JP2016069589A - Method for producing aqueous dispersion of cellulose nanofibers - Google Patents
Method for producing aqueous dispersion of cellulose nanofibers Download PDFInfo
- Publication number
- JP2016069589A JP2016069589A JP2014202762A JP2014202762A JP2016069589A JP 2016069589 A JP2016069589 A JP 2016069589A JP 2014202762 A JP2014202762 A JP 2014202762A JP 2014202762 A JP2014202762 A JP 2014202762A JP 2016069589 A JP2016069589 A JP 2016069589A
- Authority
- JP
- Japan
- Prior art keywords
- cmc
- salt
- aqueous dispersion
- cellulose
- cellulose nanofiber
- 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.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 103
- 239000001913 cellulose Substances 0.000 title claims abstract description 103
- 239000002121 nanofiber Substances 0.000 title claims abstract description 91
- 239000006185 dispersion Substances 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 121
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 113
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 113
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 113
- 150000003839 salts Chemical class 0.000 claims abstract description 86
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims description 113
- 238000000034 method Methods 0.000 claims description 39
- 238000006467 substitution reaction Methods 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 235000013305 food Nutrition 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 239000002537 cosmetic Substances 0.000 claims description 9
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 7
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000008719 thickening Effects 0.000 abstract description 9
- 239000000839 emulsion Substances 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 230000002123 temporal effect Effects 0.000 abstract 2
- 206010061592 cardiac fibrillation Diseases 0.000 abstract 1
- 230000002600 fibrillogenic effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 59
- 235000011194 food seasoning agent Nutrition 0.000 description 54
- 239000007788 liquid Substances 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000007787 solid Substances 0.000 description 37
- 230000002378 acidificating effect Effects 0.000 description 33
- 235000015067 sauces Nutrition 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 26
- 238000003756 stirring Methods 0.000 description 26
- 239000003960 organic solvent Substances 0.000 description 25
- 239000000499 gel Substances 0.000 description 24
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 22
- 238000006266 etherification reaction Methods 0.000 description 21
- 235000013361 beverage Nutrition 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000006210 lotion Substances 0.000 description 16
- 102000014171 Milk Proteins Human genes 0.000 description 14
- 108010011756 Milk Proteins Proteins 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- 235000021239 milk protein Nutrition 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000007921 spray Substances 0.000 description 12
- 239000003381 stabilizer Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 239000004310 lactic acid Substances 0.000 description 11
- 235000014655 lactic acid Nutrition 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 235000020124 milk-based beverage Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 239000002562 thickening agent Substances 0.000 description 8
- 239000004278 EU approved seasoning Substances 0.000 description 7
- 235000015140 cultured milk Nutrition 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003349 gelling agent Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 230000006920 protein precipitation Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 235000015110 jellies Nutrition 0.000 description 5
- 239000008274 jelly Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 235000013372 meat Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 235000020183 skimmed milk Nutrition 0.000 description 4
- 235000013555 soy sauce Nutrition 0.000 description 4
- 235000000346 sugar Nutrition 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 235000008452 baby food Nutrition 0.000 description 3
- 235000021168 barbecue Nutrition 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000019577 caloric intake Nutrition 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 235000021185 dessert Nutrition 0.000 description 3
- 235000015071 dressings Nutrition 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 235000008960 ketchup Nutrition 0.000 description 3
- 239000008268 mayonnaise Substances 0.000 description 3
- 235000010746 mayonnaise Nutrition 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 235000011496 sports drink Nutrition 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 235000013618 yogurt Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- YBHQCJILTOVLHD-YVMONPNESA-N Mirin Chemical compound S1C(N)=NC(=O)\C1=C\C1=CC=C(O)C=C1 YBHQCJILTOVLHD-YVMONPNESA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000015203 fruit juice Nutrition 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- VIRWKAJWTKAIMA-UHFFFAOYSA-N 2-chloroethyl acetate Chemical compound CC(=O)OCCCl VIRWKAJWTKAIMA-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000951471 Citrus junos Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 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
- 244000294411 Mirabilis expansa Species 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000015197 apple juice Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- SMJYMSAPPGLBAR-UHFFFAOYSA-N chloromethyl acetate Chemical compound CC(=O)OCCl SMJYMSAPPGLBAR-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013861 fat-free Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000021552 granulated sugar Nutrition 0.000 description 1
- 235000015201 grapefruit juice Nutrition 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229940092258 rosemary extract Drugs 0.000 description 1
- 235000020748 rosemary extract Nutrition 0.000 description 1
- 239000001233 rosmarinus officinalis l. extract Substances 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- VRYGRLBNIVQXMY-UHFFFAOYSA-M sodium;acetic acid;chloride Chemical compound [Na+].[Cl-].CC(O)=O VRYGRLBNIVQXMY-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000015193 tomato juice Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 235000008939 whole milk Nutrition 0.000 description 1
Landscapes
- Jellies, Jams, And Syrups (AREA)
- Seasonings (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Dairy Products (AREA)
- General Preparation And Processing Of Foods (AREA)
- Seeds, Soups, And Other Foods (AREA)
Abstract
Description
本発明は、部分酸型カルボキシメチルセルロース（ＣＭＣ）塩セルロースナノファイバー水分散体の製造方法、並びに該製造方法によって得られる食品および化粧料に関する。 The present invention relates to a method for producing a partial acid carboxymethylcellulose (CMC) salt cellulose nanofiber aqueous dispersion, and a food and a cosmetic obtained by the production method.
従来、有限な資源である石油由来の高分子材料が多用されていたが、近年、環境に対する負荷の少ない技術が脚光を浴びるようになり、かかる技術背景の下、天然に多量に存在するバイオマスであるセルロース繊維を使った材料が注目されている。例えば、セルロース繊維を使った材料として、ナノサイズの繊維径をもったセルロース繊維（セルロースナノファイバー）に関する技術が注目されている。特許文献１には、アニオン変性されたセルロースが高圧ホモジナイザーで処理されることを特徴とするカルボキシメチル置換度の低いセルロースナノファイバーの製造方法が開示されている。 Conventionally, petroleum-derived polymer materials, which are finite resources, have been widely used, but in recent years, technologies with low environmental impact have come to the spotlight. A material using a certain cellulose fiber has attracted attention. For example, as a material using cellulose fibers, a technique related to cellulose fibers (cellulose nanofibers) having a nano-sized fiber diameter has attracted attention. Patent Document 1 discloses a method for producing cellulose nanofibers having a low degree of carboxymethyl substitution, characterized in that anion-modified cellulose is treated with a high-pressure homogenizer.
また、部分酸型カルボキシメチルセルロースは、カルボキシメチルセルロース塩（以下、ＣＭＣ塩という）のアルカリ塩の部分を部分的に酸型に変換したものである。従来技術によれば、ＣＭＣ塩はアルカリ塩では水溶性であるのに対し、酸型では水に不溶となるので、酸型の置換基数の増大により、水への膨潤度を小さくすることができるため、この特徴が注目されている。特許文献２には、部分酸型ＣＭＣの製造方法が開示されている。 Moreover, the partial acid type carboxymethyl cellulose is obtained by partially converting an alkali salt portion of a carboxymethyl cellulose salt (hereinafter referred to as CMC salt) to an acid type. According to the prior art, CMC salt is water-soluble in alkali salt, but insoluble in water in acid form, so that the degree of swelling in water can be reduced by increasing the number of substituents in acid form. Therefore, this feature is attracting attention. Patent Document 2 discloses a method for producing a partial acid type CMC.
近年の要求性能の向上に伴い、セルロースナノファイバー水分散体外観の変化、ゲル性の変化の経時安定性が求められるようになった。また、セルロースナノファイバーを使用した増粘剤等についても、増粘性等の経時変化が小さいことが求められるようになった。 Along with the improvement in required performance in recent years, a change in appearance of cellulose nanofiber aqueous dispersion and a change in gel property over time have been required. In addition, thickeners using cellulose nanofibers are also required to have little change over time such as thickening.
本発明は、上記問題点に鑑みて為されたものであり、本発明によれば、部分酸型CMC塩セルロースナノファイバー水分散体の経時的な外観の変化、ゲル性の変化を抑制し、かつ部分酸型CMC塩セルロースナノファイバー水分散体含有品の増粘性、ゲル化性、保形性、乳化安定性、分散安定性の経時変化を抑制しうる部分酸型CMC塩セルロースナノファイバー水分散体の製造方法を提供することを課題とする。 The present invention has been made in view of the above problems, and according to the present invention, the change in appearance over time of the partial acid CMC salt cellulose nanofiber aqueous dispersion, the change in gel properties, And partial acid type CMC salt cellulose nanofiber aqueous dispersion that can suppress changes in viscosity, gelation, shape retention, emulsification stability, dispersion stability over time of products containing aqueous dispersions of partial acid type CMC salt cellulose nanofibers It is an object to provide a method for manufacturing a body.
発明者らは、上記課題を解決するために鋭意検討を行ったところ、特許文献１記載の方法では、置換度が０．３０より大きくなると一部成分が溶解して、増粘剤やゲル化剤として機能が大きく損なわれるといった問題があることが分かった。また、当該技術では、酸性条件下、例えば、ｐＨ５．０を下回る条件下で使用をする際、いわゆるｐＨショックによってセルロースナノファイバーの沈降、凝集物の発生、粘度の急激な低下、ゲルの崩壊などの現象が見られ、耐酸性に問題があることが分かった。セルロースナノファイバー水分散体は、前記の如く、幅広い用途分野での応用が期待されているが、その本来の機能を保持しながら好適に使用できるｐＨ領域が狭いという課題を抱えており、特に、酸性領域では増粘、ゲル化、保形性、乳化安定化、分散安定化などの機能が著しく低下する問題があった。例えば、人の皮膚表面のｐＨは通常４．５〜６．０の弱酸性であり、スキンケア製品や化粧品、トイレタリー製品などでは弱酸性の商品設計となっているものが多い。また、食品や飲料、調味液類、等において、その成分である、醗酵乳のｐＨは通常ｐＨ３．０〜４．５の範囲にあり、果汁としては、 レモン果汁でｐＨ３．３〜４．０、リンゴ果汁でｐＨ３．９〜４．５、グレープフルーツ果汁でｐＨ３程度、トマト果汁でｐＨ４程度であり、クエン酸やリンゴ酸、酢酸などの有機酸も同様のｐＨ値を示し、味噌でｐＨ４．５〜５．０、醤油でｐＨ４．０〜５．０である。これら成分からなる、乳酸菌飲料やヨーグルト、酸性乳飲料、スポーツドリンク（ｐＨ３．０〜３．６）、乳幼児用イオン飲料（ｐＨ３．６〜３．９）、機能型ドリンク、ゼリー飲料、カロリー摂取型ドリンク、デザートドリンク、ベビーフード、更に、ジャム、ドレッシング、マヨネーズ、ケチャップ、ウスターソース、バーベキューソース、焼肉ソース、各種食用タレ、つゆ、ジュレ状調味料、等は概ねｐＨ３．０〜６．５の範囲にあり、これら用途で添加剤として使用される増粘剤、ゲル化剤、保形剤、乳化安定化剤、分散安定化剤、等は、弱酸性領域でｐＨショックを生じることなく、性能が保持され、その性能の経時変化が小さいものが好ましい。一方、特許文献２に記載の方法は、水に不溶性の部分酸型ＣＭＣ塩を平均粒子径１０〜１００μｍ程度の粉末状、或いは、粉末を水に一部膨潤させた状態で使用するものであり、ナノファイバー由来の性能が得られるものではない。 The inventors have conducted intensive studies in order to solve the above problems. As a result, in the method described in Patent Document 1, when the degree of substitution is greater than 0.30, some components are dissolved, resulting in a thickener or gelation. It has been found that there is a problem that the function is greatly impaired as an agent. In addition, in this technique, when used under acidic conditions, for example, below pH 5.0, so-called pH shock causes precipitation of cellulose nanofibers, generation of aggregates, rapid decrease in viscosity, gel collapse, etc. It was found that there was a problem with acid resistance. As described above, the cellulose nanofiber aqueous dispersion is expected to be applied in a wide range of application fields, but has a problem that the pH range that can be suitably used while maintaining its original function is narrow, In the acidic region, there is a problem that functions such as thickening, gelation, shape retention, emulsification stabilization and dispersion stabilization remarkably deteriorate. For example, the pH of the human skin surface is usually weakly acidic, 4.5 to 6.0, and many skin care products, cosmetics, toiletries, etc. are designed to be weakly acidic. Moreover, in foods, beverages, seasonings, etc., the pH of the fermented milk, which is a component thereof, is usually in the range of pH 3.0 to 4.5, and the fruit juice is pH 3.3 to 4.0 with lemon juice. PH 3.9 to 4.5 for apple juice, pH 3 for grapefruit juice, pH 4 for tomato juice, and organic acids such as citric acid, malic acid and acetic acid show similar pH values, and pH 4.5 for miso -5.0, soy sauce and pH 4.0-5.0. Containing lactic acid bacteria beverages and yogurts, acidic milk beverages, sports drinks (pH 3.0 to 3.6), infant ion beverages (pH 3.6 to 3.9), functional drinks, jelly beverages, calorie intake type Drinks, dessert drinks, baby food, jams, dressings, mayonnaise, ketchup, Worcester sauce, barbecue sauce, grilled meat sauce, various edible sauces, soy sauce, jelly-like seasonings, etc. are generally in the range of pH 3.0 to 6.5. Yes, thickeners, gelling agents, shape-retaining agents, emulsion stabilizers, dispersion stabilizers, etc. used as additives in these applications retain their performance without causing pH shock in weakly acidic regions It is preferable that the performance change with time is small. On the other hand, the method described in Patent Document 2 uses a partial acid type CMC salt insoluble in water in the form of a powder having an average particle size of about 10 to 100 μm, or in a state where the powder is partially swollen in water. The performance derived from nanofiber is not obtained.
発明者らは、上記課題を解決するために鋭意検討を行い、セルロースナノファイバー水分散体を調製する原料として、部分的にアニオン変性されたセルロース、即ち、カルボキシメチル置換度を特に限定した低置換度カルボキシメチルセルロース塩（低置換度CMC塩）から、更に、そのアルカリ金属塩である低置換度CMC塩の一部を酸型に変換して得た部分酸型ＣＭＣ塩を用いることで、より広いｐＨ領域、特に、弱酸性領域でｐＨショックを生じることなく、増粘剤、ゲル化剤、保形剤、乳化安定化剤、分散安定化剤、等としての性能を発揮し、その性能の経時変化が小さいことを見出し、本発明を完成させるに至った。 The inventors have conducted extensive studies to solve the above-mentioned problems, and as a raw material for preparing a cellulose nanofiber aqueous dispersion, partially anion-modified cellulose, that is, a low substitution with a particularly limited degree of carboxymethyl substitution By using a partial acid type CMC salt obtained by converting a part of the low substitution CMC salt, which is an alkali metal salt thereof, into an acid form from the carboxymethyl cellulose salt (low substitution CMC salt). Demonstrates performance as a thickener, gelling agent, shape-retaining agent, emulsion stabilizer, dispersion stabilizer, etc. without causing pH shock in the pH region, particularly weakly acidic region. The present inventors have found that the change is small and have completed the present invention.
すなわち、本発明は下記に掲げる発明に関する。
（１）（i）原料パルプをアルカリセルロース化し、更に、カルボキシメチル化してカルボキシメチルセルロース（CMC）塩を製造する工程、
（ii）前記CMC塩を部分酸型CMCに変換する工程、
（v）得られた部分酸型CMC塩を解繊分散処理する工程、
を有する部分酸型CMC塩セルロースナノファイバー水分散体の製造方法。
（２）（i）原料パルプをアルカリセルロース化し、更に、カルボキシメチル化してカルボキシメチルセルロース（CMC）塩を製造する工程、
（ii）前記CMC塩を部分酸型CMCに変換する工程、
（iii）前記部分酸型CMCを洗浄する工程、
（iv）洗浄した部分酸型CMCと、所定量のアルカリを反応させる工程、
（v）得られた部分酸型CMC塩を解繊分散処理する工程、
を有する部分酸型CMC塩セルロースナノファイバー水分散体の製造方法。
（３）前記、部分酸型CMC塩が、グルコース単位当たりのカルボキシメチル置換度が０．０２〜０．８０であり、かつ、酸型置換基が全置換基の１．０〜８０．０％である、（１）または（２）記載のセルロースナノファイバー水分散体の製造方法。
（４）（１）〜（３）いずれか記載の製造方法によって得られたセルロースナノファイバー水分散体の溶媒を除去する工程、を有するセルロースナノファイバーの製造方法。
（５）（１）〜（３）いずれか記載の製造方法によって得られたセルロースナノファイバー水分散体。
（６）（１）〜（３）いずれか記載の製造方法によって得られたセルロースナノファイバー水分散体を含有する食品。
（７）２０℃におけるｐＨが３．０〜５．５である、（６）記載の食品。
（８）（１）〜（３）いずれか記載の製造方法によって得られたセルロースナノファイバー水分散体を含有する、２０℃におけるｐＨが３．０〜５．５化粧料。
That is, this invention relates to the invention hung up below.
(1) (i) Step of producing raw material pulp into alkali cellulose and further carboxymethylating to produce carboxymethyl cellulose (CMC) salt,
(Ii) converting the CMC salt into a partial acid CMC;
(V) a step of defibrating and dispersing the obtained partial acid CMC salt;
The manufacturing method of the partial acid type CMC salt cellulose nanofiber aqueous dispersion which has NO.
(2) (i) converting the raw material pulp to alkali cellulose and further carboxymethylating to produce a carboxymethylcellulose (CMC) salt;
(Ii) converting the CMC salt into a partial acid CMC;
(Iii) washing the partial acid type CMC;
(Iv) reacting the washed partial acid type CMC with a predetermined amount of alkali,
(V) a step of defibrating and dispersing the obtained partial acid CMC salt;
The manufacturing method of the partial acid type CMC salt cellulose nanofiber aqueous dispersion which has NO.
(3) In the partial acid type CMC salt, the degree of carboxymethyl substitution per glucose unit is 0.02 to 0.80, and the acid type substituent is 1.0 to 80.0% of the total substituents. The method for producing an aqueous dispersion of cellulose nanofibers according to (1) or (2).
(4) A method for producing cellulose nanofibers, comprising a step of removing the solvent of the cellulose nanofiber aqueous dispersion obtained by the production method according to any one of (1) to (3).
(5) A cellulose nanofiber aqueous dispersion obtained by the production method according to any one of (1) to (3).
(6) Foodstuff containing the cellulose nanofiber aqueous dispersion obtained by the manufacturing method in any one of (1)-(3).
(7) The food according to (6), wherein the pH at 20 ° C. is 3.0 to 5.5.
(8) A cosmetic having a pH of 3.0 to 5.5 at 20 ° C. containing the aqueous dispersion of cellulose nanofibers obtained by the production method according to any one of (1) to (3).
本発明によれば、部分酸型CMC塩セルロースナノファイバー水分散体の経時的な外観の変化、ゲル性の変化を抑制し、かつ部分酸型CMC塩セルロースナノファイバー水分散体含有品の増粘性、ゲル化性、保形性、乳化安定性、分散安定性の経時変化を抑制しうる部分酸型CMC塩セルロースナノファイバー水分散体の製造方法を提供することができる。 According to the present invention, the change in the appearance of the partial acid type CMC salt cellulose nanofiber aqueous dispersion over time, the change in gel property is suppressed, and the viscosity increase of the product containing the partial acid type CMC salt cellulose nanofiber aqueous dispersion In addition, it is possible to provide a method for producing an aqueous dispersion of partially acid CMC salt cellulose nanofibers that can suppress changes over time in gelling properties, shape retention properties, emulsion stability, and dispersion stability.
本発明の部分酸型CMC塩セルロースナノファイバー水分散体の製造方法は、（i）原料パルプをアルカリセルロース化し、更に、カルボキシメチル化（以下、エーテル化と記する場合がある）してカルボキシメチルセルロース（CMC）塩を製造する工程、（ii）前記CMC塩を部分酸型CMCに変換する工程、（v）得られた部分酸型CMC塩を解繊分散処理する工程、を有する。 The method for producing a partial acid CMC salt cellulose nanofiber aqueous dispersion of the present invention comprises: (i) alkali pulping a raw material pulp, and further carboxymethylating (hereinafter sometimes referred to as etherification) to carboxymethylcellulose. (CMC) a step of producing a salt, (ii) a step of converting the CMC salt into a partial acid type CMC, and (v) a step of defibrating and dispersing the obtained partial acid type CMC salt.
本発明において、部分酸型ＣＭＣとは、ＣＭＣ塩を酸によって部分的に遊離酸に変換したＣＭＣをいう。 In the present invention, the partial acid type CMC refers to CMC obtained by partially converting a CMC salt into a free acid with an acid.
本発明におけるセルロースナノファイバーは、数平均繊維径が２ｎｍ以上２００ｎｍ以下の状態まで解繊されていることが好ましい。 The cellulose nanofibers in the present invention are preferably defibrated to a state where the number average fiber diameter is 2 nm or more and 200 nm or less.
＜工程（i）＞
工程（i）で使用する原料パルプとしては、特に限定されないが、例えば、針葉樹系パルプ、広葉樹系パルプ、コットンリンター、コットンリント等の綿系パルプ、麦わらパルプ、バガスパルプ等の非木材系パルプなどが挙げられる。これらのうち、針葉樹系パルプ、広葉樹系パルプが好ましい。これらは１種又は２種以上を使用することができる。上記原料パルプは、叩解等の表面積を高める処理を施すと、反応効率を高めることができ、生産性を高めることができるため好ましい。また、上記原料パルプとして、単離、精製の後、乾燥させない（ネバードライ）で保存していたものを使用すると、ミクロフィブリルの集束体が膨潤しやすい状態であるため、反応効率を高め、微細化処理後の数平均繊維径を小さくすることができるため好ましい。
<Process (i)>
The raw material pulp used in step (i) is not particularly limited, and examples thereof include cotton pulp such as softwood pulp, hardwood pulp, cotton linter and cotton lint, and non-wood pulp such as straw pulp and bagasse pulp. Can be mentioned. Of these, softwood pulp and hardwood pulp are preferred. These can use 1 type (s) or 2 or more types. The raw material pulp is preferably subjected to a treatment for increasing the surface area, such as beating, because reaction efficiency can be increased and productivity can be increased. In addition, if the pulp that has been stored after being isolated and purified and not dried (never dry) is used as the raw material pulp, since the microfibril bundles are likely to swell, the reaction efficiency is improved, This is preferable because the number average fiber diameter after the crystallization treatment can be reduced.
工程（i）において、アルカリセルロース化に用いるアルカリとしては、特に限定されないが、例えば、アルカリ金属水酸化物が使用することができる。アルカリ金属水酸化物としては、特に限定されないが、例えば水酸化ナトリウム、水酸化カリウム、水酸化リチウム、等の１ 価の金属の水酸化物などが挙げられる。これらの中で、価格および得られるCMC塩の特性の点から水酸化ナトリウムが好ましい。これらは１種又は２種以上を使用することができる。 Although it does not specifically limit as an alkali used for alkali cellulose conversion in process (i), For example, an alkali metal hydroxide can be used. Although it does not specifically limit as an alkali metal hydroxide, For example, the hydroxide of monovalent metals, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are mentioned. Among these, sodium hydroxide is preferable from the viewpoint of the price and the properties of the obtained CMC salt. These can use 1 type (s) or 2 or more types.
工程（i）において、前記アルカリの使用量は、原料パルプ中のセルロースのグルコース単位量に対して、モル比で０．２〜６．０倍が好ましく、０．４〜４．０倍がより好ましい。これらの範囲であれば、アルカリセルロースを効率良く得ることができエーテル化が充分となる、また、アルカリの使用量が効率的であり粘度の観点からも好ましい。 In the step (i), the amount of the alkali used is preferably 0.2 to 6.0 times, more preferably 0.4 to 4.0 times in terms of molar ratio with respect to the glucose unit amount of cellulose in the raw pulp. preferable. Within these ranges, alkali cellulose can be obtained efficiently and etherification is sufficient, and the amount of alkali used is efficient, which is preferable from the viewpoint of viscosity.
前記アルカリセルロース化を行うときの反応温度は、２０〜６０℃が好ましく、３０〜５０℃がより好ましい。アルカリセルロース化の反応温度がこれらの範囲であれば、アルカリセルロースを充分に生成させることができ、粘度の観点からも好ましい。また、前記アルカリセルロース化を行うときの反応時間は、３０〜９０分間が好ましく、４０〜８０分間がより好ましい。反応時間がこれらの範囲であれば、アルカリセルロースを充分に生成させることができ、粘度の観点からも好ましい。 20-60 degreeC is preferable and, as for the reaction temperature when performing the said alkali cellulose conversion, 30-50 degreeC is more preferable. If the reaction temperature for alkali cellulose formation is within these ranges, alkali cellulose can be sufficiently produced, which is preferable from the viewpoint of viscosity. Moreover, 30 to 90 minutes are preferable and, as for the reaction time when performing the said alkali cellulose conversion, 40 to 80 minutes are more preferable. If reaction time is these ranges, alkali cellulose can fully be produced | generated and it is preferable also from a viscosity viewpoint.
工程（i）において、アルカリセルロース化に用いる溶媒としては、特に限定されないが、例えば、含水有機溶媒を使用することができる。含水有機溶媒は、アルカリとの相溶性の観点から好ましい。含水有機溶媒の水と有機溶媒の質量比は、特に限定されないが、水：有機溶媒が１０：９０〜４０：６０が好ましく、１５：８５〜２０：８０がより好ましい。これらの範囲であれば、反応系中のアルカリ濃度を充分に高濃度に保つことができる。有機溶媒としては、特に限定されないが、例えば、エタノール、メタノール、ｎ−プロピルアルコール、イソプロピルアルコール（ 以下、Ｉ ＰＡ という） 、ｎ−ブチルアルコール、イソブチルアルコールなどの炭素数１〜４のアルコール類、アセトン、ジエチルケトン、メチルエチルケトンなどのケトン類、ジオキサン、ジエチルエーテルなどが挙げられる。これらは１種又は２種以上を使用することができる。入手の容易さ、低価格、取り扱いやすさの点で、Ｉ ＰＡ 、エタノール、メタノールが好ましい。また、エタノール−トルエン混合溶媒など、アルコール系溶剤と芳香族系溶媒の混合溶媒も使用可能である。 Although it does not specifically limit as a solvent used for alkali cellulose conversion in process (i), For example, a water-containing organic solvent can be used. The water-containing organic solvent is preferable from the viewpoint of compatibility with alkali. The mass ratio of the water-containing organic solvent water to the organic solvent is not particularly limited, but water: organic solvent is preferably 10:90 to 40:60, and more preferably 15:85 to 20:80. Within these ranges, the alkali concentration in the reaction system can be kept sufficiently high. Although it does not specifically limit as an organic solvent, For example, C1-C4 alcohols, such as ethanol, methanol, n-propyl alcohol, isopropyl alcohol (henceforth IPA), n-butyl alcohol, isobutyl alcohol, acetone , Ketones such as diethyl ketone and methyl ethyl ketone, dioxane, diethyl ether and the like. These can use 1 type (s) or 2 or more types. IPA, ethanol, and methanol are preferable in terms of availability, low cost, and ease of handling. A mixed solvent of an alcohol solvent and an aromatic solvent such as an ethanol-toluene mixed solvent can also be used.
前記含水有機溶媒の配合量は、原料パルプに対して、重量比で２．０〜１０倍が好ましく、２．５〜８倍がより好ましい。これらの範囲であれば、含水有機溶媒と原料パルプ中のセルロースとが充分に撹拌混合されるため、撹拌時の反応機に対する負荷が大きくならず、また均一反応の観点からも好ましい。さらに原料経費の観点からも好ましい。 The blending amount of the water-containing organic solvent is preferably 2.0 to 10 times by weight and more preferably 2.5 to 8 times the raw material pulp. Within these ranges, the water-containing organic solvent and the cellulose in the raw pulp are sufficiently stirred and mixed, so that the load on the reactor during stirring does not increase, and is also preferable from the viewpoint of uniform reaction. Furthermore, it is preferable from the viewpoint of raw material costs.
工程（i）においては、次に得られたアルカリセルロースにエーテル化剤を反応させてエーテル化を行なう。エーテル化は、アルカリ過剰下で進行させることが好ましい。エーテル化剤としては、特に限定されないが、例えば、モノクロル酢酸、モノクロル酢酸ナトリウム、モノクロル酢酸メチル、モノクロル酢酸エチルなどが挙げられる。これらのうち、モノクロル酢酸が好ましい。これらは１種又は２種以上を使用することができる。 In step (i), etherification is carried out by reacting the obtained alkali cellulose with an etherifying agent. The etherification is preferably allowed to proceed under an excess of alkali. The etherifying agent is not particularly limited, and examples thereof include monochloroacetic acid, monochlorosodium acetate, monochloromethyl acetate, monochloroethyl acetate and the like. Of these, monochloroacetic acid is preferred. These can use 1 type (s) or 2 or more types.
前記エーテル化剤の使用量は、目的のエーテル化度によって決定されるため、特に制限はないが、原料パルプ中のグルコース単位量に対して、モル比で０．５〜６倍が好ましく、２〜４倍がより好ましい。エーテル化剤の配合量が、０．５倍以上であれば、ＣＭＣ塩のエーテル化度が十分であり、目的とするエーテル化度が得られやすい。一方、エーテル化剤の配合量が６倍以下であると、高価なエーテル化剤を無駄に使用することがなく、好ましい。 The amount of the etherifying agent used is determined according to the desired degree of etherification, and is not particularly limited. However, the molar ratio is preferably 0.5 to 6 times the glucose unit amount in the raw pulp. ~ 4 times is more preferable. If the blending amount of the etherifying agent is 0.5 times or more, the degree of etherification of the CMC salt is sufficient, and the desired degree of etherification is easily obtained. On the other hand, when the blending amount of the etherifying agent is 6 times or less, an expensive etherifying agent is not wasted, which is preferable.
前記エーテル化における反応温度は特に限定されないが、７５〜１００℃が好ましく、８０〜９０℃がより好ましい。反応温度が７５℃以上であれば、エーテル化が充分である。一方、反応温度が１００℃以下であれば、反応溶媒の沸点を超えず、溶媒が揮発しないことから作業性の観点から好ましい。また、反応時間は特に限定されないが、５０〜１２０分間が好ましく、５０〜９０分間がより好ましい。反応時間が５０分間以上であればエーテル化が充分である。一方、反応時間が９０分間以下であれば、作業性が良好であり、得られるＣＭＣ塩の粘度の観点からも好ましい。 Although the reaction temperature in the said etherification is not specifically limited, 75-100 degreeC is preferable and 80-90 degreeC is more preferable. If the reaction temperature is 75 ° C. or higher, etherification is sufficient. On the other hand, if the reaction temperature is 100 ° C. or lower, the boiling point of the reaction solvent is not exceeded and the solvent does not volatilize, which is preferable from the viewpoint of workability. The reaction time is not particularly limited, but is preferably 50 to 120 minutes, more preferably 50 to 90 minutes. If the reaction time is 50 minutes or longer, etherification is sufficient. On the other hand, if reaction time is 90 minutes or less, workability | operativity will be favorable and it is preferable also from a viewpoint of the viscosity of the CMC salt obtained.
前記エーテル化反応終了後、反応溶媒として用いた有機溶媒を一部除去する。有機溶媒を一部除去したＣＭＣ塩の固形分濃度は、特に限定されないが、３０〜８０重量％が好ましく、４０〜７０重量％がより好ましく、５０〜６０重量％がさらに好ましい。ＣＭＣ塩の固形分濃度が３０重量％より以上であれば、ＣＭＣ塩はスラリー状態とならず、以降の撹拌効率の観点から好ましい。一方、ＣＭＣ塩の固形分濃度が８０重量％以下であれば、ＣＭＣ塩固形分が高くならず、撹拌時の負荷が大きくならないため、作業性が良好である。 After completion of the etherification reaction, part of the organic solvent used as the reaction solvent is removed. The solid content concentration of the CMC salt from which a part of the organic solvent has been removed is not particularly limited, but is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, and further preferably 50 to 60% by weight. If the solid content concentration of the CMC salt is more than 30% by weight, the CMC salt is not in a slurry state and is preferable from the viewpoint of the subsequent stirring efficiency. On the other hand, when the solid content concentration of the CMC salt is 80% by weight or less, the CMC salt solid content does not increase and the load during stirring does not increase, so that workability is good.
＜工程（ii）＞
工程（i）で得られたCMC塩は、酸を添加することにより、部分酸型CMCに変換する工程である。酸としては、特に限定されないが、例えば、硫酸、塩酸、クエン酸、リンゴ酸、モノクロル酢酸などが挙げられる。これらは１種又は２種以上を使用することができる。
これらの中で、酸型CMCに変換する効率が高い点で、硫酸、塩酸が好ましい。
<Step (ii)>
The CMC salt obtained in the step (i) is a step of converting to a partial acid type CMC by adding an acid. Although it does not specifically limit as an acid, For example, a sulfuric acid, hydrochloric acid, a citric acid, malic acid, a monochloroacetic acid etc. are mentioned. These can use 1 type (s) or 2 or more types.
Of these, sulfuric acid and hydrochloric acid are preferred because of their high efficiency of conversion to acid type CMC.
前記酸の添加量は、理論エーテル化度に対して、モル比で０．２〜３．０倍が好ましく、０．３〜２．５倍がより好ましい。これらの範囲であれば、酸置換度が好適となる。 The addition amount of the acid is preferably 0.2 to 3.0 times, more preferably 0.3 to 2.5 times in terms of molar ratio with respect to the theoretical degree of etherification. Within these ranges, the acid substitution degree is suitable.
前記酸を添加後の反応温度は、特に限定されないが、５０〜１１０℃が好ましく、６５〜１０５℃がより好ましく、６０〜８０℃がさらに好ましい。反応温度が、これらの範囲であれば、酸置換が充分となり、酸置換の反応時間が好適となることから酸置換の均一性の観点から好ましい。また、撹拌時間は、特に限定されないが、２０〜８０分間が好ましく、４０〜６０分間がより好ましい。撹拌時間が、これらの範囲であれば、酸置換が充分であり、作業性の観点からも好ましい。 The reaction temperature after addition of the acid is not particularly limited, but is preferably 50 to 110 ° C, more preferably 65 to 105 ° C, and further preferably 60 to 80 ° C. When the reaction temperature is within these ranges, acid substitution is sufficient and the reaction time for acid substitution is suitable, which is preferable from the viewpoint of uniformity of acid substitution. Moreover, although stirring time is not specifically limited, 20-80 minutes are preferable and 40-60 minutes are more preferable. When the stirring time is within these ranges, acid substitution is sufficient, which is preferable from the viewpoint of workability.
＜工程（v）＞
工程（ii）、または後述する工程（iv）で得られた部分酸型ＣＭＣを、解繊分散処理することで、部分酸型CMC塩セルロースナノファイバー水分散体を得る工程である。
<Process (v)>
This is a step of obtaining a partial acid type CMC salt cellulose nanofiber aqueous dispersion by subjecting the partial acid type CMC obtained in the step (ii) or the step (iv) described later to defibration dispersion treatment.
工程（v）においては、特に限定されないが、例えば、高速回転下でのホモミキサー、高圧ホモジナイザー、超高圧ホモジナイザー、超音波分散処理、ビーター、ディスク型レファイナー、コニカル型レファイナー、ダブルディスク型レファイナー、グラインダー等の強力で叩解能力のある装置が好適に使用される。これらを使用することによりナノ粒子状に微細化することが可能となり、より効率的かつ高度なダウンサイジングが可能となる。これらのうち、高圧ホモジナイザーは、コンタミネーションが少ない、処理時間が短い、連続処理が可能、粒度分布がシャープで目的物の歩留まりが向上する、装置内の原料残留量が少なく回収率が向上するといった理由から、高圧ホモジナイザーが好適に使用される。本発明において、高圧ホモジナイザーとは、ポンプにより流体に加圧（高圧）し、流路に設けた非常に繊細な間隙より噴出させることにより、粒子間の衝突、圧力差による剪断力等の総合エネルギーによって乳化・分散・解細・粉砕・超微細化を行う装置をいう。なお、上記分散機としては、例えば、スクリュー型ミキサー、パドルミキサー、ディスパー型ミキサー、タービン型ミキサー等を用いても差し支えない。 In the step (v), although not particularly limited, for example, a homomixer, a high-pressure homogenizer, an ultra-high pressure homogenizer, an ultrasonic dispersion treatment, a beater, a disc type refiner, a conical type refiner, a double disc type refiner, and a grinder A device having a strong and beating ability such as the above is preferably used. By using these, it becomes possible to make the particles finer, and more efficient and advanced downsizing becomes possible. Among these, the high-pressure homogenizer has low contamination, short processing time, continuous processing is possible, sharp particle size distribution improves the yield of the target product, and there is little residual amount of raw material in the apparatus and the recovery rate is improved. For this reason, a high pressure homogenizer is preferably used. In the present invention, the high-pressure homogenizer is a total energy such as a collision between particles and a shearing force due to a pressure difference by pressurizing (high-pressure) the fluid with a pump and ejecting it from a very delicate gap provided in the flow path. Refers to a device that performs emulsification, dispersion, pulverization, pulverization, and ultrafine processing. As the disperser, for example, a screw mixer, a paddle mixer, a disper mixer, a turbine mixer, or the like may be used.
本発明におけるホモジナイザーによる処理条件としては、特に限定されるものではないが、圧力条件としては、例えば７０ＭＰａ以上、好ましくは９０ＭＰａ以上、さらに好ましくは１００ＭＰａ以上である。また、高圧ホモジナイザーでの解繊・分散処理に先立って、必要に応じて、高速せん断ミキサーなどの公知の混合、攪拌、乳化、分散装置を用いて、アニオン変性セルロースに予備処理を施すことも可能である。 The treatment condition with the homogenizer in the present invention is not particularly limited, but the pressure condition is, for example, 70 MPa or more, preferably 90 MPa or more, and more preferably 100 MPa or more. In addition, prior to defibration / dispersion with a high-pressure homogenizer, anion-modified cellulose can be pretreated using known mixing, stirring, emulsifying, and dispersing equipment such as a high-speed shear mixer as necessary. It is.
処理前の液の２０℃におけるｐＨは特に限定されないが、約３〜７の範囲で維持されることが好ましい。水溶液の温度は約４〜４０℃において任意であるが、反応は室温（２０℃）で行うことも可能であり、温度制御を行なわないことも可能である。 The pH at 20 ° C. of the liquid before treatment is not particularly limited, but is preferably maintained in the range of about 3 to 7. The temperature of the aqueous solution is arbitrary at about 4 to 40 ° C., but the reaction can be performed at room temperature (20 ° C.) or temperature control can be omitted.
本発明の部分酸型CMC塩セルロースナノファイバー水分散体の製造方法では、前記工程（ii）の後、前記工程（v）の前に、（iii）前記部分酸型CMCを洗浄する工程、（iv）洗浄した部分酸型CMCと、所定量のアルカリを反応させる工程、を有することも好ましい態様である。 In the method for producing a partial acid type CMC salt cellulose nanofiber aqueous dispersion of the present invention, after the step (ii) and before the step (v), (iii) a step of washing the partial acid type CMC, iv) It is also a preferred embodiment to have a step of reacting the washed partial acid type CMC with a predetermined amount of alkali.
＜工程（iii）＞
工程（ii）で得られた部分酸型CMCを洗浄する工程である。洗浄溶媒としては、特に限定されないが、例えば、含水有機溶媒を使用することができる。含水有機溶媒の水と有機溶媒の質量比は、特に限定されないが、水：有機溶媒が１０：９０〜３０：７０が好ましく、１５：８５〜２５：７５がより好ましい。これらの範囲であれば、作業性の観点から好ましい。有機溶媒としては、特に限定されないが、例えば、メタノール、エタノール、ｎ−プロピルアルコール、ＩＰＡ、ｎ−ブチルアルコール、イソブチルアルコールなどの炭素数１〜４のアルコール類、アセトン、ジエチルケトン、メチルエチルケトンなどのケトン類、ジオキサン、ジエチルエーテルなどが挙げられる。これらは１種又は２種以上を使用することができる。これらの中で、メタノールが入手の容易さ、低価格、蒸留・再生の操作の容易さの観点から好ましい。
<Step (iii)>
This is a step of washing the partial acid type CMC obtained in the step (ii). Although it does not specifically limit as a washing | cleaning solvent, For example, a water-containing organic solvent can be used. The mass ratio of the water-containing organic solvent water to the organic solvent is not particularly limited, but water: organic solvent is preferably 10:90 to 30:70, and more preferably 15:85 to 25:75. These ranges are preferable from the viewpoint of workability. Examples of the organic solvent include, but are not limited to, alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propyl alcohol, IPA, n-butyl alcohol, and isobutyl alcohol, and ketones such as acetone, diethyl ketone, and methyl ethyl ketone. , Dioxane, diethyl ether and the like. These can use 1 type (s) or 2 or more types. Among these, methanol is preferable from the viewpoints of availability, low cost, and ease of distillation / regeneration operation.
工程（iii）において、洗浄溶媒を分離する方法としては、公知の方法であれば、特に限定されない。例えば、遠心分離法が挙げられる。洗浄工程は１回または複数回行なうことができ、３〜５回繰り返すことが好ましい。分離された洗浄液中の遊離酸量は、特に限定されないが、０．０５重量％以下が好ましく、検出限界以下であることがより好ましい。 In the step (iii), the method for separating the washing solvent is not particularly limited as long as it is a known method. For example, a centrifugation method is mentioned. The washing step can be performed once or a plurality of times, and is preferably repeated 3 to 5 times. The amount of free acid in the separated washing liquid is not particularly limited, but is preferably 0.05% by weight or less, and more preferably below the detection limit.
洗浄液の添加量は、工程（ii）で得られた部分酸型CMCの固形分に対して重量比で１０〜３０倍が好ましく、１５〜２５倍がより好ましい。洗浄液の添加量が、これらの範囲であれば、副生塩溶出量の点から、高純度化が可能となり、原材料使用量の点から、生産効率も良好となる。 The addition amount of the cleaning liquid is preferably 10 to 30 times by weight and more preferably 15 to 25 times the solid content of the partial acid type CMC obtained in the step (ii). If the addition amount of the cleaning liquid is within these ranges, high purity can be achieved in terms of the amount of by-product salt elution, and the production efficiency is also good in terms of the amount of raw material used.
洗浄する際の温度は、１０〜５０℃が好ましく、２０〜４０℃がより好ましい。洗浄する際の温度がこれらの範囲であれば、副生塩溶出量の点から、高純度化が可能となり、溶媒気化量の点から、作業環境上も好ましい。また、撹拌時間は、３０〜６０分間が好ましい。撹拌時間がこれらの範囲であれば、副生塩の溶出量が好適であり、作業性も良好である。 10-50 degreeC is preferable and the temperature at the time of washing | cleaning has more preferable 20-40 degreeC. If the temperature at the time of washing is within these ranges, high purity can be achieved from the viewpoint of the amount of by-product salt elution, and this is preferable from the viewpoint of the working environment from the viewpoint of the amount of solvent vaporization. Further, the stirring time is preferably 30 to 60 minutes. When the stirring time is within these ranges, the amount of by-product salt eluted is suitable, and the workability is also good.
工程（ｃ）で洗浄した後の酸型ＣＭＣの固形分濃度は、３０〜７０重量％が好ましく、４０〜６０重量％がより好ましい。固形分濃度がこれらの範囲であれば、酸置換度が充分かつ均一となることから好ましい。 The solid content concentration of the acid type CMC after washing in the step (c) is preferably 30 to 70% by weight, more preferably 40 to 60% by weight. If the solid content concentration is within these ranges, it is preferable because the degree of acid substitution is sufficient and uniform.
＜工程（iv）＞
工程（iii）で得られた洗浄した部分酸型CMCと、所定量のアルカリを反応させる工程である。特に限定されないが、例えば、アルカリを含む含水有機溶媒に添加してスラリー状にし、適宜攪拌操作を行いながら、部分酸型CMCとアルカリを反応させる方法が挙げられる。
<Process (iv)>
In this step, the washed partial acid type CMC obtained in the step (iii) is reacted with a predetermined amount of alkali. Although not particularly limited, for example, there is a method of adding a hydrous organic solvent containing an alkali to form a slurry and reacting the partially acid CMC with the alkali while appropriately performing a stirring operation.
工程（iv）において使用するアルカリとしては、特に限定されないが、例えば、前記工程（i）のアルカリ金属の水酸化物を用いることができる。これらの中で、価格および得られるCMC塩の特性の点から水酸化ナトリウム、水酸化カリウムが好ましい。アルカリの添加量としては、質量比で理論酸型置換度にするために必要な量の５〜１０倍が好ましく、６〜８倍がより好ましい。 Although it does not specifically limit as an alkali used in process (iv), For example, the hydroxide of the alkali metal of the said process (i) can be used. Among these, sodium hydroxide and potassium hydroxide are preferable from the viewpoint of cost and characteristics of the obtained CMC salt. The addition amount of the alkali is preferably 5 to 10 times, more preferably 6 to 8 times the amount necessary to obtain the theoretical acid type substitution degree by mass ratio.
工程（iv）において使用する含水有機溶媒の水と有機溶媒の重量比としては、特に限定されないが、水：有機溶媒が５：９５〜２０：８０が好ましく、１０：９０〜１５：８５がより好ましい。これらの範囲であれば、反応系中のアルカリ濃度を充分に高濃度に保つことができる。工程（iv）において使用する有機溶媒としては、特に限定されないが、例えば、前記工程（i）の有機溶媒を用いることができる。入手の容易さ、低価格、取り扱いやすさの点で、Ｉ ＰＡ 、エタノール、メタノールが好ましい。 The weight ratio of the water-containing organic solvent used in step (iv) to the organic solvent is not particularly limited, but water: organic solvent is preferably 5: 95-20: 80, more preferably 10: 90-15: 85. preferable. Within these ranges, the alkali concentration in the reaction system can be kept sufficiently high. Although it does not specifically limit as an organic solvent used in process (iv), For example, the organic solvent of the said process (i) can be used. IPA, ethanol, and methanol are preferable in terms of availability, low cost, and ease of handling.
工程（iv）における温度は、１０〜８０℃が好ましく、２０〜７０℃がより好ましい。反応温度がこれらの範囲であれば、反応が充分かつ均一となることから好ましい。また、反応時間は、３０〜７０分間が好ましく、４０〜６０分間がより好ましい。反応時間がこれらの範囲であれば、反応が充分かつ作業効率も良好となる。 10-80 degreeC is preferable and, as for the temperature in process (iv), 20-70 degreeC is more preferable. A reaction temperature within these ranges is preferable because the reaction is sufficient and uniform. The reaction time is preferably 30 to 70 minutes, more preferably 40 to 60 minutes. When the reaction time is within these ranges, the reaction is sufficient and the working efficiency is good.
本発明におけるセルロースナノファイバーの製造方法は、前記工程（v）で得られたセルロースナノファイバー水分散体の溶媒を除去する工程を有する。溶媒を除去する方法としては、特に限定されないが、例えば、濾別、濃縮操作などが挙げられる。溶媒除去には、特に限定されないが、例えば、有機溶剤、或いは、水と有機溶剤の混合溶媒を用いることができる。 The manufacturing method of the cellulose nanofiber in this invention has the process of removing the solvent of the cellulose nanofiber aqueous dispersion obtained at the said process (v). Although it does not specifically limit as a method of removing a solvent, For example, filtration separation, concentration operation, etc. are mentioned. Although it does not specifically limit for solvent removal, For example, the organic solvent or the mixed solvent of water and an organic solvent can be used.
本発明におけるセルロースナノファイバー水分散体の製造方法、セルロースナノファイバーの製造方法としては前記（i）〜（iv）の各工程において、その工程終了後に、必要に応じて、精製の目的で反応粗製物を水、或いは、有機溶剤、或いは、水と有機溶剤の混合溶媒を用いて洗浄し、遠心分離、減圧蒸留などの手法を用いて、溶媒除去し、セルロースナノファイバーの濾別、或いは、濃縮操作を伴ってもよい。また、必要に応じて他の処理を行っても良い。 As the method for producing an aqueous dispersion of cellulose nanofibers and the method for producing cellulose nanofibers in the present invention, in each of the steps (i) to (iv), after completion of the steps, reaction crude for purification purposes, if necessary. The product is washed with water, an organic solvent, or a mixed solvent of water and an organic solvent, and the solvent is removed by using a method such as centrifugation or distillation under reduced pressure, and cellulose nanofibers are filtered or concentrated. It may be accompanied by an operation. Moreover, you may perform another process as needed.
前記工程（i）〜（v）によって得られる部分酸型CMC塩の全置換度（エーテル化度）は、０．０２〜０．８０であることが好ましく、０．１〜０．７５がより好ましい。これらの範囲であれば、水への膨潤あるいは溶解を抑制することができる。なお、CMC塩の全置換度（エーテル化度）は、実施例に記載の方法で算出することができる。 The total substitution degree (etherification degree) of the partial acid type CMC salt obtained by the steps (i) to (v) is preferably 0.02 to 0.80, more preferably 0.1 to 0.75. preferable. Within these ranges, swelling or dissolution in water can be suppressed. The total substitution degree (etherification degree) of the CMC salt can be calculated by the method described in the examples.
前記工程（i）〜（v）によって得られる部分酸型CMC塩の酸型置換度は全置換度（エーテル化度）の１．０〜８０．０％が好ましく、１０．０〜６５．０％がより好ましい。酸型置換度が１．０％以上であれば、酸型置換基の効果を得ることができ、一方、酸型置換度が８０．０％以下であれば、セルロースナノファイバーの解繊が容易になる。 The acid type substitution degree of the partial acid type CMC salt obtained by the steps (i) to (v) is preferably 1.0 to 80.0% of the total substitution degree (etherification degree), and 10.0 to 65.0. % Is more preferable. If the acid type substitution degree is 1.0% or more, the effect of the acid type substituent can be obtained. On the other hand, if the acid type substitution degree is 80.0% or less, the cellulose nanofibers are easily defibrated. become.
また、解繊工程中において、或いは、水分散体として保管する場合において、水中のｐＨが低下して品質を劣化させる懸念も抑制される。この観点からは、得られる部分酸型CMC塩セルロースナノファイバー、及び、その水分散体の２０℃におけるｐＨは、ｐＨ６．０以上とするのが好ましい。なお、CMC塩の酸型置換度は、実施例に記載の方法で算出することができる。ｐＨショック抑制の効果の観点からは、２０℃におけるｐＨを、ｐＨ３．０〜６．０とすることも好ましい態様である。 Moreover, in the case of storing as a water dispersion during a defibrating process, the concern that the pH in water decreases and the quality deteriorates is also suppressed. From this viewpoint, the pH of the obtained partial acid CMC salt cellulose nanofiber and the aqueous dispersion thereof at 20 ° C. is preferably pH 6.0 or more. The acid type substitution degree of the CMC salt can be calculated by the method described in the examples. From the viewpoint of the effect of suppressing the pH shock, it is also a preferable aspect that the pH at 20 ° C. is set to pH 3.0 to 6.0.
部分酸型ＣＭＣにおける残余カルボキシメチル基は、前記の工程（i）で用いられたアルカリ金属の水酸化物により得られるアルカリ塩があげられ、具体的には、ナトリウム塩、カリウム塩、リチウム塩、ルビジウム塩およびセシウム塩等があげられる。これらの中で、ナトリウム塩、カリウム塩が、一般的に好ましく用いられる。 Examples of the residual carboxymethyl group in the partial acid type CMC include alkali salts obtained from the alkali metal hydroxide used in the step (i), specifically, sodium salts, potassium salts, lithium salts, Examples thereof include a rubidium salt and a cesium salt. Of these, sodium salts and potassium salts are generally preferably used.
本発明のセルロースナノファイバー、およびその水分散体は、増粘剤、ゲル化剤、保形剤、乳化安定化剤、分散安定化剤などに利用できる。具体的には、食品、化粧品、医薬品、医療、農薬、トイレタリー用品、スプレー剤、塗料、等の用途で幅広く使用することができる。また、弱酸性領域でｐＨショックを生じることがないことから、特に、２０℃におけるｐＨが３．０〜５．５の領域において好ましく使用できる。具体的には、乳酸菌飲料やヨーグルト、酸性乳飲料、スポーツドリンク、乳幼児用イオン飲料、機能型ドリンク、ゼリー飲料、カロリー摂取型ドリンク、デザートドリンク、ベビーフード、ジャム、ドレッシング、マヨネーズ、ケチャップ、ウスターソース、バーベキューソース、焼肉ソース、各種食用タレ、つゆ、ジュレ状調味料等に好適に使用できる。また、セルロースナノファイバー水分散体を中間原料として更に化学修飾や加工して利用することもできる。 The cellulose nanofiber of the present invention and an aqueous dispersion thereof can be used as a thickener, a gelling agent, a shape retention agent, an emulsion stabilizer, a dispersion stabilizer, and the like. Specifically, it can be widely used in applications such as foods, cosmetics, pharmaceuticals, medical care, agricultural chemicals, toiletries, sprays, and paints. Moreover, since a pH shock does not occur in a weakly acidic region, it can be preferably used particularly in a region where the pH at 20 ° C. is 3.0 to 5.5. Specifically, lactic acid bacteria beverages and yogurt, acidic milk beverages, sports drinks, infant ion beverages, functional drinks, jelly drinks, calorie intake drinks, dessert drinks, baby food, jams, dressings, mayonnaise, ketchup, Worcester sauce, It can be suitably used for barbecue sauce, grilled meat sauce, various edible sauces, soup sauce, jelly-like seasonings and the like. Further, the cellulose nanofiber aqueous dispersion can be further used as an intermediate material after further chemical modification or processing.
本発明のセルロースナノファイバー、およびその水分散体を含有する前記用途（食品、化粧料等）においては、任意成分として、ｐＨ調整のためのｐＨ調整剤、或いは、ｐＨ緩衝剤、防腐剤を含有してもよい。また、乳化、分散、食感改良、テキスチャー改良、粘性改良、油脂改質など目的で、本発明の効果を損なわない範囲で界面活性剤や水溶性高分子などを含有してもよい。 In the said use (foodstuffs, cosmetics, etc.) containing the cellulose nanofiber of this invention, and its water dispersion, the pH adjuster for pH adjustment, or a pH buffer agent and a preservative is contained as an arbitrary component. May be. In addition, for the purpose of emulsification, dispersion, texture improvement, texture improvement, viscosity improvement, oil and fat modification, a surfactant or a water-soluble polymer may be contained within a range not impairing the effects of the present invention.
以下、実施例及び比較例に基づいて、本発明について詳細に説明するが、本発明はもちろんこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, of course this invention is not limited to these.
カルボキシメチル化の全置換度（エーテル化度）、塩型置換度および酸型置換度は以下の方法により測定した。 The total substitution degree (etherification degree), salt type substitution degree, and acid type substitution degree of carboxymethylation were measured by the following methods.
＜（１）工程（i）で得られたCMCの全置換度（エーテル化度） ※Ｎａ塩の場合＞
試料１ｇ（純分換算）を磁性ルツボに入れて６００℃で灰化し、灰化によって生成した酸化ナトリウムをＮ／１０のＨ２ＳＯ４ １００ｍｌを添加して中和した。次に、過剰のＨ２ＳＯ４ をＮ／１０のＮａＯＨでフェノールフタレインを指示薬として滴定し、その滴下量Ａ（ｍｌ）から下記式にて全置換度（エーテル化度）を求めた。なお、このとき、ｆ１＝Ｎ／１０のＨ２ＳＯ４の力価、ｆ２＝Ｎ／１０のＮａＯＨの力価である。
A sample 1 g (in terms of pure content) was put into a magnetic crucible and incinerated at 600 ° C., and sodium oxide produced by incineration was neutralized by adding 100 ml of N / 10 H 2 SO 4 . Next, excess H 2 SO 4 was titrated with N / 10 NaOH using phenolphthalein as an indicator, and the total degree of substitution (degree of etherification) was determined from the amount A (ml) added by the following formula. At this time, f 1 = the titer of H 2 SO 4 with N / 10, and f 2 = the titer of NaOH with N / 10.
＜（２）工程（iv）で得られた部分酸型ＣＭＣの塩型置換度および酸型置換度＞
試料１ｇ（純分換算）を純水２００ｍｌとＮ／１０のＮａＯＨ１００ｍｌが入っているフラスコ中に入れて溶解した。次に、過剰のＮ／１０のＮａＯＨをＮ／１０のＨ２ＳＯ４ でフェノールフタレインを指示薬として滴定し、その滴下量Ｂ（ｍｌ）を得た。次に、別の試料１ｇ（純分換算）を磁性ルツボに入れて６００℃で灰化し、灰化によって生成した酸化ナトリウムをＮ／１０のＨ２ＳＯ４ １００ｍｌを添加して中和した。次に、過剰のＨ２ＳＯ４ をＮ／１０のＮａＯＨでフェノールフタレインを指示薬として滴定し、その滴下量Ｃ（ｍｌ）を得た。次に、次式によって塩型置換度および酸型置換度を求めた。なお、このとき、ｆ１＝Ｎ／１０のＨ２ＳＯ４の力価、ｆ２＝Ｎ／１０のＮａＯＨの力価である。
1 g of sample (in terms of pure content) was dissolved in a flask containing 200 ml of pure water and 100 ml of N / 10 NaOH. Next, excess N / 10 NaOH was titrated with N / 10 H 2 SO 4 using phenolphthalein as an indicator to obtain a dripping amount B (ml). Next, another sample 1 g (in terms of pure content) was put in a magnetic crucible and incinerated at 600 ° C., and sodium oxide produced by incineration was neutralized by adding 100 ml of N / 10 H 2 SO 4 . Next, excess H 2 SO 4 was titrated with N / 10 NaOH using phenolphthalein as an indicator to obtain a dripping amount C (ml). Next, the salt type substitution degree and the acid type substitution degree were determined by the following equations. At this time, f 1 = the titer of H 2 SO 4 with N / 10, and f 2 = the titer of NaOH with N / 10.
＜実施例１＞
工程（i）
２軸の撹拌翼と溶剤の揮散を抑えるためのコンデンサーを備えた容量３リットルのニーダー型反応機に、表１記載の原料パルプを選択し、更に家庭用ミキサーで粉砕したパルプ１００ｇ（乾燥重量）を仕込み、IPA：水＝２８０ｇ：１２０ｇで調製した混合溶媒４００ｇに、表１記載の所定量の水酸化ナトリウムを溶解させて４０℃に調整した溶液を反応機内に仕込み、６０分間撹拌してアルカリセルロースを調製した。そののち、表１記載の所定量のモノクロル酢酸を等重量のIPAに溶解させた溶液を、反応熱を抑えながら３０〜５０℃で６０分間かけて仕込んだ。次いで、３０分間かけて８５℃に昇温し、７５〜９０℃でカルボキシルメチル化反応を６０分間行った。次いで、スラリー状の中和物を反応機より取り出し、遠心分離操作にてIPA−水混合溶媒を除去して固形分濃度５０重量％のCMC-Na塩粗製物（表１−1の実施例（Ａ）〜（Ｄ））を得た。
<Example 1>
Process (i)
100 g (dry weight) of the pulp selected from the raw pulp listed in Table 1 in a kneader reactor with a capacity of 3 liters equipped with a biaxial stirring blade and a condenser for suppressing the volatilization of the solvent, and further pulverized with a household mixer A solution prepared by dissolving a predetermined amount of sodium hydroxide described in Table 1 in 40 g of a mixed solvent prepared at IPA: water = 280 g: 120 g and adjusted to 40 ° C. was added to the reactor, and the mixture was stirred for 60 minutes for alkali. Cellulose was prepared. After that, a solution prepared by dissolving a predetermined amount of monochloroacetic acid shown in Table 1 in an equal weight of IPA was charged at 30 to 50 ° C. over 60 minutes while suppressing the heat of reaction. Subsequently, it heated up to 85 degreeC over 30 minutes, and carboxylmethylation reaction was performed for 60 minutes at 75-90 degreeC. Next, the slurry-like neutralized product was taken out from the reactor, and the IPA-water mixed solvent was removed by a centrifugal operation to obtain a CMC-Na salt crude product having a solid concentration of 50% by weight (Examples in Table 1-1). A) to (D)) were obtained.
工程（ii）〜（iii）
前記工程により得られたCMC-Na塩粗製物に対して、表１に示す２０％硫酸を添加し、３０分間撹拌後、更に、７０℃で５０分間攪拌して部分酸型CMC粗製物を得た。得られた部分酸型CMCに対して、重量比で２０倍となるように８０％メタノール水溶液を添加し、３０℃で５０分間撹拌した。撹拌後、遠心分離機でメタノール水溶液を遠心分離により除去し、この８０％メタノール水溶液による洗浄と溶媒除去の操作を４回繰り返し、遠心分離回収液の遊離液から遊離酸が検出されないことを確認して、固形分濃度５０重量％の部分酸型CMCを得た（表１−1の実施例（Ａ）〜（Ｄ））。
Steps (ii) to (iii)
20% sulfuric acid shown in Table 1 is added to the crude CMC-Na salt obtained in the above step, stirred for 30 minutes, and further stirred at 70 ° C. for 50 minutes to obtain a partially acid CMC crude product. It was. An 80% aqueous methanol solution was added to the obtained partial acid CMC so that the weight ratio was 20 times, and the mixture was stirred at 30 ° C. for 50 minutes. After stirring, the aqueous methanol solution was removed by centrifugation using a centrifuge, and the operations of washing with 80% aqueous methanol solution and removing the solvent were repeated four times to confirm that no free acid was detected from the free liquid of the centrifugally recovered liquid. Thus, a partial acid type CMC having a solid content concentration of 50% by weight was obtained (Examples (A) to (D) in Table 1-1).
工程（iv）
表1記載の通り、前記工程により得られた部分酸型CMCを秤取し、更に、所定の水酸化ナトリウムを含む８０％メタノール水溶液を添加し、スラリー状の溶液を３０℃で５０分間撹拌させて部分酸型CMC粗製物を得た。その後、遠心分離機で溶媒除去を行い、更に、８０％メタノール水溶液による洗浄と溶媒除去の操作を２回繰り返し、固形分濃度５０重量％にて部分酸型CMCを取り出した。得られた部分酸型CMCの全置換度（エーテル化度）、塩型置換度および酸型置換度を測定し、その測定結果を表１に示した。
Step (iv)
As shown in Table 1, the partial acid type CMC obtained by the above step was weighed, and further an 80% aqueous methanol solution containing predetermined sodium hydroxide was added, and the slurry solution was stirred at 30 ° C. for 50 minutes. In this way, a crude product of partial acid type CMC was obtained. Thereafter, the solvent was removed with a centrifuge, and the operation of washing with 80% methanol aqueous solution and the removal of the solvent were repeated twice, and the partial acid type CMC was taken out at a solid concentration of 50% by weight. The total substitution degree (etherification degree), salt substitution degree and acid substitution degree of the obtained partial acid type CMC were measured, and the measurement results are shown in Table 1.
工程（v）
前記工程により得られた部分酸型CMCに対して、固形分濃度３％となるよう水を添加し、更に、高圧ホモジナイザー処理の前に処理液のｐＨを水酸化ナトリウム、酢酸ナトリウム、酢酸を用いてｐＨ５．０±０．３の範囲内となるよう調整した後、高圧ホモジナイザーにより、液温２０℃から冷却操作を伴いながら１４０ＭＰａの圧力で５回処理して目的のセルロースナノファイバー水分散液を調製した（表１−1の実施例（Ａ）〜（Ｄ））。
Process (v)
Water is added to the partial acid type CMC obtained by the above process so that the solid content concentration becomes 3%, and the pH of the treatment solution is adjusted with sodium hydroxide, sodium acetate, acetic acid before the high-pressure homogenizer treatment. After adjusting the pH to be within the range of 5.0 ± 0.3, the target cellulose nanofiber aqueous dispersion is treated with a high-pressure homogenizer five times at a pressure of 140 MPa while being cooled from a liquid temperature of 20 ° C. (Examples (A) to (D) in Table 1-1).
＜実施例２＞
実施例１、及び、表１−1に記載の実施例（Ｄ）において、工程（iv）で使用する中和剤を水酸化ナトリウムから水酸化カリウムに変更し、工程（iv）で使用するｐＨ調整剤を水酸化ナトリウムから水酸化カリウムに、酢酸ナトリウムから酢酸カリウムに、変更した以外は前記操作と同様にしてセルロースナノファイバー水分散液（表１の実施例（Ｅ））を得た。
<Example 2>
In Example 1 and Example (D) described in Table 1-1, the neutralizing agent used in step (iv) was changed from sodium hydroxide to potassium hydroxide, and the pH used in step (iv). A cellulose nanofiber aqueous dispersion (Example (E) in Table 1) was obtained in the same manner as in the above operation except that the modifier was changed from sodium hydroxide to potassium hydroxide and from sodium acetate to potassium acetate.
＜実施例３＞
実施例１、及び、表１−1に記載の実施例（Ａ）において、工程（i）で使用するパルプ種を広葉樹パルプから針葉樹パルプに変更し、更に、工程（i）終了後、IPA−水混合溶媒による洗浄と溶媒除去の操作を２回繰り返し、その後、工程（ii）として、硫酸を用いてｐＨ５となるよう攪拌しながら注意深く酸を添加し、必要に応じて、工程中で水酸化ナトリウム、酢酸ナトリウムと酢酸を用いてｐＨ調整しながらが、７０℃で５０分間攪拌した以外は前記操作と同様にしてセルロースナノファイバー水分散液（表１−1の実施例（Ｆ））を得た。
<Example 3>
In Example 1 and Example (A) described in Table 1-1, the pulp type used in step (i) is changed from hardwood pulp to softwood pulp, and after step (i), IPA- Washing with a mixed solvent of water and removal of the solvent were repeated twice, and then as step (ii), acid was carefully added with stirring to pH 5 with sulfuric acid, and hydroxylation was carried out during the process if necessary. While adjusting pH using sodium, sodium acetate and acetic acid, an aqueous cellulose nanofiber dispersion (Example (F) in Table 1-1) was obtained in the same manner as above except that the mixture was stirred at 70 ° C. for 50 minutes. It was.
＜比較例１＞
実施例１、及び、表１−1に記載の工程（i）〜（v）において、各成分の仕込み量を表1−1の比較例（Ｘ）、及び、比較例（Ｙ）のように変更した以外は、前記操作と同様にしてセルロースナノファイバー水分散液（表１−１の比較例（Ｘ）、（Ｙ））を調製した。しかしながら、比較例（Ｙ）については、高圧ホモジナイザー処理中に処理液回収タンク内不均一の発生と高圧ホモジナイザーの詰まりが生じ、やむを得ず、工程（v）をした中断した。
<Comparative Example 1>
In the steps (i) to (v) described in Example 1 and Table 1-1, the charged amounts of the respective components are set as in Comparative Example (X) and Comparative Example (Y) in Table 1-1. A cellulose nanofiber aqueous dispersion (Comparative Examples (X) and (Y) in Table 1-1) was prepared in the same manner as in the above operation except that the change was made. However, in Comparative Example (Y), non-uniformity in the treatment liquid recovery tank and clogging of the high-pressure homogenizer occurred during the high-pressure homogenizer treatment, and the process (v) was interrupted.
＜比較例２＞
実施例１、及び、表１−1に記載の実施例（Ａ）において、工程（i）の操作に従ってカルボキシメチル化を行った後、IPA−水混合溶媒による洗浄と溶媒除去の操作を２回繰り返し、工程（ii）〜（iv）を省略して、続いて、前記工程（v）の操作に従って高圧ホモジナイザー処理を行い、不均一状粘稠液体（表１−１の比較例（Ｚ））を得た。比較例（Ｚ）については、酸型置換未実施の為、工程（v）にてｐＨ未調整（ｐＨ７．４）とした。
<Comparative Example 2>
In Example 1 and Example (A) described in Table 1-1, carboxymethylation was performed according to the operation of step (i), and then washing with an IPA-water mixed solvent and solvent removal were performed twice. Repeatedly, the steps (ii) to (iv) were omitted, and subsequently, a high-pressure homogenizer treatment was performed according to the operation of the step (v) to obtain a heterogeneous viscous liquid (Comparative Example (Z) in Table 1-1). Got. About comparative example (Z), since acid type substitution was not implemented, it was set as pH unadjusted (pH 7.4) at the process (v).
実施例１〜３、及び、比較例１、２にて得られたセルロースナノファイバー水分散体、実施例（Ａ）〜（Ｆ）、比較例（Ｘ）、（Ｚ）について、その性状（透明性、ゲル化の有無、曳糸性の有無）について調べた結果を表２に示す。なお、測定前に必要に応じて前記操作に準じて、ｐＨ５±０．３の範囲内となるようｐＨ調整後、各種評価を実施した。また、比較例（Ｚ＊）は、比較例（Ｚ）（ｐＨ７．４）について以下評価を実施するに当り、ｐＨ５．０±０．３に調整したものであり、供試した比較例（Ｚ＊）のｐＨはｐＨ５．０であった。 About the cellulose nanofiber aqueous dispersion obtained in Examples 1 to 3 and Comparative Examples 1 and 2, Examples (A) to (F), and Comparative Examples (X) and (Z), the properties (transparent Table 2 shows the results of examining the properties, the presence or absence of gelation, and the presence or absence of spinnability. In addition, according to the said operation as needed before measurement, various evaluation was implemented after adjusting pH so that it might become in the range of pH5 +/- 0.3. Further, Comparative Example (Z *) was adjusted to pH 5.0 ± 0.3 for the following evaluation of Comparative Example (Z) (pH 7.4). *) The pH was 5.0.
＜透明性＞
一定光源下、固形分濃度０．５％のセルロースナノファイバー水分散体を３０ｍｍの光路長を持つ透明ガラスセルに入れ、白色上質紙に印字された１２ポイントの文字（ゴシック体）をセルの向こう側に接するように配置し、その文字を判別できたものを「○」、判別できなかったものを「×」、部分的な不均一状態が認められるものを「△」と評価した。これら結果を表１−２に示した。なお、表中の「１D」は1日後、「１W」は7日後を表す。
<Transparency>
Place a cellulose nanofiber aqueous dispersion with a solid content of 0.5% in a transparent glass cell with an optical path length of 30 mm under a constant light source, and put 12-point characters (gothic) printed on white fine paper over the cell. It was arranged so as to be in contact with the side, and “◯” indicates that the character could be identified, “×” indicates that the character could not be identified, and “Δ” indicates that a partial non-uniform state was recognized. These results are shown in Table 1-2. In the table, “1D” represents one day later, and “1W” represents seven days later.
＜ゲル化性＞
固形分濃度３．０％で調製された実施例（Ａ）〜（Ｆ）、比較例（Ｘ）、（Ｚ）を所定の固形分濃度になるよう水を添加して、ディスパー型ミキサーを用いて回転数８，０００ｒｐｍで１０分間微細化処理を行って、２００ｍｌねじ口付きガラス製サンプル瓶に流し込み、評価用の試料を得た。各試料について、所定日数経過後のゲルの状態を目視で観察し、ゲル状態のものを「○」、液状（流動性あり）のものを「×」、ゲルから離水が見られたものを「△」と評価した。これら結果を表１−２に示した。なお、表中の「１D」は1日後、「１W」は7日後を表す。
<Gelability>
Add water so that Examples (A) to (F) and Comparative Examples (X) and (Z) prepared at a solid content concentration of 3.0% have a predetermined solid content concentration, and use a Disper mixer. The sample was refined for 10 minutes at a rotational speed of 8,000 rpm and poured into a 200 ml glass sample bottle with a screw cap to obtain a sample for evaluation. For each sample, the state of the gel after the lapse of a predetermined number of days was visually observed, “○” for the gel state, “×” for the liquid (with fluidity), "". These results are shown in Table 1-2. In the table, “1D” represents one day later, and “1W” represents seven days later.
＜曳糸性＞
固形分濃度３．０％で調製された実施例（Ａ）〜（Ｆ）、比較例（Ｘ）、（Ｚ）を所定の固形分濃度になるよう水を添加して、ディスパー型ミキサーを用いて回転数８，０００ｒｐｍで１０分間微細化処理を行って、２００ｍｌねじ口付きガラス製サンプル瓶に流し込み、評価用の試料を得た。各試料について、所定日数経過後に外径１０ｍｍの表面平滑なガラス棒をサンプル瓶中央に垂直に立て、その状態からガラス棒を約1秒間で引き抜き、その際のガラス棒先端における曳糸状態を目視で観察し、曳糸性が認められないものを「○」、曳糸性が認められないものを「×」、僅かな曳糸性、或いは、ガラス棒へのゲル付着などが認められるものを「△」と評価した。これら結果を表１−２に示した。なお、表中の「１D」は1日後、「１W」は7日後を表す。
<Spinning>
Add water so that Examples (A) to (F) and Comparative Examples (X) and (Z) prepared at a solid content concentration of 3.0% have a predetermined solid content concentration, and use a Disper mixer. The sample was refined for 10 minutes at a rotational speed of 8,000 rpm and poured into a 200 ml glass sample bottle with a screw cap to obtain a sample for evaluation. For each sample, a smooth glass rod with an outer diameter of 10 mm is set up vertically in the center of the sample bottle after a predetermined number of days, and the glass rod is pulled out in about 1 second from that state, and the state of the string at the tip of the glass rod at that time is visually observed. Observed with `` ○ '' if the spinnability is not recognized, `` X '' if the spinnability is not recognized, and those that show slight spinnability or gel adhesion to the glass rod Evaluated as “△”. These results are shown in Table 1-2. In the table, “1D” represents one day later, and “1W” represents seven days later.
※６： 比較例（Ｚ）（ｐＨ７．４）を評価直前にｐＨ５±０．３に調整実施。
* 6: Comparative Example (Z) (pH 7.4) was adjusted to pH 5 ± 0.3 immediately before evaluation.
《製造例：酸性乳飲料、及び、乳酸菌飲料》
弱酸性領域での分散安定性が必要とされる酸性飲料、乳酸菌飲料組成物の製造処方について、本発明の前記実施例、及び、比較例で示したセルロースナノファイバー水分散体を用いて、下記処方に従って飲料組成物を調製し、以下記載の評価方法に従って評価を行った。
<< Production Example: Acidic Milk Beverage and Lactic Acid Beverage Beverage >>
With respect to the production formulation of acidic beverages and lactic acid bacteria beverage compositions that require dispersion stability in a weakly acidic region, using the cellulose nanofiber aqueous dispersions shown in the Examples and Comparative Examples of the present invention, the following Beverage compositions were prepared according to the prescription and evaluated according to the evaluation methods described below.
＜製造例１：酸性乳飲料＞
表３記載の処方に従い、２Ｌサイズの円形ステンレス製取手付容器に固形分濃度３％で調製された本発明のセルロースナノファイバー水分散体２００ｇ（固形分換算６ｇ）を仕込み、幅広翼を装着した攪拌装置で攪拌しながら、液温を３０℃とし、ついで、脱脂粉乳４０ｇを水５００ｇとともに少しずつ投入して、攪拌、混合して均一分散させ、続いて、３０℃の温度で、１０分間かけて３０℃に調整した３％クエン酸水溶液１００ｇを徐々に滴下して脱脂粉乳混合液を得た。次に、調整水を用いてホモジナイザー通液の準備を行い、その後、脱脂粉乳混合液を１５ＭＰａにてホモジナイザーに１回通液し、更に、その脱脂粉乳混合液を９０℃まで昇温して加熱殺菌を行い、その後、水浴中で１０℃まで冷却して目的の酸性乳飲料組成物を得た。このとき、得られた酸性乳飲料組成物は、無脂乳固形分は４．０％、セルロースナノファイバー（固形分換算）０．６％を含み、２０℃におけるｐＨは４．６〜４．９であった。
<Production Example 1: Acidic milk beverage>
In accordance with the formulation shown in Table 3, 200 g of cellulose nanofiber aqueous dispersion of the present invention prepared at a solid content concentration of 3% (6 g in terms of solid content) was charged into a 2 L circular stainless steel handle container, and wide wings were mounted. While stirring with a stirrer, the liquid temperature is set to 30 ° C., and then 40 g of skim milk powder is added little by little together with 500 g of water, stirred, mixed and uniformly dispersed, and then at a temperature of 30 ° C. for 10 minutes. 100 g of 3% aqueous citric acid solution adjusted to 30 ° C. was gradually added dropwise to obtain a skim milk powder mixture. Next, preparation of homogenizer flow is performed using adjusted water, and then the skim milk powder mixture is passed once through the homogenizer at 15 MPa, and the skim milk powder mixture is heated to 90 ° C. and heated. Sterilization was performed, and then the mixture was cooled to 10 ° C. in a water bath to obtain a target acidic milk beverage composition. At this time, the obtained acidic milk beverage composition contains 4.0% non-fat milk solids and 0.6% cellulose nanofibers (solid content conversion), and the pH at 20 ° C. is 4.6 to 4. It was 9.
＜製造例２：乳酸菌飲料＞
表４記載の処方に従い、２Ｌサイズの円形ステンレス製取手付容器に固形分濃度３％で調製された本発明のセルロースナノファイバー水分散体２００ｇ（固形分換算６ｇ）を仕込み、幅広翼を装着した攪拌装置で攪拌しながら、液温を２０℃とし、別に調製した水４００ｇ、グラニュー糖１５ｇ、７０％異性化液糖９５ｇを溶解させた糖混合液を徐々に加え、攪拌を継続しながら、８０℃まで昇温して１０分間加熱殺菌を行い、その後、水浴中で２０℃まで冷却して、醗酵乳（カード）３０ｇを少量ずつ投入して、攪拌、混合して均一分散させて醗酵乳混合液を得た。次に、調整水の一部を用いてホモジナイザー通液の準備を行い、残りの調整水は醗酵乳混合液に加え、その後、醗酵乳混合液を１５ＭＰａにてホモジナイザーに１回通液し、更に、その醗酵乳混合液を９０℃まで昇温して加熱殺菌を行い、その後、水浴中で２０℃まで冷却して目的の乳酸菌飲料組成物を得た。このとき、得られた乳酸菌飲料組成物は、醗酵乳固形分は３．０％、セルロースナノファイバー（固形分換算）０．６％を含み、２０℃におけるｐＨは３．７〜４．０であった。
<Production Example 2: Lactic acid bacteria beverage>
In accordance with the formulation described in Table 4, a cellulose nanofiber aqueous dispersion 200 g (solid content conversion 6 g) of the present invention prepared at a solid content concentration of 3% was charged into a 2 L circular stainless steel handle-equipped container, and wide wings were attached. While stirring with a stirrer, the liquid temperature was set to 20 ° C., and a sugar mixture solution in which 400 g of separately prepared water, 15 g of granulated sugar, and 95 g of 70% isomerized liquid sugar were dissolved was gradually added. The temperature is raised to ℃ and sterilized by heating for 10 minutes, then cooled to 20 ℃ in a water bath, 30 g of fermented milk (curd) is added little by little, stirred, mixed and uniformly dispersed to mix the fermented milk A liquid was obtained. Next, a part of the adjusted water is used to prepare the homogenizer flow, the remaining adjusted water is added to the fermented milk mixture, and then the fermented milk mixture is passed once through the homogenizer at 15 MPa, and further The fermented milk mixture was heated to 90 ° C. and sterilized by heating, and then cooled to 20 ° C. in a water bath to obtain the intended lactic acid bacteria beverage composition. At this time, the obtained lactic acid bacteria beverage composition contains 3.0% fermented milk solids, 0.6% cellulose nanofibers (solid content conversion), and the pH at 20 ° C is 3.7 to 4.0. there were.
製造例１、２において得られた酸性乳飲料、及び、乳酸菌飲料について、以下の方法によって、乳蛋白沈澱量、及び、乳蛋白再分散性評価からセルロースナノファイバーの分散安定性を評価した。 With respect to the acidic milk beverages and lactic acid bacteria beverages obtained in Production Examples 1 and 2, the dispersion stability of cellulose nanofibers was evaluated from the milk protein precipitation amount and milk protein redispersibility evaluation by the following methods.
＜乳蛋白沈澱量＞
得られた酸性乳飲料、及び、乳酸菌飲料を、長さ２５０ｍｍ、１００ｍｌ容のガラス製円筒管に充填し、密栓して５℃にて２週間静置した。２週間後、円筒管を静かに取り出し、円筒管底部の乳蛋白沈澱量を計測した。なお、当該評価において、乳蛋白沈澱量はその数値が小さいほど乳蛋白に対する分散安定性に優れていることを示す。これら結果を表５に示した。
<Milk protein precipitation amount>
The obtained acidic milk beverage and lactic acid bacteria beverage were filled in a glass cylindrical tube having a length of 250 mm and a volume of 100 ml, sealed, and allowed to stand at 5 ° C. for 2 weeks. Two weeks later, the cylindrical tube was gently taken out, and the milk protein precipitation amount at the bottom of the cylindrical tube was measured. In addition, in the said evaluation, it shows that the milk protein precipitation amount is excellent in the dispersion stability with respect to milk protein, so that the numerical value is small. These results are shown in Table 5.
＜乳蛋白再分散性＞
上記乳蛋白沈澱量測定の後、密栓された円筒管を一旦静かに１８０°回転させて逆さにし、その後、乳蛋白の沈澱再分散性を記録しながら、円筒管を静かに３６０°回転させる操作を準じ行い、円筒管底部に付着している沈澱が再分散するまでの円筒管の回転回数を計測した。なお、当該評価において、この円筒管の回転回数が少ないほど、乳蛋白の分散性に優れていることを示す。これら結果を表５に示した。
<Milk protein redispersibility>
After measuring the milk protein precipitation amount, the sealed tube is gently rotated 180 ° and turned upside down, and then the cylinder tube is gently rotated 360 ° while recording the milk protein precipitation redispersibility. And the number of rotations of the cylindrical tube until the precipitate adhering to the bottom of the cylindrical tube was redispersed was measured. In this evaluation, the smaller the number of rotations of the cylindrical tube, the better the milk protein dispersibility. These results are shown in Table 5.
本発明のセルロースナノファイバーは、表５に示す通り、供試した実施例（Ａ）、（Ｃ）、（Ｄ）、（Ｆ）は、比較例（Ｘ）、（Ｚ）、対照例（ＣＭＣ‐Ｎａ塩）に比較して、酸性乳飲料、及び、乳酸菌飲料における２週間後の乳蛋白沈殿量を大きく低減している点において分散安定性に大きな差異があることが分かる。また、実施例（Ａ）、（Ｃ）、（Ｄ）、（Ｆ）は、一旦沈降した乳蛋白を容易に再分散性できる点で実用上極めて重要な性能を有している。本発明の実施例（Ａ）、（Ｃ）、（Ｄ）、（Ｆ）は、従来技術である低置換CMC-Na塩からのセルロースナノファイバーと異なり、Na塩の一部が酸型に変換されており、弱酸性条件下での使用に際してｐＨショックを生じ難く、そのｐＨ適用範囲が広く、上記実施例の結果の如く、本発明の技術の根幹となるセルロースナノファイバーからなる増粘、分散安定化作用が保持される結果となった。一方、比較例（Ｘ）、（Ｚ）は弱酸性条件下でｐＨショックを生じ、水中におけるセルロースナノファイバー自体の分散安定性が低下し、その結果として乳蛋白の分散安定性の悪化を招き、更に乳蛋白の再分散性を大きく低下させる結果となった。 As shown in Table 5, the cellulose nanofibers of the present invention were tested in Examples (A), (C), (D), and (F) in Comparative Examples (X), (Z), and Control Examples (CMC). It can be seen that there is a large difference in dispersion stability in that the amount of milk protein precipitated after 2 weeks in the acidic milk beverage and the lactic acid bacteria beverage is greatly reduced as compared with the -Na salt). Examples (A), (C), (D), and (F) have practically extremely important performance in that milk proteins that have once settled can be easily redispersed. In Examples (A), (C), (D), and (F) of the present invention, unlike cellulose nanofibers from a low-substituted CMC-Na salt, which is a conventional technique, a part of the Na salt is converted to an acid form. It is difficult to cause pH shock when used under weakly acidic conditions, and its pH application range is wide, and as shown in the results of the above examples, thickening and dispersion of cellulose nanofibers that are the basis of the technology of the present invention. As a result, the stabilizing effect was maintained. On the other hand, Comparative Examples (X) and (Z) cause a pH shock under weakly acidic conditions, and the dispersion stability of cellulose nanofibers itself in water is lowered, resulting in deterioration of the milk protein dispersion stability. Furthermore, the redispersibility of milk protein was greatly reduced.
《製造例：食用タレ、ゲル状（ジュレ状）調味料、ディップソース》
弱酸性領域での増粘性、並びにゲル形成能、更に、調味液組成物のチクソトロピー性が必要とされる食用タレ、ゲル状（ジュレ状）調味料、ディップソースの製造処方において、本発明の前記実施例、及び、比較例で示したセルロースナノファイバー水分散体を用いて、下記処方に従って調味液組成物を調製し、以下記載の評価方法に従って評価を行った。
<< Manufacturing examples: edible sauce, gel-like seasoning, dip sauce >>
In the preparation formulation of edible sauce, gel-like (jelly-like) seasoning, and dip sauce that require thickening in a weakly acidic region, gel forming ability, and thixotropy of the seasoning liquid composition, Using the cellulose nanofiber aqueous dispersions shown in Examples and Comparative Examples, seasoning liquid compositions were prepared according to the following formulation, and evaluated according to the evaluation methods described below.
＜製造例３：食用タレ＞
表６記載の処方に従い、２Ｌサイズの円形ステンレス製取手付容器に固形分濃度３％で調製された本発明のセルロースナノファイバー水分散体４００ｇ（固形分換算１２ｇ）を仕込み、幅広翼を装着した攪拌装置で攪拌しながら、液温を４０℃とし、ここに別途調製した砂糖１８０ｇ、粉末醤油６０ｇ、みりん２００ｇ、化学調味料２０ｇの混合溶液を調製水とともに徐々に加え、攪拌しながら、８０℃まで昇温して、更に３０分間攪拌を継続した。その後、水浴中で２０℃まで冷却して、目的の食用タレを得た。このとき、得られた食用タレ組成物は、セルロースナノファイバー（固形分換算）１．２％を含み、２０℃におけるｐＨは４．８〜５．１であった。
<Production Example 3: Edible Sauce>
In accordance with the formulation shown in Table 6, a cellulose nanofiber aqueous dispersion 400 g (12 g in terms of solid content) of the present invention prepared at a solid content concentration of 3% was charged into a 2 L circular stainless steel handle-equipped container, and wide wings were mounted. While stirring with a stirrer, the liquid temperature was set to 40 ° C., and a separately prepared mixed solution of 180 g of sugar, 60 g of powdered soy sauce, 200 g of mirin, and 20 g of chemical seasoning was gradually added with prepared water, and the mixture was stirred at 80 ° C. The temperature was raised to 30 minutes and stirring was continued for another 30 minutes. Then, it cooled to 20 degreeC in the water bath, and obtained the target edible sauce. At this time, the obtained edible sauce composition contained 1.2% of cellulose nanofiber (solid content conversion), and pH at 20 ° C. was 4.8 to 5.1.
＜製造例４：ゲル状（ジュレ状）調味料＞
表７記載の処方に従い、２Ｌサイズの円形ステンレス製取手付容器に固形分濃度３％で調製された本発明のセルロースナノファイバー水分散体３００ｇ（固形分換算９ｇ）を仕込み、幅広翼を装着した攪拌装置で攪拌しながら、液温を２０℃とし、ここに別途調製した砂糖５０ｇ、ソルビトール９０ｇと調整水の一部からなる混合溶液を、徐々に加え、更に、攪拌しながら、醤油１３０ｇ、食酢１００ｇ、みりん３０ｇ、ゆず果汁３０ｇ、残りの調整水を徐々に加え、８０℃まで昇温して、１０分間攪拌を継続し、その後、６０℃まで冷却して、蓋付きポリエチレン製パック包材に充填し、水流中に３０分間投入して目的のゲル状（ジュレ状）調味料を得た。このとき、得られたゲル状（ジュレ状）調味料組成物は、セルロースナノファイバー（固形分換算）０．９％を含み、２０℃におけるｐＨは４．４〜４．６であった。
<Production Example 4: Gel (sealed) seasoning>
According to the prescription in Table 7, 300 g of cellulose nanofiber aqueous dispersion of the present invention prepared at a solid content concentration of 3% (9 g in terms of solid content) was charged into a 2 L size circular stainless steel handle container, and wide wings were mounted. While stirring with a stirrer, the liquid temperature was set to 20 ° C., and a mixed solution consisting of 50 g of sugar and 90 g of sorbitol separately prepared here and a part of the conditioned water was gradually added. Gradually add 100 g, 30 g mirin, 30 g yuzu fruit juice, and the rest of the adjusted water, raise the temperature to 80 ° C., continue stirring for 10 minutes, then cool to 60 ° C. to make a polyethylene pack packaging with lid Filled and put into a water stream for 30 minutes to obtain the desired gel (jelly) seasoning. At this time, the obtained gel-like (jelly-like) seasoning composition contained 0.9% of cellulose nanofibers (in terms of solid content), and the pH at 20 ° C was 4.4 to 4.6.
＜製造例５：ディップソース＞
表８記載の処方に従い、２Ｌサイズの円形ステンレス製取手付容器に固形分濃度３％で調製された本発明のセルロースナノファイバー水分散体３００ｇ（固形分換算９ｇ）を仕込み、幅広翼を装着した攪拌装置で攪拌しながら、液温を４０℃とし、ここに別途調製したレモン粉末果汁１０ｇ、食塩８ｇ、全粉乳４ｇ、調味配合物８ｇと調製水からなる混合溶液を、徐々に加え、４０℃を維持しながら、更に３０分間攪拌を継続した。更に、ボディ剤３０ｇを徐々に加えて、強攪拌下で５分間攪拌した後、攪拌を低速とし、水浴中で２０℃まで冷却して、目的のディップソースを得た。このとき、得られたディップソース組成物は、セルロースナノファイバー（固形分換算）０．９％を含み、２０℃におけるｐＨは４．３〜４．６であった。
<Production Example 5: Dip sauce>
In accordance with the formulation shown in Table 8, 300 g of cellulose nanofiber aqueous dispersion of the present invention prepared at a solid content concentration of 3% (9 g in terms of solid content) was charged into a 2 L circular stainless steel handle container, and wide wings were mounted. While stirring with a stirrer, the liquid temperature was adjusted to 40 ° C., and a mixed solution consisting of 10 g of lemon powder juice separately prepared here, 8 g of salt, 4 g of whole milk powder, 8 g of seasoning blend and prepared water was gradually added to 40 ° C. While maintaining the above, stirring was continued for another 30 minutes. Further, 30 g of the body agent was gradually added, and after stirring for 5 minutes under strong stirring, stirring was slowed down and cooled to 20 ° C. in a water bath to obtain the desired dip sauce. At this time, the obtained dip source composition contained 0.9% of cellulose nanofiber (solid content conversion), and pH at 20 ° C was 4.3 to 4.6.
製造例３、４、５において得られた食用タレ、ゲル状（ジュレ状）調味料、ディップソース、等、調味液組成物について、以下の方法によって、調味液組成物の光沢、透明性、粘度、付着量、液だれの有無、スプレー塗布可否、等から、セルロースナノファイバーの弱酸性領域における増粘性、ゲル形成能、更に、調味液組成物のチクソトロピー性を評価した。 About the seasoning liquid compositions such as the edible sauce, gel-like (jelly-like) seasoning, dip sauce, etc. obtained in Production Examples 3, 4, and 5, the gloss, transparency, and viscosity of the seasoning liquid composition are as follows. From the adhesion amount, presence / absence of liquid dripping, applicability of spray application, etc., thickening in a weakly acidic region of cellulose nanofiber, gel-forming ability, and thixotropy of the seasoning liquid composition were evaluated.
＜調味液組成物の光沢、透明性＞
得られた調味液組成物の光沢、透明性、均一性を目視にて評価した。これら結果を表９に示した。なお、各試料について、調味液組成物の光沢、透明性、滑らかさがよいものを「○」、やや劣るものを「△」、劣るものを「×」と評価した。
<Gloss and transparency of seasoning liquid composition>
The gloss, transparency, and uniformity of the obtained seasoning liquid composition were visually evaluated. These results are shown in Table 9. In addition, about each sample, the glossiness, transparency, and smoothness of the seasoning liquid composition were evaluated as “◯”, the slightly inferior one as “Δ”, and the inferior one as “x”.
＜調味液組成物の粘度＞
得られた調味液組成物の２０℃における粘度をＢＨ型粘度計、回転数２０ｒｐｍにて測定し、これら結果を表９に示した。
<Viscosity of seasoning liquid composition>
The viscosity of the obtained seasoning liquid composition at 20 ° C. was measured with a BH viscometer and a rotation speed of 20 rpm, and these results are shown in Table 9.
＜調味液組成物の付着量＞
得られた調味液組成物の付着量、液垂れの有無について、「食用タレ」の場合は、串刺しの三連単団子を対象食品として、タレに三連単団子を定速（上下各１秒目処）で浸漬、引き上げする操作を２回行った後、１５秒後の調味液付着量（ｇ）を操作前後の重量差から求め、その結果を表９に示した。
また、「ゲル状（ジュレ状）調味料」の場合は、水切りした刺身用の白髭大根の「けん」を対象食品として、ステンレス製の小型のざるを透明容器の上に置き、そのざるに「けん」を盛り、その上に２０ｇのゲル状（ジュレ状）調味料をかけ、３０秒後にざるから滴り落ちる調味液の有無を目視で確認した。各試料について、ざるの下に置かれた透明容器に調味液が見られない場合を「○」、わずかに調味液が見られる場合を「△」、多量の調味液が見られる場合を「×」と評価し、その結果を表９に示した。
また、「ディップソース」の場合は、市販のプレーンクラッカー（４．５ｃｍ×４．５ｃｍ）を対象食品として、ディップソースにクラッカーの下部２．５ｃｍを定速（上下各１秒目処）で浸漬、引き上げを行い、１５秒後の調味液付着量（ｇ）を操作前後の重量差から求めた。この操作を３枚のクラッカーで３回行い、３回の調味料付着量の合計値を表９に示した。
<Adhesion amount of seasoning liquid composition>
Regarding the amount of seasoning liquid composition attached and the presence or absence of dripping, in the case of “edible sauce”, the triple-single dumplings with skewers were used as the target food, and the triple-single dumplings were fixed at a constant speed (up and down for 1 second each) After performing the operation of immersing and pulling up twice at the target), the adhesion amount (g) of the seasoning liquid after 15 seconds was determined from the weight difference before and after the operation, and the results are shown in Table 9.
In addition, in the case of “gel (seasoning) seasoning”, a small stainless steel vine is placed on a transparent container with “Ken” of sashimi white radish for draining sashimi as the target food. “Ken” was added, and 20 g of a gel-like (jelly-like) seasoning was applied thereon, and the presence or absence of a seasoning liquid that dripped after 30 seconds was visually confirmed. For each sample, “○” indicates that the seasoning liquid is not seen in the transparent container placed under the sieve, “△” indicates that the seasoning liquid is slightly seen, and “×” indicates that a large amount of seasoning liquid is seen. The results are shown in Table 9.
In the case of “dip sauce”, a commercially available plain cracker (4.5 cm × 4.5 cm) is used as a target food, and the lower part of the cracker is immersed in a dip sauce at a constant speed (up and down each 1 second). It pulled up and calculated | required the seasoning liquid adhesion amount (g) 15 seconds after from the weight difference before and behind operation. This operation was performed three times with three crackers, and the total value of the three seasonings deposits is shown in Table 9.
＜調味液組成物のスプレー塗布可否、液垂れの有無＞
得られた調味液組成物を市販のトリガー式スプレーボトルに入れ、遠心から半径１ｃｍ、４ｃｍ、８ｃｍの３つの円を記した白色光沢紙をスプレーノズルから１５ｃｍ離れた場所に垂直に置き、その遠心に向って調味液組成物を噴霧し、その後、直ちに白色光沢紙上の着滴形状と大きさからスプレー塗布の適合性を評価した。 なお、各試料について、着滴形状が概ね円状で半径８ｃｍの円を超えて着滴がある場合を「○」、着滴が概ね円状で半径４ｃｍの円を超えて、８ｃｍの円を超えていない場合を「△」、着滴が半径４ｃｍの円の内側にある場合を「×」と評価し、その結果を表９に示した。
また、液垂れの有無については、噴霧操作後、直ちに前記白色光沢紙を４５°の傾斜をつけた板の上に置き、１分経過後に着敵からの液垂れの状態を評価した。なお、各試料について、液垂れが見られない場合を「○」、前記半径８ｃｍの円内において、着滴から僅かに液垂れが認められる場合を「△」、前記半径８ｃｍの円内において、多くの着滴からの液垂れが見られる場合を「×」と評価し、その結果を表９に示した。
<Presence of spray application of seasoning liquid composition, presence or absence of dripping>
Place the obtained seasoning liquid composition into a commercially available trigger spray bottle, place white glossy paper with 3 circles with a radius of 1cm, 4cm and 8cm from the centrifuge and place it vertically 15cm away from the spray nozzle. Then, the seasoning liquid composition was sprayed toward the surface, and then the suitability of spray application was immediately evaluated from the shape and size of droplets deposited on white glossy paper. For each sample, “○” indicates that the droplet shape is approximately circular and exceeds a circle with a radius of 8 cm, and the droplet is approximately circular and exceeds a circle with a radius of 4 cm. The case where it did not exceed was evaluated as “Δ”, and the case where the droplet was inside the circle having a radius of 4 cm was evaluated as “x”. The results are shown in Table 9.
Regarding the presence or absence of liquid dripping, immediately after the spraying operation, the white glossy paper was immediately placed on a plate inclined at 45 °, and the state of liquid dripping from the enemy was evaluated after 1 minute. For each sample, the case where no dripping was observed was “◯”, in the circle with the radius of 8 cm, and the case where dripping was slightly observed from the landing “Δ”, in the circle with the radius of 8 cm, The case where dripping from many droplets was observed was evaluated as “×”, and the results are shown in Table 9.
本発明のセルロースナノファイバーは、表９に示す通り、供試した実施例（Ａ）、（Ｂ）、（Ｄ）、（Ｆ）は、比較例（Ｘ）、（Ｚ）、対照例（ＣＭＣ‐Ｎａ塩）に比較して、食用タレ、ゲル状（ジュレ状）調味料、ディップソース、等、様々な様態の酸性〜弱酸性の調味液組成物において、実用上所望される好適な増粘性、ゲル形成能を示し、更には組成物のレオロジー特性を改良し得る点で、産業上の利用価値は大きい。例えば、本発明技術の食用タレにおける利用において、食品産業において特に重要視される外観上の優位性から商品価値を高め得るばかりか、本発明のセルロースナノファイバーの高い増粘効果から、食品への食用タレの付着量を比較例、対照例に対して２倍以上高めるとともに、食用タレのスプレー噴霧を可能とせしめ、更に、調味液でしばしば問題となる液垂れの改善、調味液の歩留りの大幅改善を可能とせしめる点において、本発明は食品の生産効率向上に寄与できる点で極めて有用な技術である。
ゲル状（ジュレ状）調味料は、近年、市場要求の高い調味液の様態であって、調味液の付加価値向上の観点から、差別化製品として注目をあびている。本発明技術のゲル状（ジュレ状）調味料における利用において、比較例、並びに、対照例に比較して、外観上で目新しい商品様態の構築（商品差別化）に寄与するのみならず、食品に対する調味液の付着量を増大させ、本質的な要求である調味効率（調味液の有効利用率）を大きく増大せしめた点で産業上の利用価値は大きい。
ディップソースも前記ゲル状（ジュレ状）調味料同様に、消費者ニーズの多様化から、利用が広がっている調味液の利用形態の一つである。本利用形態においても、本発明技術は、外観上の商品差別化、調味効率（調味液の有効利用率）に関する評価項目において、比較例、並びに、対照例を上回る好適な結果を示し、本発明技術の有用性を明示している。
As shown in Table 9, the cellulose nanofibers of the present invention were tested in Examples (A), (B), (D), and (F) in Comparative Examples (X), (Z), and Control Examples (CMC). Compared to (Na salt), edible sauce, gel-like (jelly-like) seasoning, dip sauce, etc., in various forms of acidic to weakly acidic seasoning liquid compositions suitable for practical use Industrial applicability is great in that it exhibits gel-forming ability and can further improve the rheological properties of the composition. For example, in the use of the technique of the present invention in an edible sauce, not only can the commercial value be enhanced due to the superiority of appearance that is particularly important in the food industry, but also due to the high thickening effect of the cellulose nanofibers of the present invention, Increase the amount of edible sauce on the comparative example and control example more than twice, make it possible to spray edible sauce, and improve dripping, which is often a problem with seasoning liquids, and increase the yield of seasoning liquids In terms of enabling improvement, the present invention is a very useful technique in that it can contribute to the improvement of food production efficiency.
In recent years, gel-like (jelly-like) seasonings are in the form of seasoning liquids with high market demand, and are attracting attention as differentiated products from the viewpoint of improving the added value of seasoning liquids. Compared to the comparative example and the control example, the use of the technology of the present invention in the gel-like (jelly-like) seasoning not only contributes to the construction of a new product form (product differentiation), but also to food. Industrial application value is great in that the amount of seasoning liquid deposited is increased and the seasoning efficiency (effective utilization rate of seasoning liquid), which is an essential requirement, is greatly increased.
Dip sauce, like the gel (jelly) seasoning, is one of the usage forms of seasoning liquids that are widely used due to diversification of consumer needs. Also in the present usage mode, the present technology shows favorable results over the comparative example and the control example in the evaluation items regarding the product differentiation on the appearance and the seasoning efficiency (effective utilization rate of the seasoning liquid). Clarifies the usefulness of the technology.
＜製造例６：弱酸性ゲル状化粧水＞
弱酸性領域での増粘性、並びにゲル形成能、チクソトロピー性が必要とされる弱酸性ゲル状化粧水のモデル処方において、本発明の前記実施例、及び、比較例で示したセルロースナノファイバー水分散体を用いて、下記処方に従って化粧水組成物を調製し、以下記載の評価方法に従って評価を行った。
表１０記載の処方に従い、２００ｍｌのビーカーに固形分濃度３％で調製された本発明のセルロースナノファイバー水分散体２０ｇ（固形分換算０．６ｇ）を仕込み、幅広翼を装着した攪拌装置で攪拌しながら、室温でグリセリン２０．０ｇ、エタノール５ｇを徐々に加え、更に、攪拌しながら、別にクエン酸０．６ｇ、クエン酸三ナトリウム０．６ｇを調整水５０ｇに溶解させたクエン酸‐クエン酸三ナトリウム水溶液を徐々に滴下して仕込んだ。次いで、低速で撹拌しながら、残りの調整水とローズマリーエキス０．３ｇを加えて、撹拌を１０分間継続した後、市販のトリガー式スプレーボトルに組成液を充填して、目的の弱酸性ゲル状化粧水を得た。このとき、得られた各弱酸性ゲル状化粧水は、セルロースナノファイバー（固形分換算）０．６％を含み、２０℃におけるｐＨは４．４〜４．７であった。
<Production Example 6: Weakly acidic gel lotion>
In the model formulation of weak acid gel lotion that requires thickening, gel forming ability and thixotropy in weak acid region, cellulose nanofiber aqueous dispersion shown in the above-mentioned examples of the present invention and comparative examples Using the body, a lotion composition was prepared according to the following formulation, and evaluated according to the evaluation method described below.
In accordance with the formulation shown in Table 10, 20 g of cellulose nanofiber aqueous dispersion of the present invention prepared at a solid content concentration of 3% (0.6 g in terms of solid content) was charged into a 200 ml beaker and stirred with a stirrer equipped with wide blades. Then, 20.0 g of glycerin and 5 g of ethanol were gradually added at room temperature, and 0.6 g of citric acid and 0.6 g of trisodium citrate were separately dissolved in 50 g of adjusted water while stirring. A trisodium aqueous solution was gradually added dropwise. Next, while stirring at low speed, add the remaining adjusted water and 0.3 g of rosemary extract and continue stirring for 10 minutes, then fill the commercially available trigger type spray bottle with the composition liquid, and target weakly acidic gel A skin lotion was obtained. At this time, each obtained weak acidic gel lotion contained 0.6% of cellulose nanofiber (solid content conversion), and pH at 20 ° C. was 4.4 to 4.7.
製造例６において得られた弱酸性ゲル状化粧水について、以下の方法によって、化粧水組成物のゲル性、使用感（べたつきの有無、さっぱり感）を評価した。 About the weakly acidic gel lotion obtained in Production Example 6, the gel properties and feeling of use (presence of stickiness, refreshing feeling) of the lotion composition were evaluated by the following methods.
＜化粧水組成物のゲル性＞
得られた化粧水組成物が充填されたトリガー式スプレーボトルを横に倒し（９０°転回）、更に逆さま（１８０°転回）とし、ゲル形成の有無を目視で評価した。これら結果を表４−２に示した。なお、各試料について、ボトル内充填物が室温で透明、且つ、ゲル状であるものを「○」、ゲルの一部に不均一箇所がある、或いは、僅かに離水があるものを「△」、ボトル内充填物に流動性がある、或いは、全体的に不均一であるものを「×」と評価した。
<Gel properties of lotion composition>
The trigger type spray bottle filled with the obtained lotion composition was laid down (turned 90 °) and turned upside down (turned 180 °), and the presence or absence of gel formation was visually evaluated. These results are shown in Table 4-2. For each sample, “○” indicates that the filling in the bottle is transparent and gelled at room temperature, “△” indicates that there is a non-uniform portion in the gel, or there is slight water separation. In addition, the bottle filling material was fluid or was generally non-uniform, and was evaluated as “x”.
＜化粧水組成物の使用感＞
得られた化粧水組成物が充填されたトリガー式スプレーボトルから手の甲に１〜２回スプレーした後、化粧水をもう一方の手の指先で軽く円を描くように伸ばした際の使用感を社内パネラー３人（２０代女性、３０代女性、４０代女性）で評価した。これら結果を表４−２に示した。なお、各試料について、化粧水組成物の使用感はべたつきがなく、さっぱり感を感じたものを３点、僅かにべたつきがある、或いは僅かに滑らかさに劣るもの、或いは、を２点、べたつきがあり、重い感触があるもの、或いは、滑らかさに欠けるものを１点として採点し、社内パネラー３人の平均点が２．６を上回れば「○」、平均点が２．０〜２．６であれば「△」、平均点が２，０を下回れば「×」と評価した。
<Usage feeling of lotion composition>
After spraying the back of the hand once or twice from the trigger type spray bottle filled with the obtained lotion composition, the feeling of use when the lotion was extended in a light circle with the fingertip of the other hand is in-house Three panelists (20s, 30s, 40s) evaluated. These results are shown in Table 4-2. In addition, for each sample, the feeling of use of the lotion composition was not sticky, 3 points were felt refreshed, slightly sticky, or slightly inferior in smoothness, or 2 points, stickiness If the average score of three in-house panelists exceeds 2.6, “○” is given, and the average score is 2.0-2. When it was 6, it was evaluated as “Δ”, and when the average score was below 2,0, it was evaluated as “x”.
本発明のセルロースナノファイバーは、表１１に示す通り、供試した実施例（Ａ）、（Ｄ）、（Ｅ）は、弱酸性ゲル状化粧水の調製に有用で、且つ、その使用感も良好であり、比較例（Ｘ）、（Ｚ）に比較してその効果は明白である。また、本発明技術は弱酸性領域において、より高い増粘性、ゲル形成能を示す一方で、化粧水組成物のレオロジー特性を改良して、ゲル状でありながらスプレー噴霧を可能とせしめ、また更に、化粧水の使用感としてしばしば問題となるべたつきを抑え、さっぱり感を発現し得る点で、化粧料向けの増粘剤、ゲル化剤、レオロジー改良剤としての産業上の利用価値は大きい。 As shown in Table 11, the cellulose nanofibers of the present invention were tested in Examples (A), (D), and (E), which are useful for the preparation of a weakly acidic gel lotion, and the feeling of use is also It is good and the effect is obvious as compared with Comparative Examples (X) and (Z). In addition, the technology of the present invention exhibits higher thickening and gel-forming ability in the weakly acidic region, while improving the rheological properties of the lotion composition to enable spray spraying while being in a gel state, and further In terms of the ability to suppress stickiness, which is often a problem as a feeling of use of lotion, and to express a refreshing feeling, the industrial utility value as a thickener, gelling agent and rheology modifier for cosmetics is great.
本発明のセルロースナノファイバー、およびその水分散体は、増粘剤、ゲル化剤、保形剤として用いることができ、食品、化粧品、医薬品、医療、農薬、トイレタリー用品、スプレー剤、塗料、等の用途で幅広く使用することができる。加えて、前記用途分野で乳化安定性や分散安定性を所望する各種製品において乳化安定化剤や分散安定化剤として利用できる。
本発明のセルロースナノファイバー、およびその水分散体は、より広いｐＨ領域で使用可能であり、特に、弱酸性領域でｐＨショックを生じることなく、増粘剤、ゲル化剤、保形剤、乳化安定化剤、分散安定化剤、等としての性能を発揮し、その性能の経時変化が小さい特徴を有する。本発明のセルロースナノファイバー、およびその水分散体は、弱酸性の食品や飲料、調味液類、具体的には、乳酸菌飲料やヨーグルト、酸性乳飲料、スポーツドリンク、乳幼児用イオン飲料、機能型ドリンク、ゼリー飲料、カロリー摂取型ドリンク、デザートドリンク、ベビーフード、ジャム、ドレッシング、マヨネーズ、ケチャップ、ウスターソース、バーベキューソース、焼肉ソース、各種食用タレ、つゆ、ジュレ状調味料、等で増粘剤、ゲル化剤、保形剤、乳化安定化剤、分散安定化剤、として好適に使用できる。また、セルロースナノファイバー水分散体を中間原料として更に化学修飾や加工して利用することもできる。
The cellulose nanofiber of the present invention and the aqueous dispersion thereof can be used as a thickener, gelling agent, shape-retaining agent, food, cosmetics, pharmaceuticals, medical, agricultural chemicals, toiletries, sprays, paints, etc. It can be used widely in various applications. In addition, it can be used as an emulsion stabilizer or a dispersion stabilizer in various products for which emulsion stability or dispersion stability is desired in the application field.
The cellulose nanofiber of the present invention and the aqueous dispersion thereof can be used in a wider pH range, and in particular, thickeners, gelling agents, shape-retaining agents, and emulsifications without causing a pH shock in a weakly acidic range. It exhibits the performance as a stabilizer, a dispersion stabilizer, etc., and has the characteristic that the change with time of the performance is small. Cellulose nanofibers of the present invention and aqueous dispersions thereof are weakly acidic foods and beverages, seasonings, specifically, lactic acid bacteria beverages and yogurts, acidic milk beverages, sports drinks, ionic beverages for infants, functional drinks , Jelly drink, calorie intake drink, dessert drink, baby food, jam, dressing, mayonnaise, ketchup, Worcester sauce, barbecue sauce, grilled meat sauce, various edible sauces, soy sauce, jelly-like seasonings, etc. It can be suitably used as an agent, a shape-retaining agent, an emulsion stabilizer, and a dispersion stabilizer. Further, the cellulose nanofiber aqueous dispersion can be further used as an intermediate material after further chemical modification or processing.
すなわち、本発明は下記に掲げる発明に関する。
（１）（i）原料パルプをアルカリセルロース化し、更に、カルボキシメチル化してカルボキシメチルセルロース（ＣＭＣ）塩を製造する工程、
（ii）前記ＣＭＣ塩を部分酸型ＣＭＣに変換する工程、
（v）得られた部分酸型ＣＭＣ塩を解繊分散処理する工程、
を有する部分酸型ＣＭＣ塩ナノファイバー水分散体の製造方法であって、
前記、部分酸型ＣＭＣがＣＭＣ塩のアルカリ塩の部分を部分的に酸型に変換したものであり、グルコース単位当たりのカルボキシメチル置換度が０．０２〜０．８０であり、かつ、酸型置換基が全置換基の１．０〜８０．０％である部分酸型ＣＭＣ塩ナノファイバー水分散体の製造方法。
（２）（i）原料パルプをアルカリセルロース化し、更に、カルボキシメチル化してカルボキシメチルセルロース（ＣＭＣ）塩を製造する工程、
（ii）前記ＣＭＣ塩を部分酸型ＣＭＣに変換する工程、
（iii）前記部分酸型ＣＭＣを洗浄する工程、
（iv）洗浄した部分酸型ＣＭＣと、所定量のアルカリを反応させる工程、
（v）得られた部分酸型ＣＭＣ塩を解繊分散処理する工程、
を有する部分酸型ＣＭＣ塩ナノファイバー水分散体の製造方法であって、
前記、部分酸型ＣＭＣ塩がＣＭＣ塩のアルカリ塩の部分を部分的に酸型に変換したものであり、グルコース単位当たりのカルボキシメチル置換度が０．０２〜０．８０であり、かつ、酸型置換基が全置換基の１．０〜８０．０％である部分酸型ＣＭＣ塩ナノファイバー水分散体の製造方法。
（３）（１）または（２）記載の製造方法によって得られた部分酸型ＣＭＣ塩ナノファイバー水分散体の溶媒を除去する工程、を有する部分酸型ＣＭＣ塩ナノファイバーの製造方法。
（４）（１）または（２）記載の製造方法によって得られた部分酸型ＣＭＣ塩ナノファイバー水分散体。
（５）（１）または（２）記載の製造方法によって得られた部分酸型ＣＭＣ塩ナノファイバー水分散体を含有する食品。
（６）２０℃におけるｐＨが３．０〜５．５である、（５）記載の食品。
（７）（１）または（２）記載の製造方法によって得られた部分酸型ＣＭＣ塩ナノファイバー水分散体を含有する、２０℃におけるｐＨが３．０〜５．５である化粧料。
That is, this invention relates to the invention hung up below.
(1) (i) Step of producing raw material pulp into alkali cellulose and further carboxymethylating to produce carboxymethyl cellulose (CMC) salt,
(Ii) converting the CMC salt into a partial acid CMC;
(V) a step of defibrating and dispersing the obtained partial acid CMC salt;
A partial acid type CMC Siona Bruno method of manufacturing a fiber aqueous dispersion having,
The partial acid type CMC is obtained by partially converting the alkali salt portion of the CMC salt into an acid type, the degree of carboxymethyl substitution per glucose unit is 0.02 to 0.80, and the acid type The manufacturing method of the partial acid type CMC salt nanofiber aqueous dispersion whose substituent is 1.0-80.0% of all the substituents.
(2) (i) converting the raw material pulp to alkali cellulose and further carboxymethylating to produce a carboxymethylcellulose (CMC) salt;
(Ii) converting the CMC salt into a partial acid CMC;
(Iii) cleaning the partial acid type CMC;
(Iv) reacting the washed partial acid type CMC with a predetermined amount of alkali;
(V) a step of defibrating and dispersing the obtained partial acid CMC salt;
A partial acid type CMC Siona Bruno method of manufacturing a fiber aqueous dispersion having,
The partial acid type CMC salt is obtained by partially converting the alkali salt portion of the CMC salt to the acid type, the degree of carboxymethyl substitution per glucose unit is 0.02 to 0.80, and the acid The manufacturing method of the partial acid type CMC salt nanofiber aqueous dispersion whose type substituent is 1.0-80.0% of all the substituents.
(3) (1) or (2) the production method of partially acid-type CMC salt nanofibers having step, the removing the solvent of the resulting partially acid form CMC salt nanofibers aqueous dispersion by the production method described.
( 4 ) Partially acid-type CMC salt nanofiber aqueous dispersion obtained by the production method according to (1) or (2) .
( 5 ) A food containing a partial acid type CMC salt nanofiber aqueous dispersion obtained by the production method according to (1) or (2) .
( 6 ) The food according to ( 5 ), wherein the pH at 20 ° C is 3.0 to 5.5.
( 7 ) A cosmetic having a pH of 3.0 to 5.5 at 20 ° C, containing the aqueous dispersion of partial acid CMC salt nanofibers obtained by the production method according to (1) or (2) .
Claims (8)
（ii）前記CMC塩を部分酸型CMCに変換する工程、
（v）得られた部分酸型CMC塩を解繊分散処理する工程、
を有する部分酸型CMC塩セルロースナノファイバー水分散体の製造方法。 (I) alkali pulping raw pulp, and further carboxymethylating to produce a carboxymethylcellulose (CMC) salt,
(Ii) converting the CMC salt into a partial acid CMC;
(V) a step of defibrating and dispersing the obtained partial acid CMC salt;
The manufacturing method of the partial acid type CMC salt cellulose nanofiber aqueous dispersion which has NO.
（ii）前記CMC塩を部分酸型CMCに変換する工程、
（iii）前記部分酸型CMCを洗浄する工程、
（iv）洗浄した部分酸型CMCと、所定量のアルカリを反応させる工程、
（v）得られた部分酸型CMC塩を解繊分散処理する工程、
を有する部分酸型CMC塩セルロースナノファイバー水分散体の製造方法。 (I) alkali pulping raw pulp, and further carboxymethylating to produce a carboxymethylcellulose (CMC) salt,
(Ii) converting the CMC salt into a partial acid CMC;
(Iii) washing the partial acid type CMC;
(Iv) reacting the washed partial acid type CMC with a predetermined amount of alkali,
(V) a step of defibrating and dispersing the obtained partial acid CMC salt;
The manufacturing method of the partial acid type CMC salt cellulose nanofiber aqueous dispersion which has NO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014202762A JP5727660B1 (en) | 2014-10-01 | 2014-10-01 | Method for producing cellulose nanofiber aqueous dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014202762A JP5727660B1 (en) | 2014-10-01 | 2014-10-01 | Method for producing cellulose nanofiber aqueous dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP5727660B1 JP5727660B1 (en) | 2015-06-03 |
| JP2016069589A true JP2016069589A (en) | 2016-05-09 |
Family
ID=53437889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014202762A Active JP5727660B1 (en) | 2014-10-01 | 2014-10-01 | Method for producing cellulose nanofiber aqueous dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5727660B1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016208946A (en) * | 2015-05-13 | 2016-12-15 | 日本製紙株式会社 | Additive for food product |
| WO2018116660A1 (en) * | 2016-12-21 | 2018-06-28 | 日本製紙株式会社 | Acid-type carboxymethylated cellulose nanofibers and production method therefor |
| WO2019064633A1 (en) * | 2017-09-27 | 2019-04-04 | 第一工業製薬株式会社 | Production method for carboxymethyl cellulose or salt thereof |
| WO2019117197A1 (en) * | 2017-12-13 | 2019-06-20 | 味の素株式会社 | Food product exhibiting enhanced fatty flavor |
| JP2020059815A (en) * | 2018-10-11 | 2020-04-16 | 日本製紙株式会社 | Method for producing anion modified-cellulose nanofiber |
| EP3521318A4 (en) * | 2016-09-30 | 2020-04-29 | Nippon Paper Industries Co., Ltd. | Carboxymethyl cellulose or salt thereof, and electrode composition |
| JP2021010310A (en) * | 2019-07-04 | 2021-02-04 | 日本製紙株式会社 | Cellulose nanofiber-containing powder composition and method of producing the same |
| JP2021107482A (en) * | 2019-12-27 | 2021-07-29 | 日揮触媒化成株式会社 | Carboxymethyl cellulose particle and its manufacturing method, and cosmetic |
| WO2023106123A1 (en) * | 2021-12-09 | 2023-06-15 | 株式会社 資生堂 | Cosmetic |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017048293A (en) * | 2015-09-01 | 2017-03-09 | 株式会社スギノマシン | Cellulose nanofiber dispersion, method for producing the same and cellulose nanofiber film |
| JP6675852B2 (en) * | 2015-10-07 | 2020-04-08 | 日本製紙株式会社 | Method for producing anion-modified cellulose nanofiber |
| JP6308531B2 (en) * | 2015-12-16 | 2018-04-11 | 第一工業製薬株式会社 | Topical skin preparation |
| JP6653364B1 (en) * | 2018-09-28 | 2020-02-26 | 大王製紙株式会社 | Gel detergent composition and detergent product |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61243801A (en) * | 1985-04-19 | 1986-10-30 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of water-insoluble alkali metal salt of carboxyalkyl-cellulose |
| JPH0655112B2 (en) * | 1985-10-24 | 1994-07-27 | ダイセル化学工業株式会社 | Fish feed |
| JP2707304B2 (en) * | 1989-01-23 | 1998-01-28 | ダイセル化学工業株式会社 | Aqueous gel for cooling agent |
| JP2007254588A (en) * | 2006-03-23 | 2007-10-04 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for manufacturing partial acid carboxymethylcellulose |
| JP2008019344A (en) * | 2006-07-13 | 2008-01-31 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for manufacturing partial acid-type carboxymethyl cellulose |
| JP2013185122A (en) * | 2012-03-09 | 2013-09-19 | Nippon Paper Industries Co Ltd | Method for producing cellulose nano-fiber |
-
2014
- 2014-10-01 JP JP2014202762A patent/JP5727660B1/en active Active
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016208946A (en) * | 2015-05-13 | 2016-12-15 | 日本製紙株式会社 | Additive for food product |
| EP3521318A4 (en) * | 2016-09-30 | 2020-04-29 | Nippon Paper Industries Co., Ltd. | Carboxymethyl cellulose or salt thereof, and electrode composition |
| WO2018116660A1 (en) * | 2016-12-21 | 2018-06-28 | 日本製紙株式会社 | Acid-type carboxymethylated cellulose nanofibers and production method therefor |
| US11591721B2 (en) | 2016-12-21 | 2023-02-28 | Nippon Paper Industries Co., Ltd. | Acid-type carboxymethylated cellulose nanofiber and production method thereof |
| JP2019059856A (en) * | 2017-09-27 | 2019-04-18 | 第一工業製薬株式会社 | Method for producing carboxymethyl cellulose or salt thereof |
| WO2019064633A1 (en) * | 2017-09-27 | 2019-04-04 | 第一工業製薬株式会社 | Production method for carboxymethyl cellulose or salt thereof |
| WO2019117197A1 (en) * | 2017-12-13 | 2019-06-20 | 味の素株式会社 | Food product exhibiting enhanced fatty flavor |
| JPWO2019117197A1 (en) * | 2017-12-13 | 2020-12-03 | 味の素株式会社 | Foods with enhanced oiliness |
| JP7322711B2 (en) | 2017-12-13 | 2023-08-08 | 味の素株式会社 | Foods with enhanced oiliness |
| JP2020059815A (en) * | 2018-10-11 | 2020-04-16 | 日本製紙株式会社 | Method for producing anion modified-cellulose nanofiber |
| JP7239294B2 (en) | 2018-10-11 | 2023-03-14 | 日本製紙株式会社 | Method for producing anion-modified cellulose nanofiber |
| JP2021010310A (en) * | 2019-07-04 | 2021-02-04 | 日本製紙株式会社 | Cellulose nanofiber-containing powder composition and method of producing the same |
| JP2021107482A (en) * | 2019-12-27 | 2021-07-29 | 日揮触媒化成株式会社 | Carboxymethyl cellulose particle and its manufacturing method, and cosmetic |
| JP7454942B2 (en) | 2019-12-27 | 2024-03-25 | 日揮触媒化成株式会社 | Carboxymethyl cellulose particles, their production method, and cosmetics |
| WO2023106123A1 (en) * | 2021-12-09 | 2023-06-15 | 株式会社 資生堂 | Cosmetic |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5727660B1 (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5727660B1 (en) | Method for producing cellulose nanofiber aqueous dispersion | |
| JP5734436B2 (en) | High-performance cellulose composite | |
| JP7245237B2 (en) | Carboxymethylated pulp pulverized product and additive containing the pulverized product | |
| JP5953024B2 (en) | Liquid food containing fruits and / or vegetables | |
| JPWO2011125742A1 (en) | Cellulose composite | |
| JP5539748B2 (en) | Crystalline cellulose composite | |
| JP2008106178A (en) | Dry composition comprising water-soluble polymer | |
| JP2008092914A (en) | Thickening gelatinizer composed of three ingredients | |
| JP6407412B2 (en) | Cellulose composite | |
| JP5627284B2 (en) | Emulsion dressing | |
| JP6460641B2 (en) | Liquid composition containing water-insoluble components | |
| US11242446B2 (en) | Cellulose composite | |
| JP5727657B1 (en) | A method for producing a cellulose nanofiber dispersion. | |
| JP2016084397A (en) | Cellulose composite | |
| JP6457171B2 (en) | Cellulose composite | |
| JP2004248536A (en) | Heat-resistant gel | |
| JP5855386B2 (en) | Cellulose composite | |
| JP4791407B2 (en) | Sauce composition | |
| JP2018059126A (en) | Cellulose composite | |
| JP3262917B2 (en) | Fine cellulose and its manufacturing method | |
| TWI721401B (en) | Cellulose composite | |
| JP5969748B2 (en) | Liquid seasoning containing water-insoluble ingredients | |
| JP7321148B2 (en) | Dispersion composition containing carboxymethylcellulose | |
| WO2022114076A1 (en) | Additive for use in production of air bubble-containing composition | |
| TWI540142B (en) | Cellulose complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150306 |
|
| 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: 20150324 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150402 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5727660 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |