CN1268810C - Filler composition, its preparation method and use - Google Patents
Filler composition, its preparation method and use Download PDFInfo
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- CN1268810C CN1268810C CN 02118915 CN02118915A CN1268810C CN 1268810 C CN1268810 C CN 1268810C CN 02118915 CN02118915 CN 02118915 CN 02118915 A CN02118915 A CN 02118915A CN 1268810 C CN1268810 C CN 1268810C
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- surfactant
- filler composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 130
- 239000000945 filler Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 29
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 26
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000440 bentonite Substances 0.000 claims abstract description 24
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 24
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 24
- 239000000454 talc Substances 0.000 claims abstract description 24
- 235000012222 talc Nutrition 0.000 claims abstract description 24
- 229910052623 talc Inorganic materials 0.000 claims abstract description 24
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 21
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 21
- 235000012245 magnesium oxide Nutrition 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000843 powder Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- 229920002472 Starch Polymers 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000391 magnesium silicate Substances 0.000 claims description 10
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 10
- 235000019792 magnesium silicate Nutrition 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910000281 calcium bentonite Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 239000000835 fiber Substances 0.000 description 34
- 235000012216 bentonite Nutrition 0.000 description 21
- 238000011049 filling Methods 0.000 description 13
- 235000014380 magnesium carbonate Nutrition 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000005065 mining Methods 0.000 description 5
- 229910052755 nonmetal Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000378 calcium silicate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002843 nonmetals Chemical class 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000010456 wollastonite Substances 0.000 description 4
- 229910052882 wollastonite Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940009868 aluminum magnesium silicate Drugs 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008275 binding mechanism Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
-
- 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
- C09C1/42—Clays
-
- 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
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/60—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
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/22—Agents rendering paper porous, absorbent or bulky
- D21H21/24—Surfactants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种填料组合物，其制备方法及用途，尤其涉及一种造纸用填料组合物，其制备方法以及在造纸中的应用。The invention relates to a filler composition, its preparation method and application, in particular to a paper-making filler composition, its preparation method and its application in papermaking.
背景技术Background technique
造纸的主要原料为植物纤维，在纸中植物纤维交织成网状结构，从而赋予纸各种性能。造纸业中为了节省植物纤维的用量和改善纸的某些性能，通常在造纸中加填多种填料，如碳酸钙、滑石粉、白土(Kaoline)等。国际专利申请WO 01/44573公开了通过向纸浆中加入至少一种铝化合物和至少一种硅酸盐来制备纸制品。US5300147揭示了低亮度的硅酸镁SLR填料、含该填料的低亮度纸以及该填料的制备方法及在造纸中的应用。The main raw material for papermaking is plant fibers, which are interwoven into a network structure in paper, thus endowing paper with various properties. In the papermaking industry, in order to save the amount of plant fibers and improve some properties of the paper, various fillers are usually added to the papermaking industry, such as calcium carbonate, talcum powder, and clay (Kaoline). International patent application WO 01/44573 discloses the preparation of paper products by adding at least one aluminum compound and at least one silicate to pulp. US5300147 discloses a low-brightness magnesium silicate SLR filler, a low-brightness paper containing the filler, a preparation method of the filler and an application in papermaking.
另一方面，造纸业界公认，填料的加填是很有限的，过度的加填会导致纸张的各项技术指标严重恶化，尤其是力学强度(如断裂长度、撕裂强度等)。此外还会影响抄纸工艺指标和印刷性能指标。因此，通常实际加填量为20-35％，而某些制品(如新闻纸)则是基本不加填的。On the other hand, the papermaking industry recognizes that the filling of fillers is very limited, and excessive filling will lead to serious deterioration of various technical indicators of paper, especially the mechanical strength (such as breaking length, tear strength, etc.). In addition, it will also affect the papermaking process indicators and printing performance indicators. Therefore, usually the actual filling amount is 20-35%, while some products (such as newsprint) are basically not filled.
发明内容Contents of the invention
本发明的一个目的是提供一种填料组合物，它能以较高加填量加填到纸中并保持75-85％的较高实际留着率，同时使纸的各项指标满足有关标准，并使一些指标得到优化。An object of the present invention is to provide a filler composition, which can be filled into paper with a higher filling amount and maintain a higher actual retention rate of 75-85%, while making the various indicators of the paper meet the relevant standards , and optimize some metrics.
本发明还有一个目的是提供一种制备填料组合物的方法。Yet another object of the present invention is to provide a method for preparing filler compositions.
本发明再有一个目的是提供填料组合物的用途。Yet another object of the present invention is to provide the use of the filler composition.
本发明提供了一种填料组合物，该组合物的主要化学组成如下：30-38重量份SiO2，15-21重量份CaO，17-21重量份MgO，2-3重量份Al2O3，3.9-5.9重量份SO4 2-和8.8-31重量份结晶水。The invention provides a filler composition, the main chemical composition of which is as follows: 30-38 parts by weight of SiO 2 , 15-21 parts by weight of CaO, 17-21 parts by weight of MgO, 2-3 parts by weight of Al 2 O 3 , 3.9-5.9 parts by weight SO 4 2- and 8.8-31 parts by weight crystal water.
本发明的填料组合物还含有Fe2O3、Na2O和K2O，其总重量份小于整个组合物重量份数的1％。The filler composition of the present invention also contains Fe 2 O 3 , Na 2 O and K 2 O, the total weight of which is less than 1% of the whole composition.
本发明的填料组合物主要由(i)滑石、(ii)天然偏硅酸钙、(iii)膨润土、(iv)氧化镁或碳酸镁和(v)表面活性剂制得，所述表面活性剂的主要化学组成如下：10-12重量份SiO2、7-11重量份Al2O3、36-39重量份SO4 2-和27-38重量份结晶水。所述表面活性剂的化学组成中还有Fe2O3、CaO、Na2O和K2O，其总重量份小于整个表面活性剂重量份数的7.2％。The filler composition of the present invention is mainly prepared from (i) talc, (ii) natural calcium metasilicate, (iii) bentonite, (iv) magnesium oxide or magnesium carbonate and (v) surfactant, said surfactant The main chemical composition is as follows: 10-12 parts by weight of SiO 2 , 7-11 parts by weight of Al 2 O 3 , 36-39 parts by weight of SO 4 2- and 27-38 parts by weight of crystal water. The chemical composition of the surfactant also includes Fe 2 O 3 , CaO, Na 2 O and K 2 O, the total weight of which is less than 7.2% of the weight of the whole surfactant.
本发明填料组合物还包含选自石膏、沸石、硫酸铝钠、聚合硫酸硅酸铝和水合硅酸镁中的一种或多种原料。The filler composition of the present invention also includes one or more raw materials selected from gypsum, zeolite, sodium aluminum sulfate, polyaluminum sulfate silicate and hydrated magnesium silicate.
本发明的填料组合物是白色粉体，其白度≥85％，平均粒度为5-10微米，其中纤维状颗粒的重量百分含量为36-60％，所述纤维状颗粒的长径比≥10。The filler composition of the present invention is a white powder with a whiteness of ≥85%, an average particle size of 5-10 microns, wherein the weight percentage of fibrous particles is 36-60%, and the aspect ratio of the fibrous particles is ≥10.
本发明还提供了一种制备填料组合物的方法，该方法包括以下步骤：The present invention also provides a method for preparing the filler composition, the method comprising the following steps:
混合原料滑石、天然偏硅酸钙、膨润土和氧化镁或碳酸镁，预磨碎成细粒粉末；Mix raw materials talc, natural calcium metasilicate, bentonite and magnesium oxide or magnesium carbonate, pre-grind into fine powder;
将表面活性剂预磨碎成细粒粉末，或者混合表面活性剂与可任选的石膏、沸石、硫酸铝钠、聚合硫酸硅酸铝和水合硅酸镁中的一种或多种原料，预磨碎成细粒粉末；Pregrinding the surfactant into a fine-grained powder, or mixing the surfactant with optionally one or more of gypsum, zeolite, sodium aluminum sulfate, polyaluminum sulfate silicate and hydrated magnesium silicate, pre Grind into fine powder;
将上述两种细粒粉末混合均匀，并进一步研磨至粒度为5-10微米，Mix the above two fine-grained powders evenly, and further grind to a particle size of 5-10 microns,
所述表面活性剂可如下制得：向氢氧化铝中加入硫酸溶液进行酸解，再加入硅酸钠和可任选的碳酸钙和/或硫酸钠和/或硫酸钾和/或阳离子淀粉，充分搅拌，冷却结晶并干燥。The surfactant can be prepared by adding sulfuric acid solution to aluminum hydroxide for acid hydrolysis, then adding sodium silicate and optional calcium carbonate and/or sodium sulfate and/or potassium sulfate and/or cationic starch, Stir well, cool to crystallize and dry.
本发明还提供了填料组合物在造纸中的应用。The invention also provides the use of the filler composition in papermaking.
本发明还提供了包含填料组合物的纸制品，例如书写纸、胶印书刊纸等。The present invention also provides paper products, such as writing paper, offset book paper, and the like, comprising the filler composition.
本发明的填料组合物能以较高加填量加填到纸中并保持75-85％的较高实际留着率，同时使纸的各项指标满足有关标准，并使一些指标得到优化。该填料组合物具有一定的净水效果，在较高加填条件下仍具有较高的滤水性；且有助于增白、施胶；性能稳定，适合于长时间贮存。该填料组合物适用于各种主要纸种(如书写纸、印刷纸、鞋底板纸和特种纸)，其应用无需对已有造纸设备和工艺作出大的调整。此外，本发明填料组合物成本较低，可再生利用，无毒副作用，且制备方法简单，易于推广应用。The filler composition of the invention can be filled into paper with a relatively high filling amount and maintain a relatively high actual retention rate of 75-85%, while making various indexes of the paper meet relevant standards and optimize some indexes. The filler composition has a certain water purification effect, and still has high water drainage under relatively high filling conditions; and is helpful for whitening and sizing; has stable performance and is suitable for long-term storage. The filler composition is suitable for various main paper types (such as writing paper, printing paper, shoe board paper and special paper), and its application does not require major adjustments to existing papermaking equipment and processes. In addition, the filler composition of the invention has low cost, can be recycled, has no toxic and side effects, has a simple preparation method, and is easy to popularize and apply.
附图说明Description of drawings
图1a-1e是反映本发明填料组合物结构的显微照片，图1a示出滑石、膨润土与硅酸钙组成的结构；图1b示出膨润土将滑石、硅酸钙粘联成网状；图1c示出新生的亚纳米级硅酸铝和钙矾石(又称锻白，其白度很高，吸附力强)吸附在硅酸钙和滑石片上；图1d示出亚纳米级硅酸铝吸附在滑石和硅酸钙上；图1e示出滑石、膨润土、硅酸钙级上的交互嵌生。Fig. 1 a-1 e is the photomicrograph reflecting filler composition structure of the present invention, and Fig. 1 a shows the structure that talc, bentonite and calcium silicate form; Fig. 1 b shows that bentonite talc, calcium silicate are bonded into network; Fig. 1c shows that the nascent subnano-scale aluminum silicate and ettringite (also known as wrought white, which has high whiteness and strong adsorption force) are adsorbed on calcium silicate and talc flakes; Figure 1d shows the subnano-scale aluminum silicate Adsorption on talc and calcium silicate; Figure 1e shows intercalation on talc, bentonite, calcium silicate grades.
图2a-2f是反映本发明填料组合物与纸纤维组成结构的显微照片，图2a示出滑石和天然偏硅酸钙与纸纤维形成的交互网状结构，图2b示出天然偏硅酸钙和滑石附于纤维上；图2c示出天然偏硅酸钙和滑石(片状)被膨润土包覆于纤维上；图2d示出新生的阳离子淀粉硅酸溶胶缠绕纸纤维，天然偏硅酸钙和滑石网团吊在纸纤维上；图2e示出天然偏硅酸钙(针状)和滑石被膨润土粘联成网状，填充于纸纤维之间；图2f示出在纸纤维的交接处被亚纳米级膨润土和阳离子淀粉硅酸溶胶粘接。Fig. 2a-2f is the photomicrograph that reflects filler composition of the present invention and paper fiber composition structure, and Fig. 2 a shows the interactive network structure that talc and natural calcium metasilicate and paper fiber form, and Fig. 2 b shows natural metasilicate Calcium and talc are attached to the fiber; Figure 2c shows that natural calcium metasilicate and talc (flaky) are coated on the fiber by bentonite; Figure 2d shows that the nascent cationic starch silicic acid sol winds the paper fiber, and the natural metasilicate Calcium and talc network clusters are suspended on the paper fibers; Figure 2e shows that natural calcium metasilicate (acicular) and talc are bonded into a network by bentonite and filled between the paper fibers; Figure 2f shows the handover of the paper fibers It is bonded by sub-nanometer bentonite and cationic starch silicate sol.
图3是本发明填料组合物的X射线衍射图。Figure 3 is an X-ray diffraction pattern of the filler composition of the present invention.
图4是含本发明填料组合物的纸张的灰份X射线衍射图。Figure 4 is an ash X-ray diffraction pattern of paper containing the filler composition of the present invention.
具体实施方式Detailed ways
本发明填料组合物的主要化学组成，以氧化物形式表示为：30-38重量份SiO2，15-21重量份CaO，17-21重量份MgO，2-3重量份Al2O3，3.9-5.9重量份SO4 2-和8.8-31重量份结晶水；还可含有Fe2O3、Na2O和K2O，其总重量份小于整个组合物重量份数的1％。The main chemical composition of the filler composition of the present invention is expressed in the form of oxides: 30-38 parts by weight of SiO 2 , 15-21 parts by weight of CaO, 17-21 parts by weight of MgO, 2-3 parts by weight of Al 2 O 3 , 3.9 parts by weight - 5.9 parts by weight of SO 4 2 - and 8.8-31 parts by weight of water of crystallization; Fe 2 O 3 , Na 2 O and K 2 O may also be contained, the total weight of which is less than 1% by weight of the entire composition.
本发明填料组合物的原料主要是(i)滑石、(ii)天然偏硅酸钙、(iii)膨润土、(iv)氧化镁或碳酸镁和(v)表面活性剂。滑石例如可以得自四川汶川，也可从市场上购得，例如辽宁营口和广西柳州的非金属矿公司，但不限于此。天然偏硅酸钙，例如可以得自云南腾冲、吉林大顶山、江西大余等产地，也可从市场上购得，例如吉林梨树硅灰石矿业公司商品名为大鼎山牌的产品，但不限于此。膨润土例如可以得自四川双流，也可从市场上购得，例如四川双流膨润土厂、广东佛山膨润土厂，但不限于此。本发明中的氧化镁是指活性氧化镁，即菱镁矿(碳酸镁)于600-700℃低温烧制而成的轻烧氧化镁，通常主要用于涂料、橡胶、塑料、造纸填料(颜料)。所述氧化镁和碳酸镁例如可产于辽宁省大石桥，例如由辽宁大石桥非金属公司销售的产品。The raw materials of the filler composition of the present invention are mainly (i) talc, (ii) natural calcium metasilicate, (iii) bentonite, (iv) magnesium oxide or magnesium carbonate and (v) surfactant. Talc can be obtained, for example, from Wenchuan, Sichuan, or can be purchased from the market, such as non-metal mining companies in Yingkou, Liaoning and Liuzhou, Guangxi, but not limited thereto. Natural calcium metasilicate, for example, can be obtained from Tengchong, Yunnan, Dadingshan, Jilin, and Dayu, Jiangxi, etc., and can also be purchased from the market, such as the product of Jilin Lishu Wollastonite Mining Company, whose trade name is Dadingshan , but not limited to this. Bentonite can be obtained, for example, from Shuangliu, Sichuan, or can be purchased from the market, such as Sichuan Shuangliu Bentonite Factory, Guangdong Foshan Bentonite Factory, but not limited thereto. Magnesium oxide in the present invention refers to activated magnesium oxide, that is, light-burned magnesium oxide formed by magnesite (magnesium carbonate) fired at a low temperature of 600-700 ° C, and is usually mainly used for coatings, rubber, plastics, paper-making fillers (pigments) ). The magnesium oxide and magnesium carbonate can be produced, for example, in Dashiqiao, Liaoning Province, such as products sold by Liaoning Dashiqiao Non-Metal Company.
表面活性剂的主要化学组成为10-12重量份SiO2、7-11重量份Al2O3、36-39重量份SO4 2-和27-38重量份结晶水。所述表面活性剂的化学组成中还含有Fe2O3、CaO、Na2O和K2O，其总重量份小于整个表面活性剂重量份数的7.2％。The main chemical composition of the surfactant is 10-12 parts by weight of SiO 2 , 7-11 parts by weight of Al 2 O 3 , 36-39 parts by weight of SO 4 2- and 27-38 parts by weight of crystal water. The chemical composition of the surfactant also contains Fe 2 O 3 , CaO, Na 2 O and K 2 O, the total weight of which is less than 7.2% of the weight of the whole surfactant.
本发明的填料组合物还可任选地包含选自石膏、沸石、硫酸铝钠、聚合硫酸硅酸铝和水合硅酸镁中的一种或多种原料。The filler composition of the present invention may also optionally contain one or more raw materials selected from gypsum, zeolite, sodium aluminum sulfate, polyaluminum sulfate silicate and hydrated magnesium silicate.
在本发明的填料组合物中，滑石是天然产出的片状晶体，因其白度较高、硬度低因而可用于改善纸品的平滑度和适印性。In the filler composition of the present invention, talc is a naturally produced flaky crystal, which can be used to improve the smoothness and printability of paper products because of its high whiteness and low hardness.
在本发明的填料组合物中，天然偏硅酸钙为天然生成的纤维状集合体，超细粉碎后，粒度为5-10微米，长径比≥10，具有优良的细长纤维特性，可部分代替短纸纤维。传统填料均为低硬度材料(例如滑石、高岭土等的硬度均为1)，但却很少使用硬度大于3的填料。而本发明采用的纤维状偏硅酸钙的硬度为4.5-5，这些偏硅酸钙颗粒在表面活性剂的作用下表面活化，使得针状颗粒相互搭接。在填料组合物中加入大量的水解时带正电荷的胶粒(如水合硅酸镁、阳离子淀粉等)，将针状偏硅酸钙颗粒层层包裹起来(如图1所示)。这些颗粒在抄纸时由于层流水体的作用而易于平行纸的层面排列，和纸纤维一起形成平滑的纸面。因此，高硬度的偏硅酸钙也就成为一种功能性填料。In the filler composition of the present invention, natural calcium metasilicate is a naturally occurring fibrous aggregate. After ultrafine grinding, the particle size is 5-10 microns, and the aspect ratio is greater than or equal to 10. It has excellent elongated fiber characteristics and can Partially replace short paper fibers. Traditional fillers are low-hardness materials (for example, talc, kaolin, etc. have a hardness of 1), but fillers with a hardness greater than 3 are rarely used. However, the fibrous calcium metasilicate used in the present invention has a hardness of 4.5-5, and these calcium metasilicate particles are surface-activated under the action of a surfactant, so that the needle-shaped particles overlap each other. A large amount of positively charged colloidal particles (such as hydrated magnesium silicate, cationic starch, etc.) are added to the filler composition to wrap the needle-shaped calcium metasilicate particles layer by layer (as shown in Figure 1). These particles are easy to arrange parallel to the layer of paper due to the action of laminar water during papermaking, and form a smooth paper surface together with paper fibers. Therefore, calcium metasilicate with high hardness becomes a kind of functional filler.
在本发明的填料组合物中，膨润土作为滑石、天然偏硅酸钙或碳酸镁的表面包覆材料，使其与带负电荷的木材纤维形成强化学键合，提高其留着率和附着力。在成纸时提高湿强度和组合物分散的均一性，在干燥固化时形成具有一定弹性的粘结剂，将填料和纸纤维牢牢粘结起来，提高纸品强度。此外，膨润土还可作为良好的絮凝剂和脱色剂。In the filler composition of the present invention, bentonite is used as the surface coating material of talc, natural calcium metasilicate or magnesium carbonate to form a strong chemical bond with negatively charged wood fibers and improve its retention rate and adhesion. It improves the wet strength and the uniformity of composition dispersion when it is made into paper, and forms a binder with certain elasticity when it is dried and solidified, so as to firmly bond fillers and paper fibers and improve the strength of paper products. In addition, bentonite can also be used as a good flocculant and decolorizer.
在本发明的填料组合物中，氧化镁或碳酸镁用作填料的分散剂和助留剂。而在已有技术中通常使用的是有机高分子助留剂。氧化镁或碳酸镁能在填料组合物用于造纸时帮助其均匀地分散到纸浆中，使该填料组合物与纸纤维结合且难以从纤维上脱落。即便进行二次打浆、再抄纸仍能保持高留着率和高均匀度。In the filler composition of the present invention, magnesium oxide or magnesium carbonate is used as a dispersant and retention aid for the filler. And in the prior art usually use organic macromolecular retention aids. Magnesium oxide or magnesium carbonate can help the filler composition to disperse evenly in the pulp when it is used in paper making, making the filler composition bonded to the paper fibers and difficult to fall off from the fibers. Even after secondary beating and papermaking, it can still maintain high retention rate and high uniformity.
在本发明的填料组合物中，表面活性剂对所用原料进行改型和表面改性，在填料组合物的水化过程时，促使多种新硅酸盐化合物的形成。表面活性剂可如下制得：向氢氧化铝中加入硫酸溶液，于70-80℃搅拌1-2小时以进行酸解，然后再加入硅酸钠和可任选的碳酸钙和/或硫酸钠和/或硫酸钾，于70-80℃搅拌30-60分钟，冷却结晶并干燥。制备所述表面活性剂时，还可加入阳离子淀粉，形成纳米或亚纳米级的阳离子淀粉硅酸溶胶，用于造纸可提高纸品的抗张强度。阳离子淀粉的含量占表面活性剂的8-9.8重量％。In the filler composition of the present invention, the surfactant modifies and modifies the surface of the raw materials used, promoting the formation of various new silicate compounds during the hydration process of the filler composition. Surfactants can be prepared by adding sulfuric acid solution to aluminum hydroxide, stirring at 70-80°C for 1-2 hours for acid hydrolysis, then adding sodium silicate and optionally calcium carbonate and/or sodium sulfate And/or potassium sulfate, stirred at 70-80°C for 30-60 minutes, cooled to crystallize and dried. When preparing the surfactant, cationic starch can also be added to form nanometer or subnanometer cationic starch silicic acid sol, which can improve the tensile strength of paper products when used in papermaking. The content of cationic starch accounts for 8-9.8% by weight of the surfactant.
采用机械混合的方法制备本发明的填料组合物。本发明填料组合物的原料可分为两部分，第一部分是滑石、天然偏硅酸钙、膨润土和氧化镁或碳酸镁；第二部分是表面活性剂、可任选的石膏、沸石、硫酸铝钠、聚合硫酸硅酸铝和水合硅酸镁，该填料组合物的制备方法是分别将第一部分和第二部分的原料混合均匀并磨细，然后再将两种粉末混合均匀并进一步研磨至粒度为5-10微米。The filler composition of the present invention is prepared by mechanical mixing. The raw material of filler composition of the present invention can be divided into two parts, and the first part is talc, natural calcium metasilicate, bentonite and magnesium oxide or magnesium carbonate; The second part is surfactant, optional gypsum, zeolite, aluminum sulfate Sodium, polyaluminum sulfate sulfate and hydrated magnesium silicate, the preparation method of the filler composition is to mix and grind the raw materials of the first part and the second part respectively, and then mix the two powders and further grind to the particle size 5-10 microns.
所得填料组合物为白色粉体，其白度≥85％，平均粒度为5-10微米，其中纤维状颗粒的重量百分含量≥36-60％，所述纤维状颗粒的长径比(L/D)≥10。The resulting filler composition is a white powder with a whiteness of ≥85%, an average particle size of 5-10 microns, wherein the weight percentage of the fibrous particles is ≥36-60%, and the aspect ratio (L /D) ≥ 10.
本发明的填料组合物与已有技术的填料相比，结构机理不同。已有技术的填料颗粒多为片状、粒状，难以形成合理的堆砌，其充填形式主要为机械充填于纸纤维之间，结构松散。因而随加填量的增加，所得纸张的力学强度指标会急剧下降。而本发明填料组合物的主要原料之外形为纤维状、针状、片状和粒状，它们在水解时，构成产品的各种原料首先是片状和粒状颗粒以针状纤维作骨架彼此交连形成合理结构(参见图1)。与纸纤维化学键合后，纸纤维的网状结构与填料组合物网状结构交互嵌生，共同构成纸的合理结构(参见图2)。本发明的填料组合物具有结构材料的作用，因此在较高加填的情况下，不会使力学强度大幅下降。The filler composition of the present invention has a different structural mechanism than the fillers of the prior art. The filler particles in the prior art are mostly in the form of flakes and granules, which are difficult to form a reasonable stack. The filling form is mainly mechanical filling between paper fibers, and the structure is loose. Therefore, with the increase of the filling amount, the mechanical strength index of the obtained paper will drop sharply. The main raw materials of the filler composition of the present invention are fibrous, needle-like, sheet-like and granular in shape. When they are hydrolyzed, the various raw materials that constitute the product are firstly flake-like and granular particles that are cross-linked with each other with needle-like fibers as the skeleton. Form a reasonable structure (see Figure 1). After being chemically bonded to the paper fiber, the network structure of the paper fiber and the network structure of the filler composition are alternately intercalated to form a reasonable structure of the paper (see Figure 2). The filler composition of the present invention has the function of structural material, so under the condition of higher filling, the mechanical strength will not be greatly reduced.
本发明填料组合物与纸纤维的结合机理也不同于已有技术的填料。已有技术的填料与纸纤维的结合是一种物吸附作用，即自然充填以及造纸工艺中的施胶固结，其结合强度是有限的。而本发明填料组合物与纸纤维的结合主要是一种化学吸附作用，其结合强度较强。本发明超细粉的比表面能很高，在水解时于表面活性剂的强烈作用下使粉体颗粒带较强的正电荷，与带较强负电荷的纸纤维形成较强的化学键合(图1和图2)。填料组合物水解后生成的聚合硫酸硅酸铝、水合硅酸镁、高悬浮的钠镁铝硅酸溶胶及沸石和阳离子淀粉硅酸溶胶等活性分子对粉体和纸纤维发生强力粘接。在造纸的烘干过程中脱水固化并产生亚纳米级新矿物，使粉体与纸纤维牢牢地粘接起来。上述物理-化学过程使本发明填料组合物能在纸上保持较高的“留着率”和“湿强度”，成纸后仍保持较高的力学强度。The binding mechanism of the filler composition of the present invention to the paper fibers is also different from that of prior art fillers. The combination of fillers and paper fibers in the prior art is a kind of material adsorption, that is, natural filling and sizing consolidation in the papermaking process, and its bonding strength is limited. However, the combination of the filler composition of the present invention and the paper fiber is mainly a kind of chemical adsorption, and its combination strength is relatively strong. The specific surface energy of the superfine powder of the present invention is very high, and the powder particles are strongly positively charged under the strong action of the surfactant during hydrolysis, and form a strong chemical bond with paper fibers with strong negative charges ( Figure 1 and Figure 2). Active molecules such as polyaluminum sulfate silicate, hydrated magnesium silicate, highly suspended sodium magnesium aluminum silicate sol, zeolite and cationic starch silicate sol produced after hydrolysis of the filler composition are strongly bonded to the powder and paper fibers. During the drying process of papermaking, it is dehydrated and solidified to produce sub-nanometer new minerals, so that the powder and paper fibers are firmly bonded. The above physical-chemical process enables the filler composition of the present invention to maintain high "retention rate" and "wet strength" on paper, and maintain high mechanical strength after paper is formed.
以下通过实施例进一步说明本发明。The present invention is further illustrated by the following examples.
表面活性剂的制备Preparation of Surfactant
表面活性剂1Surfactant 1
向13.9克氢氧化铝中加入42.9克浓度为60重量％的硫酸溶液，于约80℃搅拌1.5小时以进行酸解，然后再加入15.4克硅酸钠，于约80℃搅拌45分钟，冷却结晶，于120℃左右干燥，然后粉碎制得表面活性剂1。Add 42.9 grams of sulfuric acid solution with a concentration of 60% by weight to 13.9 grams of aluminum hydroxide, stir at about 80°C for 1.5 hours to carry out acidolysis, then add 15.4 grams of sodium silicate, stir at about 80°C for 45 minutes, and cool to crystallize , dried at about 120°C, and then pulverized to obtain Surfactant 1.
用国际通用的化学全分析方法测得表面活性剂1的化学组成为：10.1重量份SiO2、7.2重量份Al2O3、35.8重量份SO4 2-、27.1重量份结晶水和0.30重量份Fe2O3。其中Fe2O3是由所用原料中所含杂质带来的。The chemical composition of Surfactant 1 measured by international general chemical full analysis method is: 10.1 parts by weight SiO 2 , 7.2 parts by weight Al 2 O 3 , 35.8 parts by weight SO 4 2- , 27.1 parts by weight crystal water and 0.30 parts by weight Fe 2 O 3 . Among them, Fe 2 O 3 is brought by the impurities contained in the raw materials used.
表面活性剂2Surfactant 2
向15.0克氢氧化铝中加入46.0克浓度为60重量％的硫酸溶液，于约70℃搅拌1小时以进行酸解，然后再加入16.7克硅酸钠，于约70℃搅拌60分钟，冷却结晶，于100℃左右干燥，然后粉碎制得表面活性剂2。Add 46.0 grams of sulfuric acid solution with a concentration of 60% by weight to 15.0 grams of aluminum hydroxide, stir at about 70°C for 1 hour to carry out acidolysis, then add 16.7 grams of sodium silicate, stir at about 70°C for 60 minutes, cool and crystallize , dried at about 100°C, and then pulverized to obtain Surfactant 2.
用国际通用的化学全分析方法测得表面活性剂2的化学组成为：12.3重量份SiO2、10.9重量份Al2O3、39.1重量份SO4 2-、38.2重量份结晶水和0.37重量份Fe2O3。其中Fe2O3是由所用原料中所含杂质带来的。The chemical composition of Surfactant 2 measured by international general chemical full analysis method is: 12.3 parts by weight SiO 2 , 10.9 parts by weight Al 2 O 3 , 39.1 parts by weight SO 4 2- , 38.2 parts by weight crystal water and 0.37 parts by weight Fe 2 O 3 . Among them, Fe 2 O 3 is brought by the impurities contained in the raw materials used.
表面活性剂3Surfactant 3
向12.9克氢氧化铝中加入39.9克浓度为60重量％的硫酸溶液，于约75℃搅拌2小时以进行酸解，然后再加入14.0克硅酸钠、1.5克碳酸钙、13.8克硫酸钠和4.4克硫酸钾、9.9克阳离子淀粉和1000毫升水，于约75℃搅拌30分钟，冷却结晶，于150℃左右干燥，然后粉碎制得111.0克表面活性剂3。Adding 39.9 grams of concentration in 12.9 grams of aluminum hydroxide is a sulfuric acid solution of 60% by weight, stirring for 2 hours at about 75°C to carry out acidolysis, then adding 14.0 grams of sodium silicate, 1.5 grams of calcium carbonate, 13.8 grams of sodium sulfate and 4.4 grams of potassium sulfate, 9.9 grams of cationic starch and 1000 milliliters of water were stirred at about 75°C for 30 minutes, cooled and crystallized, dried at about 150°C, and then pulverized to obtain 111.0 grams of Surfactant 3.
用国际通用的化学全分析方法测得表面活性剂3的化学组成为：11.2重量份SiO2、8.6重量份Al2O3、37.4重量份SO4 2-、33.4重量份结晶水、1.2重量份CaO、3.7重量份Na2O、1.5重量份K2O和0.35重量份Fe2O3。The chemical composition of Surfactant 3 measured by international general chemical full analysis method is: 11.2 parts by weight SiO 2 , 8.6 parts by weight Al 2 O 3 , 37.4 parts by weight SO 4 2- , 33.4 parts by weight crystal water, 1.2 parts by weight CaO, 3.7 parts by weight Na 2 O, 1.5 parts by weight K 2 O and 0.35 parts by weight Fe 2 O 3 .
填料组合物的制备Preparation of filler composition
实施例1Example 1
用塑料混合机混合原料37克滑石(购自辽宁营口非金属矿公司)、40克天然偏硅酸钙(购自吉林梨树硅灰石公司，商品名为大鼎山牌)、11克膨润土(购自四川双流膨润土粉体厂)、6克氧化镁(购自辽宁大石桥非金属公司)，预磨碎成细粒粉末；用C×132型超细粉碎机将7克表面活性剂2预磨碎成细粒粉末；用塑料混合机将上述两种细粒粉末混合均匀，并进一步研磨至平均粒度为7微米。Mix 37 grams of talc (purchased from Liaoning Yingkou Nonmetallic Mining Company), 40 grams of natural calcium metasilicate (purchased from Jilin Lishu Wollastonite Company, trade name Dadingshan brand), 11 grams of bentonite with a plastic mixer (purchased from Sichuan Shuangliu Bentonite Powder Factory), 6 grams of magnesium oxide (purchased from Liaoning Dashiqiao Non-Metal Company), pre-grinded into fine-grained powder; 7 grams of surfactant 2 Pre-grind into fine-grained powder; use a plastic mixer to mix the above two fine-grained powders evenly, and further grind to an average particle size of 7 microns.
所得组合物为白色粉体，其白度为90％。用国际通用的化学全分析方法测得，纤维状颗粒的重量百分含量为60％，用日本日立公司S-530型电镜测得，纤维颗粒的长径比为11。用国际通用的化学全分析方法测量该组合物粉体的化学组成，结果是30.2重量份SiO2，15.2重量份CaO，17.1重量份MgO，1.9重量份Al2O3，3.9重量份SO4 2-，8.9重量份结晶水和0.5重量份Fe2O3。The obtained composition is a white powder with a whiteness of 90%. Measured by international general chemical full analysis method, the weight percentage of fibrous particles is 60%. Measured by S-530 electron microscope of Hitachi, Japan, the aspect ratio of fiber particles is 11. The chemical composition of the composition powder is measured by the international general chemical full analysis method, and the result is 30.2 parts by weight SiO 2 , 15.2 parts by weight CaO, 17.1 parts by weight MgO, 1.9 parts by weight Al 2 O 3 , 3.9 parts by weight SO 4 2 - , 8.9 parts by weight of water of crystallization and 0.5 parts by weight of Fe 2 O 3 .
实施例2Example 2
用塑料混合机混合原料39克滑石(购自辽宁营口非金属矿公司)、45克天然偏硅酸钙(购自吉林梨树硅灰石公司，商品名为大鼎山牌)、13克膨润土(购自四川双流膨润土粉体厂)、8克氧化镁(购自辽宁大石桥非金属公司)，预磨碎成细粒粉末；用C×132型超细粉碎机将9克表面活性剂1预磨碎成细粒粉末；用塑料混合机将上述两种细粒粉末混合均匀，并进一步研磨至平均粒度为5微米。39 grams of talcum (purchased from Liaoning Yingkou Nonmetallic Mining Company), 45 grams of natural calcium metasilicate (purchased from Jilin Lishu Wollastonite Company, trade name Dadingshan brand), 13 grams of bentonite were mixed with a plastic mixer (purchased from Sichuan Shuangliu Bentonite Powder Factory), 8 grams of magnesium oxide (purchased from Liaoning Dashiqiao Non-Metal Company), pre-grinded into fine powder; 9 grams of surfactant 1 Pre-grind into fine-grained powder; use a plastic mixer to mix the above two fine-grained powders evenly, and further grind to an average particle size of 5 microns.
所得组合物为白色粉体，其白度为88％。用国际通用的化学全分析方法测得，纤维状颗粒的重量百分含量为52％，用日本日立公司S-530型电镜测得，纤维颗粒的长径比为11。用国际通用的化学全分析方法测量该组合物粉体的化学组成，结果是38.1重量份SiO2，21.0重量份CaO，21.1重量份MgO、3.1重量份Al2O3，5.9重量份SO4 2-，31.0重量份结晶水和0.7重量份Fe2O3。The obtained composition is a white powder with a whiteness of 88%. Measured by international general chemical full analysis method, the weight percentage of fibrous particles is 52%. Measured by S-530 electron microscope of Hitachi, Japan, the aspect ratio of fibrous particles is 11. The chemical composition of the composition powder was measured by an international general chemical analysis method, and the result was 38.1 parts by weight of SiO 2 , 21.0 parts by weight of CaO, 21.1 parts by weight of MgO, 3.1 parts by weight of Al 2 O 3 , 5.9 parts by weight of SO 4 2 - , 31.0 parts by weight of crystal water and 0.7 parts by weight of Fe 2 O 3 .
实施例3Example 3
用塑料混合机混合原料35克滑石(购自辽宁营口非金属矿公司))、35克天然偏硅酸钙(购自吉林梨树硅灰石公司，商品名为大鼎山牌)、9克膨润土(购自四川双流膨润土粉体厂)、4克碳酸镁(购自辽宁大石桥非金属公司)，预磨碎成细粒粉末；用C×132型超细粉碎机混合5克表面活性剂3与4.2克石膏、3.8克沸石、9.9克硫酸铝钠、4.8克聚合硫酸硅酸铝、13.2克水合硅酸镁并预磨碎成细粒粉末；用塑料混合机将上述两种细粒粉末混合均匀，并进一步研磨至粒度为10微米。35 grams of talcum (purchased from Liaoning Yingkou Nonmetallic Mining Company)), 35 grams of natural calcium metasilicate (purchased from Jilin Lishu Wollastonite Company, trade name Dadingshan brand), 9 grams of mixed raw materials with a plastic mixer Bentonite (purchased from Sichuan Shuangliu Bentonite Powder Factory), 4 grams of magnesium carbonate (purchased from Liaoning Dashiqiao Non-Metal Company), pre-grinded into fine powder; mixed 5 grams of surfactant with C × 132 type ultrafine pulverizer 3 and 4.2 grams of gypsum, 3.8 grams of zeolite, 9.9 grams of sodium aluminum sulfate, 4.8 grams of polysilicate aluminum sulfate, 13.2 grams of hydrated magnesium silicate and pre-grind into fine powder; use a plastic mixer to mix the above two fine powders Mix well and grind further to a particle size of 10 microns.
所得组合物为白色粉体，其白度为85％。用国际通用的化学全分析方法测得，纤维状颗粒的重量百分含量为36％，用日本日立公司S-530型电镜测得，纤维颗粒的长径比为10。用国际通用的化学全分析方法测量该组合物粉体的化学组成，结果是35.2重量份SiO2，18.2重量份CaO，20.1重量份MgO，2.7重量份Al2O3，4.8重量份SO4 2-、25.1重量份结晶水、0.4重量份Fe2O3、0.56重量份Na2O和0.07重量份K2O。The obtained composition is a white powder with a whiteness of 85%. Measured by the international general chemical total analysis method, the weight percentage of fibrous particles is 36%, and measured by the S-530 electron microscope of Hitachi, Japan, the aspect ratio of the fibrous particles is 10. The chemical composition of the composition powder is measured by the internationally accepted chemical full analysis method, and the result is 35.2 parts by weight of SiO 2 , 18.2 parts by weight of CaO, 20.1 parts by weight of MgO, 2.7 parts by weight of Al 2 O 3 , 4.8 parts by weight of SO 4 2 - , 25.1 parts by weight of crystal water, 0.4 parts by weight of Fe 2 O 3 , 0.56 parts by weight of Na 2 O and 0.07 parts by weight of K 2 O.
造纸和测试Papermaking and Testing
将所得的填料组合物用于造纸，并对所得纸张进行测试。The resulting filler composition was used in the manufacture of paper, and the resulting paper was tested.
填料组合物在用于造纸时先要制浆，即用4倍的符合造纸要求的清洁水加入填料组合物中，加热至50-60℃并搅拌40分钟，保持pH值为6.5-7.5。When the filler composition is used for papermaking, pulping is performed first, that is, 4 times the amount of clean water meeting the papermaking requirements is added to the filler composition, heated to 50-60°C and stirred for 40 minutes, and the pH value is maintained at 6.5-7.5.
常规的造纸工艺流程是纸浆打浆→调浆→稀释→抄纸，在调浆时加入如上制得的填料组合物浆液，再按常规造纸技术制造胶版印刷纸，测量所得纸张的主要技术指标。The conventional papermaking process is pulp beating → pulping → dilution → papermaking. During pulping, the filler composition slurry prepared above is added, and offset printing paper is manufactured according to conventional papermaking technology, and the main technical indicators of the obtained paper are measured.
书写纸writing paper
将实施例1的填料组合物用来制造55g/m2的书写纸，产品原料为针叶浆(15重量％)、阔叶浆(40重量％)和填料组合物(45重量％)。所得成品纸的灰份为29.1％，留着率为76％。所得纸张的检测结果见下表1。The filler composition of Example 1 was used to manufacture 55g/m 2 writing paper, and the product raw materials were softwood pulp (15% by weight), hardwood pulp (40% by weight) and filler composition (45% by weight). The ash content of the resulting finished paper was 29.1%, and the retention rate was 76%. The test results of the obtained paper are shown in Table 1 below.
表1
图3和图4分别示出了本发明填料组合物和含有该组合物的纸张的灰份的X射线衍射图，可见两者相一致。这表明在造纸过程中本发明填料组合物的化学组成和分子结构得到了很好的保持。Figure 3 and Figure 4 respectively show the X-ray diffraction patterns of the ash content of the filler composition of the present invention and the paper containing the composition, and it can be seen that the two are consistent. This indicates that the chemical composition and molecular structure of the filler composition of the present invention are well maintained during the papermaking process.
胶印书刊纸Offset book paper
将实施例2的填料组合物用来制造70g/m2的胶印书刊纸，产品原料为进口俄罗斯针叶木浆(25重量％)、思茅松漂白浆(35重量％)、兰按浆(10重量％)和填料组合物(30重量％)，所得纸张的检测结果见下表2。The filler composition of embodiment 2 is used to manufacture 70g/m The offset printing book paper, product raw material is imported Russian softwood pulp (25% by weight), Simao pine bleached pulp (35% by weight), blue press pulp (10% by weight %) and filler composition (30% by weight), the test results of the resulting paper are shown in Table 2 below.
表2
净水性能试验Water purification performance test
将实施例3的填料组合物用来制造55g/m2的书写纸，并对所得纸张进行试验，得到与上述实施例1填料组合物类似的检测结果。此外，对该造纸过程中的造纸用水和总排放口的造纸废水进行水质分析，结果表明造纸过程并未对水质造成明显不利的影响，水中大多数污染物元素(如汞、镉、砷、铅、镍、酚、氰化物、硫化物、甲醛、锌、镁等)的含量均未增加，另外，总悬浮物、铬、铜和钙的含量明显下降。The filler composition of Example 3 was used to manufacture 55g/m 2 writing paper, and the resulting paper was tested, and the detection results similar to those of the filler composition of Example 1 above were obtained. In addition, the water quality analysis of the papermaking water in the papermaking process and the papermaking wastewater at the main discharge outlet showed that the papermaking process did not cause significant adverse effects on the water quality, and most of the pollutant elements in the water (such as mercury, cadmium, arsenic, lead, etc.) , nickel, phenol, cyanide, sulfide, formaldehyde, zinc, magnesium, etc.) content did not increase, in addition, the content of total suspended solids, chromium, copper and calcium decreased significantly.
在上述实施例1填料组合物加填书写纸和实施例2填料组合物加填胶印书刊纸的过程中，同样对造纸用水和造纸废水进行水质分析，得到与上表大致相同的结果。In the process of filling writing paper with the filler composition of Example 1 and adding offset printing book paper with the filler composition of Example 2, the papermaking water and papermaking wastewater were also analyzed for water quality, and the results roughly the same as those in the above table were obtained.
因此，本发明的填料组合物用于造纸显示了良好的净水功能。传统填料对造纸用水只有机械过滤作用，因此净水作用弱。而本发明的填料组合物为超细粉体，具有胶体特征，在粉体水解时，在改性剂(如表面活性剂)的强烈作用下，新生超微的聚合硫酸硅酸铝、水合硅酸镁、高活性硅酸铝镁溶胶及沸石和阳离子淀粉硅酸溶胶等微粒，强烈吸附水中的各种重金属离子，如铜、镉、汞、砷、铬、铅等有害元素，对造纸用水有良好的净化、灭菌和防腐作用。Therefore, the filler composition of the present invention shows good water purification function when used in papermaking. Traditional fillers only have a mechanical filtration effect on papermaking water, so the water purification effect is weak. The filler composition of the present invention is an ultrafine powder with colloidal characteristics. When the powder is hydrolyzed, under the strong action of a modifying agent (such as a surfactant), new ultrafine polymerized aluminum sulfate silicate, hydrated silicon Magnesium acid, highly active aluminum magnesium silicate sol, zeolite and cationic starch silicate sol and other particles can strongly adsorb various heavy metal ions in water, such as copper, cadmium, mercury, arsenic, chromium, lead and other harmful elements, which are harmful to papermaking water. Good purification, sterilization and antiseptic effect.
试验中还发现，本发明填料组合物具有较好的脱水功能。传统填料比较单一，故几何堆砌不太合理，填料充填于纸纤维的网状结构中，堵塞了滤水通道，滤水作用差。而本发明的填料组合物是多种原料组成的复合填料。针状、片状、粒状物料在水解时形成合理堆砌(如图1所示)，与纤维结合后共同构成纸的合理网状结构(如图2)。因而，即使在较高加填情况下仍有较好的滤水和脱水作用。It is also found in the test that the filler composition of the present invention has better dehydration function. The traditional filler is relatively simple, so the geometric stacking is not reasonable. The filler is filled in the network structure of paper fibers, which blocks the water filtration channel and has poor water filtration effect. The filler composition of the present invention is a composite filler composed of various raw materials. Needle-like, flake-like, and granular materials form reasonable piles during hydrolysis (as shown in Figure 1), and combine with fibers to form a reasonable network structure of paper (Figure 2). Therefore, even in the case of higher filling, there is still better water filtration and dehydration.
本发明填料组合物的复用性高，有助于充分利用和节约资源。传统填料与纸纤维结合力弱，再生利用时填料与纤维迅速脱离，在制浆过程中被消耗殆尽。而加填有本发明填料组合物的纸张在再生利用过程中因填料与纸纤维结合力较强，因而填料组合物在不加助留剂时的回收利用率≥73％。其作用机理是：废纸在水介质和机构搅拌作用下，起键合作用的改性硅酸盐再度还原为带正电荷的粒子团。填料组合物与纸纤维分离后，仍依靠自身表面电荷差异来保持结合。The filler composition of the present invention has high reusability, and helps to fully utilize and save resources. Traditional fillers have weak binding force with paper fibers, and the fillers and fibers are separated rapidly during recycling, and are completely consumed in the pulping process. However, the paper filled with the filler composition of the present invention has a strong binding force between the filler and the paper fibers during the recycling process, so the recycling rate of the filler composition is ≥ 73% when no retention aid is added. Its mechanism of action is: under the stirring action of the water medium and the mechanism, the modified silicate that acts as a bond is reduced to positively charged particle clusters again. After the filler composition is separated from the paper fiber, it still relies on its own surface charge difference to maintain the combination.
加填本发明填料组合物的纸张，其白度、不透明度、耐折度和吸墨性等指标均有明显改善。本发明填料组合物具有较高的自然白度(通常不低于85％)，该填料组合物粉体依靠表面电位差附着在纸面上，产生物理“漂白”作用。The whiteness, opacity, folding resistance and ink absorption of the paper filled with the filler composition of the present invention are all significantly improved. The filler composition of the present invention has high natural whiteness (generally not lower than 85%), and the powder of the filler composition adheres to the paper surface by means of surface potential difference to produce physical "bleaching" effect.
此外，填料组合物中硬度较高的纤维状材料在水化时与其他组分材料组成网状骨架结构，该结构与纸纤维的网状结构彼此交互嵌生，改善了纸品的挺度、耐折度、透水性和透气度。In addition, the fibrous material with higher hardness in the filler composition forms a network skeleton structure with other component materials during hydration, and this structure and the network structure of paper fibers are inter-embedded with each other, improving the stiffness, Folding resistance, water permeability and air permeability.
Claims (10)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02118915 CN1268810C (en) | 2002-04-30 | 2002-04-30 | Filler composition, its preparation method and use |
| PCT/CN2003/000308 WO2003093578A1 (en) | 2002-04-30 | 2003-04-28 | A filter composition, a process of making the composition and the use of the same |
| AU2003236169A AU2003236169A1 (en) | 2002-04-30 | 2003-04-28 | A filter composition, a process of making the composition and the use of the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02118915 CN1268810C (en) | 2002-04-30 | 2002-04-30 | Filler composition, its preparation method and use |
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| CN1455044A CN1455044A (en) | 2003-11-12 |
| CN1268810C true CN1268810C (en) | 2006-08-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02118915 Expired - Fee Related CN1268810C (en) | 2002-04-30 | 2002-04-30 | Filler composition, its preparation method and use |
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| Country | Link |
|---|---|
| CN (1) | CN1268810C (en) |
| AU (1) | AU2003236169A1 (en) |
| WO (1) | WO2003093578A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323211C (en) * | 2004-06-21 | 2007-06-27 | 徐清明 | Paper making mineral composite retention aid and preparing process and application thereof |
| DE102007062370A1 (en) | 2007-12-22 | 2009-06-25 | S&B Industrial Minerals Gmbh | Process for the production of paper, cardboard or similar products and associated paper or cardboard product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8621680D0 (en) * | 1986-09-09 | 1986-10-15 | Du Pont | Filler compositions |
| CN1006315B (en) * | 1987-12-14 | 1990-01-03 | 潍坊造纸总厂 | High extender paper-making process using grass, wood pulp as fibric material |
| CN1157444C (en) * | 2001-12-29 | 2004-07-14 | 中国地质大学（武汉） | Process for preparing flaky heavy calcium carbonate |
-
2002
- 2002-04-30 CN CN 02118915 patent/CN1268810C/en not_active Expired - Fee Related
-
2003
- 2003-04-28 WO PCT/CN2003/000308 patent/WO2003093578A1/en not_active Application Discontinuation
- 2003-04-28 AU AU2003236169A patent/AU2003236169A1/en not_active Abandoned
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| AU2003236169A1 (en) | 2003-11-17 |
| CN1455044A (en) | 2003-11-12 |
| WO2003093578A1 (en) | 2003-11-13 |
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