WO1997001670A1 - Filler for use in paper manufacture and procedure for producing a filler - Google Patents

Filler for use in paper manufacture and procedure for producing a filler Download PDF

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Publication number
WO1997001670A1
WO1997001670A1 PCT/FI1996/000379 FI9600379W WO9701670A1 WO 1997001670 A1 WO1997001670 A1 WO 1997001670A1 FI 9600379 W FI9600379 W FI 9600379W WO 9701670 A1 WO9701670 A1 WO 9701670A1
Authority
WO
WIPO (PCT)
Prior art keywords
filler
noil
calcium carbonate
procedure
precipitation
Prior art date
Application number
PCT/FI1996/000379
Other languages
French (fr)
Inventor
Petri Silenius
Markku Leskelä
Original Assignee
Metsä-Serla 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 Metsä-Serla Oy filed Critical Metsä-Serla Oy
Priority to AT96920860T priority Critical patent/ATE205562T1/en
Priority to CA002223955A priority patent/CA2223955C/en
Priority to EP96920860A priority patent/EP0835343B1/en
Priority to NZ311044A priority patent/NZ311044A/en
Priority to DE69615192T priority patent/DE69615192T2/en
Priority to DK96920860T priority patent/DK0835343T3/en
Priority to AU62270/96A priority patent/AU699733B2/en
Priority to JP9504193A priority patent/JPH11508331A/en
Publication of WO1997001670A1 publication Critical patent/WO1997001670A1/en
Priority to US08/973,926 priority patent/US6251222B1/en

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • 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
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • 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
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
    • 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
    • C01P2006/90—Other properties not specified above
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • 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
    • D21H17/675—Oxides, hydroxides or carbonates

Definitions

  • FILLER FOR USE IN PAPER MANUFACTURE AND PROCEDURE FOR PRODUCING A FILLER
  • the present invention relates to a filler for use in paper manufacture as defined in the preamble of claim 1. Moreover, the invention relates to a proceedu ⁇ re for producing said filler.
  • ⁇ paper' refers to various kinds of paper and cardboard, manufactured with paper and cardboard machines, coated or uncoated.
  • the buyers of prin ⁇ ting paper want to reduce the postage expenses and the amount of waste produced. Further, packages are sub- ject to waste processing charges dependent on weight.
  • energy taxes and environmen ⁇ tal protection taxes are being imposed on the price of paper products as a permanent extra encumbrance. For these reasons, paper buyers want products which have a lower grammage while still meeting high quality stan ⁇ dards.
  • Specification FI 931584 presents a composite product based on chemical pulp fibre or mechanical pulp fibre, with calcium carbonate crystals precipita- ted onto the surface of the product.
  • specifi ⁇ cation FI 944355 presents a precipitated calcium car ⁇ bonate, which is in the form of calcite particle ag ⁇ gregates where at least 25% of the particles are of a prismatic shape. Precipitation is performed using a seed material.
  • specification EP 0604095 pre ⁇ sents a procedure for the processing of waste material whereby calcium carbonate is precipitated onto the surface of waste material containing inorganic matter; the waste material may contain organic waste fibre, e.g. waste fibre contained in the effluent of a paper mill, with fibre length below 75 ⁇ m.
  • the calcium car- bonate products described in the specifications refer ⁇ red to are intended to be used as fillers in paper ma ⁇ nufacture.
  • the aim is to produce the paper with a minimum amount of raw material.
  • the grammage of the paper is redu ⁇ ced, its opacity becomes a critical factor.
  • the opaci ⁇ ty can be increased by increasing the filler content of the paper, which, however, generally reduces its strength. Therefore, the aim is to alter the structure of the paper while at the same time preserving the im ⁇ portant good product qualities.
  • the printing quality of paper products has to be further improved.
  • the object of the present invention is to produce a new kind of calcium carbonate based filler for paper manufacture that meets the criteria descri ⁇ bed above.
  • a further object of the invention is to pro ⁇ cute a new kind of calcium carbonate based filler which has better optic properties than earlier calcium carbonate based fillers.
  • An additional object of the invention is to present a procedure for the manufacture of said fil- Ier.
  • the invention is based, among other things, on the fact, established via corresponding investiga- tions, that calcium carbonate can be precipitated in a way that causes it to effectively adhere to fibres and noil fibrils.
  • the precipitation can be so performed that porous calcium carbonate aggregates held together by fibrils, i.e. fine fibres, are formed, which aggre- gates contain plenty of empty space and in which the calcium carbonate particles have precipitated onto the noil fibrils, adhering to them.
  • the noil fibrils with calcium carbonate particles precipitated on them form fibres resembling pearl necklaces, and the calcium carbonate aggregates resemble clusters of pearl neck ⁇ laces.
  • the aggregates have a very large ratio of ef ⁇ fective volume to mass as compared with the correspon ⁇ ding ratio of conventional calcium carbonate used as filler; effective volume here means the volume taken up by pigment in the paper.
  • the noil fibrils used in the filler of the invention are obtained from cellulose fibre and/or mechanical pulp fibre.
  • the fibrils are produced from cellulose fibre and/or mechanical pulp fibre by refi- ning.
  • the noil fibrils are preferably di ⁇ vided into fractions, thickness 0.1 - 2 ⁇ m, length mainly 10 - 400 ⁇ m, suitably 10 - 300 ⁇ m, preferably 10 - 150 ⁇ m.
  • the noil fibrils consist of cellu ⁇ lose fibre and/or mechanical pulp fibre, which means that they contain no significant amounts of inorganic matter, preferably no inorganic matter at all.
  • the diameter of the calcium carbonate par ⁇ ticles in the aggregate is of the order of about 0.2- 3 ⁇ m, preferably about 0.3-1.5 ⁇ m.
  • the diameter of the CaC0 3 crystal aggregates is of the order of about 2-10 ⁇ m.
  • Cellulose based noil also contains roundish noil particles which, after the precipitation process, are covered with calcium carbonate particles.
  • a particle of calcium car ⁇ bonate filler corresponds in the first place to a hol- low filler particle having a small unit weight.
  • the pigment is not completely hollow, because it contains noil; however, the noil has a lower unit weight than calcium carbonate, therefore the particle has a very low unit weight.
  • the new precipitated, calcium carbonate based filler of the invention bestows paper better optic properties and a clearly greater strength than prior- art calcium carbonate based fillers do.
  • the new filler of the invention has a clearly better retention in paper manufacture than prior-art calcium carbonate based fillers.
  • the mass ratio of calcium carbonate and fibrous matter is much larger in the filler of the invention than in pore filled or lumen filled fibre.
  • the filler of the invention is a completely new product, and it should not be confused with prior-art pore filled or lumen filled fibre.
  • the filler of the invention and the procedure for its manufacture differ from the specification FI 931584 referred to in the introduction especially on the basis of the thickness and length of the noil fib ⁇ rils, i.e. in the present application, the noil fib ⁇ rils have been refined with a pulp refiner.
  • the filler and manufacturing method of the present invention likewise differ in respect of the refined noil fibrils; in addition, in the specifi ⁇ cation referred to, the calcite particles are of a prismatic shape and their production requires the use of a special seed material.
  • the product and procedure of the present in ⁇ vention likewise differ on the basis of the refinement and size of the noil fibrils; in addition, the fibre material used in the specification referred to is was ⁇ te fibre containing inorganic or other matter.
  • the filler of the present invention differs from those described in the reference specifications on the basis of the good optic properties, strength properties and very high retention achieved, and especially on the basis of the combination of exceptionally good optic and strength properties.
  • the fibre used in the procedure of the inven ⁇ tion may consist of chemical, mechanical or semi- mechancial pulp produced by any pulp or paper manufac ⁇ turing method known in itself, or a combination of these in arbitrary proportions, the proportion of each component being 0 - 100 % by weight.
  • the refining of the pulp into noil fibrils can be implemented using any pulp refiner known in itself in pulp processing industry. When desirable, the refined noil fibrils can be screened by any fractionating method known in it ⁇ self in pulp processing, e.g. using a wire screen, in ⁇ to the desired fibril size. In precipitation, the noil, i.e. e.g. pulp based or other fibre based noil, is refined with a pulp refiner and screened, preferred fractions being e.g. wire screen fractions P100-P400.
  • calcium carbonate can be precipitated from any suitable solu ⁇ tion or mixture, e.g. from a mixture of Ca(OH) 2 water solution and solid Ca(OH) 2 or from a calcium hydroxide water solution.
  • precipitation can be implemented using any substance that precipitates calcium carbona- te, e.g. carbon dioxide, such as gaseous carbon dioxi ⁇ de, suitably 1-100 %, preferably 10-100 % carbon dio ⁇ xide gas.
  • any reaction producing calcium carbonate e.g. the reaction between calcium chloride and sodium carbonate, producing calcium car ⁇ bonate and sodium chloride.
  • the precipitation of calcium carbonate is performed on the surface of noil originating from cel ⁇ lulose fibre, suitably noil fibrils.
  • concentration of noil in the precipitation process is suitably 0.0001 - 18 w-%, preferably 0.4 - 10 w-%.
  • the mass ratio of calcium hydroxide and cellulose fibres in precipitation is suitably 0.1 - 20, preferably 1.4 - 4.
  • the precipitation temperatu ⁇ re is in the range 5 - 150 °C, suitably 10 - 90 °C, preferably 15 - 80 °C.
  • the net reacti ⁇ on is
  • the precipitation can be advantageously ef- fected in a specific reactor where e.g. calcium .hydro ⁇ xide and noil are mixed.
  • the carbonation reaction is implemented by supplying carbon dioxide, e.g. gaseous carbon dioxide, into the reactor.
  • the progress of the reaction can be monitored by measuring the pH and con- ductivity of the mixture.
  • the mixing and the supply of gas can be terminated when the pH of the mixture has fallen to the value of about 7.5, depending on the pH value of the noil.
  • the carbonation is carried out e.g. in a water solution or mixture of Ca(0H) 2 .
  • a disper ⁇ sing agent e.g. sodium hexametaphosphate (Na-HMF) or other dispersing agent(s)
  • the filler of the invention can be used as filler as such or in any ratio of mixture (0-100 %) with another filler or other fillers.
  • the amount of filler used in paper is 0.1 - 50 w-%, preferably 0.1 -
  • Fig. 1 presents the equipment used in the procedure of the invention
  • Fig. 2-4 present pictures taken of the filler of the invention by means of an electron microscope
  • Fig. 5-8 present graphs representing the pro- perties of the filler of the invention as compared with those of a prior-art filler.
  • Bleached pine sulphate pulp was refined in a Valley laboratory hollander in accordance with the SCAN-C 25:-76 standard for 2.5 hours.
  • the refined pulp was screened by means of a Bauer-McNett screen, initi ⁇ ally using the wire sequence 14-50-100-200 mesh.
  • the amount of dry matter screened at a time was 45 g.
  • the fraction passed through the 200 mesh wire (P200 frac ⁇ tion) was saved and allowed to settle for 2 days, whereupon the aqueous phase on its surface was separa ⁇ ted.
  • the P200 fraction was further fractionated with the wire sequence 100-200-290-400 mesh.
  • the 100 mesh wire was used to equalize the screening process and prevent the 200 mesh wire from getting blocked at the initial stage.
  • the fraction passed through the 400 mesh wire (P400 fraction) was saved and, after the noil fraction had settled, the aqueous phase on the surface was separated.
  • Precipitation was performed at a temperature of 35 °C and the carbon content of the gas mixture was adjusted to a value of 15 % by volume; the reaction volume was 3.2 1.
  • the filler was produced using three different Ca(OH) 2 /noil ratios.
  • the proportions of raw materials are presented in Table 1.
  • the noil was homogenized by mixing it in the reactor for 5 min at a mixing speed of 600 l/min. At this stage, a small nit ⁇ rogen flow was used to prevent the gas pipes from get ⁇ ting blocked. After this, the mixing speed was adjus ⁇ ted to the value 1000 l/min, and calcium hydroxide was added into the reactor.
  • the measuring sensors were placed in the reactor and the reaction was started by opening the C0 2 flow as well. The progress of the reaction was monitored by measuring the pH, 8, and conductivity, 9, of the mixture. The mixing and gas supply were stopped when the pH, 8, had fallen to the value 7.5. Pictures of the product obtained were taken with an electron microscope (SEM), Fig. 2, 3, 4.
  • the calcium carbonate par ⁇ ticles in the aggregate have a diameter of 0.3-1.5 ⁇ m and a roundish and partly shuttle-like shape.
  • the dia- meter of the aggregates varies between about 2 - 10 ⁇ m.
  • the noil/CaC0 3 fibrils can be described as re ⁇ sembling pearl necklaces and the aggregates as re ⁇ sembling clusters of pearl necklaces. There are also roundish noil particles (Fig.
  • a pulp mixture containing 75 w-% bleached mechanical pulp and 25 w-% bleached pine sulphate pulp was prepa ⁇ red.
  • the pulp was refined in a Valley laboratory hol- lander to SR number 30 in accordance with the SCAN-C 25:76 standard, the refining time being 38 min.
  • the fillers obtained from precipitations 1 and 2 presented in Fig. 1 were used undiluted in the production of laboratory sheets, and the filler from precipitation 3 was diluted to one half of its consis ⁇ tency after precipitation.
  • solutions having a consistency of 25 g/1 were prepared from commercial CaC0 3 fillers.
  • the sheet pile was placed in the press and it was pressed by applying a pressure of 490 ⁇ kPa to the sheets for 4 minutes. After the wet pressing, the blotting boards on either side of the sheets were left sticking to the sheets and the sheets were placed in a cold drying drum. The sheets were dried in the drum at a temperature of 1000 °C for 2 h. After the drying, the blotting boards were released from the sheets and the sheets were seasoned for at least 24 h at a tempe ⁇ rature of 23 ⁇ 1 °C, the relative humidity being 50 + 2
  • the calcium carbona ⁇ te content, grammage, ISO whiteness, light-scattering coefficient and tensile index were determined.
  • the re ⁇ sults are presented in Tables 2, 3 and 4.
  • Calcium carbonate retention was on an average 92 % for the filler of the invention, 64 % for commer ⁇ cial precipitated calcium carbonate (PCC) and 62 % for commercial ground calcium carbonate (GC) .
  • PCC commer ⁇ cial precipitated calcium carbonate
  • GC commercial ground calcium carbonate
  • Fig. 5-8 present the results in the form of graphs.
  • the references Sl, S2 and S2 cor ⁇ respond to the results shown in the table with fillers obtained from precipitations 1, 2 and 3, respectively;
  • the references PCC and GC indicate results obtained with commercial precipitated calcium carbonate and ground calcium carbonate, respectively.
  • Fig. 5 and 6 indicate that the filler of the invention has better optic properties as compared with the corresponding properties with commercial CaC0 3 fillers used in the same CaC0 3 contents.
  • Fig. 7 shows that the tensile strength in the case of the filler of the invention is clearly better than in the case of commercial CaC0 3 fillers used in the same CaC0 3 contents.
  • Fig. 5-8 present the results in the form of graphs.
  • the references Sl, S2 and S2 cor ⁇ respond to the results shown in the table with fillers obtained from precipitations 1, 2 and 3, respectively;
  • the references PCC and GC indicate results obtained with commercial precipitated calcium carbonate and ground calcium carbonate, respectively.

Abstract

The invention relates to a filler used in paper manufacture and mainly consisting of calcium carbonate, and to a procedure for producing the filler. The filler consists of porous aggregates formed by precipitated calcium carbonate particles. In the procedure, calcium carbonate is precipitated.

Description

FILLER FOR USE IN PAPER MANUFACTURE AND PROCEDURE FOR PRODUCING A FILLER
The present invention relates to a filler for use in paper manufacture as defined in the preamble of claim 1. Moreover, the invention relates to a procedu¬ re for producing said filler.
In the present application, λpaper' refers to various kinds of paper and cardboard, manufactured with paper and cardboard machines, coated or uncoated. Today, the direction of development of paper products is to an increasing degree determined by cus¬ tomers and legislative measures. The buyers of prin¬ ting paper want to reduce the postage expenses and the amount of waste produced. Further, packages are sub- ject to waste processing charges dependent on weight. Generally, it seems that energy taxes and environmen¬ tal protection taxes are being imposed on the price of paper products as a permanent extra encumbrance. For these reasons, paper buyers want products which have a lower grammage while still meeting high quality stan¬ dards.
Specification FI 931584 presents a composite product based on chemical pulp fibre or mechanical pulp fibre, with calcium carbonate crystals precipita- ted onto the surface of the product. Further, specifi¬ cation FI 944355 presents a precipitated calcium car¬ bonate, which is in the form of calcite particle ag¬ gregates where at least 25% of the particles are of a prismatic shape. Precipitation is performed using a seed material. Further, specification EP 0604095 pre¬ sents a procedure for the processing of waste material whereby calcium carbonate is precipitated onto the surface of waste material containing inorganic matter; the waste material may contain organic waste fibre, e.g. waste fibre contained in the effluent of a paper mill, with fibre length below 75 μm. The calcium car- bonate products described in the specifications refer¬ red to are intended to be used as fillers in paper ma¬ nufacture.
In the manufacture of high-quality paper, the aim is to produce the paper with a minimum amount of raw material. When the grammage of the paper is redu¬ ced, its opacity becomes a critical factor. The opaci¬ ty can be increased by increasing the filler content of the paper, which, however, generally reduces its strength. Therefore, the aim is to alter the structure of the paper while at the same time preserving the im¬ portant good product qualities. For paper based commu¬ nication to remain competitive in relation to electric communication, the printing quality of paper products has to be further improved. - These general develop¬ ment trends impose very high requirements on the raw materials and manufacturing processes used in paper production. To meet the requirements, very intensive efforts have been made in recent times to develop pa- per raw materials and manufacturing processes.
The object of the present invention is to produce a new kind of calcium carbonate based filler for paper manufacture that meets the criteria descri¬ bed above. A further object of the invention is to pro¬ duce a new kind of calcium carbonate based filler which has better optic properties than earlier calcium carbonate based fillers.
A further object of the invention is to pro- duce a new kind of calcium carbonate based filler which gives the paper better strength properties, es¬ pecially a better tensile strength, than earlier cal¬ cium carbonate based fillers.
A further object of the invention is to pro- duce a new kind of calcium carbonate based filler which gives the paper a lower grammage than earlier calcium carbonate based fillers. A further object of the invention is to pro¬ duce a new kind of calcium carbonate based filler which has a higher retention than earlier calcium car¬ bonate based fillers. A further object of the invention is to pro¬ duce a new kind of calcium carbonate based filler which reduces the overall costs of paper manufacture.
An additional object of the invention is to present a procedure for the manufacture of said fil- Ier.
As for the features characteristic of the in¬ vention, reference is made to the claims.
The invention is based, among other things, on the fact, established via corresponding investiga- tions, that calcium carbonate can be precipitated in a way that causes it to effectively adhere to fibres and noil fibrils. The precipitation can be so performed that porous calcium carbonate aggregates held together by fibrils, i.e. fine fibres, are formed, which aggre- gates contain plenty of empty space and in which the calcium carbonate particles have precipitated onto the noil fibrils, adhering to them. The noil fibrils with calcium carbonate particles precipitated on them form fibres resembling pearl necklaces, and the calcium carbonate aggregates resemble clusters of pearl neck¬ laces. The aggregates have a very large ratio of ef¬ fective volume to mass as compared with the correspon¬ ding ratio of conventional calcium carbonate used as filler; effective volume here means the volume taken up by pigment in the paper.
The noil fibrils used in the filler of the invention are obtained from cellulose fibre and/or mechanical pulp fibre. The fibrils are produced from cellulose fibre and/or mechanical pulp fibre by refi- ning. Furthermore, the noil fibrils are preferably di¬ vided into fractions, thickness 0.1 - 2 μm, length mainly 10 - 400 μm, suitably 10 - 300 μm, preferably 10 - 150 μm. Thus, the noil fibrils consist of cellu¬ lose fibre and/or mechanical pulp fibre, which means that they contain no significant amounts of inorganic matter, preferably no inorganic matter at all. The diameter of the calcium carbonate par¬ ticles in the aggregate is of the order of about 0.2- 3 μm, preferably about 0.3-1.5 μm.
The diameter of the CaC03 crystal aggregates is of the order of about 2-10 μm. Cellulose based noil also contains roundish noil particles which, after the precipitation process, are covered with calcium carbonate particles. In this case, as to its properties, a particle of calcium car¬ bonate filler corresponds in the first place to a hol- low filler particle having a small unit weight. In reality, the pigment is not completely hollow, because it contains noil; however, the noil has a lower unit weight than calcium carbonate, therefore the particle has a very low unit weight. The new precipitated, calcium carbonate based filler of the invention bestows paper better optic properties and a clearly greater strength than prior- art calcium carbonate based fillers do. Furthermore, the filler of the invention allows the filler content of paper to be increased without impairing its other properties, e.g. the aforementioned strength proper¬ ties, such as tensile strength. This is a significant contribution towards lowering the grammage of paper.
Further, the new filler of the invention has a clearly better retention in paper manufacture than prior-art calcium carbonate based fillers.
In consequence of the aforesaid factors, it is generally possible to achieve cost savings in paper manufacture by using the filler of the invention. In prior art, light filler pigments are known, e.g. hollow plastic pigments, which are sup¬ posed to provide the same advantages as the calcium carbonate based filler of the present invention. Howe¬ ver, plastic pigments are expensive, which restricts their use. When the filler of the invention is compa¬ red with pore filled or lumen filled fibre, it is to be noted that, unlike in the case of aforesaid fibres, the calcium carbonate in the filler of the invention is not inside individual noil fibres but on the surfa¬ ce of the noil. In addition, the mass ratio of calcium carbonate and fibrous matter is much larger in the filler of the invention than in pore filled or lumen filled fibre. Thus, the filler of the invention is a completely new product, and it should not be confused with prior-art pore filled or lumen filled fibre.
The filler of the invention and the procedure for its manufacture differ from the specification FI 931584 referred to in the introduction especially on the basis of the thickness and length of the noil fib¬ rils, i.e. in the present application, the noil fib¬ rils have been refined with a pulp refiner. From the filler and manufacturing method described in specifi¬ cation FI 944355, the filler and manufacturing method of the present invention likewise differ in respect of the refined noil fibrils; in addition, in the specifi¬ cation referred to, the calcite particles are of a prismatic shape and their production requires the use of a special seed material. With respect to the pro¬ duct and procedure presented in specification EP 0604095, the product and procedure of the present in¬ vention likewise differ on the basis of the refinement and size of the noil fibrils; in addition, the fibre material used in the specification referred to is was¬ te fibre containing inorganic or other matter. - In general, in addition to the differences stated above, the filler of the present invention differs from those described in the reference specifications on the basis of the good optic properties, strength properties and very high retention achieved, and especially on the basis of the combination of exceptionally good optic and strength properties.
The fibre used in the procedure of the inven¬ tion may consist of chemical, mechanical or semi- mechancial pulp produced by any pulp or paper manufac¬ turing method known in itself, or a combination of these in arbitrary proportions, the proportion of each component being 0 - 100 % by weight. The refining of the pulp into noil fibrils can be implemented using any pulp refiner known in itself in pulp processing industry. When desirable, the refined noil fibrils can be screened by any fractionating method known in it¬ self in pulp processing, e.g. using a wire screen, in¬ to the desired fibril size. In precipitation, the noil, i.e. e.g. pulp based or other fibre based noil, is refined with a pulp refiner and screened, preferred fractions being e.g. wire screen fractions P100-P400.
In the procedure of the invention, calcium carbonate can be precipitated from any suitable solu¬ tion or mixture, e.g. from a mixture of Ca(OH)2 water solution and solid Ca(OH)2 or from a calcium hydroxide water solution. Thus, precipitation can be implemented using any substance that precipitates calcium carbona- te, e.g. carbon dioxide, such as gaseous carbon dioxi¬ de, suitably 1-100 %, preferably 10-100 % carbon dio¬ xide gas. Instead of calcium hydroxide and carbon dio¬ xide, it is possible to use any reaction producing calcium carbonate, e.g. the reaction between calcium chloride and sodium carbonate, producing calcium car¬ bonate and sodium chloride.
The precipitation of calcium carbonate is performed on the surface of noil originating from cel¬ lulose fibre, suitably noil fibrils. The concentration of noil in the precipitation process is suitably 0.0001 - 18 w-%, preferably 0.4 - 10 w-%. When calcium hydroxide is used, the mass ratio of calcium hydroxide and cellulose fibres in precipitation is suitably 0.1 - 20, preferably 1.4 - 4. The precipitation temperatu¬ re is in the range 5 - 150 °C, suitably 10 - 90 °C, preferably 15 - 80 °C. In the carbon dioxide method, the net reacti¬ on is
Ca(OH)2 + C02 O CaC03 + H20. In the chloride method, the net reaction is CaCl2 + Na2C03 O CaC03 + 2NaCl Calcium carbonate precipitates when the cal¬ cium compounds react according to the reaction equa¬ tions. It is possible to influence the crystal size and/or shape by adjusting the reaction conditions.
The precipitation can be advantageously ef- fected in a specific reactor where e.g. calcium .hydro¬ xide and noil are mixed. The carbonation reaction is implemented by supplying carbon dioxide, e.g. gaseous carbon dioxide, into the reactor. The progress of the reaction can be monitored by measuring the pH and con- ductivity of the mixture. The mixing and the supply of gas can be terminated when the pH of the mixture has fallen to the value of about 7.5, depending on the pH value of the noil. The carbonation is carried out e.g. in a water solution or mixture of Ca(0H)2. If desirable, it is possible to add a disper¬ sing agent, e.g. sodium hexametaphosphate (Na-HMF) or other dispersing agent(s), into the filler produced.
The filler of the invention can be used as filler as such or in any ratio of mixture (0-100 %) with another filler or other fillers. The amount of filler used in paper is 0.1 - 50 w-%, preferably 0.1 -
30 w-%.
The filler of the invention and the procedure for its manufacture are described in more detail in the following embodiment examples by referring to the attached drawings, in which
Fig. 1 presents the equipment used in the procedure of the invention;
Fig. 2-4 present pictures taken of the filler of the invention by means of an electron microscope;
Fig. 5-8 present graphs representing the pro- perties of the filler of the invention as compared with those of a prior-art filler.
EXAMPLE 1. Production of filler.
Bleached pine sulphate pulp was refined in a Valley laboratory hollander in accordance with the SCAN-C 25:-76 standard for 2.5 hours. The refined pulp was screened by means of a Bauer-McNett screen, initi¬ ally using the wire sequence 14-50-100-200 mesh. The amount of dry matter screened at a time was 45 g. The fraction passed through the 200 mesh wire (P200 frac¬ tion) was saved and allowed to settle for 2 days, whereupon the aqueous phase on its surface was separa¬ ted.
The P200 fraction was further fractionated with the wire sequence 100-200-290-400 mesh. The 100 mesh wire was used to equalize the screening process and prevent the 200 mesh wire from getting blocked at the initial stage. The fraction passed through the 400 mesh wire (P400 fraction) was saved and, after the noil fraction had settled, the aqueous phase on the surface was separated.
The P400 fraction was thickened by centrifu¬ gation to a consistency of 4.7 g/1, whereupon the noil was ready for use in the production of a filler. The filler was produced in a mixing tank reactor 1, Fig. 1. The reactor had a capacity of 5 litres and its temperature could be regulated via a water circulation system 2 in its casing. The reactor contained four vertical foul plates designed to in- crease the mixing efficiency. A gas mixture of carbon dioxide and nitrogen was supplied via a pipe 3 to a point below the mixer element. The flow and carbon dioxide content of the gas mixture could be adjusted by means of control valves 5, 6 provided in the gas pipes 3, 4. Measuring sensors 7, 8, 9 were placed in the reactor via holes in the cover. The measuring ele- ments were connected to a computer 10, in which the measurement data was collected and stored.
Precipitation was performed at a temperature of 35 °C and the carbon content of the gas mixture was adjusted to a value of 15 % by volume; the reaction volume was 3.2 1.
The filler was produced using three different Ca(OH)2/noil ratios. The proportions of raw materials are presented in Table 1.
Table 1. Proportions of raw materials
Precipit¬ Precipit¬ Precipit ation 1 ation 2 ation 3
Figure imgf000011_0001
mCa (OH) 2 ' 9 22 35 50
Vnitrogen, l /min 5.25 8. 36 11. 94
'' carbon dioxide ' 0. 93 1. 48 2. 11 l/min
Before the reaction was started, the noil was homogenized by mixing it in the reactor for 5 min at a mixing speed of 600 l/min. At this stage, a small nit¬ rogen flow was used to prevent the gas pipes from get¬ ting blocked. After this, the mixing speed was adjus¬ ted to the value 1000 l/min, and calcium hydroxide was added into the reactor. The measuring sensors were placed in the reactor and the reaction was started by opening the C02 flow as well. The progress of the reaction was monitored by measuring the pH, 8, and conductivity, 9, of the mixture. The mixing and gas supply were stopped when the pH, 8, had fallen to the value 7.5. Pictures of the product obtained were taken with an electron microscope (SEM), Fig. 2, 3, 4. From the SEM pictures it can be seen that the product con¬ sists of porous calcium carbonate aggregates held to- gether by noil fibrils and containing plenty of empty space, with CaC03 particles precipitated onto the noil fibrils, adhering to them. The calcium carbonate par¬ ticles in the aggregate have a diameter of 0.3-1.5 μm and a roundish and partly shuttle-like shape. The dia- meter of the aggregates varies between about 2 - 10 μm. The noil/CaC03 fibrils can be described as re¬ sembling pearl necklaces and the aggregates as re¬ sembling clusters of pearl necklaces. There are also roundish noil particles (Fig. 3), and these are cove- red with tiny CaC03 particles. In this case, we can even speak of a hollow CaC03 pigment, which has a low unit weight (the pigment is not completely hollow be¬ cause there is some noil inside it; however, noil has a lower unit weight than calcium carbonate) . According to an X-ray diffraction analysis, 100 % of the preci¬ pitated calcium carbonate consisted of calcite.
EXAMPLE 2. Properties of paper
To test the technical potential of the filler in paper manufacture, a series of sheet tests were performed, in which the properties of the paper were compared when two fillers as provided by the invention and calcium carbonate fillers already available in the market, PCC (Albacar LO) and GC (Fincarb 6005) were used.
For the production of laboratory sheets, a pulp mixture containing 75 w-% bleached mechanical pulp and 25 w-% bleached pine sulphate pulp was prepa¬ red. The pulp was refined in a Valley laboratory hol- lander to SR number 30 in accordance with the SCAN-C 25:76 standard, the refining time being 38 min.
The fillers obtained from precipitations 1 and 2 presented in Fig. 1 were used undiluted in the production of laboratory sheets, and the filler from precipitation 3 was diluted to one half of its consis¬ tency after precipitation. For the production of refe- rence sheets, solutions having a consistency of 25 g/1 were prepared from commercial CaC03 fillers.
In a laboratory sheet mould, 60 g/m sheets were produced without circulation water according to the standards SCAN-C 26:76 and SCAN-M 5:76 except for drum drying and corresponding wet pressing of the sheets. As retention agents, cationic starch (Raisamyl 135) 0.65 % and silica 0.15 % of the fibre mass were used.
For wet pressing corresponding to drum drying, the sheets were piled up as follows:
Top of pile - press plate
2 dried blotting boards new blotting board laboratory sheet couching board 2 dried blotting boards
Bottom of pile — > press plate
The sheet pile was placed in the press and it was pressed by applying a pressure of 490 ± kPa to the sheets for 4 minutes. After the wet pressing, the blotting boards on either side of the sheets were left sticking to the sheets and the sheets were placed in a cold drying drum. The sheets were dried in the drum at a temperature of 1000 °C for 2 h. After the drying, the blotting boards were released from the sheets and the sheets were seasoned for at least 24 h at a tempe¬ rature of 23 ± 1 °C, the relative humidity being 50 + 2
For the finished sheets, the calcium carbona¬ te content, grammage, ISO whiteness, light-scattering coefficient and tensile index were determined. The re¬ sults are presented in Tables 2, 3 and 4.
Table 2. Paper properties obtained using a filler as provided by the invention
Precipit¬ Precipit¬ Precipit¬ ation 1 ation 2 ation 3
CaC03 content, % 10.2 15.8 12.1 17.1 12.8 17. .7 grammage, g/m 65.0 66.3 65.1 65.6 65.0 66. .0 ISO whiteness, % 72.4 75.0 73.1 75.9 74.0 76. .8 light-scattering 74.4 82.6 77.0 87.2 78.6 90. .3 coeff. , m /kg tensile index, 48.8 47.4 50.0 44.9 45.4 40.7 Nm/g
Table 3. Paper properties obtained using com- mercial CaC03 fillers
PCC GC
CaC03 content, % 11.8 18.3 22.9 11.6 18.0 22.0 grammage, g/m 65.1 68.3 66.7 67.5 63.6 68.4 ISO whiteness, % 73.1 75.0 76.1 72.6 73.7 74.5 light-scattering 76.8 85.8 88.4 72.8 77.5 82.4 coeff., m2/kg tensile index, 33.3 28.4 26.6 36.9 31.6 28.7 Nm/g
Calcium carbonate retention was on an average 92 % for the filler of the invention, 64 % for commer¬ cial precipitated calcium carbonate (PCC) and 62 % for commercial ground calcium carbonate (GC) . Table 4. Paper properties with mere pulp wit¬ hout filler
CaC03 content, % 0 grammage, g/m 64.7
ISO whiteness, % 71.2 light-scattering coeff., m /kg 62.0 tensile index, Nm/g 56.2
Fig. 5-8 present the results in the form of graphs. In Fig. 5-8, the references Sl, S2 and S2 cor¬ respond to the results shown in the table with fillers obtained from precipitations 1, 2 and 3, respectively; the references PCC and GC indicate results obtained with commercial precipitated calcium carbonate and ground calcium carbonate, respectively. Fig. 5 and 6 indicate that the filler of the invention has better optic properties as compared with the corresponding properties with commercial CaC03 fillers used in the same CaC03 contents. Fig. 7 shows that the tensile strength in the case of the filler of the invention is clearly better than in the case of commercial CaC03 fillers used in the same CaC03 contents. In addition, Fig. 8 shows the light-scattering coefficient as a function of the tensile index. In this survey, both the optic properties of the paper and its runnability on a paper machine are considered. In this survey, the filler of the invention is clearly better than commer¬ cial CaC03 fillers. In other words, with the same light-scattering coefficient values, the filler of the invention gives a clearly better tensile strength than do commercial CaC03 fillers. From the graphs we can see a trend of improving optical properties and dec¬ reasing tensile strength of the paper as the ratio
Figure imgf000015_0001
in precipitation increases.
The excellent properties of the new type of porous CaC03 filler described in the foregoing allow the CaC03 content to be increased and the grammage of paper to be further reduced without impairing other important qualities of paper. Considering the improved retention of the filler of the invention in paper ma- nufacture, the aforesaid good results together also allow cost savings to be achieved.
The embodiment examples are intended to il¬ lustrate the invention without limiting it in any way.

Claims

1. Filler for use in paper manufacture, con¬ sisting of porous aggregates precipitated onto the surface of noil and formed by calcium carbonate par- tides, characterized in that the calcium carbonate is precipitated onto the surface of noil fibrils produced by refining from cellulose fibre and/or mechanical pulp fibre.
2. Filler as defined in claim 1, characteri- zed in that the calcium carbonate is precipitated onto the surface of fractionated noil fibrils forming CaC03 crystal aggregates held together by the noil fibrils.
3. Filler as defined in claim 1 or 2, charac¬ terized in that the thickness of the noil fibrils is mainly 0.1 - 2 μm and the length mainly 10 - 400 μm, suitably 10 - 300 μm, preferably 10 - 150 μm.
4. Filler as defined in any one of claims 1-
3, characterized in that the diameter of the calcium carbonate particles precipitated onto the surface of the noil fibrils is of the order of 0.2-3 μm.
5. Filler as defined in any one of claims 1-
4, characterized in that the diameter of the CaC03 crystal aggregates is 2-10 μm.
6. Filler as defined in any one of claims 1- 5, characterized in that the mass ratio of calcium carbonate and noil in the filler is 13.5 - 2700 %.
7. Procedure for producing a filler for use in paper manufacture, said filler mainly consisting of porous aggregates formed by calcium carbonate par- tides, said calcium carbonate being precipitated onto the surface of noil, characterized in that the calcium carbonate is precipitated onto the surface of noil fibrils produced by refining from cellulose fibre and/or mechanical pulp fibre.
8. Procedure as defined in claim 7, characte¬ rized in that the noil fibrils are so fractionated that their thickness is mainly 0.1 - 2 μm and their length mainly 10 - 400 μm, suitably 10 - 300 μm, pre¬ ferably 10 - 150 μm.
9. Procedure as defined in claim 7 or 8, cha- racterized in that the consistency of noil in precipi¬ tation is 0.0001 - 18 % by weight, preferably 0.4 - 10 % by weight.
10. Procedure as defined in any one of claims 7-9, characterized in that the precipitation is per- formed using carbon dioxide and that the mass ratio of calcium hydroxide and noil in precipitation is 0.1 - 20, preferably 1.4 - 4.
11. Procedure as defined in any one of claims 7-9, characterized in that the precipitation is per- formed by a chloride method and that the mass ratio of calcium chloride and noil in precipitation is 0.15 - 30, preferably 2.1 - 6.
12. Procedure as defined in any one of claims 7-11, characterized in that the precipitation tempera- ture is 5 - 150 °C, preferably 10 - 90 °C, more prefe¬ rably 15 - 80 °C.
PCT/FI1996/000379 1995-06-29 1996-06-27 Filler for use in paper manufacture and procedure for producing a filler WO1997001670A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AT96920860T ATE205562T1 (en) 1995-06-29 1996-06-27 FILLER FOR PAPER MAKING, AND METHOD FOR PRODUCING SUCH FILLER
CA002223955A CA2223955C (en) 1995-06-29 1996-06-27 Filler for use in paper manufacture and procedure for producing a filler
EP96920860A EP0835343B1 (en) 1995-06-29 1996-06-27 Filler for use in paper manufacture and procedure for producing a filler
NZ311044A NZ311044A (en) 1995-06-29 1996-06-27 Calcium carbonate filler for paper manufacture
DE69615192T DE69615192T2 (en) 1995-06-29 1996-06-27 FILLER FOR PAPER PRODUCTION AND METHOD FOR PRODUCING THIS FILLER
DK96920860T DK0835343T3 (en) 1995-06-29 1996-06-27 Filler for use in papermaking and its process
AU62270/96A AU699733B2 (en) 1995-06-29 1996-06-27 Filler for use in paper manufacture and procedure for producing a filler
JP9504193A JPH11508331A (en) 1995-06-29 1996-06-27 Papermaking filler and method for producing filler
US08/973,926 US6251222B1 (en) 1995-06-29 1997-04-04 Filler for use in paper manufacture and procedure for producing a filler

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Application Number Priority Date Filing Date Title
FI953238A FI100729B (en) 1995-06-29 1995-06-29 Filler used in papermaking and method of making the filler
FI953238 1995-06-29

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EP (1) EP0835343B1 (en)
JP (1) JPH11508331A (en)
AT (1) ATE205562T1 (en)
AU (1) AU699733B2 (en)
CA (1) CA2223955C (en)
DE (1) DE69615192T2 (en)
DK (1) DK0835343T3 (en)
ES (1) ES2163640T3 (en)
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US20010000063A1 (en) 2001-03-29
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NZ311044A (en) 1998-07-28
ATE205562T1 (en) 2001-09-15
EP0835343B1 (en) 2001-09-12
US6375794B2 (en) 2002-04-23
PT835343E (en) 2002-01-30
AU699733B2 (en) 1998-12-10
DE69615192T2 (en) 2002-07-04
US6599391B2 (en) 2003-07-29
ES2163640T3 (en) 2002-02-01
JPH11508331A (en) 1999-07-21
FI953238A0 (en) 1995-06-29
US20020084050A1 (en) 2002-07-04
CA2223955A1 (en) 1997-01-16
DK0835343T3 (en) 2001-11-12
EP0835343A1 (en) 1998-04-15
AU6227096A (en) 1997-01-30
FI953238A (en) 1996-12-30
US6251222B1 (en) 2001-06-26

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