of aluminum, magnesium and zinc, as the catalyst.
  • acid catalysts as the catalyst, in particular for dialdehyde and glyoxal crosslinkers.
  • ⁇ lulose derivative is dissolved prior to crosslinking in a selected solvent, in one preferred embodiment in water. Any suitable solvent may be used as the solvent.
  • the combination of the cellulose derivative and the solvent is in the form of a solution, sludge, suspension or dispersion. In one embodiment, the solid content in the solution of the cellulose derivative or the like is less than 10% by weight.
  • the crosslinker may be in liquid form and dissolved in a suitable solvent, e.g. water or ethanol.
  • a surface-active agent is added to the cellulose derivative prior to crosslinking.
  • the surface-active agent may be selected from the group of dispersing agents, non- ionic and anionic tensides .
  • other suitable additive required by the use is added to the cellulose derivative.
  • a preferably light-scattering porous foam structure of the pigment product is formed by foaming, e.g. heavy stirring.
  • the resultant foam structure is stabilized, e.g. by crossbinding.
  • the crosslinker is added in the step of foaming the cellulose derivative.
  • the crosslinker is added in the step of stabilizing the structure.
  • the crosslinker is added to the cellulose derivative prior to foaming.
  • the cellulose derivative is heated to provide the foam.
  • the foaming may be provided chemi- cally and/or mechanically.
  • the resultant pigment product is dried. In one embodiment, drying is performed at a temperature of 70 to 100 0 C, more preferably at a temperature of about 80 to 9O 0 C.
  • Crosslinking may be completed during drying. During drying of the pigment product, if not earlier, the crosslinking generates between the polymer chains bonds which are insoluble in water.
  • the pulveriza- tion is performed after drying.
  • the resultant pigment product is cured by heat.
  • the invention is also based on the pigment product formed in a manner described above and on the use thereof.
  • the provided pigment product may be used in the surface treatment, such as coating and covering, of a substrate, e.g. paper, and/or as a filler in a substrate, such as paper.
  • the pigment product and process for the pro- duction thereof according to the invention are applicable in the paper industry, e.g. in fine papers, newsprints, printing papers and soft tissues, in the cosmetics industry, e.g. in toothpastes, in the paint industry, hygiene product industry, plastics industry, coating industry, composite product industry, sheeting industry or in an equivalent application.
  • paper refers to any fiber- based paper or fiber product or the like.
  • the paper may have been made from chemical pulp, mechanical pulp, chemimechanical pulp, recycled pulp, and/or mixtures thereof or the like.
  • the paper may contain suitable fillers and additives and different kinds of surface treatment and coating agents.
  • the paper may be in the form of a web or a sheet, or in other form suit- able for the purpose.
  • the pigment product formed according to the invention may be used either alone or in a mixture with other agents in different kinds or pigments, pigment precursors, mixtures, compounds or the like.
  • the pigment product or particles thereof formed according to the invention may be modified e.g. by crosslinking and functionalizing in the manner required by the use.
  • the product is provided with different functional properties. Properties of the product may be tailored in terms of e.g. opacity, lightness, printing properties and oil absorption.
  • the product may also be utilized as an additive or auxiliary agent in different uses.
  • the invention provides an excellent industrially applicable way of producing an organic pigment product .
  • the process according to the invention provides a porous pigment product with lower specific gravity than in the previously known mineral-based pigments .
  • Another advantage of the pigment product according to the invention is recyclability. This permits the reduction of waste problems.
  • the pigment product according to the invention is applicable in novel paper applications in which low specific gravity of the raw materials provides the end product, such as paper, with new functional properties and improves cost-efficiency in the product supply chain from the producer to the customer.
  • the hydroxy propyl celluloses were crosslinked in an aqueous solution with glyoxal . Samples were prepared in portions of 10 to 5Og. The aqueous solution was prepared by first mixing 5Og of HPC powder mixture in hot water of a temperature of about 50 to 60 0 C, with the solid content of 8% by weight.
  • the homogenized dispersion was diluted in cold water (about 5 to 10 0 C, pH 4 to 5) under constant stirring so that the final solid content of the resultant aque- ous solution was 5% by weight.
  • Glyoxal solution (40% by weight in water)
  • a few drops of a surface-active agent (TISKO, Farmos) and an aluminum sulphate catalyst were added to the solution at room temperature under heavy stirring in a blade type mixer so as to ensure sufficient access of air to the resultant product.
  • Glyoxal was added in an amount of 10% by weight of the amount of HPC and the catalyst was added in an amount of 5% by weight of the amount of HPC.
  • the resultant product was in a foam form.
  • the resultant foam product was dried at 90°C in an oven so as to remove water and obtain a foam structure which was insoluble in water.
  • the short dwell time of the product in contact with the aqueous phase which was removed reduced film formation and softening in the structure of the foam product, improving the quality properties of the product.
  • Highly substituted high molecular weight hydroxy propyl cellulose is a non-ionic derivative which is soluble in cold water and forms a gelatinous medium at an elevated temperature of the solution and is resoluble during cooling.
  • a reaction with a hydroxyl- active glyoxal crosslinker produces a stable foam structure which is insoluble in water.
  • Dried HPC-glyoxal foam structures were pul- verized to microparticles in an air jet pulverizer with a classifier speed of lOOOOrpm. Particle sizes of the microparticles were in the range of 2 to lOO ⁇ m, and on average 8 to 25 ⁇ m.
  • the re- sultant pigment product is applicable for use both as a pigment and as a filler.
  • the hydroxy propyl cellulose was crosslinked in aqueous solutions with methyl diphenyl diisocyanate (MDI) with different concentrations of the crosslin- ker.
  • Samples were prepared in portions of 5 to 1Og.
  • the aqueous solution was prepared by first mixing 50/1Og of HPC powder in hot water at a temperature of about 50 to 60 0 C, with a solid content of 8% by weight.
  • the homogenized dispersion was diluted in cold water (about 5 to 10 0 C, pH 7) under constant stirring so that the final solid content of the resultant aqueous solution was 6% by weight.
  • the MDI solution (about 30% by weight in ethanol) in an amount of either 50, 30 or 10% by weight of the amount of HPC and a few drops of a surface-active agent (TISKO, Farmos) were added to the solution at room temperature under heavy stirring in a blade type mixer so as to ensure sufficient access of air to the resultant product.
  • the resultant product was in a foam form.
  • the resultant foam products were dried at 90 2 C in an oven so as to remove water and obtain a foam structure which was insoluble in water.
  • Reaction of the MDI in the presence of moisture produced active bubble formation in connection with drying which was preserved as fine-divided porosity in the dried foam structure.
  • the dried foam structures were opaquely white, rigidly fragile and porous, which improved the quality properties of the product.
  • a reaction of HPC with a hy- droxyl-active diisocyanate crosslinker produces a sta- ble foam structure which is insoluble in water and which could be ground to particles.
  • the refractive index of the particles in the HPC-MDI foam structure was estimated to be in the range of 1.50 to 1.55, be- ing thus higher than that of the equivalent untreated HPC (1.45 to 1.50) .
  • the process according to the invention is applicable in different embodiments for use in producing the most different kinds of pigment products.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Paper (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention relates to a process for producing a pigment product from a cellulose derivative. According to the invention, a selected cellulose derivative containing at least one OH group is crosslinked by using a hydroxyl-active crosslinker to form a substantially insoluble pigment product. Further, the invention relates to the corresponding product and to the use of the product.

Description

PROCESS FOR FORMING A PIGMENT PRODUCT FROM A CELLULOSE DERIVATIVE
FIELD OF THE INVENTION The invention relates to the process for forming a pigment product from a cellulose derivative as defined in the preamble of claim 1, to the pigment product as defined in the preamble of claim 14 and to the use of a pigment product as defined in the pream- ble of claim 15.
BACKGROUND OF THE INVENTION
Known from the prior art are different kinds of cellulose derivatives and processes for their pro- duction.
Also known from the prior art are different kinds of pigments and fillers of mineral and organic origin and processes for their production. Known from the prior art is the formation of organic pigments from starch-based materials and pure cellulose. In these cases, the pigment is usually present in a mixture with some other material or in a dispersion. Also known from the prior art is the production of organic pigments from oil-based materials. As mineral fillers and coating pigments are replaced by materials of organic origin either partly or completely, the environmental load can be reduced. By using fillers or pigments of organic origin e.g. in papermaking, the recycling of paper is enhanced and the deinking sludge is easier to process further or dispose of. This allows the application of used paper e.g. in the production of biofuels. Also, in the typi¬ cal cases, the strength of paper can be improved by organic fillers, and smoothness of the paper surface during calendering can be improved by organic pigments .
A problem with oil-based organic pigments is their price which follows the development of the oil price, and high production costs.
A problem with the known starch-based organic pigments and those formed from pure cellulose is often the complexity of their preparation due to many production steps and therefore the scarcity of industrial production.
OBJECTIVE OF THE INVENTION
The objective of the invention is to disclose a novel process for producing a pigment product from a cellulose derivative. Another objective of the invention is to provide an industrially applicable process for industrial production of a cellulose-based pigment product .
SUMMARY OF THE INVENTION
The process and the pigment product according to the invention are characterized by what has been presented in the claims.
The invention is based on a process for pro- ducing an organic pigment product from a cellulose derivative. According to the invention, a selected cellulose derivative containing at least one OH group is crosslinked by a hydroxyl-active crosslinker to form a substantially insoluble pigment product. The pigment product may be in the form of particles, a particle cluster, a dispersion or a foam.
The invention is specifically based on reprocessing cellulose and a derivative thereof to a higher degree of processing. In this context, a pigment product refers to a material or agent providing a substrate or a surface with color or other optical property. The pigment may be translucent or opaque.
In one embodiment of the invention, the provided pigment product is pulverized to microparticles . In this context, microparticles refer to micro- or nanoscale particles in the size class of preferably less than 50μm, more preferably less than 10μm. The particles may be of any shape, e.g. spherical.
In one embodiment, the microparticles are formed substantially in connection with the production of the pigment product. In one embodiment, the microparticles are formed substantially after the production of the pigment product.
In this context, pulverization refers to any pulverization, grinding, crushing or disintegration of a material to a desired particle size. Operation of the pulverizing devices, preferably mills, is typically based on application of pressure, cutting, rubbing, compression and/or the effect of an impact provided by blowing, or an equivalent principle of operation. Most mills operate as a combination of many principles of operation.
Pulverization may be performed by any suitable process known per se. In one embodiment, the pig- ment product is pulverized by air jet pulverization, preferably an air jet mill. In one embodiment, the pulverization is performed as Cryo-pulverization. The pulverization may be performed as wet or dry pulverization. In one embodiment of the invention, the cellulose derivative is cellulose ether. In one embodiment, the cellulose derivative is hydroxy propyl cellulose (HPC) . In one embodiment, the cellulose derivative is selected from the group of hydroxy ethyl cellulose and carboxy methyl cellulose. In a preferred embodiment, the cellulose derivative is selected so as to be solu- ble in water. In one embodiment, the cellulose derivative has substantially high molecular weight. The cellulose derivative may be a mixture of a number of cellulose compounds. The cellulose derivative may contain small amounts of compounds which are not cellulose- based.
In one embodiment of the invention, the crosslinker is selected from the group of divinyl sul- phones, dianhydrides, dialdehydes, formaldehydes, gly- oxal, diisocyanates, ethylene glycol, diglycidyl ether, oxalic and citric acids and inorganic salts, e.g. aluminum sulphate. The solubility of the cellulose derivative may be adjusted by crosslinkers . The crosslinkers are preferably selected so as to obtain a substantially insoluble pigment product, preferably insoluble in water, with a cellulose derivative.
In one embodiment of the invention, the crosslinker is used in an amount of 4 to 15% by weight of the amount of cellulose derivative. In one embodiment of the invention, the crosslinking reaction is activated by at least one activator selected from the group of heat, pH, catalyst, drying and radiation. In one embodiment, the catalyst is an aluminum sulphate catalyst. In one embodiment, it is possible to use metal catalysts, such as inorganic salts of aluminum, magnesium and zinc, as the catalyst. In an alternative embodiment, it is possible to use acid catalysts as the catalyst, in particular for dialdehyde and glyoxal crosslinkers. In one embodiment of the invention, the cel-
■ lulose derivative is dissolved prior to crosslinking in a selected solvent, in one preferred embodiment in water. Any suitable solvent may be used as the solvent. The combination of the cellulose derivative and the solvent is in the form of a solution, sludge, suspension or dispersion. In one embodiment, the solid content in the solution of the cellulose derivative or the like is less than 10% by weight.
In one embodiment, the crosslinker may be in liquid form and dissolved in a suitable solvent, e.g. water or ethanol.
In one embodiment of the invention, a surface-active agent is added to the cellulose derivative prior to crosslinking. The surface-active agent may be selected from the group of dispersing agents, non- ionic and anionic tensides . In one embodiment, other suitable additive required by the use is added to the cellulose derivative.
In one embodiment of the invention, a preferably light-scattering porous foam structure of the pigment product is formed by foaming, e.g. heavy stirring. In a preferred embodiment, the resultant foam structure is stabilized, e.g. by crossbinding. In one embodiment, the crosslinker is added in the step of foaming the cellulose derivative. In one embodiment, the crosslinker is added in the step of stabilizing the structure. In one embodiment, the crosslinker is added to the cellulose derivative prior to foaming. In one embodiment, the cellulose derivative is heated to provide the foam. The foaming may be provided chemi- cally and/or mechanically.
In one embodiment of the invention, the resultant pigment product is dried. In one embodiment, drying is performed at a temperature of 70 to 1000C, more preferably at a temperature of about 80 to 9O0C. Crosslinking may be completed during drying. During drying of the pigment product, if not earlier, the crosslinking generates between the polymer chains bonds which are insoluble in water.
In one preferred embodiment, the pulveriza- tion is performed after drying. In one embodiment of the invention, the resultant pigment product is cured by heat.
The invention is also based on the pigment product formed in a manner described above and on the use thereof. The provided pigment product may be used in the surface treatment, such as coating and covering, of a substrate, e.g. paper, and/or as a filler in a substrate, such as paper.
The pigment product and process for the pro- duction thereof according to the invention are applicable in the paper industry, e.g. in fine papers, newsprints, printing papers and soft tissues, in the cosmetics industry, e.g. in toothpastes, in the paint industry, hygiene product industry, plastics industry, coating industry, composite product industry, sheeting industry or in an equivalent application.
In this context, paper refers to any fiber- based paper or fiber product or the like. The paper may have been made from chemical pulp, mechanical pulp, chemimechanical pulp, recycled pulp, and/or mixtures thereof or the like. The paper may contain suitable fillers and additives and different kinds of surface treatment and coating agents. The paper may be in the form of a web or a sheet, or in other form suit- able for the purpose.
The pigment product formed according to the invention may be used either alone or in a mixture with other agents in different kinds or pigments, pigment precursors, mixtures, compounds or the like. The pigment product or particles thereof formed according to the invention may be modified e.g. by crosslinking and functionalizing in the manner required by the use. The product is provided with different functional properties. Properties of the product may be tailored in terms of e.g. opacity, lightness, printing properties and oil absorption. The product may also be utilized as an additive or auxiliary agent in different uses.
The invention provides an excellent industrially applicable way of producing an organic pigment product .
The process according to the invention provides a porous pigment product with lower specific gravity than in the previously known mineral-based pigments . Another advantage of the pigment product according to the invention is recyclability. This permits the reduction of waste problems.
The pigment product according to the invention is applicable in novel paper applications in which low specific gravity of the raw materials provides the end product, such as paper, with new functional properties and improves cost-efficiency in the product supply chain from the producer to the customer.
DETAILED DESCRIPTION OF THE INVENTION
The invention is described in more detail by the following example.
Example 1
In this example, crosslinking a commercial hydroxy propyl cellulose (HPC) and production of the pigment product according to the invention were stud- ied.
Two types of commercial hydroxy propyl cellulose were used in the tests in a 50/50 mixture; a) Klucel H (Mw = 1150000, solution = 1% in water, viscosity = 1275 to 3500mPas) and b) Klucel M (Mw = 850000, solution = 2% in water, viscosity = 3500 to 7500mPas) . The hydroxy propyl celluloses were crosslinked in an aqueous solution with glyoxal . Samples were prepared in portions of 10 to 5Og. The aqueous solution was prepared by first mixing 5Og of HPC powder mixture in hot water of a temperature of about 50 to 600C, with the solid content of 8% by weight. The homogenized dispersion was diluted in cold water (about 5 to 100C, pH 4 to 5) under constant stirring so that the final solid content of the resultant aque- ous solution was 5% by weight. Glyoxal solution (40% by weight in water) , a few drops of a surface-active agent (TISKO, Farmos) and an aluminum sulphate catalyst were added to the solution at room temperature under heavy stirring in a blade type mixer so as to ensure sufficient access of air to the resultant product. Glyoxal was added in an amount of 10% by weight of the amount of HPC and the catalyst was added in an amount of 5% by weight of the amount of HPC. The resultant product was in a foam form. The resultant foam product was dried at 90°C in an oven so as to remove water and obtain a foam structure which was insoluble in water. The short dwell time of the product in contact with the aqueous phase which was removed reduced film formation and softening in the structure of the foam product, improving the quality properties of the product.
Highly substituted high molecular weight hydroxy propyl cellulose is a non-ionic derivative which is soluble in cold water and forms a gelatinous medium at an elevated temperature of the solution and is resoluble during cooling. A reaction with a hydroxyl- active glyoxal crosslinker produces a stable foam structure which is insoluble in water.
Dried HPC-glyoxal foam structures were pul- verized to microparticles in an air jet pulverizer with a classifier speed of lOOOOrpm. Particle sizes of the microparticles were in the range of 2 to lOOμm, and on average 8 to 25μm.
It was discovered that with smaller amounts of cellulose derivative it was possible to use the crosslinker in an amount of 4 to 5% by weight of the amount of HPC. A relatively high solution viscosity of the cellulose derivative had a positive effect on foaming.
In the tests it was discovered that the re- sultant pigment product is applicable for use both as a pigment and as a filler.
Example 2
In this example, crosslinking a commercial hydroxy propyl cellulose (HPC) and production of the pigment product according to the invention were studied.
Commercial hydroxy propyl cellulose Klucel G (Mw = 370000, solution = 2% in water, viscosity = 125 to 450mPas) was used in the tests.
The hydroxy propyl cellulose was crosslinked in aqueous solutions with methyl diphenyl diisocyanate (MDI) with different concentrations of the crosslin- ker. Samples were prepared in portions of 5 to 1Og. The aqueous solution was prepared by first mixing 50/1Og of HPC powder in hot water at a temperature of about 50 to 600C, with a solid content of 8% by weight. The homogenized dispersion was diluted in cold water (about 5 to 100C, pH 7) under constant stirring so that the final solid content of the resultant aqueous solution was 6% by weight. The MDI solution (about 30% by weight in ethanol) in an amount of either 50, 30 or 10% by weight of the amount of HPC and a few drops of a surface-active agent (TISKO, Farmos) were added to the solution at room temperature under heavy stirring in a blade type mixer so as to ensure sufficient access of air to the resultant product. The resultant product was in a foam form.
The resultant foam products were dried at 902C in an oven so as to remove water and obtain a foam structure which was insoluble in water. Reaction of the MDI in the presence of moisture produced active bubble formation in connection with drying which was preserved as fine-divided porosity in the dried foam structure. In all applied concentrations of the MDI the dried foam structures were opaquely white, rigidly fragile and porous, which improved the quality properties of the product. A reaction of HPC with a hy- droxyl-active diisocyanate crosslinker produces a sta- ble foam structure which is insoluble in water and which could be ground to particles.
By liquid immersion process the refractive index of the particles in the HPC-MDI foam structure was estimated to be in the range of 1.50 to 1.55, be- ing thus higher than that of the equivalent untreated HPC (1.45 to 1.50) .
The process according to the invention is applicable in different embodiments for use in producing the most different kinds of pigment products.
The invention is not limited merely to the example referred to above; instead, many variations are possible within the scope of the inventive idea defined by the claims .

Claims

1. A process for producing a pigment product from a cellulose derivative, c h a r a c t e r i z e d in that a selected cellulose derivative containing at least one OH group is crosslinked by using a hydroxyl- active crosslinker to form a substantially insoluble pigment product .
2. The process according to claim 1, c h a r - a c t e r i z e d in that the provided pigment product is pulverized to microparticles .
3. The process according to claim 1 or 2, c h a r a c t e r i z e d in that the cellulose derivative is cellulose ether.
4. The process according to any one of claims
1 to 3, c h a r a c t e r i z e d in that the cellulose derivative is hydroxy propyl cellulose (HPC) .
5. The process according to any one of claims 1 to 4, c h a r a c t e r i z e d in that the cellulose derivative is selected from a group of hydroxy ethyl cellulose and carboxy methyl cellulose.
6. The process according to any one of claims 1 to 5, c h a r a c t e r i z e d in that the crosslinker is selected from a group of divinyl sulphones, di- anhydrides, dialdehydes, formaldehydes, glyoxal, diisocyanates, ethylene glycol, diglycidyl ether, oxalic and citric acids and inorganic salts.
7. The process according to any one of claims 1 to 6, c h a r a c t e r i z e d in that the amount of crosslinker is 4 to 15% by weight of the amount of cellulose derivative.
8. The process according to any one of claims 1 to 7, c h a r a c t e r i z e d in that the crosslink- ing reaction is activated by at least one activator selected from a group of heat, pH, catalyst, drying and radiation.
9. The process according to any one of claims 1 to 8, c h a r a c t e r i z e d in that the cellulose derivative is dissolved in a selected solvent prior to crosslinking.
10. The process according to any one of claims 1 to 9, c h a r a c t e r i z e d in that a surface-active agent is added to the cellulose derivative prior to crosslinking.
11. The process according to any one of claims 1 to 10, c h a r a c t e r i z e d in that a porous foam structure of the pigment product is formed.
12. The process according to any one of claims 1 to 11, c h a r a c t e r i z e d in that the provided pigment product is dried.
13. The process according to any one of claims 1 to 12, c h a r a c t e r i z e d in that the provided pigment product is cured by heat.
14. A cellulose-based pigment product, c h a r a c t e r i z e d in that it is formed by the process according to any one of claims 1 to 13.
15. Use of a pigment product formed by the process according to any one of claims 1 to 13, c h a r a c t e r i z e d in that the provided pigment product is used in surface-treatment of a substrate and/or in fillers.
PCT/FI2009/050434 2008-05-30 2009-05-26 Process for forming a pigment product from a cellulose derivative Ceased WO2009144372A1 (en)

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CN102580136A (en) * 2011-01-07 2012-07-18 佛山市优特医疗科技有限公司 High absorbent wound dressing capable of being removed entirely
WO2015052380A1 (en) 2013-10-11 2015-04-16 Upm-Kymmene Corporation Method for manufacturing a paper, a paper and its use, a furnish and a wood based composition
US9200084B2 (en) 2010-06-08 2015-12-01 Dow Global Technologies Llc Method for the preparation of a particulate reversibly crosslinked polymeric material

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CN113116747A (en) * 2020-01-14 2021-07-16 罗盖特公司 Natural and porous starches as white pigments in toothpaste

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US9200084B2 (en) 2010-06-08 2015-12-01 Dow Global Technologies Llc Method for the preparation of a particulate reversibly crosslinked polymeric material
CN102580136A (en) * 2011-01-07 2012-07-18 佛山市优特医疗科技有限公司 High absorbent wound dressing capable of being removed entirely
WO2015052380A1 (en) 2013-10-11 2015-04-16 Upm-Kymmene Corporation Method for manufacturing a paper, a paper and its use, a furnish and a wood based composition

Also Published As

Publication number Publication date
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FI20085526L (en) 2009-12-01
EP2291408A1 (en) 2011-03-09
FI20085526A0 (en) 2008-05-30
EP2291408A4 (en) 2013-05-29

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