JP7154451B1 - Porous particles and method for producing the same - Google Patents
Porous particles and method for producing the same Download PDFInfo
- Publication number
- JP7154451B1 JP7154451B1 JP2022086511A JP2022086511A JP7154451B1 JP 7154451 B1 JP7154451 B1 JP 7154451B1 JP 2022086511 A JP2022086511 A JP 2022086511A JP 2022086511 A JP2022086511 A JP 2022086511A JP 7154451 B1 JP7154451 B1 JP 7154451B1
- Authority
- JP
- Japan
- Prior art keywords
- water
- porous particles
- fine cellulose
- resin
- soluble
- 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.)
- Active
Links
- 239000002245 particle Substances 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 99
- 239000000835 fiber Substances 0.000 claims abstract description 80
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 238000001694 spray drying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000011342 resin composition Substances 0.000 claims description 23
- 238000009835 boiling Methods 0.000 claims description 17
- 229920003169 water-soluble polymer Polymers 0.000 claims description 10
- -1 glycol ethers Chemical class 0.000 claims description 9
- HGASFNYMVGEKTF-UHFFFAOYSA-N octan-1-ol;hydrate Chemical compound O.CCCCCCCCO HGASFNYMVGEKTF-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 35
- 239000000463 material Substances 0.000 abstract description 8
- 229920002678 cellulose Polymers 0.000 description 47
- 239000001913 cellulose Substances 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000006185 dispersion Substances 0.000 description 25
- 238000001035 drying Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 21
- 238000005259 measurement Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000004898 kneading Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 238000011282 treatment Methods 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- 238000001000 micrograph Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 229920001131 Pulp (paper) Polymers 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000005192 partition Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011362 coarse particle Substances 0.000 description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000007385 chemical modification Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 239000002655 kraft paper Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000011122 softwood Substances 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SNAQINZKMQFYFV-UHFFFAOYSA-N 1-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOC SNAQINZKMQFYFV-UHFFFAOYSA-N 0.000 description 1
- RERATEUBWLKDFE-UHFFFAOYSA-N 1-methoxy-2-[2-(2-methoxypropoxy)propoxy]propane Chemical compound COCC(C)OCC(C)OCC(C)OC RERATEUBWLKDFE-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- HRWADRITRNUCIY-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)ethanol Chemical compound CC(C)OCCOCCO HRWADRITRNUCIY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- MXVMODFDROLTFD-UHFFFAOYSA-N 2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CCCCOCCOCCOCCOCCO MXVMODFDROLTFD-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- WOMTYMDHLQTCHY-UHFFFAOYSA-N 3-methylamino-1,2-propanediol Chemical compound CNCC(O)CO WOMTYMDHLQTCHY-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 240000006248 Broussonetia kazinoki Species 0.000 description 1
- 235000006716 Broussonetia kazinoki Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241001265525 Edgeworthia chrysantha Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 241000984084 Helianthemum nummularium subsp. grandiflorum Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 101100489867 Mus musculus Got2 gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 241000186514 Warburgia ugandensis Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007070 tosylation reaction Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
【課題】樹脂に対して分散性が良好であり、環境に配慮された素材を使った多孔質粒子を簡便な手法により効率よく低コストで得ることを課題とする。【解決手段】微細セルロース繊維スラリーと水溶性多孔質化剤を混合する工程、前記混合物を噴霧乾燥装置によって多孔質粒子を得る工程を備える、製造方法。微細セルロース繊維を主成分とする多孔質粒子であって、ＢＥＴ比表面積が２０～１００ｍ２／ｇ、嵩密度が２００ｇ／L未満、微細セルロース繊維の平均繊維径が１０～１０００ｎｍであることを特徴とする多孔質粒子とする。【選択図】図１An object of the present invention is to obtain porous particles that are excellent in dispersibility in a resin and that are made of an environmentally friendly material by a simple method, efficiently and at a low cost. A production method comprising the steps of mixing a fine cellulose fiber slurry and a water-soluble porosifying agent, and subjecting the mixture to a spray drying apparatus to obtain porous particles. Porous particles containing fine cellulose fibers as a main component, characterized by having a BET specific surface area of 20 to 100 m2/g, a bulk density of less than 200 g/L, and an average fiber diameter of the fine cellulose fibers of 10 to 1000 nm. Porous particles are used. [Selection drawing] Fig. 1
Description
本発明は微細セルロース繊維を主成分とする多孔質粒子、およびその製造方法に関する。また、多孔質粒子と樹脂とを複合化させた樹脂組成物、およびその樹脂組成物の成形体に関する。 TECHNICAL FIELD The present invention relates to porous particles containing fine cellulose fibers as a main component and a method for producing the same. The present invention also relates to a resin composition in which porous particles and a resin are combined, and a molded product of the resin composition.
ミクロフィブリル化セルロースやセルロースナノファイバー（ＣＮＦ）と呼ばれる微細セルロース繊維は軽量でありながら高弾性率・高強度という特徴から、複合材料用途の開発が盛んになされてきた。微細セルロース繊維の製造方法には、TEMPO酸化処理、酸処理、酵素処理などの化学的処理による方法や、高圧ホモジナイザー、摩砕機などの機械的処理による方法があるが、いずれの方法でもパルプを水に分散させた状態で微細化させるため、微細セルロース繊維は水分散体で得られる。この水分散体は高粘度であるために固形分濃度が著しく低いスラリーである。そのため、樹脂との複合材料化の手段として、樹脂とともにドライパルプを混錬する方法、水分が揮発するまで混錬する方法、凍結乾燥や噴霧乾燥で水分を除去して樹脂に添加する方法などが提案されている。 Fine cellulose fibers called microfibrillated cellulose and cellulose nanofibers (CNF) have been actively developed for use in composite materials because of their light weight, high elastic modulus, and high strength. Methods for producing fine cellulose fibers include chemical treatments such as TEMPO oxidation treatment, acid treatment and enzyme treatment, and mechanical treatments such as high-pressure homogenizers and grinders. The fine cellulose fibers are obtained in the form of an aqueous dispersion because they are finely dispersed in the liquid. This aqueous dispersion is a slurry with a remarkably low solid content concentration due to its high viscosity. Therefore, as a means of making a composite material with resin, there are methods such as kneading dry pulp with resin, kneading until moisture volatilizes, removing moisture by freeze drying or spray drying and adding it to resin. Proposed.
水分を除去したＣＮＦを得る手法として、例えば特許文献１では、ＴＥＭＰＯ酸化処理で得られる微細セルロース繊維を噴霧乾燥装置によって粉末化する方法が提案されている。しかし、この手法では乾燥すると微細セルロース繊維の繊維間に凝集力が働いてしまい、樹脂中では単繊維に分散させることができず、微細セルロース繊維が持つ本来の性能が発揮できない。 As a technique for obtaining CNF from which moisture has been removed, for example, Patent Document 1 proposes a method of pulverizing fine cellulose fibers obtained by TEMPO oxidation treatment with a spray drying apparatus. However, in this method, cohesive force acts between the fibers of the fine cellulose fibers when dried, so that the fine cellulose fibers cannot be dispersed into single fibers in the resin, and the original performance of the fine cellulose fibers cannot be exhibited.
特許文献２では、ＣＮＦにｔ－ブタノール、ベンゼン、１，４－ジオキサンなどの有機溶剤を添加して凍結乾燥した後に粉砕することで比表面積の大きなＣＮＦを製造する方法が提案されている。いずれの溶剤も氷点下では凍結するため、凍結乾燥することにより、繊維間に働く凝集力を阻害し、比表面積の大きい乾燥したＣＮＦを得ることができ、後工程で粉末にすることも可能である。しかし、凍結乾燥はタクトタイムが長く、粉末状態でＣＮＦを得るためには粉砕工程も必要となるため、非効率である。また、凍結乾燥以外の乾燥方法では、いずれの有機溶剤も沸点が低いため、他の高沸点有機溶剤で溶媒置換しない限り、水よりも先に有機溶剤が揮発してしまい、その後に水が揮発するため、繊維間に凝集力が働き高い比表面積を得ることはできない。また、溶媒置換は多量の有機溶剤を使用するためコストアップになり、さらに生産効率の観点やカーボンニュートラルやＳＤＧｓの観点から好ましくない。 Patent Document 2 proposes a method of producing CNF having a large specific surface area by adding organic solvents such as t-butanol, benzene, and 1,4-dioxane to CNF, freeze-drying the mixture, and then pulverizing it. Since any solvent freezes below the freezing point, freeze-drying inhibits the cohesive force acting between fibers, and it is possible to obtain dry CNF with a large specific surface area, which can be powdered in a post-process. . However, freeze-drying is inefficient because it requires a long tact time and requires a pulverization step to obtain CNF in a powder state. Also, in drying methods other than freeze-drying, all organic solvents have low boiling points, so unless the solvent is replaced with another high boiling point organic solvent, the organic solvent will evaporate before water, and then water will evaporate. Therefore, a cohesive force acts between fibers and a high specific surface area cannot be obtained. In addition, solvent replacement uses a large amount of organic solvent, resulting in an increase in cost, and is not preferable from the viewpoint of production efficiency, carbon neutrality, and SDGs.
特許文献３では、バクテリアセルロース又は微小繊維状セルロースに対してグリセリンや界面活性剤などの親水性液体および水溶性多糖類などの親水性固体を添加することで繊維間に働く凝集力を抑制し、多孔質化する方法が提案されている。多孔質であれば溶媒の浸透が良好となり、再分散性の改善や細孔への樹脂のアンカリングで微細セルロース繊維が有する特性の発現が期待できる。しかし、提案されている親水性液体は親水性が著しく高いため、多孔質化させる効果は低く、またセルロースとの親和性が良いため乾燥による除去が難しい。界面活性剤も同様に乾燥での除去はできない。不純物の残留は不都合が生じるおそれがあり、例えば混練後の樹脂組成物を利用する場面では不純物、特に界面活性剤がブリードアウトしてしまい、他部材との接着性や密着性に不具合が生じる。そのため、洗浄で界面活性剤を取り除く必要があり、非効率である一方、水溶性多糖類は繊維間の水素結合を阻害する効果はないため、そもそも多孔質化に貢献しない。 In Patent Document 3, by adding a hydrophilic liquid such as glycerin or a surfactant and a hydrophilic solid such as a water-soluble polysaccharide to bacterial cellulose or microfibrous cellulose, the cohesive force acting between fibers is suppressed. A method of making porous has been proposed. If it is porous, the penetration of the solvent will be good, and it can be expected that the characteristics of the fine cellulose fibers will be manifested by improving the redispersibility and anchoring the resin in the pores. However, since the proposed hydrophilic liquid has extremely high hydrophilicity, the effect of making it porous is low, and since it has a good affinity with cellulose, it is difficult to remove it by drying. Surfactants also cannot be removed by drying. Impurities remaining may cause problems. For example, when the resin composition is used after kneading, the impurities, particularly the surfactant, bleed out, resulting in poor adhesion and adhesion to other members. Therefore, it is necessary to remove the surfactant by washing, which is inefficient. On the other hand, the water-soluble polysaccharide does not have the effect of inhibiting hydrogen bonding between fibers, so it does not contribute to the formation of porosity in the first place.
特許文献４では、微細セルロース繊維の水系分散液に、その分散溶媒よりも沸点が高い有機溶剤を加えることで、乾燥時に働く凝集力を阻害し、再分散可能な微細セルロース繊維分散液を得る方法が提案されている。しかし、沸点が高いだけでは効率的に、または均一に凝集力を阻害することができず、樹脂中に均一に単繊維で分散させることはできない。また、沸点や親水性が高い溶剤を使用した場合、微細セルロース繊維中に残留してしまう恐れもある。 In Patent Document 4, an organic solvent having a boiling point higher than that of the dispersion solvent is added to an aqueous dispersion of fine cellulose fibers to inhibit the cohesive force acting during drying and obtain a redispersible fine cellulose fiber dispersion. is proposed. However, the high boiling point alone cannot efficiently or uniformly inhibit the cohesive force, and the single fibers cannot be uniformly dispersed in the resin. Also, when a solvent with a high boiling point or high hydrophilicity is used, it may remain in the fine cellulose fibers.
特許文献５では、微細繊維状セルロースに疎水性の無機微粒子を添加して再分散が可能となる方法が提案されているが、無機微粒子にはセルロース間の凝集を防ぐ効果が低いため、多孔質化させることはできず、さらに無機微粒子が原料中に残留するため、例えば不純物の混入が性能に直結しやすいプリント基板等の電子・電気部品用途等には適さない。 Patent Document 5 proposes a method in which hydrophobic inorganic fine particles are added to fine fibrous cellulose to enable redispersion. In addition, since inorganic fine particles remain in the raw material, it is not suitable for use in electronic and electric parts such as printed circuit boards, where the contamination of impurities is likely to directly affect the performance.
さらに、近年、カーボンニュートラルであることやマイクロプラスチックによる海洋汚染の社会問題から脱プラスチックの動きが盛んになっており、プラスチック製の微粒子を天然素材の環境にやさしい素材で代替する試みも盛んである。 Furthermore, in recent years, the social problem of marine pollution caused by carbon neutrality and microplastics has led to a growing movement to eliminate plastics. .
特許文献６では、マイクロビーズをセルロース粒子で代替する方法が提案されている。この手法も特許文献１と同じで微細セルロース繊維の水分散液を噴霧乾燥するため、表面が皴状であっても凝集はしており、樹脂中に均一に単繊維で分散させることはできないおそれがある。 Patent Document 6 proposes a method of substituting cellulose particles for microbeads. Since this method is also the same as in Patent Document 1, an aqueous dispersion of fine cellulose fibers is spray-dried, so even if the surface is wrinkled, it aggregates and may not be uniformly dispersed as single fibers in the resin. There is
本発明は上述の状況を鑑みて為されたものであって、樹脂に対して分散性が良好で、効率的に樹脂と複合化できる多孔質粒子を得ることを課題とする。また、このような多孔質粒子を簡便な手法により効率よく低コストで得ることを可能とする製造方法を提供することを目的とする。さらには、環境に配慮された素材を使った多孔質粒子を目指す。 The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain porous particles that have good dispersibility in a resin and can be efficiently combined with the resin. Another object of the present invention is to provide a production method that enables such porous particles to be obtained efficiently and at low cost by a simple technique. Furthermore, we aim to create porous particles using environmentally friendly materials.
本発明者は上記課題を解決するために鋭意検討した結果、特定の物性を備える多孔質粒子が樹脂に対する分散性に優れ、樹脂と複合化した際に樹脂組成物の物性の向上が期待できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the inventors of the present invention have found that porous particles having specific physical properties are excellent in dispersibility in resins and can be expected to improve the physical properties of resin compositions when combined with resins. He found this and completed the present invention.
すなわち、本発明は微細セルロース繊維を主成分とする多孔質粒子であって、ＢＥＴ比表面積が２０～１００ｍ２／ｇ、嵩密度が２００ｇ／Ｌ未満、微細セルロース繊維の平均繊維径が１０～１０００ｎｍであることを特徴とする多孔質粒子に関する。 That is, the present invention provides porous particles containing fine cellulose fibers as a main component, having a BET specific surface area of 20 to 100 m 2 /g, a bulk density of less than 200 g/L, and an average fiber diameter of the fine cellulose fibers of 10 to 1000 nm. It relates to porous particles characterized by:
前記多孔質粒子は水溶性高分子を含むことが好ましい。 The porous particles preferably contain a water-soluble polymer.
また、本発明は前記微細セルロース繊維と共に水溶性多孔質化剤を含むスラリーから得られる多孔質粒子に関する。 The present invention also relates to porous particles obtained from a slurry containing the fine cellulose fibers and a water-soluble porosifying agent.
前記水溶性多孔質化剤の沸点が１８０℃以上、水オクタノール分配係数が－１．２～０．８であることが好ましい。 The water-soluble porosifying agent preferably has a boiling point of 180° C. or higher and a water octanol distribution coefficient of −1.2 to 0.8.
また、本発明は、前記多孔質粒子及び樹脂を含む、樹脂組成物に関する。 The present invention also relates to a resin composition containing the porous particles and a resin.
さらに、本発明は、前記樹脂組成物を含む成形体に関する。 Furthermore, the present invention relates to a molded article containing the resin composition.
よりさらに、本発明は、微細セルロース繊維スラリーと水溶性多孔質化剤を混合する工程、前記混合物を噴霧乾燥装置によって多孔質粒子を得る工程を備える、多孔質粒子の製造方法に関する。水溶性多孔質化剤の沸点が１８０℃以上、且つ、水オクタノール分配係数が－１．２～０．８であることが好ましい。また、水溶性多孔質化剤がグリコールエーテル類またはカーボネート類であることが好ましい。 Furthermore, the present invention relates to a method for producing porous particles, comprising the steps of mixing a fine cellulose fiber slurry and a water-soluble porosifying agent, and subjecting the mixture to a spray drying apparatus to obtain porous particles. It is preferable that the water-soluble porosifying agent has a boiling point of 180° C. or higher and a water octanol partition coefficient of −1.2 to 0.8. Moreover, it is preferable that the water-soluble porosity agent is a glycol ether or a carbonate.
本発明では、微細セルロース繊維を主成分とした多孔質粒子であり、その比表面積が大きいことから、樹脂と複合化した際に多孔質粒子が繊維状に離解しやすく粗大物の発生が少ないため、樹脂組成物の物性を向上することができる。さらに嵩密度が２００ｇ／Ｌ未満であることで複合化時のトルクを低くでき、樹脂組成物の成形性や生産効率に優れる。 In the present invention, since the porous particles are mainly composed of fine cellulose fibers and have a large specific surface area, the porous particles are easily disaggregated into fibers when combined with a resin, and there is little generation of coarse particles. , the physical properties of the resin composition can be improved. Further, when the bulk density is less than 200 g/L, the torque during compounding can be reduced, and the moldability and production efficiency of the resin composition are excellent.
［多孔質粒子］
本発明の第１の態様は、微細セルロース繊維を主成分とする多孔質粒子であって、ＢＥＴ比表面積が２０～１００ｍ２／ｇ、嵩密度が２００ｇ／Ｌ未満、微細セルロース繊維の平均繊維径が１０～１０００ｎｍであることを特徴とする多孔質粒子である。「主成分」とは、多孔質粒子を構成する成分の中で最も含有率が高いものをいい、その含有比率が好ましくは５０重量％以上、さらに好ましくは７０重量％以上である。
[Porous particles]
A first aspect of the present invention is a porous particle containing fine cellulose fibers as a main component, having a BET specific surface area of 20 to 100 m 2 /g, a bulk density of less than 200 g/L, and an average fiber diameter of the fine cellulose fibers. is 10 to 1000 nm. The “main component” refers to the component with the highest content among the components constituting the porous particles, and the content is preferably 50% by weight or more, more preferably 70% by weight or more.
多孔質粒子のＢＥＴ比表面積は２０～１００ｍ２／ｇである。比表面積の測定はＢＥＴ法を用いる。ＢＥＴ比表面積が２０ｍ２／ｇ未満では比表面積が小さく、樹脂と複合化した際に、繊維状に分散することができず、樹脂組成物として期待される引張強度、弾性率、靭性といった強度物性の向上や耐熱性、低い線熱膨張率といった熱安定性の向上などの効果が乏しくなるおそれがある。多孔質粒子のＢＥＴ比表面積が１００ｍ２／ｇを超えると樹脂と複合化する際の粘度が著しく上昇し、例えば混錬機のローターに係るトルクが高くなる。この混錬トルクが高くなると、良好な分散状態を得るために投入されるエネルギーや時間を過分に要してしまい、生産効率が悪くコストがかかる。 The BET specific surface area of the porous particles is 20-100 m 2 /g. The BET method is used to measure the specific surface area. If the BET specific surface area is less than 20 m 2 /g, the specific surface area is small, and when it is combined with a resin, it cannot be dispersed in a fibrous form, and the strength physical properties such as tensile strength, elastic modulus, and toughness expected as a resin composition. There is a risk that the effects of improving heat resistance, improving thermal stability such as a low coefficient of linear thermal expansion, and the like will be poor. If the BET specific surface area of the porous particles exceeds 100 m 2 /g, the viscosity during compounding with the resin will markedly increase, resulting in, for example, increased torque on the rotor of the kneader. If this kneading torque becomes high, it takes an excessive amount of energy and time to obtain a good dispersion state, resulting in poor production efficiency and high costs.
多孔質粒子は嵩密度が２００ｇ／Ｌ未満である。嵩密度は公知の嵩密度測定器を用いて測定することができる。嵩密度が２００ｇ／Ｌ以上の場合、例えば混錬機を用いて、樹脂と多孔質粒子と複合化した際、混錬トルクが小さくなるというメリットはあるが、トルクが小さいということは比表面積が小さいということであり、多孔質粒子による樹脂の補強効果が小さくなる問題がある。 The porous particles have a bulk density of less than 200 g/L. Bulk density can be measured using a known bulk density measuring instrument. When the bulk density is 200 g/L or more, for example, when a resin and porous particles are combined using a kneader, there is an advantage that the kneading torque is small, but a small torque means that the specific surface area is This means that the porous particles are small, and there is a problem that the reinforcing effect of the resin by the porous particles is reduced.
多孔質粒子は化学修飾されていてもよい。ここでの「化学修飾」とは、微細セルロース繊維の水酸基のすべて、もしくは部分的に水酸基とは異なる官能基に置換する任意の処理を意味する。混練等の樹脂との複合化の際に使用する樹脂に応じて、修飾に適切な官能基があるため、置換する官能基は任意に設計することが好ましい。例えば汎用樹脂として代表的であるポリプロピレンやポリエチレンには水酸基とアシル化やエステル化させてアルキル基、シリル基、フェニル基等の疎水性を付与する官能基で化学修飾することが好ましい。セルロースの水酸基とのアシル化、エステル化は当該技術分野で周知・慣用であり、また粉末、水分散体、有機溶媒分散体といった微細セルロース繊維の状態ごとに適用できる化学修飾方法が異なるため、使用する化学修飾材料は特に限定されるものではない。特に、化学修飾としては、疎水化剤を用いてセルロースの水酸基を疎水性基に置換することが好ましい。このような疎水化の処理としては、アシル化、エステル化、アルキル化、エーテル化、トシル化、エポキシ化等の任意の疎水化が挙げられる。 Porous particles may be chemically modified. The term "chemical modification" as used herein means any treatment for substituting all or part of the hydroxyl groups of the fine cellulose fibers with functional groups different from hydroxyl groups. Since there are functional groups suitable for modification depending on the resin used for compounding with the resin such as kneading, it is preferable to arbitrarily design the functional group to be substituted. For example, polypropylene and polyethylene, which are typical general-purpose resins, are preferably chemically modified with a functional group that imparts hydrophobicity, such as an alkyl group, a silyl group, or a phenyl group, by acylating or esterifying a hydroxyl group. Acylation and esterification with hydroxyl groups of cellulose are well known and commonly used in the art, and chemical modification methods applicable to each state of fine cellulose fibers such as powder, aqueous dispersion, and organic solvent dispersion are different. The chemical modification material to be used is not particularly limited. In particular, as the chemical modification, it is preferable to replace the hydroxyl groups of cellulose with hydrophobic groups using a hydrophobizing agent. Such hydrophobization treatments include any hydrophobization such as acylation, esterification, alkylation, etherification, tosylation, and epoxidation.
［微細セルロース繊維］
本発明における微細セルロース繊維の平均繊維径は１０ｎｍ～１０００ｎｍである。繊維径がこの範囲であることで樹脂と複合化した際の分散性が良好となり、後述するような、微細セルロース繊維により期待される種々の効果が発現する。微細セルロース繊維の平均繊維径は、好ましくは１０ｎｍ～５００ｎｍ、さらに好ましくは１０ｎｍ～３００ｎｍ、さらにより好ましくは２０ｎｍ～２００ｎｍである。平均繊維径の測定は以下の手順で行う。まず、得られた（多孔質）粒子を試料台に載せ、高分解能電子顕微鏡（ＦＥ－ＳＥＭ）で２万倍で観察し、得られたＳＥＭ画像の水平方向、および垂直方向にラインを引く。次に、二つのラインで交差する少なくとも２０本以上のすべての繊維の繊維径を拡大画像から実測し、測定結果から数平均繊維径を算出する。さらに、試料台に載せた粉末の表面の少なくとも２箇所について同様に数平均繊維径を算出し、全ての数平均繊維径の平均値を平均繊維径とする。
[Fine cellulose fiber]
The average fiber diameter of the fine cellulose fibers in the present invention is 10 nm to 1000 nm. When the fiber diameter is within this range, the dispersibility when compounded with a resin is improved, and various effects expected from fine cellulose fibers, as described later, are exhibited. The average fiber diameter of the fine cellulose fibers is preferably 10 nm to 500 nm, more preferably 10 nm to 300 nm, still more preferably 20 nm to 200 nm. Measurement of the average fiber diameter is performed by the following procedure. First, the obtained (porous) particles are placed on a sample stage and observed with a high-resolution electron microscope (FE-SEM) at a magnification of 20,000, and horizontal and vertical lines are drawn on the obtained SEM image. Next, the fiber diameters of at least 20 or more fibers intersecting the two lines are actually measured from the enlarged image, and the number average fiber diameter is calculated from the measurement results. Further, the number average fiber diameter is similarly calculated for at least two points on the surface of the powder placed on the sample stage, and the average value of all the number average fiber diameters is taken as the average fiber diameter.
このような微細セルロース繊維は、セルロース繊維を微細化処理して得られる。セルロース繊維を微細化処理する装置は特に限定されるものではないが、例えば、高圧ホモジナイザー処理（マントン・ゴーリン型分散機による高圧分散処理）、ラニエタイプ圧力式ホモジナイザー、超高圧ホモジナイザー処理（アルテマイザーＴＭ（スギノマシン株式会社製））、ビーズミルや流星ミル等の分散装置、マスコロイダー（増幸産業株式会社製）等のホモジナイザー等が挙げられる。前記微細化処理装置は、一般的に生産効率が低いため、叩解機であらかじめ前処理を施すと生産効率が高くなるため好ましい。セルロース繊維の叩解度は特に限定しないが、微細化処理する前にダブルディスクリファイナー、ビーター等製紙用で使用している叩解機を前処理に使用することも可能である。特に高圧ホモジナイザーなどのオリフィスを通すタイプの微細化処理装置の場合、前処理で叩解をしないと原料が詰まるなど、安定した微細化処理ができなくなるおそれがある。 Such fine cellulose fibers are obtained by subjecting cellulose fibers to a fine-refining treatment. The apparatus for refining cellulose fibers is not particularly limited. (manufactured by Sugino Machine Co., Ltd.)), dispersing devices such as a bead mill and a meteor mill, and homogenizers such as a masscolloider (manufactured by Masuko Sangyo Co., Ltd.). Since the production efficiency of the pulverization apparatus is generally low, it is preferable to perform pretreatment with a beating machine because the production efficiency increases. The beating degree of the cellulose fibers is not particularly limited, but it is also possible to use a beating machine such as a double disc refiner or beater used for papermaking for pretreatment before the fineness treatment. In particular, in the case of an orifice type fine processing apparatus such as a high-pressure homogenizer, if the raw material is not beaten in the pretreatment, the raw material may be clogged and stable fine processing may not be possible.
微細化処理にあたり、使用可能なセルロース繊維は、特に限定はなく公知のものが使用でき、例えば、針葉樹晒クラフトパルプ（ＮＢＫＰ）、広葉樹晒クラフトパルプ（ＬＢＫＰ）、針葉樹晒サルファイトパルプ（ＮＢＳＰ）等の木材漂白化学パルプ、砕木パルプ（ＧＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケミカルサーモメカニカルパルプ（ＢＣＴＭＰ）等の機械パルプ；麻、竹、藁、ケナフ、三椏、楮、木綿等の非木材パルプ；古紙パルプが使用できる。これらのセルロース繊維の１種を単独で又は２種以上を組み合わせて用いることができる。本発明では、特にセルロースＩ型、セルロースＩＩ型等のセルロースの型は限定されないが、好ましくはコットン、コットンリンター、木材パルプに代表されるような、セルロースＩ型の天然繊維である。さらに好ましくは、繊維の解繊時に切断よりもフィブリル化が進行しやすい針葉樹由来の漂白木材パルプのＮＢＫＰである。再生セルロースに代表されるセルロースＩＩ型の繊維はセルロースＩ型の繊維に比べ結晶化度が低くフィブリル化処理を行う際に、短繊維化しやすく、樹脂と複合化した際の強度向上の効果が低くなるおそれがあるため好ましくない。 There are no particular limitations on the cellulose fibers that can be used in the pulverization treatment, and known ones can be used. For example, bleached softwood kraft pulp (NBKP), bleached hardwood kraft pulp (LBKP), bleached softwood sulfite pulp (NBSP), etc. mechanical pulp such as wood bleached chemical pulp, groundwood pulp (GP), thermomechanical pulp (TMP), chemical thermomechanical pulp (BCTMP); non-wood pulp such as hemp, bamboo, straw, kenaf, mitsumata, kozo, cotton; Waste paper pulp can be used. One type of these cellulose fibers can be used alone or two or more types can be used in combination. In the present invention, the type of cellulose such as cellulose type I and cellulose type II is not particularly limited, but cellulose type I natural fibers such as cotton, cotton linter, and wood pulp are preferred. More preferably, it is NBKP of bleached wood pulp derived from coniferous trees, which tends to undergo fibrillation rather than cutting during fibrillation. Cellulose type II fibers represented by regenerated cellulose have a lower degree of crystallinity than cellulose type I fibers, and when subjected to fibrillation treatment, they are easily made into short fibers, and the effect of improving strength when combined with a resin is low. It is not preferable because there is a possibility that
前記セルロース繊維を主体とするが、必要に応じてこれにカチオン化パルプ、マーセル化パルプ等の変性パルプ、レーヨン、ビニロン、ナイロン、アクリル、ポリエステル、ポリオレフィン、カーボン、アラミド等の合成繊維や化学繊維、またはミクロフィブリル化パルプを単独で、あるいは混合して併用することができる。本発明の多孔質粒子を構成する繊維全体あたり、セルロース繊維の比率は５０重量％以上であり、６０重量％以上が好ましく、７０重量％以上がさらに好ましい。 The cellulose fiber is mainly used, but if necessary, modified pulp such as cationized pulp and mercerized pulp, synthetic fibers such as rayon, vinylon, nylon, acrylic, polyester, polyolefin, carbon, aramid, and chemical fibers, Alternatively, microfibrillated pulp can be used alone or in combination. The ratio of the cellulose fibers is 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more, based on the total fibers constituting the porous particles of the present invention.
セルロース繊維はセルロース分子の持つ水酸基により、水に均一に分散することが可能であるが、そのスラリーの粘度は、セルロース繊維の繊維長と表面積に依存する。例えば、同じ重量のセルロース繊維が存在する場合であっても、セルロース繊維の繊維径が細ければ必然的に繊維本数が増え、それだけセルロースの表面積が増えるため、スラリーの粘度も必然的に上昇することになる。ＴＥＭＰＯ酸化処理などの化学処理によって得られる微細セルロース繊維はシングルナノオーダーの繊維径で得られるが、上記の理由から極めて粘度が高いため高濃度のスラリーを使うことができない。微細セルロース繊維を主成分とする多孔質粒子を得る本発明においては、濃度はコストに大きく影響を受けるため、好ましくない。 Cellulose fibers can be uniformly dispersed in water due to the hydroxyl groups of the cellulose molecules, but the viscosity of the slurry depends on the fiber length and surface area of the cellulose fibers. For example, even if cellulose fibers of the same weight are present, if the fiber diameter of the cellulose fibers is small, the number of fibers will inevitably increase, and the surface area of cellulose will increase accordingly, so the viscosity of the slurry will inevitably increase. It will be. Fine cellulose fibers obtained by chemical treatment such as TEMPO oxidation treatment can be obtained with a fiber diameter of single nano-order, but due to the above reason, the viscosity is extremely high, and a high-concentration slurry cannot be used. In the present invention in which porous particles having fine cellulose fibers as a main component are obtained, the concentration is greatly affected by the cost, which is not preferred.
一方、ＴＥＭＰＯ酸化処理などの化学処理によって得られる微細セルロース繊維は平均繊維径が１０ｎｍ未満のシングルナノオーダーであり繊維間に働く凝集力が強いため、本発明では多孔質粒子として得られないおそれが高く、粒子の状態で平均繊維径を測定することも難しい。そのため、カルボキシ基含有量が０．１ｍｍｏｌ／ｇ以上、少なくとも１．２ｍｍｏｌ／ｇ以上といったＴＥＭＰＯ酸化処理されたＣＮＦは本発明には好ましくない。よって、本発明の微細セルロース繊維は、カルボキシ基含有量が１．２ｍｍｏｌ／ｇ未満が好ましく、０．１ｍｍｏｌ／ｇ未満がさらに好ましい。仮に、平均繊維径を測定するのが困難な場合は透過型電子顕微鏡を用いる。０．０５％濃度の微細セルロース繊維の分散液を調製し、この分散液を親水化処理したカーボン被覆グリッド上に塗布し、観察試料とする。観察は最も細い繊維が確認できる倍率で行い、得られたＴＥＭ画像の水平方向、および垂直方向にラインを引く。次に、二つのラインで交差する少なくとも２０本以上のすべての繊維の繊維径を拡大画像から実測し、測定結果から数平均繊維径を算出する。さらに、観察試料の表面の少なくとも２箇所について同様に数平均繊維径を算出し、全ての数平均繊維径の平均値を平均繊維径とする。また、機械処理ＣＮＦのスラリーの平均繊維径を測定する場合も同様の方法で測定することができるが、観察は2万倍での倍率で行う。 On the other hand, fine cellulose fibers obtained by chemical treatment such as TEMPO oxidation treatment have an average fiber diameter of less than 10 nm and are single nano-order, and the cohesive force acting between the fibers is strong. It is expensive and it is also difficult to measure the average fiber diameter in the form of particles. Therefore, TEMPO-oxidized CNF having a carboxy group content of 0.1 mmol/g or more, or at least 1.2 mmol/g or more, is not preferable for the present invention. Therefore, the fine cellulose fibers of the present invention preferably have a carboxy group content of less than 1.2 mmol/g, more preferably less than 0.1 mmol/g. If it is difficult to measure the average fiber diameter, use a transmission electron microscope. A dispersion of fine cellulose fibers with a concentration of 0.05% is prepared, and this dispersion is applied onto a hydrophilized carbon-coated grid to obtain an observation sample. Observation is performed at a magnification that allows the thinnest fibers to be observed, and horizontal and vertical lines are drawn on the obtained TEM image. Next, the fiber diameters of at least 20 or more fibers intersecting the two lines are actually measured from the enlarged image, and the number average fiber diameter is calculated from the measurement results. Further, the number average fiber diameter is similarly calculated for at least two points on the surface of the observation sample, and the average value of all the number average fiber diameters is taken as the average fiber diameter. Also, when measuring the average fiber diameter of the mechanically treated CNF slurry, the same method can be used, but the observation is performed at a magnification of 20,000.
前記のカルボキシ基含有量の測定方法は、次のとおりである。乾燥重量０．５ｇのセルロース繊維を１００ｍＬビーカーにとり、イオン交換水を加えて全体で５５ｍＬとし、そこに０．０１Ｍ塩化ナトリウム水溶液５ｍＬを加えて分散液を調製し、セルロース繊維が十分に分散するまで該分散液を攪拌する。この分散液に０．１Ｍ塩酸を加えてｐＨを２．５～３に調整し、自動滴定装置（ＡＵＴ－５０、東亜ディーケーケー（株）製）を用い、０．０５Ｍ水酸化ナトリウム水溶液を待ち時間６０秒の条件で該分散液に滴下し、１分ごとの電導度及びｐＨの値を測定し、ｐＨ１１程度になるまで測定を続け、電導度曲線を得る。この電導度曲線から、水酸化ナトリウム滴定量を求め、次式により、セルロース繊維のカルボキシル基含有量を算出する。
カルボキシ基含有量（ｍｍｏｌ／ｇ）＝水酸化ナトリウム滴定量×水酸化ナトリウム水溶液濃度（０．０５Ｍ）／セルロース繊維の重量（０．５ｇ）
The method for measuring the carboxy group content is as follows. Take 0.5 g of dry weight cellulose fibers in a 100 mL beaker, add deionized water to make a total of 55 mL, add 5 mL of 0.01 M sodium chloride aqueous solution to prepare a dispersion, and wait until the cellulose fibers are sufficiently dispersed. The dispersion is stirred. 0.1 M hydrochloric acid is added to this dispersion to adjust the pH to 2.5 to 3, and an automatic titrator (AUT-50, manufactured by Toa DKK Co., Ltd.) is used to add 0.05 M sodium hydroxide aqueous solution for a waiting time. It is added dropwise to the dispersion for 60 seconds, and the conductivity and pH values are measured every minute, and the measurement is continued until the pH reaches about 11 to obtain a conductivity curve. From this conductivity curve, the titration amount of sodium hydroxide is determined, and the carboxyl group content of the cellulose fiber is calculated by the following formula.
Carboxy group content (mmol/g) = sodium hydroxide titration amount x sodium hydroxide aqueous solution concentration (0.05 M)/weight of cellulose fiber (0.5 g)
セルロース繊維はその水酸基により、脱水工程において繊維同士が水素結合を行う性質を持っている。この水素結合形成の工程において例えば紙などのシートの場合は強度が発現する一方で、繊維間の相互作用により乾燥工程における収縮が生じる。特に繊維径が細くなるに従い繊維の剛度が下がり、また繊維間に働く凝集力が大きくなるため、この収縮が顕著に見られる。また極度にフィブリル化が進んだ繊維を用いて作成したシートは繊維間が完全に密着するために作成したフィルムは透明化することが知られている。つまり、通常の脱水や乾燥方法では微細セルロース繊維の状態で粒子を得ることは困難である。このため、乾燥時の収縮を抑えること、または繊維間の水素結合を阻害させることが必要となる。これまでに提案されている具体的な手法は、微細セルロース繊維をアセトンのような親水性の溶媒に置換した後、更にトルエンとアセトンの混合溶媒といったより疎水性の高い溶媒に置換して乾燥させる等の方法が提案されている。しかしながら、この手法は２つの問題点がある。まず一つは分散溶媒の水からアセトンに溶媒置換する作業である。セルロース繊維は、繊維径が細くなるに従い保水性が高くなるため、水から溶媒への置換は非常に時間のかかる作業となっており実生産の面で生産性を下げる要因となっている。また、疎水性の高い溶媒で置換されているため、水素結合は阻害されており、溶媒の表面張力も低いため、凝集力も水に比べれば小さくなるものの、収縮は生じるため、微細セルロース繊維が本来有していた大きな比表面積の低下は免れない。 Cellulose fibers have the property of hydrogen bonding between fibers in the dehydration process due to their hydroxyl groups. In the case of a sheet such as paper, for example, strength is developed in the process of hydrogen bond formation, while shrinkage occurs in the drying process due to interaction between fibers. In particular, as the fiber diameter becomes thinner, the rigidity of the fiber decreases and the cohesive force acting between the fibers increases, so this shrinkage is conspicuous. Also, it is known that a film produced by using extremely fibrillated fibers becomes transparent because the fibers are completely adhered to each other. In other words, it is difficult to obtain particles in the state of fine cellulose fibers by ordinary dehydration or drying methods. Therefore, it is necessary to suppress shrinkage during drying or inhibit hydrogen bonding between fibers. A specific method that has been proposed so far is to replace fine cellulose fibers with a hydrophilic solvent such as acetone, then replace with a more hydrophobic solvent such as a mixed solvent of toluene and acetone, and then dry. Other methods have been proposed. However, this method has two problems. The first is the task of replacing the dispersion solvent, water, with acetone. Cellulose fibers have a higher water holding capacity as the fiber diameter becomes smaller, so the replacement of water with a solvent is a very time-consuming task, which is a factor in lowering productivity in terms of actual production. In addition, since it is substituted with a highly hydrophobic solvent, hydrogen bonding is inhibited and the surface tension of the solvent is low, so although the cohesive force is smaller than that of water, shrinkage occurs. A decrease in the large specific surface area that was possessed is unavoidable.
そこで、本発明の多孔質粒子は、微細セルロース繊維と共に水溶性多孔質化剤を含むスラリーから得られるものが好ましい。具体的には、微細化処理後の微細セルロース繊維を収縮、および凝集することなく水を除去する方法として、水溶性多孔質化剤を含むスラリーを乾燥することで、生産効率を大幅に改善することができる。この水溶性多孔質化剤は沸点が１８０℃以上であることが好ましい。更に、本発明では、水溶性多孔質剤の添加量の調整により多孔質粒子の比表面積を制御することができる。例えば、本発明では、微細セルロース繊維１００重量（質量）部に対して水溶性多孔質化剤を好ましくは５０～１０００重量部の割合で使用することができる。 Therefore, the porous particles of the present invention are preferably obtained from a slurry containing fine cellulose fibers and a water-soluble porosifying agent. Specifically, as a method for removing water without shrinking or aggregating the fine cellulose fibers after the refining process, drying a slurry containing a water-soluble porosifying agent greatly improves production efficiency. be able to. This water-soluble porosifying agent preferably has a boiling point of 180° C. or higher. Furthermore, in the present invention, the specific surface area of the porous particles can be controlled by adjusting the amount of the water-soluble porosity agent added. For example, in the present invention, the water-soluble porosifying agent can be used preferably in a proportion of 50 to 1000 parts by weight per 100 parts by weight (mass) of the fine cellulose fibers.
本発明で使用される水溶性多孔質化剤は特に限定されるものではないが、水溶性多孔質化剤の沸点は、１８０℃以上であることが好ましい。繊維間の水素結合は、乾燥時の水分が１０～２０重量％の間で形成されることが知られている。この水素結合が形成される際に水溶性多孔質化剤が粒子中に存在し、かつ繊維間に働く水素結合・凝集力を阻害し、多孔質化が可能となる。沸点が１８０℃未満の水溶性多孔質化剤を用いた場合は、添加量を多くしても乾燥工程において揮発してしまい、十分に多孔質化することができない。そのため沸点が１８０℃以上の水溶性多孔質化剤が好ましいが、より好ましくは２００℃以上である。例えばヘキサノールよりも少ない分子量の一級アルコール等は、水溶性と疎水性をあわせ持つ材料であるが、乾燥工程において水よりも揮発しやすいため十分に水素結合、および凝集力を阻害することができないため本発明においては用いることはできない。但し、水溶性多孔質化剤の蒸気で満たした空気を用いて乾燥したり、水よりも蒸気圧の低い溶媒を用いて多段乾燥を用いる等の通常の乾燥条件とは異なる乾燥方法を用いた場合は必ずしも沸点が１８０℃以上である必要はない。 Although the water-soluble porosifying agent used in the present invention is not particularly limited, the boiling point of the water-soluble porosifying agent is preferably 180° C. or higher. Hydrogen bonds between fibers are known to form between 10 and 20% by weight of moisture when dry. When the hydrogen bonds are formed, the water-soluble porosifying agent is present in the particles and inhibits the hydrogen bonds and cohesive forces acting between the fibers, thereby enabling porosity. When a water-soluble porosifying agent having a boiling point of less than 180° C. is used, even if it is added in a large amount, it volatilizes during the drying process and sufficient porosity cannot be achieved. Therefore, a water-soluble porosifying agent having a boiling point of 180° C. or higher is preferred, and a boiling point of 200° C. or higher is more preferred. For example, primary alcohols with a molecular weight smaller than hexanol are materials that have both water solubility and hydrophobicity, but they are more volatile than water during the drying process, so they cannot sufficiently inhibit hydrogen bonding and cohesion. It cannot be used in the present invention. However, a drying method different from the usual drying conditions was used, such as drying using air filled with the vapor of the water-soluble porosifying agent, or using multi-stage drying using a solvent with a lower vapor pressure than water. In that case, the boiling point does not necessarily have to be 180°C or higher.
水溶性多孔質化剤は、水への溶解度が１０重量％以上のものが好ましく、２０重量％以上のものがより好ましい。水への溶解度が１０重量％未満の多孔質化剤を用いた場合には、多孔質化剤の添加量が限られるため、目的とするＢＥＴ比表面積を多孔質化剤の添加量のみでコントロールすることが困難となりうる。また乾燥が進むに従い溶媒量が減少することで溶解できない多孔質化剤が分離するため、均一に多孔化することが困難となりうる。なお、このような疎水性の多孔質化剤は乳化剤等によりエマルジョン化することで、ある程度均一に多孔化することが可能であるが、均一性は水溶性多孔質化剤に劣る。一方、水への溶解度が１０重量％以上の多孔質化剤を用いた場合には、スラリーに均一に分散可能であり、また、水への溶解性が高いので乾燥工程で分離しないため、乾燥工程において均一に水素結合を阻害することで細孔を均一に作ることができる。 The water-soluble porosifying agent preferably has a solubility in water of 10% by weight or more, more preferably 20% by weight or more. When a porosifying agent having a solubility in water of less than 10% by weight is used, the amount of the porosifying agent added is limited, so the desired BET specific surface area is controlled only by the amount of the porosifying agent added. can be difficult to do. In addition, as the drying progresses, the amount of the solvent decreases and the insoluble porosifying agent separates, making it difficult to achieve uniform porosity. Such a hydrophobic porosifying agent can be emulsified with an emulsifier or the like to make it porous to some extent uniformly, but the homogeneity is inferior to that of a water-soluble porosifying agent. On the other hand, when a porosifying agent having a solubility in water of 10% by weight or more is used, it can be uniformly dispersed in the slurry, and since it is highly soluble in water, it does not separate in the drying process, so it is difficult to dry. Pores can be made uniformly by inhibiting hydrogen bonding uniformly in the process.
水溶性多孔質化剤は、水オクタノール分配係数が－１．２～０．８であることが好ましく、－１．０～０．６であることがさらに好ましく、－０．５～０．５であることがより好ましく、０～０．４であることがさらにより好ましくい。水オクタノール分配係数は親水性および疎水性の評価値であり、ｎ－オクタノールと水を入れたフラスコ中に水溶性多孔質化剤を添加した後、振とうし、それぞれの相における水溶性多孔質化剤の濃度から以下の式で算出される。
「水オクタノール分配係数」＝Ｌｏｇ１０（オクタノール相中濃度／水相中濃度）
この水オクタノール分配係数の値が低すぎると高親水性のためにセルロース繊維間の凝集を引き起こすおそれがある。また、値が高すぎる場合は水溶性多孔質化剤の疎水性が高く、スラリーへ添加できる量が限られるため、目的とする性能が得られないおそれがある。
The water-soluble porosifying agent preferably has a water octanol partition coefficient of -1.2 to 0.8, more preferably -1.0 to 0.6, and -0.5 to 0.5. is more preferred, and 0 to 0.4 is even more preferred. The water octanol partition coefficient is a measure of hydrophilicity and hydrophobicity, and after adding a water-soluble porosifying agent into a flask containing n-octanol and water, it is shaken to determine the water-soluble porosity in each phase. It is calculated by the following formula from the concentration of the agent.
"Water octanol partition coefficient" = Log10 (concentration in octanol phase/concentration in water phase)
If the value of this water octanol partition coefficient is too low, aggregation between cellulose fibers may occur due to high hydrophilicity. On the other hand, if the value is too high, the hydrophobicity of the water-soluble porosifying agent is high and the amount that can be added to the slurry is limited, so there is a possibility that the desired performance cannot be obtained.
本発明で用いることのできる水溶性多孔質化剤としては具体的には次のようなものがある。例えば１、５－ペンタンジオール、１-メチルアミノ-２，３-プロパンジオール等の高級アルコール類、イプロシンカプロラクトン、α－アセチル－γ－ブチルラクトン等のラクトン類、ジエチレングリコール、１，３-ブチレングリコール、プロピレングリコール等のグリコール類、トリエチレングリコールジメチルエーテル、トリプロピレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールブチルメチルエーテル、テトラエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、テトラエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノイソプロピルエーテル、エチレングリコールモノイソブチルーテル、トリプロピレングリコールモノメチルエーテルジエチレングリコールジエチルエーテル等のグリコールエーテル類、プロピレンカーボネートやエチレンカーボートなどのカーボネート類、更にその他にグリセリン、Ｎ-メチルピロリドン等が挙げられるがその限りではない。これらの中でもグリコールエーテル類やカーボネート類は高沸点であり、かつ水への溶解度が高いものでも水／オクタノール分配係数が低いものが多いため、本発明において最も適している。 Specific water-soluble porosifying agents that can be used in the present invention include the following. For example, higher alcohols such as 1,5-pentanediol and 1-methylamino-2,3-propanediol, lactones such as iprocincaprolactone and α-acetyl-γ-butyllactone, diethylene glycol and 1,3-butylene glycol. , propylene glycol and other glycols, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, triethylene glycol monobutyl ether , tetraethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, tripropylene glycol monomethyl ether diethylene glycol diethyl ether, propylene carbonate, ethylene carbonate, etc. carbonates, glycerin, N-methylpyrrolidone, etc., but not limited thereto. Among these, glycol ethers and carbonates are most suitable for the present invention, since many of them have high boiling points and low water/octanol partition coefficients even though they have high solubility in water.
本発明で使用されるスラリーは、微細セルロース繊維と水溶性多孔質化剤以外に繊維間を繋ぐためのバインダーとして水溶性高分子を該セルロース繊維１００重量部に対して３～８０重量部、好ましくは５～５０重量部、さらに好ましくは１０～３０重量部含むことが好ましい。水溶性高分子は、接着剤としての機能以外に、セルロースの分散性を向上させる機能を発揮することができる。均一な細孔を得るためには、スラリー中に繊維が均一に分散する必要があるが、水溶性高分子はセルロース繊維の表面に定着することで保護コロイドに似た役割を果たすため分散性が向上する。水溶性高分子の添加量が３重量部未満となると、微細セルロース繊維の分散性が悪化するため、均一な細孔を得ることが困難となる。一方、８０重量部よりも多い場合には、水溶性高分子が細孔を埋めてしまう形となり、樹脂との複合化時に分散できないため好ましくない。 The slurry used in the present invention preferably contains 3 to 80 parts by weight of a water-soluble polymer as a binder for connecting fibers in addition to the fine cellulose fibers and the water-soluble porosifying agent, based on 100 parts by weight of the cellulose fibers. preferably contains 5 to 50 parts by weight, more preferably 10 to 30 parts by weight. The water-soluble polymer can exhibit a function of improving the dispersibility of cellulose in addition to its function as an adhesive. In order to obtain uniform pores, it is necessary to disperse the fibers uniformly in the slurry. improves. If the amount of the water-soluble polymer added is less than 3 parts by weight, the dispersibility of the fine cellulose fibers deteriorates, making it difficult to obtain uniform pores. On the other hand, if the amount is more than 80 parts by weight, the water-soluble polymer fills the pores and cannot be dispersed when being combined with the resin, which is not preferable.
前記水溶性高分子としては、メチルセルロース、カルボキシメチルセルロース（ＣＭＣ）、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシアルキルセルロース等のセルロース誘導体、リン酸エステル化デンプン、カチオン化デンプン、コーンスターチ等の多糖類の誘導体を使用することが好ましい。特に、セルロース誘導体はセルロース繊維との相性が良く、スラリー中の分散性を良好にできるため特に好ましい。 Examples of the water-soluble polymer include cellulose derivatives such as methylcellulose, carboxymethylcellulose (CMC), hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and hydroxyalkylcellulose, and polysaccharides such as phosphate esterified starch, cationic starch, and corn starch. It is preferred to use derivatives of In particular, cellulose derivatives are particularly preferred because they have good compatibility with cellulose fibers and can improve dispersibility in slurry.
この他に微細セルロース繊維、及び水溶性多孔質化剤を含むスラリーには、前記水溶性高分子以外にも填料を含むことが可能である。例えば、シリカ粒子、アルミナ粒子といった無機填料、シリコーンパウダー等の有機填料等を使用することが可能である。これらの粒子は、多孔質粒子の細孔や比表面積に影響を与えない程度に添加可能であるが、できるだけ平均粒子径が２μｍ未満のものを使用する方が好ましい。平均粒子径が２μｍ以上になると、粒子間の隙間により細孔径の大きな孔が開いてしまい、嵩が高くなりすぎるため好ましくない。なお、これらの填料はスラリーの粘度を下げる効果があるためにスラリー濃度を上げることが可能となり生産効率を上げるのに好適である。一方、添加量が多すぎると、添加する粒子によっては比表面積の低下や逆に極端な上昇が起こり、また不純物を増やすことになるため好ましくない。 In addition, a slurry containing fine cellulose fibers and a water-soluble porosifying agent may contain a filler other than the water-soluble polymer. For example, it is possible to use inorganic fillers such as silica particles and alumina particles, and organic fillers such as silicone powder. These particles can be added to the extent that they do not affect the pores and specific surface area of the porous particles, but it is preferable to use particles with an average particle size of less than 2 μm as much as possible. If the average particle diameter is 2 μm or more, pores with large pore diameters are opened due to gaps between particles, and the bulk becomes too high, which is not preferable. Since these fillers have the effect of lowering the viscosity of the slurry, it is possible to raise the slurry concentration, which is suitable for raising production efficiency. On the other hand, if the amount added is too large, depending on the particles added, the specific surface area may be decreased or, conversely, extremely increased, and impurities may be increased, which is not preferable.
本発明に用いるスラリーの溶媒は基本的に水を使用する必要があるが、乾燥効率を向上させることを目的としてメタノールやエタノール、ｔ－ブチルアルコール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、ジエチルエーテル、エチルメチルエーテル等のエーテル類等の水よりも蒸気圧の高い溶媒を溶媒全体量の５０重量％まで添加することが可能である。これらの溶媒を５０重量％以上添加すると微細セルロース繊維の分散性が悪くなり細孔が不均一になるため好ましくない。 The solvent of the slurry used in the present invention basically needs to use water, but alcohols such as methanol, ethanol and t-butyl alcohol, acetone, ketones such as A solvent having a higher vapor pressure than water, such as ethers such as diethyl ether and ethyl methyl ether, can be added up to 50% by weight of the total amount of the solvent. If 50% by weight or more of these solvents are added, the dispersibility of the fine cellulose fibers becomes poor and the pores become non-uniform, which is not preferable.
本発明において、微細セルロース繊維及び水溶性多孔質化剤を含むスラリーを粒子状に乾燥する手法としては、特に限定はされないが、噴霧乾燥を好適に用いることができる。 In the present invention, the method for drying the slurry containing the fine cellulose fibers and the water-soluble porosifying agent into particles is not particularly limited, but spray drying can be preferably used.
噴霧乾燥は、公知の噴霧乾燥装置を用いることができる。噴霧機としては、ディスク型アトマイザ―や加圧ノズルによるものがあり、加圧ノズルには２流体ノズル、３流体ノズルが挙げられる。使用する噴霧機は粒径やスラリーの性状により適宜選択することができるが、本発明においてはノズル方式の場合、微細セルロース繊維の分散不良による目詰まりの懸念があるため、ディスク型アトマイザ―が好ましい。 A known spray drying apparatus can be used for spray drying. The atomizer includes a disk-type atomizer and a pressurized nozzle, and the pressurized nozzle includes a two-fluid nozzle and a three-fluid nozzle. The atomizer to be used can be appropriately selected depending on the particle size and the properties of the slurry, but in the case of the nozzle method in the present invention, there is a concern of clogging due to poor dispersion of the fine cellulose fibers, so a disk-type atomizer is preferable. .
本発明で用いる噴霧乾燥装置としては、前記仕様に限定されるものではないが、一般に市販されている噴霧乾燥装置、例えば大川原化工機株式会社製のＣＬ－８ｉなどを用いることができる。 The spray drying apparatus used in the present invention is not limited to the specifications described above, but a generally commercially available spray drying apparatus such as CL-8i manufactured by Okawara Kakoki Co., Ltd. can be used.
噴霧機は一般的に乾燥炉内に設置してあるため、得られる粒子は乾燥状態で回収されるが、さらに他の乾燥装置を用いて、残留溶媒を揮発させてもよい。 The atomizer is generally installed in a drying oven so that the resulting particles are recovered in a dry state, but other drying equipment may be used to volatilize residual solvent.
多孔質粒子の固形分は８０重量％以上であることが好ましく、８５重量％以上であることがさらに好ましく、９０重量％以上であることがより好ましい。 The solid content of the porous particles is preferably 80% by weight or more, more preferably 85% by weight or more, and even more preferably 90% by weight or more.
［樹脂組成物］
本発明の第２の態様は、前記の多孔質粒子及び樹脂を含む、樹脂組成物である。
[Resin composition]
A second aspect of the present invention is a resin composition comprising the above porous particles and a resin.
本発明の樹脂組成物には熱可塑性樹脂、熱硬化性樹脂、ゴムを用いることができる。使用できる樹脂の種類に特に制限はないが、熱可塑性樹脂の例としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ乳酸樹脂、ポリビニルアルコール樹脂、ポリアミド樹脂、アクリロニトリル－ ブタジエン－ スチレン樹脂、アクリロニトリル－ スチレン樹脂、ポリメチルメタクリレート樹脂、ポリ塩化ビニリデン樹脂、エチレンビニルアルコール樹脂、ポリアクリロニトリル樹脂、ポリアセタール樹脂、ポリケトン樹脂、および環状ポリオレフィン樹脂が挙げられる。熱硬化性樹脂の例としては、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂などが挙げられる。ゴムの例としては天然ゴム、ポリイソプレンゴム、スチレン－ ブタジエン共重合体ゴム 、ポリブタジエンゴム、ブチルゴム、ニトリルゴム、クロロプレンゴム、アクリルゴム、フッ素ゴム、エチレンプロピレンゴム、クロロスルホン化ポリエチレン、ウレタンゴム、シリコーンゴムなど挙げられる。その他、本発明の性能を損なわない範囲で、樹脂組成物には消泡剤、防腐剤、充填剤、着色剤、可塑剤、レベリング剤、導電剤、帯電防止剤、紫外線吸収剤、消臭剤、耐熱材等の助剤等や強化繊維、導電繊維、耐熱繊維等の繊維材料を適宜混合することできる。 Thermoplastic resins, thermosetting resins, and rubbers can be used for the resin composition of the present invention. The type of resin that can be used is not particularly limited, but examples of thermoplastic resins include polyethylene resin, polypropylene resin, polylactic acid resin, polyvinyl alcohol resin, polyamide resin, acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, poly Examples include methyl methacrylate resins, polyvinylidene chloride resins, ethylene vinyl alcohol resins, polyacrylonitrile resins, polyacetal resins, polyketone resins, and cyclic polyolefin resins. Examples of thermosetting resins include epoxy resins, phenolic resins, melamine resins, urea resins, unsaturated polyester resins, and the like. Examples of rubber include natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, butyl rubber, nitrile rubber, chloroprene rubber, acrylic rubber, fluororubber, ethylene propylene rubber, chlorosulfonated polyethylene, urethane rubber, and silicone. Examples include rubber. In addition, the resin composition contains antifoaming agents, preservatives, fillers, colorants, plasticizers, leveling agents, conductive agents, antistatic agents, ultraviolet absorbers, and deodorants within the range that does not impair the performance of the present invention. , auxiliaries such as heat-resistant materials, and fiber materials such as reinforcing fibers, conductive fibers, and heat-resistant fibers can be appropriately mixed.
本発明の樹脂組成物は、様々な成形方法で成形品として得ることができる。樹脂の種類や求める成形品の形によって適切な成形方法は適宜使い分ける必要があるが、例えば、押出成形、射出成形、熱プレス成形、溶融押出成形、ブロー成形、真空成型、加熱成形などが挙げられる。 The resin composition of the present invention can be obtained as molded articles by various molding methods. Depending on the type of resin and the desired shape of the molded product, it is necessary to select an appropriate molding method. Examples include extrusion molding, injection molding, hot press molding, melt extrusion molding, blow molding, vacuum molding, and heat molding. .
多孔質粒子は、本発明の第１の態様における上記説明が第２の態様にも当てはまる。 As for the porous particles, the above description of the first aspect of the invention also applies to the second aspect.
多孔質粒子及び樹脂を複合化させる手法としては特に限定はなく、溶融混練、乾式混合等の公知の手法が挙げられるが、溶融混練をすることが好ましい。混練にあたり、微細セルロース繊維が多孔質の粒子状であることにより、樹脂と均一に分散することができる。また、樹脂の種類に応じた化学修飾を付与しておくことができる。混練には、押出機、ミキシングローラ、ニーダ、ミキサー等の公知の混練機を用いることができる。 The method for combining the porous particles and the resin is not particularly limited, and includes known methods such as melt-kneading and dry-mixing, but melt-kneading is preferred. In kneading, fine cellulose fibers can be uniformly dispersed with the resin because they are in the form of porous particles. Moreover, it is possible to impart chemical modification in accordance with the type of resin. For kneading, known kneaders such as extruders, mixing rollers, kneaders and mixers can be used.
［成形体］
本発明の第３の態様は、樹脂組成物を含有する成形体である。
[Molded body]
A third aspect of the present invention is a molded article containing a resin composition.
樹脂組成物は、本発明の第２の態様における上記説明が第３の態様にも当てはまる。 Regarding the resin composition, the above description of the second aspect of the present invention also applies to the third aspect.
成形体とは、フィルム状、シート状、構造体等の任意の形態を指し、樹脂組成物を用いて作製される。成形体を作製する方法は特に限定はなく公知の手法が用いられ、例えば、射出成形、押出成形、ブロー成形、プレス成形等が適用できる。 A molded article refers to any form such as a film, sheet, or structure, and is produced using a resin composition. The method for producing the molded article is not particularly limited, and a known technique is used, for example, injection molding, extrusion molding, blow molding, press molding, etc. can be applied.
成形体は、使用目的に応じて、その形態や作製方法を選択できる。電子機器、家電製品、各種の容器、建材、家具、文具、自動車、家庭用品に使用されている部材に代えて用いることができる。例えば、電子機器や家電製品の筐体および外装部品、各種の収納ケース、食器類、建材のインテリア部材、自動車の内装材、その他の日常生活用品にも使用することができる。 The shape and production method of the molded body can be selected according to the purpose of use. It can be used in place of members used in electronic equipment, home appliances, various containers, building materials, furniture, stationery, automobiles, and household goods. For example, it can be used for housings and exterior parts of electronic devices and home appliances, various storage cases, tableware, interior materials for building materials, interior materials for automobiles, and other daily necessities.
［多孔質粒子の製造方法］
本発明の第４の態様は、微細セルロース繊維スラリーと水溶性多孔質化剤を混合する工程、前記混合物を噴霧乾燥装置によって多孔質粒子を得る工程を備える、多孔質粒子の製造方法である。ここでの微細セルロース繊維、スラリー、水溶性多孔質化剤及び多孔質粒子については、本発明の他の態様における説明が第４の態様にも当てはまる。また、本発明の第４の態様の製造方法により、本発明の第１の態様である多孔質粒子を効率的に製造することができる。
[Method for producing porous particles]
A fourth aspect of the present invention is a method for producing porous particles, comprising the steps of mixing a fine cellulose fiber slurry and a water-soluble porosifying agent, and subjecting the mixture to a spray drying apparatus to obtain porous particles. Regarding the fine cellulose fibers, the slurry, the water-soluble porosifying agent and the porous particles herein, the description of the other aspects of the invention also applies to the fourth aspect. Moreover, the porous particles of the first aspect of the present invention can be efficiently produced by the production method of the fourth aspect of the present invention.
本発明の多孔質粒子は、微細セルロース繊維スラリーと水溶性多孔質化剤を混合する工程、及び、前記混合物を噴霧乾燥装置によって多孔質粒子を得る工程を少なくとも含む製造方法により得ることができる。微細セルロース繊維スラリーと水溶性多孔質化剤を混合する工程には、さらに水溶性高分子を混合してもよい。水溶性高分子は、本発明の他の態様における説明がここでも当てはまる。 The porous particles of the present invention can be obtained by a production method including at least a step of mixing a fine cellulose fiber slurry and a water-soluble porosifying agent, and a step of subjecting the mixture to a spray drying apparatus to obtain porous particles. A water-soluble polymer may be further mixed in the step of mixing the fine cellulose fiber slurry and the water-soluble porosifying agent. As for the water-soluble polymer, the description in the other aspects of the invention applies here as well.
以下、本発明を実施例及び比較例を用いてより具体的に説明するが、本発明の範囲は実施例に限定されるものではない。
（実施例中の測定項目および試験方法）
EXAMPLES The present invention will be described in more detail below using examples and comparative examples, but the scope of the present invention is not limited to the examples.
(Measurement items and test methods in Examples)
［セルロース粒子の固形分測定］
セルロース粒子を５ｇ採取し、秤量瓶に入れて乾燥前の重量を測定後、１０５℃のオーブンで恒量に達するまで乾燥し、乾燥後の重量を測定する。秤量瓶の重量を差し引いた乾燥前後のセルロース粒子の重量から次式で算出した。
固形分（％） ＝ 乾燥後重量（ｇ）／ 乾燥前重量（ｇ） × １００
[Measurement of solid content of cellulose particles]
5 g of cellulose particles are sampled, placed in a weighing bottle, weighed before drying, dried in an oven at 105° C. until constant weight is reached, and weighed after drying. It was calculated by the following formula from the weight of the cellulose particles before and after drying after subtracting the weight of the weighing bottle.
Solid content (%) = weight after drying (g) / weight before drying (g) x 100
［ＢＥＴ比表面積の測定］
測定には比表面積測定機（Ｂｅｌｓｏｒｐ ｍａｘ、マイクロトラック・ベル社製）を用いた。吸着ガス：窒素、サンプル量：０．１ｇ、前処理：１２０℃・3時間の条件で測定を行い、相対圧０．０５～０．３０（Ｐ／Ｐ０）の範囲の測定データからＢＥＴ Ｐｌｏｔを作成し、ＢＥＴ比表面積を算出した。
[Measurement of BET specific surface area]
A specific surface area measuring machine (Belsorp max, manufactured by Microtrack Bell) was used for the measurement. Adsorbed gas: nitrogen, sample amount: 0.1 g, pretreatment: Measured under the conditions of 120 ° C. and 3 hours, and BET plot from the measurement data in the range of relative pressure 0.05 to 0.30 (P / P0) It was created and the BET specific surface area was calculated.
［粒子径測定］
測定にはレーザー回折式粒度分布計（型式：ＬＡ－９５０、堀場製作所社製）を用いた。セルロース粒子をアセトン１０ｍＬに少量添加し、マグネチックスターラーで攪拌した後、超音波洗浄機（ブランソン社製）で１０秒間分散させる。予めアセトンを入れておいた測定セルに測定領域に達するまで分散液を添加した後、測定を行う。屈折率はセルロース粒子：１．４７、アセトン：１．３５９１に設定し、粒度分布を得た。平均粒子径はメディアン径（ｄ５０）とした。
[Particle size measurement]
A laser diffraction particle size distribution meter (model: LA-950, manufactured by Horiba, Ltd.) was used for the measurement. A small amount of cellulose particles is added to 10 mL of acetone, stirred with a magnetic stirrer, and then dispersed with an ultrasonic cleaner (manufactured by Branson) for 10 seconds. The measurement is carried out after the dispersion has been added to the measuring cell previously filled with acetone until the measuring area is reached. The refractive index was set to cellulose particles: 1.47 and acetone: 1.3591 to obtain the particle size distribution. The median diameter (d50) was taken as the average particle diameter.
［嵩密度測定］
測定には嵩密度測定器（型式：ＫＡＭ－１、アズワン社製）を用いて測定した。測定器のシュートにセルロース粒子を仕込み、シュート口を開いて下に設置した１００ｍＬの容器に落下させる。余剰分のセルロース粒子をすりきって除去した後、容器中のセルロース粒子の重量を測定し、次式から算出した。
嵩密度（ｇ／ｍＬ） ＝ 粒子重量（ｇ）／ 粒子体積（ｍＬ）
[Bulk density measurement]
For the measurement, a bulk density measuring instrument (model: KAM-1, manufactured by AS ONE) was used. Cellulose particles are charged into the chute of the measuring device, and the chute opening is opened to allow the particles to drop into a 100 mL container placed below. After removing the excess cellulose particles by scraping, the weight of the cellulose particles in the container was measured and calculated from the following formula.
Bulk density (g/mL) = particle weight (g)/particle volume (mL)
[複合化試験]
複合化試験には混錬機（商品名：ラボプラストミル、型式：４Ｃ－１５０、東洋精機社製）、ミキサー（型式：Ｒ６０、東洋精機社製）を用いた。ポリプロピレン樹脂（型番：Ｊ１０５Ｇ、プライムポリマー社製）を４１ｇ計量し、２２０℃に加熱したミキサーに投入し、１０ｒｐｍで予備混錬を行った。その後、３０ｒｐｍに回転数を変更し、微細セルロース繊維粉末を１ｇ計量して投入し、投入が完了したのちは５０ｒｐｍに回転数を変更し、１０分間混錬した。そして混錬終了時のトルク値を読み取った。
また、前記ポリプロピレン樹脂のみのトルク値を予め測定しておき、以下の基準において△以上を合格とした。
○：樹脂のみのトルク値の１．２倍以上～１．５倍未満
△：樹脂のみのトルク値の１．５倍以上２．０倍未満、もしくは１．１倍以上、１．２倍未満
×：樹脂のみのトルク値の２．０倍以上、もしくは１．０倍以上１．１倍未満
[Composite test]
A kneader (trade name: Laboplastomill, model: 4C-150, manufactured by Toyo Seiki Co., Ltd.) and a mixer (model: R60, manufactured by Toyo Seiki Co., Ltd.) were used for the compounding test. 41 g of polypropylene resin (model number: J105G, manufactured by Prime Polymer Co., Ltd.) was weighed, put into a mixer heated to 220° C., and preliminarily kneaded at 10 rpm. After that, the rotation speed was changed to 30 rpm, and 1 g of fine cellulose fiber powder was weighed and added. After the addition was completed, the rotation speed was changed to 50 rpm and kneaded for 10 minutes. Then, the torque value at the end of kneading was read.
In addition, the torque value of only the polypropylene resin was measured in advance, and a value of Δ or higher was regarded as acceptable in the following criteria.
○: 1.2 times or more and less than 1.5 times the torque value of the resin alone △: 1.5 times or more and less than 2.0 times the torque value of the resin alone, or 1.1 times or more and less than 1.2 times ×: 2.0 times or more, or 1.0 times or more and less than 1.1 times the torque value of the resin alone
[分散性評価]
複合樹脂を３０ｍｇ計量し、スライドガラスに載せ、２４０℃のホットスターラー（商品名：ＲＥＸＩＭ、型式：ＲＳＨ－６ＤＮ、アズワン社製）で加熱する。樹脂が溶融したところで、もう一枚のスライドガラスをかぶせてプレスし、冷却することで分散評価用サンプルを得る。
分散性評価には微分干渉装置と位相差装置を備えた生物顕微鏡（商品名：エクリプス、型式：Ｎｉ－Ｕ、ニコン社製）を用いた。倍率２００倍でランダムに１０視野を観察し、１０μｍ以上の粗大物をカウントし、１０視野の合計数をもとに以下の基準で△以上を合格とした。
〇：粗大物が１０個未満
△：粗大物が１０個以上～１００個未満
×：粗大物が１００個以上
[Dispersibility evaluation]
30 mg of the composite resin is weighed, placed on a slide glass, and heated at 240° C. with a hot stirrer (trade name: REXIM, model: RSH-6DN, manufactured by AS ONE). After the resin has melted, another slide glass is placed over the resin, and the resin is cooled to obtain a dispersion evaluation sample.
A biological microscope (trade name: Eclipse, model: Ni-U, manufactured by Nikon Corporation) equipped with a differential interference device and a phase contrast device was used for evaluation of dispersibility. 10 fields of view were randomly observed at a magnification of 200 times, and coarse objects of 10 μm or more were counted.
○: Less than 10 large items △: 10 or more to less than 100 large items ×: 100 or more large items
[平均繊維径の測定]
微細セルロース繊維１および２で多孔質粒子が得られた場合、粒子表面を高分解能電子顕微鏡（型式：ＳＵ－８０２０、日立ハイテク社製）で観察し、得られた２万倍のＳＥＭ画像の水平方向、および垂直方向にラインを引く。次に、二つのラインに交差する少なくとも20本以上のすべての繊維の繊維径を拡大画像から実測し、測定結果から数平均繊維径を算出する。さらに、繊維シートの表面の２箇所について同様に数平均繊維径を算出し、数平均繊維径の平均値を平均繊維径とすし、多孔質粒子で得られなかった場合や微細セルロース繊維３の場合は、０．０５％濃度の微細セルロース繊維の分散液を調製し、この分散液を親水化処理したカーボン被覆グリッド上に塗布し、観察試料とし、透過型電子顕微鏡（型式：ＪＳＭ－２１００、日本電子社製）で観察する。機械処理ＣＮＦの場合は2万倍、TEMPO酸化処理されたＣＮＦの場合は最も細い繊維が確認できる倍率で得られたＴＥＭ画像の水平方向、および垂直方向にラインを引く。次に、二つのラインで交差する少なくとも２０本以上のすべての繊維の繊維径を拡大画像から実測し、測定結果から数平均繊維径を算出する。さらに、観察試料の表面の少なくとも２箇所について同様に数平均繊維径を算出し、全ての数平均繊維径の平均値を平均繊維径とする。
[Measurement of average fiber diameter]
When porous particles were obtained with fine cellulose fibers 1 and 2, the particle surface was observed with a high-resolution electron microscope (model: SU-8020, manufactured by Hitachi High-Tech). Directional, and vertical lines. Next, the fiber diameters of at least 20 or more fibers intersecting the two lines are actually measured from the enlarged image, and the number average fiber diameter is calculated from the measurement results. Furthermore, the number average fiber diameter is similarly calculated for two points on the surface of the fiber sheet, and the average value of the number average fiber diameters is taken as the average fiber diameter. prepared a dispersion of fine cellulose fibers with a concentration of 0.05%, applied this dispersion on a hydrophilized carbon-coated grid, used it as an observation sample, and examined it with a transmission electron microscope (model: JSM-2100, Japan (manufactured by Denshi Co., Ltd.). Lines are drawn horizontally and vertically on the TEM images obtained at a magnification of 20,000 times for the mechanically treated CNF and at a magnification at which the finest fibers can be identified for the TEMPO-oxidized CNF. Next, the fiber diameters of at least 20 or more fibers intersecting the two lines are actually measured from the enlarged image, and the number average fiber diameter is calculated from the measurement results. Further, the number average fiber diameter is similarly calculated for at least two points on the surface of the observation sample, and the average value of all the number average fiber diameters is taken as the average fiber diameter.
（実施例１）
［微細セルロース繊維の調成工程１］
針葉樹晒クラフトパルプをイオン交換水中に２重量％濃度になるように分散させ、前処理としてダブルディスクリファイナーを用いて叩解し、さらに高圧ホモジナイザー（型式：ＬＡＢ１０００、エスエムテー社製）を用いて７５０ｂａｒの圧力に調整して１０回処理することにより微細セルロース繊維スラリー１を得た。
(Example 1)
[Preparation step 1 of fine cellulose fibers]
Softwood bleached kraft pulp is dispersed in deionized water to a concentration of 2% by weight, beaten using a double disc refiner as a pretreatment, and further subjected to a pressure of 750 bar using a high pressure homogenizer (model: LAB1000, manufactured by SMTE). A fine cellulose fiber slurry 1 was obtained by adjusting the temperature to 10 times and treating it 10 times.
［調合工程］
上記調成工程で得られた微細セルロース繊維スラリー１に微細セルロース繊維の固形分１００重量部に対し、１重量％濃度になるようイオン交換水に溶解したカルボキシメチルセルロース（商品名：サンローズ 型番：ＭＡＣ－２００ＨＣ、日本製紙社製）を２０重量部、水溶性多孔質化剤としてプロピレンカーボネートを５００重量部添加し、最終的に固形分濃度が０．７重量％となるようにイオン交換水を加えたスラリーをホモミキサー（型式：ＣＭ－１００、アズワン社製） で均一に混ざるまで分散を行い、微細セルロース繊維含有物１を得た。
[Mixing process]
Carboxymethyl cellulose (trade name: Sunrose, model number: MAC -200HC, manufactured by Nippon Paper Industries Co., Ltd.), 500 parts by weight of propylene carbonate as a water-soluble porosifying agent, and ion-exchanged water is added so that the final solid content concentration is 0.7% by weight. The resulting slurry was dispersed with a homomixer (model: CM-100, manufactured by AS ONE) until it was uniformly mixed to obtain a material 1 containing fine cellulose fibers.
［噴霧乾燥工程］
上記調合工程で得られた微細セルロース繊維含有物１をディスクアトマイザーＭＣ－５０を備えたスプレードライヤー（型式：ＣＬ－８ｉ、大川原化工機社製）を用いて噴霧乾燥し、セルロース粒子１を得た。噴霧乾燥は流量：３５ｍＬ／ｍｉｎ、アトマイザ回転数：３５，０００ｒｐｍ、入口温度：１８０℃、出口温度：１００℃、サイクロン差圧：０．６０ｋＰａの条件で実施した。
[Spray drying process]
The fine cellulose fiber-containing material 1 obtained in the above preparation step was spray-dried using a spray dryer (model: CL-8i, manufactured by Okawara Kakoki Co., Ltd.) equipped with a disc atomizer MC-50 to obtain cellulose particles 1. . The spray drying was carried out under the following conditions: flow rate: 35 mL/min, atomizer rotation speed: 35,000 rpm, inlet temperature: 180°C, outlet temperature: 100°C, cyclone differential pressure: 0.60 kPa.
（実施例２）
上記調合工程で、カルボキシメチルセルロースを無添加とする以外は実施例１と全く同様にして、セルロース粒子２を得た。
(Example 2)
Cellulose particles 2 were obtained in exactly the same manner as in Example 1, except that carboxymethylcellulose was not added in the above preparation step.
（実施例３）
上記調合工程で、プロピレンカーボネートをジエチレングリコールモノブチルエーテルに変え、添加部数を３５０重量部とした以外は実施例1と同様にして、セルロース粒子３を得た。
(Example 3)
Cellulose particles 3 were obtained in the same manner as in Example 1, except that propylene carbonate was changed to diethylene glycol monobutyl ether in the above preparation step and the number of parts added was changed to 350 parts by weight.
（実施例４）
［微細セルロース繊維の調成工程２］
上記微細セルロース繊維調成工程１で、得られた微細セルロース繊維スラリー１を０．３重量％に希釈し、１５００Ｇで上澄みの濃度が０．０４～０．０６％になるよう時間を調整して遠心分離を行い、上澄み液を採取した。その上澄みを、ポアサイズ０．０５μｍのポリエーテルスルホン製ＭＦ膜をセットしたガラスフィルターに入れ、卓上撹拌機で攪拌しながら１重量％濃度になるまで上澄み液をつぎ足しながら濃縮を行い、微細セルロース繊維スラリー２を得た。
(Example 4)
[Preparation step 2 of fine cellulose fibers]
In the fine cellulose fiber preparation step 1, the fine cellulose fiber slurry 1 obtained is diluted to 0.3% by weight, and the time is adjusted so that the concentration of the supernatant becomes 0.04 to 0.06% at 1500 G. Centrifugation was performed and the supernatant was collected. The supernatant is placed in a glass filter set with a polyethersulfone MF membrane with a pore size of 0.05 μm, and while stirring with a tabletop stirrer, the supernatant is added to concentrate until the concentration reaches 1% by weight, resulting in a fine cellulose fiber slurry. got 2.
［調合工程］
微細セルロース繊維スラリー１から、この微細セルロース繊維スラリー２に変えた以外は実施例１と全く同様にして、セルロース粒子４を得た。
[Mixing process]
Cellulose particles 4 were obtained in exactly the same manner as in Example 1 except that the fine cellulose fiber slurry 1 was changed to this fine cellulose fiber slurry 2 .
（比較例１）
上記調合工程で、プロピレンカーボネートを無添加とする以外は実施例１と同様にしてセルロース粒子Ａを得た。
(Comparative example 1)
Cellulose particles A were obtained in the same manner as in Example 1, except that propylene carbonate was not added in the above preparation step.
（比較例２）
［微細セルロース繊維の調成工程３］
針葉樹晒クラフトパルプを用い、酸化触媒としてＴＥＭＰＯ（Ａｌｄｒｉｃｈ社製）を用い、酸化剤として次亜塩素酸ナトリウム（富士フィルム和光純薬社製、Ｃｌ：５％）を用い、共酸化剤として臭化ナトリウム（富士フィルム和光純薬社製）を用いた。針葉樹晒クラフトパルプをイオン交換水中に１重量％になるように分散させ、ＴＥＭＰＯを対パルプ１．２５重量％、臭化ナトリウムを対パルプ１２．５重量％、次亜塩素酸ナトリウムを対パルプ２８．４重量％、それぞれを順に添加し、０．５Ｍの水酸化ナトリウムの滴下により、ｐＨを１０．５に保持し、酸化反応を行った。１２０分間の酸化時間で水酸化ナトリウムの滴下を停止し、酸化パルプを得た。この酸化パルプをイオン交換水で十分に洗浄し、再度１重量％になるように希釈し、ホモミキサー（型式：ＣＭ－１００、アズワン社製）で解繊し、微細セルロース繊維スラリー３を得た。
(Comparative example 2)
[Preparation step 3 of fine cellulose fibers]
Using softwood bleached kraft pulp, using TEMPO (manufactured by Aldrich) as an oxidation catalyst, using sodium hypochlorite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Cl: 5%) as an oxidizing agent, and bromide as a co-oxidizing agent. Sodium (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used. Bleached softwood kraft pulp is dispersed in ion-exchanged water to a concentration of 1% by weight, and TEMPO is 1.25% by weight, sodium bromide is 12.5% by weight, and sodium hypochlorite is 28% by weight. 0.4% by weight of each was added in order, and the pH was maintained at 10.5 by dropping 0.5M sodium hydroxide, and an oxidation reaction was carried out. After the oxidation time of 120 minutes, the dropwise addition of sodium hydroxide was stopped to obtain an oxidized pulp. The oxidized pulp was thoroughly washed with ion-exchanged water, diluted again to 1% by weight, and defibrated by a homomixer (model: CM-100, manufactured by AS ONE) to obtain a fine cellulose fiber slurry 3. .
［調合工程］
微細セルロース繊維スラリー１から、この微細セルロース繊維スラリー３に変えた以外は実施例２と全く同様にして、セルロース粒子Ｂを得た。
[Mixing process]
Cellulose particles B were obtained in exactly the same manner as in Example 2, except that the fine cellulose fiber slurry 1 was changed to this fine cellulose fiber slurry 3.
（比較例３）
調合工程でカルボキシメチルセルロースを無添加とし、酸化チタン（型番：TTO-51(C)、石原産業社製）を１０重量部添加した以外は比較例１と同様にして、セルロース粒子Ｃを得た。
(Comparative Example 3)
Cellulose particles C were obtained in the same manner as in Comparative Example 1, except that carboxymethylcellulose was not added in the preparation step and 10 parts by weight of titanium oxide (model number: TTO-51(C), manufactured by Ishihara Sangyo Co., Ltd.) was added.
（比較例４）
調合工程で、プロピレンカーボネートをトリエチレングリコールモノメチルエーテルに変え、添加部数を３５０重量部とした以外は実施例1と同様にして、セルロース粒子Dを得た。
(Comparative Example 4)
Cellulose particles D were obtained in the same manner as in Example 1, except that propylene carbonate was changed to triethylene glycol monomethyl ether in the preparation step and the number of parts added was changed to 350 parts by weight.
（比較例５）
調合工程で、プロピレンカーボネートをジプロピレングリコールジメチルエーテルに変え、添加部数を３５０重量部とした以外は実施例1と同様にして、セルロース粒子Ｅを得た。
(Comparative Example 5)
Cellulose particles E were obtained in the same manner as in Example 1, except that propylene carbonate was changed to dipropylene glycol dimethyl ether in the preparation step and the number of parts added was changed to 350 parts by weight.
図１～４は実施例１～４で得られた粒子の電子顕微鏡画像であり、これらの画像から得られた粒子が多孔質であることがわかる。さらに、表３に示す実施例１～４の結果から、本発明の微細セルロースを主成分とする多孔質粒子が樹脂との複合化において、混錬時に樹脂添加による混錬トルクの上昇が確認できており、かつ分散性が良好であるため、樹脂の性能向上が期待できることがわかる。 Figures 1-4 are electron microscope images of the particles obtained in Examples 1-4, and it can be seen from these images that the particles obtained are porous. Furthermore, from the results of Examples 1 to 4 shown in Table 3, when the porous particles containing fine cellulose as the main component of the present invention are combined with a resin, an increase in kneading torque due to the addition of the resin during kneading can be confirmed. It can be seen that the performance improvement of the resin can be expected because it has good dispersibility.
比較例１では、水溶性多孔質化剤が無添加であるため、図５の電子顕微鏡画像で示されるように細孔がなく、表３に示すＢＥＴ比表面積が小さい。このことにより混錬時の分散性が悪く粗大物が目立ち、またトルクが樹脂のみと同等であったため、樹脂の性能向上が期待できないことがわかる。比較例１は非多孔質のため、繊維径は微細セルロース繊維１が分散液の状態でのＴＥＭ観察による測定結果を記載した。 In Comparative Example 1, since no water-soluble porosifying agent was added, there were no pores as shown in the electron microscope image of FIG. 5, and the BET specific surface area shown in Table 3 was small. As a result, the dispersibility during kneading was poor, coarse particles were conspicuous, and the torque was the same as that of the resin alone. Since Comparative Example 1 is non-porous, the fiber diameter was measured by TEM observation when the fine cellulose fibers 1 were in a dispersion state.
比較例２では、微細セルロース繊維に平均繊維径が１０ｎｍ未満のＴＥＭＰＯ酸化処理されたＣＮＦを用いているため、繊維間の凝集力が強く、図６の電子顕微鏡画像で皺状の外観がみられるが細孔が生じておらず、ＢＥＴ比表面積が小さい。このことにより、混錬時の分散性が悪く粗大物が目立ち、またトルクが樹脂のみと同等であったため、樹脂の性能向上が期待できないことがわかる。 In Comparative Example 2, since TEMPO-oxidized CNF with an average fiber diameter of less than 10 nm is used as the fine cellulose fibers, the cohesive force between the fibers is strong, and the electron microscope image in FIG. 6 shows a wrinkled appearance. However, pores are not generated and the BET specific surface area is small. As a result, the dispersibility at the time of kneading was poor, coarse particles were conspicuous, and the torque was the same as that of the resin alone.
比較例３では、水溶性多孔質化剤が無添加でかわりに酸化チタンを配合しているが、セルロース繊維間の凝集を防ぐことができず、図７で示されるように細孔が生じず、ＢＥＴ比表面積が小さい。このことにより混錬時の分散性が悪く粗大物が目立ち、またトルクが樹脂のみと同等であったため、樹脂の性能向上が期待できないことがわかる。比較例３は非多孔質のため、繊維径は微細セルロース繊維１が分散液の状態でのＴＥＭ観察による測定結果を記載した。 In Comparative Example 3, no water-soluble porosifying agent was added, and instead titanium oxide was added. , BET specific surface area is small. As a result, the dispersibility during kneading was poor, coarse particles were conspicuous, and the torque was the same as that of the resin alone. Since Comparative Example 3 is non-porous, the fiber diameter is the measurement result obtained by TEM observation of the fine cellulose fibers 1 in a dispersion state.
比較例４では、水溶性多孔質化剤の種類を水／オクタノール分配係数の数値がマイナス側に大きく、親水性の高いトリエチレングリコールモノメチルエーテルに変えたところ、セルロース繊維間の凝集を防ぐことができず、図８で示されるように細孔が生じないため、ＢＥＴ比表面積が小さい。このことにより混錬時の分散性が悪く粗大物が目立ち、またトルクが樹脂のみと同等であったため、樹脂の性能向上が期待できないことがわかる。さらに、親水性が高いため、セルロースとの親和性が高く、粒子への残留が多くなり、樹脂との複合材料にした際、悪影響を及ぼす可能性がある。比較例４は非多孔質のため、繊維径は微細セルロース繊維１が分散液の状態でのＴＥＭ観察による測定結果を記載した。 In Comparative Example 4, when the type of water-soluble porosifying agent was changed to triethylene glycol monomethyl ether, which has a large water/octanol partition coefficient on the negative side and is highly hydrophilic, aggregation between cellulose fibers was prevented. As shown in FIG. 8, the BET specific surface area is small because pores are not generated. As a result, the dispersibility during kneading was poor, coarse particles were conspicuous, and the torque was the same as that of the resin alone. Furthermore, because of its high hydrophilicity, it has a high affinity with cellulose, so that a large amount of it remains in the particles, which may have an adverse effect when it is used as a composite material with a resin. Since Comparative Example 4 is non-porous, the fiber diameter is the measurement result obtained by TEM observation of the fine cellulose fibers 1 in a dispersion state.
比較例５では、水溶性多孔質化剤の種類を沸点が１８０℃未満であるトリエチレングリコールモノメチルエーテルに変えたところ、スラリーの乾燥時に水よりも先にとりエチレングリコールモノメチルエーテルが揮発してしまうためにセルロース繊維間の凝集を防ぐことができず、図９で示されるように細孔が生じないため、ＢＥＴ比表面積が小さい。このことにより混錬時の分散性が悪く粗大物が目立ち、またトルクが樹脂のみと同等であったため、樹脂の性能向上が期待できないことがわかる。比較例５は非多孔質のため、繊維径は微細セルロース繊維１が分散液の状態でのＴＥＭ観察による測定結果を記載した。 In Comparative Example 5, when the type of water-soluble porosifying agent was changed to triethylene glycol monomethyl ether having a boiling point of less than 180°C, ethylene glycol monomethyl ether volatilized before water during drying of the slurry. However, the BET specific surface area is small because aggregation between cellulose fibers cannot be prevented and pores are not generated as shown in FIG. As a result, the dispersibility during kneading was poor, coarse particles were conspicuous, and the torque was the same as that of the resin alone. Since Comparative Example 5 is non-porous, the fiber diameter is the measurement result obtained by TEM observation of the fine cellulose fibers 1 in a dispersion state.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022086511A JP7154451B1 (en) | 2022-05-27 | 2022-05-27 | Porous particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022086511A JP7154451B1 (en) | 2022-05-27 | 2022-05-27 | Porous particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP7154451B1 true JP7154451B1 (en) | 2022-10-17 |
| JP2023173941A JP2023173941A (en) | 2023-12-07 |
Family
ID=83637952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022086511A Active JP7154451B1 (en) | 2022-05-27 | 2022-05-27 | Porous particles and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7154451B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073286A1 (en) | 2004-01-30 | 2005-08-11 | Asahi Kasei Chemicals Corporation | Porous cellulose aggregate and formed product composition comprising the same |
| US20200032454A1 (en) | 2017-03-30 | 2020-01-30 | Borregaard As | Microfibrillated cellulose foams |
| JP2021172671A (en) | 2020-04-17 | 2021-11-01 | 特種東海製紙株式会社 | Powdery fine cellulose fiber, resin composition, molding and method for producing the same |
| JP2022030885A (en) | 2020-08-07 | 2022-02-18 | 国立大学法人広島大学 | Cellulose/magnetic substance composite particle and method for producing the same |
-
2022
- 2022-05-27 JP JP2022086511A patent/JP7154451B1/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073286A1 (en) | 2004-01-30 | 2005-08-11 | Asahi Kasei Chemicals Corporation | Porous cellulose aggregate and formed product composition comprising the same |
| US20200032454A1 (en) | 2017-03-30 | 2020-01-30 | Borregaard As | Microfibrillated cellulose foams |
| JP2021172671A (en) | 2020-04-17 | 2021-11-01 | 特種東海製紙株式会社 | Powdery fine cellulose fiber, resin composition, molding and method for producing the same |
| JP2022030885A (en) | 2020-08-07 | 2022-02-18 | 国立大学法人広島大学 | Cellulose/magnetic substance composite particle and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023173941A (en) | 2023-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5622412B2 (en) | Molding material and manufacturing method thereof | |
| US9243128B2 (en) | Composite material | |
| CN107805851B (en) | Phosphorylated fine cellulose fiber and process for producing the same | |
| Lavoine et al. | Microfibrillated cellulose–Its barrier properties and applications in cellulosic materials: A review | |
| Missoum et al. | Effect of chemically modified nanofibrillated cellulose addition on the properties of fiber-based materials | |
| CN112673133B (en) | Molded body of cellulose fiber and method for producing same | |
| JP2014015512A (en) | Cellulose fiber-containing resin composition | |
| JP6345925B2 (en) | Nanocomposite and method for producing nanocomposite | |
| JP2012007247A (en) | Composite sheet of fine fibrous cellulose and inorganic compound nanoparticles | |
| JP2021509416A (en) | Film of microfibrillated cellulose | |
| Hashemzehi et al. | A comprehensive review of nanocellulose modification and applications in papermaking and packaging: Challenges, technical solutions, and perspectives | |
| EP3728450B1 (en) | A method to produce a fibrous product comprising microfibrillated cellulose | |
| Guo et al. | Improving the compatibility, surface strength, and dimensional stability of cellulosic fibers using glycidyl methacrylate grafting | |
| JP7154451B1 (en) | Porous particles and method for producing the same | |
| JP6186982B2 (en) | Nonwoven fabric / resin composite and method for producing the same | |
| JP6102719B2 (en) | Rubber modifier, rubber latex dispersion and rubber composition | |
| JP6083376B2 (en) | Rubber modifier, rubber latex dispersion and rubber composition | |
| JP2023079480A (en) | Cellulose particles and cellulose particle dispersion | |
| JP7346018B2 (en) | Method for producing cellulose fiber slurry | |
| JP6264735B2 (en) | Adhesive tape base paper | |
| Iglesias | Lignin-containing cellulose nanofibrils (LCNF): processing and characterization | |
| JP6255683B2 (en) | Base paper for wallpaper | |
| JP7265333B2 (en) | Method for producing molded body of cellulose fiber | |
| EP4365227A1 (en) | Polysaccharide nanofiber-blended polysaccharide composition production method | |
| WO2022118875A1 (en) | Wet sheet of cellulose fibers and method for producing molded body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220601 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20220602 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220822 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220823 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20221003 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20221004 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7154451 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |