CN112761020A - Ultra-light paper pulp molding material and preparation method thereof - Google Patents
Ultra-light paper pulp molding material and preparation method thereof Download PDFInfo
- Publication number
- CN112761020A CN112761020A CN202110243242.3A CN202110243242A CN112761020A CN 112761020 A CN112761020 A CN 112761020A CN 202110243242 A CN202110243242 A CN 202110243242A CN 112761020 A CN112761020 A CN 112761020A
- Authority
- CN
- China
- Prior art keywords
- pulp
- molding material
- ultralight
- fiber
- pulp molding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012778 molding material Substances 0.000 title claims abstract description 91
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 124
- 229920000103 Expandable microsphere Polymers 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 29
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 29
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 29
- 239000011425 bamboo Substances 0.000 claims abstract description 29
- 240000000111 Saccharum officinarum Species 0.000 claims abstract description 28
- 235000007201 Saccharum officinarum Nutrition 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 17
- 230000014759 maintenance of location Effects 0.000 claims abstract description 14
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 13
- 238000004513 sizing Methods 0.000 claims abstract description 13
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 8
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 8
- 244000082204 Phyllostachys viridis Species 0.000 claims abstract 2
- 239000002002 slurry Substances 0.000 claims description 63
- 239000000725 suspension Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229920002401 polyacrylamide Polymers 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 28
- 125000002091 cationic group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 125000000129 anionic group Chemical group 0.000 claims description 16
- 238000007731 hot pressing Methods 0.000 claims description 14
- 229920002472 Starch Polymers 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 8
- 229920000881 Modified starch Polymers 0.000 claims description 7
- -1 alkyl ketene dimer Chemical compound 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000297 Rayon Polymers 0.000 claims description 5
- 235000019426 modified starch Nutrition 0.000 claims description 5
- 229920001206 natural gum Polymers 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 229920002085 Dialdehyde starch Polymers 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004368 Modified starch Substances 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 229920006221 acetate fiber Polymers 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 3
- 239000011122 softwood Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 1
- 230000003139 buffering effect Effects 0.000 abstract description 5
- 239000005022 packaging material Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 80
- 241001330002 Bambuseae Species 0.000 description 27
- 230000001965 increasing effect Effects 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 12
- 239000004005 microsphere Substances 0.000 description 11
- 239000000872 buffer Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004537 pulping Methods 0.000 description 10
- 238000007670 refining Methods 0.000 description 9
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 241001397809 Hakea leucoptera Species 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000011087 paperboard Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- ONGGURNBDHMMTE-UHFFFAOYSA-N ClCC(C[Na])O Chemical compound ClCC(C[Na])O ONGGURNBDHMMTE-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000006173 Good's buffer Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000021197 fiber intake Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
- D21H13/06—Cellulose esters
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
- D21H13/08—Synthetic cellulose fibres from regenerated 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/24—Polyesters
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
- D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
-
- 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
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- 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
- D21H21/06—Paper forming aids
- D21H21/12—Defoamers
-
- 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
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H21/18—Reinforcing agents
-
- 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
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
-
- 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
- D21H21/50—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 form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J3/00—Manufacture of articles by pressing wet fibre pulp, or papier-mâché, between moulds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Paper (AREA)
Abstract
The invention discloses an ultralight paper pulp molding material and a preparation method thereof, and the ultralight paper pulp molding material comprises the following components: 10-30 parts of bamboo pulp fiber, 30-50 parts of sugarcane pulp fiber, 20-40 parts of wood pulp fiber, 5-10 parts of synthetic fiber, 1-4 parts of sizing agent, 1-3 parts of wet strength agent, 1-3 parts of reinforcing agent, 1-3 parts of expandable microspheres, 5-10 parts of filler, 0.1-0.3 part of retention agent and 0.1-0.4 part of defoaming agent. The ultra-light paper pulp molding material adopts expandable microspheres as low-density filler, has the advantages of good mechanical property, good buffering effect, environmental protection, no toxicity and low density, and can replace foamed plastic to be used as a packaging material.
Description
Technical Field
The invention relates to a paper pulp molding material, in particular to an ultra-light paper pulp molding material and a preparation method thereof.
Background
The pulp moulding material is a stereo paper-making technology. The paper material is made by using commodity raw pulp as raw material and moulding with a specific shaped mould in a pulp moulding machine. The pulp molding material is a novel packaging material which is rapidly developed in recent years and is a potential substitute for various plastic material packaging materials.
The existing paper pulp molding material is a packaging material which is generally obtained by using primary fibers (bamboo pulp, sugarcane pulp and wood pulp) or secondary fibers (waste paper pulp) as main raw materials, dehydrating and molding the fibers by using a special mold, and then drying and shaping the fibers. The concrete process can refer to the current research situation and development trend of the pulp molded product in the literature, and the raw materials and process routes used by the pulp molded product and the future development trend in the literature are briefly explained. The pulp molding material has the advantages of rich raw material sources, low price, easy obtainment, no pollution in the production process, low cost, recoverability, easy degradation and the like; has certain rigidity, strength and air permeability; the anti-seismic anti-static positioning device can play roles in shock resistance, buffering, positioning, pressure resistance, static resistance and the like. Therefore, the paper pulp molding material has wide application prospect in the packaging field of electronic products, daily chemical products, fresh products and the like. The buffer liner can be used for buffer liners and packages of fresh fruits, foods, furniture and other products, and can also be used for vessels for non-packaging purposes, such as a flowerpot and the like.
The disadvantages of the existing commonly used pulp molding materials are that the mass is relatively heavy (high density), the bearing capacity is insufficient, and the structural strength and the buffering performance are inferior to those of the foamed plastic. Manufacturers generally increase the stiffness of the pulp molding material by increasing the thickness of the pulp molding material, so as to enhance the bearing capacity of the pulp molding material, the minimum thickness of the existing pulp molding material is about 0.6mm, the maximum thickness can reach about 1.5-2.0mm, and the common thickness is about 0.8-1.0 mm. The pulp molding manufacturers increase the thickness of the pulp molding material mainly by increasing the amount of the pulp, and the disadvantage of this method is that the cost of the material is increased and the difficulty of manufacturing is increased.
The existing pulp molding material is not as good as foamed plastic in buffer memory performance and structural strength, so that although the existing pulp molding material is already used for buffer memory packaging of a plurality of products, the existing pulp molding material is limited in buffer memory material packaging of precision equipment such as mobile phones, watches, earphones and the like due to poor buffer memory effect, and the existing pulp molding material can not meet the requirements of large household appliance products, such as electronic product packaging of televisions, computers, kinescopes and the like. Therefore, there is a need to improve the strength and the cushioning property of pulp molded products.
Disclosure of Invention
Aiming at the defects of the existing pulp molding material, the invention aims to provide the ultralight pulp molding material which has the advantages of small density, good rebound resilience and the like and can replace the existing foamed plastic.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the ultralight paper pulp molding material comprises the following raw materials in parts by weight:
preferably, the surface of the expandable microspheres carries anionic groups.
Preferably, the above anionic groups are selected from carboxylate, sulfonate, phosphate or hydroxyl ions.
Preferably, the expandable microspheres are composed of a polymer shell and a foaming agent inside the polymer shell, and the polymer shell is a single-layer or multi-layer structure composed of acrylic polymers.
Preferably, the foaming agent is one or more selected from ethane, propane, isobutane, n-pentane and isopentane.
Preferably, the bamboo pulp fibers have an average length of about 1.5-2mm, an aspect ratio of about 150-200, and a cell wall thickness of about 5 Lm.
Preferably, the sugar cane pulp fibers have an average length of about 1 to 2mm, a width of about 14 to 28 microns, and a fiber aspect ratio of about 60 to 80.
Preferably, the wood pulp is selected from softwood long fibers having a length of about 2-3 mm.
Preferably, the synthetic fiber is selected from one or more of glass fiber, acetate fiber, nylon fiber, viscose fiber and polyester fiber.
Preferably, the sizing agent is selected from a mixture of one or more of an anionic dispersed rosin, a cationic dispersed rosin, Alkyl Ketene Dimer (AKD) and Alkenyl Succinic Anhydride (ASA).
Preferably, the defoaming agent is selected from one or more of polyether modified silicones, polyethers, non-silicone polymers, modified polymethylsiloxanes and silicones.
Preferably, the above-mentioned wet strength agent is selected from one or more of urea formaldehyde resin, melamine formaldehyde resin, PAE resin, dialdehyde starch, glyoxal-propylene graft copolymer, glutaraldehyde and polyethyleneimine.
Preferably, the above-mentioned retention agent is selected from one or more of cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, polyethyleneimine and cationic starch.
Preferably, the above reinforcing agent is selected from one or more of modified starch, polyacrylamide and its derivatives, natural gum, chitosan and aldehyde cellulose.
Preferably, the modified starch is selected from one or more of nonionic starch, oxidized starch, amphoteric starch and carboxymethyl starch.
Preferably, the polyacrylamide is selected from one or more of nonionic polyacrylamide, cationic polyacrylamide and anionic polyacrylamide.
Preferably, the natural gum is selected from one or a mixture of two of bean gum and guar gum.
Preferably, the filler is selected from one or more of talc, calcium carbonate, kaolin and titanium dioxide.
Another object of the present invention is to provide a method for preparing the above ultralight pulp molding material, the method comprising the steps of:
(1) adding bamboo pulp fibers, sugarcane pulp fibers and wood pulp fibers into water to prepare a suspension with the total fiber mass concentration of 2-8%, and dispersing for 10-30 min;
(2) adding synthetic fibers into the suspension after pulp dispersing, and sequentially performing defibering and pulp grinding to ensure that the freeness of the mixed fibers is 400-500 ml;
(3) and sequentially adding the water diluent of the sizing agent, the water diluent of the wet strength agent, the water diluent of the reinforcing agent, the water diluent of the expandable microspheres, the water diluent of the filler, the water diluent of the retention agent and the defoaming agent, wherein each component is added and then mixed for 5-40 min, and then the next component is added.
(4) Diluting the slurry obtained in the step (3) into slurry with the mass concentration of 3-5 per mill by using water, forming by using a forming machine to obtain the ultralight paper pulp molding material,
wherein the temperature of the upper and lower dies of the forming machine is 100-200 ℃, and the hot pressing time is 100-200 s.
It is an object of a further aspect of the present invention to provide the use of expandable microspheres in the preparation of ultralight pulp moulding materials.
The paper pulp molding material takes bamboo pulp fiber, cane pulp fiber and wood pulp fiber as main raw materials, wherein the bamboo pulp fiber and the wood pulp fiber are used as long fibers in a paper pulp molding product, and a framework structure of the paper pulp molding product is provided. The sugarcane pulp fiber is used as a short fiber form in a pulp molding product and is filled in the bamboo pulp fiber and the wood pulp bamboo pulp fiber, so that the sugarcane pulp fiber as the short fiber, the wood pulp fiber as the long fiber and the bamboo pulp fiber are combined with each other to form a compact fiber network structure. The whole skeleton structure is filled with the sugarcane pulp fibers, the physical strength of the skeleton structure is further improved, including tensile strength, tear resistance, interlayer bonding strength, stiffness and the like, and meanwhile, because the sugarcane pulp fibers contain a large amount of hemicellulose, surface plasticization can occur under the heated condition, and the method is particularly beneficial to the improvement of the stiffness of a three-dimensional packaging product. In addition, the effect of sugar cane pulp fibers on the wet strength of pulp molded products is particularly significant. Moreover, when the number of the sugarcane pulp fibers as short fibers is increased, the pulp molding material is more uniform in the adsorption molding process, the separation of the pulp molding material and a mold in the demolding process is facilitated, and the apparent defects such as the tensile crack of the pulp molding material in the transferring process are reduced.
The expandable microspheres used in the pulp molding material of the invention are ultra-light fillers, and the density of the expandable microspheres after sufficient expansion can be only 0.02g/cm3And the density is extremely low. Because of the characteristic of the expandable microspheres as the ultra-light filler, the expandable microspheres are added into the pulp molding material, and after full expansion, uniform hollow foaming spheres are formed in pulp fibers, so that the volume of the pulp molding material is obviously increased, the density of the pulp molding material is reduced, and the stiffness of the pulp molding material is improved on the premise that the fiber consumption is not adjusted; with a fixed die gap, the thickness of the material can be increased significantly. At the same time, the expandable microspheresThe paper pulp molding material has excellent rebound resilience, can improve the buffer property of the paper pulp molding material, and solves the problem that the use of the existing paper pulp molding material is limited due to insufficient buffer property. Particularly surface-modified expandable microspheres, namely, anion groups are introduced to the surfaces of the expandable microspheres, and the anion groups are utilized to increase the uniformity of mixing of the expandable microspheres and fibers, so that the retention rate of the expandable microspheres in a system is improved. Therefore, the foam holes formed by the expandable microspheres after foaming are of uniform closed-cell structures, the foam holes cannot be crossed, and the foam holes are uniform in size, regular in distribution and high in elasticity. Further endows the pulp molding material with excellent caching performance.
Compared with the prior art, the paper pulp molding material has the following beneficial effects:
the ultra-light paper pulp molding material of the invention uses the expandable microspheres as ultra-light filler, has the advantages of small density, high stiffness, good resilience and good buffer performance, and can be used as a packaging material of precise instruments and equipment.
By using various functional additives and expandable microspheres, the ultralight paper pulp molding material disclosed by the invention has the advantages that the density of the material is reduced, the thickness and the buffer performance of the material are improved, and meanwhile, various physical indexes of the material are basically consistent with those of a base paper pulp molding material. Namely, the density of the pulp molding material is reduced and the cache performance of the pulp molding material is improved under the condition that the original physical index of the pulp molding material is not changed.
Detailed Description
In the present description, blowing agents for use as expandable microspheres include, but are not limited to, one or more of ethane, propane, isobutane, n-pentane, and isopentane. In a preferred embodiment of the present invention, the particle size of the expandable microspheres is 7-30 microns, the maximum expansion ratio is 5-10 times, the size of the expanded microspheres is 40-80 microns, and the expansion temperature is 100-160 ℃.
In the description of the present invention, the bamboo pulp fiber is a bamboo pulp fiber commonly used in the art. For example, Chongqing bamboo pulp, Guizhou bamboo pulp of Chitian type, Yongfeng bamboo pulp, Huajin bamboo pulp, and Jinrong bamboo pulp.
In the description of the present invention, sugar cane pulp fiber is commonly used in the art. For example, Thai Earth sugarcane pulp, Guangxi Guinea sugar cane pulp, Yunnan south China sugarcane pulp, Guangxi Boguan sugarcane pulp.
In the description of the present invention, long softwood fibers are commonly used in the art. For example, silver star needle wood long fibers, black needle wood long fibers, moon needle wood long fibers, Keliper needle wood long fibers, North needle wood long fibers.
In the description of the present invention, the synthetic fibers include, but are not limited to, glass fibers, acetate fibers, nylon fibers, viscose fibers and polyester fibers. The synthetic fiber plays a role in the pulp molding material in improving the folding resistance and the supporting property of a molded product by introducing long fiber.
Sizing agents in the context of the present invention include, but are not limited to, anionic dispersed rosins, cationic dispersed rosins, Alkyl Ketene Dimers (AKD) and Alkenyl Succinic Anhydrides (ASA). The sizing agent plays a role in the pulp molding material as an in-pulp teaching agent to improve the water resistance and wet strength of a molded product; and demolding is increased, and mold sticking is prevented.
In the description of the present invention, the defoaming agent includes, but is not limited to, silicones, polyethers, polyether modifications, tributyl phosphate, mineral oils, non-silicone polymers. The defoaming agent plays a role in eliminating foams in a system in the pulp making process, improving the evenness of a formed product, and reducing the problems of apparent paper defects and product shortage caused by bubbles
In the context of the present invention, wet strength agents include, but are not limited to, urea formaldehyde resins, melamine formaldehyde resins, PAE resins, dialdehyde starch, glyoxal-propylene graft copolymers, glutaraldehyde and polyethylene imine. The wet strength agent plays a role in the pulp molding material in improving the wet strength of a finished product, reducing the tension crack of the product in the transfer process and easily deforming paper defects.
In the context of the present invention, retention agents include, but are not limited to, cationic polyacrylamides, anionic polyacrylamides, amphoteric polyacrylamides, polyethylene imines, and cationic starches. The retention agent plays a role in the pulp molding material to improve the retention of fine fibers and increase the physical strength of a finished product; the retention efficiency of the expandable microspheres is improved.
In the context of the present invention, enhancing agents include, but are not limited to, modified starches, polyacrylamides and derivatives thereof, natural gums, chitosan, and aldehydized cellulose. The reinforcing agent plays a role in the pulp molding material to improve the dry strength of the finished product.
In the context of the present invention, modified starches include, but are not limited to, nonionic starches, oxidized starches, amphoteric starches, and carboxymethyl starches.
In the description of the present invention, polyacrylamides include, but are not limited to, nonionic polyacrylamides, cationic polyacrylamides, and anionic polyacrylamides.
In the context of the present invention, natural gums include, but are not limited to, soy gum and guar gum.
In the context of the present invention, fillers include, but are not limited to, mixtures of one or more of talc, calcium carbonate, kaolin and titanium dioxide. The filler plays a role in the pulp molding material to improve the hardness and stiffness of the product.
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The structure of the expandable microspheres RICC100WE of Yun & Industrie materials science and technology (Shanghai) limited (abbreviated as "Yun & Industrie science and technology limited") mentioned in the following examples is a core-shell structure, the shell is formed by copolymerizing acrylonitrile, vinylidene chloride and methyl acrylonitrile, and the interior of the microspheres contains liquid isopentane. Tstart is 90-100 ℃, Tmax is 140-150 ℃, and the minimum density is less than Dmin and is less than 12kg/m3The sphere of the microsphere can be increased to about 60 times of the original sphere in volume.
The materials science and technology (Shanghai) company, referred to in the following examples (abbreviated as "science and technology Co., Ltd") The structure of the RICC100WET expandable microsphere is a core-shell structure, the shell is formed by copolymerizing acrylonitrile, vinylidene chloride and methyl acrylonitrile, and the interior of the RICC100WET expandable microsphere comprises liquid isopentane. Tstart is 90-100 ℃, Tmax is 145-155 ℃, and the minimum density is less than Dmin and is less than 12kg/m3The sphere of the microsphere can be increased to about 60 times of the original sphere in volume. Compared with the expandable microspheres RICC100WE, the expandable microspheres have the difference that the surfaces of the expandable microspheres are coated by acrylic monomers, and the surfaces of the expandable microspheres have more carboxylate anion groups.
Example 1
The components and the amounts of the ultralight pulp molding material of this example are shown in table 1. The expandable microspheres used in this example were RICC100WE, a product of research and technology, Inc.
The preparation method of the ultralight paper pulp molding material comprises the following steps:
(1) putting 20 parts by weight of bamboo pulp fiber (Chongqing bamboo pulp fiber, the average length of the fiber is 1.5-2.0mm), 20 parts by weight of wood pulp fiber (silver star needle-leaved wood long fiber, the average length of the fiber is 2-3mm) and 50 parts by weight of sugarcane pulp fiber (Thailand Earth brand sugarcane pulp, the average length of the fiber is 1.5-1.9mm) into a pulp scattering machine, adding water to prepare suspension with the total mass concentration of the three fibers being 5%, starting the pulp scattering machine (the power of the pulp scattering machine is 55kw), scattering the pulp for 15min, and transferring the pulp after scattering to a pulp scattering storage barrel for later use;
(2) adding 10 parts by weight of glass fiber (12 mm chopped glass fiber of Jiacheng fiber Co., Ltd., Taian city) into the pulp obtained in the step (1), dispersing the pulp for 3min, defibering by using a defibering machine, grinding by using a refiner (adjusting the feed scale of the refiner and controlling the refining current to be 80-90A) to control the freeness of the whole pulp to be 440-500ml, and transferring the pulp subjected to refining into a thick pulp barrel for later use after refining;
(3) adding 2 parts by weight of a 50-time diluted sizing agent (Yiqu chemical Co., Ltd., YK-16-06, a mixture of ketene dimer and cationic starch) into the slurry obtained in the step (2), and mixing for 15min in a 60r/min mixing barrel for later use;
(4) adding 3 parts by weight of 50-time diluted wet strength agent (WS-125C, polyamide polyamine epichlorohydrin resin PAE) into the slurry obtained in the step (3), and mixing in a mixing tank of 60r/min for 10 min;
(5) adding 1 weight part of 50-time diluted reinforcing agent (PCL-3200, amphoteric polyacrylamide reinforcing agent) into the slurry obtained in the step (4), and mixing in a 60r/min mixing barrel for 10 min;
(6) adding water into 1 part by weight of expandable microspheres to prepare a suspension with the mass concentration of 1%, uniformly mixing, slowly adding the suspension into the slurry obtained in the step (5), and mixing in a mixing barrel at a speed of 60r/min for 30min for later use;
(7) adding 5 parts by weight of filler talcum powder (T-2, Tandongtiansi flame retardant materials science and technology Co., Ltd.) into water to prepare suspension with the concentration of 10%, adding the suspension into the slurry obtained in the step (6), and mixing the suspension in a mixing barrel of 60r/min for 20min for later use;
(8) adding 0.1 part by weight of 0.1 mass percent resident agent solution (JH-8502, cationic polyacrylamide with molecular weight of 300-85ten thousand and ionic degree of 20-40) into the slurry obtained in the step (7), and mixing for 15min in a mixing barrel at a speed of 60r/min for later use;
(9) adding 0.2 part by weight of defoaming agent (DF-1250, type of organic silicon, Defeng defoaming agent Co., Ltd., Dongguan) into the slurry obtained in the step (8), and mixing for 10min for later use;
(10) and (3) diluting the slurry obtained in the step (9) into slurry with the mass concentration of 3 per mill, forming by using a forming machine, absorbing the slurry, forming, and drying to obtain the ultralight paper pulp molding material, wherein the temperatures of an upper mold and a lower mold of a hot pressing mold of the forming machine in the forming process are 160/155 ℃ respectively, and the hot pressing time is 140 s.
Example 2
The components and the amounts of the ultralight pulp molding material of this example are shown in table 1. The expandable microspheres used in this example were RICC100WE, a product of research and technology, Inc.
The preparation method of the ultralight paper pulp molding material comprises the following steps:
(1) putting 15 parts by weight of bamboo pulp fiber (Guizhou Chitian bamboo pulp fiber, the average length of the fiber is 1.5-2.0mm), 30 parts by weight of wood pulp fiber (Yinxing needle-leaved wood long fiber, the average length of the fiber is 2-3mm) and 50 parts by weight of sugarcane pulp fiber (Thailand Earth brand sugarcane pulp, the average length of the fiber is 1.5-1.9mm) into a pulp scattering machine, adding water to prepare suspension with the total mass concentration of the three fibers being 5%, starting the pulp scattering machine (the power of the pulp scattering machine is 55kw), scattering the pulp for 20min, and transferring the pulp after scattering pulp into a storage barrel for standby after scattering pulp;
(2) adding 5 parts by weight of viscose (the average length of the fibers is 20mm) into the pulp obtained in the step (1), dispersing the pulp for 5min, defibering by using a defibering machine, grinding by using a pulping machine (the feed scale of the pulping machine is adjusted, and the pulping current is controlled to be 80-90A) so that the freeness of the whole pulp is controlled to be 440-500ml, and transferring the pulp subjected to pulping into a thick pulp barrel for standby after pulping;
(3) adding 2 parts by weight of a 50-time diluted sizing agent (SIZEPINE E-50, available from Mitsukawa chemical Co., Ltd., anion-dispersed rosin size) into the slurry obtained in the step (2), and mixing in a mixing tank of 60r/min for 15min for later use;
(4) adding 3 parts by weight of wet strength agent (PLF 032, polyethyleneimine wet strength resin) diluted by 50 times into the slurry obtained in the step (3), and mixing for 10min in a mixing barrel of 60r/min for later use;
(5) adding 2 weight parts of 50-time diluted reinforcing agent (CP-1, cationic starch with substitution degree of 0.025-0.035, Jinshan modified starch Co., Ltd., Taian) into the slurry obtained in the step (4), and mixing in a mixing barrel of 60r/min for 20min for later use;
(6) adding water into 2 parts by weight of expandable microspheres to prepare a suspension with the concentration of 1%, uniformly mixing, slowly adding the suspension into the slurry obtained in the step (5), and mixing in a mixing barrel at a speed of 60r/min for 40min for later use;
(7) 8 parts by weight of filler talcum powder (T-2, Tandongtiansi flame retardant materials science and technology Co., Ltd.) is added with water to prepare suspension with the mass concentration of 10%, and the suspension is added into the slurry obtained in the step (6) and mixed in a mixing barrel with the speed of 60r/min for 25min for later use;
(8) adding 0.3 part by weight of 0.1% by mass of a resident agent solution (JH-8502, cationic polyacrylamide with molecular weight of 300-85ten thousand and ionic degree of 20-40) into the slurry obtained in the step (7), and mixing for 15min in a mixing barrel at a speed of 60r/min for later use;
(9) adding 0.3 weight part of defoaming agent (DF-1, polyether type, Hangzhou Harlima chemical Co., Ltd.) into the slurry obtained in step (8), and mixing for 10 min;
(10) and (3) diluting the slurry obtained in the step (9) into slurry with the mass concentration of 3 per mill, forming by using a forming machine, absorbing the slurry, forming, and drying to obtain the ultralight paper pulp molding material, wherein the temperatures of an upper mold and a lower mold of a hot pressing mold of the forming machine in the forming process are 160/155 ℃ respectively, and the hot pressing time is 140 s.
Example 3
The components and the amounts of the ultralight pulp molding material of this example are shown in table 1. The expandable microspheres used in the embodiment are modified products of RICC100WET of science and technology Limited, and 3-chloro-2-hydroxypropyl sodium sulfonate is used for modifying the surfaces of the RICC100WE microspheres, so that anionic charged groups on the surfaces of the microspheres are increased, and the combination of the microspheres and a retention agent with positive charges is facilitated, so that the combination of the microspheres and fibers with negative charges is facilitated, and the retention efficiency of the microspheres is improved.
The preparation method of the ultralight paper pulp molding material comprises the following steps:
(1) putting 15 parts by weight of bamboo pulp fiber (Guizhou Chitian bamboo pulp fiber, the average length of the fiber is 1.5-2.0mm), 30 parts by weight of wood pulp fiber (Yinxing needle-leaved wood long fiber, the average length of the fiber is 2-3mm) and 50 parts by weight of sugarcane pulp fiber (Thailand Earth brand sugarcane pulp, the average length of the fiber is 1.5-1.9mm) into a pulp scattering machine, adding water to prepare suspension with the total mass concentration of the three fibers being 5%, starting the pulp scattering machine (the power of the pulp scattering machine is 55kw), scattering the pulp for 20min, and transferring the pulp after scattering pulp into a storage barrel for standby after scattering pulp;
(2) adding 5 parts by weight of viscose (the average length of the fibers is 20mm) into the pulp obtained in the step (1), dispersing the pulp for 5min, defibering by using a defibering machine, grinding by using a pulping machine (the feed scale of the pulping machine is adjusted, and the pulping current is controlled to be 80-90A) so that the freeness of the whole pulp is controlled to be 440-500ml, and transferring the pulp subjected to pulping into a thick pulp barrel for standby after pulping;
(3) adding 2 parts by weight of a 50-time diluted sizing agent (SIZEPINE E-50, available from Mitsukawa chemical Co., Ltd., anion-dispersed rosin size) into the slurry obtained in the step (2), and mixing in a mixing tank of 60r/min for 15min for later use;
(4) adding 3 parts by weight of wet strength agent (PLF 032, polyethyleneimine wet strength resin) diluted by 50 times into the slurry obtained in the step (3), and mixing for 10min in a mixing barrel of 60r/min for later use;
(5) adding 2 weight parts of 50-time diluted reinforcing agent (CP-1, cationic starch with substitution degree of 0.025-0.035, Jinshan modified starch Co., Ltd., Taian) into the slurry obtained in the step (4), and mixing in a mixing barrel of 60r/min for 20min for later use;
(6) adding water into 2 parts by weight of expandable microspheres to prepare a suspension with the mass concentration of 1%, uniformly mixing, slowly adding the suspension into the slurry obtained in the step (5), and mixing in a mixing barrel at a speed of 60r/min for 40min for later use;
(7) 8 parts by weight of filler talcum powder (T-2, Tandongtiansi flame retardant materials science and technology Co., Ltd.) is added with water to prepare suspension with the mass concentration of 10%, and the suspension is added into the slurry obtained in the step (6) and mixed in a mixing barrel with the speed of 60r/min for 25min for later use;
(8) adding 0.3 part by weight of 0.1% by mass of a resident agent solution (JH-8502, cationic polyacrylamide with molecular weight of 300-85ten thousand and ionic degree of 20-40) into the slurry obtained in the step (7), and mixing for 15min in a mixing barrel at a speed of 60r/min for later use;
(9) adding 0.3 weight part of defoaming agent (DF-1, polyether type, Hangzhou Harlima chemical Co., Ltd.) into the slurry obtained in step (8), and mixing for 10 min;
(10) and (3) diluting the slurry obtained in the step (9) into slurry with the mass concentration of 3 per mill, forming by using a forming machine, absorbing the slurry, forming, and drying to obtain the ultralight paper pulp molding material, wherein the temperatures of an upper mold and a lower mold of a hot pressing mold of the forming machine in the forming process are 160/155 ℃ respectively, and the hot pressing time is 140 s.
Example 4
The components and the amounts of the ultralight pulp molding material of this example are shown in table 1. The expandable microspheres used in this example were RICC100WE, a product of research and technology, Inc.
The preparation method of the ultralight paper pulp molding material comprises the following steps:
(1) putting 25 parts by weight of bamboo pulp fiber (Chongqing bamboo pulp fiber, the average length of the fiber is 1.5-2.0mm), 20 parts by weight of wood pulp fiber (silver star needle-leaved wood long fiber, the average length of the fiber is 2-3mm), 45 parts by weight of sugarcane pulp fiber (Guangxi Guiguo brand sugarcane pulp, the average length of the fiber is 1.3-1.7mm) into a pulp scattering machine, adding water to prepare suspension with the total mass concentration of the three fibers being 5%, starting the pulp scattering machine (the pulp scattering machine power is 55kw), scattering the pulp for 30min, and transferring the pulp after scattering into a storage barrel for standby after scattering pulp;
(2) adding 10 parts by weight of polyester fibers (the average length of the polyester fibers is 19mm) into the pulp obtained in the step (1), dispersing the pulp for 10min, defibering by using a defibering machine, grinding by using a pulp grinder (the feed scale of the pulp grinder is adjusted, and the grinding current is controlled to be 80-90A) so that the freeness of the whole pulp is controlled to be 440-500ml, and transferring the pulp subjected to grinding into a thick pulp barrel for later use after grinding;
(3) adding 2.5 weight parts of 50-fold diluted sizing agent (SIZEPINE K-903-20, ketene dimer and cationic starch) into the slurry obtained in the step (2), and mixing in a mixing tank of 60r/min for 20 min;
(4) adding 2 parts by weight of a 50-time diluted wet strength agent (FT-688, polyamide polyamine epichlorohydrin resin) into the slurry obtained in the step (3), and mixing in a mixing tank of 60r/min for 20 min;
(5) adding 2 parts by weight of 50-time diluted reinforcing agent (PCL-3200, amphoteric polyacrylamide) into the slurry obtained in the step (4), and mixing in a 60r/min mixing barrel for 15 min;
(6) adding water into 2.5 parts by weight of expandable microspheres to prepare a suspension with the mass concentration of 1%, uniformly mixing, slowly adding the suspension into the slurry obtained in the step (5), and mixing in a 60r/min mixing barrel for 35min for later use;
(7) adding 7 parts by weight of filler (T-2, talcum powder, Tandong Tiancii flame-retardant materials science and technology Limited, Inc.) into water to prepare suspension with the mass concentration of 10%, adding the suspension into the slurry obtained in the step (6), and mixing the suspension in a mixing barrel of 60r/min for 30min for later use;
(8) adding 0.25 part by weight of 0.1% by mass of a resident agent solution (JH-8502, cationic polyacrylamide with molecular weight of 300-85ten thousand and ionic degree of 20-40) into the slurry obtained in the step (7), and mixing in a 60r/min mixing barrel for 25min for backup;
(9) adding 0.3 part by weight of defoaming agent (DF-1336, modified polyether type, Defeng defoaming agent, Inc. of Dongguan city) into the slurry obtained in the step (8), and mixing for 15min for later use;
(10) and (3) diluting the slurry obtained in the step (9) into slurry with the mass concentration of 3 per mill, forming by using a forming machine, absorbing the slurry, forming, and drying to obtain the ultralight paper pulp molding material, wherein the temperatures of an upper mold and a lower mold of a hot pressing mold of the forming machine in the forming process are 160/160 ℃ respectively, and the hot pressing time is 80 s.
Example 5
The components and the amounts of the ultralight pulp molding material of this example are shown in table 1. The expandable microspheres used in this example were RICC100WE, a product of research and technology, Inc.
The preparation method of the ultralight paper pulp molding material comprises the following steps:
(1) 30 parts by weight of bamboo pulp fiber (Chongqing bamboo pulp fiber, the average length of the fiber is 1.5-2.0mm), 35 parts by weight of wood pulp fiber (Russian wuzhen needle wood long fiber, the average length of the fiber is 2.5-3.5mm), 30 parts by weight of sugarcane pulp fiber (Thailand Earth brand sugarcane pulp, the average length of the fiber is 1.5-1.9mm) are put into a pulp scattering machine, water is added to prepare suspension liquid with the total mass concentration of the three fibers being 5%, the pulp scattering machine is started (the pulp scattering machine power is 55kw), the pulp is scattered for 30min, and the pulp after pulp scattering is transferred to a pulp scattering storage barrel for standby;
(2) adding 5 parts by weight of polyester fibers (the average length of the glass fibers is 3mm) into the pulp obtained in the step (1), dispersing the pulp for 5min, defibering by using a defibering machine, grinding by using a refiner (the feed scale of the refiner is adjusted, and the refining current is controlled to be 80-90A) so that the freeness of the whole pulp is controlled to be 440-500ml, and transferring the pulp subjected to refining into a thick pulp barrel for later use after refining;
(3) adding 1.5 parts by weight of a 50-time diluted sizing agent (SIZEPINE C-500, SiZEPINE rosin size, Seisakusho chemical Co., Ltd.) into the slurry obtained in the step (2), and mixing in a mixing tank of 60r/min for 25 min;
(4) adding 2 weight parts of 50-time diluted wet strength agent (WS-125C, polyamide polyamine epichlorohydrin resin, Hangzhou Harlima chemical Co., Ltd.) into the slurry obtained in the step (3), and mixing in a mixing barrel of 60r/min for 15min for later use;
(5) adding 1.5 weight parts of 50-time diluted reinforcing agent (PCL-3200, amphoteric polyacrylamide) into the slurry obtained in the step (4), and mixing in a 60r/min mixing barrel for 20 min;
(6) adding water into 3 parts by weight of expandable microspheres to prepare a suspension with the mass concentration of 1%, uniformly mixing, slowly adding the suspension into the slurry obtained in the step (5), and mixing in a mixing barrel with the speed of 60r/min for 25min for later use;
(7) adding 6 parts by weight of filler (T-2, talcum powder, Tandong Tiancii flame retardant materials science and technology Limited, Inc.) into water to prepare suspension with the mass concentration of 10%, adding the suspension into the slurry obtained in the step (6), and mixing the suspension in a mixing barrel of 60r/min for 30min for later use;
(8) adding 0.20 part by weight of 0.1% by mass of a resident agent solution (JH-8502, cationic polyacrylamide with molecular weight of 300-85ten thousand and ionic degree of 20-40) into the slurry obtained in the step (7), and mixing in a mixing barrel of 60r/min for 20min for later use;
(9) adding 0.1 part by weight of defoaming agent (DF-1250, type of organic silicon, Defeng defoaming agent Co., Ltd., Dongguan) into the slurry obtained in the step (8), and mixing for 15min for later use;
(10) and (3) diluting the slurry obtained in the step (9) into slurry with the mass concentration of 3 per mill, forming by using a forming machine, absorbing the slurry, forming, and drying to obtain the ultralight paper pulp molding material, wherein the upper mold temperature and the lower mold temperature of a hot pressing mold of the forming machine in the forming process are 155/150 ℃, and the hot pressing time is 100 seconds.
Comparative example 1
The components and the amounts of the ultralight pulp molding material of the present comparative example are shown in table 1.
The preparation method of the ultralight paper pulp molding material comprises the following steps:
(1) 30 parts by weight of bamboo pulp fiber (Chongqing bamboo pulp fiber, the average length of the fiber is 1.5-2.0mm), 35 parts by weight of wood pulp fiber (Russian wuzhen needle wood long fiber, the average length of the fiber is 2.5-3.5mm), 30 parts by weight of sugarcane pulp fiber (Thailand Earth brand sugarcane pulp, the average length of the fiber is 1.5-1.9mm) are put into a pulp scattering machine, water is added to prepare suspension liquid with the total mass concentration of the three fibers being 5%, the pulp scattering machine is started (the pulp scattering machine power is 55kw), the pulp is scattered for 30min, and the pulp after pulp scattering is transferred to a pulp scattering storage barrel for standby;
(2) adding 5 parts by weight of polyester fibers (the average length of the glass fibers is 3mm) into the pulp obtained in the step (1), dispersing the pulp for 5min, defibering by using a defibering machine, grinding by using a refiner (the feed scale of the refiner is adjusted, and the refining current is controlled to be 80-90A) so that the freeness of the whole pulp is controlled to be 440-500ml, and transferring the pulp subjected to refining into a thick pulp barrel for later use after refining;
(3) adding 1.5 parts by weight of a 50-time diluted sizing agent (SIZEPINE C-500, SiZEPINE rosin size, Seisakusho chemical Co., Ltd.) into the slurry obtained in the step (2), and mixing in a mixing tank of 60r/min for 25 min;
(4) adding 2 weight parts of 50-time diluted wet strength agent (WS-125C, polyamide polyamine epichlorohydrin resin, Hangzhou Harlima chemical Co., Ltd.) into the slurry obtained in the step (3), and mixing in a mixing barrel of 60r/min for 15min for later use;
(5) adding 1.5 weight parts of 50-time diluted reinforcing agent (PCL-3200, amphoteric polyacrylamide) into the slurry obtained in the step (4), and mixing in a 60r/min mixing barrel for 20 min;
(6) adding 6 parts by weight of filler (T-2, talcum powder, Tandong Tiancii flame-retardant materials science and technology Limited, Inc.) into water to prepare suspension with the mass concentration of 10%, adding the suspension into the slurry obtained in the step (5), and mixing the suspension in a mixing barrel of 60r/min for 30min for later use;
(7) adding 0.20 part by weight of 0.1% by mass of a resident agent solution (JH-8502, cationic polyacrylamide with molecular weight of 300-85ten thousand and ionic degree of 20-40) into the slurry obtained in the step (6), and mixing in a mixing barrel of 60r/min for 20min for later use;
(8) adding 0.1 part by weight of defoaming agent (DF-1250, type of organic silicon, Defeng defoaming agent Co., Ltd., Dongguan) into the slurry obtained in the step (7), and mixing for 15min for later use;
(9) and (3) diluting the slurry obtained in the step (8) into slurry with the mass concentration of 3 per mill, forming by using a forming machine, absorbing slurry, forming and drying to obtain the ultralight paper pulp molding material, wherein the upper mold temperature and the lower mold temperature of a hot pressing mold of the forming machine in the forming process are 155/150 ℃, and the hot pressing time is 100 seconds.
TABLE 1 Components and amounts thereof (parts by weight) of examples 1-5 and comparative example 1.
Performance detection
The thicknesses (as measured by GB/T451.3-2002 paper and paperboard thickness measurements), basis weights (as measured by GB/T451.2-2002 paper and paperboard basis weight measurements), tensile strengths (as measured by GB/T12914 paper and paperboard tensile strength-constant rate draw), burst strengths (as measured by ISO2759 paperboard burst strength measurements), stiffness (as measured by GB2679-3 paperboard stiffness measurements), and ply-to-ply bond strengths (as measured by GB/T26203-2010 paper and paperboard internal bond strength measurements) of the materials prepared in examples 1-5 and comparative example 1 were tested. The details are shown in Table 2.
The grammage is the weight of the individual product.
Basis weight is the weight per unit area of the product.
TABLE 2 Performance test data for the materials of examples 1-5 and comparative example 1
Comparison of the performance test data of the materials of example 5 and comparative example 1 in table 2 shows that under the condition of substantially the same grammage, the thickness of the pulp molding material is obviously increased by the expandable microspheres, the thickness is increased by 13.9% (the components of example 5 and comparative example 1 are the same except for the expandable microspheres, the thickness of the former is increased by 13.9% compared with the thickness of comparative example 1), and other physical indexes (such as burst resistance and interlayer bonding force of tear strength) are slightly reduced, but the subsequent use is not influenced.
Comparison of examples 1 to 5 with comparative example 1 shows that the pulp moulding material according to the invention has a maximum decrease in density of about 18%, a maximum increase in thickness of 21%, a maximum increase in stiffness of 26%, a decrease in burst strength of 4.4%, a decrease in tensile strength of 2.99%, a decrease in tear strength of 3.75% and a decrease in interlaminar bonding strength of 5.11% at substantially the same grammage. After the microspheres are added, the density of the pulp molding material is obviously reduced, the thickness and the stiffness are obviously improved, and other physical properties are reduced to a certain degree but are less than 5 percent, so that the normal use is not influenced. From the above data of the pulp molding materials of comparative examples 1, 2, 4, and 5, it can be seen that the higher the addition amount of the expandable microspheres, the more remarkable the decrease in density and the increase in thickness stiffness of the pulp molding material, and the more remarkable the effect of weight reduction and thickening of the material. Although other physical indexes are influenced and reduced to a certain degree, the maximum reduction amplitude is less than 5 percent, and the subsequent use is basically not influenced.
Comparing the properties of the pulp molding materials of example 2 and example 3, it can be seen that the thickness increase of the surface-treated expandable microspheres (with more anionic groups) is higher than that of the unmodified product under the same addition amount, and the thickness increase of the modified microspheres is 5.19% higher than that of the unmodified product. This shows that the thickness of the pulp molding material can be improved more significantly by the expandable microspheres with anionic groups on the surface than by the expandable microspheres without anionic groups on the surface, probably because anionic groups are introduced on the surface of the expandable microspheres, and the expandable microspheres are easier to combine with the retention agent by attraction of negative and positive charges and combine with fibers with negative charges together as a whole, so that the retention efficiency of the expandable microspheres is improved, the effect after foaming is more significant, and the effect of improving the thickness is more significant.
Through the embodiment, the application of the expandable microspheres can be realized, and the thickness of the material can be improved under the condition that the gram weight of the product is not increased, so that the bearing capacity of the pulp molding material is improved. The closed cell structure formed after the expandable microspheres are foamed is rich in elasticity and has good buffering performance. The application of the expandable microspheres successfully solves the problems that the existing pulp molding material cannot manufacture products with high thickness due to the process problem, and the use is limited due to insufficient thickness and buffer property in the use process, thereby expanding the application range of the pulp molding products. Under the condition of not changing the existing process route, the thickness of the material is increased and the buffering performance of the product is improved. The weight of the product is obviously reduced under the condition of ensuring the thickness of the original low-gram-weight material to be unchanged, and the effects of saving fiber raw materials and reducing the material consumption are achieved.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (12)
1. The ultralight paper pulp molding material is characterized in that the raw materials for preparing the ultralight paper pulp molding material comprise the following components in parts by weight:
2. the ultralight pulp molding material of claim 1, wherein the expandable microspheres have anionic groups on their surfaces.
3. The ultralight pulp molding material according to claim 1, wherein the wood pulp is selected from softwood long fibers.
4. The ultra-light pulp molding material according to claim 1, wherein the synthetic fiber is selected from one or more of glass fiber, acetate fiber, nylon fiber, viscose fiber and polyester fiber.
5. The ultralight pulp molding material of claim 1, wherein the sizing agent is selected from the group consisting of one or more mixtures of anionic dispersed rosin, cationic dispersed rosin, alkyl ketene dimer, and alkenyl succinic anhydride.
6. The ultralight pulp molding material of claim 1, wherein the defoamer is selected from one or more of silicones, polyethers, polyether modifications, tributyl phosphate, mineral oils, non-silicone polymers.
7. The ultralight pulp molding material of claim 1, wherein the wet strength agent is selected from a mixture of one or more of urea formaldehyde resin, melamine formaldehyde resin, PAE resin, dialdehyde starch, glyoxal-propylene graft copolymer, glutaraldehyde and polyethyleneimine.
8. The ultralight pulp molding material of claim 1, wherein the retention agent is selected from a mixture of one or more of cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, polyethyleneimine, and cationic starch.
9. The ultralight pulp molding material according to claim 1, wherein the reinforcing agent is selected from one or more of modified starch, polyacrylamide and its derivatives, natural gum, chitosan, and aldehydized cellulose.
10. The ultralight pulp molding material of claim 1, wherein the filler is selected from a mixture of one or more of talc, calcium carbonate, kaolin and titanium dioxide.
11. The method for preparing an ultralight pulp molding material according to any one of claims 1 to 10, characterized in that the preparation method comprises the steps of:
(1) adding bamboo pulp fibers, sugarcane pulp fibers and wood pulp fibers into water to prepare a suspension with the total fiber mass concentration of 2-8%, and dispersing for 10-30 min;
(2) adding synthetic fibers into the suspension after pulp dispersing, and sequentially performing defibering and pulp grinding to ensure that the freeness of the synthetic fibers is 400-500 ml;
(3) and sequentially adding the water diluent of the sizing agent, the water diluent of the wet strength agent, the water diluent of the reinforcing agent, the water diluent of the expandable microspheres, the water diluent of the filler, the water diluent of the retention agent and the defoaming agent, wherein each component is added and then mixed for 5-40 min, and then the next component is added.
(4) Diluting the slurry obtained in the step (3) into slurry with the mass concentration of 3-5 per mill by using water, forming by using a forming machine to obtain the ultralight paper pulp molding material,
wherein the temperature of the upper die and the lower die of the forming machine is 100-200 ℃, and the hot pressing time is 100-200 s.
12. Use of expandable microspheres in the preparation of ultralight pulp moulding materials.
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| US5391424A (en) * | 1991-02-05 | 1995-02-21 | Kolzer; Klaus | Lightweight filler and a process for its manufacture |
| US20070044929A1 (en) * | 2005-03-11 | 2007-03-01 | Mohan Krishna K | Compositions containing expandable microspheres and an ionic compound, as well as methods of making and using the same |
| CN111794017A (en) * | 2020-06-29 | 2020-10-20 | 快思瑞科技(上海)有限公司 | High-stiffness pulp molding buffer material and preparation method thereof |
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| US5391424A (en) * | 1991-02-05 | 1995-02-21 | Kolzer; Klaus | Lightweight filler and a process for its manufacture |
| US20070044929A1 (en) * | 2005-03-11 | 2007-03-01 | Mohan Krishna K | Compositions containing expandable microspheres and an ionic compound, as well as methods of making and using the same |
| CN111794017A (en) * | 2020-06-29 | 2020-10-20 | 快思瑞科技(上海)有限公司 | High-stiffness pulp molding buffer material and preparation method thereof |
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