JP2021004236A - Hydrogel particle - Google Patents
Hydrogel particle Download PDFInfo
- Publication number
- JP2021004236A JP2021004236A JP2020107720A JP2020107720A JP2021004236A JP 2021004236 A JP2021004236 A JP 2021004236A JP 2020107720 A JP2020107720 A JP 2020107720A JP 2020107720 A JP2020107720 A JP 2020107720A JP 2021004236 A JP2021004236 A JP 2021004236A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogel particles
- agar
- mass
- aqueous solution
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 148
- 239000000017 hydrogel Substances 0.000 title claims abstract description 111
- 229920001817 Agar Polymers 0.000 claims abstract description 68
- 235000010419 agar Nutrition 0.000 claims abstract description 68
- 239000008272 agar Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 32
- 229920000615 alginic acid Polymers 0.000 claims abstract description 32
- 229960001126 alginic acid Drugs 0.000 claims abstract description 24
- 239000000783 alginic acid Substances 0.000 claims abstract description 24
- 150000004781 alginic acids Chemical class 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- HZLCGUXUOFWCCN-UHFFFAOYSA-N 2-hydroxynonadecane-1,2,3-tricarboxylic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)(C(O)=O)CC(O)=O HZLCGUXUOFWCCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940040563 agaric acid Drugs 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000499 gel Substances 0.000 abstract description 21
- 238000007906 compression Methods 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 26
- 239000008213 purified water Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 17
- 239000002537 cosmetic Substances 0.000 description 16
- 235000015110 jellies Nutrition 0.000 description 16
- 239000008274 jelly Substances 0.000 description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 15
- 235000010413 sodium alginate Nutrition 0.000 description 15
- 239000000661 sodium alginate Substances 0.000 description 15
- 229940005550 sodium alginate Drugs 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 13
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 11
- 235000013305 food Nutrition 0.000 description 11
- 229960005323 phenoxyethanol Drugs 0.000 description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 10
- 229960005069 calcium Drugs 0.000 description 10
- 229960002713 calcium chloride Drugs 0.000 description 10
- 229910001424 calcium ion Inorganic materials 0.000 description 10
- 239000000679 carrageenan Substances 0.000 description 10
- 229920001525 carrageenan Polymers 0.000 description 10
- 229940113118 carrageenan Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 8
- 229940072056 alginate Drugs 0.000 description 8
- 235000010418 carrageenan Nutrition 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 6
- 239000002775 capsule Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- -1 rame Species 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 235000010410 calcium alginate Nutrition 0.000 description 4
- 239000000648 calcium alginate Substances 0.000 description 4
- 229960002681 calcium alginate Drugs 0.000 description 4
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002674 hyaluronan Polymers 0.000 description 3
- 229960003160 hyaluronic acid Drugs 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000825 pharmaceutical preparation Substances 0.000 description 3
- 229940127557 pharmaceutical product Drugs 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- 241001474374 Blennius Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000199919 Phaeophyceae Species 0.000 description 2
- 241000206572 Rhodophyta Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 239000001527 calcium lactate Substances 0.000 description 2
- 229960002401 calcium lactate Drugs 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000003779 hair growth Effects 0.000 description 2
- BJRNKVDFDLYUGJ-RMPHRYRLSA-N hydroquinone O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-RMPHRYRLSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000004804 polysaccharides Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000008279 sol Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 235000013799 ultramarine blue Nutrition 0.000 description 2
- 239000000984 vat dye Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- WZYRMLAWNVOIEX-MOJAZDJTSA-N (2s)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyacetaldehyde Chemical compound O=C[C@@H](O)[C@@H]1OC[C@H](O)[C@H]1O WZYRMLAWNVOIEX-MOJAZDJTSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 description 1
- XLTMWFMRJZDFFD-UHFFFAOYSA-N 1-[(2-chloro-4-nitrophenyl)diazenyl]naphthalen-2-ol Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C([N+]([O-])=O)C=C1Cl XLTMWFMRJZDFFD-UHFFFAOYSA-N 0.000 description 1
- GNCOVOVCHIHPHP-UHFFFAOYSA-N 2-[[4-[4-[(1-anilino-1,3-dioxobutan-2-yl)diazenyl]-3-chlorophenyl]-2-chlorophenyl]diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(C)=O)C(=O)NC1=CC=CC=C1 GNCOVOVCHIHPHP-UHFFFAOYSA-N 0.000 description 1
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 description 1
- 201000004384 Alopecia Diseases 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 1
- YDNKGFDKKRUKPY-JHOUSYSJSA-N C16 ceramide Natural products CCCCCCCCCCCCCCCC(=O)N[C@@H](CO)[C@H](O)C=CCCCCCCCCCCCCC YDNKGFDKKRUKPY-JHOUSYSJSA-N 0.000 description 1
- ACTIUHUUMQJHFO-UHFFFAOYSA-N Coenzym Q10 Natural products COC1=C(OC)C(=O)C(CC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 102000004127 Cytokines Human genes 0.000 description 1
- 108090000695 Cytokines Proteins 0.000 description 1
- 239000004287 Dehydroacetic acid Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000016942 Elastin Human genes 0.000 description 1
- 108010014258 Elastin Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000206581 Gracilaria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-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
- 241001466453 Laminaria Species 0.000 description 1
- 241001491708 Macrocystis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- CRJGESKKUOMBCT-VQTJNVASSA-N N-acetylsphinganine Chemical compound CCCCCCCCCCCCCCC[C@@H](O)[C@H](CO)NC(C)=O CRJGESKKUOMBCT-VQTJNVASSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 240000002871 Tectona grandis Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001261506 Undaria pinnatifida Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- AGBQKNBQESQNJD-UHFFFAOYSA-N alpha-Lipoic acid Natural products OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940125715 antihistaminic agent Drugs 0.000 description 1
- 239000000739 antihistaminic agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003908 antipruritic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960000271 arbutin Drugs 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 1
- 239000001168 astaxanthin Substances 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CYHOWEBNQPOWEI-UHFFFAOYSA-L calcium 3-carboxy-1-phenyldiazenylnaphthalen-2-olate Chemical compound OC=1C(=CC2=CC=CC=C2C1N=NC1=CC=CC=C1)C(=O)[O-].OC=1C(=CC2=CC=CC=C2C1N=NC1=CC=CC=C1)C(=O)[O-].[Ca+2] CYHOWEBNQPOWEI-UHFFFAOYSA-L 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229960004256 calcium citrate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940095643 calcium hydroxide Drugs 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 1
- FYPVXEILSNEKOO-UHFFFAOYSA-L calcium;butanoate Chemical compound [Ca+2].CCCC([O-])=O.CCCC([O-])=O FYPVXEILSNEKOO-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940106189 ceramide Drugs 0.000 description 1
- ZVEQCJWYRWKARO-UHFFFAOYSA-N ceramide Natural products CCCCCCCCCCCCCCC(O)C(=O)NC(CO)C(O)C=CCCC=C(C)CCCCCCCCC ZVEQCJWYRWKARO-UHFFFAOYSA-N 0.000 description 1
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000017471 coenzyme Q10 Nutrition 0.000 description 1
- 229940110767 coenzyme Q10 Drugs 0.000 description 1
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940061632 dehydroacetic acid Drugs 0.000 description 1
- 235000019258 dehydroacetic acid Nutrition 0.000 description 1
- JEQRBTDTEKWZBW-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1=C(O)OC(C)=CC1=O JEQRBTDTEKWZBW-UHFFFAOYSA-N 0.000 description 1
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920002549 elastin Polymers 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229960004949 glycyrrhizic acid Drugs 0.000 description 1
- 235000019410 glycyrrhizin Nutrition 0.000 description 1
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 208000024963 hair loss Diseases 0.000 description 1
- 230000003676 hair loss Effects 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000416 hydrocolloid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NFIDBGJMFKNGGQ-UHFFFAOYSA-N isopropylmethylphenol Natural products CC(C)CC1=CC=CC=C1O NFIDBGJMFKNGGQ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229960004705 kojic acid Drugs 0.000 description 1
- BEJNERDRQOWKJM-UHFFFAOYSA-N kojic acid Chemical compound OCC1=CC(=O)C(O)=CO1 BEJNERDRQOWKJM-UHFFFAOYSA-N 0.000 description 1
- WZNJWVWKTVETCG-UHFFFAOYSA-N kojic acid Natural products OC(=O)C(N)CN1C=CC(=O)C(O)=C1 WZNJWVWKTVETCG-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 235000019136 lipoic acid Nutrition 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 229960005015 local anesthetics Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- VVGIYYKRAMHVLU-UHFFFAOYSA-N newbouldiamide Natural products CCCCCCCCCCCCCCCCCCCC(O)C(O)C(O)C(CO)NC(=O)CCCCCCCCCCCCCCCCC VVGIYYKRAMHVLU-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- BJRNKVDFDLYUGJ-UHFFFAOYSA-N p-hydroxyphenyl beta-D-alloside Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-UHFFFAOYSA-N 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AZLXCBPKSXFMET-UHFFFAOYSA-M sodium 4-[(4-sulfophenyl)diazenyl]naphthalen-1-olate Chemical compound [Na+].C12=CC=CC=C2C(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 AZLXCBPKSXFMET-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000002316 solid fats Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229960002663 thioctic acid Drugs 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 229960000401 tranexamic acid Drugs 0.000 description 1
- GYDJEQRTZSCIOI-LJGSYFOKSA-N tranexamic acid Chemical compound NC[C@H]1CC[C@H](C(O)=O)CC1 GYDJEQRTZSCIOI-LJGSYFOKSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
本発明は、ハイドロゲル粒子およびその製造方法並びにこのハイドロゲル粒子を含む皮膚外用剤等に関する。 The present invention relates to hydrogel particles, a method for producing the same, an external preparation for skin containing the hydrogel particles, and the like.
例えば、化粧品市場では、化粧品の塗布後の肌の美しさや保湿等のスキンケア効果だけでなく、化粧品自体の外観や使用感等の視覚的演出も商品の魅力の一つである。特に、メークアップ化粧品においては、顔料粒子を肌へ塗布することによって崩壊させ、均一に分散させる等の技術は、使用時の視覚的演出として有効である。 For example, in the cosmetics market, not only skin care effects such as skin beauty and moisturizing after application of cosmetics, but also visual effects such as appearance and usability of cosmetics themselves are one of the attractive points of products. In particular, in make-up cosmetics, techniques such as disintegrating pigment particles by applying them to the skin and uniformly dispersing them are effective as visual effects during use.
例えば、特許文献１には、水中油型エマルションを内包したカプセルを含有する化粧料であって、カプセル膜がカプセル全量に対し０．１〜１．０重量％のアルギン酸カルシウムからなる、エマルション内包カプセル含有化粧料が開示されている。また、特許文献２には、アルギン酸塩の少なくとも一部がバリウム塩を必須成分とする多価金属塩の形で存在しているアルギン酸バリウムカプセルが、ｐＨ調整されたカルボキシビニルポリマーの水溶液からなる外相中に存在しているカプセル入り化粧料が開示されている。さらに、特許文献３には、非架橋型ハイドロゲルを含む連続相および油性成分を含む分散相を有し、油性成分が固体脂および／または液体油からなるハイドロゲル粒子が開示されている。 For example, Patent Document 1 describes a cosmetic containing a capsule containing an oil-in-water emulsion, wherein the capsule membrane is composed of 0.1 to 1.0% by weight of calcium alginate based on the total amount of the capsule. The contained cosmetics are disclosed. Further, in Patent Document 2, barium alginate capsules in which at least a part of alginate exists in the form of a polyvalent metal salt containing a barium salt as an essential component is an external phase composed of an aqueous solution of a pH-adjusted carboxyvinyl polymer. The capsule-encapsulated cosmetics present therein are disclosed. Further, Patent Document 3 discloses hydrogel particles having a continuous phase containing a non-crosslinked hydrogel and a dispersed phase containing an oily component, and the oily component is a solid fat and / or a liquid oil.
しかしながら、特許文献１および２で使用されるアルギン酸塩系カプセルは、例えば、水溶性アルギン酸塩と水溶性カルシウム塩とを反応させて水不溶性のアルギン酸カルシウムを生成させることによって製造されているため、皮膚に適用したときにカプセルのカスが皮膚上に残留して違和感が生じるという問題がある。また、特許文献３に記載のハイドロゲル粒子は、例えば、乳化分散剤を用いて油性成分を乳化または分散させているため透明性に欠け、透明感の高いハイドロゲル粒子としては適していない。 However, the alginate-based capsules used in Patent Documents 1 and 2 are produced, for example, by reacting a water-soluble alginate with a water-soluble calcium salt to produce water-insoluble calcium alginate, and thus skin. There is a problem that the residue of the capsule remains on the skin when it is applied to the skin, causing a feeling of strangeness. Further, the hydrogel particles described in Patent Document 3 lack transparency because, for example, an oily component is emulsified or dispersed using an emulsifying dispersant, and are not suitable as hydrogel particles having a high transparency.
本発明は、皮膚に塗布した際の指等による崩壊をスムーズに行うことができ、伸びが良好でカス残りの無い新たなハイドロゲル粒子を提供することを目的とする。 An object of the present invention is to provide new hydrogel particles which can be smoothly disintegrated by a finger or the like when applied to the skin, have good elongation, and have no residue residue.
上記課題を解決するために、本発明者らは鋭意検討を行った結果、ゲル形成剤として、寒天およびアルギン酸またはその塩を溶解した水溶液から、最初にカルシウムイオンによりアルギン酸カルシウムの皮膜を形成した粒子を作製し、続いてこの粒子の温度を低下させて寒天をゲル化し、さらにこのゲル化した粒子からカルシウムイオンの濃度を低下させることによって、崩壊しやすくかつ透明性の高いハイドロゲル粒子が得られることを見出した。すなわち、本発明は、以下の実施形態を含む。 As a result of diligent studies in order to solve the above problems, the present inventors first formed a calcium alginate film with calcium ions from an aqueous solution prepared by dissolving agar and alginic acid or a salt thereof as a gel-forming agent. The agar is gelled by lowering the temperature of the particles, and then the concentration of calcium ions is lowered from the gelled particles to obtain hydrogel particles that are easily disintegrated and have high transparency. I found that. That is, the present invention includes the following embodiments.
（１）寒天およびアルギン酸またはその塩を含むゲル形成剤と、含水率が９４．２０質量％以上の水と、を含み、圧縮破断強度が５０ｋＰａ以下であるハイドロゲル粒子。
（２）原子吸光法で測定した濃度が０を超えて３５０ｐｐｍ以下のカルシウムを含む（１）に記載のハイドロゲル粒子。
（３）含水率が、９４．４０質量％以上９９．６０質量％以下である（１）または（２）に記載のハイドロゲル粒子。
（４）圧縮破断強度が０．１５ｋＰａ以上３５ｋＰａ以下である（１）〜（３）のいずれか一項に記載のハイドロゲル粒子。
（５）内包させる所望の物質を含む（１）〜（４）のいずれか一項に記載のハイドロゲル粒子。
（６）（１）〜（５）のいずれか一項に記載のハイドロゲル粒子を含む皮膚外用剤。
（７）寒天およびアルギン酸またはその塩を含むゲル形成剤と、所望の物質と、水と、を混合および加熱して混合液を調製する工程と、この混合液を、ノズルを介して塩化カルシウム水溶液中に滴下して液滴を形成する工程と、この液滴を回収および洗浄する工程と、を含むハイドロゲル粒子の製造方法。
(1) Hydrogel particles containing agar, a gel forming agent containing alginic acid or a salt thereof, and water having a water content of 94.20% by mass or more, and having a compressive breaking strength of 50 kPa or less.
(2) The hydrogel particle according to (1), which contains calcium having a concentration of more than 0 and 350 ppm or less measured by an atomic absorption method.
(3) The hydrogel particles according to (1) or (2), wherein the water content is 94.40% by mass or more and 99.60% by mass or less.
(4) The hydrogel particle according to any one of (1) to (3), wherein the compressive breaking strength is 0.15 kPa or more and 35 kPa or less.
(5) The hydrogel particle according to any one of (1) to (4), which contains a desired substance to be included.
(6) An external preparation for skin containing the hydrogel particles according to any one of (1) to (5).
(7) A step of mixing and heating a gel-forming agent containing agar and alginic acid or a salt thereof, a desired substance, and water to prepare a mixed solution, and a calcium chloride aqueous solution of the mixed solution via a nozzle. A method for producing hydrogel particles, which comprises a step of dropping into a droplet to form a droplet and a step of collecting and washing the droplet.
本発明によれば、皮膚に塗布した際の指等による崩壊をスムーズに行うことができ、伸びが良好でカス残りの無い新たなハイドロゲル粒子が提供される。 According to the present invention, new hydrogel particles that can be smoothly disintegrated by a finger or the like when applied to the skin, have good elongation, and have no residue residue are provided.
（ハイドロゲル粒子）
本発明の一実施形態のハイドロゲル粒子は、（Ａ）寒天およびアルギン酸またはその塩を含むゲル形成剤と、（Ｂ）９４．２０質量％以上の水と、を含む。ここで、「ハイドロゲル粒子」とは、ハイドロゲル中に所望の成分を溶解または分散させた１個乃至複数個の粒子をいう。また、本明細書において「ハイドロゲル」とは、水を溶媒として寒天およびアルギン酸を含むゲル形成剤から得られたゲルをいう。
(Hydrogel particles)
The hydrogel particles of one embodiment of the present invention include (A) a gel-forming agent containing agar and alginic acid or a salt thereof, and (B) 94.20% by mass or more of water. Here, the "hydrogel particles" refer to one or more particles in which a desired component is dissolved or dispersed in a hydrogel. Further, as used herein, the term "hydrogel" refers to a gel obtained from a gel-forming agent containing agar and alginic acid using water as a solvent.
ハイドロゲル粒子の形状は、特に限定されるものではないが、形状の安定性および美観の観点から、球状体であることが好ましい。ここでいう球状とは、真球だけでなく、断面が楕円のものであってもよいが、真球が好ましい。 The shape of the hydrogel particles is not particularly limited, but is preferably spherical from the viewpoint of shape stability and aesthetics. The sphere referred to here may be not only a true sphere but also an elliptical cross section, but a true sphere is preferable.
本実施形態のハイドロゲル粒子の平均粒径は、例えば球状体の粒子を作製する際においてこの粒子をより作製しやすくするために、好ましくは下限が０．０５ｍｍ以上、より好ましくは０．５ｍｍ以上、さらに好ましくは６．０ｍｍ以上であり、好ましくは上限が１０ｍｍ以下、より好ましくは６．０ｍｍ以下、更に好ましくは４．０ｍｍ以下である。ハイドロゲル粒子の平均粒径は、レーザー回折／散乱式または篩法により測定することができる。レーザー回折／散乱式による方法は、粒度分布測定装置（例えば、堀場製作所社製、型番：ＬＡ−９２０）を用いてメジアン径を測定し、それを平均粒径とするものである。篩法は、各種目開きのフルイを用い、ハイドロゲル粒子１００ｇを水中で湿式分級して余分な水分をろ紙で除去した後の質量を測定し、その重量平均粒径を平均粒径とするものである。 The average particle size of the hydrogel particles of the present embodiment preferably has a lower limit of 0.05 mm or more, more preferably 0.5 mm or more, in order to make the particles easier to produce, for example, when producing spherical particles. , More preferably 6.0 mm or more, preferably the upper limit is 10 mm or less, more preferably 6.0 mm or less, still more preferably 4.0 mm or less. The average particle size of the hydrogel particles can be measured by laser diffraction / scattering or sieving. In the laser diffraction / scattering method, the median diameter is measured using a particle size distribution measuring device (for example, manufactured by HORIBA, Ltd., model number: LA-920), and the median diameter is used as the average particle size. In the sieving method, 100 g of hydrogel particles are wet-classified in water using a sieve having various openings, the mass is measured after removing excess water with a filter paper, and the weight average particle size is used as the average particle size. Is.
また、使用時における感触の向上の観点から、本実施形態のハイドロゲル粒子の圧縮破断強度が５０ｋＰａ以下であることが好ましい。ハイドロゲル粒子の形状を維持して皮膚外用剤や化粧品等により配合しやすくする観点で、本実施形態のハイドロゲル粒子の圧縮破断強度は、好ましくは０．１５ｋＰａ以上であり、より好ましくは０．２０ｋＰａ以上であり、さらに好ましくは０．２５ｋＰａ以上である。また、肌に塗布したときに皮膚上での伸びやなじみが良好で、スムーズに崩壊させることがよりできるようにする観点で、本実施形態のハイドロゲル粒子の圧縮破断強度は、より好ましくは４０ｋＰａ以下であり、３５ｋＰａ以下である。 Further, from the viewpoint of improving the feel during use, the compressive breaking strength of the hydrogel particles of the present embodiment is preferably 50 kPa or less. From the viewpoint of maintaining the shape of the hydrogel particles and facilitating the formulation with an external preparation for skin, cosmetics, etc., the compressive breaking strength of the hydrogel particles of the present embodiment is preferably 0.15 kPa or more, more preferably 0. It is 20 kPa or more, more preferably 0.25 kPa or more. Further, the compressive breaking strength of the hydrogel particles of the present embodiment is more preferably 40 kPa from the viewpoint that when applied to the skin, it spreads and fits well on the skin and can be disintegrated more smoothly. It is less than or equal to 35 kPa or less.
なお、ここで圧縮破断強度とは、ゲル試料に圧縮荷重を加えた時に、ゲル試料が破断する最大応力のことをいう。圧縮破断強度は、球状のゲル試料に対して、１軸荷重をかけた時の圧縮力をその軸に垂直な断面積で割った値（ｋＰａ（Ｎ／ｍ２））で表わすことができる。圧縮破断強度は、圧縮破断応力とも称され、公知の測定機器を用いて、公知の方法で調べることができる。圧縮破断強度測定機器としては、たとえば、サン科学社製の圧縮試験機（Ｒｈｅｏ Ｍｅｔｅｒ：ＣＲ−０００ＥＸ）があげられる。本実施形態において規定する圧縮破断強度は、以下に示す実施例に記載の測定方法によって測定された値である。 Here, the compressive breaking strength means the maximum stress at which the gel sample breaks when a compressive load is applied to the gel sample. The compressive breaking strength can be expressed by a value (kPa (N / m 2 )) obtained by dividing the compressive force when a uniaxial load is applied to a spherical gel sample by the cross-sectional area perpendicular to the axis. The compressive breaking strength is also referred to as compressive breaking stress, and can be examined by a known method using a known measuring instrument. Examples of the compression breaking strength measuring device include a compression tester (Rheo Meter: CR-000EX) manufactured by Sun Scientific Co., Ltd. The compressive breaking strength defined in this embodiment is a value measured by the measuring method described in the examples shown below.
本実施形態のハイドロゲル粒子には、所望の成分を内包させることができ、また、本発明の効果を損わない限り任意成分を含んでもよい。以下、本実施形態のハイドロゲル粒子の配合成分について詳細に説明する。 The hydrogel particles of the present embodiment can contain a desired component, and may contain an arbitrary component as long as the effects of the present invention are not impaired. Hereinafter, the compounding components of the hydrogel particles of the present embodiment will be described in detail.
＜（Ａ）ゲル形成剤＞
ゲル形成剤としては、（Ａ１）寒天および（Ａ２）アルギン酸またはその塩を含む。
<(A) Gel forming agent>
Gel-forming agents include (A1) agar and (A2) alginic acid or salts thereof.
（Ａ１）寒天
寒天は、天草やオゴノリなどの紅藻類から熱水抽出され、ろ過精製し、ゲル化後脱水乾燥させた乾物である。この乾物状の寒天は、一般に７５℃以上の熱水に溶解しゾルとなり、３０〜４５℃に冷却すると構造転移してゲルとなるハイドロコロイドである。このゲルは、再加熱により溶解してゾルに戻る熱可逆性の性質を有する。本実施形態で用いられる寒天としては、通常の寒天のほか、様々な寒天を用いることができるが、使用時の感触がよいという観点から、そのゼリー強度が、好ましくは１９．６ｋＰａ（２００ｇ／ｃｍ２）以上、より好ましくは５０．０ｋＰａ（５１０ｇ／ｃｍ２）以上の寒天である。また、同様の観点から、ゼリー強度が好ましくは１４７ｋＰａ（１５００ｇ／ｃｍ２）以下、より好ましくは１２７ｋＰａ（１３００ｇ／ｃｍ２）以下である。寒天のゼリー強度は、日寒水式法により求めることができる。具体的には、寒天のゼリー強度は、寒天の１．５質量％水溶液を調製し、その水溶液を２０℃で１５時間放置して凝固させたハイドロゲルに、日寒水式ゼリー強度測定器（（株）木屋製作所製）により荷重をかけ、２０℃においてハイドロゲルが２０秒間その荷重に耐えるときの表面積１ｃｍ２あたりの最大質量（ｇ）として測定される。
(A1) Agar Agar is a dry product extracted from red algae such as Amakusa and Gracilaria with hot water, filtered and purified, gelled, and dehydrated and dried. This dry agar is a hydrocolloid that is generally dissolved in hot water at 75 ° C. or higher to form a sol, and when cooled to 30 to 45 ° C., the structure is transferred to form a gel. This gel has the property of thermoreversibility to dissolve and return to the sol by reheating. As the agar used in the present embodiment, various agars can be used in addition to ordinary agar, but the jelly strength is preferably 19.6 kPa (200 g / cm) from the viewpoint of good feel at the time of use. 2 ) or more, more preferably 50.0 kPa (510 g / cm 2 ) or more agar. From the same viewpoint, the jelly strength is preferably 147 kPa (1500 g / cm 2 ) or less, and more preferably 127 kPa (1300 g / cm 2 ) or less. The jelly strength of agar can be determined by the Nichikansui method. Specifically, for the jelly strength of agar, a 1.5% by mass aqueous solution of agar was prepared, and the aqueous solution was left at 20 ° C. for 15 hours to coagulate the hydrogel. applying a load by Ltd.) Kiya Seisakusho), the hydrogel is measured as the maximum mass (g) per surface area 1 cm 2 when withstand the load for 20 seconds at 20 ° C..
本実施形態のハイドロゲル粒子中における寒天の含有量は、ハイドロゲル粒子の皮膚外用剤や化粧料への配合時における壊れを防止する観点から、０．４質量％以上が好ましく、０．６質量％以上がより好ましく、０．８質量％以上がさらに好ましい。また、水溶液中で均一に分散および溶解するために２．０質量％以下が好ましく、１．７５質量％以下がより好ましく、１．５質量％以下がさらに好ましい。 The content of agar in the hydrogel particles of the present embodiment is preferably 0.4% by mass or more, preferably 0.6% by mass, from the viewpoint of preventing breakage of the hydrogel particles when blended into an external preparation for skin or cosmetics. % Or more is more preferable, and 0.8% by mass or more is further preferable. Further, in order to uniformly disperse and dissolve in the aqueous solution, 2.0% by mass or less is preferable, 1.75% by mass or less is more preferable, and 1.5% by mass or less is further preferable.
（Ａ２）アルギン酸またはその塩
アルギン酸は、コンブ、ワカメ、アラメなどの褐藻類に含まれる多糖類で、β−Ｄ−マンヌロン酸（Ｍ）とα−Ｌ−グルロン酸（Ｇ）がブロック重合したポリマーである。アルギン酸またはその塩は、海藻抽出物を使用することが可能であり、主な工業的原料としては、マクロシスティス、アスコフィリウム、ダービリア、レソニア、ラミナリアなどの褐藻類から抽出され、精製、乾燥、粉砕された乾物を用いることができる。
(A2) Alginic acid or a salt thereof Alginic acid is a polysaccharide contained in brown algae such as kelp, wakame seaweed, and arame, and is a polymer in which β-D-mannuronic acid (M) and α-L-gluuronic acid (G) are block-polymerized. Is. Alginic acid or its salt can be extracted from seaweed, and the main industrial raw materials are extracted from brown algae such as macrocystis, ascophyllium, darbilia, resonia, laminaria, etc., purified and dried. , Crushed dry matter can be used.
また、アルギン酸塩としては、アルギン酸中のカルボキシル基の水素が、ナトリウムやカリウム、マグネシウム、アンモニウムなどの各イオンと置換されて、水溶性のアルギン酸塩として製品化されたものを用いることができる。 Further, as the alginate, a product commercialized as a water-soluble alginate in which the hydrogen of the carboxyl group in alginic acid is replaced with each ion such as sodium, potassium, magnesium and ammonium can be used.
アルギン酸またはその水溶性塩は、カルシウムイオンなどの二価金属イオンの存在下でゲル化し、寒天やゼラチンなどの熱可塑性ゲルと異なり、一定の温度でゾル−ゲル変化するリオトロピックゲルを形成する。このアルギン酸ゲルの物理化学的性質は、ＭとＧの比率、ブロック組成、二価金属イオンの種類およびその結合度によって変化する。ＧＧブロックの割合が大きいほど二価金属イオンとの結合度は大きく、そのゲルの粘弾性も大きくなる。カルシウムイオンを添加して架橋ゲル化したアルギン酸ゲルにゲルの形成に関与しないナトリウムイオンなどの対イオンを添加すると、橋かけ領域内のグルロン酸ブロック間にスタッキングされたカルシウムイオンが対イオンにより交換されることにより橋かけ構造は崩壊し、溶解することが報告されている。 Alginic acid or its water-soluble salt gels in the presence of divalent metal ions such as calcium ions, forming a sol-gel-changing liotropic gel at a constant temperature, unlike thermoplastic gels such as agar and gelatin. The physicochemical properties of this alginate gel vary depending on the ratio of M and G, block composition, type of divalent metal ion and its degree of binding. The larger the proportion of GG blocks, the greater the degree of binding to divalent metal ions and the greater the viscoelasticity of the gel. When a counterion such as sodium ion, which is not involved in gel formation, is added to the cross-gelled alginate gel by adding calcium ion, the calcium ions stacked between the glulonic acid blocks in the crosslinked region are exchanged by the counterion. It has been reported that the bridging structure collapses and dissolves.
本実施形態のハイドロゲル粒子中におけるアルギン酸またはその塩の含有量は、ハイドロゲル粒子を球状に成形する観点から、０．５質量％以上が好ましく、０．７質量％以上がより好ましく、０．８質量％以上がさらに好ましい。また、水溶液中で均一に分散および溶解するために２．０質量％以下が好ましく、１．７５質量％以下がより好ましく、１．５質量％以下がさらに好ましい。 The content of alginic acid or a salt thereof in the hydrogel particles of the present embodiment is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, from the viewpoint of forming the hydrogel particles into a spherical shape. 8% by mass or more is more preferable. Further, in order to uniformly disperse and dissolve in the aqueous solution, 2.0% by mass or less is preferable, 1.75% by mass or less is more preferable, and 1.5% by mass or less is further preferable.
（Ａ３）カラギーナン
本発明の他の実施形態では、例えば、上記アルギン酸またはその塩の代わりにカラギーナンを用いてもよく、上記アルギン酸またはその塩とカラギーナンとを併用して用いてもよい。本実施形態におけるカラギーナンとは、紅藻類から抽出され、アンヒドロガラクトースとガラクトースの硫酸エステルを構成糖とする多糖類である。カラギーナンは硫酸エステル含量によりκ（カッパ）、ι（イオタ）、λ（ラムダ）があり、本発明においては、特に限定されるものではないが、ι−カラギーナンが好ましい。また、ι−カラギーナンは市販のものをそのまま用いてもよい。例えば、「ソアギーナＴＭ、ＭＶ２０１」（ＭＲＣポリサッカライド社製）等が挙げられる。
(A3) Carrageenan In another embodiment of the present invention, for example, carrageenan may be used in place of the alginic acid or a salt thereof, or the alginic acid or a salt thereof and carrageenan may be used in combination. Carrageenan in the present embodiment is a polysaccharide extracted from red algae and having anhydrogalactose and a sulfate ester of galactose as constituent sugars. Carrageenan has κ (kappa), ι (iota), and λ (lambda) depending on the sulfate ester content, and is not particularly limited in the present invention, but ι-carrageenan is preferable. Further, as the ι-carrageenan, a commercially available product may be used as it is. For example, "Soagina TM , MV201" (manufactured by MRC Polysaccharide Co., Ltd.) and the like can be mentioned.
本実施形態におけるカラギーナンの含有量は、ハイドロゲル粒子を球状に成形する観点から、０．５質量％以上が好ましく、０．７質量％以上がより好ましく、０．８質量％以上がさらに好ましい。また、水溶液中で均一に分散および溶解するために４．０質量％以下が好ましく、３．０質量％以下がより好ましく、２．５質量％以下がさらに好ましい。 The content of carrageenan in the present embodiment is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, still more preferably 0.8% by mass or more, from the viewpoint of forming the hydrogel particles into a spherical shape. Further, in order to uniformly disperse and dissolve in the aqueous solution, 4.0% by mass or less is preferable, 3.0% by mass or less is more preferable, and 2.5% by mass or less is further preferable.
＜（Ｂ）水＞
水としては、例えば、蒸留水、イオン交換水等が挙げられる。本実施形態のハイドロゲル粒子中における水の含有量（含水率）は９４．２０質量％以上であることが好ましい。ハイドロゲル粒子の透明度が増やす観点で、本実施形態のハイドロゲル粒子中における水の含水率は、好ましくは９４．２０質量％以上であり、より好ましくは９４．４０質量％以上であり、更に好ましくは９４．６０質量％以上である。また、粒子をつぶした後の感触を有するようにする観点で、本実施形態のハイドロゲル粒子中における水の含水率は、好ましくは９９．６０質量％以下であり、より好ましくは９９．４０質量以下であり、更に好ましくは９９．２０質量％以下である。
<(B) Water>
Examples of water include distilled water, ion-exchanged water and the like. The water content (moisture content) in the hydrogel particles of the present embodiment is preferably 94.20% by mass or more. From the viewpoint of increasing the transparency of the hydrogel particles, the water content of the water in the hydrogel particles of the present embodiment is preferably 94.20% by mass or more, more preferably 94.40% by mass or more, and further preferably. Is 94.60% by mass or more. Further, from the viewpoint of giving a feeling after crushing the particles, the water content of water in the hydrogel particles of the present embodiment is preferably 99.60% by mass or less, more preferably 99.40% by mass. It is less than or equal to 99.20% by mass or less.
＜カルシウム塩＞
本実施形態のハイドロゲル粒子は、アルギン酸またはその塩を含む水溶液の液滴を、カルシウムイオンを含む溶液に滴下することによって、アルギン酸カルシウムとなりゲル球を形成することができる。このとき用いるカルシウム塩としては、例えば、水酸化カルシウム、塩化カルシウム、炭酸カルシウム、酢酸カルシウム、酪酸カルシウム、クエン酸カルシウム、乳酸カルシウム、サリチル酸カルシウム、グルコン酸カルシウムなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、ゲル形成速度に優れる点で、塩化カルシウムがより好ましい。
<Calcium salt>
The hydrogel particles of the present embodiment can become calcium alginate and form gel spheres by dropping droplets of an aqueous solution containing alginic acid or a salt thereof into a solution containing calcium ions. Examples of the calcium salt used at this time include calcium hydroxide, calcium chloride, calcium carbonate, calcium acetate, calcium butyrate, calcium citrate, calcium lactate, calcium salicylate, calcium gluconate and the like. These may be used alone or in combination of two or more. Among these, calcium chloride is more preferable in terms of excellent gel formation rate.
また、ゲル化したハイドロゲル粒子を水で洗浄することにより、粒子中に含まれるカルシウムイオンの濃度を低下させること又はカルシウムイオンをなくすことができる。これにより、ゲル化したアルギン酸の一部が再可溶化されてもよい。これにより、ハイドロゲル粒子中のアルギン酸は仕込み時に用いた水溶液の濃度から低下する場合がある。 Further, by washing the gelled hydrogel particles with water, the concentration of calcium ions contained in the particles can be reduced or the calcium ions can be eliminated. As a result, a part of the gelled alginic acid may be resolubilized. As a result, alginic acid in the hydrogel particles may decrease from the concentration of the aqueous solution used at the time of preparation.
本実施形態のハイドロゲル粒子は、カルシウムを含まないこともあるが、カルシウムを含む場合は、原子吸光法で測定したカルシウム濃度が０を超えるが、粒子が硬くなりすぎないようにする観点等で、好ましくは原子吸光法で測定したカルシウム濃度が、３５０ｐｐｍ以下であり、より好ましくは３３０ｐｐｍ以下であり、更に好ましくは２５０ｐｐｍ以下である。 The hydrogel particles of the present embodiment may not contain calcium, but when calcium is contained, the calcium concentration measured by the atomic absorption method exceeds 0, but from the viewpoint of preventing the particles from becoming too hard, etc. The calcium concentration measured by the atomic absorption method is preferably 350 ppm or less, more preferably 330 ppm or less, and further preferably 250 ppm or less.
＜内包させる所望の物質＞
本実施形態のハイドロゲル粒子は、所望の物質を内包させることができる。この内包物は、必要に応じて、香粧学的活性または薬理活性を示す活性成分が含まれていてもよい。このような活性成分としては、特に制限されないが、例えば、水溶性のビタミン、油溶性のビタミン、グリチルリチン酸、アスタキサンチン、コエンザイムＱ１０、α−リポ酸、セラミド、リノール酸、アルブチン、トラネキサム酸、コウジ酸、酵素、ペプチド、ホルモン、各種サイトカイン、ヒアルロン酸、コラーゲン、エラスチン、糖類等の生理活性物質またはそれらの誘導体、各種動植物抽出物、微生物による発酵で得られる物質、ステロイド剤、抗ヒスタミン、局所麻酔剤、抗炎症剤、抗菌剤、抗菌剤、鎮痒剤、皮膚保護剤、血行促進剤、ステロール類等が挙げられる。これらの活性成分は、１種単独で使用してもよく、また２種以上を組み合わせて使用してもよい。
<Desired substance to be included>
The hydrogel particles of the present embodiment can contain a desired substance. This inclusion may contain an active ingredient exhibiting cosmetic or pharmacological activity, if necessary. Such active ingredients are not particularly limited, but are, for example, water-soluble vitamins, oil-soluble vitamins, glycyrrhizinic acid, astaxanthin, coenzyme Q10, α-lipoic acid, ceramide, linoleic acid, arbutin, tranexamic acid, and kojic acid. , Enzymes, peptides, hormones, various cytokines, hyaluronic acid, collagen, elastin, sugars and other physiologically active substances or derivatives thereof, various animal and plant extracts, substances obtained by fermentation with microorganisms, steroids, antihistamines, local anesthetics , Anti-inflammatory agents, antibacterial agents, antibacterial agents, antipruritic agents, skin protectants, blood circulation promoters, sterols and the like. These active ingredients may be used alone or in combination of two or more.
＜その他の成分＞
他の任意成分として、皮膚外用剤や化粧料等に通常使用される各種の成分（例えば、着色剤、防腐剤、油剤、界面活性剤、増粘剤、粉体、キレート剤、ｐＨ調整剤、等）を、本発明の効果を損なわない範囲で、適宜配合してもよい。
<Other ingredients>
As other optional ingredients, various ingredients usually used for external preparations for skin, cosmetics, etc. (for example, colorants, preservatives, oils, surfactants, thickeners, powders, chelating agents, pH adjusters, etc. Etc.) may be appropriately blended as long as the effects of the present invention are not impaired.
着色剤としては、顔料および染料が挙げられる。これらの着色剤は、それぞれ単独でまたは２種以上を混合して用いることができる。顔料としては、例えば、カーボンブラック、タルク、カオリン、雲母、雲母チタン、ベンガラ、オキシ塩化ビスマス、珪酸マグネシウム、酸化チタン、酸化鉄、群青等の無機顔料、および赤色２０２号、赤色２０４号、赤色２０５号、赤色２０６号、赤色２１９号、赤色２２８号、赤色４０４号、黄色２０５号、黄色４０１号、だいだい色４０１号、青色４０４号等の有機顔料が挙げられる。染料としては、油溶性染料、建染染料、レーキ染料等が挙げられる。油溶性染料としては、例えば、赤色５０５号、赤色５０１号、赤色２２５号、黄色４０４号、黄色４０５号、黄色２０４号、だいだい色４０３号、青色４０３号、緑色２０２号、紫色２０１号等が挙げられる。建染染料としては、例えば、赤色２２６号、青色２０４号、青色２０１号等が挙げられる。レーキ染料としては、例えば、種々の酸性染料をアルミニウムやバリウムでレーキしたもの等が挙げられる。 Colorants include pigments and dyes. These colorants can be used alone or in admixture of two or more. Examples of pigments include inorganic pigments such as carbon black, talc, kaolin, mica, mica titanium, red iron oxide, bismuth oxychloride, magnesium silicate, titanium oxide, iron oxide, and ultramarine blue, and red 202, red 204, and red 205. Examples thereof include organic pigments such as No. 206, Red No. 219, Red No. 228, Red No. 404, Yellow No. 205, Yellow No. 401, Orange No. 401, and Blue No. 404. Examples of the dye include oil-soluble dyes, vat dyes, and rake dyes. Examples of oil-soluble dyes include red 505, red 501, red 225, yellow 404, yellow 405, yellow 204, orange 403, blue 403, green 202, and purple 201. Can be mentioned. Examples of the vat dye include red 226, blue 204, blue 201 and the like. Examples of the rake dye include those obtained by rake of various acid dyes with aluminum or barium.
防腐剤としては、パラオキシ安息香酸メチル、イソプロピルメチルフェノール、エタノール、フェノキシエタノール、デヒドロ酢酸およびその塩類、パラオキシ安息香酸エチル、パラオキシ安息香酸プロピル、パラオキシ安息香酸ブチル、エチルアルコール等が挙げられ、これらは単独でまたは２種以上を混合して用いることができる。 Examples of preservatives include methyl paraoxybenzoate, isopropylmethylphenol, ethanol, phenoxyethanol, dehydroacetic acid and salts thereof, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, ethyl alcohol and the like, and these are used alone. Alternatively, two or more types can be mixed and used.
（ハイドロゲル粒子の製造方法）
本発明のハイドロゲル粒子の製造方法は、例えば、寒天およびアルギン酸またはその塩を含むゲル形成剤と、所望の物質と、水と、を混合および加熱して混合液を調製する工程と、この混合液を、ノズルを介してカルシウム塩の溶液（例えば、塩化カルシウム水溶液、乳酸カルシウム水溶液）中に滴下して液滴を形成する工程と、そして、形成された液滴を回収および洗浄する工程と、を含む。なお、粒子のゲル形成の速度を遅くする場合は、このカルシウム塩の溶液にキレート剤（例えば、ＥＤＴＡ）を含有する場合もある。ゲル形成剤と、所望の物質とを含む水溶液を調製する工程は、最初に、アルギン酸またはその塩を水中にて１〜数時間攪拌混合してアルギン酸を十分に溶解することが好ましい。続いてゲル化剤である寒天を投入し、７５〜８５℃程度まで加熱して寒天を溶解させる。ハイドロゲル粒子に内包させる物質は、最初から加えてもよいし、あるいは寒天を完全にゲル化してから添加してもよい。温度安定性の低い物質は、寒天を溶解させたゲル化液を５０℃程度まで冷却した保温液中に添加することが好ましい。
(Manufacturing method of hydrogel particles)
The method for producing hydrogel particles of the present invention includes, for example, a step of mixing and heating a gel-forming agent containing agar and alginic acid or a salt thereof, a desired substance, and water to prepare a mixed solution, and the mixing thereof. A step of dropping the liquid into a solution of a calcium salt (for example, an aqueous solution of calcium chloride or an aqueous solution of calcium lactate) via a nozzle to form droplets, and a step of collecting and washing the formed droplets. including. When the rate of gel formation of particles is slowed down, a chelating agent (for example, EDTA) may be contained in the solution of the calcium salt. In the step of preparing an aqueous solution containing a gel-forming agent and a desired substance, it is preferable that alginic acid or a salt thereof is first stirred and mixed in water for 1 to several hours to sufficiently dissolve alginic acid. Subsequently, agar, which is a gelling agent, is added and heated to about 75 to 85 ° C. to dissolve the agar. The substance to be included in the hydrogel particles may be added from the beginning, or may be added after the agar is completely gelled. The substance having low temperature stability is preferably added to a heat insulating solution in which a gelled solution in which agar is dissolved is cooled to about 50 ° C.
このようにして得られた分散液から一般的な滴下法および攪拌法により、ハイドロゲル粒子を製造する。なお、ハイドロゲル粒子からの油性成分の漏れ防止の観点から、ハイドロゲル粒子は、滴下法で製造することが好ましい。 Hydrogel particles are produced from the dispersion liquid thus obtained by a general dropping method and stirring method. From the viewpoint of preventing leakage of oily components from the hydrogel particles, the hydrogel particles are preferably produced by a dropping method.
滴下法は、孔から分散液を吐出し、吐出された分散液がその表面張力または界面張力によって液滴になる性質を利用して製造する方法である。孔から吐出される分散液には、ハイドロゲル粒子の粒径の均一性の観点から、振動を与えてもよい。滴下法により形成された液滴は、固化（例えば、空気等の気相中若しくは液相中で冷却固化及び／又は空気等の気相中若しくは液相中でイオン（カルシウムイオンなど）により架橋が起こり固化）され、粒子となる。 The dropping method is a method in which a dispersion liquid is discharged from a hole, and the discharged dispersion liquid is produced by utilizing the property of becoming droplets due to its surface tension or interfacial tension. The dispersion liquid discharged from the pores may be subjected to vibration from the viewpoint of the uniformity of the particle size of the hydrogel particles. The droplets formed by the dropping method are solidified (for example, cooled and solidified in the gas phase or liquid phase such as air and / or crosslinked by ions (calcium ions, etc.) in the gas phase or liquid phase such as air. It occurs and solidifies) and becomes particles.
滴下法において、液滴を生成させる場所は、気相であってもよく、あるいは液相であってもよい。なお、液相で形成させる場合には、液流れのない静液中で形成させても、あるいは液滴形成管を用いて下降流、上昇流あるいは平行流に同伴させて形成させてもよい。また、孔の端面は、気相および液相のいずれの中に存在していてもよいが、液相中で液滴を形成させる場合には、液相中に存在していることが好ましい。 In the dropping method, the place where the droplet is generated may be a gas phase or a liquid phase. When it is formed in a liquid phase, it may be formed in a static liquid having no liquid flow, or it may be formed by accompanying a downward flow, an upward flow, or a parallel flow using a droplet forming tube. The end face of the pore may be present in either the gas phase or the liquid phase, but when droplets are formed in the liquid phase, it is preferably present in the liquid phase.
攪拌法は、分散液とは実質的に混じり合わない性状を有し、かつ寒天のゲル化温度以上の温度に調整した液に分散液を投入し、攪拌によるせん断力により分散液を微粒化させ、界面張力によって液滴になる性質を利用して製造する方法である。攪拌法により形成された液滴は、分散液とは実質的に混ざり合わない液中で固化（例えば、冷却固化）され、粒子となる。 In the stirring method, the dispersion has a property of being substantially immiscible with the dispersion, and the dispersion is added to a liquid adjusted to a temperature equal to or higher than the gelling temperature of agar, and the dispersion is atomized by the shearing force of stirring. , It is a method of manufacturing by utilizing the property of forming droplets by interfacial tension. The droplets formed by the stirring method are solidified (for example, cooled and solidified) in a liquid that is substantially immiscible with the dispersion liquid to become particles.
吐出時または投入時の分散液の温度は、特に限定されないが、寒天のゲル化温度以上の温度でかつ１００℃以下が好ましい。また、美観に優れた球状の粒子の製造のしやすさの観点から、分散液の温度は、ゲル化温度＋１０℃以上、好ましくはゲル化温度＋２０℃以上であることが望ましい。なお、温度の上限値は、水の沸点以下である１００℃であることが望ましい。 The temperature of the dispersion liquid at the time of discharging or charging is not particularly limited, but is preferably a temperature equal to or higher than the gelling temperature of agar and 100 ° C. or lower. Further, from the viewpoint of easiness of producing spherical particles having excellent aesthetics, it is desirable that the temperature of the dispersion liquid is gelling temperature + 10 ° C. or higher, preferably gelling temperature + 20 ° C. or higher. The upper limit of the temperature is preferably 100 ° C., which is equal to or lower than the boiling point of water.
分散液の粘度は、Ｂ型粘度計で測定することができる。分散液の粘度は、特に限定されないが、その吐出時または投入時の温度において、通常、０．１〜１０００ｍＰａ・ｓ、好ましくは１〜８００ｍＰａ・ｓであることが望ましい。 The viscosity of the dispersion can be measured with a B-type viscometer. The viscosity of the dispersion is not particularly limited, but it is usually 0.1 to 1000 mPa · s, preferably 1 to 800 mPa · s at the temperature at the time of discharging or charging.
（用途）
本発明のハイドロゲル粒子は、例えば、皮膚外用剤（例えば、毛髪や体毛に塗布するための剤（染毛剤、育毛剤、脱毛防止剤、除毛剤など）、口腔（唇など）に塗布等により投与するものも含む）として、クリーム、乳液、美容液等のスキンケア化粧料、石鹸、クレンジングクリーム、クレンジングローション、洗顔料等の皮膚洗浄料、シャンプー、リンス、トリートメント等の洗髪用化粧料や、ヘアクリーム、ヘアスプレー、ヘアトニック、ヘアジェル、ヘアローション、ヘアオイル、ヘアエッセンス、ヘアウォーター、ヘアワックス、ヘアフォーム等の整髪料、育毛・養毛料、ファンデーション、アンダーメーク、フェイスカラー、チークカラー、アイカラー、リップカラー等のメークアップ化粧料、薬用化粧品、外用医薬部外品，外用医薬品等が挙げられる。
(Use)
The hydrogel particles of the present invention are applied to, for example, an external agent for skin (for example, an agent for applying to hair or body hair (hair dye, hair growth agent, hair loss inhibitor, hair remover, etc.), oral cavity (lips, etc.)). Skin care cosmetics such as creams, milky lotions, beauty liquids, skin cleansing products such as soaps, cleansing creams, cleansing lotions, and pigments, hair washing cosmetics such as shampoos, rinses, and treatments. , Hair cream, hair spray, hair tonic, hair gel, hair lotion, hair oil, hair essence, hair water, hair wax, hair styling products such as hair foam, hair growth / hair styling products, foundation, undermake, face color, teak color, eye Examples include make-up cosmetics such as color and lip color, medicated cosmetics, external pharmaceutical products, and external pharmaceutical products.
皮膚外用剤は、化粧品、医薬部外品および医薬品等に慣用される他の成分、例えば、粉末成分、液体油脂、固体油脂、ロウ、炭化水素、高級脂肪酸、高級アルコール、エステル、シリコーン、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤、保湿剤、水溶性高分子、増粘剤、皮膜剤、紫外線吸収剤、金属イオン封鎖剤、低級アルコール、多価アルコール、糖、アミノ酸、有機アミン、高分子エマルジョン、ｐＨ調整剤、皮膚栄養剤、ビタミン、酸化防止剤、酸化防止助剤、香料、水等を必要に応じて配合し、常法により製造することもできる。 Skin external preparations include other components commonly used in cosmetics, non-pharmaceutical products, pharmaceuticals, etc., such as powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, esters, silicones, and anionic surfactants. Activators, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, thickeners, film agents, UV absorbers, metal ion blockers, lower alcohols, polyhydric alcohols, Sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc. can be blended as needed and manufactured by a conventional method. ..
（ハイドロゲル粒子の作製）
＜実施例１＞
１．５ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）と、０．３８ｇのフェノキシエタノールと、を精製水に溶解し、全量９９．６ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．４ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。
(Preparation of hydrogel particles)
<Example 1>
Dissolve 1.5 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) and 0.38 g of phenoxyethanol in purified water, and add a total amount of 99.6 g (from 100 g to the amount of agar added). An aqueous solution of (minus mass) was prepared. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.4 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC.
この水溶液を、２０ｍＭの塩化カルシウム水溶液中にスポイトを用いて滴下し、球状のハイドロゲル粒子を形成した。滴下から１分以内に篩を用いて粒子を回収し、約１０倍量の精製水で洗浄した。これを、１質量％のフェノキシエタノール水溶液に５０質量％となるように浸漬し、４℃にて冷蔵保存した。 This aqueous solution was dropped into a 20 mM calcium chloride aqueous solution using a dropper to form spherical hydrogel particles. Particles were collected using a sieve within 1 minute of the dropping and washed with about 10 times the amount of purified water. This was immersed in a 1% by mass phenoxyethanol aqueous solution so as to have a concentration of 50% by mass, and stored in a refrigerator at 4 ° C.
＜実施例２＞
ゲル形成剤として用いた寒天の配合量を、１．２ｇとしたことを除いて実施例１と同様にしてハイドロゲル粒子を作製し、これを実施例２とした。この実施例２では、実施例１に比べて３倍量の寒天を用いている。
<Example 2>
Hydrogel particles were prepared in the same manner as in Example 1 except that the amount of agar used as the gel-forming agent was 1.2 g, and this was designated as Example 2. In this Example 2, three times as much agar as in Example 1 is used.
＜実施例３＞
１．０ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）と、０．２５ｇのフェノキシエタノールと、を精製水に溶解し、全量９９．４ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．６ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。この水溶液を実施例１と同様の方法にて滴下法によりハイドロゲル粒子を形成した。この実施例３で作製したハイドロゲル粒子は、実施例２に比べてゲル形成剤の使用量が、アルギン酸ナトリウムは２／３に、寒天は１／２に減少している。
<Example 3>
Dissolve 1.0 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) and 0.25 g of phenoxyethanol in purified water, and add a total amount of 99.4 g (from 100 g to the amount of agar added). An aqueous solution of (minus mass) was prepared. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.6 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC. Hydrogel particles were formed by dropping this aqueous solution in the same manner as in Example 1. In the hydrogel particles produced in Example 3, the amount of the gel-forming agent used was reduced to 2/3 for sodium alginate and 1/2 for agar as compared with Example 2.
＜実施例４＞
ゲル形成剤を含む水溶液に０．０１ｇのヒアルロン酸を添加したことを除いて実施例３と同様にしてハイドロゲル粒子を作製し、これを実施例４とした。
<Example 4>
Hydrogel particles were prepared in the same manner as in Example 3 except that 0.01 g of hyaluronic acid was added to the aqueous solution containing the gel-forming agent, and this was designated as Example 4.
＜実施例５＞
ヒアルロン酸の代わりにスクアランを０．０１ｇ添加したことを除いて実施例４と同様にしてハイドロゲル粒子を作製し、これを実施例５とした。
<Example 5>
Hydrogel particles were prepared in the same manner as in Example 4 except that 0.01 g of squalane was added instead of hyaluronic acid, and this was designated as Example 5.
＜実施例６＞
１．０ｇのアルギン酸ナトリウム（株式会社キミカ製、Ｉ−３Ｇ、粘度：３５０ｍＰａ・ｓ）を精製水に溶解し、全量９９．４ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．６ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。この水溶液を実施例１と同様の方法にて滴下法によりハイドロゲル粒子を形成した。この実施例６では、実施例３と比較して用いたアルギン酸ナトリウムの粘度が大きく、またフェノキシエタノールを添加していない点で異なる。
<Example 6>
1.0 g of sodium alginate (manufactured by Kimika Co., Ltd., I-3G, viscosity: 350 mPa · s) was dissolved in purified water to prepare an aqueous solution having a total amount of 99.4 g (mass obtained by subtracting the amount of agar added from 100 g). .. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.6 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC. Hydrogel particles were formed by dropping this aqueous solution in the same manner as in Example 1. This Example 6 is different in that the viscosity of the sodium alginate used is larger than that of Example 3 and that phenoxyethanol is not added.
＜実施例７＞
１．０ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）を精製水に溶解し、全量９８．８ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、１．２ｇの寒天（伊那食品工業株式会社製、ＢＸ２００、ゼリー強度：２２０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。この水溶液を実施例１と同様の方法にて滴下法によりハイドロゲル粒子を形成した。この実施例７では、実施例１〜６と比較して用いた寒天のゼリー強度が異なる。
<Example 7>
1.0 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) was dissolved in purified water to prepare an aqueous solution having a total amount of 98.8 g (mass obtained by subtracting the amount of agar added from 100 g). .. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 1.2 g of agar (manufactured by Ina Food Industry Co., Ltd., BX200, jelly strength: 220) is added, and the mixture is further heated at 85 ° C. for 20 minutes. The agar was completely dissolved while holding. Then, it cooled until the liquid temperature became 50 degreeC. Hydrogel particles were formed by dropping this aqueous solution in the same manner as in Example 1. In this Example 7, the jelly strength of the agar used is different from that in Examples 1 to 6.
＜実施例８＞
ゲル形成剤として用いたアルギン酸ナトリウムの粘度を大きくしたことを除いて実施例７と同様にしてハイドロゲル粒子を作製し、これを実施例８とした。この実施例２では、実施例１に比べて３倍量の寒天を用いている。
<Example 8>
Hydrogel particles were prepared in the same manner as in Example 7 except that the viscosity of sodium alginate used as a gel-forming agent was increased, and this was designated as Example 8. In this Example 2, three times as much agar as in Example 1 is used.
＜実施例９＞
１．５ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）を精製水に溶解し、全量９９．４ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．６ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。この水溶液を実施例１と同様の方法にて滴下法によりハイドロゲル粒子を形成した。この実施例９で作製したハイドロゲル粒子は、実施例３〜５に比べてゲル形成剤として用いたアルギン酸ナトリウムの量が１．５倍に増加している。
<Example 9>
1.5 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) was dissolved in purified water to prepare an aqueous solution having a total amount of 99.4 g (100 g minus the amount of agar added). .. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.6 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC. Hydrogel particles were formed by dropping this aqueous solution in the same manner as in Example 1. In the hydrogel particles produced in Example 9, the amount of sodium alginate used as a gel-forming agent was increased 1.5 times as compared with Examples 3 to 5.
＜実施例１０＞
１．５ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）と、０．３８ｇのフェノキシエタノールと、０．００１ｇの酸化鉄を精製水に溶解し、全量９９．２ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．８ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。この水溶液を実施例１と同様の方法にて滴下法によりハイドロゲル粒子を形成した。
<Example 10>
Dissolve 1.5 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s), 0.38 g of phenoxyethanol, and 0.001 g of iron oxide in purified water, and the total amount is 99.2 g (100 g). An aqueous solution (mass obtained by subtracting the amount of agar added) was prepared. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.8 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC. Hydrogel particles were formed by dropping this aqueous solution in the same manner as in Example 1.
＜実施例１１＞
酸化鉄の代わりに群青を０．１ｇ添加したことを除いて実施例１０と同様にしてハイドロゲル粒子を作製し、これを実施例１１とした。
<Example 11>
Hydrogel particles were prepared in the same manner as in Example 10 except that 0.1 g of ultramarine blue was added instead of iron oxide, and this was designated as Example 11.
＜比較例１＞
１．０ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）を精製水に溶解し、全量９９．９ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．１ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。
<Comparative example 1>
1.0 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) was dissolved in purified water to prepare an aqueous solution having a total amount of 99.9 g (mass obtained by subtracting the amount of agar added from 100 g). .. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.1 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC.
この水溶液を、２０ｍＭの塩化カルシウム水溶液中にスポイトを用いて滴下したところ水中で溶解し、球状のハイドロゲル粒子を形成することができなかった。 When this aqueous solution was dropped into a 20 mM calcium chloride aqueous solution using a dropper, it was dissolved in water and spherical hydrogel particles could not be formed.
＜比較例２＞
１．５ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）を精製水に溶解し、全量９８．０ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、２．０ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。
<Comparative example 2>
1.5 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) was dissolved in purified water to prepare an aqueous solution having a total amount of 98.0 g (mass of 100 g minus the amount of agar added). .. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 2.0 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC.
この水溶液を、２０ｍＭの塩化カルシウム水溶液中にスポイトを用いて滴下し、球状のハイドロゲル粒子を形成した。滴下から１分以内に篩を用いて粒子を回収し、約１０倍量の精製水で洗浄した。これを、１質量％のフェノキシエタノール水溶液に５０質量％となるように浸漬し、４℃にて冷蔵保存した。 This aqueous solution was dropped into a 20 mM calcium chloride aqueous solution using a dropper to form spherical hydrogel particles. Particles were collected using a sieve within 1 minute of the dropping and washed with about 10 times the amount of purified water. This was immersed in a 1% by mass phenoxyethanol aqueous solution so as to have a concentration of 50% by mass, and stored in a refrigerator at 4 ° C.
＜比較例３＞
１．５ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）と、０．３８ｇのフェノキシエタノールと、を精製水に溶解し、全量９９．２ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．８ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。
<Comparative example 3>
Dissolve 1.5 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) and 0.38 g of phenoxyethanol in purified water, and add a total amount of 99.2 g (from 100 g to the amount of agar added). An aqueous solution of (minus mass) was prepared. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.8 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC.
この水溶液を、５０ｍＭの塩化カルシウム水溶液中にスポイトを用いて滴下し、球状のハイドロゲル粒子を形成した。滴下から３時間後に篩を用いて粒子を回収した。これを、１質量％のフェノキシエタノール水溶液に５０質量％となるように浸漬し、４℃にて冷蔵保存した。 This aqueous solution was dropped into a 50 mM calcium chloride aqueous solution using a dropper to form spherical hydrogel particles. Particles were collected using a sieve 3 hours after the dropping. This was immersed in a 1% by mass phenoxyethanol aqueous solution so as to have a concentration of 50% by mass, and stored in a refrigerator at 4 ° C.
（試験評価方法）
＜圧縮破断強度と平均粒径＞
ハイドロゲル粒子の圧縮破断強度は、サン科学社製のレオメーター（ＲＨＥＯ ＭＥＴＥＲ、ＭＯＤＥＬ：ＣＲ−３０００ＥＸ）を用いて測定した。実施例および比較例で作製した粒子を測定前に粒重量の１０倍量の精製水で洗浄し、表面の水分を拭き取って測定した。なお、この圧縮破断強度の測定は、直径２０ｍｍの治具を取り付けたレオメーターを用い、レオメーターの測定部の円盤状の試料台上にサンプルを置いて１０ｍｍ／分の速度で上昇させた。進入距離２．２ｍｍにて圧縮して破断させた。この時、目視、感触で破断を確認するとともに、荷重−歪み曲線から破断強度を求め、この測定を５個のサンプルについて繰り返し、その平均値を求めた。
測定に用いたハイドロゲル粒子の厚みを測定してサンプルの粒径とし、この粒径から面積算出し、先に測定した荷重（Ｎ）を、断面積を除して破断強度（ｋＰａ）とした。そして、この「サンプルの粒径」を平均粒径とした。
(Test evaluation method)
<Compressive breaking strength and average particle size>
The compressive breaking strength of the hydrogel particles was measured using a rheometer (RHEO METER, MODEL: CR-3000EX) manufactured by Sun Scientific Co., Ltd. Before the measurement, the particles prepared in Examples and Comparative Examples were washed with 10 times the weight of the particles in purified water, and the water on the surface was wiped off for measurement. The compression breaking strength was measured by using a rheometer equipped with a jig having a diameter of 20 mm, placing the sample on a disk-shaped sample table of the measuring part of the rheometer, and raising the sample at a speed of 10 mm / min. It was compressed and fractured at an approach distance of 2.2 mm. At this time, the fracture was confirmed visually and by touch, and the fracture strength was obtained from the load-strain curve, and this measurement was repeated for 5 samples to obtain the average value.
The thickness of the hydrogel particles used in the measurement was measured to obtain the particle size of the sample, the area was calculated from this particle size, and the previously measured load (N) was divided by the cross-sectional area to obtain the breaking strength (kPa). .. Then, this "sample particle size" was taken as the average particle size.
＜含水率＞
ハイドロゲル粒子の含水率は、ＡＤＶＡＮＴＥＣ社製の乾燥機（ＤＲＮ４２０ＤＤ）を用いて測定した。実施例および比較例で作製した粒子を測定前に粒重量の１０倍量の精製水で洗浄し、表面の水分を拭き取って測定した。測定条件としては、秤量瓶を前日乾燥させ風袋重量を測定した。２０ｇのハイドロゲル粒子を入れ、乾燥温度１０５℃で２４時間乾燥後、以下の式にて含水率を計算した。
含水率＝（１−（乾燥後粒重量／乾燥前粒重量））×１００（％）
<Moisture content>
The water content of the hydrogel particles was measured using a dryer (DRN420DD) manufactured by ADVANTEC. Before the measurement, the particles prepared in Examples and Comparative Examples were washed with 10 times the weight of the particles in purified water, and the water on the surface was wiped off for measurement. As the measurement conditions, the weighing bottle was dried the day before and the tare weight was measured. After adding 20 g of hydrogel particles and drying at a drying temperature of 105 ° C. for 24 hours, the water content was calculated by the following formula.
Moisture content = (1- (weight after drying / weight before drying)) x 100 (%)
＜カルシウム濃度＞
ハイドロゲル粒子のカルシウム濃度（カルシウムイオン濃度）は、原子吸光法により測定した。実施例および比較例で作製した粒子を測定前に粒重量の１０倍量の精製水で洗浄し、表面の水分を拭き取った。３ｇのハイドロゲル粒子を３％塩酸水溶液２７ｍｌに１日浸漬し、ろ過した。メスフラスコに１０ｐｐｍとなるようにカルシウム標準液と塩化ランタンが１％となるよう加え、上記ろ過液でメスアップし測定試料とした。
<Calcium concentration>
The calcium concentration (calcium ion concentration) of the hydrogel particles was measured by the atomic absorption method. The particles prepared in Examples and Comparative Examples were washed with 10 times the weight of the particles of purified water before measurement, and the water on the surface was wiped off. 3 g of hydrogel particles were immersed in 27 ml of a 3% aqueous hydrochloric acid solution for 1 day and filtered. A calcium standard solution and lanthanum chloride were added to a measuring flask so as to have a concentration of 10 ppm, and the solution was used as a measuring sample.
島津製作所社製ＡＡ−６８００型原子吸光分光分析装置を用い、測定波長：４２２．７ｎｍ（Ｃａ極大波長）にて、空気−アセチレン炎によるフレーム方式で原子化して測定した。 Using an AA-6800 type atomic absorption spectrophotometer manufactured by Shimadzu Corporation, the measurement was carried out by atomizing at a measurement wavelength of 422.7 nm (Ca maximum wavelength) by a frame method using an air-acetylene flame.
＜Ｆｅイオン濃度＞
ハイドロゲル粒子の鉄濃度（鉄イオン濃度）は、原子吸光法により測定した。この測定で用いた試料を次の手順により準備した。
<Fe ion concentration>
The iron concentration (iron ion concentration) of the hydrogel particles was measured by the atomic absorption method. The sample used in this measurement was prepared by the following procedure.
以下で記載の実施例１３に係る粒子と実施例１４に係る粒子について、当該測定前に、粒重量の１０倍量の精製水で洗浄し、表面の水分を拭き取った。３ｇの粒子（実施例１３と実施例１４）を、３％塩酸水溶液２７ｍｌに１日浸漬し、当該浸漬後にろ過した。メスフラスコに１０ｐｐｍとなるように鉄標準液を加え、上記ろ過液でメスアップし、測定試料を作製した。 The particles according to Example 13 and the particles according to Example 14 described below were washed with purified water in an amount 10 times the weight of the particles before the measurement, and the water on the surface was wiped off. 3 g of particles (Example 13 and Example 14) were immersed in 27 ml of a 3% aqueous hydrochloric acid solution for 1 day, and filtered after the immersion. An iron standard solution was added to a volumetric flask so as to have a concentration of 10 ppm, and the volumetric solution was used to prepare a measurement sample.
当該試料について、島津製作所社製ＡＡ−６８００型原子吸光分光分析装置を用い、測定波長２４８．３ｎｍ（Ｆｅ極大波長）にて、空気−アセチレン炎によるフレーム方式で原子化して測定した。 The sample was atomized and measured using an AA-6800 type atomic absorption spectrophotometer manufactured by Shimadzu Corporation at a measurement wavelength of 248.3 nm (Fe maximum wavelength) by a frame method using an air-acetylene flame.
＜Ｂａイオン濃度＞
ハイドロゲル粒子のバリウム濃度は、比濁分析法（参考文献：ＴＨＥ ＣＨＥＭＩＣＡＬ ＴＩＭＥＳ ２００５ Ｎｏ．２、１９〜２１ページ、化学分析における基礎技術の重要性（２）重量法及び比濁分析法の実際）によって測定した。この測定で用いた試料を次の手順により準備した。
<Ba ion concentration>
The barium concentration of hydrogel particles is determined by the turbidimetric analysis method (Reference: THE CHEMICAL TIMES 2005 No. 2, pp. 19-21, Importance of basic technology in chemical analysis (2) Practice of gravimetric analysis method and turbidimetric analysis method) Measured by. The sample used in this measurement was prepared by the following procedure.
実施例１２に係る粒子を、希釈してろ過して、ろ液を作製した。並行して、硫酸試薬を精製水で１０ｍｇ／ｍｌに調製した。当該調製した硫酸に塩化バリウムを加えると白濁することを確認した後、１０ｍｇ／ｍｌ硫酸１質量に対し前記ろ液を２質量加え、測定試料を作製した。 The particles according to Example 12 were diluted and filtered to prepare a filtrate. In parallel, the sulfuric acid reagent was prepared with purified water to 10 mg / ml. After confirming that barium chloride was added to the prepared sulfuric acid to make it cloudy, 2 mass of the filtrate was added to 1 mass of 10 mg / ml sulfuric acid to prepare a measurement sample.
島津製作所製ＵＶ−２６００ｉを用い、測定波長４３０．０ｎｍにて、吸光度を求め、サンプル中のバリウム濃度を算出した。 Using a UV-2600i manufactured by Shimadzu Corporation, the absorbance was determined at a measurement wavelength of 430.0 nm, and the barium concentration in the sample was calculated.
＜官能評価＞
５人のパネラーにより、ハイドロゲル粒子を手に取って皮膚の上で潰したときの感触を、以下の評価基準で官能評価し、その平均値を求め、４以上を○、２以上４未満を△、２未満を×として示した。
<Sensory evaluation>
The feel of the hydrogel particles picked up by five panelists and crushed on the skin was sensorimetrically evaluated according to the following evaluation criteria, and the average value was calculated. Δ, less than 2 is shown as ×.
〔評価基準〕
＜透明性＞
透明なプラスチックシャーレに、ハイドロゲル粒子が高さ方向に積み重ならないように敷き詰め、シャーレの下に白色（ＤＩＣ−５８３）の紙を置き、次に白色から黒色（ＤＩＣ−５８２）の紙に変え、シャーレの上からハイドロゲル粒子を観察し、白色の紙を下に置いたときよりも、黒色の紙を下に置いたときに粒子が暗く見えた場合、「透明感があり＝○」とし、粒子の見え方に変化が無かった場合は「透明感が無い＝×」、若干の変化があった場合に「△」として評価した。
<Transparency>
Spread the hydrogel particles on a transparent plastic dish so that they do not stack in the height direction, place white (DIC-583) paper under the dish, and then change from white to black (DIC-582) paper. , Observe the hydrogel particles from the top of the petri dish, and if the particles look darker when the black paper is placed below than when the white paper is placed underneath, it is marked as "transparent = ○". , When there was no change in the appearance of the particles, it was evaluated as "no transparency = ×", and when there was a slight change, it was evaluated as "Δ".
以上の方法で作製したハイドロゲル粒子の各構成成分の配合量および試験評価結果を表２及び表３に示す。なお、表中の「−」は、構成成分が配合されていないことを示す。 Tables 2 and 3 show the blending amount of each component of the hydrogel particles prepared by the above method and the test evaluation results. In addition, "-" in the table indicates that the constituent component is not blended.
表２および表３に示した結果より、実施例１〜１１で作製したハイドロゲル粒子の圧縮破断強度は３２ｋＰａ以下であり容易に潰すことができたが、比較例１の配合量では寒天濃度が低いために水中で崩壊し、ハイドロゲル粒子が形成されなかった。比較例２のハイドロゲル粒子は、圧縮破断強度は２６ｋＰａであったが、含水率が９４．１８％と低いためゲルの潰しやすさ、カス残りおよび透明感が十分ではなかった。 From the results shown in Tables 2 and 3, the hydrogel particles prepared in Examples 1 to 11 had a compressive breaking strength of 32 kPa or less and could be easily crushed, but the agar concentration was high in the blending amount of Comparative Example 1. Due to its low concentration, it collapsed in water and hydrogel particles were not formed. The hydrogel particles of Comparative Example 2 had a compressive breaking strength of 26 kPa, but had a low water content of 94.18%, so that the gel was not easily crushed, residue residue, and transparency were not sufficient.
カルシウム濃度が高い（３３４８ｐｐｍ）こと等から、比較例３で作製したハイドロゲル粒子の圧縮破断強度は３１６ｋＰａと硬く、指で潰すことができなかった。なお、実施例３、４、５、１０および１１の結果より、ハイドロゲル粒子に内包する物質は、圧縮破断強度に大きな影響を与えないものと推測される。 Due to the high calcium concentration (3348 ppm) and the like, the hydrogel particles produced in Comparative Example 3 had a hard compressive breaking strength of 316 kPa and could not be crushed with a finger. From the results of Examples 3, 4, 5, 10 and 11, it is presumed that the substance contained in the hydrogel particles does not significantly affect the compressive breaking strength.
含水率については、寒天は、アルギン酸に比べて離水が多いことが一般に知られているが、寒天濃度の上昇による含水率（自由水）低下が認められるものの、実施例１〜１１で作製したハイドロゲル粒子の含水率は９４．２０質量％以上であるため潰しやすさや透明感に優れていた。なお、実施例１１で作製したハイドロゲル粒子のカルシウム濃度は２１０ｐｐｍとなり、実施例の中では最も高かったが、この濃度では粒子の崩壊性に問題なかった。 Regarding the water content, it is generally known that agar has more water separation than alginic acid, and although a decrease in water content (free water) is observed due to an increase in agar concentration, the hydro prepared in Examples 1 to 11 is observed. Since the water content of the gel particles was 94.20% by mass or more, it was excellent in crushability and transparency. The calcium concentration of the hydrogel particles prepared in Example 11 was 210 ppm, which was the highest in the examples, but there was no problem in the disintegration property of the particles at this concentration.
＜実施例１２＞
１ｇのアルギン酸ナトリウム（株式会社キミカ製、ＩＬ−６Ｇ、粘度：６５ｍＰａ・ｓ）を９８．４ｇの精製水に溶解し、全量９９．４ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．６ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。
<Example 12>
1 g of sodium alginate (manufactured by Kimika Co., Ltd., IL-6G, viscosity: 65 mPa · s) is dissolved in 98.4 g of purified water, and an aqueous solution of 99.4 g (mass of 100 g minus the amount of agar added) is added. Prepared. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.6 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC.
この水溶液を、５０ｍＭの塩化バリウム（ＢａＣｌ２）水溶液中にスポイトを用いて滴下し、球状のハイドロゲル粒子を形成した。滴下から１分後に篩を用いて粒子を回収し、約１０倍量の精製水で洗浄した。これを、１質量％のフェノキシエタノール水溶液に５０質量％となるように浸漬し、４℃にて冷蔵保存した。 This aqueous solution was dropped into a 50 mM barium chloride (BaCl 2 ) aqueous solution using a dropper to form spherical hydrogel particles. After 1 minute from the dropping, the particles were collected using a sieve and washed with about 10 times the amount of purified water. This was immersed in a 1% by mass phenoxyethanol aqueous solution so as to have a concentration of 50% by mass, and stored in a refrigerator at 4 ° C.
＜実施例１３及び１４＞
ハイドロゲル粒子の形成に用いた５０ｍＭの塩化バリウム水溶液の代わりに、２００ｍＭの塩化第一鉄（ＦｅＣｌ２）水溶液を用いたこと以外は実施例１２と同様にしてハイドロゲル粒子を作製し、これを実施例１３とした。また、塩化第一鉄水溶液への浸漬時間を３０分間としたこと以外は実施例１３と同様にしてハイドロゲル粒子を作製し、これを実施例１４とした。
<Examples 13 and 14>
Hydrogel particles were prepared in the same manner as in Example 12 except that a 200 mM ferrous chloride (FeCl 2 ) aqueous solution was used instead of the 50 mM barium chloride aqueous solution used for forming the hydrogel particles. It was referred to as Example 13. Further, hydrogel particles were prepared in the same manner as in Example 13 except that the immersion time in the ferrous chloride aqueous solution was set to 30 minutes, and this was designated as Example 14.
＜実施例１５＞
２ｇのι（イオタ）−カラギーナン（ソアギーナＴＭ、ＭＶ２０１、購入先：株式会社マツモト交商）を、を９７．４ｇの精製水に溶解し、全量９９．４ｇ（１００ｇから寒天の添加量を差し引いた質量）の水溶液を調製した。この水溶液を攪拌しながら加熱し、７０℃程度になったときに、０．６ｇの寒天（伊那食品工業株式会社製、ＰＳ−６、ゼリー強度：８６０）を加え、さらに加熱して８５℃で２０分間保持しながら寒天を完全に溶解させた。その後、液温が５０℃になるまで冷却した。
<Example 15>
2 g of ι (Iota) -carrageenan (Soagina TM , MV201, purchased from: Matsumoto Trading Co., Ltd.) was dissolved in 97.4 g of purified water, and the total amount was 99.4 g (100 g minus the amount of agar added). An aqueous solution of (mass) was prepared. This aqueous solution is heated with stirring, and when it reaches about 70 ° C., 0.6 g of agar (manufactured by Ina Food Industry Co., Ltd., PS-6, jelly strength: 860) is added, and further heated at 85 ° C. The agar was completely dissolved while holding for 20 minutes. Then, it cooled until the liquid temperature became 50 degreeC.
この水溶液を、１００ｍＭの塩化カルシウム水溶液中にスポイトを用いて滴下し、球状のハイドロゲル粒子を形成した。滴下から１分後に篩を用いて粒子を回収し、約１０倍量の精製水で洗浄した。これを、１質量％のフェノキシエタノール水溶液に５０質量％となるように浸漬し、４℃にて冷蔵保存した。 This aqueous solution was dropped into a 100 mM calcium chloride aqueous solution using a dropper to form spherical hydrogel particles. After 1 minute from the dropping, the particles were collected using a sieve and washed with about 10 times the amount of purified water. This was immersed in a 1% by mass phenoxyethanol aqueous solution so as to have a concentration of 50% by mass, and stored in a refrigerator at 4 ° C.
＜実施例１６＞
実施例１５において、塩化カルシウム水溶液への浸漬時間を３０分間としたことを除き同様の条件にしてハイドロゲル粒子を作製し、これを実施例１６とした。
<Example 16>
In Example 15, hydrogel particles were prepared under the same conditions except that the immersion time in the calcium chloride aqueous solution was set to 30 minutes, and this was designated as Example 16.
このようにして作製した実施例１２〜１６のハイドロゲル粒子を、上述した方法と同様の試験方法にて圧縮破断強度及び含水率を測定し、並びに官能試験評価を行った。その結果を以下の表４に示す。表４に示したように、カルシウム塩の代わりにバリウム塩及び鉄塩を用いた場合、並びにアルギン酸ナトリウムの代わりにカラギーナンを用いた場合においても、５０ｋＰａ以下の破断強度を有し、皮膚に塗布した際の指等による崩壊をスムーズに行うことができる。また、官能試験評価の結果も、伸びが良好でカス残りの無いハイドロゲル粒子が得られることが分かった。なお、実施例１４のハイドロゲル粒子においては、透明感は「△」ではあるが、上述のとおり若干ではあるが透明感の変化が確認された。 The hydrogel particles of Examples 12 to 16 thus prepared were measured for compression breaking strength and water content by the same test method as the above-mentioned method, and sensory test evaluation was performed. The results are shown in Table 4 below. As shown in Table 4, even when barium salt and iron salt were used instead of calcium salt, and carrageenan was used instead of sodium alginate, they had a breaking strength of 50 kPa or less and were applied to the skin. It can be smoothly collapsed by a finger or the like. In addition, as a result of the sensory test evaluation, it was found that hydrogel particles having good elongation and no residue residue could be obtained. In the hydrogel particles of Example 14, the transparency was "Δ", but as described above, a slight change in the transparency was confirmed.
以上、本発明の実施形態（実施例も含め）について、表も参照して説明してきたが、本発明の具体的構成は、これに限られるものではなく、本発明の要旨を逸脱しない範囲において、設計変更等があっても、本発明に含まれるものである。
Although the embodiments (including examples) of the present invention have been described above with reference to the table, the specific configuration of the present invention is not limited to this, and is not deviating from the gist of the present invention. , Design changes, etc. are included in the present invention.
Claims (7)
前記混合液を、ノズルを介して塩化カルシウム水溶液中に滴下して液滴を形成する工程と、
前記液滴を回収および洗浄する工程と、を含むハイドロゲル粒子の製造方法。
A step of preparing a mixed solution by mixing and heating a gel-forming agent containing agar and alginic acid or a salt thereof, a desired substance, and water.
A step of dropping the mixed solution into a calcium chloride aqueous solution via a nozzle to form droplets, and
A method for producing hydrogel particles, which comprises a step of collecting and washing the droplets.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019117679 | 2019-06-25 | ||
| JP2019117679 | 2019-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021004236A true JP2021004236A (en) | 2021-01-14 |
Family
ID=74096968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020107720A Pending JP2021004236A (en) | 2019-06-25 | 2020-06-23 | Hydrogel particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021004236A (en) |
-
2020
- 2020-06-23 JP JP2020107720A patent/JP2021004236A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2002041847A1 (en) | Cosmetic or dermatological agent in the form of a creamy permanent mousse or a stable foamed cream | |
| WO2015155639A1 (en) | A gel-like agarose admixture for intermediate cosmetics product | |
| CN102378625A (en) | External preparation for skin | |
| EA025197B1 (en) | Highly concentrated, spherical biopolymer gel particle suspensions prepared by hipe-gelation process | |
| CN102883702A (en) | An aerosol shave composition comprising a hydrophobical agent forming at least one microdroplet | |
| JP5421554B2 (en) | Composition comprising alpha gel | |
| CN104254312A (en) | Kit containing two separate compositions, in particular for cosmetic application | |
| JP2007001994A (en) | Cosmetic | |
| JP2016008181A (en) | Kit for skin external preparation | |
| KR20090057044A (en) | Emulsion composition with good feeling of use | |
| JPH03178917A (en) | Hair cosmetic base with stereoscopic pattern | |
| EP0863192B1 (en) | Humectant composition, base containing the same, and cosmetic material or external preparation containing said humectant composition | |
| CN102917684A (en) | Method of making an aerosol shave composition comprising a hydrophobical agent forming at least one microdroplet | |
| KR20200102915A (en) | Oil-in-water emulsion for lip makeup and care | |
| WO2023206707A1 (en) | Hydrogel microcapsule compatible with cationic daily chemical product | |
| JP2021004236A (en) | Hydrogel particle | |
| JP5869296B2 (en) | Water-in-oil emulsion composition | |
| JP3736761B2 (en) | Skin cosmetics | |
| JP2012171892A (en) | External preparation for skin | |
| CN104434566A (en) | Composition containing acrylic acid (ester)/sodium acryloyl nitrogen copolymer as well as preparation and preparation method thereof | |
| KR20230148815A (en) | Composition in the form of a stable macroscopic emulsion containing a percentage of ingredients of natural origin of at least 95% according to ISO standard 16128 | |
| JP6247043B2 (en) | Cosmetics and external preparation for skin | |
| CN109069353B (en) | Cosmetic preparation | |
| KR101932687B1 (en) | Composition for Lipgloss, Method of Preparation there of | |
| JP2022011029A (en) | Granular cosmetics and cosmetics containing granular cosmetics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230324 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240214 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240402 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20240410 |